In-line bulk supersaturation measurement by electrical conductometry in KDP crystal growth from aqueous solution

NASA Astrophysics Data System (ADS)

Bordui, P. F.; Loiacono, G. M.

1984-07-01

A method is presented for in-line bulk supersaturation measurement in crystal growth from aqueous solution. The method is based on a computer-controlled concentration measurement exploiting an experimentally predetermined cross-correlation between the concentration, electrical conductivity, and temperature of the growth solution. The method was applied to Holden crystallization of potassium dihydrogen phosphate (KDP). An extensive conductivity-temperature-concentration data base was generated for this system over a temperature range of 31 to 41°C. The method yielded continous, automated bulk supersaturation output accurate to within ±0.05 g KDP100 g water (±0.15% relative supersaturation).

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

Bulk Moisture and Salinity Sensor

NASA Technical Reports Server (NTRS)

Nurge, Mark; Monje, Oscar; Prenger, Jessica; Catechis, John

2013-01-01

Measurement and feedback control of nutrient solutions in plant root zones is critical to the development of healthy plants in both terrestrial and reduced-gravity environments. In addition to the water content, the amount of fertilizer in the nutrient solution is important to plant health. This typically requires a separate set of sensors to accomplish. A combination bulk moisture and salinity sensor has been designed, built, and tested with different nutrient solutions in several substrates. The substrates include glass beads, a clay-like substrate, and a nutrient-enriched substrate with the presence of plant roots. By measuring two key parameters, the sensor is able to monitor both the volumetric water content and salinity of the nutrient solution in bulk media. Many commercially available moisture sensors are point sensors, making localized measurements over a small volume at the point of insertion. Consequently, they are more prone to suffer from interferences with air bubbles, contact area of media, and root growth. This makes it difficult to get an accurate representation of true moisture content and distribution in the bulk media. Additionally, a network of point sensors is required, increasing the cabling, data acquisition, and calibration requirements. measure the dielectric properties of a material in the annular space of the vessel. Because the pore water in the media often has high salinity, a method to measure the media moisture content and salinity simultaneously was devised. Characterization of the frequency response for capacitance and conductance across the electrodes was completed for 2-mm glass bead media, 1- to 2-mm Turface (a clay like media), and 1- to 2-mm fertilized Turface with the presence of root mass. These measurements were then used to find empirical relationships among capacitance (C), the dissipation factor (D), the volumetric water content, and the pore water salinity.

Enthalpic Breakdown of Water Structure on Protein Active-Site Surfaces

PubMed Central

Haider, Kamran; Wickstrom, Lauren; Ramsey, Steven; Gilson, Michael K.; Kurtzman, Tom

2016-01-01

The principles underlying water reorganization around simple non-polar solutes are well understood and provide the framework for classical hydrophobic effect, whereby water molecules structure themselves around solutes so that they maintain favorable energetic contacts with both the solute and with other water molecules. However, for certain solute surface topographies, water molecules, due to their geometry and size, are unable to simultaneously maintain favorable energetic contacts with both the surface and neighboring water molecules. In this study, we analyze the solvation of ligand-binding sites for six structurally diverse proteins using hydration site analysis and measures of local water structure, in order to identify surfaces at which water molecules are unable to structure themselves in a way that maintains favorable enthalpy relative to bulk water. These surfaces are characterized by a high degree of enclosure, weak solute-water interactions, and surface constraints that induce unfavorable pair interactions between neighboring water molecules. Additionally, we find that the solvation of charged side-chains in an active site generally results in favorable enthalpy but can also lead to pair interactions between neighboring water molecules that are significantly unfavorable relative to bulk water. We find that frustrated local structure can occur not only in apolar and weakly polar pockets, where overall enthalpy tends to be unfavorable, but also in charged pockets, where overall water enthalpy tends to be favorable. The characterization of local water structure in these terms may prove useful for evaluating the displacement of water from diverse protein active-site environments. PMID:27169482

Hierarchical viscosity of aqueous solution of tilapia scale collagen investigated via dielectric spectroscopy between 500 MHz and 2.5 THz

PubMed Central

Kawamata, H.; Kuwaki, S.; Mishina, T.; Ikoma, T.; Tanaka, J.; Nozaki, R.

2017-01-01

Aqueous solutions of biomolecules such as proteins are very important model systems for understanding the functions of biomolecules in actual life processes because interactions between biomolecules and the surrounding water molecules are considered to be important determinants of biomolecules’ functions. Globule proteins have been extensively studied via dielectric spectroscopy; the results indicate three relaxation processes originating from fluctuations in the protein molecule, the bound water and the bulk water. However, the characteristics of aqueous solutions of collagens have rarely been investigated. In this work, based on broadband dielectric measurements between 500 MHz and 2.5 THz, we demonstrate that the high viscosity of a collagen aqueous solution is due to the network structure being constructed of rod-like collagen molecules surrounding free water molecules and that the water molecules are not responsible for the viscosity. We determine that the macroscopic viscosity is related to the mean lifetime of the collagen-collagen interactions supporting the networks and that the local viscosity of the water surrounded by the networks is governed by the viscosity of free water as in the bulk. This hierarchical structure in the dynamics of the aqueous solution of biomolecules has been revealed for the first time. PMID:28345664

Molecular conformation of linear alkane molecules: From gas phase to bulk water through the interface

NASA Astrophysics Data System (ADS)

Murina, Ezequiel L.; Fernández-Prini, Roberto; Pastorino, Claudio

2017-08-01

We studied the behavior of long chain alkanes (LCAs) as they were transferred from gas to bulk water, through the liquid-vapor interface. These systems were studied using umbrella sampling molecular dynamics simulation and we have calculated properties like free energy profiles, molecular orientation, and radius of gyration of the LCA molecules. The results show changes in conformation of the solutes along the path. LCAs adopt pronounced molecular orientations and the larger ones extend appreciably when partially immersed in the interface. In bulk water, their conformations up to dodecane are mainly extended. However, larger alkanes like eicosane present a more stable collapsed conformation as they approach bulk water. We have characterized the more probable configurations in all interface and bulk regions. The results obtained are of interest for the study of biomatter processes requiring the transfer of hydrophobic matter, especially chain-like molecules like LCAs, from gas to bulk aqueous systems through the interface.

Nanostructured protic ionic liquids retain nanoscale features in aqueous solution while precursor Brønsted acids and bases exhibit different behavior.

PubMed

Greaves, Tamar L; Kennedy, Danielle F; Weerawardena, Asoka; Tse, Nicholas M K; Kirby, Nigel; Drummond, Calum J

2011-03-10

Small- and wide-angle X-ray scattering (SWAXS) has been used to investigate the effect that water has on the nanoscale structure of protic ionic liquids (PILs) along with their precursor Brønsted acids and bases. The series of PILs consisted of primary, secondary, and tertiary alkylammonium cations in conjunction with formate, nitrate, or glycolate anions. Significant differences were observed for these systems. The nanoscale aggregates present in neat protic ionic liquids were shown to be stable in size on dilution to high concentrations of water, indicating that the water is localized in the ionic region and has little effect on the nonpolar domains. The Brønsted acid-water solutions did not display nanostructure at any water concentration. Primary amine Brønsted bases formed aggregates in water, which generally displayed characteristics of poorly structured microemulsions or a form of bicontinuous phase. Exceptions were butyl- and pentylamine with high water concentrations, for which the SWAXS patterns fitted well to the Teubner-Strey model for microemulsions. Brønsted base amines containing multiple alkyl chains or hydroxyl groups did not display nanostructure at any water concentration. IR spectroscopy was used to investigate the nature of water in the various solutions. For low PIL concentrations, the water was predominately present as bulk water for PIL molar fractions less than 0.4-0.5. At high PIL concentrations, in addition to the bulk water, there was a significant proportion of perturbed water, which is water influenced in some way by the cations and anions. The molecular state of the water in the studied amines was predominately present as bulk water, with smaller contributions from perturbed water than was seen in the PILs. © 2011 American Chemical Society

Effects of a type I antifreeze protein (AFP) on the melting of frozen AFP and AFP+solute aqueous solutions studied by NMR microimaging experiment.

PubMed

Ba, Yong; Mao, Yougang; Galdino, Luiz; Günsen, Zorigoo

2013-01-01

The effects of a type I AFP on the bulk melting of frozen AFP solutions and frozen AFP+solute solutions were studied through an NMR microimaging experiment. The solutes studied include sodium chloride and glucose and the amino acids alanine, threonine, arginine, and aspartic acid. We found that the AFP is able to induce the bulk melting of the frozen AFP solutions at temperatures lower than 0 °C and can also keep the ice melted at higher temperatures in the AFP+solute solutions than those in the corresponding solute solutions. The latter shows that the ice phases were in super-heated states in the frozen AFP+solute solutions. We have tried to understand the first experimental phenomenon via the recent theoretical prediction that type I AFP can induce the local melting of ice upon adsorption to ice surfaces. The latter experimental phenomenon was explained with the hypothesis that the adsorption of AFP to ice surfaces introduces a less hydrophilic water-AFP-ice interfacial region, which repels the ionic/hydrophilic solutes. Thus, this interfacial region formed an intermediate chemical potential layer between the water phase and the ice phase, which prevented the transfer of water from the ice phase to the water phase. We have also attempted to understand the significance of the observed melting phenomena to the survival of organisms that express AFPs over cold winters.

Temporal trends of bulk precipitation and stream water chemistry (1977-1997) in a small forested area, Krusne hory, northern Bohemia, Czech Republic

USGS Publications Warehouse

Peters, N.E.; Cerny, J.; Havel, M.; Krejci, R.

1999-01-01

The Krusne hory (Erzgebirge or Ore Mountains) has been heavily affected by high atmospheric pollutant deposition caused by fossil fuel combustion in an adjacent Tertiary coal basin. Long-term routine sampling of bulk precipitation (1977-1996) and stream water (1977-1998) in a forested area on the south-eastern slope of the mountains were used to evaluate trends and patterns in solute concentration and flux with respect to controlling processes. From 1977 to 1996, the annual volume-weighted Ca2+ and SO42- concentrations decreased in bulk precipitation. However, after 1989, when a pronounced and continuous decrease occurred in coal production, annual volume-weighted concentrations decreased for most solutes, except H+. The concentration decreases were marked, with 1996 levels at or below 50% of those in 1989. The lack of a trend in H+ is attributed to similar decreases in both acid anions and neutralizing base cations. Stream water concentrations of most solutes, i.e. H+, Ca2+, Mg2+, SO42- and NO3-, were highest at the onset of sampling in 1977, decreased markedly from 1977 to 1983 and decreased more gradually from 1983 to 1998. The spruce forest die-back and removal reduced dry deposition of these solutes by reducing the filtering action, which was provided by the forest canopy. A notable decrease in stream water Ca2+ concentrations occurred after 1995 and may be due to the depletion of Ca2+, which was provided by catchment liming in 1986, 1988 and 1989. Solute flux trends in bulk atmospheric deposition and stream water generally were not significant and the lack of trend is attributed to the large interannual variability in precipitation quantity and runoff, respectively. All solutes except Na+ varied seasonally. The average seasonal concentrations varied between the solutes, but for most solutes were highest in winter and spring and lowest in summer, correlating with the seasonal trend and runoff. For Ca2+, Mg2+ and SO42-, the concentration minimum occurs in September and the maximum occurs in February or March, correlating with the seasonal baseflow. These solutes are primarily controlled by the contribution of soil water and groundwater to stream flow. During snowmelt, the meltwater generally causes concentrations to decrease as soil water and groundwater are diluted. For NO3, average minimum concentrations occur in August at the end of the growing season concurrent with the lowest stream flow, and the maximum occurs in February and March with high stream flow during snowmelt. Seasonal stream water NO3- concentration variations are large compared with the long-term decrease.The Krusne hory (Erzgebirge or Ore Mountains) has been heavily affected by high atmospheric pollutant deposition caused by fossil fuel combustion in an adjacent Tertiary coal basin. Long-term routine sampling of bulk precipitation (1977-1996) and stream water (1977-1998) in a forested area on the south-eastern slope of the mountains were used to evaluate trends and patterns in solute concentration and flux with respect to controlling processes. From 1977 to 1996, the annual volume-weighted Ca2+ and SO42- concentrations decreased in bulk precipitation. However, after 1989, when a pronounced and continuous decrease occurred in coal production, annual volume-weighted concentrations decreased for most solutes, except H+. The concentration decreases were marked, with 1996 levels at or below 50% of those in 1989. The lack of a trend in H+ is attributed to similar decreases in both acid anions and neutralizing base cations. Stream water concentrations of most solutes, i.e. H+, Ca2+, Mg2+, SO42- and NO3-, were highest at the onset of sampling in 1977, decreased markedly from 1977 to 1983 and decreased more gradually from 1983 to 1998. The spruce forest die-back and removal reduced dry deposition of these solutes by reducing the filtering action, which was provided by the forest canopy. A notable decrease in stream water Ca2+ concentrations occurred after 1995 an

Study of the influence of surfactants on the transfer of gases into liquids by inverse gas chromatography.

PubMed

Atta, Khan Rashid; Gavril, Dimitrios; Loukopoulos, Vassilios; Karaiskakis, George

2004-01-16

The experimental technique of the reversed-flow version of inverse gas chromatography was applied for the study of effects of surfactants in reducing air-water exchange rates. The vinyl chloride (VC)-water system was used as a model, which is of great importance in environmental chemistry. Using suitable mathematical analysis, various physicochemical quantities were calculated, among which the most significant are: Partition coefficients of the VC gas between the surfactant interface and the carrier gas nitrogen, as well as between the bulk of the water + surfactant solution and the carrier gas nitrogen, overall mass transfer coefficients of VC in the liquid (water + surfactant) and the gas (nitrogen) phases, water and surfactant film transfer coefficients, nitrogen, water and surfactant phase resistances for the transfer of VC into the water solution, relative resistance of surfactant in the transfer of VC into the bulk of solution, exchange velocity of VC between nitrogen and the liquid solution, and finally the thickness of the surfactant stagnant film in the liquid phase, according to the three phase resistance model. From the variation of the above parameters with the surfactant's concentration, important conclusions concerning the effects of surfactants on the transfer of a gas at the air-liquid interface, as well as to the bulk of the liquid were extracted. An interesting finding of this work was also that by successive addition of surfactant, the critical micelle concentration of surfactant was obtained, after which follows a steady-state for the transfer of the gas into the water body, which could be attributed to the transition from mono- to multi-layer state.

Temperature dependence of water-water and ion-water correlations in bulk water and electrolyte solutions probed by femtosecond elastic second harmonic scattering

NASA Astrophysics Data System (ADS)

Chen, Yixing; Dupertuis, Nathan; Okur, Halil I.; Roke, Sylvie

2018-06-01

The temperature dependence of the femtosecond elastic second harmonic scattering (fs-ESHS) response of bulk light and heavy water and their electrolyte solutions is presented. We observe clear temperature dependent changes in the hydrogen (H)-bond network of water that show a decrease in the orientational order of water with increasing temperature. Although D2O has a more structured H-bond network (giving rise to more fs-ESHS intensity), the relative temperature dependence is larger in H2O. The changes are interpreted in terms of the symmetry of H-bonds and are indicators of nuclear quantum effects. Increasing the temperature in electrolyte solutions decreases the influence of the total electrostatic field from ions on the water-water correlations, as expected from Debye-Hückel theory, since the Debye length becomes longer. The effects are, however, 1.9 times (6.3 times) larger than those predicted for H2O (D2O). Since fs-ESHS responses can be computed from known molecular coordinates, our observations provide a unique opportunity to refine quantum mechanical models of water.

Role of Spatial Ionic Distribution on the Energetics of Hydrophobic Assembly and Properties of the Water/Hydrophobe Interface†

PubMed Central

Bauer, Brad A.; Ou, Shuching; Patel, Sandeep

2014-01-01

We present results from all-atom molecular dynamics simulations of large-scale hydrophobic plates solvated in NaCl and NaI salt solutions. As observed in studies of ions at the air-water interface, the density of iodide near the water-plate interface is significantly enhanced relative to chloride and in the bulk. This allows for the partial hydration of iodide while chloride remains more fully hydrated. In 1M solutions, iodide directly pushes the hydrophobes together (contributing −2.51 kcal/mol) to the PMF. Chloride, however, strengthens the water-induced contribution to the PMF by ~ −2.84 kcal/mol. These observations are enhanced in 3M solutions, consistent with the increased ion density in the vicinity of the hydrophobes. The different salt solutions influence changes in the critical hydrophobe separation distance and characteristic wetting/dewetting transitions. These differences are largely influenced by the ion-specific expulsion of iodide from bulk water. Results of this study are of general interest to the study of ions at interfaces and may lend insight to the mechanisms underlying the Hofmeister series. PMID:22231014

Nucleation via an unstable intermediate phase.

PubMed

Sear, Richard P

2009-08-21

The pathway for crystallization from dilute vapors and solutions is often observed to take a detour via a liquid or concentrated-solution phase. For example, in moist subzero air, droplets of liquid water form, which then freeze. In this example and in many others, an intermediate phase (here liquid water) is dramatically accelerating the kinetics of a phase transition between two other phases (water vapor and ice). Here we study this phenomenon via exact computer simulations of a simple lattice model. Surprisingly, we find that the rate of nucleation of the new equilibrium phase is actually fastest when the intermediate phase is slightly unstable in the bulk, i.e., has a slightly higher free energy than the phase we start in. Nucleation occurs at a concave part of the surface and microscopic amounts of the intermediate phase can form there even before the phase is stable in the bulk. As the nucleus of the equilibrium phase is microscopic, this allows nucleation to occur effectively in the intermediate phase before it is stable in the bulk.

Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

DOE PAGES

Greathouse, Jeffery A.; Hart, David; Bowers, Geoffrey M.; ...

2015-07-20

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water andmore » ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.« less

Bubble formation in water with addition of a hydrophobic solute.

PubMed

Okamoto, Ryuichi; Onuki, Akira

2015-07-01

We show that phase separation can occur in a one-component liquid outside its coexistence curve (CX) with addition of a small amount of a solute. The solute concentration at the transition decreases with increasing the difference of the solvation chemical potential between liquid and gas. As a typical bubble-forming solute, we consider O2 in ambient liquid water, which exhibits mild hydrophobicity and its critical temperature is lower than that of water. Such a solute can be expelled from the liquid to form gaseous domains while the surrounding liquid pressure is higher than the saturated vapor pressure p cx. This solute-induced bubble formation is a first-order transition in bulk and on a partially dried wall, while a gas film grows continuously on a completely dried wall. We set up a bubble free energy ΔG for bulk and surface bubbles with a small volume fraction ϕ. It becomes a function of the bubble radius R under the Laplace pressure balance. Then, for sufficiently large solute densities above a threshold, ΔG exhibits a local maximum at a critical radius and a minimum at an equilibrium radius. We also examine solute-induced nucleation taking place outside CX, where bubbles larger than the critical radius grow until attainment of equilibrium.

URANIUM EXTRACTION

DOEpatents

Harrington, C.D.; Opie, J.V.

1958-07-01

The recovery of uranium values from uranium ore such as pitchblende is described. The ore is first dissolved in nitric acid, and a water soluble nitrate is added as a salting out agent. The resulting feed solution is then contacted with diethyl ether, whereby the bulk of the uranyl nitrate and a portion of the impurities are taken up by the ether. This acid ether extract is then separated from the aqueous raffinate, and contacted with water causing back extractioa of the uranyl nitrate and impurities into the water to form a crude liquor. After separation from the ether extract, this crude liquor is heated to about 118 deg C to obtain molten uranyl nitrate hexahydratc. After being slightly cooled the uranyl nitrate hexahydrate is contacted with acid free diethyl ether whereby the bulk of the uranyl nitrate is dissolved into the ethcr to form a neutral ether solution while most of the impurities remain in the aqueous waste. After separation from the aqueous waste, the resultant ether solution is washed with about l0% of its volume of water to free it of any dissolved impurities and is then contacted with at least one half its volume of water whereby the uranyl nitrate is extracted into the water to form an aqueous product solution.

Fourier transform infrared and Raman spectroscopic characterization of homogeneous solution concentration gradients near a container wall at different temperatures

NASA Technical Reports Server (NTRS)

Loo, B. H.; Burns, D. H.; Lee, Y. G. L.; Emerson, M. T.

1991-01-01

Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to study the solution concentration gradient in succino nitrile-rich and water-rich homogeneous solutions. The spectroscopic data shows significant concentration dependency. Although FTIR-attenuated total reflectance could not yield surface spectra since the evanescent infrared wave penetrated deep into the bulk solution, it showed that water-rich clusters were decreased at higher temperatures. This result is consistent with the calorimetric results reported earlier.

Microwave Dielectric Constant Dependence on Soil Tension.

DTIC Science & Technology

1983-10-01

water to be only a single monolayer thick .1 (OA) with Ice-like dielectric properties EWS = (3.15, JO). The first approach apportions the soil solution Into...mixing model that accounts explicitly for the presence of a hydrationU layer of bound water adjacent to hydrophilic soil particle surfaces. The soil ... solution is differentiated Into (1) a bound, ice-like component and (2) a bulk solution component, by a physical soil model dependent upon either soil

Compressibility of the protein-water interface

NASA Astrophysics Data System (ADS)

Persson, Filip; Halle, Bertil

2018-06-01

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (˜0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ˜45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in bulk water, whereas its self part is 15%-20% lower. These large reductions are caused mainly by the proximity to the more rigid protein and are not a consequence of the perturbed water structure.

Compressibility of the protein-water interface.

PubMed

Persson, Filip; Halle, Bertil

2018-06-07

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (∼0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ∼45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in bulk water, whereas its self part is 15%-20% lower. These large reductions are caused mainly by the proximity to the more rigid protein and are not a consequence of the perturbed water structure.

Pretreatment of Hanford medium-curie wastes by fractional crystallization.

PubMed

Nassif, Laurent; Dumont, George; Alysouri, Hatem; Rousseau, Ronald W

2008-07-01

Acceleration of the schedule for decontamination of the Hanford site using bulk vitrification requires implementation of a pretreatment operation. Medium-curie waste must be separated into two fractions: one is to go to a waste treatment and immobilization plant and a second, which is low-activity waste, is to be processed by bulk vitrification. The work described here reports research on using fractional crystallization for that pretreatment. Sodium salts are crystallized by evaporation of water from solutions simulating those removed from single-shell tanks, while leaving cesium in solution. The crystalline products are then recovered and qualified as low-activity waste, which is suitable upon redissolution for processing by bulk vitrification. The experimental program used semibatch operation in which a feed solution was continuously added to maintain a constant level in the crystallizer while evaporating water. The slurry recovered at the end of a run was filtered to recover product crystals, which were then analyzed to determine their composition. The results demonstrated that targets on cesium separation from the solids, fractional recovery of sodium salts, and sulfate content of the recovered salts can be achieved by the process tested.

Quantum chemistry in arbitrary dielectric environments: Theory and implementation of nonequilibrium Poisson boundary conditions and application to compute vertical ionization energies at the air/water interface

NASA Astrophysics Data System (ADS)

Coons, Marc P.; Herbert, John M.

2018-06-01

Widely used continuum solvation models for electronic structure calculations, including popular polarizable continuum models (PCMs), usually assume that the continuum environment is isotropic and characterized by a scalar dielectric constant, ɛ. This assumption is invalid at a liquid/vapor interface or any other anisotropic solvation environment. To address such scenarios, we introduce a more general formalism based on solution of Poisson's equation for a spatially varying dielectric function, ɛ(r). Inspired by nonequilibrium versions of PCMs, we develop a similar formalism within the context of Poisson's equation that includes the out-of-equilibrium dielectric response that accompanies a sudden change in the electron density of the solute, such as that which occurs in a vertical ionization process. A multigrid solver for Poisson's equation is developed to accommodate the large spatial grids necessary to discretize the three-dimensional electron density. We apply this methodology to compute vertical ionization energies (VIEs) of various solutes at the air/water interface and compare them to VIEs computed in bulk water, finding only very small differences between the two environments. VIEs computed using approximately two solvation shells of explicit water molecules are in excellent agreement with experiment for F-(aq), Cl-(aq), neat liquid water, and the hydrated electron, although errors for Li+(aq) and Na+(aq) are somewhat larger. Nonequilibrium corrections modify VIEs by up to 1.2 eV, relative to models based only on the static dielectric constant, and are therefore essential to obtain agreement with experiment. Given that the experiments (liquid microjet photoelectron spectroscopy) may be more sensitive to solutes situated at the air/water interface as compared to those in bulk water, our calculations provide some confidence that these experiments can indeed be interpreted as measurements of VIEs in bulk water.

Quantum chemistry in arbitrary dielectric environments: Theory and implementation of nonequilibrium Poisson boundary conditions and application to compute vertical ionization energies at the air/water interface.

PubMed

Coons, Marc P; Herbert, John M

2018-06-14

Widely used continuum solvation models for electronic structure calculations, including popular polarizable continuum models (PCMs), usually assume that the continuum environment is isotropic and characterized by a scalar dielectric constant, ε. This assumption is invalid at a liquid/vapor interface or any other anisotropic solvation environment. To address such scenarios, we introduce a more general formalism based on solution of Poisson's equation for a spatially varying dielectric function, ε(r). Inspired by nonequilibrium versions of PCMs, we develop a similar formalism within the context of Poisson's equation that includes the out-of-equilibrium dielectric response that accompanies a sudden change in the electron density of the solute, such as that which occurs in a vertical ionization process. A multigrid solver for Poisson's equation is developed to accommodate the large spatial grids necessary to discretize the three-dimensional electron density. We apply this methodology to compute vertical ionization energies (VIEs) of various solutes at the air/water interface and compare them to VIEs computed in bulk water, finding only very small differences between the two environments. VIEs computed using approximately two solvation shells of explicit water molecules are in excellent agreement with experiment for F - (aq), Cl - (aq), neat liquid water, and the hydrated electron, although errors for Li + (aq) and Na + (aq) are somewhat larger. Nonequilibrium corrections modify VIEs by up to 1.2 eV, relative to models based only on the static dielectric constant, and are therefore essential to obtain agreement with experiment. Given that the experiments (liquid microjet photoelectron spectroscopy) may be more sensitive to solutes situated at the air/water interface as compared to those in bulk water, our calculations provide some confidence that these experiments can indeed be interpreted as measurements of VIEs in bulk water.

Radiofrequency Electric Field Heating of Conductive Media: Understanding Aqueous and Nanoparticle Heating Mechanisms and a Method for Heating Optimization

NASA Astrophysics Data System (ADS)

Lara, Nadia Chantal

Use of radiofrequency (RF) electric fields coupled with nanoparticles to enhance non-invasive hyperthermia in cancer cells and tumors sparked debate over the RF heating mechanisms of nanoparticles and the role of salts in heating. Under RF field exposure at 13.56 MHz, aqueous systems including electrolyte solutions, buffers, and blood, were shown to heat according to bulk material properties, regardless of composition. This universal aqueous heating behavior extended to suspensions of nanoparticles such as gold nanoparticles, full-length and ultra-short single-walled carbon nanotubes, and water-soluble fullerene derivatives. These suspensions displayed the same RF heating properties as saline solutions of the same conductivity, indicating that these nanoparticles themselves do not contribute to RF heating by any unique mechanism; rather, they modulate bulk conductivity, which in turn affects bulk RF heating. At 13.56 MHz, peak heating for an aqueous system occurs at a conductivity of 0.06 S/m, beyond which increases in conductivity result in reduced heating rates. Biologically relevant materials, such as blood, intra- and extracellular fluids, and most human tissues, exceed this peak heating conductivity, precluding the use of conductive materials for RF heating rate enhancement. Instead, kosmotropic or water-structuring materials, including sugars, glycols, zwitterionic molecules, and a water-soluble fullerene derivative, when added to blood or phosphate buffered saline reduced the bulk conductivity of these materials and enhanced their heating rates accordingly. A dielectric heating rate model taking into account the geometry of the sample under RF exposure was used to explain the experimental RF heating behavior of aqueous solutions and semi-aqueous materials, which generated distinct RF heating curves due to differences in bulk dielectric and physical properties.

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.

Effects of flow on insulin fibril formation at an air/water interface

NASA Astrophysics Data System (ADS)

Posada, David; Heldt, Caryn; Sorci, Mirco; Belfort, Georges; Hirsa, Amir

2009-11-01

The amyloid fibril formation process, which is implicated in several diseases such as Alzheimer's and Huntington's, is characterized by the conversion of monomers to oligomers and then to fibrils. Besides well-studied factors such as pH, temperature and concentration, the kinetics of this process are significantly influenced by the presence of solid or fluid interfaces and by flow. By studying the nucleation and growth of a model system (insulin fibrils) in a well-defined flow field with an air/water interface, we can identify the flow conditions that impact protein aggregation kinetics both in the bulk solution and at the air/water interface. The present flow system (deep-channel surface viscometer) consists of an annular region bounded by stationary inner and outer cylinders, an air/water interface, and a floor driven at constant rotation. We show the effects of Reynolds number on the kinetics of the fibrillation process both in the bulk solution and at the air/water interface, as well as on the structure of the resultant amyloid aggregates.

Changes in apparent molar water volume and DKP solubility yield insights on the Hofmeister effect.

PubMed

Payumo, Alexander Y; Huijon, R Michael; Mansfield, Deauna D; Belk, Laurel M; Bui, Annie K; Knight, Anne E; Eggers, Daryl K

2011-12-15

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the nonideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water.

Changes in Apparent Molar Water Volume and DKP Solubility Yield Insights on the Hofmeister Effect

PubMed Central

Payumo, Alexander Y.; Huijon, R. Michael; Mansfield, Deauna D.; Belk, Laurel M.; Bui, Annie K.; Knight, Anne E.; Eggers, Daryl K.

2011-01-01

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the non-ideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water. PMID:22029390

Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

NASA Astrophysics Data System (ADS)

Rezus, Y. L. A.; Bakker, H. J.

2008-06-01

We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at a low concentration in the water. We find that the OD vibration of HDO relaxes via an intermediate level, that is characterized by a hydrogen-bond that is stronger than in the ground state. With increasing concentration the lifetime of the excited state increases from 1.8 ps to 2.4 ps and the lifetime of the intermediate level from 0.6 ps to 1.0 ps. Regarding the orientational dynamics we observe biexponential behavior, which finds its origin in the presence of two classes of water molecules. There is a fraction of water molecules that has bulk-like orientational dynamics ( τrot = 2.5 ps) and a fraction of immobilized water molecules ( τrot > 10 ps). The relative abundance of the two fractions is determined by the nature and concentration of the solute. We find that the hydrophobic solute groups are responsible for the immobilization of water molecules. Every methyl group causes the immobilization of approximately 4 water OH groups. The hydrophilic solute groups, on the other hand, do not hinder the reorientation and the water molecules solvating them reorient with the same rate as in the bulk liquid.

Particle characterization of poorly water-soluble drugs using a spray freeze drying technique.

PubMed

Kondo, Masahiro; Niwa, Toshiyuki; Okamoto, Hirokazu; Danjo, Kazumi

2009-07-01

A spray freeze drying (SFD) method was developed to prepare the composite particles of poorly water-soluble drug. The aqueous solution dissolved drug and the functional polymer was sprayed directly into liquid nitrogen. Then, the iced droplets were lyophilized with freeze-dryer to prepare solid particles. Tolbutamide (TBM) and hydroxypropylmethylcellulose (HPMC) were used as a model drug and water-soluble polymeric carrier in this study, respectively. The morphological observation of particles revealed that the spherical particles having porous structure could be obtained by optimizing the loading amount of drug and polymer in the spray solution. Especially, SFD method was characterized that the prepared particles had significantly larger specific surface area comparing with those prepared by the standard spray drying technique. The physicochemical properties of the resultant particles were found to be dependent on the concentration of spray solution. When the solution with high content of drug and polymer was used, the particle size of the resulting composite particles increased and they became spherical. The specific surface area of the particles also increased as a result of higher concentration of solution. The evaluation of spray solution indicated that these results were dependent on the viscosity of spray solution. In addition, when composite particles of TBM were prepared using the SFD method with HPMC as a carrier, the crystallinity of TBM decreased as the proportion of HPMC increased. When the TBM : HPMC ratio reached 1 : 5, the crystallinity of the particles completely disappeared. The dissolution tests showed that the release profiles of poorly water-soluble TBM from SFD composite particles were drastically improved compared to bulk TBM. The 70% release time T(70) of composite particles prepared by the SFD method in a solution of pH 1.2 was quite smaller than that of bulk TBM, while in a solution of pH 6.8, it was slightly lower. In addition, the release rates were faster than those of standard spray dried (SD) composite particles for solutions of pH 1.2 and 6.8, respectively. When composite particles were prepared from mixtures with various composition ratios, T(70) was found to decrease as the proportion of HPMC increased; the release rate was faster than that of bulk TBM in a solution of pH 6.8, as well as solution of pH 1.2.

Thermodynamic and Structural Properties of Methanol-Water Solutions Using Non-Additive Interaction Models

PubMed Central

Zhong, Yang; Warren, G. Lee; Patel, Sandeep

2014-01-01

We study bulk structural and thermodynamic properties of methanol-water solutions via molecular dynamics simulations using novel interaction potentials based on the charge equilibration (fluctuating charge) formalism to explicitly account for molecular polarization at the atomic level. The study uses the TIP4P-FQ potential for water-water interactions, and the CHARMM-based (Chemistry at HARvard Molecular Mechanics) fluctuating charge potential for methanol-methanol and methanol-water interactions. In terms of bulk solution properties, we discuss liquid densities, enthalpies of mixing, dielectric constants, self-diffusion constants, as well as structural properties related to local hydrogen bonding structure as manifested in radial distribution functions and cluster analysis. We further explore the electronic response of water and methanol in the differing local environments established by the interaction of each species predominantly with molecules of the other species. The current force field for the alcohol-water interaction performs reasonably well for most properties, with the greatest deviation from experiment observed for the excess mixing enthalpies, which are predicted to be too favorable. This is qualitatively consistent with the overestimation of the methanol-water gas-phase interaction energy for the lowest-energy conformer (methanol as proton donor). Hydration free energies for methanol in TIP4P-FQ water are predicted to be −5.6±0.2 kcal/mole, in respectable agreement with the experimental value of −5.1 kcal/mole. With respect to solution micro-structure, the present cluster analysis suggests that the micro-scale environment for concentrations where select thermodynamic quantities reach extremal values is described by a bi-percolating network structure. PMID:18074339

Methylene blue adsorption on a DMPA lipid langmuir monolayer.

PubMed

Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

2010-07-12

Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free-energy profile associated with MB transfer from water to the lipid monolayer shows two minima of -66 and -60 kJ mol(-1) for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free-energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed.

Partition of nonionic organic compounds in aquatic systems

USGS Publications Warehouse

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

1988-01-01

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

Mechanisms of the anomalous Pockels effect in bulk water

NASA Astrophysics Data System (ADS)

Yukita, Shunpei; Suzuki, Yuto; Shiokawa, Naoyuki; Kobayashi, Takayoshi; Tokunaga, Eiji

2018-04-01

The "anomalous" Pockels effect is a phenomenon that a light beam passing between two electrodes in an aqueous electrolyte solution is deflected by an AC voltage applied between the electrodes: the deflection angle is proportional to the voltage such that the incident beam alternately changes its direction. This phenomenon, the Pockels effect in bulk water, apparently contradicts what is believed in nonlinear optics, i.e., macroscopic inversion symmetry should be broken for the second-order nonlinear optical effect to occur such as the first-order electro-optic effect, i.e., the Pockels effect. To clarify the underlying mechanism, the dependence of the effect on the electrode material is investigated to find that the Pockels coefficient with Pt electrodes is two orders of magnitude smaller than with indium tin oxide (ITO) electrodes. It is experimentally confirmed that the Pockels effect of interfacial water in the electric double layer (EDL) on these electrodes shows an electrode dependence similar to the effect in bulk water while the effects depend on the frequency of the AC voltage such that the interfacial signal decreases with frequency but the bulk signal increases with frequency up to 221 Hz. These experimental results lead to a conclusion that the beam deflection is caused by the refractive index gradient in the bulk water region, which is formed transiently by the Pockels effect of interfacial water in the EDL when an AC electric field is applied. The refractive index gradient is caused by the diffuse layer spreading into the bulk region to work as a breaking factor of inversion symmetry of bulk water due to its charge-biased ionic distribution. This mechanism does not contradict the principle of nonlinear optics.

The Role of Concentration and Solvent Character in the Molecular Organization of Humic Acids.

PubMed

Klučáková, Martina; Věžníková, Kateřina

2016-10-27

The molecular organization of humic acids in different aqueous solutions was studied over a wide concentration range (0.01-10 g·dm -3 ). Solutions of humic acids were prepared in three different media: NaOH, NaCl, and NaOH neutralized by HCl after dissolution of the humic sample. Potentiometry, conductometry, densitometry, and high resolution ultrasound spectrometry were used in order to investigate conformational changes in the humic systems. The molecular organization of humic acids in the studied systems could be divided into three concentration ranges. The rearrangements were observed at concentrations of ~0.02 g·dm -3 and ~1 g·dm -3 . The first "switch-over point" was connected with changes in the hydration shells of humic particles resulting in changes in their elasticity. The compressibility of water in the hydration shells is less than the compressibility of bulk water. The transfer of hydration water into bulk water increased the total compressibility of the solution, reducing the ultrasonic velocity. The aggregation of humic particles and the formation of rigid structures in systems with concentrations higher than 1 g·dm -3 was detected.

What befalls the proteins and water in a living cell when the cell dies?

PubMed

Ling, Gilbert N; Fu, Ya-zhen

2005-01-01

The solvency of solutes of varying molecular size in the intracellular water of freshly-killed Ehrlich carcinoma cells fits the same theoretical curve that describes the solvency of similar solutes in a 36% solution of native bovine hemoglobin--a protein found only in red blood cells and making up 97.3% of the red cell's total intracellular proteins. The merging of the two sets of data confirms the prediction of the AI Hypothesis that key intracellular protein(s) in dying cells undergo(es) a transition from: (1) one in which the polypeptide NHCO groups assume a fully-extended conformation with relatively strong power of polarizing and orienting the bulk-phase water in multilayers; to (2) one in which most of the polypeptide NHCO groups are engaged in alpha-helical and other "introvert" conformations (see below for definition) with much weaker power in polarizing-orienting multilayers of bulk-phase water. This concordance of the two sets of data also shows that what we now call native hemoglobin--supposedly denoting hemoglobin found in its natural state in living red blood cells--, in fact, more closely resembles the water-polarizing, and -orienting intracellular proteins in dead cells. Although in the dead Ehrlich carcinoma cells as well as in the 36% solution of native hemoglobin, much of the protein's polypeptide NHCO groups are engaged in alpha-helical and other "introvert" conformation (Perutz 1969; Weissbluth 1974), both systems produce a weak but nonetheless pervasive and "long-range" water polarization and orientation. It is suggested that in both the dead Ehrlich carcinoma ascites cells and in the 36% native bovine hemoglobin solution, enough polypeptide NHCO groups assume the fully-extended conformation to produce the weak but far-reaching multilayer water polarization and orientation observed.

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.

Pressure effects on collective density fluctuations in water and protein solutions

PubMed Central

Russo, Daniela; Laloni, Alessio; Filabozzi, Alessandra; Heyden, Matthias

2017-01-01

Neutron Brillouin scattering and molecular dynamics simulations have been used to investigate protein hydration water density fluctuations as a function of pressure. Our results show significant differences between the pressure and density dependence of collective dynamics in bulk water and in concentrated protein solutions. Pressure-induced changes in the tetrahedral order of the water HB network have direct consequences for the high-frequency sound velocity and damping coefficients, which we find to be a sensitive probe for changes in the HB network structure as well as the wetting of biomolecular surfaces. PMID:29073065

Self-assembly of water-soluble nanocrystals

DOEpatents

Fan, Hongyou [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM; Lopez, Gabriel P [Albuquerque, NM

2012-01-10

A method for forming an ordered array of nanocrystals where a hydrophobic precursor solution with a hydrophobic core material in an organic solvent is added to a solution of a surfactant in water, followed by removal of a least a portion of the organic solvent to form a micellar solution of nanocrystals. A precursor co-assembling material, generally water-soluble, that can co-assemble with individual micelles formed in the micellar solution of nanocrystals can be added to this micellar solution under specified reaction conditions (for example, pH conditions) to form an ordered-array mesophase material. For example, basic conditions are used to precipitate an ordered nanocrystal/silica array material in bulk form and acidic conditions are used to form an ordered nanocrystal/silica array material as a thin film.

Thermodynamics of the sorption of water-soluble vitamins in reverse-phase high performance liquid chromatography

NASA Astrophysics Data System (ADS)

Chirkin, V. A.; Karpov, S. I.; Selemenev, V. F.

2012-12-01

The thermodynamics of the sorption of certain water-soluble vitamins on a C18 reverse phase from water-acetonitrile solutions of different compositions is studied. The thermodynamic characteristics of the investigated chromatographic systems are calculated. The dependences of standard molar enthalpy and changes in entropy when the sorbate transfers from the bulk solution to the surface layer on the concentration of the organic component in the mobile phase are analyzed. The boundaries for applying the main retention models describing the sorption of the investigated compounds are discussed.

Organic ion association in aqueous phase and ab initio-based force fields: The case of carboxylate/ammonium salts

NASA Astrophysics Data System (ADS)

Houriez, Céline; Vallet, Valérie; Réal, Florent; Meot-Ner Mautner, Michael; Masella, Michel

2017-10-01

We performed molecular dynamics simulations of carboxylate/methylated ammonium ion pairs solvated in bulk water and of carboxylate/methylated ammonium salt solutions at ambient conditions using an ab initio-based polarizable force field whose parameters are assigned to reproduce only high end quantum computations, at the Møller-Plesset second-order perturbation theory/complete basis set limit level, regarding single ions and ion pairs as isolated and micro-hydrated in gas phase. Our results agree with the available experimental results regarding carboxylate/ammonium salt solutions. For instance, our force field approach predicts the percentage of acetate associated with ammonium ions in CH3 COO-/CH3 NH3+ solutions at the 0.2-0.8M concentration scale to range from 14% to 35%, in line with the estimates computed from the experimental ion association constant in liquid water. Moreover our simulations predict the number of water molecules released from the ion first hydration shell to the bulk upon ion association to be about 2.0 ± 0.6 molecules for acetate/protonated amine ion pairs, 3.1 ± 1.5 molecules for the HCOO-/NH4+ pair and 3.3 ± 1.2 molecules for the CH3COO-/(CH3)4N+ pair. For protonated amine-based ion pairs, these values are in line with experiment for alkali/halide pairs solvated in bulk water. All these results demonstrate the promising feature of ab initio-based force fields, i.e., their capacity in accurately modeling chemical systems that cannot be readily investigated using available experimental techniques.

Study on the number density of nanobubbles at varying concentration of ethanol in ethanol-water solution

NASA Astrophysics Data System (ADS)

Rajib, Md. Mahadi; Farzeen, Parisa; Ali, Mohammad

2017-12-01

In recent years, nanobubble technology has drawn great attention due to its extensive incorporation to substantial aspects of science and technology such as water treatment, drug delivery enhancement to cells, solvent and nutritional supplements manufacturing and many others. Bulk nanobubbles may be present in most aqueous solutions, possibly being constantly created by cosmic radiation and agitation and surface nanobubbles are present at most surfaces [1,2]. But, for utilizing these nanobubbles in a definitive way it's important to know whether an added amount of solution making substance has constructive or adverse effect on the nanobubble. In this work, the change of number density of nanobubbles in ethanol-water solution was studied by varying the ethanol concentration.

Impact of ultrasound on hydrophobic interactions in solutions: ultrasonic retardation of benzoin condensation.

PubMed

Hagu, Hannes; Salmar, Siim; Tuulmets, Ants

2007-04-01

Kinetics of the benzoin condensation of benzaldehyde in presence of KCN as the catalyst in water and in ethanol-water binary solutions were investigated without sonication and under ultrasound at 22 kHz. A statistically significant 20% decrease of the rate was observed in water. The retardation effect of ultrasound gradually decreases up to 45 wt% ethanol content. We report an evidence of ultrasonic retardation of reactions and thereby a direct evidence for sonochemical processes in the bulk solution. Ultrasound can disturb solvation of the species in the solution. If breaking down the stabilization of the encounter complexes between the reagents, sonication hinders the reaction while perturbation of the solvent-stabilization of the reagents accelerates the reaction.

Water and Benefit Sharing in Transboundary River Basins

NASA Astrophysics Data System (ADS)

Arjoon, D.; Tilmant, A.; Herrmann, M.

2015-12-01

Growing water scarcity underlies the importance of cooperation for the effective management of river basins, particularly in the context of international rivers in which unidirectional externalities can lead to asymmetric relationships between riparian countries. Studies have shown that significant economic benefits can be expected through basin-wide cooperation, however, the equitable partitioning of these benefits over the basin is less well studied and tends to overlook the importance of stakeholder input in the definition of equitability. In this study, an institutional arrangement to maximize welfare and then share the scarcity cost in a river basin is proposed. A river basin authority plays the role of a bulk water market operator, efficiently allocating bulk water to the users and collecting bulk water charges which are then equitably redistributed among water users. This highly regulated market restrains the behaviour of water users to control externalities and to ensure basin-wide coordination, enhanced efficiency, and the equitable redistribution of the scarcity cost. The institutional arrangement is implemented using the Eastern Nile River basin as a case study. The importance of this arrangement is that it can be adopted for application in negotiations to cooperate in trans-boundary river basins. The benefit sharing solution proposed is more likely to be perceived as equitable because water users help define the sharing rule. As a result, the definition of the sharing rule is not in question, as it would be if existing rules, such as bankruptcy rules or cooperative game theory solutions, are applied, with their inherent definitions of fairness. Results of the case study show that the sharing rule is predictable. Water users can expect to receive between 93.5% and 95% of their uncontested benefits (benefits that they expect to receive if water was not rationed), depending on the hydrologic scenario.

The behaviour of water and sodium chloride solution confined into asbestos nanotube

NASA Astrophysics Data System (ADS)

Fomin, Yu. D.; Ryzhov, V. N.; Tsiok, E. N.

2016-08-01

We present the molecular simulation study of the behaviour of water and sodium chloride solution confined in lizardite asbestos nanotube which is a typical example of hydrophilic confinement. The local structure and orientational and dynamic properties are studied. It is shown that at low enough temperatures there is a well-defined orientational ordering of the water molecules. At high local densities corresponding to the maxima of the density distribution function, the water molecules are oriented parallel to the axis of the tube. It is also shown that the diffusion coefficient drops about two orders of magnitude comparing to the bulk case. The behaviour of sodium chloride solutions is also considered and the formation of double layer is observed.

On the solvation of the phosphocholine headgroup in an aqueous propylene glycol solution

NASA Astrophysics Data System (ADS)

Rhys, Natasha H.; Al-Badri, Mohamed Ali; Ziolek, Robert M.; Gillams, Richard J.; Collins, Louise E.; Lawrence, M. Jayne; Lorenz, Christian D.; McLain, Sylvia E.

2018-04-01

The atomic-scale structure of the phosphocholine (PC) headgroup in 30 mol. % propylene glycol (PG) in an aqueous solution has been investigated using a combination of neutron diffraction with isotopic substitution experiments and computer simulation techniques—molecular dynamics and empirical potential structure refinement. Here, the hydration of the PC headgroup remains largely intact compared with the hydration of this group in a bilayer and in a bulk water solution, with the PG molecules showing limited interactions with the headgroup. When direct PG interactions with PC do occur, they are most likely to coordinate to the 3+N (CH 3 ) motifs. Further, PG does not affect the bulk water structure and the addition of PC does not perturb the PG-solvent interactions. This suggests that the reason why PG is able to penetrate into membranes easily is that it does not form strong-hydrogen bonding or electrostatic interactions with the headgroup allowing it to easily move across the membrane barrier.

ULTRASTRUCTURAL STUDIES OF VASOPRESSIN EFFECT ON ISOLATED PERFUSED RENAL COLLECTING TUBULES OF THE RABBIT

PubMed Central

Ganote, Charles E.; Grantham, Jared J.; Moses, Harold L.; Burg, Maurice B.; Orloff, Jack

1968-01-01

Isolated cortical collecting tubules from rabbit kidney were studied during perfusion with solutions made either isotonic or hypotonic to the external bathing medium. Examination of living tubules revealed a reversible increase in thickness of the cellular layer, prominence of lateral cell membranes, and formation of intracellular vacuoles during periods of vasopressin-induced osmotic water transport. Examination in the electron microscope revealed that vasopressin induced no changes in cell structure in collecting tubules in the absence of an osmotic difference and significant bulk water flow across the tubule wall. In contrast, tubules fixed during vasopressin-induced periods of high osmotic water transport showed prominent dilatation of lateral intercellular spaces, bulging of apical cell membranes into the tubular lumen, and formation of intracellular vacuoles. It is concluded that the ultrastructural changes are secondary to transepithelial bulk water flow and not to a direct effect of vasopressin on the cells, and that vasopressin induces osmotic flow by increasing water permeability of the luminal cell membrane. The lateral intercellular spaces may be part of the pathway for osmotically induced transepithelial bulk water flow. PMID:4867134

Laboratory studies of aqueous-phase oxidation of polyols in submicron particles

NASA Astrophysics Data System (ADS)

Daumit, K. E.; Carrasquillo, A. J.; Hunter, J. F.; Kroll, J. H.

2013-12-01

Aqueous-phase oxidation has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. However most aqueous oxidation studies are performed in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation is carried out within submicron particles, allowing for gas-particle partitioning of reactants, intermediates, and products. Using Fenton chemistry as a source of hydroxyl radicals, and a high-resolution aerosol mass spectrometer (AMS) for online characterization of particle composition, we find that aqueous oxidation can be quite rapid. The formation of high concentrations of oxalic acid is observed in the particle phase with some loss of carbon to the gas phase, indicating the formation of volatile products. We see a rapid degradation of condensed-phase oxidation products upon exposure to ultraviolet lights (centered at 350 nm) suggesting that these products may exist as iron(III)-oxalate complexes. Similar results are also seen when oxidation is carried out in bulk solution (with AMS analysis of the atomized solution); however in some cases the mass loss is less than is observed for submicron particles, likely due to differences in partitioning of early-generation products. Such products can partition out of the aqueous phase at the low liquid water contents in the chamber but remain in solution for further aqueous processing in bulk oxidation experiments. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different than those in bulk oxidation, pointing to the need to carry out aqueous oxidation studies under atmospherically relevant partitioning conditions (with liquid water contents mimicking those of cloud droplets or wet aerosol).

Water flow and solute transport in the soil-plant-atmosphere continuum: Upscaling from rhizosphere to root zone

NASA Astrophysics Data System (ADS)

Lazarovitch, Naftali; Perelman, Adi; Guerra, Helena; Vanderborght, Jan; Pohlmeier, Andreas

2016-04-01

Root water and nutrient uptake are among the most important processes considered in numerical models simulating water content and fluxes in the subsurface, as they control plant growth and production as well as water flow and nutrient transport out of the root zone. Root water uptake may lead to salt accumulation at the root-soil interface, resulting in rhizophere salt concentrations much higher than in the bulk soil. This salt accumulation is caused by soluble salt transport towards the roots by mass flow through the soil, followed by preferential adsorption of specific nutrients by active uptake, thereby excluding most other salts at the root-soil interface or in the root apoplast. The salinity buildup can lead to large osmotic pressure gradients across the roots thereby effectively reducing root water uptake. The initial results from rhizoslides (capillary paper growth system) show that sodium concentration is decreasing with distance from the root, compared with the bulk that remained more stable. When transpiration rate was decreased under high salinity levels, sodium concentration was more homogenous compared with low salinity levels. Additionally, sodium and gadolinium distributions were measured nondestructively around tomato roots using magnetic resonance imaging (MRI). This technique could also observe the root structure and water content around single roots. Results from the MRI confirm the solutes concentration pattern around roots and its relation to their initial concentration. We conclude that local water potentials at the soil-root interface differ from bulk potentials. These relative differences increase with decreasing root density, decreasing initial salt concentration and increasing transpiration rate. Furthermore, since climate may significantly influence plant response to salinity a dynamic climate-coupled salinity reduction functions are critical in while using macroscopic numerical models.

On the possible origin of bulk third harmonic generation in skin cells

NASA Astrophysics Data System (ADS)

Su, Tung-Yu; Liao, Chien-Sheng; Yang, Chih-Yuan; Zhuo, Guan-Yu; Chen, Szu-Yu; Chu, Shi-Wei

2011-09-01

We studied third harmonic generation (THG) of melanin solution with concentrations similar to melanocytes in human skin. In contrast to conventional observation of THG at interface, bulk THG was detected inside the solution due to the formation of melanin hydrocolloids. A linear relationship between melanin concentration and THG intensity was found, suggesting THG originated from high-order hyper-Rayleigh scattering. By fitting this linear relationship, third-order hyperpolarizability of melanin hydrocolloids was determined to be three orders larger than that of water. Our result will be useful for interpretation of THG signals in skin and other tissues containing colloidal particles.

Statics and dynamics of free and hydrogen-bonded OH groups at the air/water interface.

PubMed

Vila Verde, Ana; Bolhuis, Peter G; Campen, R Kramer

2012-08-09

We use classical atomistic molecular dynamics simulations of two water models (SPC/E and TIP4P/2005) to investigate the orientation and reorientation dynamics of two subpopulations of OH groups belonging to water molecules at the air/water interface at 300 K: those OH groups that donate a hydrogen bond (called "bonded") and those that do not (called "free"). Free interfacial OH groups reorient in two distinct regimes: a fast regime from 0 to 1 ps and a slow regime thereafter. Qualitatively similar behavior was reported by others for free OH groups near extended hydrophobic surfaces. In contrast, the net reorientation of bonded OH groups occurs at a rate similar to that of bulk water. This similarity in reorientation rate results from compensation of two effects: decreasing frequency of hydrogen-bond breaking/formation (i.e., hydrogen-bond exchange) and faster rotation of intact hydrogen bonds. Both changes result from the decrease in density at the air/water interface relative to the bulk. Interestingly, because of the presence of capillary waves, the slowdown of hydrogen-bond exchange is significantly smaller than that reported for water near extended hydrophobic surfaces, but it is almost identical to that reported for water near small hydrophobic solutes. In this sense water at the air/water interface has characteristics of water of hydration of both small and extended hydrophobic solutes.

Links between soil properties and steady-state solute transport through cultivated topsoil at the field scale

NASA Astrophysics Data System (ADS)

Koestel, J. K.; Norgaard, T.; Luong, N. M.; Vendelboe, A. L.; Moldrup, P.; Jarvis, N. J.; Lamandé, M.; Iversen, B. V.; Wollesen de Jonge, L.

2013-02-01

It is known that solute transport through soil is heterogeneous at all spatial scales. However, little data are available to allow quantification of these heterogeneities at the field scale or larger. In this study, we investigated the spatial patterns of soil properties, hydrologic state variables, and tracer breakthrough curves (BTCs) at the field scale for the inert solute transport under a steady-state irrigation rate which produced near-saturated conditions. Sixty-five undisturbed soil columns approximately 20 cm in height and diameter were sampled from the loamy topsoil of an agricultural field site in Silstrup (Denmark) at a sampling distance of approximately 15 m (with a few exceptions), covering an area of approximately 1 ha (60 m × 165 m). For 64 of the 65 investigated soil columns, we observed BTC shapes indicating a strong preferential transport. The strength of preferential transport was positively correlated with the bulk density and the degree of water saturation. The latter suggests that preferential macropore transport was the dominating transport process. Increased bulk densities were presumably related with a decrease in near-saturated hydraulic conductivities and as a consequence to larger water saturation and the activation of larger macropores. Our study provides further evidence that it should be possible to estimate solute transport properties from soil properties such as soil texture or bulk density. We also demonstrated that estimation approaches established for the column scale have to be upscaled when applied to the field scale or larger.

Low temperature reduction of free-standing graphene oxide papers with metal iodides for ultrahigh bulk conductivity.

PubMed

Liu, Chenyang; Hao, Feng; Zhao, Xiaochong; Zhao, Qiancheng; Luo, Songping; Lin, Hong

2014-02-05

Here we report a green and facile route for highly efficient reduction of free-standing graphene oxide (GO) papers with metal iodide aqueous solutions at low cost. The metal iodides (MgI2, AlI3, ZnI2, FeI2) were synthesized directly from metal and iodine powder with water as a catalyzer. An extremely high bulk conductivity of 55088 S/m for reduced graphene oxide (rGO) papers were obtained with FeI2 solution of which pH = 0 at 95°C for 6 hours. The catalytic effect of strong Lewis acid for the promotion of the nucleophilic substitution reaction is responsible for the greatly improved bulk conductivity. Furthermore, it was found that the layer-to-layer distance (dL) and the crystallinity of the rGO papers are regarded as two main factors affecting the bulk conductivity rather than C/O ratio and defect concentration.

Dynamics of Hydration Water in Sugars and Peptides Solutions

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

Perticaroli, Stefania; Nakanishi, Masahiro; Pashkovski, Eugene

2013-01-01

We analyzed solute and solvent dynamics of sugars and peptides aqueous solutions using extended epolarized light scattering (EDLS) and broadband dielectric spectroscopies (BDS). Spectra measured with both techniques reveal the same mechanism of rotational diffusion of peptides molecules. In the case of sugars, this solute reorientational relaxation can be isolated by EDLS measurements, whereas its ontribution to the dielectric spectra is almost negligible. In the presented analysis, we characterize the hydration water in terms of hydration number and retardation ratio between relaxation times of hydration and bulk water. Both techniques provide similar estimates of . The retardation imposed on themore » hydration water by sugars is 3.3 1.3 and involves only water molecules hydrogen-bonded (HB) to solutes ( 3 water molecules per sugar OH-group). In contrast, polar peptides cause longer range erturbations beyond the first hydration shell, and between 2.8 and 8, increasing with the number of chemical groups engaged in HB formation. We demonstrate that chemical heterogeneity and specific HB interactions play a crucial role in hydration dynamics around polar solutes. The obtained results help to disentangle the role of excluded volume and enthalpic contributions in dynamics of hydration water at the interface with biological molecules.« less

Influence of surface groups of proteins on water studied by freezing/thawing hysteresis and infrared spectroscopy.

PubMed

Zelent, Bogumil; Bryan, Michael A; Sharp, Kim A; Vanderkooi, Jane M

2009-05-01

The influence of proteins and solutes on hysteresis of freezing and melting of water was measured by infrared (IR) spectroscopy. Of the solutes examined, poly-L-arginine and flounder antifreeze protein produced the largest freezing point depression of water, with little effect on the melting temperature. Poly-L-lysine, poly-L-glutamate, cytochrome c and bovine serum albumin had less effect on the freezing of water. Small compounds used to mimic non-polar (trimethylamine N-oxide, methanol), positively charged (guanidinium chloride, NH(4)Cl, urea) and negatively charged (Na acetate) groups on protein surfaces were also examined. These molecules and ions depress water's freezing point and the melting profiles became broad. Since infrared absorption measures both bulk solvent and solvent bound to the solutes, this result is consistent with solutes interacting with liquid water. The amide I absorption bands of antifreeze protein and poly-L-arginine do not detectably change with the phase transition of water. An interpretation is that the antifreeze protein and poly-L-arginine order liquid water such that the water around the group is ice-like.

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

Water's hydrogen bonds in the hydrophobic effect: a simple model.

PubMed

Xu, Huafeng; Dill, Ken A

2005-12-15

We propose a simple analytical model to account for water's hydrogen bonds in the hydrophobic effect. It is based on computing a mean-field partition function for a water molecule in the first solvation shell around a solute molecule. The model treats the orientational restrictions from hydrogen bonding, and utilizes quantities that can be obtained from bulk water simulations. We illustrate the principles in a 2-dimensional Mercedes-Benz-like model. Our model gives good predictions for the heat capacity of hydrophobic solvation, reproduces the solvation energies and entropies at different temperatures with only one fitting parameter, and accounts for the solute size dependence of the hydrophobic effect. Our model supports the view that water's hydrogen bonding propensity determines the temperature dependence of the hydrophobic effect. It explains the puzzling experimental observation that dissolving a nonpolar solute in hot water has positive entropy.

Identification of Multiple Water-Iodide Species in Concentrated NaI Solutions Based on the Raman Bending Vibration of Water.

PubMed

Besemer, Matthieu; Bloemenkamp, Rob; Ariese, Freek; van Manen, Henk-Jan

2016-02-11

The influence of aqueous electrolytes on the water bending vibration was studied with Raman spectroscopy. For all salts investigated (NaI, NaBr, NaCl, and NaSCN), we observed a nonlinear intensity increase of the water bending vibration with increasing concentration. Different lasers and a tunable frequency-doubled optical parametric oscillator system were used to achieve excitation wavelengths between 785 and 374 nm. Focusing on NaI solutions, the relative enhancement of the water bending vibration was found to increase strongly with excitation photon energy, in line with a preresonance effect from the iodide-water charge-transfer transition. We used multivariate curve resolution (MCR) to decompose the measured Raman spectra of NaI solutions into three interconverting spectral components assigned to bulk water and water molecules interacting with one (X···H-O-H···O) and two (X···H-O-H···X) iodide ions (X = I(-)). The Raman spectrum of solid sodium iodide dihydrate supports the assignment of the latter. Using the MCR results, relative Raman scattering cross sections of 4.0 ± 0.6 and 14.0 ± 0.1 were calculated for the mono- and di-iodide species, respectively (compared to that of bulk water set to unity). In addition, it was found that at relatively low concentrations each iodide ion affects the Raman spectrum of roughly 22 surrounding water molecules, indicating that the influence of iodide extends beyond the first solvation shell. Our results demonstrate that the Raman bending vibration of water is a sensitive probe, providing new insights into anion solvation in aqueous environments.

Liquid structure of the urea-water system studied by dielectric spectroscopy.

PubMed

Hayashi, Yoshihito; Katsumoto, Yoichi; Omori, Shinji; Kishii, Noriyuki; Yasuda, Akio

2007-02-08

Dielectric spectroscopy measurements for aqueous urea solutions were performed at 298 K through a concentration range from 0.5 to 9.0 M with frequencies between 200 MHz and 40 GHz. Observed dielectric spectra were well represented by the superposition of two Debye type relaxation processes attributable to the bulk-water clusters and the urea-water coclusters. Our quantitative analysis of the spectra shows that the number of hydration water molecules is approximately two per urea molecule for the lower concentration region below 5.0 M, while the previous molecular dynamics studies predicted approximately six water molecules. It was also indicated by those studies, however, that there are two types of hydration water molecule in urea solution, which are strongly and weakly associated to the urea molecule, respectively. Only the strongly associated water was distinguishable in our analysis, while the weakly associated water exhibited the same dynamic feature as bulk water. This implies that urea retains the weakly associated water in the tetrahedral structure and, thus, is not a strong structure breaker of water. We also verified the model of liquid water where water consists of two states: the icelike-ordered and dense-disordered phases. Our dielectric data did not agree with the theoretical prediction based on the two-phase model. The present work supports the argument that urea molecules can easily replace near-neighbor water in the hydrogen-bonding network and do not require the presence of the disordered phase of water to dissolve into water.

Single water entropy: hydrophobic crossover and application to drug binding.

PubMed

Sasikala, Wilbee D; Mukherjee, Arnab

2014-09-11

Entropy of water plays an important role in both chemical and biological processes e.g. hydrophobic effect, molecular recognition etc. Here we use a new approach to calculate translational and rotational entropy of the individual water molecules around different hydrophobic and charged solutes. We show that for small hydrophobic solutes, the translational and rotational entropies of each water molecule increase as a function of its distance from the solute reaching finally to a constant bulk value. As the size of the solute increases (0.746 nm), the behavior of the translational entropy is opposite; water molecules closest to the solute have higher entropy that reduces with distance from the solute. This indicates that there is a crossover in translational entropy of water molecules around hydrophobic solutes from negative to positive values as the size of the solute is increased. Rotational entropy of water molecules around hydrophobic solutes for all sizes increases with distance from the solute, indicating the absence of crossover in rotational entropy. This makes the crossover in total entropy (translation + rotation) of water molecule happen at much larger size (>1.5 nm) for hydrophobic solutes. Translational entropy of single water molecule scales logarithmically (Str(QH) = C + kB ln V), with the volume V obtained from the ellipsoid of inertia. We further discuss the origin of higher entropy of water around water and show the possibility of recovering the entropy loss of some hypothetical solutes. The results obtained are helpful to understand water entropy behavior around various hydrophobic and charged environments within biomolecules. Finally, we show how our approach can be used to calculate the entropy of the individual water molecules in a protein cavity that may be replaced during ligand binding.

Color Stability of the Bulk-Fill Composite Resins with Different Thickness in Response to Coffee/Water Immersion

PubMed Central

Sheikh-Al-Eslamian, Seyedeh Mahsa; Hasani, Elham; Abrandabadi, Ahmad Najafi

2016-01-01

We aimed to evaluate the color stability of bulk-fill and conventional composite resin with respect to thickness and storage media. Twenty specimens of a conventional composite resin (6 mm diameter and 2 mm thick) and 40 specimens of the bulk-fill Tetric EvoCeram composite resin at two different thicknesses (6 mm diameter and 2 mm thick or 4 mm thick, n = 20) were prepared. The specimens were stored in distilled water during the study period (28 d). Half of the specimens were remained in distilled water and the other half were immersed in coffee solution 20 min/d and kept in distilled water between the cycles. Color changes (ΔE) were measured using the CIE L ⁎ a ⁎ b ⁎ color space and a digital imaging system at 1, 7, 14, and 28 days of storage. Data were analyzed using Two-way ANOVA and Tukey's HSD post hoc test (P < 0.05). Composite resins showed significant increase in color changes by time (bulk-fill > conventional; P < 0.001). Coffee exhibited significantly more staining susceptibility than that of distilled water (P < 0.001). There was greater color changes with increasing the increment thickness, which was significant at 14 (P < 0.001) and 28 d (P < 0.01). Color change of bulk-fill composite resin was greater than that of the conventional one after coffee staining and is also a function of increment thicknesses. PMID:27403163

Controlled Bulk Properties of Composite Polymeric Solutions for Extensive Structural Order of Honeycomb Polysulfone Membranes

PubMed Central

Gugliuzza, Annarosa; Perrotta, Maria Luisa; Drioli, Enrico

2016-01-01

This work provides additional insights into the identification of operating conditions necessary to overcome a current limitation to the scale-up of the breath figure method, which is regarded as an outstanding manufacturing approach for structurally ordered porous films. The major restriction concerns, indeed, uncontrolled touching droplets at the boundary. Herein, the bulk of polymeric solutions are properly managed to generate honeycomb membranes with a long-range structurally ordered texture. Water uptake and dynamics are explored as chemical environments are changed with the intent to modify the hydrophilic/hydrophobic balance and local water floatation. In this context, a model surfactant such as the polyoxyethylene sorbitan monolaurate is used in combination with alcohols at different chain length extents and a traditional polymer such as the polyethersufone. Changes in the interfacial tension and kinematic viscosity taking place in the bulk of composite solutions are explored and examined in relation to competitive droplet nucleation and growth rate. As a result, extensive structurally ordered honeycomb textures are obtained with the rising content of the surfactant while a broad range of well-sized pores is targeted as a function of the hydrophilic-hydrophobic balance and viscosity of the composite polymeric mixture. The experimental findings confirm the consistency of the approach and are expected to give propulsion to the commercially production of breath figures films shortly. PMID:27196938

Controlled Bulk Properties of Composite Polymeric Solutions for Extensive Structural Order of Honeycomb Polysulfone Membranes.

PubMed

Gugliuzza, Annarosa; Perrotta, Maria Luisa; Drioli, Enrico

2016-05-16

This work provides additional insights into the identification of operating conditions necessary to overcome a current limitation to the scale-up of the breath figure method, which is regarded as an outstanding manufacturing approach for structurally ordered porous films. The major restriction concerns, indeed, uncontrolled touching droplets at the boundary. Herein, the bulk of polymeric solutions are properly managed to generate honeycomb membranes with a long-range structurally ordered texture. Water uptake and dynamics are explored as chemical environments are changed with the intent to modify the hydrophilic/hydrophobic balance and local water floatation. In this context, a model surfactant such as the polyoxyethylene sorbitan monolaurate is used in combination with alcohols at different chain length extents and a traditional polymer such as the polyethersufone. Changes in the interfacial tension and kinematic viscosity taking place in the bulk of composite solutions are explored and examined in relation to competitive droplet nucleation and growth rate. As a result, extensive structurally ordered honeycomb textures are obtained with the rising content of the surfactant while a broad range of well-sized pores is targeted as a function of the hydrophilic-hydrophobic balance and viscosity of the composite polymeric mixture. The experimental findings confirm the consistency of the approach and are expected to give propulsion to the commercially production of breath figures films shortly.

Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

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

Yao, Yi; Berkowitz, Max L., E-mail: maxb@unc.edu, E-mail: ykanai@unc.edu; Kanai, Yosuke, E-mail: maxb@unc.edu, E-mail: ykanai@unc.edu

2015-12-28

The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicatemore » that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na{sup +} and K{sup +} ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.« less

Passivation of high temperature superconductors

NASA Technical Reports Server (NTRS)

Vasquez, Richard P. (Inventor)

1991-01-01

The surface of high temperature superconductors such as YBa2Cu3O(7-x) are passivated by reacting the native Y, Ba and Cu metal ions with an anion such as sulfate or oxalate to form a surface film that is impervious to water and has a solubility in water of no more than 10(exp -3) M. The passivating treatment is preferably conducted by immersing the surface in dilute aqueous acid solution since more soluble species dissolve into the solution. The treatment does not degrade the superconducting properties of the bulk material.

Anomalous dynamics of aqueous solutions of di-propylene glycol methylether confined in MCM-41 by quasielastic neutron scattering

NASA Astrophysics Data System (ADS)

Swenson, Jan; Elamin, Khalid; Chen, Guo; Lohstroh, Wiebke; Sakai, Victoria Garcia

2014-12-01

The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H2O (or D2O) confined in 28 Å pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0-90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement, but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Å. The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.

Anomalous dynamics of aqueous solutions of di-propylene glycol methylether confined in MCM-41 by quasielastic neutron scattering

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

Swenson, Jan, E-mail: jan.swenson@chalmers.se; Elamin, Khalid; Chen, Guo

2014-12-07

The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H{sub 2}O (or D{sub 2}O) confined in 28 Å pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0–90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement,more » but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Å. The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.« less

Fiber Treatment Effects on Bioreactor Bulk Fluid Trends

NASA Technical Reports Server (NTRS)

Ellis, Ronald II

2013-01-01

In order to facilitate the exploration of worlds beyond the borders of our planet, it is necessary to maintain sustainable levels of clean water. The remediation of water via Membrane Aerated Bioreactors (MABRs) is one such method, and the focus of this study. MARRs rely on healthy biofilms grown on hollow fiber membranes to clean non-potable water. These biofilms can take weeks to months to establish. Therefore, various fiber treatments and two inoculums were evaluated for their effect on rapid biofilm formation. Fiber treatments are as follows: sanding of the fibers with 1500 and 8000 grit sandpaper, immersion of the fibers in a 1% hydrofluoric acid solution for 12 seconds and 15 minutes, and the immersion of the fibers in a Fluoroetch® solution for 18 seconds and 5 minutes. The two inoculums utilized were sourced from healthy, established MARRs; Texas Tech University (TTU) MABR "TRL5" and Kennedy Space Center (KSC) MABR "R3". Data attained from direct bacterial cell counts of the reactor bulk fluids via fluorescent microscopy, suggests that the fluoroetching treatment combined with the TTU inoculum show the greatest biofilm creation.

Tensiometry and dilational rheology of mixed β-lactoglobulin/ionic surfactant adsorption layers at water/air and water/hexane interfaces.

PubMed

Dan, Abhijit; Gochev, Georgi; Miller, Reinhard

2015-07-01

Oscillating drop tensiometry was applied to study adsorbed interfacial layers at water/air and water/hexane interfaces formed from mixed solutions of β-lactoglobulin (BLG, 1 μM in 10 mM buffer, pH 7 - negative net charge) and the anionic surfactant SDS or the cationic DoTAB. The interfacial pressure Π and the dilational viscoelasticity modulus |E| of the mixed layers were measured for mixtures of varying surfactant concentrations. The double capillary technique was employed which enables exchange of the protein solution in the drop bulk by surfactant solution (sequential adsorption) or by pure buffer (washing out). The first protocol allows probing the influence of the surfactant on a pre-adsorbed protein layer thus studying the protein/surfactant interactions at the interface. The second protocol gives access to the residual values of Π and |E| measured after the washing out procedure thus bringing information about the process of protein desorption. The DoTAB/BLG complexes exhibit higher surface activity and higher resistance to desorption in comparison with those for the SDS/BLG complexes due to hydrophobization via electrostatic binding of surfactant molecules. The neutral DoTAB/BLG complexes achieve maximum elastic response of the mixed layer. Mixed BLG/surfactant layers at the water/oil interface are found to reach higher surface pressure and lower maximum dilational elasticity than those at the water/air surface. The sequential adsorption mode experiments and the desorption study reveal that binding of DoTAB to pre-adsorbed BLG globules is somehow restricted at the water/air surface in comparison with the case of complex formation in the solution bulk and subsequently adsorbed at the water/air surface. Maximum elasticity is achieved with washed out layers obtained after simultaneous adsorption, i.e. isolation of the most surface active DoTAB/BLG complex. These specific effects are much less pronounced at the W/H interface. Copyright © 2015 Elsevier Inc. All rights reserved.

Hydration shell parameters of aqueous alcohols: THz excess absorption and packing density.

PubMed

Matvejev, V; Zizi, M; Stiens, J

2012-12-06

Solvation in water requires minimizing the perturbations in its hydrogen bonded network. Hence solutes distort water molecular motions in a surrounding domain, forming a molecule-specific hydration shell. The properties of those hydration shells impact the structure and function of the solubilized molecules, both at the single molecule and at higher order levels. The size of the hydration shell and the picoseconds time-scale water dynamics retardation are revealed by terahertz (THz) absorption coefficient measurements. Room-temperature absorption coefficient at f = 0.28 [THz] is measured as a function of alcohol concentration in aqueous methanol, ethanol, 1,2-propanol, and 1-butanol solutions. Highly diluted alcohol measurements and enhanced overall measurement accuracy are achieved with a THz absorption measurement technique of nL-volume liquids in a capillary tube. In the absorption analysis, bulk and interfacial molecular domains of water and alcohol are considered. THz ideal and excess absorption coefficients are defined in accordance with thermodynamics mixing formulations. The parameter extraction method is developed based on a THz excess absorption model and hydrated solute molecule packing density representation. First, the hydration shell size is deduced from the hydrated solute packing densities at two specific THz excess absorption nonlinearity points: at infinite alcohol dilution (IAD) and at the THz excess absorption extremum (EAE). Consequently, interfacial water and alcohol molecular domain absorptions are deduced from the THz excess absorption model. The hydration shell sizes obtained at the THz excess absorption extremum are in excellent agreement with other reports. The hydration shells of methanol, ethanol, 1- and 2-propanol consist of 13.97, 22.94, 22.99, and 31.10 water molecules, respectively. The hydration shell water absorption is on average 0.774 ± 0.028 times the bulk water absorption. The hydration shell parameters might shed light on hydration dynamics of biomolecules.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

DOE PAGES

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; ...

2015-11-03

We studied the dynamics of water in polyethylene oxide (PEO)/LiCl solution with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. Furthermore, the measured diffusion coefficient of interfacial water remained 5–10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li +. Detailed analysis of MD trajectories suggests that Li + is favorably found at the surface of the hydration layer, and the probability to find the caged Li + configuration formed by themore » PEO is lower than for the noncaged Li +-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li + hydration complexes. Moreover, performing the MD simulation with different ions (Na + and K +) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.« less

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; Jalarvo, Niina H.; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S.; Do, Changwoo

2015-11-01

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li+ . Detailed analysis of MD trajectories suggests that Li+ is favorably found at the surface of the hydration layer, and the probability to find the caged Li+ configuration formed by the PEO is lower than for the noncaged Li+-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li+ hydration complexes. Performing the MD simulation with different ions (Na+ and K+ ) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide.

PubMed

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O; Jalarvo, Niina H; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S; Do, Changwoo

2015-11-06

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li(+). Detailed analysis of MD trajectories suggests that Li(+) is favorably found at the surface of the hydration layer, and the probability to find the caged Li(+) configuration formed by the PEO is lower than for the noncaged Li(+)-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li(+) hydration complexes. Performing the MD simulation with different ions (Na(+) and K(+)) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same

DOEpatents

Simmons, Blake A [San Francisco, CA; Talin, Albert Alec [Livermore, CA

2009-11-27

A method for producing metal nanoparticles that when associated with an analyte material will generate an amplified SERS spectrum when the analyte material is illuminated by a light source and a spectrum is recorded. The method for preparing the metal nanoparticles comprises the steps of (i) forming a water-in-oil microemulsion comprising a bulk oil phase, a dilute water phase, and one or more surfactants, wherein the water phase comprises a transition metal ion; (ii) adding an aqueous solution comprising a mild reducing agent to the water-in-oil microemulsion; (iii) stirring the water-in-oil microemulsion and aqueous solution to initiate a reduction reaction resulting in the formation of a fine precipitate dispersed in the water-in-oil microemulsion; and (iv) separating the precipitate from the water-in-oil microemulsion.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, L.B.; Thurman, E.M.; Runnells, D.R.; ,

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on solution of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is < 0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Toxicity of silver and copper to Cucurbita pepo: differential effects of nano and bulk-size particles.

PubMed

Musante, Craig; White, Jason C

2012-09-01

The phytotoxicity of bulk and nanoparticle Cu and Ag was directly compared. NP Ag reduced biomass and transpiration by 66-84% when compared with bulk Ag. The Ag ion concentration was 4.4-10-times greater in NP than bulk particle solutions. The Cu ion concentration was 1.4-4.4-times greater in bulk than NP amended solutions. Humic acid (50 mg/L) decreased the ion content of bulk Cu solution by 38-42% but increased ion Cu content of NP solutions by 1.4-2.9 times. Bulk and NP Cu were highly phytotoxic; growth and transpiration were reduced by 60-70% relative to untreated controls. NP Cu phytotoxicity was unaffected by solution type, but humic acid (50 mg/L) completely alleviated phytotoxicity caused by bulk Cu. The data demonstrate differential toxicity of Ag NP relative to bulk Ag. The finding that humic acid and solution chemistry differentially impact bulk and NP behavior highlights the importance of evaluating nanoparticles under environmentally relevant conditions. Copyright © 2010 Wiley Periodicals, Inc.

Predicting the pKa and stability of organic acids and bases at an oil-water interface.

PubMed

Andersson, M P; Olsson, M H M; Stipp, S L S

2014-06-10

We have used density functional theory and the implicit solvent model, COSMO-RS, to investigate how the acidity constant, pKa, of organic acids and bases adsorbed at the organic compound-aqueous solution interface changes, compared to its value in the aqueous phase. The pKa determine the surface charge density of the molecules that accumulate at the fluid-fluid interface. We have estimated the pKa by comparing the stability of the protonated and unprotonated forms of a series of molecules in the bulk aqueous solution and at an interface where parts of each molecule reside in the hydrophobic phase and the rest remains in the hydrophilic phase. We found that the pKa for acids is shifted by ∼1 pH unit to higher values compared to the bulk water pKa, whereas they are shifted to lower values by a similar amount for bases. Because this pKa shift is similar in magnitude for each of the molecules studied, we propose that the pKa for molecules at a water-organic compound interface can easily be predicted by adding a small shift to the aqueous pKa. This shift is general and correlates with the functional group. We also found that the relative composition of molecules at the fluid-fluid interface is not the same as in the bulk. For example, species such as carboxylic acids are enriched at the interface, where they can dominate surface properties, even when they are a modest component in the bulk fluid. For high surface concentrations of carboxylic acid groups at an interface, such as a self-assembled monolayer, we have demonstrated that the pKa depends on the degree of deprotonation through direct hydrogen bonding between protonated and deprotonated acidic headgroups.

Synthesis and properties of mecoprop-intercalated layered double hydroxide

NASA Astrophysics Data System (ADS)

Ahmed Khan, Modabber; Choi, Choong-Lyeal; Lee, Dong-Hoon; Park, Man; Lim, Bu-Kug; Lee, Jong-Yoon; Choi, Jyung

2007-08-01

This study carried out to elucidate the synthesis of MCPP LDH hybrid, release pattern of MCPP from MCPP LDH hybrid and their properties. MCPP LDH hybrid was synthesized from MCPP and Mg Al complex. Release pattern of MCPP from MCPP LDH hybrid was slower in distilled water and soil solution but it was slower in distilled water than soil solution. MCPP LDH hybrid has shown more stable condition than CO32- form of LDH in thermal and acidic condition. Therefore, MCPP LDH hybrid would lead as functional and benign pesticide to minimize the harmful effects on soil environment by bulk herbicides.

Poly(imide-siloxane) segmented copolymer structural adhesives prepared by bulk and solution thermal imidization

NASA Technical Reports Server (NTRS)

Bott, R. H.; Summers, J. D.; Arnold, C. A.; Blankenship, C. P., Jr.; Taylor, L. T.

1988-01-01

The improved properties that have been demonstrated through thermal solution imidization in the case of polyimides and poly(imide-siloxane) segmented copolymers suggests significant potential for application of these new materials. Specifically, the enhancement in solubility, moisture reduction, and processability observed through this solution technique is quite dramatic. Previous work has shown that the presence of low amounts of siloxane does not detract significantly from the lap shear strength of these materials to titanium in the case of bulk thermal imidization synthesis. In addition, the siloxane incorporation results in the added advantage of resistance to hot, wet environments. This added durability is presumably due to the hydrophobic siloxane segments preventing the uptake of water at the critical interphase between the adhesive and the adherend. This paper discusses the extension of this work to the solution imidization synthesis technique recently developed in our laboratory. Results dealing with the absolute bond strengths as well as durability and failure surface analysis will be presented.

Accuracy limit of rigid 3-point water models

NASA Astrophysics Data System (ADS)

Izadi, Saeed; Onufriev, Alexey V.

2016-08-01

Classical 3-point rigid water models are most widely used due to their computational efficiency. Recently, we introduced a new approach to constructing classical rigid water models [S. Izadi et al., J. Phys. Chem. Lett. 5, 3863 (2014)], which permits a virtually exhaustive search for globally optimal model parameters in the sub-space that is most relevant to the electrostatic properties of the water molecule in liquid phase. Here we apply the approach to develop a 3-point Optimal Point Charge (OPC3) water model. OPC3 is significantly more accurate than the commonly used water models of same class (TIP3P and SPCE) in reproducing a comprehensive set of liquid bulk properties, over a wide range of temperatures. Beyond bulk properties, we show that OPC3 predicts the intrinsic charge hydration asymmetry (CHA) of water — a characteristic dependence of hydration free energy on the sign of the solute charge — in very close agreement with experiment. Two other recent 3-point rigid water models, TIP3PFB and H2ODC, each developed by its own, completely different optimization method, approach the global accuracy optimum represented by OPC3 in both the parameter space and accuracy of bulk properties. Thus, we argue that an accuracy limit of practical 3-point rigid non-polarizable models has effectively been reached; remaining accuracy issues are discussed.

Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

PubMed

Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

2009-05-07

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions

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

Marenich, Aleksandr; Cramer, Christopher J; Truhlar, Donald G

2009-04-30

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which amore » few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.« less

How to examine soil sorption of ionizable organic compounds and avoid varying pH?

NASA Astrophysics Data System (ADS)

Borisover, Mikhail

2017-04-01

Multiple natural and anthropogenic organic compounds including new and emerging pollutants undergo ionization in aqueous solutions, and their sorption by soils and sediments is contributed by presence of both molecular and ionized species. Better understanding of environmental fate of organic chemicals requires taking into account interactions of molecular and ionized species with environmental sorbents. A "standard" (and undoubtedly important) procedure for differentiating contributions of molecular and ionized species into the overall soil sorption of an organic compound involves varying pH of solution in batch sorption experiments. However, varying pH is (1) often not possible, without destroying a sorbent, e.g., due to the buffer capacity of soils containing carbonates, (2) difficult for further interpretation, since it changes not only the ionization status of a solute in a solution but also the sorbent structure, e.g., a conformation of organic matter, and/or ionization of surface functional groups, (3) making difficult (or even impossible) to explicitly evaluate the role of dissolved species-bulk water interactions, directly affecting the affinity of a sorbate to distribute between water and a sorbent. Indeed, both molecular and ionized species undergo interactions with the solvent bulk and, at least in the case of the ionized ones, there was no a simple way to quantify organic ion-water interactions and their role in organic ion distribution between soil and water phases. This paper presents a "counter-intuitive" approach to examine sorption interactions of an ionizable compound, without experimenting with varied pH. The approach is based on an idea of replacing an initial state in sorption transfer of an ionizable compound from the solvent bulk to a solvated (hydrated) sorbed state: a traditional coefficient describing distribution of a partially ionized compound between a hydrated sorbent and a co-equilibrated aqueous phase is converted to the coefficient describing the transfer of the sorbing compound from its initial molecular (non-ionized) state (in a solution or in the gas phase) to the final hydrated sorbed state equilibrated with the actual aqueous solution of this ionizable compound. In this way, any contributions from the bulk solvent-organic ion interactions into the sorption transfer may be excluded; in addition, further any solute-solvent interactions may be taken out of the consideration. Therefore, compound's sorption characteristics "cleared" of solute-solvent interactions may be obtained, and a better understanding of relations between interactions in a sorbed phase and a molecular structure of organic sorbates can be reached. The approach is illustrated by examining sorption of variously ionized organic compounds, i.e., those belonging to the pharmaceuticals and personal care products (triclosan, gemfibrozil, galaxolide), and aliphatic organic acids on natural and organic amendment-enriched soils. Specifically, it is demonstrated how the greater H-donating ability of trifluoroacetic acid, as compared with acetic acid, strengthens the acid interactions in the soil phase. In another series of examples, it is shown how hydrophobic and non-ionizing galaxolide interacts weakly with soils, as compared with partially ionized triclosan and almost fully ionized gemfibrozil, i.e., leading to the conclusions not reachable based only on the direct comparison of experimentally measured distribution coefficients.

The dynamic crossover in water does not require bulk water.

PubMed

Turton, David A; Corsaro, Carmelo; Martin, David F; Mallamace, Francesco; Wynne, Klaas

2012-06-14

Many of the anomalous properties of water may be explained by invoking a second critical point that terminates the coexistence line between the low- and high-density amorphous states in the liquid. Direct experimental evidence of this point, and the associated polyamorphic liquid-liquid transition, is elusive as it is necessary for liquid water to be cooled below its homogeneous-nucleation temperature. To avoid crystallization, water in the eutectic LiCl solution has been studied but then it is generally considered that "bulk" water cannot be present. However, recent computational and experimental studies observe cooperative hydration in which case it is possible that sufficient hydrogen-bonded water is present for the essential characteristics of water to be preserved. For femtosecond optical Kerr-effect and nuclear magnetic resonance measurements, we observe in each case a fractional Stokes-Einstein relation with evidence of the dynamic crossover appearing near 220 K and 250 K respectively. Spectra obtained in the glass state also confirm the complex nature of the hydrogen-bonding modes reported for neat room-temperature water and support predictions of anomalous diffusion due to "worm-hole" structure.

Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay

NASA Astrophysics Data System (ADS)

Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mârtensson, Lena; Swenson, Jan

2014-07-01

The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the α-relaxation, indicating that the two relaxation processes are independent of each other. This can only occur if the two processes do not occur in the same parts of the confined solutions. Most likely the hydration shell of the interlayer Na+ ions is causing this water relaxation, which does not participate in the α-relaxation at any temperature.

Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay.

PubMed

Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mårtensson, Lena; Swenson, Jan

2014-07-21

The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the α-relaxation, indicating that the two relaxation processes are independent of each other. This can only occur if the two processes do not occur in the same parts of the confined solutions. Most likely the hydration shell of the interlayer Na(+) ions is causing this water relaxation, which does not participate in the α-relaxation at any temperature.

Purified phenolics from hydrothermal treatments of biomass: ability to protect sunflower bulk oil and model food emulsions from oxidation.

PubMed

Conde, Enma; Moure, Andrés; Domínguez, Herminia; Gordon, Michael H; Parajó, Juan Carlos

2011-09-14

The phenolic fractions released during hydrothermal treatment of selected feedstocks (corn cobs, eucalypt wood chips, almond shells, chestnut burs, and white grape pomace) were selectively recovered by extraction with ethyl acetate and washed with ethanol/water solutions. The crude extracts were purified by a relatively simple adsorption technique using a commercial polymeric, nonionic resin. Utilization of 96% ethanol as eluting agent resulted in 47.0-72.6% phenolic desorption, yielding refined products containing 49-60% w/w phenolics (corresponding to 30-58% enrichment with respect to the crude extracts). The refined extracts produced from grape pomace and from chestnut burs were suitable for protecting bulk oil and oil-in-water and water-in-oil emulsions. A synergistic action with bovine serum albumin in the emulsions was observed.

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

PubMed

Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

2014-10-28

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.

Phase-referenced nonlinear spectroscopy of the α-quartz/water interface

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

Ohno, Paul E.; Saslow, Sarah A.; Wang, Hong-fei

2016-12-13

Probing the polarization of water molecules at charged interfaces by second harmonic generation spectroscopy has been heretofore limited to isotropic materials. Here we report non-resonant nonlinear optical measurements at the interface of anisotropic z-cut α-quartz and water under conditions of dynamically changing ionic strength and bulk solution pH. We find that the product of the third-order susceptibility and the interfacial potential, χ (3) × Φ(0), is given by (χ1 (3)–iχ2 (3)) × Φ(0), and that the interference between this product and the second-order susceptibility of bulk quartz depends on the rotation angle of α-quartz around the z axis. Our experimentsmore » show that this newly identified term, iχ (3) × Φ(0), which is out of phase from the surface terms, is of bulk origin. Lastly, the possibility of internally phase referencing the interfacial response for the interfacial orientation analysis of species or materials in contact with α-quartz is discussed along with the implications for conditions of resonance enhancement.« less

Evolution of the electrical resistivity anisotropy during saline tracer tests: insights from geoelectrical milli-fluidic experiments

NASA Astrophysics Data System (ADS)

Jougnot, D.; Jimenez-Martinez, J.; Legendre, R.; Le Borgne, T.; Meheust, Y.; Linde, N.

2017-12-01

The use of time-lapse electrical resistivity tomography has been largely developed in environmental studies to remotely monitor water saturation and contaminant plumes migration. However, subsurface heterogeneities, and corresponding preferential transport paths, yield a potentially large anisotropy in the electrical properties of the subsurface. In order to study this effect, we have used a newly developed geoelectrical milli-fluidic experimental set-up with a flow cell that contains a 2D porous medium consisting of a single layer of cylindrical solid grains. We performed saline tracer tests under full and partial water saturations in that cell by jointly injecting air and aqueous solutions with different salinities. The flow cell is equipped with four electrodes to measure the bulk electrical resistivity at the cell's scale. The spatial distribution of the water/air phases and the saline solute concentration field in the water phase are captured simultaneously with a high-resolution camera by combining a fluorescent tracer with the saline solute. These data are used to compute the longitudinal and transverse effective electrical resistivity numerically from the measured spatial distributions of the fluid phases and the salinity field. This approach is validated as the computed longitudinal effective resistivities are in good agreement with the laboratory measurements. The anisotropy in electrical resistivity is then inferred from the computed longitudinal and transverse effective resistivities. We find that the spatial distribution of saline tracer, and potentially air phase, drive temporal changes in the effective resistivity through preferential paths or barriers for electrical current at the pore scale. The resulting heterogeneities in the solute concentrations lead to strong anisotropy of the effective bulk electrical resistivity, especially for partially saturated conditions. Therefore, considering the electrical resistivity as a tensor could improve our understanding of transport properties from field-scale time-lapse ERT.

Vibrational dephasing and frequency shifts of hydrogen-bonded pyridine-water complexes

NASA Astrophysics Data System (ADS)

Kalampounias, A. G.; Tsilomelekis, G.; Boghosian, S.

2015-01-01

In this paper we present the picosecond vibrational dynamics and Raman shifts of hydrogen-bonded pyridine-water complexes present in aqueous solutions in a wide concentration range from dense to extreme dilute solutions. We studied the vibrational dephasing and vibrational frequency modulation by calculating time correlation functions of vibrational relaxation by fits in the frequency domain. The concentration induced variations in bandwidths, band frequencies and characteristic dephasing times have been estimated and interpreted as effects due to solute-solvent interactions. The time-correlation functions of vibrational dephasing were obtained for the ring breathing mode of both "free" and hydrogen-bonded pyridine molecules and it was found that sufficiently deviate from the Kubo model. There is a general agreement in the whole concentration range with the modeling proposed by the Rothschild approach, which applies to complex liquids. The results have shown that the reorientation of pyridine aqueous solutions is very slow and hence in both scattering geometries only vibrational dephasing is probed. It is proposed that the spectral changes depend on the perturbations induced by the dynamics of the water molecules in the first hydration cell and water in bulk, while at extreme dilution conditions, the number of bulk water molecules increases and the interchange between molecules belonging to the first hydration cell may not be the predominant modulation mechanism. The evolution of several parameters, such as the characteristic times, the percentage of Gaussian character in the peak shape and the a parameter are indicative of drastic variations at extreme dilution revealing changes in the vibrational relaxation of the pyridine complexes in the aqueous environment. The higher dilution is correlated to diffusion of water molecules into the reference pyridine system in agreement with the jump diffusion model, while at extreme dilutions, almost all pyridine molecules are elaborated in hydrogen bonding. The results are discussed in the framework of the current phenomenological status of the field.

Comment on "Horizontal aquifer movement in a theis-theim confined system, by Donald C. Helm

USGS Publications Warehouse

Hsieh, Paul A.; Cooley, Richard L.

1995-01-01

In a recent paper, Helm [1994] presents an analysis of horizontal aquifer movement induced by groundwater withdrawal from a confined aquifer in which fluid and grains are incompressible. The analysis considers the aquifer in isolation (ignoring overlying and underlying strata) and assumes that the aquifer deforms purely in the horizontal direction (with no vertical movement). Helm's solution for grain displacement is obtained through introduction of a quantity known as bulk flux, qb, defined asqb = nvw + (1 - n)vswhere n is porosity, vw is velocity of water, and vs is the velocity of the solid grains. On the basis of the bulk flux concept, Helm develops an explanation for the driving force on the bulk material.It is our view that Helm's analysis is subject to four limitations. First, Helm's assumption of zero vertical displacement is not supported by field observations and could result in over- estimation of radial displacement. Second, in ignoring the role of overlying and underlying strata, Helm's solution does not yield reliable estimates of aquifer deformation. Third, Helm's solution method works only for problems that involve one spatial coordinate (for example, x or r) but does not generally work for problems involving three-dimensional flow and de- formation. Fourth, Helm's explanation of the driving force on the bulk material is faulty for general three-dimensional problems. The purpose of our comment is to discuss these four issues.

Laboratory and field studies of stratospheric aerosols: Phase changes under high supersaturation

NASA Technical Reports Server (NTRS)

Hallet, John

1991-01-01

It is well known that water in the form of isolated small droplets supercool as much as 40 C below their equilibrium melting point. Solutions similarly supercool (with respect to water) and supersaturate (with respect of the solute). Experiments are described in which bulk solutions typical of atmospheric aerosols (nitric acid, sulfuric acid, and hydrates; ammonium sulfate; ammonium bisulfate; sodium chloride) are supercooled and/or supersaturated and nucleated to initiate crystal growth. Supersaturation of 300 percent is readily attainable, with linear growth of crystals increasing roughly as (supercooling/supersaturation)sup 2. The implication of the experiments is that the situation of metastability in polar stratosphere clouds is very likely, with nucleation only occuring under a high degree of supercooling or supersaturation.

Efficient "on-the-fly" calculation of Raman spectra from ab-initio molecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water.

PubMed

Partovi-Azar, Pouya; Kühne, Thomas D

2015-11-05

We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra. © 2015 Wiley Periodicals, Inc.

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

USGS Publications Warehouse

Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P.

1988-01-01

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH.The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

Characterization, sorption, and exhaustion of metal oxide nanoparticles as metal adsorbents

NASA Astrophysics Data System (ADS)

Engates, Karen Elizabeth

Safe drinking water is paramount to human survival. Current treatments do not adequately remove all metals from solution, are expensive, and use many resources. Metal oxide nanoparticles are ideal sorbents for metals due to their smaller size and increased surface area in comparison to bulk media. With increasing demand for fresh drinking water and recent environmental catastrophes to show how fragile water supplies are, new approaches to water conservation incorporating new technologies like metal oxide nanoparticles should be considered as an alternative method for metal contaminant adsorbents from typical treatment methods. This research evaluated the potential of manufactured iron, anatase, and aluminum nanoparticles (Al2O3, TiO2, Fe2O3) to remove metal contaminants (Pb, Cd, Cu, Ni, Zn) in lab-controlled and natural waters in comparison to their bulk counterparts by focusing on pH, contaminant and adsorbent concentrations, particle size, and exhaustive capabilities. Microscopy techniques (SEM, BET, EDX) were used to characterize the adsorbents. Adsorption experiments were performed using 0.01, 0.1, or 0.5 g/L nanoparticles in pH 8 solution. When results were normalized by mass, nanoparticles adsorbed more than bulk particles but when surface area normalized the opposite was observed. Adsorption was pH-dependent and increased with time and solid concentration. Aluminum oxide was found to be the least acceptable adsorbent for the metals tested, while titanium dioxide anatase (TiO2) and hematite (alpha-Fe2O3) showed great ability to remove individual and multiple metals from pH 8 and natural waters. Intraparticle diffusion was likely part of the complex kinetic process for all metals using Fe2O3 but not TiO 2 nanoparticles within the first hour of adsorption. Adsorption kinetics for all metals tested were described by a modified first order rate equation used to consider the diminishing equilibrium metal concentrations with increasing metal oxides, showing faster adsorption rates for nanoparticles compared to bulk particles. Isotherms were best fit with most correlations of r=0.99 or better using the Langmuir-Freundlich equation which describes a heterogeneous surface with monolayer adsorption. Calculated rate constants and distribution coefficients (Kd) showed TiO2 nanoparticles were very good sorbents and more rapid in removing metals than other nanoparticles studied here and reported in the literature. Desorption studies concluded Pb, Cd, and Zn appear to be irreversibly sorbed to TiO2 surfaces at pH 8. TiO2 and Fe2O3 nanoparticles were capable of multiple metal loadings, with exhaustion for both adsorbents at pH 6. Exhaustion studies at pH 8 showed hematite exhausted after four consecutive cycles while anatase showed no exhaustion after 8 cycles. Their bulk counterparts exhausted in earlier cycles indicating the lack of ability to adsorb much of the multiple metals in solution. The increased surface area of TiO2 and Fe 2O3 nanoparticles, coupled with strong adsorption at the pH of most natural waters and resistance to desorption of some metals, may offer a potential remediation method for removal of metals from water in the future.

Effect of composition on physical properties of food powders

NASA Astrophysics Data System (ADS)

Szulc, Karolina; Lenart, Andrzej

2016-04-01

The paper presents an influence of raw material composition and technological process applied on selected physical properties of food powders. Powdered multi-component nutrients were subjected to the process of mixing, agglomeration, coating, and drying. Wetting liquids ie water and a 15% water lactose solution, were used in agglomeration and coating. The analyzed food powders were characterized by differentiated physical properties, including especially: particle size, bulk density, wettability, and dispersibility. The raw material composition of the studied nutrients exerted a statistically significant influence on their physical properties. Agglomeration as well as coating of food powders caused a significant increase in particle size, decreased bulk density, increased apparent density and porosity, and deterioration in flowability in comparison with non-agglomerated nutrients.

Effects of salt or cosolvent addition on solubility of a hydrophobic solute in water: Relevance to those on thermal stability of a protein

NASA Astrophysics Data System (ADS)

Murakami, Shota; Hayashi, Tomohiko; Kinoshita, Masahiro

2017-02-01

The solubility of a nonpolar solute in water is changed upon addition of a salt or cosolvent. Hereafter, "solvent" is formed by water molecules for pure water, by water molecules, cations, and anions for water-salt solution, and by water and cosolvent molecules for water-cosolvent solution. Decrease and increase in the solubility, respectively, are ascribed to enhancement and reduction of the hydrophobic effect. Plenty of experimental data are available for the change in solubility of argon or methane arising from the addition. We show that the integral equation theory combined with a rigid-body model, in which the solute and solvent particles are modeled as hard spheres with different diameters, can reproduce the data for the following items: salting out by an alkali halide and salting in by tetramethylammonium bromide, increase in solubility by a monohydric alcohol, and decrease in solubility by sucrose or urea. The orders of cation or anion species in terms of the power of decreasing the solubility can also be reproduced for alkali halides. With the rigid-body model, the analyses are focused on the roles of entropy originating from the translational displacement of solvent particles. It is argued by decomposing the solvation entropy of a nonpolar solute into physically insightful constituents that the solvent crowding in the bulk is a pivotal factor of the hydrophobic effect: When the solvent crowding in the bulk becomes more serious, the effect is strengthened, and when it becomes less serious, the effect is weakened. It is experimentally known that the thermal stability of a protein is also influenced by the salt or cosolvent addition. The additions which decrease and increase the solubility of a nonpolar solute, respectively, usually enhance and lower the thermal stability. This suggests that the enhanced or reduced hydrophobic effect is also a principal factor governing the stability change. However, urea decreases the solubility but lowers the stability. Bromide and iodide ions decrease the solubility but lower the stability of a protein with a large, positive total charge. In these cases, the urea- or ion-protein van der Waals interaction energy as well as the hydrophobic effect needs to be taken into account in arguing the stability change. We also present a new view on the so-called Hofmeister series: We show how it is expressed when the change in hydrophobic effect dominates and how it is modified when other factors are also influential.

Hydration of AMP and ATP molecules in aqueous solution and solid films.

PubMed

Faizullin, Dzhigangir; Zakharchenko, Nataliya; Zuev, Yuriy; Puzenko, Alexander; Levy, Evgeniya; Feldman, Yuri

2013-11-20

Water enables life and plays a critical role in biology. Considered as a versatile and adaptive component of the cell, water engages a wide range of biomolecular interactions. An organism can exist and function only if its self-assembled molecular structures are hydrated. It was shown recently that switching of AMP/ATP binding to the insulin-independent glucose transporter Human Erythrocyte Glucose Transport Protein (GLUT1) may greatly influence the ratio of bulk and bound water during regulation of glucose uptake by red blood cells. In this paper, we present the results on the hydration properties of AMP/ATP obtained by means of dielectric spectroscopy in aqueous solution and for fully ionized forms in solid amorphous films with the help of gravimetric studies.

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

DOE PAGES

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.; ...

2017-09-06

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

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

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

Investigating the Effects of Environmental Solutes on the Reaction Environment in Ice and at Ice Surfaces

NASA Astrophysics Data System (ADS)

Malley, Philip Patrick Anthony

The reaction environments present in water, ice, and at ice surfaces are physically distinct from one another and studies have shown that photolytic reactions can take place at different rates in the different media. Kinetics of reactions in frozen media are measured in snow and ice prepared from deionized water. This reduces experimental artifacts, but is not relevant to snow in the environment, which contains solutes. We have monitored the effect of nonchromophoric (will not absorb sunlight) organic matter on the photolytic fate of the polycyclic aromatic hydrocarbons (PAHs) phenanthrene, pyrene, and anthracene in ice and at ice surfaces. Nonchromophoric organic matter reduced photolysis rates to below our detection limit in bulk ice, and reduced rates at ice surfaces to a lesser extent due to the PAHs partially partitioning to the organics present. In addition, we have monitored the effect of chromophoric (will absorb sunlight) dissolved organic matter (cDOM) on the fate of anthracene in water, ice, and ice surfaces. cDOM reduced rates in all three media. Suppression in liquid water was due to physical interactions between anthracene and the cDOM, rather than to competitive photon absorbance. More suppression was observed in ice cubes and ice granules than in liquid water due to a freeze concentrating effect. Sodium Chloride (NaCl) is another ubiquitous environmental solute that can influence reaction kinetics in water, ice, and at ice surfaces. Using Raman microscopy, we have mapped the surface of ice of frozen NaCl solutions at 0.02M and 0.6M, as well as the surface of frozen samples of Sargasso Sea Water. At temperatures above and below the eutectic temperature (-21.1°C). Above the eutectic, regions of ice and liquid water were observed in all samples. Liquid regions generally took the form of channels. Channel widths and fractional liquid surface coverage increased with NaCl concentration and temperature. Volume maps of the three samples at temperatures above the eutectic point, showed that liquid channels were distributed throughout the ice sample. Liquid fractions were similar at ice surfaces and in the bulk at depths of at least 80 microm.

Fragile to strong crossover and Widom line in supercooled water: A comparative study

NASA Astrophysics Data System (ADS)

De Marzio, Margherita; Camisasca, Gaia; Rovere, Mauro; Gallo, Paola

2018-02-01

The aim of this paper is to discuss the relationship between the dynamics and thermodynamics of water in the supercooled region. Reviewed case studies comprehend bulk water simulated with the SPC/E, TIP4P and TIP4P/2005 potentials, water at protein interfaces, and water in solution with electrolytes. Upon supercooling, the fragile to strong crossover in the α-relaxation of water is found to occur when the Widom line emanating from the liquid-liquid critical point is crossed. This appears to be a general characteristic of supercooled water, not depending on the applied interaction potential and/or different local environments.

Sucrose diffusion in aqueous solution

PubMed Central

Murray, Benjamin J.

2016-01-01

The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes–Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle. PMID:27364512

Milk whey proteins and xanthan gum interactions in solution and at the air-water interface: a rheokinetic study.

PubMed

Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

2010-11-01

In this contribution, we present experimental information about the effect of xanthan gum (XG) on the adsorption behaviour of two milk whey protein samples (MWP), beta-lactoglobulin (beta-LG) and whey protein concentrate (WPC), at the air-water interface. The MWP concentration studied corresponded to the protein bulk concentration which is able to saturate the air-water interface (1.0 wt%). Temperature, pH and ionic strength of aqueous systems were kept constant at 20 degrees C, pH 7 and 0.05 M, respectively, while the XG bulk concentration varied in the range 0.00-0.25 wt%. Biopolymer interactions in solution were analyzed by extrinsic fluorescence spectroscopy using 1-anilino-8-naphtalene sulphonic acid (ANS) as a protein fluorescence probe. Interfacial biopolymer interactions were evaluated by dynamic tensiometry and surface dilatational rheology. Adsorption behaviour was discussed from a rheokinetic point of view in terms of molecular diffusion, penetration and conformational rearrangement of adsorbed protein residues at the air-water interface. Differences in the interaction magnitude, both in solution and at the interface vicinity, and in the adsorption rheokinetic parameters were observed in MWP/XG mixed systems depending on the protein type (beta-LG or WPC) and biopolymer relative concentration. beta-LG adsorption in XG presence could be promoted by mechanisms based on biopolymer segregative interactions and thermodynamic incompatibility in the interface vicinity, resulting in better surface and viscoelastic properties. The same mechanism could be responsible of WPC interfacial adsorption in the presence of XG. The interfacial functionality of WPC was improved by the synergistic interactions with XG, although WPC chemical complexity might complicate the elucidation of molecular events that govern adsorption dynamics of WPC/XG mixed systems at the air-water interface. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Dynamic analysis of bulk-fill composites: Effect of food-simulating liquids.

PubMed

Eweis, Ahmed Hesham; Yap, Adrian U-Jin; Yahya, Noor Azlin

2017-10-01

This study investigated the effect of food simulating liquids on visco-elastic properties of bulk-fill restoratives using dynamic mechanical analysis. One conventional composite (Filtek Z350 [FZ]), two bulk-fill composites (Filtek Bulk-fill [FB] and Tetric N Ceram [TN]) and a bulk-fill giomer (Beautifil-Bulk Restorative [BB]) were evaluated. Specimens (12 × 2 × 2mm) were fabricated using customized stainless steel molds. The specimens were light-cured, removed from their molds, finished, measured and randomly divided into six groups. The groups (n = 10) were conditioned in the following mediums for 7 days at 37°C: air (control), artificial saliva (SAGF), distilled water, 0.02N citric acid, heptane, 50% ethanol-water solution. Specimens were assessed using dynamic mechanical testing in flexural three-point bending mode and their respective mediums at 37°C and a frequency range of 0.1-10Hz. The distance between the supports were fixed at 10mm and an axial load of 5N was employed. Data for elastic modulus, viscous modulus and loss tangent were subjected to ANOVA/Tukey's tests at significance level p < 0.05. Significant differences in visco-elastic properties were observed between materials and mediums. Apart from bulk-fill giomer, elastic modulus was the highest after conditioning in heptane. No apparent trends were noted for viscous modulus. Generally, loss tangent was the highest after conditioning in ethanol. The effect of food-simulating liquids on the visco-elastic properties of bulk-fill composites was material and medium dependent. Copyright © 2017 Elsevier Ltd. All rights reserved.

Water-mediated interactions between hydrophobic and ionic species in cylindrical nanopores

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

Vaitheeswaran, S.; Reddy, G.; Thirumalai, D.

2009-03-07

We use Metropolis Monte Carlo and umbrella sampling to calculate the free energies of interaction of two methane molecules and their charged derivatives in cylindrical water-filled pores. Confinement strongly alters the interactions between the nonpolar solutes and completely eliminates the solvent separated minimum (SSM) that is seen in bulk water. The free energy profiles show that the methane molecules are either in contact or at separations corresponding to the diameter and the length of the cylindrical pore. Analytic calculations that estimate the entropy of the solutes, which are solvated at the pore surface, qualitatively explain the shape of the freemore » energy profiles. Adding charges of opposite sign and magnitude 0.4e or e (where e is the electronic charge) to the methane molecules decreases their tendency for surface solvation and restores the SSM. We show that confinement induced ion-pair formation occurs whenever l{sub B}/D{approx}O(1), where l{sub B} is the Bjerrum length and D is the pore diameter. The extent of stabilization of the SSM increases with ion charge density as long as l{sub B}/D<1. In pores with D{<=}1.2 nm, in which the water is strongly layered, increasing the charge magnitude from 0.4e to e reduces the stability of the SSM. As a result, ion-pair formation that occurs with negligible probability in the bulk is promoted. In larger diameter pores that can accommodate a complete hydration layer around the solutes, the stability of the SSM is enhanced.« less

Interactions of PAMAM dendrimers with SDS at the solid-liquid interface.

PubMed

Arteta, Marianna Yanez; Eltes, Felix; Campbell, Richard A; Nylander, Tommy

2013-05-14

This work addresses structural and nonequilibrium effects of the interactions between well-defined cationic poly(amidoamine) PAMAM dendrimers of generations 4 and 8 and the anionic surfactant sodium dodecyl sulfate (SDS) at the hydrophilic silica-water interface. Neutron reflectometry and quartz crystal microbalance with dissipation monitoring were used to reveal the adsorption from premixed dendrimer/surfactant solutions as well as sequential addition of the surfactant to preadsorbed layers of dendrimers. PAMAM dendrimers of both generations adsorb to hydrophilic silica as a compact monolayer, and the adsorption is irreversible upon rinsing with salt solution. SDS adsorbs on the dendrimer layer and at low bulk concentrations causes the expansion of the dendrimer layers on the surface. When the bulk concentration of SDS is increased, the surfactant layer consists of aggregates or bilayer-like structures. The adsorption of surfactant is reversible upon rinsing, but slight changes of the structure of the preadsorbed PAMAM monolayer were observed. The adsorption from premixed solutions close to charge neutrality results in thick multilayers, but the surface excess is lower when the bulk complexes have a net negative charge. A critical examination of the pathway of adsorption for the interactions of SDS with preadsorbed PAMAM monolayers and premixed PAMAM/SDS solutions with hydrophilic silica revealed that nonequilibrium effects are important only in the latter case, and the application of a thermodynamic model to such experimental data would be inappropriate.

Understanding the Origins of Dipolar Couplings and Correlated Motion in the Vibrational Spectrum of Water.

PubMed

Heyden, Matthias; Sun, Jian; Forbert, Harald; Mathias, Gerald; Havenith, Martina; Marx, Dominik

2012-08-16

The combination of vibrational spectroscopy and molecular dynamics simulations provides a powerful tool to obtain insights into the molecular details of water structure and dynamics in the bulk and in aqueous solutions. Applying newly developed approaches to analyze correlations of charge currents, molecular dipole fluctuations, and vibrational motion in real and k-space, we compare results from nonpolarizable water models, widely used in biomolecular modeling, to ab initio molecular dynamics. For the first time, we unfold the infrared response of bulk water into contributions from correlated fluctuations in the three-dimensional, anisotropic environment of an average water molecule, from the OH-stretching region down to the THz regime. Our findings show that the absence of electronic polarizability in the force field model not only results in differences in dipolar couplings and infrared absorption but also induces artifacts into the correlated vibrational motion between hydrogen-bonded water molecules, specifically at the intramolecular bending frequency. Consequently, vibrational motion is partially ill-described with implications for the accuracy of non-self-consistent, a posteriori methods to add polarizability.

Amount of leachant and water absorption levels of wood treated with borates and water repellents.

PubMed

Baysal, Ergun; Sonmez, Abdullah; Colak, Mehmet; Toker, Hilmi

2006-12-01

Wood protection efficacy of borates against biological agents, flame retardancy, and suitability to the environment is well known. Since borates can be applied to timber as water based solutions, they are preferred economically as well. Even though they are highly mobile in wood, boron compounds are widely used in timber preservation. Borates migrate in liquid and increase the hygroscopicity of wood in damp conditions. This study deals with the physical restriction of water access in wood by impregnating water repellent agents into wood to limit amount of leachant and water absorption levels of wood after boron treatment. Borates were incorporated with polyethylene glycol-400 (PEG-400) their bulking effect in wood was considered. Results indicated that the amount of leachates from wood treated with borates in PEG-400 was remarkably higher compared to those of wood treated with the aqueous solutions of borates. Water absorption (WA) levels of wood treated with aqueous solutions of borates were higher than those of their treated samples with the solutions in PEG-400. Secondary treatments of wood with the water repellent (WR) chemicals following borate impregnation reduced the leaching of chemicals from wood in water and also WA of the specimens were less than those of the wood treated with only borates from aqueous and PEG solutions. Styrene (St) was the most effective monomer among the other agents used in terms of immobility effect on borates and WA.

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.

Water Interfaces, Solvation, and Spectroscopy

NASA Astrophysics Data System (ADS)

Geissler, Phillip L.

2013-04-01

Liquid water consistently expands our appreciation of the rich statistical mechanics that can emerge from simple molecular constituents. Here I review several interrelated areas of recent work on aqueous systems that aim to explore and explain this richness by revealing molecular arrangements, their thermodynamic origins, and the timescales on which they change. Vibrational spectroscopy of OH stretching features prominently in these discussions, with an emphasis on efforts to establish connections between spectroscopic signals and statistics of intermolecular structure. For bulk solutions, the results of these efforts largely verify and enrich existing physical pictures of hydrogen-bond network connectivity, dynamics, and response. For water at interfaces, such pictures are still emerging. As an important example I discuss the solvation of small ions at the air-water interface, whose surface propensities challenge a basic understanding of how aqueous fluctuations accommodate solutes in heterogeneous environments.

Mixed Valence in Conjugated Anion Radicals. Solution and Solid State Studies

DTIC Science & Technology

1991-05-24

voltammetry was performed using a BAS-100 electrochemical analyzer. Bulk electrolyses were performed with a Princeton Applied Research (PAR) model 173...extracted with several small portions of CH 2 CI 2. The combined organic layers are then washed once again with water . After drying over Na2 SO4 the

Do Clustering Monoclonal Antibody Solutions Really Have a Concentration Dependence of Viscosity?

PubMed Central

Pathak, Jai A.; Sologuren, Rumi R.; Narwal, Rojaramani

2013-01-01

Protein solution rheology data in the biophysics literature have incompletely identified factors that govern hydrodynamics. Whereas spontaneous protein adsorption at the air/water (A/W) interface increases the apparent viscosity of surfactant-free globular protein solutions, it is demonstrated here that irreversible clusters also increase system viscosity in the zero shear limit. Solution rheology measured with double gap geometry in a stress-controlled rheometer on a surfactant-free Immunoglobulin solution demonstrated that both irreversible clusters and the A/W interface increased the apparent low shear rate viscosity. Interfacial shear rheology data showed that the A/W interface yields, i.e., shows solid-like behavior. The A/W interface contribution was smaller, yet nonnegligible, in double gap compared to cone-plate geometry. Apparent nonmonotonic composition dependence of viscosity at low shear rates due to irreversible (nonequilibrium) clusters was resolved by filtration to recover a monotonically increasing viscosity-concentration curve, as expected. Although smaller equilibrium clusters also existed, their size and effective volume fraction were unaffected by filtration, rendering their contribution to viscosity invariant. Surfactant-free antibody systems containing clusters have complex hydrodynamic response, reflecting distinct bulk and interface-adsorbed protein as well as irreversible cluster contributions. Literature models for solution viscosity lack the appropriate physics to describe the bulk shear viscosity of unstable surfactant-free antibody solutions. PMID:23442970

Interfacial Water at Protein Surfaces: Wide-Line NMR and DSC Characterization of Hydration in Ubiquitin Solutions

PubMed Central

Tompa, Kálmán; Bánki, Péter; Bokor, Mónika; Kamasa, Pawel; Lasanda, György; Tompa, Péter

2009-01-01

Wide-line 1H-NMR and differential scanning calorimetry measurements were done in aqueous solutions and on lyophilized samples of human ubiquitin between −70°C and +45°C. The measured properties (size, thermal evolution, and wide-line NMR spectra) of the protein-water interfacial region are substantially different in the double-distilled and buffered-water solutions of ubiquitin. The characteristic transition in water mobility is identified as the melting of the nonfreezing/hydrate water. The amount of water in the low-temperature mobile fraction is 0.4 g/g protein for the pure water solution. The amount of mobile water is higher and its temperature dependence more pronounced for the buffered solution. The specific heat of the nonfreezing/hydrate water was evaluated using combined differential scanning calorimetry and NMR data. Considering the interfacial region as an independent phase, the values obtained are 5.0–5.8 J·g−1·K−1, and the magnitudes are higher than that of pure/bulk water (4.2 J·g−1·K−1). This unexpected discrepancy can only be resolved in principle by assuming that hydrate water is in tight H-bond coupling with the protein matrix. The specific heat for the system composed of the protein molecule and its hydration water is 2.3 J·g−1·K−1. It could be concluded that the protein ubiquitin and its hydrate layer behave as a highly interconnected single phase in a thermodynamic sense. PMID:19348762

Colloid Mobilization in a Fractured Soil: Effect of Pore-Water Exchange between Preferential Flow Paths and Soil Matrix.

PubMed

Mohanty, Sanjay K; Saiers, James E; Ryan, Joseph N

2016-03-01

Exchange of water and solutes between contaminated soil matrix and bulk solution in preferential flow paths has been shown to contribute to the long-term release of dissolved contaminants in the subsurface, but whether and how this exchange can affect the release of colloids in a soil are unclear. To examine this, we applied rainfall solutions of different ionic strength on an intact soil core and compared the resulting changes in effluent colloid concentration through multiple sampling ports. The exchange of water between soil matrix and the preferential flow paths leading to each port was characterized on the basis of the bromide (conservative tracer) breakthrough time at the port. At individual ports, two rainfalls of a certain ionic strength mobilized different amounts of colloids when the soil was pre-exposed to a solution of lower or higher ionic strength. This result indicates that colloid mobilization depended on rainfall solution history, which is referred as colloid mobilization hysteresis. The extent of hysteresis was increased with increases in exchange of pore water and solutes between preferential flow paths and matrix. The results indicate that the soil matrix exchanged the old water from the previous infiltration with new infiltrating water during successive infiltration and changed the pore water chemistry in the preferential flow paths, which in turn affected the release of soil colloids. Therefore, rainfall solution history and soil heterogeneity must be considered to assess colloid mobilization in the subsurface. These findings have implications for the release of colloids, colloid-associated contaminants, and pathogens from soils.

The effect of a solid surface on the segregation and melting of salt hydrates.

PubMed

Zhang, Yu; Anim-Danso, Emmanuel; Dhinojwala, Ali

2014-10-22

Considering the importance of salt and water on earth, the crystallization of salt hydrates next to solid surfaces has important implications in physical and biological sciences. Heterogeneous nucleation is driven by surface interactions, but our understanding of hydrate formation near surfaces is limited. Here, we have studied the hydrate formation of three commonly prevalent salts, MgCl2, CaCl2, and NaCl, next to a sapphire substrate using surface sensitive infrared-visible sum frequency generation (SFG) spectroscopy. SFG spectroscopy can detect the crystallization and melting of salt hydrates at the interface by observing the changes in the intensity and the location of the cocrystallized water hydroxyl peaks (3200-3600 cm(-1)). The results indicate that the surface crystal structures of these three hydrates are similar to those in the bulk. For the NaCl solution, the brine solution is segregated next to the sapphire substrate after the formation of the ice phase. In contrast, the MgCl2 and CaCl2 surface hydrate crystals are interdispersed with nanometer-size ice crystals. The nanosize ice crystals melt at much lower temperatures than bulk ice crystals. For NaCl and MgCl2 solution, the NaCl hydrates prefer to crystallize next to the sapphire substrate instead of the ice crystals and MgCl2 hydrates.

Intermolecular Interactions of Pyridine in Liquid Phase and Aqueous Solution Studied by Soft X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Nagasaka, Masanari; Yuzawa, Hayato; Kosugi, Nobuhiro

2018-05-01

Intermolecular interactions of pyridine in liquid and in aqueous solution are studied by using soft X-ray absorption spectroscopy (XAS) at the C, N, and O K-edges. XAS of liquid pyridine shows that the N 1s→π* peak is blue shifted and the C 1s→π* peak of the meta and para sites is red shifted, respectively, as compared with XAS of pyridine gas. These shifts in liquid are smaller than those in clusters, indicating that the intermolecular interaction of liquid pyridine is weaker than that of pyridine cluster, as supported by the combination of quantum chemical calculations of the core excitation and molecular dynamics simulations of the liquid structure. On the other hand, XAS spectra of aqueous pyridine solutions (C5H5N)x(H2O)1-x measured at different molar fractions show that in the pyridine rich region, x>0.7, the C and N 1s→π* peak energies are not so different from pure liquid pyridine (x=1.0). In this region, antiparallel displaced structures of pyridine molecules are dominant as in pure pyridine liquid. In the O K-edge XAS, the pre-edge peaks sensitive to the hydrogen bond (HB) network of water molecules show the red shift of -0.15 eV from that of bulk water, indicating that small water clusters with no large-scale HB network are formed in the gap space of structured pyridine molecules. In the water rich region, 0.7>x, the N 1s→π* peaks and the O 1s pre-edge peaks are blue shifted, and the C 1s→π* peaks of the meta and para sites are red-shifted by increasing molar fraction of water. The HB network of bulk water is dominant, but quantum chemical calculations indicate that small pyridine clusters with the HB interaction between the H atom in water and the N atom in pyridine are still existent even in very dilute pyridine solutions.

Electroactive microorganisms in bulk solution contribute significantly to methane production in bioelectrochemical anaerobic reactor.

PubMed

Feng, Qing; Song, Young-Chae; Ahn, Yongtae

2018-07-01

The role of anaerobic microorganisms suspended in the bulk solution on methane production was investigated in a bioelectrochemical anaerobic reactor with the electrode polarized at 0.5 V. The electron transfer from substrate to methane and hydrogen were 25% and 7.5%, respectively, in the absence of the anaerobic microorganisms in the bulk solution. As the anaerobic microorganisms increased to 4400 mg/L, the electrons transferred to methane increased to 83.3% but decreased to 0.3% in hydrogen. The electroactive microorganisms (EAM), including exoelectrogens and electrotrophs, enriched in the bulk solution that confirmed by the redox peaks in the cyclic voltammogram was proportional to the anaerobic microorganism. The methane yield based on COD removal was dependent on the anaerobic microorganisms in the bulk solution rather than on the bioelectrode surface. The EAM suspended in the bulk solution are enriched by the polarized electrode, and significantly improve methane production in bioelectrochemical anaerobic reactor. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of volcanic deposit disaggregation on exposed water composition

NASA Astrophysics Data System (ADS)

Back, W. E.; Genareau, K. D.

2016-12-01

Explosive volcanic eruptions produce a variety of hazards. Pyroclastic material can be introduced to water through ash fallout, pyroclastic flows entering water bodies, and/or lahars. Remobilization of tephras can occur soon after eruption or centuries later, introducing additional pyroclastic material into the environment. Introduction of pyroclastic material may alter the dissolved element concentration and pH of exposed waters, potentially impacting drinking water supplies, agriculture, and ecology. This study focuses on the long-term impacts of volcanic deposits on water composition due to the mechanical breakup of volcanic deposits over time. Preliminary work has shown that mechanical milling of volcanic deposits will cause significant increases in dissolved element concentrations, conductivity, and pH of aqueous solutions. Pyroclastic material from seven eruptions sites was collected, mechanically milled to produce grain sizes <32 microns, and a standard ash leachate protocol was performed. Milled tephras were analyzed using X-Ray Fluorescence (XRF) and water leachates were analyzed with Inductively Coupled Plasma Optical-Emission Spectroscopy (ICP-OES). Mechanical disaggregation increases the surface area of the material as well as the amount of active surface sites for leaching. The samples tested consist of felsic (Taupo and Valles Caldera), intermediate (Kelud, Soufriere Hills, Ruapehu), mafic (Lathrop Wells) and ultramafic (mantle xenoliths) volcanic deposits. Lathrop Wells has an average bulk concentration of 49.15 wt.% SiO2, 6.11 wt. % MgO, and 8.39 wt. % CaO and produces leachate concentrations of 85.69 mg/kg for Ca and 37.22 mg/kg for Mg. Taupo and Valles Caldera samples have a bulk concentration of 72.9 wt.% SiO2, 0.59 wt. % MgO, and 1.48 wt. % CaO, and produces leachate concentrations of 4.08 mg/kg for Ca and 1.56 mg/kg for Mg. Similar testing will be conducted on the intermediate and ultramafic samples to test the hypothesis that bulk magma composition and mineralogy will directly relate to the increased dissolved element concentration of exposed waters. The measured effects on aqueous solutions will aid in evaluation of impacts to marine and freshwater systems exposed to volcanic deposits.

Hunting liquid micro-pockets in snow and ice: Phase transition in salt solutions at the bulk and interface with X-ray photoelectron spectroscopy.

NASA Astrophysics Data System (ADS)

Bartels-Rausch, Thorsten; Orlando, Fabrizio; Kong, Xiangrui; Waldner, Astrid; Artiglia, Luca; Ammann, Markus; Huthwelker, Thomas

2016-04-01

Sea salt, and in particular chloride, is an important reactant in the atmosphere. Chloride in air-borne sea salt aerosol is - once chemically converted to a molecular halogen (Cl2, BrCl) and released to the atmosphere - well known as important atmospheric reactant, driving large-scale changes to the atmospheric composition and in particular to ozone levels in remote areas, but also in coastal mega cities. Similar chemistry has been proposed for sea salt deposits in polar snow covers. A crucial factor determining the overall reactivity is the local physical environment of the chloride ion. For example, the reactivity of liquid aerosols decreases significantly upon crystallization. Surprisingly, the phases of NaCl-containing systems are still under debate, partially due to the limited availability of in situ measurements directly probing the local environment at the surface of frozen NaCl-water binary systems. Using core electron spectroscopy of the oxygen atoms in water, we previously showed that these systems follow the phase rules at the air-ice interface. This finding contrasts some earlier observations, where the presence of liquid below the eutectic point of bulk solutions was postulated. In the present study, we present new electron yield near-edge X-ray absorption fine structure spectroscopy (NEXAFS) data obtained at near-ambient pressures up to 20 mbar of NaCl frozen solutions. The method is sensitive to small changes in the local environment of the chlorine atom. The measurements were performed at the PHOENIX beamline at SLS. The study indicates frapant differences in the phases of NaCl - water mixtures at temperatures blow the freezing point for the surface of the ice vs. the bulk. This has significant impact on modelling chemical reactions in snow or ice and it's environmental consequences.

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.

Non-stationarity in experimental travel time measured in a lysimeter: theoretical and modeling lessons from a simplified hydrological system

NASA Astrophysics Data System (ADS)

Queloz, Pierre; Carraro, Luca; Bertuzzo, Enrico; Botter, Gianluca; Rao, P. Suresh C.; Rinaldo, Andrea

2014-05-01

Experimental data have been collected over a year-long period in a large weighing lysimeter. Natural climatic forcing occurs, except for rainfall which is artificially generated as a given Poisson process at a daily timescale. A constant water table is maintained and excess infiltrated water is discharged through the outlet at the bottom of the lysimeter. Soil water storage and evapotranspiration fluxes (accentuated by a willow tree planted in the lysimeter) were monitored throughout the experiment, so that accurate time series of all in- and out-fluxes are available. Five rainfall inputs were marked with individually traceable passive solutes (fluorobenzoic acids) at various initial soil moisture conditions during the first month of the experiment. Tracer concentrations were measured in the soil water and in the discharge at high temporal resolution. We aim here at directly measuring solute travel times, a proxy of hydrological transport with the main advantage to blend the bulk effects of water velocity distributions. The drivers of water displacement in this hydrological setting - and in any other realistic case - have intrinsically a non-stationary nature (e.g. random rainfall occurrence, seasonal evapotranspiration cycles and moisture-related soil connectivity), but the integration of these processes over a larger time scale (i.e. typically the time scale of the mean travel time) often lead to the stationary assumption thus considerably simplifying the data interpretation. Results clearly show that even in such a hydrological system with reduced complexity, experimental travel time distributions are non-stationary and are strongly influenced by the states encountered by the system during the transport phase. The measurements help at identifying the relevant key features influencing the experimental bulk transport. Modeling efforts have demonstrated the inability of a plug-flow reactor (old-water first reservoir) to reproduce the solute outfluxes dynamics. On the other hand, the well-mixed reactor performs well at long term, but hardly applies for the period directly following the tracer injection.

Protein Adsorption in Three Dimensions

PubMed Central

Vogler, Erwin A.

2011-01-01

Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and initially-adsorbed protein. Interphase protein concentration CI increases as VI decreases, resulting in slow reduction in interfacial energetics. Steady-state is governed by a net partition coefficient P=(/CBCI). In the process of occupying space within the interphase, adsorbing protein molecules must displace an equivalent volume of interphase water. Interphase water is itself associated with surface-bound water through a network of transient hydrogen bonds. Displacement of interphase water thus requires an amount of energy that depends on the adsorbent surface chemistry/energy. This “adsorption-dehydration” step is the significant free-energy cost of adsorption that controls the maximum amount of protein that can be adsorbed at steady state to a unit adsorbent-surface area (the adsorbent capacity). As adsorbent hydrophilicity increases, protein adsorption monotonically decreases because the energetic cost of surface dehydration increases, ultimately leading to no protein adsorption near an adsorbent water wettability (surface energy) characterized by a water contact angle θ → 65°. Consequently, protein does not adsorb (accumulate at interphase concentrations greater than bulk solution) to more hydrophilic adsorbents exhibiting θ < 65° . For adsorbents bearing strong Lewis acid/base chemistry such as ion-exchange resins, protein/surface interactions can be highly favorable, causing protein to adsorb in multilayers in a relatively thick interphase. A straightforward, three-component free energy relationship captures salient features of protein adsorption to all surfaces predicting that the overall free energy of protein adsorption ΔGadso is a relatively small multiple of thermal energy for any surface chemistry (except perhaps for bioengineered surfaces bearing specific ligands for adsorbing protein) because a surface chemistry that interacts chemically with proteins must also interact with water through hydrogen bonding. In this way, water moderates protein adsorption to any surface by competing with adsorbing protein molecules. This Leading Opinion ends by proposing several changes to the protein-adsorption paradigm that might advance answers to the three core questions that frame the “protein-adsorption problem” that is so fundamental to biomaterials surface science. PMID:22088888

Analysis of radiation-induced small Cu particle cluster formation in aqueous CuCl2

USGS Publications Warehouse

Jayanetti, Sumedha; Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2001-01-01

Radition-induced small Cu particle cluster formation in aqueous CuCl2 was analyzed. It was noticed that nearest neighbor distance increased with the increase in the time of irradiation. This showed that the clusters approached the lattice dimension of bulk copper. As the average cluster size approached its bulk dimensions, an increase in the nearest neighbor coordination number was found with the decrease in the surface to volume ratio. Radiolysis of water by incident x-ray beam led to the reduction of copper ions in the solution to themetallic state.

Boron sorption from aqueous solution by hydrotalcite and its preliminary application in geothermal water deboronation.

PubMed

Guo, Qinghai; Zhang, Yin; Cao, Yaowu; Wang, Yanxin; Yan, Weide

2013-11-01

Hydrotalcite and its calcination product were used to treat pure water spiked with various concentrations of boron and geothermal water containing boron as a major undesirable element. The kinetics process of boron sorption by uncalcined hydrotalcite is controlled by the diffusion of boron from bulk solution to sorbent-solution boundary film and its exchange with interlayer chloride of hydrotalcite, whereas the removal rate of boron by calcined hydrotalcite rests with the restoration process of its layered structure. The results of isotherm sorption experiments reveal that calcined hydrotalcite generally has much stronger ability to lower solution boron concentration than uncalcined hydrotalcite. The combination of adsorption of boron on the residue of MgO-Al2O3 solid solution and intercalation of boron into the reconstructed hydrotalcite structure due to "structural memory effect" is the basic mechanism based on which the greater boron removal by calcined hydrotalcite was achieved. As 15 geothermal water samples were used to test the deboronation ability of calcined hydrotalcite at 65 °C, much lower boron removal efficiencies were observed. The competitive sorption of the other anions in geothermal water, such as HCO3-, SO4(2-), and F-, is the reason why calcined hydrotalcite could not remove boron from geothermal water as effectively as from pure boron solution. However, boron removal percents ranging from 89.3 to 99.0% could be obtained if 50 times of sorbent were added to the geothermal water samples. Calcined hydrotalcite is a good candidate for deboronation of geothermal water.

In Situ Infrared Spectroelectrochemistry.

DTIC Science & Technology

1986-07-30

The serious if the solvent is water , which staLe of the incident light, mechanism of absorption involves in- absorbs strongly throughout most of In...reflection uses a 3b shows spectra taken with the same thin-layer cell. where bulk electrolyses potentials as in 3a (this time using a of solution species...away from tion of both s-polarized and p-polar- ing neutral species and the highly con- the regions of strong water absorpt ion. ized light, and thought

Driving forces for adsorption of amphiphilic peptides to the air-water interface.

PubMed

Engin, Ozge; Villa, Alessandra; Sayar, Mehmet; Hess, Berk

2010-09-02

We have studied the partitioning of amphiphilic peptides at the air-water interface. The free energy of adsorption from bulk to interface was calculated by determining the potential of mean force via atomistic molecular dynamics simulations. To this end a method is introduced to restrain or constrain the center of mass of a group of molecules in a periodic system. The model amphiphilic peptides are composed of alternating valine and asparagine residues. The decomposition of the free energy difference between the bulk and interface is studied for different peptide block lengths. Our analysis revealed that for short amphiphilic peptides the surface driving force dominantly stems from the dehydration of hydrophobic side chains. The only opposing force is associated with the loss of orientational freedom of the peptide at the interface. For the peptides studied, the free energy difference scales linearly with the size of the molecule, since the peptides mainly adopt extended conformations both in bulk and at the interface. The free energy difference depends strongly on the water model, which can be rationalized through the hydration thermodynamics of hydrophobic solutes. Finally, we measured the reduction of the surface tension associated with complete coverage of the interface with peptides.

The Use of Index-Matched Beads in Optical Particle Counters

PubMed Central

Hu, Zhishang; Ripple, Dean C

2014-01-01

In this paper, we demonstrate the use of 2-pyridinemethanol (2P) aqueous solutions as a refractive index matching liquid. The high refractive index and low viscosity of 2P-water mixtures enables refractive index matching of beads that cannot be index matched with glycerol-water or sucrose-water solutions, such as silica beads that have the refractive index of bulk fused silica or of polymethylmethacrylate beads. Suspensions of beads in a nearly index-matching liquid are a useful tool to understand the response of particle counting instruments to particles of low optical contrast, such as aggregated protein particles. Data from flow imaging and light obscuration instruments are presented for bead diameters ranging from 6 µm to 69 µm, in a matrix liquid spanning the point of matched refractive index. PMID:26601049

Physicochemical Study of Viral Nanoparticles at the Air/Water Interface.

PubMed

Torres-Salgado, Jose F; Comas-Garcia, Mauricio; Villagrana-Escareño, Maria V; Durán-Meza, Ana L; Ruiz-García, Jaime; Cadena-Nava, Ruben D

2016-07-07

The assembly of most single-stranded RNA (ssRNA) viruses into icosahedral nucleocapsids is a spontaneous process driven by protein-protein and RNA-protein interactions. The precise nature of these interactions results in the assembly of extremely monodisperse and structurally indistinguishable nucleocapsids. In this work, by using a ssRNA plant virus (cowpea chlorotic mottle virus [CCMV]) as a charged nanoparticle we show that the diffusion of these nanoparticles from the bulk solution to the air/water interface is an irreversible adsorption process. By using the Langmuir technique, we measured the diffusion and adsorption of viral nucleocapsids at the air/water interface at different pH conditions. The pH changes, and therefore in the net surface charge of the virions, have a great influence in the diffusion rate from the bulk solution to the air/water interface. Moreover, assembly of mesoscopic and microscopic viral aggregates at this interface depends on the net surface charge of the virions and the surface pressure. By using Brewster's angle microscopy we characterized these structures at the interface. Most common structures observed were clusters of virions and soap-frothlike micron-size structures. Furthermore, the CCMV films were compressed to form monolayers and multilayers from moderate to high surface pressures, respectively. After transferring the films from the air/water interface onto mica by using the Langmuir-Blodgett technique, their morphology was characterized by atomic force microscopy. These viral monolayers showed closed-packing nano- and microscopic arrangements.

Dramatically stabilizing multiprotein complex structure in the absence of bulk water using tuned Hofmeister salts.

PubMed

Han, Linjie; Hyung, Suk-Joon; Ruotolo, Brandon T

2013-01-01

The role that water plays in the salt-based stabilization of proteins is central to our understanding of protein biophysics. Ion hydration and the ability of ions to alter water surface tension are typically invoked, along with direct ion-protein binding, to describe Hofmeister stabilization phenomena observed for proteins experimentally, but the relative influence of these forces has been extraordinarily difficult to measure directly. Recently, we have used gas-phase measurements of proteins and large multiprotein complexes, using a combination of innovative ion mobility (IM) and mass spectrometry (MS) techniques, to assess the ability of bound cations and anions to stabilize protein ions in the absence of the solvation forces described above. Our previous work has studied a broad set of 12 anions bound to a range of proteins and protein complexes, and while primarily motivated by the analytical challenges surrounding the gas-phase measurement of solution-phase relevant protein structures, our work has also lead to a detailed physical mechanism of anion-protein complex stabilization in the absence of bulk solvent. Our more-recent work has screened a similarly-broad set of cations for their ability to stabilize gas-phase protein structure, and we have discovered surprising differences between the operative mechanisms for cations and anions in gas-phase protein stabilization. In both cases, cations and anions affect protein stabilization in the absence of solvent in a manner that is generally reversed relative to their ability to stabilize the same proteins in solution. In addition, our evidence suggests that the relative solution-phase binding affinity of the anions and cations studied here is preserved in our gas-phase measurements, allowing us to study the influence of such interactions in detail. In this report, we collect and summarize such gas-phase measurements to distill a generalized picture of salt-based protein stabilization in the absence of bulk water. Further, we communicate our most recent efforts to study the combined effects of stabilizing cations and anions on gas-phase proteins, and identify those salts that bear anion/cation pairs having the strongest stabilizing influence on protein structures

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH

PubMed Central

2017-01-01

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery. PMID:28872838

Enhancing boron rejection in FO using alkaline draw solutions.

PubMed

Wang, Yi-Ning; Li, Weiyi; Wang, Rong; Tang, Chuyang Y

2017-07-01

This study provides a novel method to enhance boron removal in a forward osmosis (FO) process. It utilizes the reverse solute diffusion (RSD) of ions from alkaline draw solutions (DSs) and the concentration polarization of the hydroxyl ions to create a highly alkaline environment near the membrane active surface. The results show that boron rejection can be significantly enhanced by increasing the pH of NaCl DS to 12.5 in the active-layer-facing-feed-solution (AL-FS) orientation. The effect of RSD enhanced boron rejection was further promoted in the presence of concentration polarization (e.g., in the active-layer-facing-draw-solution (AL-DS) orientation). The current study opens a new dimension for controlling contaminant removal by FO using tailored DS chemistry, where the RSD-induced localized water chemistry change is taken advantage in contrast to the conventional method of chemical dosing to the bulk feed water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cloud water composition during HCCT-2010: Scavenging efficiencies, solute concentrations, and droplet size dependence of inorganic ions and dissolved organic carbon

NASA Astrophysics Data System (ADS)

van Pinxteren, Dominik; Wadinga Fomba, Khanneh; Mertes, Stephan; Müller, Konrad; Spindler, Gerald; Schneider, Johannes; Lee, Taehyoung; Collett, Jeffrey L.; Herrmann, Hartmut

2016-03-01

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a three-stage and a five-stage collector were applied and samples were analysed for inorganic ions (SO42-,NO3-, NH4+, Cl-, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 µmol L-1 for ammonium, nitrate, and sulfate respectively, between 4 and 27 µmol L-1 for minor ions, 5.4 µmol L-1 for H2O2 (aq), 1.9 µmol L-1 for S(IV), and 3.9 mgC L-1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC × 1.8) contributed 20-40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60-66 % for solute concentrations and 52-80 % for cloud water loadings (CWLs). The similar variability of solute concentrations and CWLs together with the results of back-trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC), were the main factor controlling bulk solute concentrations for the cloud studied. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CVI) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56-0.94, 0.79-0.99, 0.71-98, and 0.67-0.92 for SO42-, NO3-, NH4+, and DOC respectively when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42-, NO3-, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and "U" shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the three-stage collector and somewhat more pronounced from the five-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the five-stage collector was capable of resolving some features of solute size dependencies not seen in the three-stage data, especially sharp concentration increases (up to a factor of 5-10) in the smallest droplets for many solutes.

Cloud water composition during HCCT-2010: Scavenging efficiencies, solute concentrations, and droplet size dependence of inorganic ions and dissolved organic carbon

NASA Astrophysics Data System (ADS)

van Pinxteren, D.; Fomba, K. W.; Mertes, S.; Müller, K.; Spindler, G.; Schneider, J.; Lee, T.; Collett, J.; Herrmann, H.

2015-09-01

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a 3-stage and a 5-stage collector were applied and samples were analysed for inorganic ions (SO42-, NO3-, NH4+, Cl-, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 μmol L-1 for ammonium, nitrate, and sulfate, respectively, between 4 and 27 μmol L-1 for minor ions, 5.4 μmol L-1 for H2O2 (aq), 1.9 μmol L-1 for S(IV), and 3.9 mgC L-1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC · 1.8) contributed 20-40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60-66 % for solute concentrations and 52-80 % for cloud water loadings (CWLs). Contrary to some earlier suggestions, the similar variability of solute concentrations and CWLs together with the results of back trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC) was the main factor controlling bulk solute concentrations at Mt. Schmücke. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CV) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56-0.94, 0.79-0.99, 0.71-98, and 0.67-0.92 for SO42-, NO3-, NH4+, and DOC, respectively, when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42-, NO3-, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and "U"-shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the 3-stage collector and somewhat more pronounced from the 5-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the 5-stage collector was capable of resolving some features of solute size dependencies not seen in the 3-stage data, especially sharp concentration increases (up to a factor of 5-10) in the smallest droplets for many solutes.

Regulation of amniotic fluid volume: mathematical model based on intramembranous transport mechanisms

PubMed Central

Anderson, Debra F.; Cheung, Cecilia Y.

2014-01-01

Experimentation in late-gestation fetal sheep has suggested that regulation of amniotic fluid (AF) volume occurs primarily by modulating the rate of intramembranous transport of water and solutes across the amnion into underlying fetal blood vessels. In order to gain insight into intramembranous transport mechanisms, we developed a computer model that allows simulation of experimentally measured changes in AF volume and composition over time. The model included fetal urine excretion and lung liquid secretion as inflows into the amniotic compartment plus fetal swallowing and intramembranous absorption as outflows. By using experimental flows and solute concentrations for urine, lung liquid, and swallowed fluid in combination with the passive and active transport mechanisms of the intramembranous pathway, we simulated AF responses to basal conditions, intra-amniotic fluid infusions, fetal intravascular infusions, urine replacement, and tracheoesophageal occlusion. The experimental data are consistent with four intramembranous transport mechanisms acting in concert: 1) an active unidirectional bulk transport of AF with all dissolved solutes out of AF into fetal blood presumably by vesicles; 2) passive bidirectional diffusion of solutes, such as sodium and chloride, between fetal blood and AF; 3) passive bidirectional water movement between AF and fetal blood; and 4) unidirectional transport of lactate into the AF. Further, only unidirectional bulk transport is dynamically regulated. The simulations also identified areas for future study: 1) identifying intramembranous stimulators and inhibitors, 2) determining the semipermeability characteristics of the intramembranous pathway, and 3) characterizing the vesicles that are the primary mediators of intramembranous transport. PMID:25186112

Comparative study of urea and betaine solutions by dielectric spectroscopy: liquid structures of a protein denaturant and stabilizer.

PubMed

Hayashi, Yoshihito; Katsumoto, Yoichi; Oshige, Ikuya; Omori, Shinji; Yasuda, Akio

2007-10-11

We performed dielectric spectroscopy measurements on aqueous solutions of glycine betaine (N,N,N-trimethylglycine), which is known to be a strong stabilizer of globular proteins, over a wide concentration range (3-62 wt %) and compared the results with our previously published data for aqueous solutions of urea, a representative protein denaturant. The hydration number of betaine (9), calculated on the basis of the reduction in the dielectric relaxation strength of bulk water with addition of betaine, is significantly larger than that of urea (2). Furthermore, the dielectric relaxation time increased with betaine concentration, while that remained nearly constant for the urea-water system over a wide concentration range. This difference between urea and betaine is probably related to their opposite effects on the protein stabilization.

Process for disposal of aqueous solutions containing radioactive isotopes

DOEpatents

Colombo, Peter; Neilson, Jr., Robert M.; Becker, Walter W.

1979-01-01

A process for disposing of radioactive aqueous waste solutions whereby the waste solution is utilized as the water of hydration to hydrate densified powdered portland cement in a leakproof container; said waste solution being dispersed without mechanical inter-mixing in situ in said bulk cement, thereafter the hydrated cement body is impregnated with a mixture of a monomer and polymerization catalyst to form polymer throughout the cement body. The entire process being carried out while maintaining the temperature of the components during the process at a temperature below 99.degree. C. The container containing the solid polymer-impregnated body is thereafter stored at a radioactive waste storage dump such as an underground storage dump.

Thick layered semiconductor devices with water top-gates: High on-off ratio field-effect transistors and aqueous sensors.

PubMed

Huang, Yuan; Sutter, Eli; Wu, Liangmei; Xu, Hong; Bao, Lihong; Gao, Hong-Jun; Zhou, Xingjiang; Sutter, Peter

2018-06-21

Layered semiconductors show promise as channel materials for field-effect transistors (FETs). Usually, such devices incorporate solid back or top gate dielectrics. Here, we explore de-ionized (DI) water as a solution top gate for field-effect switching of layered semiconductors including SnS2, MoS2, and black phosphorus. The DI water gate is easily fabricated, can sustain rapid bias changes, and its efficient coupling to layered materials provides high on-off current ratios, near-ideal sub-threshold swing, and enhanced short-channel behavior even for FETs with thick, bulk-like channels where such control is difficult to realize with conventional back-gating. Screening by the high-k solution gate eliminates hysteresis due to surface and interface trap states and substantially enhances the field-effect mobility. The onset of water electrolysis sets the ultimate limit to DI water gating at large negative gate bias. Measurements in this regime show promise for aqueous sensing, demonstrated here by the amperometric detection of glucose in aqueous solution. DI water gating of layered semiconductors can be harnessed in research on novel materials and devices, and it may with further development find broad applications in microelectronics and sensing.

Draft framework for watershed-based trading

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

NONE

1996-05-30

Effluent trading is an innovative way for water quality agencies and community stakeholders to develop common-sense, cost-effective solutions for water quality problems in their watersheds. Trading can allow communities to grow and prosper while retaining their commitment to water quality. The bulk of this framework discusses effluent trading in watersheds. Remaining sections discuss transactions that, while not technically fulfilling the definition of `effluent` trade, do involve the exchange of valued water quality or other ecological improvements between partners responding to market initiatives. This document therefore includes activities such as trades within a facility (intra-plant trading) and wetland mitigation banking, effluentmore » trading/watersheds/watershed management/water quality protection/water quality management.« less

Hydration index--a better parameter for explaining small molecule hydration in inhibition of ice recrystallization.

PubMed

Tam, Roger Y; Ferreira, Sandra S; Czechura, Pawel; Chaytor, Jennifer L; Ben, Robert N

2008-12-24

Several simple mono- and disaccharides have been assessed for their ability to inhibit ice recrystallization. Two carbohydrates were found to be effective recrystallization inhibitors. D-galactose (1) was the best monosaccharide and D-melibiose (5) was the most active disaccharide. The ability of each carbohydrate to inhibit ice growth was correlated to its respective hydration number reported in the literature. A hydration number reflects the number of tightly bound water molecules to the carbohydrate and is a function of carbohydrate stereochemistry. It was discovered that using the absolute hydration number of a carbohydrate does not allow one to accurately predict its ability to inhibit ice recrystallization. Consequently, we have defined a hydration index in which the hydration number is divided by the molar volume of the carbohydrate. This new parameter not only takes into account the number of water molecules tightly bound to a carbohydrate but also the size or volume of a particular solute and ultimately the concentration of hydrated water molecules. The hydration index of both mono- and disaccharides correlates well with experimentally measured RI activity. C-Linked derivatives of the monosaccharides appear to have RI activity comparable to that of their O-linked saccharides but a more thorough investigation is required. The relationship between carbohydrate concentration and RI activity was shown to be noncolligative and a 0.022 M solution of D-galactose (1) and C-linked galactose derivative (10) inhibited recrystallization as well as a 3% DMSO solution. The carbohydrates examined in this study did not possess any thermal hysteresis activity (selective depression of freezing point relative to melting point) or dynamic ice shaping. As such, we propose that they are inhibiting recrystallization at the interface between bulk water and the quasi liquid layer (a semiordered interface between ice and bulk water) by disrupting the preordering of water.

A simple approach to determine reactive solute transport using time domain reflectometry

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

Vogeler, I.; Duwig, C.; Clothier, B.E.

2000-02-01

Time domain reflectometry (TDR) possesses potential for determining solute-transport parameters, such as dispersion coefficients and retardation factors for reactive solutes. The authors developed a simple method based on peak-to-peak measurements of water and solute velocities through the soil using TDR. The method was tested by carrying out unsaturated leaching experiments in the laboratory on two soil columns packed with a South Pacific soil from Mare, which is a ferrasol with variable surface charge. One column was left bare and the other was planted with mustard. Pulses of CaBr{sub 2} and Ca(NO{sub 3}){minus}{sub 2} were applied to the surface of eithermore » wet or dry soil and then leached by water from a rainfall simulator applied at a steady rate of between 30 and 45 mm h{sup {minus}1}. Water and solute transport were monitored by collecting the effluent. Contemporaneous in situ measurements of the water content and electrical conductivity were made using TDR. Transport parameters for the convection-dispersion equation, with a linear adsorption isotherm, were obtained from the flux concentration and the solute resident concentrations measured by TDR. Anion retardations between 1.2 and 1.7, and dispersivities between 1 and 9 mm, were found. Retardations also were calculated using the authors simple approach based on TDR-measured water and solute front velocities. These used TDR measurements of soil water content and bulk soil electrical conductivity with time, and were similar to those obtained from the effluent. The agreement suggests TDR could be a valuable in situ technique for obtaining the parameters relating to reactive solute transport through soil.« less

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

Driving force for hydrophobic interaction at different length scales.

PubMed

Zangi, Ronen

2011-03-17

We study by molecular dynamics simulations the driving force for the hydrophobic interaction between graphene sheets of different sizes down to the atomic scale. Similar to the prediction by Lum, Chandler, and Weeks for hard-sphere solvation [J. Phys. Chem. B 1999, 103, 4570-4577], we find the driving force to be length-scale dependent, despite the fact that our model systems do not exhibit dewetting. For small hydrophobic solutes, the association is purely entropic, while enthalpy favors dissociation. The latter is demonstrated to arise from the enhancement of hydrogen bonding between the water molecules around small hydrophobes. On the other hand, the attraction between large graphene sheets is dominated by enthalpy which mainly originates from direct solute-solute interactions. The crossover length is found to be inside the range of 0.3-1.5 nm(2) of the surface area of the hydrophobe that is eliminated in the association process. In the large-scale regime, different thermodynamic properties are scalable with this change of surface area. In particular, upon dimerization, a total and a water-induced stabilization of approximately 65 and 12 kJ/mol/nm(2) are obtained, respectively, and on average around one hydrogen bond is gained per 1 nm(2) of graphene sheet association. Furthermore, the potential of mean force between the sheets is also scalable except for interplate distances smaller than 0.64 nm which corresponds to the region around the barrier for removing the last layer of water. It turns out that, as the surface area increases, the relative height of the barrier for association decreases and the range of attraction increases. It is also shown that, around small hydrophobic solutes, the lifetime of the hydrogen bonds is longer than in the bulk, while around large hydrophobes it is the same. Nevertheless, the rearrangement of the hydrogen-bond network for both length-scale regimes is slower than in bulk water. © 2011 American Chemical Society

Possible existence of convective currents in surfactant bulk solution in experimental pendant-bubble dynamic surface tension measurements.

PubMed

Moorkanikkara, Srinivas Nageswaran; Blankschtein, Daniel

2009-02-03

Traditionally, surfactant bulk solutions in which dynamic surface tension (DST) measurements are conducted using the pendant-bubble apparatus are assumed to be quiescent. Consequently, the transport of surfactant molecules in the bulk solution is often modeled as being purely diffusive when analyzing the experimental pendant-bubble DST data. In this Article, we analyze the experimental pendant-bubble DST data of the alkyl poly (ethylene oxide) nonionic surfactants, C12E4 and C12E6, and demonstrate that both surfactants exhibit "superdiffusive" adsorption kinetics behavior with characteristics that challenge the traditional assumption of a quiescent surfactant bulk solution. In other words, the observed superdiffusive adsorption behavior points to the possible existence of convection currents in the surfactant bulk solution. The analysis presented here involves the following steps: (1) constructing an adsorption kinetics model that corresponds to the fastest rate at which surfactant molecules adsorb onto the actual pendant-bubble surface from a quiescent solution, (2) predicting the DST behaviors of C12E4 and C12E6 at several surfactant bulk solution concentrations using the model constructed in step 1, and (3) comparing the predicted DST profiles with the experimental DST profiles. This comparison reveals systematic deviations for both C12E4 and C12E6 with the following characteristics: (a) the experimental DST profiles exhibit adsorption kinetics behavior, which is faster than the predicted fastest rate of surfactant adsorption from a quiescent surfactant bulk solution at time scales greater than 100 s, and (b) the experimental DST profiles and the predicted DST behaviors approach the same equilibrium surface tension values. Characteristic (b) indicates that the cause of the observed systematic deviations may be associated with the adsorption kinetics mechanism adopted in the model used rather than with the equilibrium behavior. Characteristic (a) indicates that the actual surfactant bulk solution in which the DST measurement was conducted, most likely, cannot be considered to be quiescent at time scales greater than 100 s. Accordingly, the observed superdiffusive adsorption behavior is interpreted as resulting from convection currents present in a nonquiescent surfactant bulk solution. Convection currents accelerate the surfactant adsorption process by increasing the rate of surfactant transport in the bulk solution. The systematic nature of the deviations observed between the predicted DST profiles and the experimental DST behavior for C12E4 and C12E6 suggests that the nonquiescent nature of the surfactant bulk solution may be intrinsic to the experimental pendant-bubble DST measurement approach. To validate this possibility, we identified generic features in the experimental DST data when DST measurements are conducted in a nonquiescent surfactant bulk solution, and the DST measurements are analyzed assuming that the surfactant bulk solution is quiescent. An examination of the DST literature reveals that these identified generic features are quite general and are observed in the experimental DST data of several other surfactants (decanol, nonanol, C10E8, C14E8, C12E8, and C10E4) measured using the pendant-bubble apparatus.

Ion specific effects: decoupling ion-ion and ion-water interactions

PubMed Central

Song, Jinsuk; Kang, Tae Hui; Kim, Mahn Won; Han, Songi

2015-01-01

Ion-specific effects in aqueous solution, known as the Hofmeister effect is prevalent in diverse systems ranging from pure ionic to complex protein solutions. The objective of this paper is to explicitly demonstrate how complex ion-ion and ion-water interactions manifest themselves in the Hofmeister effects, based on a series of recent experimental observation. These effects are not considered in the classical description of ion effects, such as the Deryaguin-Landau-Verwey-Overbeek (DLVO) theory that, likely for that reason, fail to describe the origin of the phenomenological Hofmeister effect. However, given that models considering the basic forces of electrostatic and van der Waals interactions can offer rationalization for the core experimental observations, a universal interaction model stands a chance to be developed. In this perspective, we separately derive the contribution from ion-ion electrostatic interaction and ion-water interaction from second harmonic generation (SHG) data at the air-ion solution interface, which yields an estimate of ion-water interactions in solution. Hofmeister ion effects observed on biological solutes in solution should be similarly influenced by contributions from ion-ion and ion-water interactions, where the same ion-water interaction parameters derived from SHG data at the air-ion solution interface could be applicable. A key experimental data set available from solution systems to probe ion-water interaction is the modulation of water diffusion dynamics near ions in bulk ion solution, as well as near biological liposome surfaces. It is obtained from Overhauser dynamic nuclear polarization (ODNP), a nuclear magnetic resonance (NMR) relaxometry technique. The surface water diffusivity is influenced by the contribution from ion-water interactions, both from localized surface charges and adsorbed ions, although the relative contribution of the former is larger on liposome surfaces. In this perspective, ion-water interaction energy values derived from experimental data for various ions are compared with theoretical values in the literature. Ultimately, quantifying ion-induced changes in surface energy for the purpose of developing valid theoretical models for ion-water interaction, will be critical to rationalizing the Hofmeister effect. PMID:25761273

The Clusters-in-a-Liquid Approach for Solvation: New Insights from the Conformer Specific Gas Phase Spectroscopy and Vibrational Optical Activity Spectroscopy

PubMed Central

Perera, Angelo S.; Thomas, Javix; Poopari, Mohammad R.; Xu, Yunjie

2016-01-01

Vibrational optical activity spectroscopies, namely vibrational circular dichroism (VCD) and Raman optical activity (ROA), have been emerged in the past decade as powerful spectroscopic tools for stereochemical information of a wide range of chiral compounds in solution directly. More recently, their applications in unveiling solvent effects, especially those associated with water solvent, have been explored. In this review article, we first select a few examples to demonstrate the unique sensitivity of VCD spectral signatures to both bulk solvent effects and explicit hydrogen-bonding interactions in solution. Second, we discuss the induced solvent chirality, or chiral transfer, VCD spectral features observed in the water bending band region in detail. From these chirality transfer spectral data, the related conformer specific gas phase spectroscopic studies of small chiral hydration clusters, and the associated matrix isolation VCD experiments of hydrogen-bonded complexes in cold rare gas matrices, a general picture of solvation in aqueous solution emerges. In such an aqueous solution, some small chiral hydration clusters, rather than the chiral solutes themselves, are the dominant species and are the ones that contribute mainly to the experimentally observed VCD features. We then review a series of VCD studies of amino acids and their derivatives in aqueous solution under different pHs to emphasize the importance of the inclusion of the bulk solvent effects. These experimental data and the associated theoretical analyses are the foundation for the proposed “clusters-in-a-liquid” approach to account for solvent effects effectively. We present several approaches to identify and build such representative chiral hydration clusters. Recent studies which applied molecular dynamics simulations and the subsequent snapshot averaging approach to generate the ROA, VCD, electronic CD, and optical rotatory dispersion spectra are also reviewed. Challenges associated with the molecular dynamics snapshot approach are discussed and the successes of the seemingly random “ad hoc explicit solvation” reported before are also explained. To further test and improve the “clusters-in-a-liquid” model in practice, future work in terms of conformer specific gas phase spectroscopy of sequential solvation of a chiral solute, matrix isolation VCD measurements of small chiral hydration clusters, and more sophisticated models for the bulk solvent effects would be highly valuable. PMID:26942177

Characterization of pH-fractionated humic acids with respect to their dissociation behaviour.

PubMed

Klučáková, Martina

2016-04-01

Humic acids were divided into several fractions using buffer solutions as extraction agents with different pH values. Two methods of fractionation were used. The first one was subsequent dissolution of bulk humic acids in buffers adjusted to different pH. The second one was sequential dissolution in buffers with increasing pH values. Experimental data were compared with hypothesis of partial solubility of humic acids in aqueous solutions. Behaviour of humic fractions obtained by sequential dissolution, original bulk sample and residual fractions obtained by subsequent dissolution at pH 10 and 12 agrees with the hypothesis. Results demonstrated that regardless the common mechanism, solubility and dissociation degree of various humic fractions may be very different and can be estimated using parameters of the model based on the proposed mechanism. Presented results suggest that dissolving of solid humic acids in water environment is more complex than conventional solubility behaviour of sparingly soluble solids.

Effect of guar gum and salt concentrations on drag reduction and shear degradation properties of turbulent flow of water in a pipe.

PubMed

Sokhal, Kamaljit Singh; Gangacharyulu, Dasaroju; Bulasara, Vijaya Kumar

2018-02-01

Concentrated solutions of guar gum in water (1000-3000ppm) with and without KCl salt (1000-4000ppm) were injected near the wall for a short period (2.5min) to investigate their effect on drag reduction in turbulent flow of water through a pipe (Re≈17000-45000). Relative to bulk solution, the concentrations of polymer and salt were 50-150ppm and 50-200ppm, respectively. A drag reduction of 71.45% was observed for 3000ppm of biopolymer without salt. Guar gum experienced mechanical degradation under high shear conditions and addition of KCl improved shear stability up to 47% (for Re≈45000). A polymer concentration of 3000ppm and salt concentration of 2000ppm in the injection fluid were found to be optimum for achieving the highest drag reduction with better shear stability. Results indicated that boundary layer injection shows better drag reduction ability than pre-mixed solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

CH4 Hydrate Formation between Silica and Graphite Surfaces: Insights from Microsecond Molecular Dynamics Simulations.

PubMed

He, Zhongjin; Linga, Praveen; Jiang, Jianwen

2017-10-31

Microsecond simulations have been performed to investigate CH 4 hydrate formation from gas/water two-phase systems between silica and graphite surfaces, respectively. The hydrophilic silica and hydrophobic graphite surfaces exhibit substantially different effects on CH 4 hydrate formation. The graphite surface adsorbs CH 4 molecules to form a nanobubble with a flat or negative curvature, resulting in a low aqueous CH 4 concentration, and hydrate nucleation does not occur during 2.5 μs simulation. Moreover, an ordered interfacial water bilayer forms between the nanobubble and graphite surface thus preventing their direct contact. In contrast, the hydroxylated-silica surface prefers to be hydrated by water, with a cylindrical nanobubble formed in the solution, leading to a high aqueous CH 4 concentration and hydrate nucleation in the bulk region; during hydrate growth, the nanobubble is gradually covered by hydrate solid and separated from the water phase, hence slowing growth. The silanol groups on the silica surface can form strong hydrogen bonds with water, and hydrate cages need to match the arrangements of silanols to form more hydrogen bonds. At the end of the simulation, the hydrate solid is separated from the silica surface by liquid water, with only several cages forming hydrogen bonds with the silica surface, mainly due to the low CH 4 aqueous concentrations near the surface. To further explore hydrate formation between graphite surfaces, CH 4 /water homogeneous solution systems are also simulated. CH 4 molecules in the solution are adsorbed onto graphite and hydrate nucleation occurs in the bulk region. During hydrate growth, the adsorbed CH 4 molecules are gradually converted into hydrate solid. It is found that the hydrate-like ordering of interfacial water induced by graphite promotes the contact between hydrate solid and graphite. We reveal that the ability of silanol groups on silica to form strong hydrogen bonds to stabilize incipient hydrate solid, as well as the ability of graphite to adsorb CH 4 molecules and induce hydrate-like ordering of the interfacial water, are the key factors to affect CH 4 hydrate formation between silica and graphite surfaces.

Spatial Decomposition of Translational Water–Water Correlation Entropy in Binding Pockets

PubMed Central

2015-01-01

A number of computational tools available today compute the thermodynamic properties of water at surfaces and in binding pockets by using inhomogeneous solvation theory (IST) to analyze explicit-solvent simulations. Such methods enable qualitative spatial mappings of both energy and entropy around a solute of interest and can also be applied quantitatively. However, the entropy estimates of existing methods have, to date, been almost entirely limited to the first-order terms in the IST’s entropy expansion. These first-order terms account for localization and orientation of water molecules in the field of the solute but not for the modification of water–water correlations by the solute. Here, we present an extension of the Grid Inhomogeneous Solvation Theory (GIST) approach which accounts for water–water translational correlations. The method involves rewriting the two-point density of water in terms of a conditional density and utilizes the efficient nearest-neighbor entropy estimation approach. Spatial maps of this second order term, for water in and around the synthetic host cucurbit[7]uril and in the binding pocket of the enzyme Factor Xa, reveal mainly negative contributions, indicating solute-induced water–water correlations relative to bulk water; particularly strong signals are obtained for sites at the entrances of cavities or pockets. This second-order term thus enters with the same, negative, sign as the first order translational and orientational terms. Numerical and convergence properties of the methodology are examined. PMID:26636620

[H2O ortho-para spin conversion in aqueous solutions as a quantum factor of Konovalov paradox].

PubMed

Pershin, S M

2014-01-01

Recently academician Konovalov and co-workers observed an increase in electroconductivity and biological activity simultaneously with diffusion slowing (or nanoobject diameter increasing) and extremes of other parameters (ζ-potential, surface tension, pH, optical activity) in low concentration aqueous solutions. This phenomenon completely disappeared when samples were shielded against external electromagnetic fields by a Faraday cage. A conventional theory of water and water solutions couldn't explain "Konovalov paradox" observed in numerous experiments (representative sampling about 60 samples and 7 parameters). The new approach was suggested to describe the physics of water and explain "Konovalov paradox". The proposed concept takes into account the quantum differences of ortho-para spin isomers of H2O in bulk water (rotational spin-selectivity upon hydration and spontaneous formation of ice-like structures, quantum beats and spin conversion induced in the presence of a resonant electromagnetic radiation). A size-dependent self-assembly of amorphous complexes of H2O molecules more than 275 leading to the ice Ih structure observed in the previous experiments supports this concept.

Enzyme kinetics in acoustically levitated droplets of supercooled water: a novel approach to cryoenzymology.

PubMed

Weis, David D; Nardozzi, Jonathan D

2005-04-15

The rate of the alkaline phosphatase-catalyzed hydrolysis of 4-methylumbelliferone phosphate was measured in acoustically levitated droplets of aqueous tris (50 mM) at pH 8.5 at 22 +/- 2 degrees C and in supercooled solution at -6 +/- 2 degrees C. At 22 degrees C, the rate of product formation was in excellent agreement with the rate observed in bulk solution in a cuvette, indicating that the acoustic levitation process does not alter the enzyme activity. The rate of the reaction decreased 6-fold in supercooled solution at -6 +/- 2 degrees C. The acoustic levitator apparatus is described in detail.

Description of Hydration Water in Protein (Green Fluorescent Protein) Solution

DOE PAGES

Perticaroli, Stefania; Ehlers, Georg; Stanley, Christopher B.; ...

2016-10-26

The structurally and dynamically perturbed hydration shells that surround proteins and biomolecules have a substantial influence upon their function and stability. This makes the extent and degree of water perturbation of practical interest for general biological study and industrial formulation. Here, we present an experimental description of the dynamical perturbation of hydration water around green fluorescent protein in solution. Less than two shells (~5.5 Å) were perturbed, with dynamics a factor of 2–10 times slower than bulk water, depending on their distance from the protein surface and the probe length of the measurement. Furthermore, this dependence on probe length demonstratesmore » that hydration water undergoes subdiffusive motions (τ ∝ q –2.5 for the first hydration shell, τ ∝ q –2.3 for perturbed water in the second shell), an important difference with neat water, which demonstrates diffusive behavior (τ ∝ q –2). Our results help clarify the seemingly conflicting range of values reported for hydration water retardation as a logical consequence of the different length scales probed by the analytical techniques used.« less

Comment on `Electrical conductance of a sandstone partially saturated with varying concentrations of NaCl solutions' by R. Umezawa, N. Nishiyama, M. Katsura and S. Nakashima

NASA Astrophysics Data System (ADS)

Revil, André; Soueid Ahmed, Abdellahi

2017-11-01

Umezawa et al. investigated the dependence of the electrical conductivity of rocks with respect to the saturation of the water phase. Four issues can be underlined in their work: (1) The conductivity model they used mixes bulk and surface tortuosities in the same linear equation (i.e., between the conductivity and the conductivity of the pore water). This conflicts with the fact that the conductivity is a concave down increasing function of the pore water conductivity and bulk tortuosity is defined only at high salinity while surface tortuosity is defined only at very low salinity. (2) The specific surface conductance obtained by Umezawa et al. is too low and conflicts with independent evaluations obtained with double layer models for aluminosilicates and silicates. (3) The expression given for the resistivity index conflicts with the inclusion of a surface conductivity term in the conductivity equation.

Dynamics of water in LiCl and CaCl 2 aqueous solutions confined in silica matrices: A backscattering neutron spectroscopy study

NASA Astrophysics Data System (ADS)

Mamontov, E.; Cole, D. R.; Dai, S.; Pawel, M. D.; Liang, C. D.; Jenkins, T.; Gasparovic, G.; Kintzel, E.

2008-09-01

Backscattering neutron spectroscopy was used to probe the dynamics of water molecules in LiCl and CaCl 2 aqueous solutions confined in 2.7, 1.9, and 1.4 nm diameter pores of various silica matrices. The pore size of 2.7 nm was found to be sufficiently large for the confined liquids to exhibit characteristic traits of bulk behavior, such as a freezing-melting transition and a phase separation. On the other hand, none of the fluids in the 1.4 nm pores exhibited a clear freezing-melting transition; instead, their dynamics at low temperatures gradually became too slow for the nanosecond resolution of the experiment. The greatest suppression of water mobility was observed in the CaCl 2 solutions, which suggests that cation charge and perhaps the cation hydration environment have a profound influence on the dynamics of the water molecules. Quasielastic neutron scattering measurements of pure H 2O and 1 m LiCl-H 2O solution confined in 1.9 nm pores revealed a dynamic transition in both liquids at practically the same temperature of 225-226 K, even though the dynamics of the solution at room temperature appeared to slow down by more than an order of magnitude compared to the pure water. The observation of the dynamic transition in the solution suggests that this transition may be a universal feature of water governed by processes acting on the local scale, such as a change in the hydrogen bonding.

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

DOE PAGES

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.; ...

2013-12-30

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

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

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

The principle of minimal episteric distortion of the water matrix and its steering role in protein folding

NASA Astrophysics Data System (ADS)

Fernández, Ariel

2013-08-01

A significant episteric ("around a solid") distortion of the hydrogen-bond structure of water is promoted by solutes with nanoscale surface detail and physico-chemical complexity, such as soluble natural proteins. These structural distortions defy analysis because the discrete nature of the solvent at the interface is not upheld by the continuous laws of electrostatics. This work derives and validates an electrostatic equation that governs the episteric distortions of the hydrogen-bond matrix. The equation correlates distortions from bulk-like structural patterns with anomalous polarization components that do not align with the electrostatic field of the solute. The result implies that the interfacial energy stored in the orthogonal polarization correlates with the distortion of the water hydrogen-bond network. The result is validated vis-à-vis experimental data on protein interfacial thermodynamics and is interpreted in terms of the interaction energy between the electrostatic field of the solute and the dipole moment induced by the anomalous polarization of interfacial water. Finally, we consider solutes capable of changing their interface through conformational transitions and introduce a principle of minimal episteric distortion (MED) of the water matrix. We assess the importance of the MED principle in the context of protein folding, concluding that the native fold may be identified topologically with the conformation that minimizes the interfacial tension or disruption of the water matrix.

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.

Hydration of amino acids: FTIR spectra and molecular dynamics studies.

PubMed

Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

2015-11-01

The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

Comparison of vapor formation of water at the solid/water interface to colloidal solutions using optically excited gold nanostructures.

PubMed

Baral, Susil; Green, Andrew J; Livshits, Maksim Y; Govorov, Alexander O; Richardson, Hugh H

2014-02-25

The phase transformation properties of liquid water to vapor is characterized by optical excitation of the lithographically fabricated single gold nanowrenches and contrasted to the phase transformation properties of gold nanoparticles located and optically excited in a bulk solution system [two and three dimensions]. The 532 nm continuous wave excitation of a single gold nanowrench results in superheating of the water to the spinodal decomposition temperature of 580 ± 20 K with bubble formation below the spinodal decomposition temperature being a rare event. Between the spinodal decomposition temperature and the boiling point liquid water is trapped into a metastable state because a barrier to vapor nucleation exists that must be overcome before the thermodynamically stable state is realized. The phase transformation for an optically heated single gold nanowrench is different from the phase transformation of optically excited colloidal gold nanoparticles solution where collective heating effects dominates and leads to the boiling of the solution exactly at the boiling point. In the solution case, the optically excited ensemble of nanoparticles collectively raises the ambient temperature of water to the boiling point where liquid is converted into vapor. The striking difference in the boiling properties of the single gold nanowrench and the nanoparticle solution system can be explained in terms of the vapor-nucleation mechanism, the volume of the overheated liquid, and the collective heating effect. The interpretation of the observed regimes of heating and vaporization is consistent with our theoretical modeling. In particular, we explain with our theory why the boiling with the collective heating in a solution requires 3 orders of magnitude less intensity compared to the case of optically driven single nanowrench.

Modulating surface rheology by electrostatic protein/polysaccharide interactions.

PubMed

Ganzevles, Renate A; Zinoviadou, Kyriaki; van Vliet, Ton; Cohen, Martien A; de Jongh, Harmen H

2006-11-21

There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.

Elution of monomer from different bulk fill dental composite resins.

PubMed

Cebe, Mehmet Ata; Cebe, Fatma; Cengiz, Mehmet Fatih; Cetin, Ali Rıza; Arpag, Osman Fatih; Ozturk, Bora

2015-07-01

The purpose of this study was to evaluate the elution of Bis-GMA, TEGDMA, HEMA, and Bis-EMA monomers from six bulk fill composite resins over four different time periods, using HPLC. Six different composite resin materials were used in the present study: Tetric Evo Ceram Bulk Fill (Ivoclar Vivadent, Amherst, NY), X-tra Fill (VOCO, Cuxhaven, Germany), Sonic Fill (Kerr, Orange, CA, USA), Filtek Bulk Fill (3M ESPE Dental Product, St. Paul, MN), SDR (Dentsply, Konstanz, Germany), EQUIA (GC America INC, Alsip, IL). The samples (4mm thickness, 5mm diameter) were prepared and polymerized for 20s with a light emitted diode unit. After fabrication, each sample was immediately immersed in 75wt% ethanol/water solution used as extraction fluid and stored in the amber colored bottles at room temperature. Ethanol/water samples were taken (0.5mL) at predefined time intervals:10m (T1), 1h (T2), 24h (T3) and 30 days (T4). These samples were analyzed by HPLC. The obtained data were analyzed with one-way ANOVA and Tukey HSD at significance level of p<0.05. Amount of eluted Bis-EMA and Bis-GMA from Tetric Evo Ceram Bulk Fill and amount of eluted TEGDMA and HEMA from X-tra Fill higher than others composites (p<0.05). Residual monomers were eluted from bulk fill composite resins in all time periods and the amount of eluted monomers was increased with time. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Water-soluble cavitands promote hydrolyses of long-chain diesters

PubMed Central

Shi, Qixun; Mower, Matthew P.; Blackmond, Donna G.; Rebek, Julius

2016-01-01

Water-soluble, deep cavitands serve as chaperones of long-chain diesters for their selective hydrolysis in aqueous solution. The cavitands bind the diesters in rapidly exchanging, folded J-shape conformations that bury the hydrocarbon chain and expose each ester group in turn to the aqueous medium. The acid hydrolyses in the presence of the cavitand result in enhanced yields of monoacid monoester products. Product distributions indicate a two- to fourfold relative decrease in the hydrolysis rate constant of the second ester caused by the confined space in the cavitand. The rate constant for the first acid hydrolysis step is enhanced approximately 10-fold in the presence of the cavitand, compared with control reactions of the molecules in bulk solution. Hydrolysis under basic conditions (saponification) with the cavitand gave >90% yields of the corresponding monoesters. Under basic conditions the cavitand complex of the monoanion precipitates from solution and prevents further reaction. PMID:27482089

Boron nitride colloidal solutions, ultralight aerogels and freestanding membranes through one-step exfoliation and functionalization

PubMed Central

Lei, Weiwei; Mochalin, Vadym N.; Liu, Dan; Qin, Si; Gogotsi, Yury; Chen, Ying

2015-01-01

Manufacturing of aerogels and membranes from hexagonal boron nitride (h-BN) is much more difficult than from graphene or graphene oxides because of the poor dispersibility of h-BN in water, which limits its exfoliation and preparation of colloidal solutions. Here, a simple, one-step mechano-chemical process to exfoliate and functionalize h-BN into highly water-dispersible, few-layer h-BN containing amino groups is presented. The colloidal solutions of few-layer h-BN can have unprecedentedly high concentrations, up to 30 mg ml−1, and are stable for up to several months. They can be used to produce ultralight aerogels with a density of 1.4 mg cm−3, which is ∼1,500 times less than bulk h-BN, and freestanding membranes simply by cryodrying and filtration, respectively. The material shows strong blue light emission under ultraviolet excitation, in both dispersed and dry state. PMID:26611437

Dielectric spectroscopy in aqueous solutions of oligosaccharides: Experiment meets simulation

NASA Astrophysics Data System (ADS)

Weingärtner, Hermann; Knocks, Andrea; Boresch, Stefan; Höchtl, Peter; Steinhauser, Othmar

2001-07-01

We report the frequency-dependent complex dielectric permittivity of aqueous solutions of the homologous saccharides D(+)-glucose, maltose, and maltotriose in the frequency range 200 MHz⩽ν⩽20 GHz. For each solute, solutions having concentrations between 0.01 and 1 mol dm-3 were studied. In all measured spectra two dispersion/loss regions could be discerned. With the exception of the two most concentrated maltotriose solutions, a good description of the spectra by the superposition of two Debye processes was possible. The amplitudes and correlation times of the glucose and maltose solutions determined from fits of the experimental data were compared to those obtained in an earlier molecular dynamics study of such systems; the overall agreement between experiment and simulation is quite satisfactory. A dielectric component analysis of the simulation results permitted a more detailed assignment of the relaxation processes occurring on the molecular level. The physical picture emerging from this analysis is compared with traditional hydration models used in the interpretation of measured dielectric data. It is shown that the usual standard models do not capture an important contribution arising from cross terms due to dipolar interactions between solute and water, as well as between hydration water and bulk water. This finding suggests that conventional approaches to determine molecular dipole moments of the solutes may be problematic. This is certainly the case for solutes with small molecular dipole moments, but strong solute-solvent interactions, such as the saccharides studied here.

Graphene oxide-based efficient and scalable solar desalination under one sun with a confined 2D water path

PubMed Central

Li, Xiuqiang; Xu, Weichao; Tang, Mingyao; Zhou, Lin; Zhu, Bin; Zhu, Shining; Zhu, Jia

2016-01-01

Because it is able to produce desalinated water directly using solar energy with minimum carbon footprint, solar steam generation and desalination is considered one of the most important technologies to address the increasingly pressing global water scarcity. Despite tremendous progress in the past few years, efficient solar steam generation and desalination can only be achieved for rather limited water quantity with the assistance of concentrators and thermal insulation, not feasible for large-scale applications. The fundamental paradox is that the conventional design of direct absorber−bulk water contact ensures efficient energy transfer and water supply but also has intrinsic thermal loss through bulk water. Here, enabled by a confined 2D water path, we report an efficient (80% under one-sun illumination) and effective (four orders salinity decrement) solar desalination device. More strikingly, because of minimized heat loss, high efficiency of solar desalination is independent of the water quantity and can be maintained without thermal insulation of the container. A foldable graphene oxide film, fabricated by a scalable process, serves as efficient solar absorbers (>94%), vapor channels, and thermal insulators. With unique structure designs fabricated by scalable processes and high and stable efficiency achieved under normal solar illumination independent of water quantity without any supporting systems, our device represents a concrete step for solar desalination to emerge as a complementary portable and personalized clean water solution. PMID:27872280

Graphene oxide-based efficient and scalable solar desalination under one sun with a confined 2D water path.

PubMed

Li, Xiuqiang; Xu, Weichao; Tang, Mingyao; Zhou, Lin; Zhu, Bin; Zhu, Shining; Zhu, Jia

2016-12-06

Because it is able to produce desalinated water directly using solar energy with minimum carbon footprint, solar steam generation and desalination is considered one of the most important technologies to address the increasingly pressing global water scarcity. Despite tremendous progress in the past few years, efficient solar steam generation and desalination can only be achieved for rather limited water quantity with the assistance of concentrators and thermal insulation, not feasible for large-scale applications. The fundamental paradox is that the conventional design of direct absorber-bulk water contact ensures efficient energy transfer and water supply but also has intrinsic thermal loss through bulk water. Here, enabled by a confined 2D water path, we report an efficient (80% under one-sun illumination) and effective (four orders salinity decrement) solar desalination device. More strikingly, because of minimized heat loss, high efficiency of solar desalination is independent of the water quantity and can be maintained without thermal insulation of the container. A foldable graphene oxide film, fabricated by a scalable process, serves as efficient solar absorbers (>94%), vapor channels, and thermal insulators. With unique structure designs fabricated by scalable processes and high and stable efficiency achieved under normal solar illumination independent of water quantity without any supporting systems, our device represents a concrete step for solar desalination to emerge as a complementary portable and personalized clean water solution.

Adsorption of mixtures of poly(amidoamine) dendrimers and sodium dodecyl sulfate at the air-water interface.

PubMed

Arteta, Marianna Yanez; Campbell, Richard A; Nylander, Tommy

2014-05-27

We relate the adsorption from mixtures of well-defined poly(amidoamine) (PAMAM) dendrimers of generations 4 and 8 with sodium dodecyl sulfate (SDS) at the air-water interface to the bulk solution properties. The anionic surfactant shows strong attractive interactions with the cationic dendrimers at pH 7, and electrophoretic mobility measurements indicate that the association is primarily driven by electrostatic interactions. Optical density measurements highlight the lack of colloidal stability of the formed bulk aggregates at compositions close to charge neutrality, the time scale of which is dependent on the dendrimer generation. Adsorption at the air-water interface was followed from samples immediately after mixing using a combination of surface tension, neutron reflectometry, and ellipsometry measurements. In the phase separation region for dendrimers of generation 4, we observed high surface tension corresponding to a depleted surfactant solution but only when the aggregates carried an excess of surfactant. Interestingly, these depleted adsorption layers contained spontaneously adsorbed macroscopic aggregates, and these embedded particles do not rearrange to spread monomeric material at the interface. These findings are discussed in relation to the interfacial properties of mixtures involving dendrimers of generation 8 as well as polydisperse linear and hyperbranched polyelectrolytes where there is polyelectrolyte bound to a surfactant monolayer. The results presented here demonstrate the capability of dendrimers to sequester anionic surfactants in a controllable manner, with potential applications as demulsification and antifoaming agents.

Regulation of amniotic fluid volume: mathematical model based on intramembranous transport mechanisms.

PubMed

Brace, Robert A; Anderson, Debra F; Cheung, Cecilia Y

2014-11-15

Experimentation in late-gestation fetal sheep has suggested that regulation of amniotic fluid (AF) volume occurs primarily by modulating the rate of intramembranous transport of water and solutes across the amnion into underlying fetal blood vessels. In order to gain insight into intramembranous transport mechanisms, we developed a computer model that allows simulation of experimentally measured changes in AF volume and composition over time. The model included fetal urine excretion and lung liquid secretion as inflows into the amniotic compartment plus fetal swallowing and intramembranous absorption as outflows. By using experimental flows and solute concentrations for urine, lung liquid, and swallowed fluid in combination with the passive and active transport mechanisms of the intramembranous pathway, we simulated AF responses to basal conditions, intra-amniotic fluid infusions, fetal intravascular infusions, urine replacement, and tracheoesophageal occlusion. The experimental data are consistent with four intramembranous transport mechanisms acting in concert: 1) an active unidirectional bulk transport of AF with all dissolved solutes out of AF into fetal blood presumably by vesicles; 2) passive bidirectional diffusion of solutes, such as sodium and chloride, between fetal blood and AF; 3) passive bidirectional water movement between AF and fetal blood; and 4) unidirectional transport of lactate into the AF. Further, only unidirectional bulk transport is dynamically regulated. The simulations also identified areas for future study: 1) identifying intramembranous stimulators and inhibitors, 2) determining the semipermeability characteristics of the intramembranous pathway, and 3) characterizing the vesicles that are the primary mediators of intramembranous transport. Copyright © 2014 the American Physiological Society.

Dynamic nuclear polarization enhanced nuclear magnetic resonance and electron spin resonance studies of hydration and local water dynamics in micelle and vesicle assemblies.

PubMed

McCarney, Evan R; Armstrong, Brandon D; Kausik, Ravinath; Han, Songi

2008-09-16

We present a unique analysis tool for the selective detection of local water inside soft molecular assemblies (hydrophobic cores, vesicular bilayers, and micellar structures) suspended in bulk water. Through the use of dynamic nuclear polarization (DNP), the (1)H NMR signal of water is amplified, as it interacts with stable radicals that possess approximately 658 times higher spin polarization. We utilized stable nitroxide radicals covalently attached along the hydrophobic tail of stearic acid molecules that incorporate themselves into surfactant-based micelle or vesicle structures. Here, we present a study of local water content and fluid viscosity inside oleate micelles and vesicles and Triton X-100 micelles to serve as model systems for soft molecular assemblies. This approach is unique because the amplification of the NMR signal is performed in bulk solution and under ambient conditions with site-specific spin labels that only detect the water that is directly interacting with the localized spin labels. Continuous wave (cw) electron spin resonance (ESR) analysis provides rotational dynamics of the spin-labeled molecular chain segments and local polarity parameters that can be related to hydration properties, whereas we show that DNP-enhanced (1)H NMR analysis of fluid samples directly provides translational water dynamics and permeability of the local environment probed by the spin label. Our technique therefore has the potential to become a powerful analysis tool, complementary to cw ESR, to study hydration characteristics of surfactant assemblies, lipid bilayers, or protein aggregates, where water dynamics is a key parameter of their structure and function. In this study, we find that there is significant penetration of water inside the oleate micelles with a higher average local water viscosity (approximately 1.8 cP) than in bulk water, and Triton X-100 micelles and oleate vesicle bilayers mostly exclude water while allowing for considerable surfactant chain motion and measurable water permeation through the soft structure.

Aqueous solvation from the water perspective.

PubMed

Ahmed, Saima; Pasti, Andrea; Fernández-Terán, Ricardo J; Ciardi, Gustavo; Shalit, Andrey; Hamm, Peter

2018-06-21

The response of water re-solvating a charge-transfer dye (deprotonated Coumarin 343) after photoexcitation has been measured by means of transient THz spectroscopy. Two steps of increasing THz absorption are observed, a first ∼10 ps step on the time scale of Debye relaxation of bulk water and a much slower step on a 3.9 ns time scale, the latter of which reflecting heating of the bulk solution upon electronic relaxation of the dye molecules from the S 1 back into the S 0 state. As an additional reference experiment, the hydroxyl vibration of water has been excited directly by a short IR pulse, establishing that the THz signal measures an elevated temperature within ∼1 ps. This result shows that the first step upon dye excitation (10 ps) is not limited by the response time of the THz signal; it rather reflects the reorientation of water molecules in the solvation layer. The apparent discrepancy between the relatively slow reorientation time and the general notion that water is among the fastest solvents with a solvation time in the sub-picosecond regime is discussed. Furthermore, non-equilibrium molecular dynamics simulations have been performed, revealing a close-to-quantitative agreement with experiment, which allows one to disentangle the contribution of heating to the overall THz response from that of water orientation.

How water manifests the structural regimes in ionic liquids.

PubMed

Singh, Akhil Pratap; Gardas, Ramesh L; Senapati, Sanjib

2017-03-22

Ionic liquids (ILs) are being considered as greener alternatives to the conventional organic solvents. However, highly viscous nature of ILs often limits their applications. Hence studies on IL/water binary mixtures have received tremendous attention. These mixtures exhibit much lower viscosity, but almost similar density, compressibility and other properties as that of the neat ILs, up to certain water content. Hence, determining the IL-water ratio till which the solution behaves like IL and subsequently changes to a state of solute IL dissolved in continuous water phase is of paramount importance. Noting the very different and characteristic behaviours of neat ILs and pure water over a temperature range, herein, we measured the various thermophysical properties of the binary mixtures of tetramethylguanidinium benzoate/water and tetramethylguanidinium salicylate/water with water content varying from 20 wt% to 95 wt% for a temperature range of 298 K to 343 K. The results show that similar to neat ILs, the measured densities and compressibility of these mixtures display a linear change, and viscosity decreases rapidly as temperature is increased for water content up to 50 wt%. At higher water concentrations, the measured density and compressibility exhibit nonlinear behaviour and the decrease in viscosity with increased temperature is minute, mimicking the behaviour of bulk water. MD simulations were carried out to explain the experimental observations. Simulation results show a greater temperature-induced disintegration of IL ion-water interactions in dense systems, explaining the rapid decay of the properties with temperature. The results also exhibit the presence of a neat, IL-like, H-bond mediated expanded structure in concentrated solution versus a collapsed IL structure in dilute solution.

Oscillatory phase separation in giant lipid vesicles induced by transmembrane osmotic differentials

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

Oglęcka, Kamila; Rangamani, Padmini; Liedberg, Bo

Giant lipid vesicles are closed compartments consisting of semi-permeable shells, which isolate femto- to pico-liter quantities of aqueous core from the bulk. Although water permeates readily across vesicular walls, passive permeation of solutes is hindered. In this study, we show that, when subject to a hypotonic bath, giant vesicles consisting of phase separating lipid mixtures undergo osmotic relaxation exhibiting damped oscillations in phase behavior, which is synchronized with swell–burst lytic cycles: in the swelled state, osmotic pressure and elevated membrane tension due to the influx of water promote domain formation. During bursting, solute leakage through transient pores relaxes the pressuremore » and tension, replacing the domain texture by a uniform one. This isothermal phase transition—resulting from a well-coordinated sequence of mechanochemical events—suggests a complex emergent behavior allowing synthetic vesicles produced from simple components, namely, water, osmolytes, and lipids to sense and regulate their micro-environment.« less

Anomalous cation diffusion in salt-doped confined bilayer ice.

PubMed

Qiu, Hu; Xue, Minmin; Shen, Chun; Guo, Wanlin

2018-05-17

The diffusive dynamics of aqueous electrolyte solutions in nanoconfined spaces has attracted considerable attention due to their potential applications in desalination, biosensors and supercapacitors. Here we show by molecular dynamics simulations that lithium and sodium ions diffuse at a rate at least an order of magnitude higher than that of water molecules when the ions are trapped in an ice bilayer confined between two parallel plates. This novel picture is in sharp contrast to the prevailing view that the diffusion rate of ions is comparable to or even lower than that of water in both bulk and confined solutions. The predicted high ion mobility stems from frequent lateral hopping of ions along the coordination sites inside the hydrogen-bonding network connecting the two water layers of the ice bilayer. This anomalous diffusion should provide new insights into the physics of confined aqueous electrolytes.

Oscillatory phase separation in giant lipid vesicles induced by transmembrane osmotic differentials

DOE PAGES

Oglęcka, Kamila; Rangamani, Padmini; Liedberg, Bo; ...

2014-10-15

Giant lipid vesicles are closed compartments consisting of semi-permeable shells, which isolate femto- to pico-liter quantities of aqueous core from the bulk. Although water permeates readily across vesicular walls, passive permeation of solutes is hindered. In this study, we show that, when subject to a hypotonic bath, giant vesicles consisting of phase separating lipid mixtures undergo osmotic relaxation exhibiting damped oscillations in phase behavior, which is synchronized with swell–burst lytic cycles: in the swelled state, osmotic pressure and elevated membrane tension due to the influx of water promote domain formation. During bursting, solute leakage through transient pores relaxes the pressuremore » and tension, replacing the domain texture by a uniform one. This isothermal phase transition—resulting from a well-coordinated sequence of mechanochemical events—suggests a complex emergent behavior allowing synthetic vesicles produced from simple components, namely, water, osmolytes, and lipids to sense and regulate their micro-environment.« less

A New Approach to Look at the Electrical Conductivity of Streamflow: Decomposing a Bulk Signal to Recover Individual Solute Concentrations at High-Frequency

NASA Astrophysics Data System (ADS)

Benettin, P.; Van Breukelen, B. M.

2017-12-01

The ability to evaluate stream hydrochemistry is often constrained by the capacity to sample streamwater at an adequate frequency. While technology is no longer a limiting factor, economic and management efforts can still be a barrier to high-resolution water quality instrumentation. We propose a new framework to investigate the electrical conductivity (EC) of streamwater, which can be measured continuously through inexpensive sensors. We show that EC embeds information on ion content which can be isolated to retrieve solute concentrations at high resolution. The approach can already be applied to a number of datasets worldwide where water quality campaigns are conducted, provided continuous EC measurements can be collected. The essence of the approach is the decomposition of the EC signal into its "harmonics", i.e. the specific contributions of the major ions which conduct current in water. The ion contribution is used to explore water quality patterns and to develop algorithms that reconstruct solute concentrations during periods where solute measurements are not available. The approach is validated on a hydrochemical dataset from Plynlimon, Wales. Results show that the decomposition of EC is feasible and for at least two major elements the methodology provided improved estimates of high-frequency solute dynamics. Our results support the installation of EC probes to complement water quality campaigns and suggest that the potential of EC measurements in rivers is currently far from being fully exploited.

Optimal N:P ratios of growth media: quantification of nutrient-replete growth rates in five ion hyperspace for Chlorella vulgaris (Dinophyceae) and Peridinium cinctum (Dinophyceae).

USDA-ARS?s Scientific Manuscript database

In this study our principal goal was to quantify the main effects and interactions of several primary nutrient and bulk solution ions. The total ion concentration range chosen spans fresh to brackish waters (1-30 milliMolar) and explores most of the hypervolume delineated by the five ion/concentrat...

Liquid Between Macromolecules in Protein Crystals: Static Versus Dynamics

NASA Technical Reports Server (NTRS)

Chernov, A. A.

2005-01-01

Protein crystals are so fragile that they often can not be handled by tweezers. Indeed, measurements of the Young modulus, E, of lysozyme crystals resulted in E approx. equals 0.1 - 1 GPa, the lower figures, 0.1 - 0.5 GPa, being obtained from triple point bending of as-grown and not cross-linked crystals sitting in solution. The bending strength was found to be approx.10(exp -2) E. On the other hand, ultrasound speed and Mandelstam-Raman-Brilloin light scattering experiments led to much higher figures, E approx. equals 2.7 GPa. The lower figures for E were found from static or low frequency crystal deformations measurements, while the higher moduli are based on high frequency lattice vibrations, 10(exp 7) - 10(exp 10) 1/s. The physical reason for the about an order of magnitude discrepancy is in different behavior of water filling space between protein molecules. At slow lattice deformation, the not-bound intermolecular water has enough time to flow from the compressed to expanded regions of the deformed crystal. At high deformation frequencies in the ultra- and hypersound waves, the water is confined in the intermolecular space and, on that scale, behaves like a solid, thus contributing to the elastic crystal moduli. In this case, the reciprocal crystal modulus is expected to be an average of the water protein and water compressibilities (reciprocal compressibilities): the bulk modulus for lysozyme is 26 GPa, for water it is 7 GPa. Anisotropy of the crystal moduli comes from intermolecular contacts within the lattice while the high frequency hardness comes from the bulk of protein molecules and water bulk moduli. These conclusions are based on the analysis of liquid flow in porous medium to be presented.

Utilizing a Water-Soluble Cryptophane with Fast Xenon Exchange Rates for Picomolar Sensitivity NMR Measurements

PubMed Central

Bai, Yubin; Hill, P. Aru; Dmochowski, Ivan J.

2012-01-01

Hyperpolarized 129Xe chemical exchange saturation transfer (129Xe Hyper-CEST) NMR is a powerful technique for the ultrasensitive, indirect detection of Xe host molecules (e.g., cryptophane-A). Irradiation at the appropriate Xe-cryptophane resonant radio frequency results in relaxation of the bound hyperpolarized 129Xe and rapid accumulation of depolarized 129Xe in bulk solution. The cryptophane effectively ‘catalyzes’ this process by providing a unique molecular environment for spin depolarization to occur, while allowing xenon exchange with the bulk solution during the hyperpolarized lifetime (T1 ≈ 1 min). Following this scheme, a triacetic acid cryptophane-A derivative (TAAC) was indirectly detected at 1.4 picomolar concentration at 320 K in aqueous solution, which is the record for a single-unit xenon host. To investigate this sensitivity enhancement, the xenon binding kinetics of TAAC in water was studied by NMR exchange lifetime measurement. At 297 K, kon ≈ 1.5 × 106 M−1s−1 and koff = 45 s−1, which represent the fastest Xe association and dissociation rates measured for a high-affinity, water-soluble xenon host molecule near rt. NMR linewidth measurements provided similar exchange rates at rt, which we assign to solvent-Xe exchange in TAAC. At 320 K, koff was estimated to be 1.1 × 103 s−1. In Hyper-CEST NMR experiments, the rate of 129Xe depolarization achieved by 14 pM TAAC in the presence of RF pulses was calculated to be 0.17 µM·s−1. On a per cryptophane basis, this equates to 1.2 × 104 129Xe atoms s−1 (or 4.6 × 104 Xe atoms s−1, all Xe isotopes), which is more than an order of magnitude faster than koff, the directly measurable Xe-TAAC exchange rate. This compels us to consider multiple Xe exchange processes for cryptophane-mediated bulk 129Xe depolarization, which provide at least 107-fold sensitivity enhancements over directly detected hyperpolarized 129Xe NMR signals. PMID:23106513

Analysis of experimental heats of dilution of aqueous solutions of NaBPh 4 by use of the mean spherical approximation and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

M'halla, Jalel; M'halla, Sondes; Wipff, Georges

2003-03-01

Calorimetric measurements of heats of dilution: QDC→0 =- nsφL,sexp, of aqueous solutions of NaBPh 4 are determined at 25 °C in the concentration range: 0

Hydration properties of adenosine phosphate series as studied by microwave dielectric spectroscopy.

PubMed

Mogami, George; Wazawa, Tetsuichi; Morimoto, Nobuyuki; Kodama, Takao; Suzuki, Makoto

2011-02-01

Hydration properties of adenine nucleotides and orthophosphate (Pi) in aqueous solutions adjusted to pH=8 with NaOH were studied by high-resolution microwave dielectric relaxation (DR) spectroscopy at 20 °C. The dielectric spectra were analyzed using a mixture theory combined with a least-squares Debye decomposition method. Solutions of Pi and adenine nucleotides showed qualitatively similar dielectric properties described by two Debye components. One component was characterized by a relaxation frequency (f(c)=18.8-19.7 GHz) significantly higher than that of bulk water (17 GHz) and the other by a much lower f(c) (6.4-7.6 GHz), which are referred to here as hyper-mobile water and constrained water, respectively. By contrast, a hydration shell of only the latter type was found for adenosine (f(c)~6.7 GHz). The present results indicate that phosphoryl groups are mostly responsible for affecting the structure of the water surrounding the adenine nucleotides by forming one constrained water layer and an additional three or four layers of hyper-mobile water. Copyright © 2010 Elsevier B.V. All rights reserved.

Nontrivial behavior of water in the vicinity and inside lipid bilayers as probed by molecular dynamics simulations.

PubMed

Krylov, Nikolay A; Pentkovsky, Vladimir M; Efremov, Roman G

2013-10-22

The atomic-scale diffusion of water in the presence of several lipid bilayers mimicking biomembranes is characterized via unconstrained molecular dynamics (MD) simulations. Although the overall water dynamics corresponds well to literature data, namely, the efficient braking near polar head groups of lipids, a number of interesting and biologically relevant details observed in this work have not been sufficiently discussed so far; for instance, the fact that waters "sense" the membrane unexpectedly early, before water density begins to decrease. In this "transitional zone" the velocity distributions of water and their H-bonding patterns deviate from those in the bulk solution. The boundaries of this zone are well preserved even despite the local (<1 nm size) perturbation of the lipid bilayer, thus indicating a decoupling of the surface and bulk dynamics of water. This is in excellent agreement with recent experimental data. Near the membrane surface, water movement becomes anisotropic, that is, solvent molecules preferentially move outward the bilayer. Deep in the membrane interior, the velocities can even exceed those in the bulk solvent and undergo large-scale fluctuations. The analysis of MD trajectories of individual waters in the middle part of the acyl chain region of lipids reveals a number of interesting rare phenomena, such as the fast (ca. 50 ps) breakthrough across the membrane or long-time (up to 750 ps) "roaming" between lipid leaflets. The analysis of these events was accomplished to delineate the mechanisms of spontaneous water permeation inside the hydrophobic membrane core. It was shown that such nontrivial dynamics of water in an "alien" environment is driven by the dynamic heterogeneities of the local bilayer structure and the formation of transient atomic-scale "defects" in it. The picture observed in lipid bilayers is drastically different from that in a primitive membrane mimic, a hydrated cyclohexane slab. The possible biological impact of such phenomena in equilibrated lipid bilayers is discussed.

Post-irradiation hardness development, chemical softening, and thermal stability of bulk-fill and conventional resin-composites.

PubMed

Alshali, Ruwaida Z; Salim, Nesreen A; Satterthwaite, Julian D; Silikas, Nick

2015-02-01

To measure bottom/top hardness ratio of bulk-fill and conventional resin-composite materials, and to assess hardness changes after dry and ethanol storage. Filler content and kinetics of thermal decomposition were also tested using thermogravimetric analysis (TGA). Six bulk-fill (SureFil SDR, Venus bulk fill, X-tra base, Filtek bulk fill flowable, Sonic fill, and Tetric EvoCeram bulk-fill) and eight conventional resin-composite materials (Grandioso flow, Venus Diamond flow, X-flow, Filtek Supreme Ultra Flowable, Grandioso, Venus Diamond, TPH Spectrum, and Filtek Z250) were tested (n=5). Initial and 24h (post-cure dry storage) top and bottom microhardness values were measured. Microhardness was re-measured after the samples were stored in 75% ethanol/water solution. Thermal decomposition and filler content were assessed by TGA. Results were analysed using one-way ANOVA and paired sample t-test (α=0.05). All materials showed significant increase of microhardness after 24h of dry storage which ranged from 100.1% to 9.1%. Bottom/top microhardness ratio >0.9 was exhibited by all materials. All materials showed significant decrease of microhardness after 24h of storage in 75% ethanol/water which ranged from 14.5% to 74.2%. The extent of post-irradiation hardness development was positively correlated to the extent of ethanol softening (R(2)=0.89, p<0.001). Initial thermal decomposition temperature assessed by TGA was variable and was correlated to ethanol softening. Bulk-fill resin-composites exhibit comparable bottom/top hardness ratio to conventional materials at recommended manufacturer thickness. Hardness was affected to a variable extent by storage with variable inorganic filler content and initial thermal decomposition shown by TGA. The manufacturer recommended depth of cure of bulk-fill resin-composites can be reached based on the microhardness method. Characterization of the primary polymer network of a resin-composite material should be considered when evaluating its stability in the aqueous oral environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Trench formation in <110> silicon for millimeter-wave switching device

NASA Astrophysics Data System (ADS)

Datta, P.; Kumar, Praveen; Nag, Manoj; Bhattacharya, D. K.; Khosla, Y. P.; Dahiya, K. K.; Singh, D. V.; Venkateswaran, R.; Kumar, Devender; Kesavan, R.

1999-11-01

Anisotropic etching using alkaline solution has been adopted to form trenches in silicon while fabricating surface oriented bulk window SPST switches. An array pattern has been etched on silicon with good control on depth of trenches. KOH-water solution is seen to yield a poor surface finish. Use of too much of additive like isopropyl alcohol improves the surface condition but distorts the array pattern due to loss of anisotropy. However, controlled use of this additive during the last phase of trench etching is found to produce trenched arrays with desired depth, improved surface finish and minimum distortion of lateral dimensions.

Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy

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

Mandal, Aritra; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139; Tokmakoff, Andrei, E-mail: tokmakoff@uchicago.edu

2015-11-21

We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm{sup −1}. We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occursmore » in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions.« less

Acid-base equilibria inside amine-functionalized mesoporous silica.

PubMed

Yamaguchi, Akira; Namekawa, Manato; Kamijo, Toshio; Itoh, Tetsuji; Teramae, Norio

2011-04-15

Acid-base equilibria and effective proton concentration inside a silica mesopore modified with a trimethyl ammonium (TMAP) layer were studied by steady-state fluorescence experiments. The mesoporous silica with a dense TMAP layer (1.4 molecules/nm(2)) was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at surfactant-templated mesoporous silica (diameter of silica framework =3.1 nm). The resulting TMAP-modified mesoporous silica strongly adsorbed of anionic fluorescence indicator dyes (8-hydroxypyrene-1,3,6-trisulfonate (pyranine), 8-aminopyrene-1,3,6-trisulfonate (APTS), 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid disulfuric acid (TPPS), 2-naphthol-3,6-disulfonate (2NT)) and fluorescence excitation spectra of these dyes within TMAP-modified mesoporous silica were measured by varying the solution pH. The fluorescence experiments revealed that the acid-base equilibrium reactions of all pH indicator dyes within the TMAP-modified silica mesopore were quite different from those in bulk water. From the analysis of the acid-base equilibrium of pyranine, the following relationships between solution pH (pH(bulk)) and the effective proton concentration inside the pore (pH(pore)) were obtained: (1) shift of pH(pore) was 1.8 (ΔpH(pore)=1.8) for the pH(bulk) change from 2.1 to 9.1 (ΔpH(bulk)=7.0); (2) pH(pore) was not simply proportional to pH(bulk); (3) the inside of the TMAP-modified silica mesopore was suggested to be in a weak acidic or neutral condition when pH(bulk) was changed from 2.0 to 9.1. Since these relationships between pH(bulk) and pH(pore) could explain the acid-base equilibria of other pH indicator dyes (APTS, TPPS, 2NT), these relationships were inferred to describe the effective proton concentration inside the TMAP-modified silica mesopore. © 2011 American Chemical Society

Ion Association in AlCl3 Aqueous Solutions from Constrained First-Principles Molecular Dynamics

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

Cauet, Emilie L.; Bogatko, Stuart A.; Bylaska, Eric J.

2012-10-15

Ab initio molecular dynamics was used to investigate the ion pairing behavior between Cl- and the Al3+ ion in an aqueous AlCl3 solution containing 63 water molecules. A series of constrained simulations was carried out at 300 K for up to 16 ps each, by fixing the inter-nuclear separation (rAl-Cl) between the Al3+ ion and one of the Cl- ions. The calculated potential of mean force of the Al3+-Cl- ion pair shows a pronounced minimum at rAl-Cl = 2.3 Å corresponding to a contact ion pair (CIP). Two local minima assigned to solvent separated ion pairs (SSIP) are identified atmore » rAl-Cl= 4.4 and 6.0 Å. The positions of the free energy minima coincide with the hydration shell intervals of the Al3+ cation suggesting that the Cl- ion is inclined to reside in regions of low concentration of waters, i.e. between the 1st and 2nd shells of Al3+ and between the 2nd shell and bulk. A detailed analysis of solvent structure around the Al3+ and Cl- ions as a function of rAl-Cl is presented. The results are compared to structure data from X-ray measurements and unconstrained AIMD simulations of single ions Al3+ and Cl- and AlCl3 solutions. The dipole moment of the water molecules inside the 1st and 2nd hydration shells of Al3+ and in the bulk region and those of the Clion were calculated as a function of rAl-Cl. Major changes in the electronic structure of the system result from the removal of Cl- from the 1st hydration shell of the Al3+ cation. Finally, two unconstrained AIMD simulations of aqueous AlCl3 solutions corresponding to CIP and SSIP configurations were performed (17 ps, 300 K). Only minor structural changes are observed in these systems, confirming their stability.« less

Inner and Outer Coordination Shells of Mg(2+) in CorA Selectivity Filter from Molecular Dynamics Simulations.

PubMed

Kitjaruwankul, Sunan; Wapeesittipan, Pattama; Boonamnaj, Panisak; Sompornpisut, Pornthep

2016-01-28

Structural data of CorA Mg(2+) channels show that the five Gly-Met-Asn (GMN) motifs at the periplasmic loop of the pentamer structure form a molecular scaffold serving as a selectivity filter. Unfortunately, knowledge about the cation selectivity of Mg(2+) channels remains limited. Since Mg(2+) in aqueous solution has a strong first hydration shell and apparent second hydration sphere, the coordination structure of Mg(2+) in a CorA selectivity filter is expected to be different from that in bulk water. Hence, this study investigated the hydration structure and ligand coordination of Mg(2+) in a selectivity filter of CorA using molecular dynamics (MD) simulations. The simulations reveal that the inner-shell structure of Mg(2+) in the filter is not significantly different from that in aqueous solution. The major difference is the characteristic structural features of the outer shell. The GMN residues engage indirectly in the interactions with the metal ion as ligands in the second shell of Mg(2+). Loss of hydrogen bonds between inner- and outer-shell waters observed from Mg(2+) in bulk water is mostly compensated by interactions between waters in the first solvation shell and the GMN motif. Some water molecules in the second shell remain in the selectivity filter and become less mobile to support the metal binding. Removal of Mg(2+) from the divalent cation sensor sites of the protein had an impact on the structure and metal binding of the filter. From the results, it can be concluded that the GMN motif enhances the affinity of the metal binding site in the CorA selectivity filter by acting as an outer coordination ligand.

Bulk elastic moduli and solute potentials in leaves of freshwater, coastal and marine hydrophytes. Are marine plants more rigid?

PubMed Central

Touchette, Brant W.; Marcus, Sarah E.; Adams, Emily C.

2014-01-01

Bulk modulus of elasticity (ɛ), depicting the flexibility of plant tissues, is recognized as an important component in maintaining internal water balance. Elevated ɛ and comparatively low osmotic potential (Ψπ) may work in concert to effectively maintain vital cellular water content. This concept, termed the ‘cell water conservation hypothesis’, may foster tolerance for lower soil-water potentials in plants while minimizing cell dehydration and shrinkage. Therefore, the accumulation of solutes in marine plants, causing decreases in Ψπ, play an important role in plant–water relations and likely works with higher ɛ to achieve favourable cell volumes. While it is generally held that plants residing in marine systems have higher leaf tissue ɛ, to our knowledge no study has specifically addressed this notion in aquatic and wetland plants residing in marine and freshwater systems. Therefore, we compared ɛ and Ψπ in leaf tissues of 38 freshwater, coastal and marine plant species using data collected in our laboratory, with additional values from the literature. Overall, 8 of the 10 highest ɛ values were observed in marine plants, and 20 of the lowest 25 ɛ values were recorded in freshwater plants. As expected, marine plants often had lower Ψπ, wherein the majority of marine plants were below −1.0 MPa and the majority of freshwater plants were above −1.0 MPa. While there were no differences among habitat type and symplastic water content (θsym), we did observe higher θsym in shrubs when compared with graminoids, and believe that the comparatively low θsym observed in aquatic grasses may be attributed to their tendency to develop aerenchyma that hold apoplastic water. These results, with few exceptions, support the premise that leaf tissues of plants acclimated to marine environments tend to have higher ɛ and lower Ψπ, and agree with the general tenets of the cell water conservation hypothesis. PMID:24876296

Origin of the blueshift of water molecules at interfaces of hydrophilic cyclic compounds

PubMed Central

Tomobe, Katsufumi; Yamamoto, Eiji; Kojić, Dušan; Sato, Yohei; Yasui, Masato; Yasuoka, Kenji

2017-01-01

Water molecules at interfaces of materials exhibit enigmatic properties. A variety of spectroscopic studies have observed a high-frequency motion in these water molecules, represented by a blueshift, at both hydrophobic and hydrophilic interfaces. However, the molecular mechanism behind this blueshift has remained unclear. Using Raman spectroscopy and ab initio molecular dynamics simulations, we reveal the molecular mechanism of the blueshift of water molecules around six monosaccharide isomers. In the first hydration shell, we found weak hydrogen-bonded water molecules that cannot have a stable tetrahedral water network. In the water molecules, the vibrational state of the OH bond oriented toward the bulk solvent strongly contributes to the observed blueshift. Our work suggests that the blueshift in various solutions originates from the vibrational motions of these observed water molecules. PMID:29282448

Linearized Israel matching conditions for cosmological perturbations in a moving brane background

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

Bucher, Martin; DAMTP, University of Cambridge, Cambridge CB3 0WA; Carvalho, Carla

2005-04-15

In the Randall-Sundrum cosmological models, a (3+1)-dimensional brane subject to a Z{sub 2} orbifold symmetry is embedded in a (4+1)-dimensional bulk spacetime empty except for a negative cosmological constant. The unperturbed braneworld cosmological solutions, subject to homogeneity and isotropy in the three transverse spatial dimensions, are most simply presented by means of a moving brane description. Owing to a generalization of Birkhoff's theorem, as long as there are no perturbations violating the three-dimensional spatial homogeneity and isotropy, the bulk spacetime remains stationary and trivial. For the spatially flat case, the bulk spacetime is described by one of three bulk solutions:more » a pure AdS{sup 5} solution, an AdS{sup 5}-Schwarzschild black hole solution, or an AdS{sup 5}-Schwarzschild naked singularity solution. The brane moves on the boundary of one of these simple bulk spacetimes, its trajectory determined by the evolution of the stress-energy localized on the brane. We derive here the form of the Israel matching conditions for the linearized cosmological perturbations in this moving brane picture. These Israel matching conditions must be satisfied in any gauge. However, they are not sufficient to determine how to describe in a specific gauge the reflection of the bulk gravitational waves off the brane boundary. In this paper we adopt a fully covariant Lorentz gauge condition in the bulk and find the supplementary gauge conditions that must be imposed on the boundary to ensure that the reflected waves do not violate the Lorentz gauge condition. Compared to the form obtained from Gaussian normal coordinates, the form of the Israel matching conditions obtained here is more complex. However, the propagation of the bulk gravitons is simpler because the coordinates used for the background exploit fully the symmetry of the bulk background solution.« less

Solutions for the diurnally forced advection-diffusion equation to estimate bulk fluid velocity and diffusivity in streambeds from temperature time series

Treesearch

Charles H. Luce; Daniele Tonina; Frank Gariglio; Ralph Applebee

2013-01-01

Work over the last decade has documented methods for estimating fluxes between streams and streambeds from time series of temperature at two depths in the streambed. We present substantial extension to the existing theory and practice of using temperature time series to estimate streambed water fluxes and thermal properties, including (1) a new explicit analytical...

Functional lignocellulosic material for the remediation of copper(II) ions from water: Towards the design of a wood filter.

PubMed

Vitas, Selin; Keplinger, Tobias; Reichholf, Nico; Figi, Renato; Cabane, Etienne

2018-05-09

In this study, the chemical modification of bulk beech wood is described along with its utilization as biosorbent for the remediation of copper from water. The material was prepared by esterification using anhydrides, and reaction conditions were optimized to propose a greener process, in particular by reducing the amount of solvent. This modification yields a lignocellulosic material whose native structure is preserved, with an increased amount of carboxylic groups (up to 3 mmol/g). We demonstrate that the material can remove up to 95% of copper from low concentration solutions (100- 500 ppm). The adsorption efficiency decreases with concentrated copper solutions, and we show that a limited number of -COOH groups participate in copper binding (ca. 0.1 Cu/-COOH). This result suggests a limited accessibility of -COOH groups in the wood scaffold. This was demonstrated by the characterization of -COOH and copper distributions inside wood. Raman and EDX imaging confirmed that most -COOH groups are located inside the wood cell walls, thereby limiting interactions with copper. According to this study, critical limitations of bulk wood as a biosorbent were identified, and the results will be used to improve the material and design an efficient wood filter for heavy metal remediation. Copyright © 2018 Elsevier B.V. All rights reserved.

Mechanical properties of bulk graphene oxide/poly(acrylic acid)/poly(ethylenimine) ternary polyelectrolyte complex.

PubMed

Duan, Yipin; Wang, Chao; Zhao, Mengmeng; Vogt, Bryan D; Zacharia, Nicole S

2018-05-30

Ternary complexes formed in a single pot process through the mixing of cationic (branched polyethylenimine, BPEI) and anionic (graphene oxide, GO, and poly(acrylic acid), PAA) aqueous solutions exhibit superior mechanical performance in comparison to their binary analogs. The composition of the ternary complex can be simply tuned through the composition of the anionic solution, which influences the water content and mechanical properties of the complex. Increasing the PAA content in the complex decreases the overall water content due to improved charge compensation with the BPEI, but this change also significantly improves the toughness of the complex. Ternary complexes containing ≤32 wt% PAA were too brittle to generate samples for tensile measurements, while extension in excess of 250% could be reached with 57 wt% PAA. From this work, the influence of GO and PAA on the mechanical properties of GO/PAA/BPEI complexes were elucidated with GO sheets acting to restrain the viscous flow and improve the mechanical strength at low loading (<12.6 wt%) and PAA more efficiently complexes with BPEI than GO to generate a less swollen and stronger network. This combination overcomes the brittle nature of GO-BPEI complexes and viscous creep of PAA-BPEI complexes. Ternary nanocomposite complexes appear to provide an effective route to toughen and strengthen bulk polyelectrolyte complexes.

Development of property-transfer models for estimating the hydraulic properties of deep sediments at the Idaho National Engineering and Environmental Laboratory, Idaho

USGS Publications Warehouse

Winfield, Kari A.

2005-01-01

Because characterizing the unsaturated hydraulic properties of sediments over large areas or depths is costly and time consuming, development of models that predict these properties from more easily measured bulk-physical properties is desirable. At the Idaho National Engineering and Environmental Laboratory, the unsaturated zone is composed of thick basalt flow sequences interbedded with thinner sedimentary layers. Determining the unsaturated hydraulic properties of sedimentary layers is one step in understanding water flow and solute transport processes through this complex unsaturated system. Multiple linear regression was used to construct simple property-transfer models for estimating the water-retention curve and saturated hydraulic conductivity of deep sediments at the Idaho National Engineering and Environmental Laboratory. The regression models were developed from 109 core sample subsets with laboratory measurements of hydraulic and bulk-physical properties. The core samples were collected at depths of 9 to 175 meters at two facilities within the southwestern portion of the Idaho National Engineering and Environmental Laboratory-the Radioactive Waste Management Complex, and the Vadose Zone Research Park southwest of the Idaho Nuclear Technology and Engineering Center. Four regression models were developed using bulk-physical property measurements (bulk density, particle density, and particle size) as the potential explanatory variables. Three representations of the particle-size distribution were compared: (1) textural-class percentages (gravel, sand, silt, and clay), (2) geometric statistics (mean and standard deviation), and (3) graphical statistics (median and uniformity coefficient). The four response variables, estimated from linear combinations of the bulk-physical properties, included saturated hydraulic conductivity and three parameters that define the water-retention curve. For each core sample,values of each water-retention parameter were estimated from the appropriate regression equation and used to calculate an estimated water-retention curve. The degree to which the estimated curve approximated the measured curve was quantified using a goodness-of-fit indicator, the root-mean-square error. Comparison of the root-mean-square-error distributions for each alternative particle-size model showed that the estimated water-retention curves were insensitive to the way the particle-size distribution was represented. Bulk density, the median particle diameter, and the uniformity coefficient were chosen as input parameters for the final models. The property-transfer models developed in this study allow easy determination of hydraulic properties without need for their direct measurement. Additionally, the models provide the basis for development of theoretical models that rely on physical relationships between the pore-size distribution and the bulk-physical properties of the media. With this adaptation, the property-transfer models should have greater application throughout the Idaho National Engineering and Environmental Laboratory and other geographic locations.

Solvent fluctuations and nuclear quantum effects modulate the molecular hyperpolarizability of water

NASA Astrophysics Data System (ADS)

Liang, Chungwen; Tocci, Gabriele; Wilkins, David M.; Grisafi, Andrea; Roke, Sylvie; Ceriotti, Michele

2017-07-01

Second-harmonic scattering (SHS) experiments provide a unique approach to probe noncentrosymmetric environments in aqueous media, from bulk solutions to interfaces, living cells, and tissue. A central assumption made in analyzing SHS experiments is that each molecule scatters light according to a constant molecular hyperpolarizability tensor β(2 ). Here, we investigate the dependence of the molecular hyperpolarizability of water on its environment and internal geometric distortions, in order to test the hypothesis of constant β(2 ). We use quantum chemistry calculations of the hyperpolarizability of a molecule embedded in point-charge environments obtained from simulations of bulk water. We demonstrate that both the heterogeneity of the solvent configurations and the quantum mechanical fluctuations of the molecular geometry introduce large variations in the nonlinear optical response of water. This finding has the potential to change the way SHS experiments are interpreted: In particular, isotopic differences between H2O and D2O could explain recent SHS observations. Finally, we show that a machine-learning framework can predict accurately the fluctuations of the molecular hyperpolarizability. This model accounts for the microscopic inhomogeneity of the solvent and represents a step towards quantitative modeling of SHS experiments.

Time domain reflectometry measurements of solute transport across a soil layer boundary

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

Nissen, H.H.; Moldrup, P.; Kachanoski, R.G.

2000-02-01

The mechanisms governing solute transport through layered soil are not fully understood. Solute transport at, above, and beyond the interface between two soil layers during quasi-steady-state soil water movement was investigated using time domain reflectometry (TDR). A 0.26-m sandy loam layer was packed on top of a 1.35-m fine sand layer in a soil column. Soil water content ({theta}) and bulk soil electrical conductivity (EC{sub b}) were measured by 50 horizontal and 2 vertical TDR probes. A new TDR calibration method that gives a detailed relationship between apparent relative dielectric permittivity (K{sub s}) and {theta} was applied. Two replicate solutemore » transport experiments were conducted adding a conservative tracer (CCl) to the surface as a short pulse. The convective lognormal transfer function model (CLT) was fitted to the TDR-measured time integral-normalized resident concentration breakthrough curves (BTCs). The BTCs and the average solute-transport velocities showed preferential flow occurred across the layer boundary. A nonlinear decrease in TDR-measured {theta} in the upper soil toward the soil layer boundary suggests the existence of a 0.10-m zone where water is confined towards fingered flow, creating lateral variations in the area-averaged water flux above the layer boundary. A comparison of the time integral-normalized flux concentration measured by vertical and horizontal TDR probes at the layer boundary also indicates a nonuniform solute transport. The solute dispersivity remained constant in the upper soil layer, but increased nonlinearly (and further down, linearly) with depth in the lower layer, implying convective-dispersive solute transport in the upper soil, a transition zone just below the boundary, and stochastic-convective solute transport in the remaining part of the lower soil.« less

Atomic scale behavior of oxygen-based radicals in water

NASA Astrophysics Data System (ADS)

Verlackt, C. C. W.; Neyts, E. C.; Bogaerts, A.

2017-03-01

Cold atmospheric pressure plasmas in and in contact with liquids represent a growing field of research for various applications. Understanding the interactions between the plasma generated species and the liquid is crucial. In this work we perform molecular dynamics (MD) simulations based on a quantum mechanical method, i.e. density-functional based tight-binding (DFTB), to examine the interactions of OH radicals and O atoms in bulk water. Our calculations reveal that the transport of OH radicals through water is not only governed by diffusion, but also by an equilibrium reaction of H-abstraction with water molecules. Furthermore, when two OH radicals encounter each other, they either form a stable cluster, or react, resulting in the formation of a new water molecule and an O atom. In addition, the O atoms form either oxywater (when in singlet configuration) or they remain stable in solution (when in triplet configuration), stressing the important role that O atoms can play in aqueous solution, and in contact with biomolecules. Our observations are in line with both experimental and ab initio results from the literature.

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2010 CFR

2010-10-01

... polyacrylate solution III Tetrasodium salt of Ethylenediaminetetraaacetic acid solution, see... 46 Shipping 5 2010-10-01 2010-10-01 false Cargoes Not Regulated Under Subchapters D or O of This..., DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID...

On the molecular origin of the cooperative coil-to-globule transition of poly(N-isopropylacrylamide) in water.

PubMed

Tavagnacco, L; Zaccarelli, E; Chiessi, E

2018-04-18

By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the water soluble states of PNIPAM we detect a correlation between polymer segmental dynamics and diffusion motion of bound water, occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently, the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in the proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in the bulk displays a decreased structuring of solvent at the hydrophobic polymer-water interface across the transition temperature, as expected because of the topological extension along the chain of such interface. No evidence of an upper critical solution temperature behaviour, postulated in theoretical and thermodynamics studies of PNIPAM aqueous solution, is observed in the low temperature domain.

Combining Neutron and Magnetic Resonance Imaging to Study the Interaction of Plant Roots and Soil

NASA Astrophysics Data System (ADS)

Oswald, Sascha E.; Tötzke, Christian; Haber-Pohlmeier, Sabina; Pohlmeier, Andreas; Kaestner, Anders P.; Lehmann, Eberhard

The soil in direct vicinity of the roots, the root-soil interface or so called rhizosphere, is heavily modified by the activity of roots, compared to bulk soil, e.g. in respect to microbiology and soil chemistry. It has turned out that the root-soil interface, though small in size, also plays a decisive role in the hydraulics controlling the water flow from bulk soil into the roots. A promising approach for the non-invasive investigation of water dynamics, water flow and solute transport is the combination of the two imaging techniques magnetic resonance imaging (MRI) and neutron imaging (NI). Both methods are complementary, because NI maps the total proton density, possibly amplified by NI tracers, which usually corresponds to total water content, and is able to detect changes and spatial patterns with high resolution. On the other side, nuclear magnetic resonance relaxation times reflect the interaction between fluid and matrix, while also a mapping of proton spin density and thus water content is possible. Therefore MRI is able to classify different water pools via their relaxation times additionally to the water distribution inside soil as a porous medium. We have started such combined measurements with the approach to use the same samples and perform tomography with each imaging method at different location and short-term sample transfer.

46 CFR 151.50-75 - Ferric chloride solution.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution...

Optimizing the use of surfactants and water with foams: a comparison between soapy solutions and foams for sebum detergency

NASA Astrophysics Data System (ADS)

Restagno, Frederic; Valois, Pauline; Petit, Pauline; Cazeneuve, Colette; Nicolas-Morgantini, Luc; Rio, Emmnauelle; Luengo, Gustavo

Human sebum is excreted at the skin surface by the sebaceous glands. Surfactants are the core ingredients of shampoos and other cosmetics to eliminate the excess of sebum as detergency is the classical mechanism used for hair cleaning.. In this study, we add a precise amount of sebum on different hair. We developed a new protocol to measure the cleaning efficiency of surfactant solutions and foams made with the same surfactant solutions based on a spectroscopic method. More precisely, we add a well-controlled amount of colored sebum, we clean the hair with our test foam or solution and we remove completely the unwashed sebum. The sebum remaining after washing is quantified by visible spectroscopy. We tested either classical detergents such as SLES at different concentrations or white egg. The studies were performed on natural or bleached hair. In all the studied case, it was not possible to observe any difference in the cleaning efficiency between the bulk solutions and the foams made from the solutions. This study could allow to develop new shampoos formulations or dispensers in order to replace washing solutions by foams that could have the same cleaning efficiency with a lower amount of surfactants; diminishing the water rinsing needs during application.

A computer simulation study of the temperature dependence of the hydrophobic hydration

NASA Astrophysics Data System (ADS)

Guillot, B.; Guissani, Y.

1993-11-01

The test particle method is used to evaluate by molecular dynamics calculations the solubility of rare gases and of methane in water between the freezing point and the critical point. A quantitative agreement is obtained between solubility data and simulation results when the simulated water is modeled by the extended simple point charge model (SPCE). From a thermodynamical point of view, it is shown that the hierarchy of rare gases solubilities in water is governed by the solute-water interaction energy while an entropic term of cavity formation is found to be responsible for the peculiar temperature dependence of the solubility along the coexistence curve, and more precisely, of the solubility minimum exhibited by all the investigated solutes. Near the water critical point, the asymptotic behaviors of the Henry's constant and of the vapor-liquid partition coefficient, respectively, as deduced from the simulation data follow with a good accuracy the critical laws recently proposed in the literature for these quantities. Moreover, the calculated partial molar volume of the solute shows a steep increase above 473 K and becomes proportional to the isothermal compressibility of the pure solvent in the vicinity of the critical point as it is observed experimentally. From a microscopic point of view, the evaluation of the solute-solvent pair distribution functions permits to establish a relationship between the increase of the solubility with the decrease of the temperature in cold water on the one hand, and the formation of cages of the clathrate-type around the solute on the other hand. Nevertheless, as soon as the boiling point of water is reached the computer simulation shows that the water molecules of the first hydration shell are no longer oriented tangentially to the solute and tend to reorientate towards the bulk. At higher temperatures a deficit of water molecules progressively appears around the solute, a deficit which is directly associated with an increase of the partial molar volume. Although this phenomenon could be related to what is observed in supercritical mixtures it is emphasized that no long range critical fluctuation is present in the simulated sample.

Spectrophotometric Determination of Poorly Water Soluble Drug Rosiglitazone Using Hydrotropic Solubilization technique.

PubMed

Sherje, A P; Desai, K J

2011-09-01

In the present investigation, hydrotropic solution of urea was employed as a solubilizing agent for spectrophotometric determination of poorly water-soluble drug rosiglitazone maleate. In solubility determination study, it was found that there was more than 14-folds enhancement in solubility of rosiglitazone maleate in a 6M solution of urea. Rosiglitazone maleate obeys Beer's law in concentration range of 5-300 μg/ml. Linearity of rosiglitazone maleate was found in the range of 80-120% of the label claim. The proposed method has been applied successfully to the analysis of the cited drug in pharmaceutical formulations with good accuracy and precision. The method herein described is new, simple, eco-friendly, economic, and accurate and can be utilized in routine analysis of rosiglitazone maleate in bulk drug and tablet dosage form.

Spectrophotometric Determination of Poorly Water Soluble Drug Rosiglitazone Using Hydrotropic Solubilization technique

PubMed Central

Sherje, A. P.; Desai, K. J.

2011-01-01

In the present investigation, hydrotropic solution of urea was employed as a solubilizing agent for spectrophotometric determination of poorly water-soluble drug rosiglitazone maleate. In solubility determination study, it was found that there was more than 14-folds enhancement in solubility of rosiglitazone maleate in a 6M solution of urea. Rosiglitazone maleate obeys Beer's law in concentration range of 5-300 μg/ml. Linearity of rosiglitazone maleate was found in the range of 80-120% of the label claim. The proposed method has been applied successfully to the analysis of the cited drug in pharmaceutical formulations with good accuracy and precision. The method herein described is new, simple, eco-friendly, economic, and accurate and can be utilized in routine analysis of rosiglitazone maleate in bulk drug and tablet dosage form. PMID:22923874

Electrochemical Ion-Exchange Regeneration and Fluidized Bed Crystallization for Zero-Liquid-Discharge Water Softening.

PubMed

Chen, Yingying; Davis, Jake R; Nguyen, Chi H; Baygents, James C; Farrell, James

2016-06-07

This research investigated the use of an electrochemical system for regenerating ion-exchange media and for promoting the crystallization of hardness minerals in a fluidized bed crystallization reactor (FBCR). The closed-loop process eliminates the creation of waste brine solutions that are normally produced when regenerating ion-exchange media. A bipolar membrane electrodialysis stack was used to generate acids and bases from 100 mM salt solutions. The acid was used to regenerate weak acid cation (WAC) ion-exchange media used for water softening. The base solutions were used to absorb CO2 gas and to provide a source of alkalinity for removing noncarbonate hardness by WAC media operated in H(+) form. The base solutions were also used to promote the crystallization of CaCO3 and Mg(OH)2 in a FBCR. The overall process removes hardness ions from the water being softened and replaces them with H(+) ions, slightly decreasing the pH value of the softened water. The current utilization efficiency for acid and base production was ∼75% over the operational range of interest, and the energy costs for producing acids and bases were an order of magnitude lower than the costs for purchasing acid and base in bulk quantities. Ion balances indicate that the closed-loop system will accumulate SO4(2-), Cl(-), and alkali metal ions. Acid and base balances indicate that for a typical water, small amounts of base will be accumulated.

Modifying Poisson equation for near-solute dielectric polarization and solvation free energy

NASA Astrophysics Data System (ADS)

Yang, Pei-Kun

2016-06-01

The dielectric polarization P is important for calculating the stability of protein conformation and the binding affinity of protein-protein/ligand interactions and for exploring the nonthermal effect of an external electric field on biomolecules. P was decomposed into the product of the electric dipole moment per molecule p; bulk solvent density Nbulk; and relative solvent molecular density g. For a molecular solute, 4πr2p(r) oscillates with the distance r to the solute, and g(r) has a large peak in the near-solute region, as observed in molecular dynamics (MD) simulations. Herein, the Poisson equation was modified for computing p based on the modified Gauss's law of Maxwell's equations, and the potential of the mean force was used for computing g. For one or two charged atoms in a water cluster, the solvation free energies of the solutes obtained by these equations were similar to those obtained from MD simulations.

Microelectrode generator-collector systems for electrolytic titration: theoretical and practical considerations.

PubMed

Bell, Christopher G; Seelanan, Parinya; O'Hare, Danny

2017-10-23

Electochemical generator-collector systems, where one electrode is used to generate a reagent, have a potentially large field of application in sensing and measurement. We present a new theoretical description for coplanar microelectrode disc-disc systems where the collector is passive (such as a potentiometric sensor) and the generator is operating at constant flux. This solution is then used to develop a leading order solution for such a system where the reagent reacts reversibly in solution, such as in acid-base titration, where a hydrogen ion flux is generated by electrolysis of water. The principal novel result of the theory is that such devices are constrained by a maximum reagent flux. The hydrogen ion concentration at the collector will only reflect the buffer capacity of the bulk solution if this constraint is met. Both mathematical solutions are evaluated with several microfabricated devices and reasonable agreement with theory is demonstrated.

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

NASA Technical Reports Server (NTRS)

Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

PubMed Central

De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

2009-01-01

The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

[Spatial variation characteristics of surface soil water content, bulk density and saturated hydraulic conductivity on Karst slopes].

PubMed

Zhang, Chuan; Chen, Hong-Song; Zhang, Wei; Nie, Yun-Peng; Ye, Ying-Ying; Wang, Ke-Lin

2014-06-01

Surface soil water-physical properties play a decisive role in the dynamics of deep soil water. Knowledge of their spatial variation is helpful in understanding the processes of rainfall infiltration and runoff generation, which will contribute to the reasonable utilization of soil water resources in mountainous areas. Based on a grid sampling scheme (10 m x 10 m) and geostatistical methods, this paper aimed to study the spatial variability of surface (0-10 cm) soil water content, soil bulk density and saturated hydraulic conductivity on a typical shrub slope (90 m x 120 m, projected length) in Karst area of northwest Guangxi, southwest China. The results showed that the surface soil water content, bulk density and saturated hydraulic conductivity had different spatial dependence and spatial structure. Sample variogram of the soil water content was fitted well by Gaussian models with the nugget effect, while soil bulk density and saturated hydraulic conductivity were fitted well by exponential models with the nugget effect. Variability of soil water content showed strong spatial dependence, while the soil bulk density and saturated hydraulic conductivity showed moderate spatial dependence. The spatial ranges of the soil water content and saturated hydraulic conductivity were small, while that of the soil bulk density was much bigger. In general, the soil water content increased with the increase of altitude while it was opposite for the soil bulk densi- ty. However, the soil saturated hydraulic conductivity had a random distribution of large amounts of small patches, showing high spatial heterogeneity. Soil water content negatively (P < 0.01) correlated with the bulk density and saturated hydraulic conductivity, while there was no significant correlation between the soil bulk density and saturated hydraulic conductivity.

Water at surfaces with tunable surface chemistries

NASA Astrophysics Data System (ADS)

Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

2018-03-01

Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

Polythiophene Derivative with a Side Chain Chromophore as Photovoltaic and Photorefractive Materials

DTIC Science & Technology

1993-11-17

the desired bulk property in the polymer such as water solubility,1 8 optical activity,19 ionic conductivity 20 or liquid crystalline properties. 2 1...photoexcitation, which is similar to photoinduced polarization observed in the Langmuir - Blodgett (L-B) films of donor-acceptor molecules. 23 But due to...Maximum 200 Words) A new, solution processable, thiophene copolymer with a side chain nonlinear optical (NLO) chromophore namely Poly (3-octylthiophene

URANIUM DECONTAMINATION

DOEpatents

Buckingham, J.S.; Carroll, J.L.

1959-12-22

A process is described for reducing the extractability of ruthenium, zirconium, and niobium values into hexone contained in an aqueous nitric acid uranium-containing solution. The solution is made acid-deficient, heated to between 55 and 70 deg C, and at that temperature a water-soluble inorganic thiosulfate is added. By this, a precipitate is formed which carries the bulk of the ruthenium, and the remainder of the ruthenium as well as the zirconium and niobium are converted to a hexone-nonextractable form. The rutheniumcontaining precipitate can either be removed from the solu tion or it can be dissolved as a hexone-non-extractable compound by the addition of sodium dichromate prior to hexone extraction.

A coupled melt-freeze temperature index approach in a one-layer model to predict bulk volumetric liquid water content dynamics in snow

NASA Astrophysics Data System (ADS)

Avanzi, Francesco; Yamaguchi, Satoru; Hirashima, Hiroyuki; De Michele, Carlo

2016-04-01

Liquid water in snow rules runoff dynamics and wet snow avalanches release. Moreover, it affects snow viscosity and snow albedo. As a result, measuring and modeling liquid water dynamics in snow have important implications for many scientific applications. However, measurements are usually challenging, while modeling is difficult due to an overlap of mechanical, thermal and hydraulic processes. Here, we evaluate the use of a simple one-layer one-dimensional model to predict hourly time-series of bulk volumetric liquid water content in seasonal snow. The model considers both a simple temperature-index approach (melt only) and a coupled melt-freeze temperature-index approach that is able to reconstruct melt-freeze dynamics. Performance of this approach is evaluated at three sites in Japan. These sites (Nagaoka, Shinjo and Sapporo) present multi-year time-series of snow and meteorological data, vertical profiles of snow physical properties and snow melt lysimeters data. These data-sets are an interesting opportunity to test this application in different climatic conditions, as sites span a wide latitudinal range and are subjected to different snow conditions during the season. When melt-freeze dynamics are included in the model, results show that median absolute differences between observations and predictions of bulk volumetric liquid water content are consistently lower than 1 vol%. Moreover, the model is able to predict an observed dry condition of the snowpack in 80% of observed cases at a non-calibration site, where parameters from calibration sites are transferred. Overall, the analysis show that a coupled melt-freeze temperature-index approach may be a valid solution to predict average wetness conditions of a snow cover at local scale.

7 CFR 1780.63 - Sewage treatment and bulk water sales contracts.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 7 Agriculture 12 2011-01-01 2011-01-01 false Sewage treatment and bulk water sales contracts. 1780... UTILITIES SERVICE, DEPARTMENT OF AGRICULTURE (CONTINUED) WATER AND WASTE LOANS AND GRANTS Planning, Designing, Bidding, Contracting, Constructing and Inspections § 1780.63 Sewage treatment and bulk water...

7 CFR 1780.63 - Sewage treatment and bulk water sales contracts.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 7 Agriculture 12 2010-01-01 2010-01-01 false Sewage treatment and bulk water sales contracts. 1780... UTILITIES SERVICE, DEPARTMENT OF AGRICULTURE (CONTINUED) WATER AND WASTE LOANS AND GRANTS Planning, Designing, Bidding, Contracting, Constructing and Inspections § 1780.63 Sewage treatment and bulk water...

Investigating Liquid Leak from Pre-Filled Syringes upon Needle Shield Removal: Effect of Air Bubble Pressure.

PubMed

Chan, Edwin; Maa, Yuh-Fun; Overcashier, David; Hsu, Chung C

2011-01-01

This study is to investigate the effect of headspace air pressure in pre-filled syringes on liquid leak (dripping) from the syringe needle upon needle shield removal. Drip tests to measure drip quantity were performed on syringes manually filled with 0.5 or 1.0 mL of various aqueous solutions. Parameters assessed included temperature (filling and test), bulk storage conditions (tank pressure and the type of the pressurized gas), solution composition (pure water, 0.9% sodium chloride, and a monoclonal antibody formulation), and testing procedures. A headspace pressure analyzer was used to verify the drip test method. Results suggested that leakage is indeed caused by headspace pressure increase, and the temperature effect (ideal gas expansion) is a major, but not the only, factor. The dissolved gases in the liquid bulk prior to or during filling may contribute to leakage, as these gases could be released into the headspace due to solubility changes (in response to test temperature and pressure conditions) and cause pressure increase. Needle shield removal procedures were found to cause dripping, but liquid composition played little role. Overall, paying attention to the processing history (pressure and temperature) of the liquid bulk is the key to minimize leakage. The headspace pressure could be reduced by decreasing liquid bulk storage pressure, filling at a higher temperature, or employing lower solubility gas (e.g., helium) for bulk transfer and storage. Leakage could also be mitigated by simply holding the syringe needle pointing upward during needle shield removal. Substantial advances in pre-filled syringe technology development, particularly in syringe filling accuracy, have been made. However, there are factors, as subtle as how the needle shield (or tip cap) is removed, that may affect dosing accuracy. We recently found that upon removal of the tip cap from a syringe held vertically with needle pointed downwards, a small amount of solution, up to 3-4% of the 1 mL filled volume or higher for filled volume of <1 mL, leaked out from the needle. This paper identified the root causes of this problem and offered solutions from the perspectives of the syringe fill process and the end user procedure. The readers will benefit from this paper by understanding how each process step prior to and during syringe filling may affect delivery performance of the pre-filled syringe device.

Mechanism of Hg(II) Immobilization in Sediments by Sulfate-Cement Amendment.

PubMed

Serrano, Susana; Vlassopoulos, Dimitri; O'Day, Peggy A

2016-04-01

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO 4 amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L III - and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca 6 Al 2 (SO 4 ) 3 (OH) 12 . 26H 2 O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20-25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg-Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg-Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt as the primary immobilization mechanism.

Oscillatory phase separation in giant lipid vesicles induced by transmembrane osmotic differentials

PubMed Central

Oglęcka, Kamila; Rangamani, Padmini; Liedberg, Bo; Kraut, Rachel S; Parikh, Atul N

2014-01-01

Giant lipid vesicles are closed compartments consisting of semi-permeable shells, which isolate femto- to pico-liter quantities of aqueous core from the bulk. Although water permeates readily across vesicular walls, passive permeation of solutes is hindered. In this study, we show that, when subject to a hypotonic bath, giant vesicles consisting of phase separating lipid mixtures undergo osmotic relaxation exhibiting damped oscillations in phase behavior, which is synchronized with swell–burst lytic cycles: in the swelled state, osmotic pressure and elevated membrane tension due to the influx of water promote domain formation. During bursting, solute leakage through transient pores relaxes the pressure and tension, replacing the domain texture by a uniform one. This isothermal phase transition—resulting from a well-coordinated sequence of mechanochemical events—suggests a complex emergent behavior allowing synthetic vesicles produced from simple components, namely, water, osmolytes, and lipids to sense and regulate their micro-environment. DOI: http://dx.doi.org/10.7554/eLife.03695.001 PMID:25318069

Solute segregation and deviation from bulk thermodynamics at nanoscale crystalline defects.

PubMed

Titus, Michael S; Rhein, Robert K; Wells, Peter B; Dodge, Philip C; Viswanathan, Gopal Babu; Mills, Michael J; Van der Ven, Anton; Pollock, Tresa M

2016-12-01

It has long been known that solute segregation at crystalline defects can have profound effects on material properties. Nevertheless, quantifying the extent of solute segregation at nanoscale defects has proven challenging due to experimental limitations. A combined experimental and first-principles approach has been used to study solute segregation at extended intermetallic phases ranging from 4 to 35 atomic layers in thickness. Chemical mapping by both atom probe tomography and high-resolution scanning transmission electron microscopy demonstrates a markedly different composition for the 4-atomic-layer-thick phase, where segregation has occurred, compared to the approximately 35-atomic-layer-thick bulk phase of the same crystal structure. First-principles predictions of bulk free energies in conjunction with direct atomistic simulations of the intermetallic structure and chemistry demonstrate the breakdown of bulk thermodynamics at nanometer dimensions and highlight the importance of symmetry breaking due to the proximity of interfaces in determining equilibrium properties.

Solute segregation and deviation from bulk thermodynamics at nanoscale crystalline defects

PubMed Central

Titus, Michael S.; Rhein, Robert K.; Wells, Peter B.; Dodge, Philip C.; Viswanathan, Gopal Babu; Mills, Michael J.; Van der Ven, Anton; Pollock, Tresa M.

2016-01-01

It has long been known that solute segregation at crystalline defects can have profound effects on material properties. Nevertheless, quantifying the extent of solute segregation at nanoscale defects has proven challenging due to experimental limitations. A combined experimental and first-principles approach has been used to study solute segregation at extended intermetallic phases ranging from 4 to 35 atomic layers in thickness. Chemical mapping by both atom probe tomography and high-resolution scanning transmission electron microscopy demonstrates a markedly different composition for the 4–atomic-layer–thick phase, where segregation has occurred, compared to the approximately 35–atomic-layer–thick bulk phase of the same crystal structure. First-principles predictions of bulk free energies in conjunction with direct atomistic simulations of the intermetallic structure and chemistry demonstrate the breakdown of bulk thermodynamics at nanometer dimensions and highlight the importance of symmetry breaking due to the proximity of interfaces in determining equilibrium properties. PMID:28028543

Bulk properties of solution-synthesized chevron-like graphene nanoribbons.

PubMed

Vo, Timothy H; Shekhirev, Mikhail; Lipatov, Alexey; Korlacki, Rafal A; Sinitskii, Alexander

2014-01-01

Graphene nanoribbons (GNRs) have received a great deal of attention due to their promise for electronic and optoelectronic applications. Several recent studies have focused on the synthesis of GNRs by the bottom-up approaches that could yield very narrow GNRs with atomically precise edges. One type of GNRs that has received a considerable attention is the chevron-like GNR with a very distinct periodic structure. Surface-assisted and solution-based synthetic approaches for the chevron-like GNRs have been developed, but their electronic properties have not been reported yet. In this work, we synthesized chevron-like GNRs in bulk by a solution-based method, characterized them by a number of spectroscopic techniques and measured their bulk conductivity. We demonstrate that solution-synthesized chevron-like GNRs are electrically conductive in bulk, which makes them a potentially promising material for applications in organic electronics and photovoltaics.

Trichloroethene (TCE) hydrodechlorination by NiFe nanoparticles: Influence of aqueous anions on catalytic pathways.

PubMed

Han, Yanlai; Liu, Changjie; Horita, Juske; Yan, Weile

2018-08-01

Amending bulk and nanoscale zero-valent iron (ZVI) with catalytic metals significantly accelerates hydrodechlorination of groundwater contaminants such as trichloroethene (TCE). The bimetallic design benefits from a strong synergy between Ni and Fe in facilitating the production of active hydrogen for TCE reduction, and it is of research and practical interest to understand the impacts of common groundwater solutes on catalyst and ZVI functionality. In this study, TCE hydrodechlorination reaction was conducted using fresh NiFe bimetallic nanoparticles (NiFe BNPs) and those aged in chloride, sulfate, phosphate, and humic acid solutions with concurrent analysis of carbon fractionation of TCE and its daughter products. The apparent kinetics suggest that the reactivity of NiFe BNPs is relatively stable in pure water and chloride or humic acid solutions, in contrast to significant deactivation observed of PdFe bimetallic particles in similar media. Exposure to phosphate at greater than 0.1 mM led to a severe decrease in TCE reaction rate. The change in kinetic regimes from first to zeroth order with increasing phosphate concentration is consistent with consumption of reactive sites by phosphate. Despite severe kinetic effect, there is no significant shift in TCE 13 C bulk enrichment factor between the fresh and the phosphate-aged particles. Instead, pronounced retardation of TCE reaction by NiFe BNPs in deuterated water (D 2 O) points to the importance of hydrogen spillover in controlling TCE reduction rate by NiFe BNPs, and such process can be strongly affected by groundwater chemistry. Copyright © 2018 Elsevier Ltd. All rights reserved.

Phase-Transfer Energetics of Small-Molecule Alcohols Across the Water-Hexane Interface: Molecular Dynamics Simulation Using Charge Equilibration Models

PubMed Central

Bauer, Brad A.; Zhong, Yang; Meninger, David J.; Davis, Joseph E.; Patel, Sandeep

2010-01-01

We study the water-hexane interface using molecular dynamics (MD) and polarizable charge equilibration (CHEQ) force fields. Bulk densities for TIP4P-FQ water and hexane, 1.0086±0.0002 g/cm3 and 0.6378±0.0001 g/cm3, demonstrate excellent agreement with experiment. Interfacial width and interfacial tension are consistent with previously reported values. The in-plane component of the dielectric permittivity (ε∥) for water is shown to decrease from 81.7±0.04 to unity, transitioning longitudinally from bulk water to bulk hexane. ε∥ for hexane reaches a maximum in the interface, but this term represents only a small contribution to the total dielectric constant (as expected for a non-polar species). Structurally, net orientations of the molecules arise in the interfacial region such that hexane lies slightly parallel to the interface and water reorients to maximize hydrogen bonding. Interfacial potentials due to contributions of the water and hexane are calculated to be -567.9±0.13mV and 198.7±0.01mV, respectively, giving rise to a total potential in agreement with the range of values reported from previous simulations of similar systems. Potentials of mean force (PMF) calculated for methanol, ethanol, and 1-propanol for the transfer from water to hexane indicate an interfacial free energy minimum, corresponding to the amphiphilic nature of the molecules. The magnitudes of transfer free energies were further characterized from the solvation free energies of alcohols in water and hexane using thermodynamic integration. This analysis shows that solvation free energies for alcohols in hexane are 0.2-0.3 kcal/mol too unfavorable, whereas solvation of alcohols in water is approximately 1 kcal/mol too favorable. For the pure hexane-water interfacial simulations, we observe a monotonic decrease of the water dipole moment to near-vacuum values. This suggests that the electrostatic component of the desolvation free energy is not as severe for polarizable models than for fixed-charge force fields. The implications of such behavior pertain to the modeling of polar and charged solutes in lipidic environments. PMID:21414823

Evaluating the Role of the Air-Solution Interface on the Mechanism of Subvisible Particle Formation Caused by Mechanical Agitation for an IgG1 mAb.

PubMed

Ghazvini, Saba; Kalonia, Cavan; Volkin, David B; Dhar, Prajnaparamita

2016-05-01

Mechanical agitation of monoclonal antibody (mAb) solutions often leads to protein particle formation. In this study, various formulations of an immunoglobulin G (IgG) 1 mAb were subjected to different controlled interfacial stresses using a Langmuir trough, and protein particles formed at the interface and measured in bulk solution were characterized using atomic force microscopy and flow digital imaging. Results were compared to mAb solutions agitated in glass vials and unstressed controls. At lower pH, mAb solutions exhibited larger hysteresis in their surface pressure versus area isotherms and increased number of particles in bulk solution, when subjected to interfacial stresses. mAb samples subjected to 750-1000 interfacial compression-expansion cycles in 6 h contained high particle numbers in bulk solution, and displayed similar particulation trends when agitated in vials. At compression rates of 50 cycles in 6 h, however, particle levels in mAb solutions were comparable to unstressed controls, despite protein aggregates being present at the air-solution interface. These results suggest that while the air-solution interface serves as a nucleation site for initiating protein aggregation, the number of protein particles measured in bulk mAb solutions depends on the total number of compression cycles that proteins at the air-solution interface are subjected to within a fixed time. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Motion-based, high-yielding, and fast separation of different charged organics in water.

PubMed

Xuan, Mingjun; Lin, Xiankun; Shao, Jingxin; Dai, Luru; He, Qiang

2015-01-12

We report a self-propelled Janus silica micromotor as a motion-based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self-propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s(-1) . Biotin-functionalized Janus micromotors can specifically capture and rapidly transport streptavidin-modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self-propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab-on-chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unexpected inhibition of CO 2 gas hydrate formation in dilute TBAB solutions and the critical role of interfacial water structure

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

Nguyen, Ngoc N.; Nguyen, Anh V.; Nguyen, Khoi T.

Gas hydrates formed under moderated conditions open up novel approaches to tackling issues related to energy supply, gas separation, and CO 2 sequestration. Several additives like tetra-n-butylammonium bromide (TBAB) have been empirically developed and used to promote gas hydrate formation. Here we report unexpected experimental results which show that TBAB inhibits CO 2 gas hydrate formation when used at minuscule concentration. We also used spectroscopic techniques and molecular dynamics simulation to gain further insights and explain the experimental results. They have revealed the critical role of water alignment at the gas-water interface induced by surface adsorption of tetra-n-butylammonium cation (TBAmore » +) which gives rise to the unexpected inhibition of dilute TBAB solution. The water perturbation by TBA + in the bulk is attributed to the promotion effect of high TBAB concentration on gas hydrate formation. We explain our finding using the concept of activation energy of gas hydrate formation. Our results provide a step toward to mastering the control of gas hydrate formation.« less

Analysis of Structure and Composition of Bacterial Core Communities in Mature Drinking Water Biofilms and Bulk Water of a Citywide Network in Germany

PubMed Central

Henne, Karsten; Kahlisch, Leila; Brettar, Ingrid

2012-01-01

The bacterial core communities of bulk water and corresponding biofilms of a more than 20-year-old drinking water network were compared using 16S rRNA single-strand confirmation polymorphism (SSCP) fingerprints based on extracted DNA and RNA. The structure and composition of the bacterial core community in the bulk water was highly similar (>70%) across the city of Braunschweig, Germany, whereas all biofilm samples contained a unique community with no overlapping phylotypes from bulk water. Biofilm samples consisted mainly of Alphaproteobacteria (26% of all phylotypes), Gammaproteobacteria (11%), candidate division TM6 (11%), Chlamydiales (9%), and Betaproteobacteria (9%). The bulk water community consisted primarily of Bacteroidetes (25%), Betaproteobacteria (20%), Actinobacteria (16%), and Alphaproteobacteria (11%). All biofilm communities showed higher relative abundances of single phylotypes and a reduced richness compared to bulk water. Only biofilm communities sampled at nearby sampling points showed similar communities irrespective of support materials. In all of our bulk water studies, the community composition determined from 16S rRNA was completely different from the 16S rRNA gene-based community composition, whereas in biofilms both molecular fractions resulted in community compositions that were similar to each other. We hypothesize that a higher fraction of active bacterial phylotypes and a better protection from oxidative stress in drinking water biofilms are responsible for this higher similarity. PMID:22389373

Analysis of structure and composition of bacterial core communities in mature drinking water biofilms and bulk water of a citywide network in Germany.

PubMed

Henne, Karsten; Kahlisch, Leila; Brettar, Ingrid; Höfle, Manfred G

2012-05-01

The bacterial core communities of bulk water and corresponding biofilms of a more than 20-year-old drinking water network were compared using 16S rRNA single-strand confirmation polymorphism (SSCP) fingerprints based on extracted DNA and RNA. The structure and composition of the bacterial core community in the bulk water was highly similar (>70%) across the city of Braunschweig, Germany, whereas all biofilm samples contained a unique community with no overlapping phylotypes from bulk water. Biofilm samples consisted mainly of Alphaproteobacteria (26% of all phylotypes), Gammaproteobacteria (11%), candidate division TM6 (11%), Chlamydiales (9%), and Betaproteobacteria (9%). The bulk water community consisted primarily of Bacteroidetes (25%), Betaproteobacteria (20%), Actinobacteria (16%), and Alphaproteobacteria (11%). All biofilm communities showed higher relative abundances of single phylotypes and a reduced richness compared to bulk water. Only biofilm communities sampled at nearby sampling points showed similar communities irrespective of support materials. In all of our bulk water studies, the community composition determined from 16S rRNA was completely different from the 16S rRNA gene-based community composition, whereas in biofilms both molecular fractions resulted in community compositions that were similar to each other. We hypothesize that a higher fraction of active bacterial phylotypes and a better protection from oxidative stress in drinking water biofilms are responsible for this higher similarity.

Hydration water and bulk water in proteins have distinct properties in radial distributions calculated from 105 atomic resolution crystal structures.

PubMed

Chen, Xianfeng; Weber, Irene; Harrison, Robert W

2008-09-25

Water plays a critical role in the structure and function of proteins, although the experimental properties of water around protein structures are not well understood. The water can be classified by the separation from the protein surface into bulk water and hydration water. Hydration water interacts closely with the protein and contributes to protein folding, stability, and dynamics, as well as interacting with the bulk water. Water potential functions are often parametrized to fit bulk water properties because of the limited experimental data for hydration water. Therefore, the structural and energetic properties of the hydration water were assessed for 105 atomic resolution (

The Influence of Land-Use Change on Soil and Dissolved Organic Matter Age, Lability, and Chemical Characteristics in Brazilian Oxisols

NASA Astrophysics Data System (ADS)

James, J. N.; Harrison, R. B.; Gross, C. D.; Dwivedi, P.; Myers, T.; Butman, D. E.

2017-12-01

Recent advances in freshwater research indicate that the age of carbon exported from major rivers globally increases with greater human disturbance in the watershed. This implies that human land-use can release old, previously mineral-associated C into solution with subsequent export to groundwater and ultimately freshwater systems where terrestrial organic matter is either mineralized to CO2, stored in aquatic sediments, or exported to the ocean. It is important to understand the mechanisms that cause the release of mineral-bound soil organic matter (SOM) into solution in response to human disturbance and land-use change. To better characterize the response of the total soil organic matter (SOM) pool to disturbance, this study examines the interactions between dissolved and bulk soil pools in response to conversion of Brazilian Cerrado (savannah forest) to Eucalyptus plantations. Water-extractable organic matter (WEOM) was obtained from soil samples down to 150 cm at 4 sites in Sao Paulo State, Brazil. These WEOM samples were characterized using fluorescence and NMR spectroscopy, incubated to assess biolability, and carbon-dated. Simultaneously, bulk mineral soil samples were analyzed for microbial biomass, carbon content and age, and characterized using Fourier Transform Infrared Spectroscopy. FTIR spectra of SOM were obtained by washing subsamples with sodium hypochlorite and subtracting the subsequent mineral matrix spectra from bulk soil spectra. Preliminary results show that microbial biomass decreases much more quickly with depth than WEOM, suggesting that C released into solution from deeper horizons may be less likely to be intercepted, and thus preferentially leached to groundwater. Native Cerrado forests had substantially more roots compared to Eucalyptus, and also released substantially larger quantities of WEOM from their O horizons. Furthermore, the age of WEOM released under Eucalyptus forest was more similar in age to bulk SOM, while Cerrado forest WEOM was substantially younger than the bulk SOM. Processes operating at the interface between solid and liquid, terrestrial and aquatic are a key unknown in the global carbon cycle. This research permits a unique snapshot into the relationship between DOM and SOM and the response of these pools to forest conversion and management in Brazil.

Theoretical investigation on the dimerization of the deprotonated aquo ion of Al(III) in water.

PubMed

Qian, Zhaosheng; Feng, Hui; Zhang, Zhenjiang; Yang, Wenjing; Jin, Jing; Miao, Qiang; He, Lina; Bi, Shuping

2009-01-21

Reaction pathways, solvent effects and energy barriers have been investigated for the dimerization of the deprotonated aquo ion of Al(III) in aqueous solution by performing supramolecule density functional theory calculations. Two competing reaction pathways were investigated, sharing a common first step and third step, i.e. the formation of the aggregate II of two aluminium monomers and the doubly bridged dimer. One pathway involves a nucleophilic attack to undercoordinated metal center in the first step and then the loss of a coordinated water molecule. Another pathway involves a water exchange reaction in the first step and then the formation of the hydroxo bridge. The calculated results indicate that both pathways I and II are possible in aqueous solution. The direct participation of the solvent water molecule facilitates the dimerization, but the extremely large solvent shifts of the energy barriers for each reaction are attributed mainly to the bulk effect. The computed activation energies for the water exchange reactions are in good agreement with the available experimental values, namely, the calculated value 37.5 kJ mol(-1) compared to the experimental value 36.4 (+/-5) kJ mol(-1). In agreement with experimental observations in aqueous solution, the calculated results favor the transformation of singly-bridged to doubly-bridged aluminium ion, which is helpful to understand the complicated hydrolytic polymerizaiton of Al(III).

Hydrodynamic and Nonhydrodynamic Contributions to the Bimolecular Collision Rates of Solute Molecules in Supercooled Bulk Water

PubMed Central

2015-01-01

Bimolecular collision rate constants of a model solute are measured in water at T = 259–303 K, a range encompassing both normal and supercooled water. A stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, is studied using electron paramagnetic resonance spectroscopy (EPR), taking advantage of the fact that the rotational correlation time, τR, the mean time between successive spin exchanges within a cage, τRE, and the long-time-averaged spin exchange rate constants, Kex, of the same solute molecule may be measured independently. Thus, long- and short-time translational diffusion behavior may be inferred from Kex and τRE, respectively. In order to measure Kex, the effects of dipole–dipole interactions (DD) on the EPR spectra must be separated, yielding as a bonus the DD broadening rate constants that are related to the dephasing rate constant due to DD, Wdd. We find that both Kex and Wdd behave hydrodynamically; that is to say they vary monotonically with T/η or η/T, respectively, where η is the shear viscosity, as predicted by the Stokes–Einstein equation. The same is true of the self-diffusion of water. In contrast, τRE does not follow hydrodynamic behavior, varying rather as a linear function of the density reaching a maximum at 276 ± 2 K near where water displays a maximum density. PMID:24874024

Ge/Si Ratios Record the Impact of Forest Conversion to Cropland on Soil Chemical Weathering Processes and Solutes Export to Rivers

NASA Astrophysics Data System (ADS)

Ameijeiras-Marino, Y.; Opfergelt, S.; Derry, L. A.; Robinet, J.; Delmelle, P.

2016-12-01

Soil weathering processes influence solute fluxes to rivers, playing a major role in global biogeochemical cycles. Land use change such as forest conversion to cropland enhances soil erosion, which mobilizes solutes and exposes new mineral surfaces to weathering processes, changing soil weathering degree. However, the impact of forest conversion to cropland on soil weathering degree and solute fluxes exported from soils to rivers remain poorly quantified. This study assesses the soil weathering degree and uses a geochemical tracer of weathering, Ge/Si ratio, to provide new insights on the impact of soil weathering processes under anthropogenic forcing on the transfer of solutes to rivers. A subtropical site was studied in Rio Grande do Sul (Brazil). This area is characterized by mean annual rainfall of 1800 mm, with strong rain events mobilizing high sediment load. A forested catchment is considered as the reference and compared to a catchment cultivated for the past 100 years (similar lithology and climate). Bedrock, soil, soil pore water and stream water (during base flow and rain events) samples were analysed for their chemical and mineralogical compositions and Ge/Si ratios (combined isotope dilution, HR-ICP-MS and hydride generation). Chemical and mineralogical analyses highlight that forest conversion to cropland decreases the soil weathering degree on steep slopes. Ge/Si ratios (μmol/mol) are comparable in bulk soils between the forested (2.33 ± 0.50) and the cultivated catchment (2.61 ± 0.62), but differ in soil pore waters between forest (0.47 ± 0.16) and culture (0.73 ± 0.15) indicating differences on soil weathering processes. The response of Ge/Si ratios in stream waters to a rain event differs between forest and culture, highlighting a larger contribution from soil pore waters to stream waters under culture. Altogether, our data support that land use history has an impact on the present day soil weathering processes and on the solute export to rivers.

High Interfacial Barriers at Narrow Carbon Nanotube-Water Interfaces.

PubMed

Varanasi, Srinivasa Rao; Subramanian, Yashonath; Bhatia, Suresh K

2018-06-26

Water displays anomalous fast diffusion in narrow carbon nanotubes (CNTs), a behavior that has been reproduced in both experimental and simulation studies. However, little is reported on the effect of bulk water-CNT interfaces, which is critical to exploiting the fast transport of water across narrow carbon nanotubes in actual applications. Using molecular dynamics simulations, we investigate here the effect of such interfaces on the transport of water across arm-chair CNTs of different diameters. Our results demonstrate that diffusion of water is significantly retarded in narrow CNTs due to bulk regions near the pore entrance. The slowdown of dynamics can be attributed to the presence of large energy barriers at bulk water-CNT interfaces. The presence of such intense barriers at the bulk-CNT interface arises due to the entropy contrast between the bulk and confined regions, with water molecules undergoing high translational and rotational entropy gain on entering from the bulk to the CNT interior. The intensity of such energy barriers decreases with increase in CNT diameter. These results are very important for emerging technological applications of CNTs and other nanoscale materials, such as in nanofluidics, water purification, nanofiltration, and desalination, as well as for biological transport processes.

Water at protein surfaces studied with femtosecond nonlinear spectroscopy

NASA Astrophysics Data System (ADS)

Bakker, Huib J.

We report on an investigation of the structure and dynamics of water molecules near protein surfaces with femtosecond nonlinear spectroscopic techniques. We measured the reorientation dynamics of water molecules near the surface of several globular protein surfaces, using polarization-resolved femtosecond infrared spectroscopy. We found that water molecules near the protein surface have a much slower reorientation than water molecules in bulk liquid water. The number of slow water molecules scales scales with the size of the hydrophobic surface of the protein. When we denature the proteins by adding an increasing amount of urea to the protein solution, we observe that the water-exposed surface increases by 50% before the secondary structure of the proteins changes. This finding indicates that protein unfolding starts with the protein structure becoming less tight, thereby allowing water to enter. With surface vibrational sum frequency generation (VSFG) spectroscopy, we studied the structure of water at the surface of antifreeze protein III. The measured VSFG spectra showed the presence of ice-like water layers at the ice-binding site of the protein in aqueous solution, at temperatures well above the freezing point. This ordered ice-like hydration layers at the protein surface likely plays an important role in the specific recognition and binding of anti-freeze protein III to nascent ice crystallites, and thus in its anti-freeze mechanism. This research is supported by the ''Nederlandse organisatie voor Wetenschappelijk Onderzoek (NWO).

An integrated theoretical and experimental investigation of insensitive munition compounds adsorption on cellulose, cellulose triacetate, chitin and chitosan surfaces.

PubMed

Gurtowski, Luke A; Griggs, Chris S; Gude, Veera G; Shukla, Manoj K

2018-02-01

This manuscript reports results of combined computational chemistry and batch adsorption investigation of insensitive munition compounds, 2,4-dinitroanisole (DNAN), triaminotrinitrobenzene (TATB), 1,1-diamino-2,2-dinitroethene (FOX-7) and nitroguanidine (NQ), and traditional munition compound 2,4,6-trinitrotoluene (TNT) on the surfaces of cellulose, cellulose triacetate, chitin and chitosan biopolymers. Cellulose, cellulose triacetate, chitin and chitosan were modeled as trimeric form of the linear chain of 4 C 1 chair conformation of β-d-glucopyranos, its triacetate form, β-N-acetylglucosamine and D-glucosamine, respectively, in the 1➔4 linkage. Geometries were optimized at the M062X functional level of the density functional theory (DFT) using the 6-31G(d,p) basis set in the gas phase and in the bulk water solution using the conductor-like polarizable continuum model (CPCM) approach. The nature of potential energy surfaces of the optimized geometries were ascertained through the harmonic vibrational frequency analysis. The basis set superposition error (BSSE) corrected interaction energies were obtained using the 6-311G(d,p) basis set at the same theoretical level. The computed BSSE in the gas phase was used to correct interaction energy in the bulk water solution. Computed and experimental results regarding the ability of considered surfaces in adsorbing the insensitive munitions compounds are discussed. Copyright © 2017. Published by Elsevier B.V.

Coarse-grained modeling of proline rich protein 1 (PRP-1) in bulk solution and adsorbed to a negatively charged surface.

PubMed

Skepö, Marie; Linse, Per; Arnebrant, Thomas

2006-06-22

Structural properties of the acidic proline rich protein PRP-1 of salivary origin in bulk solution and adsorbed onto a negatively charged surface have been studied by Monte Carlo simulations. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. In addition to PRP-1, some mutants were considered to assess the role of the interactions in the systems. Contrary to polyelectrolytes, the protein has a compact structure in salt-free bulk solutions, whereas at high salt concentration the protein becomes more extended. The protein adsorbs to a negatively charged surface, although its net charge is negative. The adsorbed protein displays an extended structure, which becomes more compact upon addition of salt. Hence, the conformational response upon salt addition in the adsorbed state is the opposite as compared to that in bulk solution. The conformational behavior of PRP-1 in bulk solution and at charged surfaces as well as its propensity to adsorb to surfaces with the same net charge are rationalized by the block polyampholytic character of the protein. The presence of a triad of positively charged amino acids in the C-terminal was found to be important for the adsorption of the protein.

Anomalously enhanced hydration of aqueous electrolyte solution in hydrophobic carbon nanotubes to maintain stability.

PubMed

Ohba, Tomonori

2014-02-24

An understanding of the structure and behavior of electrolyte solutions in nanoenvironements is crucial not only for a wide variety of applications, but also for the development of physical, chemical, and biological processes. We demonstrate the structure and stability of electrolyte in carbon nanotubes using hybrid reverse Monte Carlo simulations of X-ray diffraction patterns. Hydrogen bonds between water are adequately formed in carbon nanotubes, although some hydrogen bonds are restricted by the interfaces of carbon nanotubes. The hydrogen bonding network of water in electrolyte in the carbon nanotubes is further weakened. On the other hand, formation of the ion hydration shell is significantly enhanced in the electrolyte in the carbon nanotubes in comparison to ion hydration in bulk electrolyte. The significant hydrogen bond and hydration shell formation are a result of gaining stability in the hydrophobic nanoenvironment. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel system for water soluble protein encapsulation with high efficiency: "micelles enhanced" polyelectrolyte capsules.

PubMed

Li, Xiaodong; Li, Xiaohui; Zhang, Jianxiang; Zhao, Shifang; Shen, Jiacong

2008-06-01

Novel "micelles enhanced" polyelectrolyte (PE) capsules based on functional templates of hybrid calcium carbonate were fabricated. Evidences suggested that the structure of capsule wall was different from that of conventional PE capsules, and the wall permeability of these PE capsules changed significantly. Lysozyme, a positively charged protein in neutral solution, was studied as a model protein to be encapsulated into the "micelles enhanced" PE capsules. Confocal laser scanning microscope was used to observe the entrapping process in real time, while UV-Vis spectroscope and scanning force microscope measurements suggested the high efficiency of encapsulation. In addition, the fluorescence recovery after photobleaching technique was employed to determine the existence form of deposited molecules. Further studies showed even negatively charged water-soluble peptides or proteins can be encapsulated into these hybrid capsules by modulating the pH value in bulk solution under its isoelectronic point as well. Copyright 2007 Wiley Periodicals, Inc.

The geometry of protein hydration

NASA Astrophysics Data System (ADS)

Persson, Filip; Söderhjelm, Pär; Halle, Bertil

2018-06-01

Based on molecular dynamics simulations of four globular proteins in dilute aqueous solution, with three different water models, we examine several, essentially geometrical, aspects of the protein-water interface that remain controversial or incompletely understood. First, we compare different hydration shell definitions, based on spatial or topological proximity criteria. We find that the best method for constructing monolayer shells with nearly complete coverage is to use a 5 Å water-carbon cutoff and a 4 Å water-water cutoff. Using this method, we determine a mean interfacial water area of 11.1 Å2 which appears to be a universal property of the protein-water interface. We then analyze the local coordination and packing density of water molecules in the hydration shells and in subsets of the first shell. The mean polar water coordination number in the first shell remains within 1% of the bulk-water value, and it is 5% lower in the nonpolar part of the first shell. The local packing density is obtained from additively weighted Voronoi tessellation, arguably the most physically realistic method for allocating space between protein and water. We find that water in all parts of the first hydration shell, including the nonpolar part, is more densely packed than in the bulk, with a shell-averaged density excess of 6% for all four proteins. We suggest reasons why this value differs from previous experimental and computational results, emphasizing the importance of a realistic placement of the protein-water dividing surface and the distinction between spatial correlation and packing density. The protein-induced perturbation of water coordination and packing density is found to be short-ranged, with an exponential decay "length" of 0.6 shells. We also compute the protein partial volume, analyze its decomposition, and argue against the relevance of electrostriction.

Electronic desalting for controlling the ionic environment in droplet-based biosensing platforms

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

Swaminathan, Vikhram Vilasur; Dak, Piyush; Alam, Muhammad A., E-mail: rbashir@illinois.edu, E-mail: alam@purdue.edu

2015-02-02

The ability to control the ionic environment in saline waters and aqueous electrolytes is useful for desalination as well as electronic biosensing. We demonstrate a method of electronic desalting at micro-scale through on-chip micro electrodes. We show that, while desalting is limited in bulk solutions with unlimited availability of salts, significant desalting of ≥1 mM solutions can be achieved in sub-nanoliter volume droplets with diameters of ∼250 μm. Within these droplets, by using platinum-black microelectrodes and electrochemical surface treatments, we can enhance the electrode surface area to achieve >99% and 41% salt removal in 1 mM and 10 mM salt concentrations, respectively. Through self-consistentmore » simulations and experimental measurements, we demonstrate that conventional double-layer theory over-predicts the desalting capacity and, hence, cannot be used to model systems that are mass limited or undergoing significant salt removal from the bulk. Our results will provide a better understanding of capacitive desalination, as well as a method for salt manipulation in high-throughput droplet-based microfluidic sensing platforms.« less

Electronic desalting for controlling the ionic environment in droplet-based biosensing platforms

NASA Astrophysics Data System (ADS)

Swaminathan, Vikhram Vilasur; Dak, Piyush; Reddy, Bobby; Salm, Eric; Duarte-Guevara, Carlos; Zhong, Yu; Fischer, Andrew; Liu, Yi-Shao; Alam, Muhammad A.; Bashir, Rashid

2015-02-01

The ability to control the ionic environment in saline waters and aqueous electrolytes is useful for desalination as well as electronic biosensing. We demonstrate a method of electronic desalting at micro-scale through on-chip micro electrodes. We show that, while desalting is limited in bulk solutions with unlimited availability of salts, significant desalting of ≥1 mM solutions can be achieved in sub-nanoliter volume droplets with diameters of ˜250 μm. Within these droplets, by using platinum-black microelectrodes and electrochemical surface treatments, we can enhance the electrode surface area to achieve >99% and 41% salt removal in 1 mM and 10 mM salt concentrations, respectively. Through self-consistent simulations and experimental measurements, we demonstrate that conventional double-layer theory over-predicts the desalting capacity and, hence, cannot be used to model systems that are mass limited or undergoing significant salt removal from the bulk. Our results will provide a better understanding of capacitive desalination, as well as a method for salt manipulation in high-throughput droplet-based microfluidic sensing platforms.

Final Report: “Energetics of Nanomaterials”

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

Woodfield, Brian F.; navrotsky, alexandra; Ross, Nancy

2016-08-30

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less

Final Report: "Energetics of Nanomaterials

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

Navrotsky, Alexandra; Ross, Nancy; Woodfield, Brian

2015-02-14

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less

Aqueous TMAO solutions as seen by theoretical THz spectroscopy: hydrophilic versus hydrophobic water.

PubMed

Imoto, Sho; Forbert, Harald; Marx, Dominik

2018-02-28

Solvation of trimethylamine-N-oxide (TMAO) by water is of great fundamental interest because this small molecule has both strongly hydrophilic and large hydrophobic groups at its opposite ends and, furthermore, stabilizes proteins against temperature and pressure denaturation. Since hydrophilic and hydrophobic groups affect the structural dynamics of the respective solvation water molecules in vastly different ways, we dissect their distinct influences on the THz spectrum of TMAO(aq) by using ab initio molecular dynamics simulations. In particular, we demonstrate that exclusively electronic polarization and charge transfer effects, being absent in the usual fixed-charge biomolecular force fields, are responsible for the significant enhancement of the effective molecular dipole moment of hydrophilic solvation water. This, in turn, leads to pronounced solute-solvent couplings and thus to specific THz modes that involve well-defined H-bond bending and stretching motion being characteristic to hydrophilic solvation. The THz response of individual H-bonded pairs of water molecules involving hydrophobic solvation water, in stark contrast, is nearly indistinguishable from such pairs in bulk water. Transcending the specific case, THz spectroscopy is suggested to be an ideal experimental approach to unravel the controversial piezolytic properties of TMAO including its counteracting effect on pressure-induced denaturation of proteins.

Alkaline hydrolysis of ethylene phosphate: an ab initio study by supermolecule model and polarizable continuum approach.

PubMed

Xia, Futing; Zhu, Hua

2011-09-01

The alkaline hydrolysis reaction of ethylene phosphate (EP) has been investigated using a supermolecule model, in which several explicit water molecules are included. The structures and single-point energies for all of the stationary points are calculated in the gas phase and in solution at the B3LYP/6-31++G(df,p) and MP2/6-311++G(df,2p) levels. The effect of water bulk solvent is introduced by the polarizable continuum model (PCM). Water attack and hydroxide attack pathways are taken into account for the alkaline hydrolysis of EP. An associative mechanism is observed for both of the two pathways with a kinetically insignificant intermediate. The water attack pathway involves a water molecule attacking and a proton transfer from the attacking water to the hydroxide in the first step, followed by an endocyclic bond cleavage to the leaving group. While in the first step of the hydroxide attack pathway the nucleophile is the hydroxide anion. The calculated barriers in aqueous solution for the water attack and hydroxide attack pathways are all about 22 kcal/mol. The excellent agreement between the calculated and observed values demonstrates that both of the two pathways are possible for the alkaline hydrolysis of EP. Copyright © 2011 Wiley Periodicals, Inc.

Solvation effect on isomer stability and electronic structures of protonated serotonin

NASA Astrophysics Data System (ADS)

Omidyan, Reza; Amanollahi, Zohreh; Azimi, Gholamhassan

2017-07-01

Microsolvation effect on geometry and transition energies of protonated serotonin has been investigated by MP2 and CC2 quantum chemical methods. Also, conductor-like screening model, implemented recently in the MP2 and ADC(2) methods, was examined to address the bulk water environment's effect on the isomer stability and electronic transition energies of protonated serotonin. It has been predicted that the dipole moment of gas phase isomers plays the main role on the isomer stabilization in water solution and electronic transition shifts. Also, both red- and blue-shift effects have been predicted to take place on electronic transition energies, upon hydration.

Soil mineralogy and chemistry on Mars - Possible clues from salts and clays in SNC meteorites

NASA Technical Reports Server (NTRS)

Gooding, James L.

1992-01-01

If the shergottite, nakhlite, and chassignite (SNC) meteorites' parent planet is Mars, then the aqueous precipitates found in them imply that oxidizing, water-based solutions may have been chemically active on that planet over the past 200-1300 million yrs. It is suggested that the mixture of aqueous precipitates found in the SNCs furnish a self-consistent model for the bulk elemental composition of surface sediments at the Viking Lander sites. Further mineralogical and stable-isotope studies of the secondary minerals may establish the limits for biological activity over the last 1300 million years of Mars' water-based chemistry.

Methane hydrate formation and decomposition: structural studies via neutron diffraction and empirical potential structure refinement.

PubMed

Thompson, Helen; Soper, Alan K; Buchanan, Piers; Aldiwan, Nawaf; Creek, Jefferson L; Koh, Carolyn A

2006-04-28

Neutron diffraction studies with hydrogen/deuterium isotope substitution measurements are performed to investigate the water structure at the early, medium, and late periods of methane clathrate hydrate formation and decomposition. These measurements are coupled with simultaneous gas consumption measurements to track the formation of methane hydrate from a gas/water mixture, and then the complete decomposition of hydrate. Empirical potential structure refinement computer simulations are used to analyze the neutron diffraction data and extract from the data the water structure in the bulk methane hydrate solution. The results highlight the significant changes in the water structure of the remaining liquid at various stages of hydrate formation and decomposition, and give further insight into the way in which hydrates form. The results also have important implications on the memory effect, suggesting that the water structure in the presence of hydrate crystallites is significantly different at equivalent stages of forming compared to decomposing. These results are in sharp contrast to the previously reported cases when all remaining hydrate crystallites are absent from the solution. For these systems there is no detectable change in the water structure or the methane hydration shell before hydrate formation and after decomposition. Based on the new results presented in this paper, it is clear that the local water structure is affected by the presence of hydrate crystallites, which may in turn be responsible for the "history" or "memory" effect where the production of hydrate from a solution of formed and then subsequently melted hydrate is reportedly much quicker than producing hydrate from a fresh water/gas mixture.

Atmospheric photochemistry at a fatty acid-coated air-water interface

NASA Astrophysics Data System (ADS)

Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D. James; George, Christian

2016-08-01

Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.

46 CFR 153.1065 - Sodium chlorate solutions.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 46 Shipping 5 2013-10-01 2013-10-01 false Sodium chlorate solutions. 153.1065 Section 153.1065 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Special Cargo...

46 CFR 153.1065 - Sodium chlorate solutions.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 46 Shipping 5 2014-10-01 2014-10-01 false Sodium chlorate solutions. 153.1065 Section 153.1065 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Special Cargo...

Microdroplets Accelerate Ring Opening of Epoxides

NASA Astrophysics Data System (ADS)

Lai, Yin-Hung; Sathyamoorthi, Shyam; Bain, Ryan M.; Zare, Richard N.

2018-05-01

The nucleophilic opening of an epoxide is a classic organic reaction that has widespread utility in both academic and industrial applications. We have studied the reaction of limonene oxide with morpholine to form 1-methyl-2-morpholino-4-(prop-1-en-2-yl) cyclohexan-1-ol in bulk solution and in electrosprayed microdroplets with a 1:1 v/ v water/methanol solvent system. We find that even after 90 min at room temperature, there is no product detected by nuclear magnetic resonance spectroscopy in bulk solution whereas in room-temperature microdroplets (2-3 μm in diameter), the yield is already 0.5% in a flight time of 1 ms as observed by mass spectrometry. This constitutes a rate acceleration of 105 in the microdroplet environment, if we assume that as much as 5% of product is formed in bulk after 90 min of reaction time. We examine how the reaction rate depends on droplet size, solvent composition, sheath gas pressure, and applied voltage. These factors profoundly influence the extent of reaction. This dramatic acceleration is not limited to just one system. We have also found that the nucleophilic opening of cis-stilbene oxide by morpholine is similarly accelerated. Such large acceleration factors in reaction rates suggest the use of microdroplets for ring opening of epoxides in other systems, which may have practical significance if such a procedure could be scaled. [Figure not available: see fulltext.

Mixed system of Eudragit s-100 with a designed amphipathic peptide: control of interfacial elasticity by solution composition.

PubMed

Dexter, Annette F; Malcolm, Andrew S; Zeng, Biyun; Kennedy, Debora; Middelberg, Anton P J

2008-04-01

We report an interfacially active system based on an informational peptide surfactant mixed with an oppositely charged polyelectrolyte. The 21-residue cationic peptide, AM1, has previously been shown to respond reversibly to pH and metal ions at fluid interfaces, forming elastic films that can be rapidly switched to collapse foams or emulsions on demand. Here we report the reversible association of AM1 with the methacrylate-based anionic polymer Eudragit S-100. The strength of the association, in bulk aqueous solution, is modulated by added metal ions and by ionic strength. Addition of zinc ions to the peptide-polymer system promotes complex formation and phase separation, while addition of a chelating agent reverses the association. The addition of salt weakens peptide-polymer interactions in the presence or absence of zinc. At the air-water interface, Eudragit S-100 forms an elastic mixed film with AM1 in the absence of metal, under conditions where the peptide alone does not show interfacial elasticity. When zinc is present, the elasticity of the mixed film is increased, but the rate of interfacial adsorption slows due to formation of peptide-polymer complexes in bulk solution. An understanding of these interactions can be used to identify favorable foam-forming conditions in the mixed system.

Relationship between Solvation Thermodynamics from IST and DFT Perspectives.

PubMed

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

2017-04-20

Inhomogeneous solvation theory (IST) and classical density functional theory (DFT) each provide a framework for relating distribution functions of solutions to their thermodynamic properties. As reviewed in this work, both IST and DFT can be formulated in a way that use two "end point" simulations, one of the pure solvent and the other of the solution, to determine the solute chemical potential and other thermodynamic properties of the solution and of subvolumes in regions local to the solute containing hydrating waters. In contrast to IST, where expressions for the excess energy and entropy of solution are the object of analysis, in the DFT end point formulation of the problem, the solute-solvent potential of mean force (PMF) plays a central role. The indirect part of the PMF corresponds to the lowest order (1-body) truncation of the IST expression. Because the PMF is a free energy function, powerful numerical methods can be used to estimate it. We show that the DFT expressions for the solute excess chemical potential can be written in a form which is local, involving integrals only over regions proximate to the solute. The DFT end point route to estimating solvation free energies provides an alternative path to that of IST for analyzing solvation effects on molecular recognition and conformational changes in solution, which can lead to new insights. In order to illustrate the kind of information that is contained in the solute-solvent PMF, we have carried out simulations of β-cyclodextrin in water. This solute is a well studied "host" molecule to which "guest" molecules bind; host-guest systems serve as models for molecular recognition. We illustrate the range of values the direct and indirect parts of the solute-solvent PMF can have as a water molecule is brought to the interface of β-cyclodextrin from the bulk; we discuss the "competition" between these two terms, and the role it plays in molecular recognition.

Effect of confinement in nano-porous materials on the solubility of a supercritical gas

NASA Astrophysics Data System (ADS)

Hu, Yaofeng; Huang, Liangliang; Zhao, Shuangliang; Liu, Honglai; Gubbins, Keith E.

2016-11-01

By combining Gibbs Ensemble Monte Carlo simulations and density functional theory, we investigate the influence of confinement in a slit-shaped carbon pore on the solubility of a supercritical solute gas in a liquid solvent. In the cases studied here, competing adsorption of the solvent and solute determines whether the solubility is enhanced or suppressed for larger pores. We find that the solubility in the confined system is strongly dependent on pore width, and that molecular packing effects are important for small pore widths. In addition, the solubility decreases on increase in the temperature, as for the bulk mixture, but the rate of decrease is greater in the pore due to a decrease in the partial molar enthalpy of the solute in the pore; this effect becomes greater as pore width is decreased. The solubility is increased on increasing the bulk pressure of the gas in equilibrium with the pore, and obeys Henry's law at lower pressures. However, the Henry constant differs significantly from that for the bulk mixture, and the range of pressure over which Henry's law applies is reduced relative to that for the bulk mixture. The latter observation indicates that solute-solute interactions become more important in the pore than for the bulk at a given bulk pressure. Finally, we note that different authors use different definitions of the solubility in pores, leading to some confusion over the reported phenomenon of 'oversolubility'. We recommend that solubility be defined as the overall mole fraction of solute in the pores, since it takes into account the increase in density of the solvent in the pores, and avoids ambiguity in the definition of the pore volume.

A survey of biofilms on wastewater aeration diffusers suggests bacterial community composition and function vary by substrate type and time.

PubMed

Noble, Peter A; Park, Hee-Deung; Olson, Betty H; Asvapathanagul, Pitiporn; Hunter, M Colby; Garrido-Baserba, Manel; Lee, Sang-Hoon; Rosso, Diego

2016-07-01

Aeration diffusers in wastewater treatment plants generate air bubbles that promote mixing, distribution of dissolved oxygen, and microbial processing of dissolved and suspended matter in bulk solution. Biofouling of diffusers represents a significant problem to wastewater treatment plants because biofilms decrease oxygen transfer efficiency and increase backpressure on the blower. To better understand biofouling, we conducted a pilot study to survey the bacterial community composition and function of biofilms on different diffuser substrates and compare them to those in the bulk solution. DNA was extracted from the surface of ethylene-propylene-diene monomer (EPDM), polyurethane, and silicone diffusers operated for 15 months in a municipal treatment plant and sampled at 3 and 9 months. The bacterial community composition and function of the biofilms and bulk solution were determined by amplifying the 16S rRNA genes and pyrosequencing the amplicons and raw metagenomic DNA. The ordination plots and dendrograms of the 16S rRNA and functional genes showed that while the bacterial community composition and function of the bulk solution was independent of sampling time, the composition and function of the biofilms differed by diffuser type and testing time. For the EPDM and silicone diffusers, the biofilm communities were more similar in composition to the bulk solution at 3 months than 9 months. In contrast, the bacteria on the polyurethane diffusers were more dissimilar to the bulk solution at 3 months than 9 months. Taken together, the survey showed that the community composition and function of bacterial biofilms depend on the diffuser substrate and testing time, which warrants further elucidation.

Effect of different bulking agents on water variation and thermal balance and their respective contribution to bio-generated heat during long-term storage sludge biodrying process.

PubMed

Liu, Tiantian; Cui, Chongwei; He, Junguo; Tang, Jian

2018-04-17

Biodrying was first used for the post-treatment of long-term storage sludge with vinasse as bulking agents. The effect of different bulking agents on water and heat variation and their respective contributions to bio-generated heat during storage sludge biodrying were investigated. Three different bulking agents (beer lees and distillers grains, with conventional straw used for comparison) were mixed with storage sludge for biodrying for an 18-day period. The results revealed the treatment with beer lees as bulking agent achieved the best performance with the highest water removal capacity (658 g kg -1 initial water). The extent of organic degradation in the mixture was related to the degradation ability of the bulking agents. The degradation of C- and H-containing materials (e.g., carboxylic acid) accounted for volatile solids (VS) loss. Water and thermal analyses showed that evaporation was the main way of water loss (accounting for 90%), while evaporation heat was the main component of heat consumption (accounting for 56.67-60.62%).The biodegradation of bulking agents contributed a high proportion of the bio-generated heat consumed by water evaporation (82.35-86.67%).

Solution influence on biomolecular equilibria - Nucleic acid base associations

NASA Technical Reports Server (NTRS)

Pohorille, A.; Pratt, L. R.; Burt, S. K.; Macelroy, R. D.

1984-01-01

Various attempts to construct an understanding of the influence of solution environment on biomolecular equilibria at the molecular level using computer simulation are discussed. First, the application of the formal statistical thermodynamic program for investigating biomolecular equilibria in solution is presented, addressing modeling and conceptual simplications such as perturbative methods, long-range interaction approximations, surface thermodynamics, and hydration shell. Then, Monte Carlo calculations on the associations of nucleic acid bases in both polar and nonpolar solvents such as water and carbon tetrachloride are carried out. The solvent contribution to the enthalpy of base association is positive (destabilizing) in both polar and nonpolar solvents while negative enthalpies for stacked complexes are obtained only when the solute-solute in vacuo energy is added to the total energy. The release upon association of solvent molecules from the first hydration layer around a solute to the bulk is accompanied by an increase in solute-solvent energy and decrease in solvent-solvent energy. The techniques presented are expectd to displace less molecular and more heuristic modeling of biomolecular equilibria in solution.

Reprint of "How do components of real cloud water affect aqueous pyruvate oxidation?"

NASA Astrophysics Data System (ADS)

Boris, Alexandra J.; Desyaterik, Yury; Collett, Jeffrey L.

2015-01-01

Chemical oxidation of dissolved volatile or semi-volatile organic compounds within fog and cloud droplets in the atmosphere could be a major pathway for secondary organic aerosol (SOA) formation. This proposed pathway consists of: (1) dissolution of organic chemicals from the gas phase into a droplet; (2) reaction with an aqueous phase oxidant to yield low volatility products; and (3) formation of particle phase organic matter as the droplet evaporates. The common approach to simulating aqueous SOA (aqSOA) reactions is photo-oxidation of laboratory standards in pure water. Reactions leading to aqSOA formation should be studied within real cloud and fog water to determine whether additional competing processes might alter apparent rates of reaction as indicated by rates of reactant loss or product formation. To evaluate and identify the origin of any cloud water matrix effects on one example of observed aqSOA production, pyruvate oxidation experiments simulating aqSOA formation were monitored within pure water, real cloud water samples, and an aqueous solution of inorganic salts. Two analysis methods were used: online electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR-ToF-MS), and offline anion exchange chromatography (IC) with quantitative conductivity and qualitative ESI-HR-ToF-MS detection. The apparent rate of oxidation of pyruvate was slowed in cloud water matrices: overall measured degradation rates of pyruvate were lower than in pure water. This can be at least partially accounted for by the observed formation of pyruvate from reactions of other cloud water components. Organic constituents of cloud water also compete for oxidants and/or UV light, contributing to the observed slowed degradation rates of pyruvate. The oxidation of pyruvate was not significantly affected by the presence of inorganic anions (nitrate and sulfate) at cloud-relevant concentrations. Future bulk studies of aqSOA formation reactions using simplified simulated cloud solutions and model estimates of generated aqSOA mass should take into account possible generation of, or competition for, oxidant molecules by organic components found in the complex matrices typically associated with real atmospheric water droplets. Additionally, it is likely that some components of real atmospheric waters have not yet been identified as aqSOA precursors, but could be distinguished through further simplified bulk oxidations of known atmospheric water components.

Influence of growth temperature on bulk and surface defects in hybrid lead halide perovskite films

NASA Astrophysics Data System (ADS)

Peng, Weina; Anand, Benoy; Liu, Lihong; Sampat, Siddharth; Bearden, Brandon E.; Malko, Anton V.; Chabal, Yves J.

2016-01-01

The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (~1017 cm-3) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites.The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (~1017 cm-3) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06222e

PREFACE: Water at interfaces Water at interfaces

NASA Astrophysics Data System (ADS)

Gallo, P.; Rovere, M.

2010-07-01

This special issue is devoted to illustrating important aspects and significant results in the field of modeling and simulation of water at interfaces with solutes or with confining substrates, focusing on a range of temperatures from ambient to supercooled. Understanding the behavior of water, in contact with different substrates and/or in solutions, is of pivotal importance for a wide range of applications in physics, chemistry and biochemistry. Simulations of confined and/or interfacial water are also relevant for testing how different its behavior is with respect to bulk water. Simulations and modeling in this field are of particular importance when studying supercooled regions where water shows anomalous properties. These considerations motivated the organization of a workshop at CECAM in the summer of 2009 which aimed to bring together scientists working with computer simulations on the properties of water in various environments with different methodologies. In this special issue, we collected a variety of interesting contributions from some of the speakers of the workshop. We have roughly classified the contributions into four groups. The papers of the first group address the properties of interfacial and confined water upon supercooling in an effort to understand the relation with anomalous behavior of supercooled bulk water. The second group deals with the specific problem of solvation. The next group deals with water in different environments by considering problems of great importance in technological and biological applications. Finally, the last group deals with quantum mechanical calculations related to the role of water in chemical processes. The first group of papers is introduced by the general paper of Stanley et al. The authors discuss recent progress in understanding the anomalies of water in bulk, nanoconfined, and biological environments. They present evidence that liquid water may display 'polymorphism', a property that can be present in other liquids also. Recent evidence of a close relation between thermodynamical properties and dynamical behaviour of water are also discussed. Gallo et al present the results of a computer simulation of water confined in a cylindrical pore of MCM-41 silica material. The mobile portion of the confined water shows a fragile to strong dynamic transition similar to the bulk. In the bound water, an anomalous diffusion connected to the residence time distribution is found. Franzese et al report calculations on lattice models adapted to describe general properties of water in contact with protein surfaces. The results of Monte Carlo and mean field calculations show the presence of two-dynamical crossovers. Corradini et al investigate the supercooled region of ionic aqueous solutions in order to study the effect of ions on the limit of mechanical stability, the lines of maximum density and the liquid-liquid critical point for different ionic concentrations. The paper by Vallauri et al deals with the dynamical behavior of water close to the liquid-liquid transition by considering the velocity correlation functions calculated in three supercooled states. Suffritti et al study water adsorbed in zeolites with a new empirical potential, structural and dynamical properties are studied in the supercooled region. The second group starts with a paper on the problem of solvation by Lynden-Bell. The author shows how the properties of water and, in particular, solvation properties are modified by changes in the site-site interaction potential of water. Henchman et al derive equations for different thermodynamical quantities like partial enthalpy and partial entropy for dilute solutions of noble gases. The third group starts with Buldyrev et al who study the swelling of bead-on-a-string polymers in Jagla water-like particles, finding similarities with respect to cold denaturation of protein in water. Pellenq et al consider water confined in pores of different materials with different size scales. Silicalite and tobermorite, a layered calcio-silicate model of cement and Vycor are analyzed. Gordillo and Martí consider structural and dynamical properties of water confined or close to carbon nanotubes or inside a slit pore of a single graphene sheet. Jedlovszky et al introduce a new method to determine the molecules located right at the boundary of two phases in a computer simulation. The new method is applied to the analysis of the interface of water with different apolar phases. Melchionna et al consider phenomena related to water in contact with thermophilic protein interfaces. In particular, they discuss the role of water in stabilizing these proteins. Rotenberg et al report results on the structure and dynamics of water at a clay surface. They analyze, in particular, the influence on the H-bond network of the surface oxygens and ions and investigate the surface H-bond formation and dissociation dynamics. Smirnov and Bougeard present examples of the spatial organization of molecules and of the short- and long-time dynamical behaviour of water confined in the pores of crystalline aluminosilicates, such as zeolites and clays, and in nanostructured materials. The last group opens with Sulpizi and Sprik who present density functional calculations of the dissociation constant of liquid water, implemented with a proton insertion/removal method. Jung and Marcus consider, more specifically, the properties of water in organic catalysis and discuss theoretical models and results obtained with quantum mechanical calculations. As organizers of the CECAM workshop 'Modeling and Simulation of Water at Interfaces from Ambient to Supercooled Conditions' we would like to thank CECAM, ESF-Simbioma, Wanda Andreoni, Emilie Bernard and Jordi Brusa. As guest editors of this special issue we would like to thank Gerhard Kahl and Philip Semple.

Spatial Variability of Soil Physical Properties Obtained with Laboratory Methods and Their Relation to Field Electrical Resistivity Measurements

NASA Astrophysics Data System (ADS)

Dathe, A.; Nemes, A.; Bloem, E.; Patterson, M.; Gimenez, D.; Angyal, A.; Koestel, J. K.; Jarvis, N.

2017-12-01

Soil spatial heterogeneity plays a critical role for describing water and solute transport processes in the unsaturated zone. Although we have a sound understanding of the physical properties underlying this heterogeneity (like macropores causing preferential water flow), their quantification in a spatial context is still a challenge. To improve existing knowledge and modelling approaches we established a field experiment on an agriculturally used silty clay loam (Stagnosol) in SE Norway. Centimeter to decimeter scale heterogeneities were investigated in the field using electrical resistivity tomography (ERT) in a quasi-3D and a real 3D approach. More than 100 undisturbed soil samples were taken in the 2x1x1 m3plot investigated with 3D ERT to determine soil water retention, saturated and unsaturated hydraulic conductivities and bulk density in the laboratory. A subset of these samples was scanned at the computer tomography (CT) facility at the Swedish University of Agricultural Sciences in Uppsala, Sweden, with special emphasis on characterizing macroporosity. Results show that the ERT measurements captured the spatial distribution of bulk densities and reflected soil water contents. However, ERT could not resolve the large variation observed in saturated hydraulic conductivities from the soil samples. Saturated hydraulic conductivity was clearly related to the macroporosity visible in the CT scans obtained from the respective soil cores. Hydraulic conductivities close to saturation mainly changed with depths in the soil profile and therefore with bulk density. In conclusion, to quantify the spatial heterogeneity of saturated hydraulic conductivities scanning methods with a resolution smaller than the size of macropores have to be used. This is feasible only when the information obtained from for example CT scans of soil cores would be upscaled in a meaningful way.

Detection of aniline oligomers on polyaniline-gold interface using resonance Raman scattering.

PubMed

Trchová, Miroslava; Morávková, Zuzana; Dybal, Jiří; Stejskal, Jaroslav

2014-01-22

In situ deposited conducting polyaniline films prepared by the oxidation of aniline with ammonium peroxydisulfate in aqueous media of various acidities on gold and silicon supports were characterized by Raman spectroscopy. Enhanced Raman bands were found in the spectra of polyaniline films produced in the solutions of weak acids or in water on gold surface. These bands were weak for the films prepared in solutions of a strong acid on a gold support. The same bands are present in the Raman spectra of the reaction intermediates deposited during aniline oxidation in water or aqueous solutions of weak or strong acids on silicon removed from the reaction mixture at the beginning of the reaction. Such films are formed by aniline oligomers adsorbed on the surface. They were detected on the polyaniline-gold interface using resonance Raman scattering on the final films deposited on gold. The surface resonance Raman spectroscopy of the monolayer of oligomers found in the bulk polyaniline film makes this method advantageous in surface science, with many applications in electrochemistry, catalysis, and biophysical, polymer, or analytical chemistry.

Probing pH difference between micellar solution and nanoscale water within common black film by fluorescent dye

NASA Astrophysics Data System (ADS)

Fu, Jingni; Zhang, Luning

2018-03-01

The protonation/deprotonation equilibrium of a fluorescent pH probe (carboxy-seminaphthorhodafluor-1, SNARF-1) within the nanoscale water layer confined in common black films (CBFs) has been studied. We find that SNARF-1 molecules feel a more acidic environment in CBFs than when they are in the bulk micellar solution, using the base/acid peak area ratio of the dye to indicate its microenvironment pH. Three surfactants are used to study the dependence of the pH drop versus charge: cationic (cetyltrimethylammonium bromide, CTAB), anionic (sodium dodecylsulphate, SDS) and nonionic (Triton X-100) species. The decrease of CBFs pH versus the pH of the micellar solution is the following: ΔpH ≈ 1.5 for CTAB (pH: 7.0-9.0), ΔpH ≈ 0.8 for SDS, and ΔpH ≈ 0.4 for Triton X-100. With the addition of electrolyte in CBFs, we observe large decrease the amplitude of the pH anomaly, thus suggesting an electrostatic origin of the pH change at nanoscale environment.

Method for exfoliation of hexagonal boron nitride

NASA Technical Reports Server (NTRS)

Lin, Yi (Inventor); Connell, John W. (Inventor)

2012-01-01

A new method is disclosed for the exfoliation of hexagonal boron nitride into mono- and few-layered nanosheets (or nanoplatelets, nanomesh, nanoribbons). The method does not necessarily require high temperature or vacuum, but uses commercially available h-BN powders (or those derived from these materials, bulk crystals) and only requires wet chemical processing. The method is facile, cost efficient, and scalable. The resultant exfoliated h-BN is dispersible in an organic solvent or water thus amenable for solution processing for unique microelectronic or composite applications.

Time- and angle-resolved photoemission spectroscopy of hydrated electrons near a liquid water surface.

PubMed

Yamamoto, Yo-ichi; Suzuki, Yoshi-Ichi; Tomasello, Gaia; Horio, Takuya; Karashima, Shutaro; Mitríc, Roland; Suzuki, Toshinori

2014-05-09

We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1,4-diazabicyclo[2,2,2]octane and I- in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed.

Change in the Nd isotopic composition of the bottom water and detrital sediments on the Bering Slope over the last 500 kyrs with implications for the formation of the North Pacific Intermediate Water

NASA Astrophysics Data System (ADS)

Jang, K.; Huh, Y.; Han, Y.

2015-12-01

The Bering Sea is a potential location for the formation of the North Pacific Intermediate/Deep Water (NPIW/NPDW) and may play an important role in the global heat distribution. We reconstructed the neodymium isotopic ratio (ɛNd) of authigenic Fe-Mn oxide coatings and detrital sediments on the Bering Slope (IODP Expedition 323 site U1345; water depth 1008 m) over the last 500 kyrs. The ɛNd is a quasi-conservative water mass tracer. We compared three different leaching techniques to assure that authigenic signals are captured without contamination from terrigenous sources: (1) leaching (3 hours) with 0.02 M hydroxylamine hydrochloride (HH) in 25% buffered acetic acid after decarbonation; sediment/solution (v/v) > 10, (2) leaching (1 hour) with 0.02 M HH in 25% buffered acetic acid without decarbonation; sediment/solution ~ 1, and (3) leaching (1 hour) with 0.005 M HH in 1.5% buffered acetic acid-0.003 M Na-EDTA without decarbonation; sediment/solution > 40. The low Al concentrations and less radiogenic ɛNdvalues indicated that method (2) is the most appropriate leaching process. The average ɛNd of the authigenic fraction over the last 500 kyrs is -3.3 ± 0.9 (1σ, n=38), with large temporal fluctuations. The ɛNd of authigenic and detrital fractions are well correlated (r2 ~ 0.66), suggesting that the bottom water composition in the Bering Sea was governed by terrigenous inflow from surrounding areas. Radiogenic ɛNd peaks (up to -1.9) seem to be influenced by radiogenic water inflow from the the Kamchatka or Aluetian arcs. The high bulk density and low b* values imply higher terrigenous versus biological contribution and enhanced sea ice formation. Subsequent brine formation would have triggered sinking of radiogenic surface water, forming the NPIW. On the other hand, non-radiogenic ɛNd troughs (down to -5.3) are observed at times of low bulk density and high b* values. We presume higher biological productivity which is supported by the high opal content at these intervals (Kanematsu et al., 2013). Sea level rise and boundary exchange with terrigenous sediment derived from N. America is a likely mechanism. This work was supported by the Basic Science Research Program through the NRF funded by Ministry of Science, ICT and Future Planning (No. 2014 0498836)

Characterization of a backbone cleavage product of BMS-196854 (Oncostatin M), a recombinant anti-inflammatory cytokine.

PubMed

Zhao, F; Stein, D J; Paborji, M; Cash, P W; Root, B J; Wei, Z; Knupp, C J

2001-01-01

BMS-196843 (Oncostatin M) is a therapeutic recombinant protein in development. Scale-up process changes led to unexpected instability of the bulk drug substance solution during storage. A product with an apparent higher MW than the parent protein was observed by the size-exclusion chromatography (SEC). This study was aimed to fully characterize the product and to identify a solution to stabilize the protein. SEC, SDS-PAGE, tryptic mapping, and N-terminal sequencing were performed to characterize the unknown product. The effect of pH, temperature, bulk concentration, and immobilized trypsin inhibitor on the degradation rate was studied to elucidate the mechanism and to identify stabilization strategies. Despite the apparent high MW indicated initially by SEC, the unknown was characterized to be a degradation product resulted from a backbone cleavage between residues Arg145-Gly146. The resulting fragments from the backbone cleavage were, however, still linked through an intramolecular disulfide bond. Thus, the final product had a more open structure with an increased hydrodynamic radius compared to the parent protein, which explains the initial SEC results. The site-specific backbone cleavage was suspected to be catalyzed by trypsin-like protease impurities in the bulk solution. The bulk drug substance solution was subsequently treated with immobilized soybean trypsin inhibitor, and the degradation rate was significantly reduced. Furthermore, increasing the solution pH from 5 to 8 led to an increase in the degradation rate, which was consistent with the expected pH dependency of trypsin activity. In addition, the effect of bulk concentration also supported the involvement of protease impurities rather than a spontaneous peptide bond hydrolysis reaction. Trace trypsin-like protease impurities led to an unusual site-specific backbone cleavage of BMS-196854. The proteolytic degradation can be minimized by treating the bulk solution with immobilized soybean trypsin inhibitor and/or controlling the solution pH and storage temperature.

Pressure probe study of the water relations of Phycomyces blakesleeanus sporangiophores

NASA Technical Reports Server (NTRS)

Cosgrove, D. J.; Ortega, J. K.; Shropshire, W. Jr

1987-01-01

The physical characteristics which govern the water relations of the giant-celled sporangiophore of Phycomyces blakesleeanus were measured with the pressure probe technique and with nanoliter osmometry. These properties are important because they govern water uptake associated with cell growth and because they may influence expansion of the sporangiophore wall. Turgor pressure ranged from 1.1 to 6.6 bars (mean = 4.1 bars), and was the same for stage I and stage IV sporangiophores. Sporangiophore osmotic pressure averaged 11.5 bars. From the difference between cell osmotic pressure and turgor pressure, the average water potential of the sporangiophore was calculated to be about -7.4 bars. When sporangiophores were submerged under water, turgor remained nearly constant. We propose that the low cell turgor pressure is due to solutes in the cell wall solution, i.e., between the cuticle and the plasma membrane. Membrane hydraulic conductivity averaged 4.6 x 10(-6) cm s-1 bar-1, and was significantly greater in stage I sporangiophores than in stage IV sporangiophores. Contrary to previous reports, the sporangiophore is separated from the supporting mycelium by septa which prevent bulk volume flow between the two regions. The presence of a wall compartment between the cuticle and the plasma membrane results in anomalous osmosis during pressure clamp measurements. This behavior arises because of changes in solute concentration as water moves into or out of the wall compartment surrounding the sporangiophore. Theoretical analysis shows how the equations governing transient water flow are altered by the characteristics of the cell wall compartment.

Measurement and modification of forces between lecithin bilayers.

PubMed Central

LeNeveu, D M; Rand, R P

1977-01-01

We probe in two different ways the competing attractive and repulsive forces that create lamellar arrays of the phospholipid lecithin when in equilibrium with pure water. The first probe involves the addition of low molecular weight solutes, glucose and sucrose, to a system where the phospholipid is immersed in a large excess of water. Small solutes can enter the aqueous region between bilayers. Their effect is first to increase and then to decrease the separation between bilayers as sugar concentration increases. We interpret this waxing and waning of the lattice spacing in terms of the successive weakening and strengthening of the attractive van der Waals forces originally responsible for creation of a stable lattice. The second probe is an "osmotic stress method," in which very high molecular weight neutral polymer is added to the pure water phase but is unable to enter the multilayers. The polymer competes for water with the lamellar lattice, and thereby compresses it. From the resulting spacing (determined by X-ray diffraction) and the directly measured osmotic pressure, we find a force vs. distance curve for compressing the lattice (or, equivalently, the free energy of transfer to bulk water of water between bilayers. This method reveals a very strong, exponentially varying "hydration force" with a decay distance of about 2 A. PMID:861359

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Kinetics of proton migration in liquid water.

PubMed

Chen, Hanning; Voth, Gregory A; Agmon, Noam

2010-01-14

We have utilized multistate empirical valence bond (MS-EVB3) simulations of protonated liquid water to calculate the relative mean-square displacement (MSD) and the history-independent time correlation function, c(t), of the hydrated proton center of excess charge (CEC) with respect to the water molecule on which it has initially resided. The MSD is nonlinear for the first 15 ps, suggesting that the relative diffusion coefficient increases from a small value, D(0), at short separations to its larger bulk value, D(infinity), at large separations. With the ensuing distance-dependent diffusion coefficient, D(r), the time dependence of both the MSD and c(t) agrees quantitatively with the solution of a diffusion equation for reversible geminate recombination. This suggests that the relative motion of the CEC is not independent from the nearby water molecules, in agreement with theoretical and experimental observations that large water clusters participate in the mechanism of proton mobility.

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.

Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

PubMed

Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

2012-10-11

Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

Microdroplet fusion mass spectrometry: accelerated kinetics of acid-induced chlorophyll demetallation

PubMed Central

Lee, Jae Kyoo; Nam, Hong Gil; Zare, Richard N.

2017-01-01

Kinetics of acid-induced chlorophyll demetallation was recorded in microdroplets by fusing a stream of microdroplets containing 40 μM chlorophyll a or b dissolved in methanol with a stream of aqueous microdroplets containing 35 mM hydrochloric acid (pH = 1·46). The kinetics of the demetallation of chlorophyll in the fused microdroplets (14 ± 6 μm diameter; 84 ± 18 m s−1 velocity) was recorded by controlling the traveling distance of the fused microdroplets between the fusion region and the inlet of a mass spectrometer. The rate of acid-induced chlorophyll demetallation was about 960 ± 120 times faster in the charged microdroplets compared with that reported in bulk solution. If no voltage was applied to the sprayed microdroplets, then the acceleration factor was about 580 ± 90, suggesting that the applied voltage is not a major factor determining the acceleration. Chlorophyll a was more rapidly demetallated than chlorophyll b by a factor of ~26 in bulk solution and ~5 in charged microdroplets. The demetallation kinetics was second order in the H+ concentration, but the acceleration factor of microdroplets compared with bulk solution appeared to be unchanged in going from pH = 1·3 to 7·0. The water:methanol ratio of the fused microdroplets was varied from 7:3 to 3:7 causing an increase in the reaction rate of chlorophyll a demetallation by 20%. This observation demonstrates that the solvent composition, which has different evaporation rates, does not significantly affect the acceleration. We believe that a major portion of the acceleration can be attributed to confinement effects involving surface reactions rather than either to evaporation of solvents or to the introduction of charges to the microdroplets. PMID:29233214

Microdroplet fusion mass spectrometry: accelerated kinetics of acid-induced chlorophyll demetallation.

PubMed

Lee, Jae Kyoo; Nam, Hong Gil; Zare, Richard N

2017-01-01

Kinetics of acid-induced chlorophyll demetallation was recorded in microdroplets by fusing a stream of microdroplets containing 40 µM chlorophyll a or b dissolved in methanol with a stream of aqueous microdroplets containing 35 mM hydrochloric acid (pH = 1·46). The kinetics of the demetallation of chlorophyll in the fused microdroplets (14 ± 6 µm diameter; 84 ± 18 m s-1 velocity) was recorded by controlling the traveling distance of the fused microdroplets between the fusion region and the inlet of a mass spectrometer. The rate of acid-induced chlorophyll demetallation was about 960 ± 120 times faster in the charged microdroplets compared with that reported in bulk solution. If no voltage was applied to the sprayed microdroplets, then the acceleration factor was about 580 ± 90, suggesting that the applied voltage is not a major factor determining the acceleration. Chlorophyll a was more rapidly demetallated than chlorophyll b by a factor of ~26 in bulk solution and ~5 in charged microdroplets. The demetallation kinetics was second order in the H+ concentration, but the acceleration factor of microdroplets compared with bulk solution appeared to be unchanged in going from pH = 1·3 to 7·0. The water:methanol ratio of the fused microdroplets was varied from 7:3 to 3:7 causing an increase in the reaction rate of chlorophyll a demetallation by 20%. This observation demonstrates that the solvent composition, which has different evaporation rates, does not significantly affect the acceleration. We believe that a major portion of the acceleration can be attributed to confinement effects involving surface reactions rather than either to evaporation of solvents or to the introduction of charges to the microdroplets.

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.

Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

NASA Technical Reports Server (NTRS)

Nadarajah, Arunan

1996-01-01

Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

Enhancing the stability of lithium ion Li1+x+yAlxTi2-xSiyP3-yO12 glass - ceramic conductors in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Ioanniti, Marina Maria; Tenhaeff, Wyatt E.

2017-12-01

The stability of NASICON-type conducting glass-ceramic electrolyte, Li1+x+yAlxTi2-xSiyP3-yO12 (Ohara LICGC) has been characterized after prolonged exposure to deionized water and HCl(aq) solutions supported with LiCl. X-ray diffraction shows that the bulk crystallographic structure of the LICGC membranes remains unchanged when exposed to these solutions. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of LICGC membranes immersed in deionized water remains stable over a one month period, while there is a significant increase in resistance when exposed to the acidic solutions. When exposed to pH 4 and 2 solutions for just 24 h, the resistances of the LICGC membrane increase by a factor of 8.5 and 23.5, respectively. EIS coupled with morphological characterization by scanning electron microscopy, shows that this resistance growth is due to the development of a surface layer on the LICGC membrane. However, this substantial increase in resistance can be mitigated by adding LiCl to the HCl solutions. For a pH 4 solution supported with 6.75 M LiCl, the impedance spectrum and surface morphology are qualitatively comparable to pristine, dry LICGC material, suggesting that surface layer formation was suppressed. This was also confirmed via cyclic voltammetry measurements in four-electrode electrochemical cells.

Evaluation of wireless sensor networks (WSNs) for remote wetland monitoring: design and initial results.

PubMed

Watras, Carl J; Morrow, Michael; Morrison, Ken; Scannell, Sean; Yaziciaglu, Steve; Read, Jordan S; Hu, Yu-Hen; Hanson, Paul C; Kratz, Tim

2014-02-01

Here, we describe and evaluate two low-power wireless sensor networks (WSNs) designed to remotely monitor wetland hydrochemical dynamics over time scales ranging from minutes to decades. Each WSN (one student-built and one commercial) has multiple nodes to monitor water level, precipitation, evapotranspiration, temperature, and major solutes at user-defined time intervals. Both WSNs can be configured to report data in near real time via the internet. Based on deployments in two isolated wetlands, we report highly resolved water budgets, transient reversals of flow path, rates of transpiration from peatlands and the dynamics of chromophoric-dissolved organic matter and bulk ionic solutes (specific conductivity)-all on daily or subdaily time scales. Initial results indicate that direct precipitation and evapotranspiration dominate the hydrologic budget of both study wetlands, despite their relatively flat geomorphology and proximity to elevated uplands. Rates of transpiration from peatland sites were typically greater than evaporation from open waters but were more challenging to integrate spatially. Due to the high specific yield of peat, the hydrologic gradient between peatland and open water varied with precipitation events and intervening periods of dry out. The resultant flow path reversals implied that the flux of solutes across the riparian boundary varied over daily time scales. We conclude that WSNs can be deployed in remote wetland-dominated ecosystems at relatively low cost to assess the hydrochemical impacts of weather, climate, and other perturbations.

Dissecting the THz spectrum of liquid water from first principles via correlations in time and space.

PubMed

Heyden, Matthias; Sun, Jian; Funkner, Stefan; Mathias, Gerald; Forbert, Harald; Havenith, Martina; Marx, Dominik

2010-07-06

Solvation of molecules in water is at the heart of a myriad of molecular phenomena and of crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy in the THz frequency domain offers new insights into hydration from small solutes to proteins. Upon introducing spatially-resolved analyses of the absorption cross section by simulations, the sensitivity of THz spectroscopy is traced back to characteristic distance-dependent modulations of absorption intensities for bulk water. The prominent peak at approximately 200 cm(-1) is dominated by first-shell dynamics, whereas a concerted motion involving the second solvation shell contributes most significantly to the absorption at about 80 cm(-1) approximately 2.4 THz. The latter can be understood in terms of an umbrella-like motion of two hydrogen-bonded tetrahedra along the connecting hydrogen bond axis. Thus, a modification of the hydrogen bond network, e.g., due to the presence of a solute, is expected to affect vibrational motion and THz absorption intensity at least on a length scale that corresponds to two layers of solvating water molecules. This result provides a molecular mechanism explaining the experimentally determined sensitivity of absorption changes in the THz domain in terms of distinct, solute-induced dynamical properties in solvation shells of (bio)molecules--even in the absence of well-defined resonances.

Time-domain fiber loop ringdown sensor and sensor network

NASA Astrophysics Data System (ADS)

Kaya, Malik

Optical fibers have been mostly used in fiber optic communications, imaging optics, sensing technology, etc. Fiber optic sensors have gained increasing attention for scientific and structural health monitoring (SHM) applications. In this study, fiber loop ringdown (FLRD) sensors were fabricated for scientific, SHM, and sensor networking applications. FLRD biosensors were fabricated for both bulk refractive index (RI)- and surface RI-based DNA sensing and one type of bacteria sensing. Furthermore, the effect of glucose oxidase (GOD) immobilization at the sensor head on sensor performance was evaluated for both glucose and synthetic urine solutions with glucose concentration between 0.1% and 10%. Detection sensitivities of the glucose sensors were achieved as low as 0.05%. For chemical sensing, heavy water, ranging from 97% to 10%, and several elemental solutions were monitored by using the FLRD chemical sensors. Bulk index-based FLRD sensing showed that trace elements can be detected in deionized water. For physical sensing, water and cracking sensors were fabricated and embedded into concrete. A partially-etched single-mode fiber (SMF) was embedded into a concrete bar for water monitoring while a bare SMF without any treatment was directly embedded into another concrete bar for monitoring cracks. Furthermore, detection sensitivities of water and crack sensors were investigated as 10 ml water and 0.5 mm surface crack width, respectively. Additionally fiber loop ringdown-fiber Bragg grating temperature sensors were developed in the laboratory; two sensor units for water, crack, and temperature sensing were deployed into a concrete cube in a US Department of Energy test bed (Miami, FL). Multi-sensor applications in a real concrete structure were accomplished by testing the six FLRD sensors. As a final stage, a sensor network was assembled by multiplexing two or three FLRD sensors in series and parallel. Additionally, two FLRD sensors were combined in series and parallel by using a 2x1 micro-electromechanical system optical switch to control sensors individually. For both configurations, contributions of each sensor to two or three coupled signals were simulated theoretically. Results show that numerous FLRD sensors can be connected in different configurations, and a sensor network can be built up for multi-function sensing applications.

Solution electrostatic levitator for measuring surface properties and bulk structures of an extremely supersaturated solution drop above metastable zone width limit.

PubMed

Lee, Sooheyong; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Lee, Geun Woo

2017-05-01

We report on the first integrated apparatus for measuring surface and thermophysical properties and bulk structures of a highly supersaturated solution by combining electrostatic levitation with real-time laser/x-ray scattering. Even today, a proper characterization of supersaturated solutions far above their solubility limits is extremely challenging because heterogeneous nucleation sites such as container walls or impurities readily initiate crystallization before the measurements can be performed. In this work, we demonstrate simultaneous measurements of drying kinetics and surface tension of a potassium dihydrogen phosphate (KH 2 PO 4 ) aqueous solution droplet and its bulk structural evolution beyond the metastable zone width limit. Our experimental finding shows that the noticeable changes of the surface properties are accompanied by polymerizations of hydrated monomer clusters. The novel electrostatic levitation apparatus presented here provides an effective means for studying a wide range of highly concentrated solutions and liquids in deep metastable states.

Solutions on a brane in a bulk spacetime with Kalb–Ramond field

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

Chakraborty, Sumanta, E-mail: sumanta@iucaa.in; SenGupta, Soumitra, E-mail: tpssg@iacs.res.in

Effective gravitational field equations on a brane have been derived, when the bulk spacetime is endowed with the second rank antisymmetric Kalb–Ramond field. Since both the graviton and the Kalb–Ramond field are closed string excitations, they can propagate in the bulk. After deriving the effective gravitational field equations on the brane, we solve them for a static spherically symmetric solution. It turns out that the solution so obtained represents a black hole or naked singularity depending on the parameter space of the model. The stability of this model is also discussed. Cosmological solutions to the gravitational field equations have beenmore » obtained, where the Kalb–Ramond field is found to behave as normal pressure free matter. For certain specific choices of the parameters in the cosmological solution, the solution exhibits a transition in the behaviour of the scale factor and hence a transition in the expansion history of the universe. The possibility of accelerated expansion of the universe in this scenario is also discussed.« less

Evaluating the multimedia fate of organic chemicals: A level III fugacity model

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

Mackay, D.; Paterson, S.

A multimedia model is developed and applied to selected organic chemicals in evaluative and real regional environments. The model employs the fugacity concept and treats four bulk compartments: air, water, soil, and bottom sediment, which consist of subcompartments of varying proportions of air, water, and mineral and organic matter. Chemical equilibrium is assumed to apply within (but not between) each bulk compartment. Expressions are included for emissions, advective flows, degrading reactions, and interphase transport by diffusive and non-diffusive processes. Input to the model consists of a description of the environment, the physical-chemical and reaction properties of the chemical, and emissionmore » rates. For steady-state conditions the solution is a simple algebraic expression. The model is applied to six chemicals in the region of southern Ontario and the calculated fate and concentrations are compared with observations. The results suggest that the model may be used to determine the processes that control the environmental fate of chemicals in a region and provide approximate estimates of relative media concentrations.« less

Electrically controlled cloud of bulk nanobubbles in water solutions

PubMed Central

Postnikov, Alexander V.; Uvarov, Ilia V.; Lokhanin, Mikhail V.

2017-01-01

Using different experimental techniques we visualize a cloud of gas in water that is produced electrochemically by the alternating polarity process. Liquid enriched with gas does not contain bubbles strongly scattering visible light but its refractive index changes significantly near the electrodes. The change of the refractive index is a collective effect of bulk nanobubbles with a diameter smaller than 200 nm. Any alternative explanation fails to explain the magnitude of the effect. Spatial structure of the cloud is investigated with the optical lever method. Its dynamics is visualised observing optical distortion of the electrode images or using differential interference contrast method. The cloud covers concentric electrodes, in a steady state it is roughly hemispherical with a size two times larger than the size of the electrode structure. When the electrical pulses are switched off the cloud disappears in less than one second. The total concentration of gases can reach very high value estimated as 3.5 × 1020 cm−3 that corresponds to an effective supersaturation of 500 and 150 for hydrogen and oxygen, respectively. PMID:28727812

Multistep building of a soft plant protein film at the air-water interface.

PubMed

Poirier, Alexandre; Banc, Amélie; Stocco, Antonio; In, Martin; Ramos, Laurence

2018-09-15

Gliadins are edible wheat storage proteins well known for their surface active properties. In this paper, we present experimental results on the interfacial properties of acidic solutions of gliadin studied over 5 decades of concentrations, from 0.001 to 110 g/L. Dynamic pendant drop tensiometry reveals that the surface pressure Π of gliadin solutions builds up in a multistep process. The series of curves of the time evolution of Π collected at different bulk protein concentrations C can be merged onto a single master curve when Π is plotted as a function of αt where t is the time elapsed since the formation of the air/water interface and α is a shift parameter that varies with C as a power law with an exponent 2. The existence of such time-concentration superposition, which we evidence for the first time, indicates that the same mechanisms govern the surface tension evolution at all concentrations and are accelerated by an increase of the bulk concentration. The scaling of α with C is consistent with a kinetic of adsorption controlled by the diffusion of the proteins in the bulk. Moreover, we show that the proteins adsorption at the air/water interface is kinetically irreversible. Correlated evolutions of the optical and elastic properties of the interfaces, as probed by ellipsometry and surface dilatational rheology respectively, provide a consistent physical picture of the building up of the protein interfacial layer. A progressive coverage of the interface by the proteins occurs at low Π. This stage is followed, at higher Π, by conformational rearrangements of the protein film, which are identified by a strong increase of the dissipative viscoelastic properties of the film concomitantly with a peculiar evolution of its optical profile that we have rationalized. In the last stage, at even higher surface pressure, the adsorption is arrested; the optical profile is not modified while the elasticity of the interfacial layer dramatically increases with the surface pressure, presumably due to the film ageing. Copyright © 2018 Elsevier Inc. All rights reserved.

First principles studies on the redox ability of (Ga(1-x)Zn(x))N(1-x)O(x) solid solutions and thermal reactions for H2 and O2 production on their surfaces.

PubMed

Du, Yaojun A; Chen, Yun-Wen; Kuo, Jer-Lai

2013-12-07

The (Ga1-xZnx)N1-xOx solid solution has been emerging as an effective photocatalyst for water splitting utilizing the visible solar spectrum, regarded as a host GaN bulk doped with ZnO impurities. H2 and O2 production occur simultaneously and stoichiometrically on the surface of (Ga1-xZnx)N1-xOx particles. In this work, we characterize the redox ability of (Ga1-xZnx)N1-xOx and find that a solid solution with a ZnO concentration of 0.125 < x < 0.250 is optimal for water splitting. This is consistent with the experimental finding that the maximum photocatalytic activity of (Ga1-xZnx)N1-xOx is achieved at x = 0.13. The thermal reactions of water splitting are modeled on both the GaN and an idealized (Ga1-xZnx)N1-xOx (101[combining macron]0) surface. The computed activation barriers allow us to gain some clues on the efficiency of water splitting on a specific photocatalyst surface. Our results suggest that the non-polar (101[combining macron]0) and polar (0001) surfaces may play different roles in water splitting, i.e., the (101[combining macron]0) surface is responsible for O2 production, while hydroxyl groups could dissociate on the (0001) surface.

Competition between organics and bromide at the aqueous solution-air interface as seen from ozone uptake kinetics and X-ray photoelectron spectroscopy.

PubMed

Lee, Ming-Tao; Brown, Matthew A; Kato, Shunsuke; Kleibert, Armin; Türler, Andreas; Ammann, Markus

2015-05-14

A more detailed understanding of the heterogeneous chemistry of halogenated species in the marine boundary layer is required. Here, we studied the reaction of ozone (O3) with NaBr solutions in the presence and absence of citric acid (C6H8O7) under ambient conditions. Citric acid is used as a proxy for oxidized organic material present at the ocean surface or in sea spray aerosol. On neat NaBr solutions, the observed kinetics is consistent with bulk reaction-limited uptake, and a second-order rate constant for the reaction of O3 + Br(-) is 57 ± 10 M(-1) s(-1). On mixed NaBr-citric acid aqueous solutions, the uptake kinetics was faster than that predicted by bulk reaction-limited uptake and also faster than expected based on an acid-catalyzed mechanism. X-ray photoelectron spectroscopy (XPS) on a liquid microjet of the same solutions at 1.0 × 10(-3)-1.0 × 10(-4) mbar was used to obtain quantitative insight into the interfacial composition relative to that of the bulk solutions. It revealed that the bromide anion becomes depleted by 30 ± 10% while the sodium cation gets enhanced by 40 ± 20% at the aqueous solution-air interface of a 0.12 M NaBr solution mixed with 2.5 M citric acid in the bulk, attributed to the role of citric acid as a weak surfactant. Therefore, the enhanced reactivity of bromide solutions observed in the presence of citric acid is not necessarily attributable to a surface reaction but could also result from an increased solubility of ozone at higher citric acid concentrations. Whether the acid-catalyzed chemistry may have a larger effect on the surface than in the bulk to offset the effect of bromide depletion also remains open.

Impact of small-scale saline tracer heterogeneity on electrical resistivity monitoring in fully and partially saturated porous media: Insights from geoelectrical milli-fluidic experiments

NASA Astrophysics Data System (ADS)

Jougnot, Damien; Jiménez-Martínez, Joaquín; Legendre, Raphaël; Le Borgne, Tanguy; Méheust, Yves; Linde, Niklas

2018-03-01

Time-lapse electrical resistivity tomography (ERT) is a geophysical method widely used to remotely monitor the migration of electrically-conductive tracers and contaminant plumes in the subsurface. Interpretations of time-lapse ERT inversion results are generally based on the assumption of a homogeneous solute concentration below the resolution limits of the tomogram depicting inferred electrical conductivity variations. We suggest that ignoring small-scale solute concentration variability (i.e., at the sub-resolution scale) is a major reason for the often-observed apparent loss of solute mass in ERT tracer studies. To demonstrate this, we developed a geoelectrical milli-fluidic setup where the bulk electric conductivity of a 2D analogous porous medium, consisting of cylindrical grains positioned randomly inside a Hele-Shaw cell, is monitored continuously in time while saline tracer tests are performed through the medium under fully and partially saturated conditions. High resolution images of the porous medium are recorded with a camera at regular time intervals, and provide both the spatial distribution of the fluid phases (aqueous solution and air), and the saline solute concentration field (where the solute consists of a mixture of salt and fluorescein, the latter being used as a proxy for the salt concentration). Effective bulk electrical conductivities computed numerically from the measured solute concentration field and the spatial distributions of fluid phases agree well with the measured bulk conductivities. We find that the effective bulk electrical conductivity is highly influenced by the connectivity of high electrical conductivity regions. The spatial distribution of air, saline tracer fingering, and mixing phenomena drive temporal changes in the effective bulk electrical conductivity by creating preferential paths or barriers for electrical current at the pore-scale. The resulting heterogeneities in the solute concentrations lead to strong anisotropy of the effective bulk electrical conductivity, especially for partially saturated conditions. We highlight how these phenomena contribute to the typically large apparent mass loss observed when conducting field-scale time-lapse ERT.

Contribution of galloylation and polymerization to the antioxidant activity of polyphenols in fish lipid systems.

PubMed

Iglesias, Jacobo; Pazos, Manuel; Lois, Salomé; Medina, Isabel

2010-06-23

Polyphenolic fractions extracted from pine (Pinus pinaster) bark, grape (Vitis vinifera) pomace, and witch hazel (Hamamelis virginiana) bark were selected for investigating the influence of the number of phenolic units, polymerization, and the content of esterified galloyl residues (galloylation) on their efficacy for inhibiting lipid oxidation in fish lipid enriched foodstuffs. Experiments carried out with nongalloylated pine bark fractions with different polymerization degrees demonstrated that the number of catechin residues per molecule modulates their reducing and chelating properties in solution. In real food systems such as bulk fish oil and fish oil-in-water emulsions, the efficacy against lipid oxidation was highly dependent on the physical location of the antioxidant at the oxidative sensitive sites. The lowest polymerized fractions were the most efficient in bulk fish oil samples, whereas proanthocyanidins with an intermediate polymerization degree showed the highest activity in fish oil-in-water emulsions. Galloylation did not influence the antioxidant effectiveness of proanthocyanidins in bulk fish oils. The presence of galloyl groups favored the antioxidant activity of the polyphenols in emulsions, although results indicated that a high degree of galloylation did not improve significantly the activity found with medium galloylated proanthocyanidins. The results obtained in this research provide useful information about the relationship between structure and antioxidant activity in order to design antioxidant additives with application in fish oil-enriched functional foods.

Anions dramatically enhance proton transfer through aqueous interfaces

PubMed Central

Mishra, Himanshu; Enami, Shinichi; Nielsen, Robert J.; Hoffmann, Michael R.; Goddard, William A.; Colussi, Agustín J.

2012-01-01

Proton transfer (PT) through and across aqueous interfaces is a fundamental process in chemistry and biology. Notwithstanding its importance, it is not generally realized that interfacial PT is quite different from conventional PT in bulk water. Here we show that, in contrast with the behavior of strong nitric acid in aqueous solution, gas-phase HNO3 does not dissociate upon collision with the surface of water unless a few ions (> 1 per 106 H2O) are present. By applying online electrospray ionization mass spectrometry to monitor in situ the surface of aqueous jets exposed to HNO3(g) beams we found that production increases dramatically on > 30-μM inert electrolyte solutions. We also performed quantum mechanical calculations confirming that the sizable barrier hindering HNO3 dissociation on the surface of small water clusters is drastically lowered in the presence of anions. Anions electrostatically assist in drawing the proton away from lingering outside the cluster, whose incorporation is hampered by the energetic cost of opening a cavity therein. Present results provide both direct experimental evidence and mechanistic insights on the counterintuitive slowness of PT at water-hydrophobe boundaries and its remarkable sensitivity to electrostatic effects. PMID:22689964

A computational method for the coupled solution of reaction-diffusion equations on evolving domains and manifolds: Application to a model of cell migration and chemotaxis.

PubMed

MacDonald, G; Mackenzie, J A; Nolan, M; Insall, R H

2016-03-15

In this paper, we devise a moving mesh finite element method for the approximate solution of coupled bulk-surface reaction-diffusion equations on an evolving two dimensional domain. Fundamental to the success of the method is the robust generation of bulk and surface meshes. For this purpose, we use a novel moving mesh partial differential equation (MMPDE) approach. The developed method is applied to model problems with known analytical solutions; these experiments indicate second-order spatial and temporal accuracy. Coupled bulk-surface problems occur frequently in many areas; in particular, in the modelling of eukaryotic cell migration and chemotaxis. We apply the method to a model of the two-way interaction of a migrating cell in a chemotactic field, where the bulk region corresponds to the extracellular region and the surface to the cell membrane.

Elimination of Naegleria fowleri from bulk water and biofilm in an operational drinking water distribution system.

PubMed

Miller, Haylea C; Morgan, Matthew J; Wylie, Jason T; Kaksonen, Anna H; Sutton, David; Braun, Kalan; Puzon, Geoffrey J

2017-03-01

Global incidence of primary amoebic meningoencephalitis cases associated with domestic drinking water is increasing. The need for understanding disinfectant regimes capable of eliminating the causative microorganism, Naegleria fowleri, from bulk water and pipe wall biofilms is critical. This field study demonstrated the successful elimination of N. fowleri from the bulk water and pipe wall biofilm of a persistently colonised operational drinking water distribution system (DWDS), and the prevention of further re-colonisation. A new chlorination unit was installed along the pipe line to boost the free chlorine residual to combat the persistence of N. fowleri. Biofilm and bulk water were monitored prior to and after re-chlorination (RCl), pre-rechlorination (pre-RCl) and post-rechlorination (post-RCl), respectively, for one year. A constant free chlorine concentration of > 1 mg/L resulted in the elimination of N. fowleri from both the bulk water and biofilm at the post-RCl site. Other amoeba species were detected during the first two months of chlorination, but all amoebae were eliminated from both the bulk water and biofilm at post-RCl after 60 days of chlorination with free chlorine concentrations > 1 mg/L. In addition, a dynamic change in the biofilm community composition and a four log reduction in biofilm cell density occurred post-RCl. The pre-RCl site continued to be seasonally colonised by N. fowleri, but the constant free chlorine residual of > 1 mg/L prevented N. fowleri from recolonising the bulk and pipe wall biofilm at the post-RCl site. To our knowledge, this is the first study to demonstrate successful removal of N. fowleri from both the bulk and pipe wall biofilm and prevention of re-colonisation of N. fowleri in an operational DWDS. The findings of this study are of importance to water utilities in addressing the presence of N. fowleri and other amoeba in susceptible DWDSs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling of energy release systems from OTEC plants

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

Denno, K.

1983-12-01

This paper presents analytical scope for the controlling functions of OTEC operation for the ultimate production of sizable bulk ..delta..T as well as H/sub 2/, N/sub 2/ and NH/sub 3/. The controlling parametric functions include the oceanic and ammonia Reynolds numbers which depend implicitly and explicitly on the ocean water velocity, mass-volume, duration of ..delta..T extraction, and the inlet and outlet water temperatures internally and externally. Solutions for the oceanic and amonia Reynolds numbers have been established setting the deciding constraints on water velocity, boundary temperatures, mass-volume as well as other plant parameters. Linkage between OTEC plant and other conventionalmore » as well as advanced energy systems has been expressed in terms of a set of balance and coordinating energy equations.« less

Molecular mechanisms of cryoprotection in aqueous proline: light scattering and molecular dynamics simulations.

PubMed

Troitzsch, R Z; Vass, H; Hossack, W J; Martyna, G J; Crain, J

2008-04-10

Free proline amino acid is a natural cryoprotectant expressed by numerous organisms under low-temperature stress. Previous reports have suggested that complex assemblies underlie its functional properties. We investigate here aqueous proline solutions as a function of temperature using combinations of Raman spectroscopy, Rayleigh-Brillouin light scattering, and molecular dynamics simulations with the view to revealing the molecular origins of the mixtures' functionality as a cryoprotectant. The evolution of the Brillouin frequency shifts and line widths with temperature shows that, above a critical proline concentration, the water-like dynamics is suppressed and viscoelastic behavior emerges: Here, the Landau-Placzek ratio also shows a temperature-independent maximum arising from concentration fluctuations. Molecular dynamics simulations reveal that the water-water correlations in the mixtures depend much more weakly on temperature than does bulk water. By contrast, the water OH Raman bands exhibit strong red-shifts on cooling similar to those seen in ices; however, no evidence of ice lattice phonons is observed in the low-frequency spectrum. We attribute this primarily to enhanced proline-water hydrogen bonding. In general, the picture that emerges is that aqueous proline is a heterogeneous mixture on molecular length scales (characterized by significant concentration fluctuations rather than well-defined aggregates). Simulations reveal that proline also appears to suppress the normal dependence of water structure on temperature and preserves the ambient-temperature correlations even in very cold solutions. The water structure in cold proline solutions therefore appears to be similar to that at a higher effective temperature. This, coupled with the emergence of glassy dynamics offers a molecular explanation for the functional properties of proline as a cryoprotectant without the need to invoke previously proposed complex aggregates.

Mechanism of vibrational energy dissipation of free OH groups at the air-water interface.

PubMed

Hsieh, Cho-Shuen; Campen, R Kramer; Okuno, Masanari; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

2013-11-19

Interfaces of liquid water play a critical role in a wide variety of processes that occur in biology, a variety of technologies, and the environment. Many macroscopic observations clarify that the properties of liquid water interfaces significantly differ from those of the bulk liquid. In addition to interfacial molecular structure, knowledge of the rates and mechanisms of the relaxation of excess vibrational energy is indispensable to fully understand physical and chemical processes of water and aqueous solutions, such as chemical reaction rates and pathways, proton transfer, and hydrogen bond dynamics. Here we elucidate the rate and mechanism of vibrational energy dissipation of water molecules at the air-water interface using femtosecond two-color IR-pump/vibrational sum-frequency probe spectroscopy. Vibrational relaxation of nonhydrogen-bonded OH groups occurs at a subpicosecond timescale in a manner fundamentally different from hydrogen-bonded OH groups in bulk, through two competing mechanisms: intramolecular energy transfer and ultrafast reorientational motion that leads to free OH groups becoming hydrogen bonded. Both pathways effectively lead to the transfer of the excited vibrational modes from free to hydrogen-bonded OH groups, from which relaxation readily occurs. Of the overall relaxation rate of interfacial free OH groups at the air-H2O interface, two-thirds are accounted for by intramolecular energy transfer, whereas the remaining one-third is dominated by the reorientational motion. These findings not only shed light on vibrational energy dynamics of interfacial water, but also contribute to our understanding of the impact of structural and vibrational dynamics on the vibrational sum-frequency line shapes of aqueous interfaces.

Mechanism of vibrational energy dissipation of free OH groups at the air–water interface

PubMed Central

Hsieh, Cho-Shuen; Campen, R. Kramer; Okuno, Masanari; Backus, Ellen H. G.; Nagata, Yuki; Bonn, Mischa

2013-01-01

Interfaces of liquid water play a critical role in a wide variety of processes that occur in biology, a variety of technologies, and the environment. Many macroscopic observations clarify that the properties of liquid water interfaces significantly differ from those of the bulk liquid. In addition to interfacial molecular structure, knowledge of the rates and mechanisms of the relaxation of excess vibrational energy is indispensable to fully understand physical and chemical processes of water and aqueous solutions, such as chemical reaction rates and pathways, proton transfer, and hydrogen bond dynamics. Here we elucidate the rate and mechanism of vibrational energy dissipation of water molecules at the air–water interface using femtosecond two-color IR-pump/vibrational sum-frequency probe spectroscopy. Vibrational relaxation of nonhydrogen-bonded OH groups occurs at a subpicosecond timescale in a manner fundamentally different from hydrogen-bonded OH groups in bulk, through two competing mechanisms: intramolecular energy transfer and ultrafast reorientational motion that leads to free OH groups becoming hydrogen bonded. Both pathways effectively lead to the transfer of the excited vibrational modes from free to hydrogen-bonded OH groups, from which relaxation readily occurs. Of the overall relaxation rate of interfacial free OH groups at the air–H2O interface, two-thirds are accounted for by intramolecular energy transfer, whereas the remaining one-third is dominated by the reorientational motion. These findings not only shed light on vibrational energy dynamics of interfacial water, but also contribute to our understanding of the impact of structural and vibrational dynamics on the vibrational sum-frequency line shapes of aqueous interfaces. PMID:24191016

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.

Characterization of cobalt(II) chloride-modified condensation polyimide films

NASA Technical Reports Server (NTRS)

Rancourt, J. D.; Taylor, L. T.

1988-01-01

The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

Typhoon impacts on chemical weathering source provenance of a High Standing Island watershed, Taiwan

NASA Astrophysics Data System (ADS)

Meyer, Kevin J.; Carey, Anne E.; You, Chen-Feng

2017-10-01

Chemical weathering source provenance changes associated with Typhoon Mindulle (2004) were identified for the Choshui River Watershed in west-central Taiwan using radiogenic Sr isotope (87Sr/86Sr) and major ion chemistry analysis of water samples collected before, during, and following the storm event. Storm water sampling over 72 h was conducted in 3 h intervals, allowing for novel insight into weathering regime changes in response to intense rainfall events. Chemical weathering sources were determined to be bulk silicate and disseminated carbonate minerals at the surface and silicate contributions from deep thermal waters. Loss on ignition analysis of collected rock samples indicate disseminated carbonate can compose over 25% by weight of surface mineralogy, but typically makes up ∼2-3% of watershed rock. 87Sr/86Sr and major element molar ratios indicate that Typhoon Mindulle caused a weathering regime switch from normal flow incorporating a deep thermal signature to that of a system dominated by surface weathering. The data suggest release of silicate solute rich soil pore waters during storm events, creating a greater relative contribution of silicate weathering to the solute load during periods of increased precipitation and runoff. Partial depletion of this soil solute reservoir and possible erosion enhanced carbonate weathering lead to increased importance of carbonates to the weathering regime as the storm continues. Major ion data indicate that complex mica weathering (muscovite, biotite, illite, chlorite) may represent an important silicate weathering pathway in the watershed. Deep thermal waters represent an important contribution to river solutes during normal non-storm flow conditions. Sulfuric acid sourced from pyrite weathering is likely a major weathering agent in the Choshui River watershed.

Sliding over the Blocks in Enzyme-Free RNA Copying – One-Pot Primer Extension in Ice

PubMed Central

Löffler, Philipp M. G.; Groen, Joost; Dörr, Mark; Monnard, Pierre-Alain

2013-01-01

Template-directed polymerization of RNA in the absence of enzymes is the basis for an information transfer in the ‘RNA-world’ hypothesis and in novel nucleic acid based technology. Previous investigations established that only cytidine rich strands are efficient templates in bulk aqueous solutions while a few specific sequences completely block the extension of hybridized primers. We show that a eutectic water/ice system can support Pb2+/Mg2+-ion catalyzed extension of a primer across such sequences, i.e. AA, AU and AG, in a one-pot synthesis. Using mixtures of imidazole activated nucleotide 5′-monophosphates, the two first “blocking” residues could be passed during template-directed polymerization, i.e., formation of triply extended products containing a high fraction of faithful copies was demonstrated. Across the AG sequence, a mismatch sequence was formed in similar amounts to the correct product due to U·G wobble pairing. Thus, the template-directed extension occurs both across pyrimidine and purine rich sequences and insertions of pyrimidines did not inhibit the subsequent insertions. Products were mainly formed with 2′-5′-phosphodiester linkages, however, the abundance of 3′–5′-linkages was higher than previously reported for pyrimidine insertions. When enzyme-free, template-directed RNA polymerization is performed in a eutectic water ice environment, various intrinsic reaction limitations observed in bulk solution can then be overcome. PMID:24058695

Subsonic leaky Rayleigh waves at liquid-solid interfaces.

PubMed

Mozhaev, V G; Weihnacht, M

2002-05-01

The paper is devoted to the study of leaky Rayleigh waves at liquid-solid interfaces close to the border of the existence domain of these modes. The real and complex roots of the secular equation are computed for interface waves at the boundary between water and a binary isotropic alloy of gold and silver with continuously variable composition. The change of composition of the alloy allows one to cross a critical velocity for the existence of leaky waves. It is shown that, contrary to popular opinion, the critical velocity does not coincide with the phase velocity of bulk waves in liquid. The true threshold velocity is found to be smaller, the correction being of about 1.45%. Attention is also drawn to the fact that using the real part of the complex phase velocity as a velocity of leaky waves gives only approximate value. The most interesting feature of the waves under consideration is the presence of energy leakage in the subsonic range of the phase velocities where, at first glance, any radiation by harmonic waves is not permitted. A simple physical explanation of this radiation with due regard for inhomogeneity of radiated and radiating waves is given. The controversial question of the existence of leaky Rayleigh waves at a water/ice interface is reexamined. It is shown that the solution considered previously as a leaky wave is in fact the solution of the bulk-wave-reflection problem for inhomogeneous waves.

Solvent Electrostatic Response: From Simple Solutes to Proteins

NASA Astrophysics Data System (ADS)

Dinpajooh, Mohammadhasan

How water behaves at interfaces is relevant to many scientific and technological applications; however, many subtle phenomena are unknown in aqueous solutions. In this work, interfacial structural transition in hydration shells of a polarizable solute at critical polarizabilities is discovered. The transition is manifested in maximum water response, the reorientation of the water dipoles at the interface, and an increase in the density of dangling OH bonds. This work also addresses the role of polarizability of the active site of proteins in biological catalytic reactions. For proteins, the hydration shell becomes very heterogeneous and involves a relatively large number of water molecules. The molecular dynamics simulations show that the polarizability, along with the atomic charge distribution, needs to be a part of the picture describing how enzymes work. Non Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are also analyzed. Additionally, a theoretical formalism is presented to show that when preferential orientations of water dipoles exist at the interface, electrophoretic charges can be produced without free charge carriers, i.e., neutral solutes can move in a constant electric field due to the divergence of polarization at the interface. Furthermore, the concept of interface susceptibility is introduced. It involves the fluctuations of the surface charge density caused by thermal motion and its correlation over the characteristic correlation length with the fluctuations of the solvent charge density. Solvation free energy and interface dielectric constant are formulated accordingly. Unlike previous approaches, the solvation free energy scales quite well in a broad range of ion sizes, namely in the range of 2-14 A. Interface dielectric constant is defined such that the boundary conditions in the Laplace equation describing a micro- or mesoscopic interface are satisfied. The effective dielectric constant of interfacial water is found to be significantly lower than its bulk value. Molecular dynamics simulation results show that the interface dielectric constant for a TIP3P water model changes from nine to four when the effective solute radius is increased from 5 Ato 18 A. The small value of the interface dielectric constant of water has potentially dramatic consequences for hydration.

Sensitivity of polarization fluctuations to the nature of protein-water interactions: Study of biological water in four different protein-water systems

NASA Astrophysics Data System (ADS)

Ghosh, Rikhia; Banerjee, Saikat; Hazra, Milan; Roy, Susmita; Bagchi, Biman

2014-12-01

Since the time of Kirkwood, observed deviations in magnitude of the dielectric constant of aqueous protein solution from that of neat water (˜80) and slower decay of polarization have been subjects of enormous interest, controversy, and debate. Most of the common proteins have large permanent dipole moments (often more than 100 D) that can influence structure and dynamics of even distant water molecules, thereby affecting collective polarization fluctuation of the solution, which in turn can significantly alter solution's dielectric constant. Therefore, distance dependence of polarization fluctuation can provide important insight into the nature of biological water. We explore these aspects by studying aqueous solutions of four different proteins of different characteristics and varying sizes, chicken villin headpiece subdomain (HP-36), immunoglobulin binding domain protein G (GB1), hen-egg white lysozyme (LYS), and Myoglobin (MYO). We simulate fairly large systems consisting of single protein molecule and 20000-30000 water molecules (varied according to the protein size), providing a concentration in the range of ˜2-3 mM. We find that the calculated dielectric constant of the system shows a noticeable increment in all the cases compared to that of neat water. Total dipole moment auto time correlation function of water ⟨δMW(0)δMW(t)⟩ is found to be sensitive to the nature of the protein. Surprisingly, dipole moment of the protein and total dipole moment of the water molecules are found to be only weakly coupled. Shellwise decomposition of water molecules around protein reveals higher density of first layer compared to the succeeding ones. We also calculate heuristic effective dielectric constant of successive layers and find that the layer adjacent to protein has much lower value (˜50). However, progressive layers exhibit successive increment of dielectric constant, finally reaching a value close to that of bulk 4-5 layers away. We also calculate shellwise orientational correlation function and tetrahedral order parameter to understand the local dynamics and structural re-arrangement of water. Theoretical analysis providing simple method for calculation of shellwise local dielectric constant and implication of these findings are elaborately discussed in the present work.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, Larry B.; Thurman, E. Michael; Runnells, Donald D.

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5–25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Cloud condensation nuclei activation of limited solubility organic aerosol

NASA Astrophysics Data System (ADS)

Huff Hartz, Kara E.; Tischuk, Joshua E.; Chan, Man Nin; Chan, Chak K.; Donahue, Neil M.; Pandis, Spyros N.

The cloud condensation nuclei (CCN) activation of 19 organic species with water solubilities ( Csat) ranging from 10 -4 to 10 2 g solute 100 g -1 H 2O was measured. The organic particles were generated by nebulization of an aqueous or an alcohol solution. Use of alcohols as solvents enables the measurement of low solubility, non-volatile organic CCN activity and reduces the likelihood of residual water in the aerosol. The activation diameter of organic species with very low solubility in water ( Csat<0.3 g 100 g -1 H 2O) is in agreement with Köhler theory using the bulk solubility (limited solubility case) of the organic in water. Many species, including 2-acetylbenzoic acid, aspartic acid, azelaic acid, glutamic acid, homophthalic acid, phthalic acid, cis-pinonic acid, and salicylic acid are highly CCN active in spite of their low solubility (0.3 g 100 g -1 H 2O< Csat<1 g 100 g -1 H 2O), and activate almost as if completely water soluble. The CCN activity of most species is reduced, if the particles are produced using non-aqueous solvents. The existence of the particles in a metastable state at low RH can explain the observed enhancement in CCN activity beyond the levels suggested by their solubility.

Soil water sensor response to bulk electrical conductivity

USDA-ARS?s Scientific Manuscript database

Soil water monitoring using electromagnetic (EM) sensors can facilitate observations of water content at high temporal and spatial resolutions. These sensors measure soil dielectric permittivity (Ka) which is largely a function of volumetric water content. However, bulk electrical conductivity BEC c...

Aerial thermography studies of power plant heated lakes

NASA Astrophysics Data System (ADS)

Villa-Aleman, Eliel; Garrett, Alfred J.; Kurzeja, Robert J.; Pendergast, Malcolm M.

2000-03-01

Remote sensing temperature measurements of water bodies is complicated by the temperature differences between the true surface or `skin' water and the bulk water below. Weather conditions control the reduction of the skin temperature relative to the bulk water temperature. Typical skin temperature depressions range from a few tenths of a degree Celsius to more than one degree. In this research project, the Savannah River Technology Center used aerial thermography and surface-based meteorological and water temperature measurements to study a power plant cooling lake in South Carolina. Skin and bulk water temperatures were measured simultaneously for imagery calibration and to product a database for modeling of skin temperature depressions as a function of weather and bulk water temperatures. This paper will present imagery that illustrates how the skin temperature depression was affected by different conditions in several locations on the lake and will present skin temperature modeling results.

Combined effects of the drug distribution and mucus diffusion properties of self-microemulsifying drug delivery systems on the oral absorption of fenofibrate.

PubMed

Sunazuka, Yushi; Ueda, Keisuke; Higashi, Kenjirou; Tanaka, Yusuke; Moribe, Kunikazu

2018-05-24

We present the absorption improvement mechanism of fenofibrate (FFB), a Biopharmaceutics Classification System (BCS) class II drug, from self-microemulsifying drug delivery systems (SMEDDS), centered on improving the diffusion of FFB through the unstirred water layer (UWL). Four SMEDDS formulations containing Labrafac™ lipophile WL 1349 (WL1349) or Labrafil ® M 1944CS (M1944) oils and NIKKOL HCO-40 (HCO40) or NIKKOL HCO-60 (HCO60) surfactants were prepared. Every SMEDDS formulation formed microemulsion droplets of approximately 30 nm. In vitro tests showed that the microemulsion droplets containing M1944 had relatively small FFB solubilization capacities, causing larger amounts of FFB to be dissolved in the bulk water phase, compared to the droplets containing WL1349. The diffusivity of the microemulsion droplets through the mucin solution layer was enhanced when using HCO40 compared to HCO60. The oral absorption in rats was the highest when using the SMEDDS formulation containing M1944 and HCO40. High FFB distribution in the bulk water phase and fast diffusion of microemulsion droplets through the mucus layer contributed to the efficient delivery of FFB molecules through the UWL to the epithelial cells, leading to enhanced FFB absorption. Copyright © 2018 Elsevier B.V. All rights reserved.

Oxide or carbide nanoparticles synthesized by laser ablation of a bulk Hf target in liquids and their structural, optical, and dielectric properties

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

Semaltianos, N. G., E-mail: nsemaltianos@yahoo.com; Friedt, J.-M.; Blondeau-Patissier, V.

2016-05-28

Laser ablation of a bulk Hf target in deionized (DI) water, ethanol, or toluene was carried out for the production of nanoparticles' colloidal solutions. Due to the interaction of the ablation plasma plume species with the species which are produced by the liquid decomposition at the plume-liquid interface, hafnia (HfO{sub 2}) nanoparticles are synthesized in DI water, hafnium carbide (HfC) nanoparticles in toluene, and a mixture of these in ethanol. The hafnia nanoparticles are in the monoclinic low temperature phase and in the tetragonal and fcc high temperature phases. Their size distribution follows log-normal function with a median diameter inmore » the range of 4.3–5.3 nm. Nanoparticles synthesized in DI water have band gaps of 5.6 and 5.4 eV, in ethanol 5.72 and 5.65 eV (using low and high pulse energy), and in toluene 3 eV. The values for the relative permittivity in the range of 7.74–8.90 were measured for hafnia nanoparticles' thin films deposited on substrates by drop-casting (self-assembled layers) in parallel plate capacitor structures.« less

Influence of addition of degassed water on bulk nanobubbles.

PubMed

Tuziuti, Toru; Yasui, Kyuichi; Kanematsu, Wataru

2018-05-01

The effects of the addition of degassed water on bulk nanobubbles (ultrafine bubbles) of air in liquid water were investigated by measuring the volumetric concentration and size distribution at different dissolved air degree of saturation (DOS) values. The proportion of degassed water mixed with water containing bulk nanobubbles was increased to prepare samples having lower DOS values. It was found that the volumetric concentration of nanobubbles mostly decreased and the average nanobubble size became larger as the DOS was decreased. In our proposed mechanism, smaller nanobubbles are selectively dissolved into the surrounding liquid by Laplace pressure due to surface tension as the DOS is reduced. These results demonstrate that stable bulk nanobubbles are present even in water undersaturated with gas. The role of nanobubble under an ultrasound is also discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

33 CFR 127.313 - Bulk storage.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 33 Navigation and Navigable Waters 2 2011-07-01 2011-07-01 false Bulk storage. 127.313 Section 127.313 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED... Waterfront Facilities Handling Liquefied Natural Gas Operations § 127.313 Bulk storage. (a) The operator...

33 CFR 127.313 - Bulk storage.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 33 Navigation and Navigable Waters 2 2012-07-01 2012-07-01 false Bulk storage. 127.313 Section 127.313 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED... Waterfront Facilities Handling Liquefied Natural Gas Operations § 127.313 Bulk storage. (a) The operator...

33 CFR 127.313 - Bulk storage.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false Bulk storage. 127.313 Section 127.313 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED... Waterfront Facilities Handling Liquefied Natural Gas Operations § 127.313 Bulk storage. (a) The operator...

33 CFR 127.313 - Bulk storage.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 33 Navigation and Navigable Waters 2 2014-07-01 2014-07-01 false Bulk storage. 127.313 Section 127.313 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED... Waterfront Facilities Handling Liquefied Natural Gas Operations § 127.313 Bulk storage. (a) The operator...

33 CFR 127.313 - Bulk storage.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 33 Navigation and Navigable Waters 2 2013-07-01 2013-07-01 false Bulk storage. 127.313 Section 127.313 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED... Waterfront Facilities Handling Liquefied Natural Gas Operations § 127.313 Bulk storage. (a) The operator...

Microelectrodes Based investigation of the Impacts of Water Chemistry on Copper and Iron Corrosion

EPA Science Inventory

The effect of bulk drinking water quality on copper and iron pipe corrosion has been extensively studied. Despite past research, many have argued that bulk water quality does not necessarily reflect water quality near the water-metal interface and that such knowledge is necessary...

Poly(ethylene glycol)s in Semidilute Regime: Radius of Gyration in the Bulk and Partitioning into a Nanopore

DOE PAGES

Gurnev, Philip A.; Stanley, Christopher B.; Aksoyoglu, M. Alphan; ...

2017-03-09

In this work, using two approaches, small-angle neutron scattering (SANS) from bulk solutions and nanopore conductance-fluctuation analysis, we studied structural and dynamic features of poly(ethylene glycol) (PEG) water/salt solutions in the dilute and semidilute regimes. SANS measurements on PEG 3400 at the zero-average contrast yielded the single chain radius of gyration (R g) over 1–30 wt %. We observed a small but statistically reliable decrease in R g with increasing PEG concentration: at 30 wt % the chain contracts by a factor of 0.94. Analyzing conductance fluctuations of the α-hemolysin nanopore in the mixtures of PEG 200 with PEG 3400,more » we demonstrated that polymer partitioning into the nanopore is mostly due to PEG 200. Specifically, for a 1:1 wt/wt mixture the smaller polymer dominates to the extent that only about 1/25 of the nanopore volume is taken by the larger polymer. In conclusion, these findings advance our conceptual and quantitative understanding of nanopore polymer partitioning; they also support the main assumptions of the recent “polymers-pushing-polymers” model.« less

Conductivity measurements on H 2O-bearing CO 2-rich fluids

DOE PAGES

Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; ...

2014-09-10

Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H 2O to CO 2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO 2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H 2O concentrationsmore » up to ~1600 ppmw (xH 2O ≈ 3.9 x 10 -3), corresponding to the H 2O solubility limit in liquid CO 2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO 2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

Influence of growth temperature on bulk and surface defects in hybrid lead halide perovskite films.

PubMed

Peng, Weina; Anand, Benoy; Liu, Lihong; Sampat, Siddharth; Bearden, Brandon E; Malko, Anton V; Chabal, Yves J

2016-01-21

The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (∼10(17) cm(-3)) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites.

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy.

PubMed

Choi, Man Yee; Chan, Chak K

2005-02-17

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.

Characterization of the hydrogen-bond network of water around sucrose and trehalose: Microwave and terahertz spectroscopic study

NASA Astrophysics Data System (ADS)

Shiraga, Keiichiro; Adachi, Aya; Nakamura, Masahito; Tajima, Takuro; Ajito, Katsuhiro; Ogawa, Yuichi

2017-03-01

Modification of the water hydrogen bond network imposed by disaccharides is known to serve as a bioprotective agent in living organisms, though its comprehensive understanding is still yet to be reached. In this study, aiming to characterize the dynamical slowing down and destructuring effect of disaccharides, we performed broadband dielectric spectroscopy, ranging from 0.5 GHz to 12 THz, of sucrose and trehalose aqueous solutions. The destructuring effect was examined in two ways (the hydrogen bond fragmentation and disordering) and our result showed that both sucrose and trehalose exhibit an obvious destructuring effect with a similar strength, by fragmenting hydrogen bonds and distorting the tetrahedral-like structure of water. This observation strongly supports a chaotropic (structure-breaking) aspect of disaccharides on the water structure. At the same time, hydration water was found to exhibit slower dynamics and a greater reorientational cooperativity than bulk water because of the strengthened hydrogen bonds. These results lead to the conclusion that strong disaccharide-water hydrogen bonds structurally incompatible with native water-water bonds lead to the rigid but destructured hydrogen bond network around disaccharides. Another important finding in this study is that the greater dynamical slowing down of trehalose was found compared with that of sucrose, at variance with the destructuring effect where no solute dependent difference was observed. This discovery suggests that the exceptionally greater bioprotective impact especially of trehalose among disaccharides is mainly associated with the dynamical slowing down (rather than the destructuring effect).

Water and solute mass balance of five small, relatively undisturbed watersheds in the U.S.

USGS Publications Warehouse

Peters, N.E.; Shanley, J.B.; Aulenbach, Brent T.; Webb, R.M.; Campbell, D.H.; Hunt, R.; Larsen, M.C.; Stallard, R.F.; Troester, J.; Walker, J.F.

2006-01-01

Geochemical mass balances were computed for water years 1992-1997 (October 1991 through September 1997) for the five watersheds of the U.S. Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) Program to determine the primary regional controls on yields of the major dissolved inorganic solutes. The sites, which vary markedly with respect to climate, geology, physiography, and ecology, are: Allequash Creek, Wisconsin (low-relief, humid continental forest); Andrews Creek, Colorado (cold alpine, taiga/tundra, and subalpine boreal forest); Ri??o Icacos, Puerto Rico (lower montane, wet tropical forest); Panola Mountain, Georgia (humid subtropical piedmont forest); and Sleepers River, Vermont (humid northern hardwood forest). Streamwater output fluxes were determined by constructing empirical multivariate concentration models including discharge and seasonal components. Input fluxes were computed from weekly wet-only or bulk precipitation sampling. Despite uncertainties in input fluxes arising from poorly defined elevation gradients, lack of dry-deposition and occult-deposition measurements, and uncertain sea-salt contributions, the following was concluded: (1) for solutes derived primarily from rock weathering (Ca, Mg, Na, K, and H4SiO4), net fluxes (outputs in streamflow minus inputs in deposition) varied by two orders of magnitude, which is attributed to a large gradient in rock weathering rates controlled by climate and geologic parent material; (2) the net flux of atmospherically derived solutes (NH4, NO3, SO4, and Cl) was similar among sites, with SO4 being the most variable and NH4 and NO3 generally retained (except for NO 3 at Andrews); and (3) relations among monthly solute fluxes and differences among solute concentration model parameters yielded additional insights into comparative biogeochemical processes at the sites. ?? 2005 Elsevier B.V. All rights reserved.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Soil permittivity response to bulk electrical conductivity for selected soil water sensors

USDA-ARS?s Scientific Manuscript database

Bulk electrical conductivity can dominate the low frequency dielectric loss spectrum in soils, masking changes in the real permittivity and causing errors in estimated water content. We examined the dependence of measured apparent permittivity (Ka) on bulk electrical conductivity in contrasting soil...

Brane f(R) gravity cosmologies

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

Balcerzak, Adam; DaPbrowski, Mariusz P.

2010-06-15

By the application of the generalized Israel junction conditions we derive cosmological equations for the fourth-order f(R) brane gravity and study their cosmological solutions. We show that there exists a nonstatic solution which describes a four-dimensional de Sitter (dS{sub 4}) brane embedded in a five-dimensional anti-de Sitter (AdS{sub 5}) bulk for a vanishing Weyl tensor contribution. On the other hand, for the case of a nonvanishing Weyl tensor contribution, there exists a static brane solution only. We claim that in order to get some more general nonstatic f(R) brane configurations, one needs to admit a dynamical matter energy-momentum tensor inmore » the bulk rather than just a bulk cosmological constant.« less

Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

PubMed

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2015-09-23

The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

Enhancing Localized Evaporation through Separated Light Absorbing Centers and Scattering Centers

PubMed Central

Zhao, Dengwu; Duan, Haoze; Yu, Shengtao; Zhang, Yao; He, Jiaqing; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2015-01-01

This report investigates the enhancement of localized evaporation via separated light absorbing particles (plasmonic absorbers) and scattering particles (polystyrene nanoparticles). Evaporation has been considered as one of the most important phase-change processes in modern industries. To improve the efficiency of evaporation, one of the most feasible methods is to localize heat at the top water layer rather than heating the bulk water. In this work, the mixture of purely light absorptive plasmonic nanostructures such as gold nanoparticles and purely scattering particles (polystyrene nanoparticles) are employed to confine the incident light at the top of the solution and convert light to heat. Different concentrations of both the light absorbing centers and the light scattering centers were evaluated and the evaporation performance can be largely enhanced with the balance between absorbing centers and scattering centers. The findings in this study not only provide a new way to improve evaporation efficiency in plasmonic particle-based solution, but also shed lights on the design of new solar-driven localized evaporation systems. PMID:26606898

Attaining 2D Black Phosphorus and Investigations into Floating-Electrode Dielectric Barrier Discharge Treatment of Solutions

NASA Astrophysics Data System (ADS)

Smith, Joshua Benjamin

Since the discovery and isolation of the 2D carbon allotrope, graphene, research into additional 2D materials has significantly expanded. Electrical components continue to decrease in size so there is an ever-growing need for smaller circuitry to keep up with the demand. Research with graphene and additional 2D layered materials, such as transition metal dichalcogenides, brought about a realization of many unique properties that have never been previously explored for applications in electronics, photonics, and optoelectronics. Phosphorene, a novel 2D material isolated from bulk black phosphorus, is an intrinsic p-type material with a variable band gap for a variety of applications. However, these applications are limited by the inability to isolate films of phosphorene. This work investigates some of the previously found techniques for use with graphene isolation and their adaptations to phosphorene. Isolation of phosphorene from black phosphorus was investigated by exfoliation from bulk, chemical vapor deposition, and thin film conversion. Mechanical exfoliation with a tape method, drawing method, and tape/drawing method were used to isolate few-layer black phosphorus samples from bulk material. These methods were also briefly compared to liquid exfoliation of black phosphorus. A chemical vapor deposition approach led to the discovery of a novel method for growth of amorphous red phosphorus thin films from bulk red phosphorus/black phosphorus. An in situ chemical vapor deposition type approach was developed using these thin films for growth of a variety of 2D phosphorus allotropes. Successful conversion has provided fibrous phosphorus wires and hexagons, along with violet phosphorus and eventually black phosphorus. This approach demonstrates progress towards direct growth of 2D black phosphorus onto substrates with average areas >3 microm2 and thicknesses representing samples around 4 layers. Thicker samples were also observed with average areas >100 microm2. X-ray diffraction, transmission electron microscopy, and Raman spectroscopy have confirmed successful growth of 2D black phosphorus from red phosphorus thin films for potential uses in 2D semiconductor applications. Additionally, this work discusses some of the chemistry occurring in solution as a result of nonthermal plasma treatment from a floating-electrode dielectric barrier discharge (FE-DBD) configuration. Nonthermal plasma generation allows for the treatment of heat sensitive materials. This has opened up the field to numerous clinical applications of nonthermal plasma treatment including sterilization and wound healing along with potentials in dentistry, dermatology, and even food industries. FE-DBD plasma treatment of water was found to provide a wide-range antimicrobial solution that remained active following 2 years of aging. This plasma-treated water was found to generate a number of ROS/RNS and the formation of these components was studied and verified with UV/Vis and ESR spectroscopy. Enhanced effects were observed when cell culture medium was plasma treated, suggesting the formation of additional reactive species from the plasma treatment of a variety of biomolecules. It is essential to understand these effects for a number of reasons. The possibility to generate a wide range of antimicrobial solutions from air, water, and basic biomolecules could provide a solution for those bacteria that have developed antibiotic resistances. Simultaneously, information into the reaction mechanisms of this FE-DBD plasma treatment can be investigated. All of the applications mentioned above involve complex networks of basic biomolecules, from skin tissue to bacteria cell walls. This work analyzes the effects of plasma treatment on several biomolecule solutions and simultaneously takes aim at understanding some of the potential mechanisms of plasma treatment. Studies were carried out using NMR and GC/MS. This information was used to investigate the possible targeted areas for FE-DBD plasma treatment and to simultaneously explain the antimicrobial effects.

Cavitation inception from bubble nuclei

PubMed Central

Mørch, K. A.

2015-01-01

The tensile strength of ordinary water such as tap water or seawater is typically well below 1 bar. It is governed by cavitation nuclei in the water, not by the tensile strength of the water itself, which is extremely high. Different models of the nuclei have been suggested over the years, and experimental investigations of bubbles and cavitation inception have been presented. These results suggest that cavitation nuclei in equilibrium are gaseous voids in the water, stabilized by a skin which allows diffusion balance between gas inside the void and gas in solution in the surrounding liquid. The cavitation nuclei may be free gas bubbles in the bulk of water, or interfacial gaseous voids located on the surface of particles in the water, or on bounding walls. The tensile strength of these nuclei depends not only on the water quality but also on the pressure–time history of the water. A recent model and associated experiments throw new light on the effects of transient pressures on the tensile strength of water, which may be notably reduced or increased by such pressure changes. PMID:26442138

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.

Role of quantum fluctuations in structural dynamics of liquids of light molecules

DOE PAGES

Agapov, A.; Novikov, V. N.; Kisliuk, A.; ...

2016-12-16

A possible role of quantum effects, such as tunneling and zero-point energy, in the structural dynamics of supercooled liquids is studied by dielectric spectroscopy. Our results demonstrate that the liquids, bulk 3-methyl pentane and confined normal and deuterated water, have low glass transition temperature and unusually low for their class of materials steepness of the temperature dependence of structural relaxation (fragility). Although we do not find any signs of tunneling in the structural relaxation of these liquids, their unusually low fragility can be well described by the influence of the quantum fluctuations. Confined water presents an especially interesting case inmore » comparison to the earlier data on bulk low-density amorphous and vapor deposited water. Confined water exhibits a much weaker isotope effect than bulk water, although the effect is still significant. Here, we show that it can be ascribed to the change of the energy barrier for relaxation due to a decrease in the zeropoint energy upon D/H substitution. We observed a difference in the behavior of confined and bulk water demonstrates high sensitivity of quantum effects to the barrier heights and structure of water. Moreover, these results demonstrate that extrapolation of confined water properties to the bulk water behavior is questionable.« less

Exploring the Free Energy Landscape of Solutes Embedded in Lipid Bilayers.

PubMed

Jämbeck, Joakim P M; Lyubartsev, Alexander P

2013-06-06

Free energy calculations are vital for our understanding of biological processes on an atomistic scale and can offer insight to various mechanisms. However, in some cases, degrees of freedom (DOFs) orthogonal to the reaction coordinate have high energy barriers and/or long equilibration times, which prohibit proper sampling. Here we identify these orthogonal DOFs when studying the transfer of a solute from water to a model membrane. Important DOFs are identified in bulk liquids of different dielectric nature with metadynamics simulations and are used as reaction coordinates for the translocation process, resulting in two- and three-dimensional space of reaction coordinates. The results are in good agreement with experiments and elucidate the pitfalls of using one-dimensional reaction coordinates. The calculations performed here offer the most detailed free energy landscape of solutes embedded in lipid bilayers to date and show that free energy calculations can be used to study complex membrane translocation phenomena.

Influence of osmolytes on protein and water structure: a step to understanding the mechanism of protein stabilization.

PubMed

Bruździak, Piotr; Panuszko, Aneta; Stangret, Janusz

2013-10-03

Results concerning the thermostability of hen egg white lysozyme in aqueous solutions with stabilizing osmolytes, trimethylamine-N-oxide (TMAO), glycine (Gly), and its N-methyl derivatives, N-methylglycine (NMG), N,N-dimethylglycine (DMG), and N,N,N-trimethylglycine (betaine, TMG), have been presented. The combination of spectroscopic (IR) and calorimetric (DSC) data allowed us to establish a link between osmolytes' influence on water structure and their ability to thermally stabilize protein molecule. Structural and energetic characteristics of stabilizing osmolytes' and lysozyme's hydration water appear to be very similar. The osmolytes increase lysozyme stabilization in the order bulk water < TMAO < TMG < Gly < DMG < NMG, which is consistent with the order corresponding to the value of the most probable oxygen-oxygen distance of water molecules affected by osmolytes in their surrounding. Obtained results verified the hypothesis concerning the role of water molecules in protein stabilization, explained the osmophobic effect, and finally helped to bring us nearer to the exact mechanism of protein stabilization by osmolytes.

Generating Singlet Oxygen Bubbles: A New Mechanism for Gas-Liquid Oxidations in Water

PubMed Central

Bartusik, Dorota; Aebisher, David; Ghafari, BiBi

2012-01-01

Laser-coupled microphotoreactors were developed to bubble singlet oxygen [1O2 (1Δg)] into an aqueous solution containing an oxidizable compound. The reactors consisted of custom-modified SMA fiber-optic receptacles loaded with 150-μm silicon phthalocyanine glass sensitizer particles, where the particles were isolated from direct contact with water by a membrane adhesively bonded to the bottom of each device. A tube fed O2 gas to the reactor chambers. In the presence of O2, singlet oxygen was generated by illuminating the sensitizer particles with 669-nm light from an optical fiber coupled to the top of the reactor. The generated 1O2 was transported through the membrane by the O2 stream and formed bubbles in solution. In solution, singlet oxygen reacted with probe compounds (either 9,10-anthracene dipropionate dianion, trans-2-methyl-2-pentanoate anion, N-benzoyl-D,L-methionine, and N-acetyl-D,L-methionine) to give oxidized products in two stages. The early stage was rapid and showed that 1O2 transfer occurred via bubbles mainly in the bulk water solution. The later stage was slow, it arose only from 1O2-probe molecule contact at the gas/liquid interface. A mechanism is proposed that involves 1O2 mass transfer and solvation, where smaller bubbles provide better penetration of 1O2 into the flowing stream due to higher surface-to-volume contact between the probe molecules and 1O2. PMID:22260325

Dynamics in a Water Interfacial Boundary Layer Investigated with IR Polarization-Selective Pump-Probe Experiments.

PubMed

Yuan, Rongfeng; Yan, Chang; Nishida, Jun; Fayer, Michael D

2017-05-04

The dynamics of water molecules near the surfactant interface in large Aerosol-OT reverse micelles (RMs) (w 0 = 16-25) was investigated with IR polarization-selective pump-probe experiments using the SeCN - anion as a vibrational probe. Linear absorption spectra of RMs (w 0 = 25-2) can be decomposed into the weighted sum of the SeCN - spectra in bulk water and the spectrum of the SeCN - anion interacting with the interfacial sulfonate head groups (w 0 = 1). The spectra of the large RMs, w 0 ≥ 16, are overwhelmingly dominated by the bulk water component. Anisotropy decays (orientational relaxation) of the anion for w 0 ≥ 16 displayed bulk water relaxation (1.4 and 4.5 ps) plus an additional slow decay with a time constant of ∼13 ps. The amplitude of the slow decay was too large to be associated with SeCN - in contact with the interface on the basis of the linear spectrum decomposition. The results indicate that the observed slow components arise from SeCN - in a water boundary layer, in which water molecules are perturbed by the interface but are not directly associated with it. This layer is the transition between water in direct contact with the interface and bulk water in the large RM cores. In the boundary layer, the water dynamics is slow compared to that in bulk water.

Effect of Sequence Blockiness on the Morphologies of Surface-grafted Elastin-like Polypeptides

NASA Astrophysics Data System (ADS)

Albert, Julie; Sintavanon, Kornkanok; Mays, Robin; MacEwan, Sarah; Chilkoti, Ashutosh; Genzer, Jan

2014-03-01

The inter- and intra- molecular interactions among monomeric units of copolymers and polypeptides depend strongly on monomer sequence distribution and dictate the phase behavior of these species both in solution and on surfaces. To study the relationship between sequence and phase behavior, we have designed a series of elastin-like polypeptides (ELPs) with controlled monomer sequences that mimic copolymers with various co-monomer sequence distributions and attached them covalently to silicon substrates from buffer solutions at temperatures below and above the bulk ELPs' lower critical solution temperatures (LCSTs). The dependence of ELP grafting density on solution temperature was examined by ellipsometry and the resultant surface morphologies were examined in air and under water with atomic force microscopy. Depositions performed above the LCST resulted in higher grafting densities and greater surface roughness of ELPs relative to depositions carried out below the LCST. In addition, we are using gradient substrates to examine the effect of ELP grafting density on temperature responsiveness.

Physical Quality Indicators and Mechanical Behavior of Agricultural Soils of Argentina.

PubMed

Imhoff, Silvia; da Silva, Alvaro Pires; Ghiberto, Pablo J; Tormena, Cássio A; Pilatti, Miguel A; Libardi, Paulo L

2016-01-01

Mollisols of Santa Fe have different tilth and load support capacity. Despite the importance of these attributes to achieve a sustainable crop production, few information is available. The objectives of this study are i) to assess soil physical indicators related to plant growth and to soil mechanical behavior; and ii) to establish relationships to estimate the impact of soil loading on the soil quality to plant growth. The study was carried out on Argiudolls and Hapludolls of Santa Fe. Soil samples were collected to determine texture, organic matter content, bulk density, water retention curve, soil resistance to penetration, least limiting water range, critical bulk density for plant growth, compression index, pre-consolidation pressure and soil compressibility. Water retention curve and soil resistance to penetration were linearly and significantly related to clay and organic matter (R2 = 0.91 and R2 = 0.84). The pedotransfer functions of water retention curve and soil resistance to penetration allowed the estimation of the least limiting water range and critical bulk density for plant growth. A significant nonlinear relationship was found between critical bulk density for plant growth and clay content (R2 = 0.98). Compression index was significantly related to bulk density, water content, organic matter and clay plus silt content (R2 = 0.77). Pre-consolidation pressure was significantly related to organic matter, clay and water content (R2 = 0.77). Soil compressibility was significantly related to initial soil bulk density, clay and water content. A nonlinear and significantly pedotransfer function (R2 = 0.88) was developed to predict the maximum acceptable pressure to be applied during tillage operations by introducing critical bulk density for plant growth in the compression model. The developed pedotransfer function provides a useful tool to link the mechanical behavior and tilth of the soils studied.

Physical Quality Indicators and Mechanical Behavior of Agricultural Soils of Argentina

PubMed Central

Pires da Silva, Alvaro; Ghiberto, Pablo J.; Tormena, Cássio A.; Pilatti, Miguel A.; Libardi, Paulo L.

2016-01-01

Mollisols of Santa Fe have different tilth and load support capacity. Despite the importance of these attributes to achieve a sustainable crop production, few information is available. The objectives of this study are i) to assess soil physical indicators related to plant growth and to soil mechanical behavior; and ii) to establish relationships to estimate the impact of soil loading on the soil quality to plant growth. The study was carried out on Argiudolls and Hapludolls of Santa Fe. Soil samples were collected to determine texture, organic matter content, bulk density, water retention curve, soil resistance to penetration, least limiting water range, critical bulk density for plant growth, compression index, pre-consolidation pressure and soil compressibility. Water retention curve and soil resistance to penetration were linearly and significantly related to clay and organic matter (R2 = 0.91 and R2 = 0.84). The pedotransfer functions of water retention curve and soil resistance to penetration allowed the estimation of the least limiting water range and critical bulk density for plant growth. A significant nonlinear relationship was found between critical bulk density for plant growth and clay content (R2 = 0.98). Compression index was significantly related to bulk density, water content, organic matter and clay plus silt content (R2 = 0.77). Pre-consolidation pressure was significantly related to organic matter, clay and water content (R2 = 0.77). Soil compressibility was significantly related to initial soil bulk density, clay and water content. A nonlinear and significantly pedotransfer function (R2 = 0.88) was developed to predict the maximum acceptable pressure to be applied during tillage operations by introducing critical bulk density for plant growth in the compression model. The developed pedotransfer function provides a useful tool to link the mechanical behavior and tilth of the soils studied. PMID:27099925

Runoff and Solute Mobilisation in a Semi-arid Headwater Catchment

NASA Astrophysics Data System (ADS)

Hughes, J. D.; Khan, S.; Crosbie, R.; Helliwell, S.; Michalk, D.

2006-12-01

Runoff and solute transport processes contributing to stream flow were determined in a small headwater catchment in the eastern Murray-Darling Basin of Australia using hydrometric and tracer methods. Stream flow and electrical conductivity were monitored from two gauges draining a portion of upper catchment area (UCA), and a saline scalded area respectively. Results show that the bulk of catchment solute export, occurs via a small saline scald (< 2% of catchment area) where solutes are concentrated in the near surface zone (0-40 cm). Non-scalded areas of the catchment are likely to provide the bulk of catchment runoff, although the scalded area is a higher contributor on an areal basis. Runoff from the non-scalded area is about two orders of magnitude lower in electrical conductivity than the scalded area. This study shows that the scalded zone and non-scalded parts of the catchment can be managed separately since they are effectively de-coupled except over long time scales, and produce runoff of contrasting quality. Such differences are "averaged out" by investigations that operate at larger scales, illustrating that observations need to be conducted at a range of scales. EMMA modelling using six solutes shows that "event" or "new" water dominated the stream hydrograph from the scald. This information together with hydrometric data and soil physical properties indicate that saturated overland flow is the main form of runoff generation in both the scalded area and the UCA. Saturated areas make up a small proportion of the catchment, but are responsible for production of all run off in conditions experienced throughout the experimental period. The process of saturation and runoff bears some similarities to the VSA concept (Hewlett and Hibbert 1967).

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

A simple method to model the reduced environment of lake bottom sapropel formation

NASA Astrophysics Data System (ADS)

Gaskova, Olga L.; Strakhovenko, Vera D.; Ermolaeva, Nadezhda I.; Zarubina, Eugene Yu.; Ovdina, Ekaterina A.

2017-07-01

The Kambala and Barchin brackish lakes (Baraba steppe, southern West Siberia) contain an organic-rich sapropel layer that was formed in oxygen-depleted waters. We measured the bulk sediment elemental composition, the water chemistry and determined the mineralogical composition and predominant biota species (Diatoms and Cyanobacteria in phytoplankton community respectively) in the lakes. The result indicates that the first lake has a siliceous type of sapropel and the second a carbonaceous one. A computer thermodynamic model was developed for chemical interaction in water-bottom sediment systems of the Kambala and Barchin Lakes. The surface sodium bicarbonate waters are supersaturated with respect to calcite, magnesite (or low Mg-calcite), quartz and chlorite with minor strontianite, apatite and goethite (pH 8.9-9.3, Eh 0.3 V). Nevertheless, it is shown that during sapropel deposition, deep silt waters should be anoxic (Eh<0 V). The virtual component CH2O has been used to create an anoxic environment suitable for pyrite formation due to the biotic community impact and abiotic reduction. Thermodynamic calculation has shown that silt water is not necessarily euxinic (anoxic and sulfidic). Depending on Eh, sulfate sulfur can dominate in solution, causing the formation of gypsum together with pyrite. An attempt was made to find a reason for solution supersaturation with respect to Ca and Mg ions due to their complexation with humic acids.

Concentration Dependent Physical Properties of Ge1-xSnx Solid Solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Jani, A. R.

2011-12-01

Our own proposed potential is used to investigate few physical properties like total energy, bulk modulus, pressure derivative of bulk modulus, elastic constants, pressure derivative of elastic constants, Poisson's ratio and Young's modulus of Ge1-xSnx solid solution with x is atomic concentration of α-Sn. The potential combines linear plus quadratic types of electron-ion interaction. First time screening function proposed by Sarkar et al is used to investigate the properties of the Ge-Sn solid solution system.

Investigation of Solution Polymerizations in Microgravity and 1 G

NASA Technical Reports Server (NTRS)

Kennedy, Alvin P.

1998-01-01

The in-situ dielectric spectra for the solution polymerization of polydiacetylene has been successfully measured. The results show a distinct difference between the response for the bulk solution and surface polymerization. It also shows a low frequency peak in the dissipation factor which is present in both the bulk and surface polymerizations. These features may prove to be significant indicators for important polymerization processes. Future studies will investigate the mechanisms responsible for these dielectric responses. This technique will eventually be used to monitor microgravity polymerizations and provide in-situ data on how microgravity affects solution polymerization.

The Excess Chemical Potential of Water at the Interface with a Protein from End Point Simulations.

PubMed

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

2018-05-03

We use end point simulations to estimate the excess chemical potential of water in the homogeneous liquid and at the interface with a protein in solution. When the pure liquid is taken as the reference, the excess chemical potential of interfacial water is the difference between the solvation free energy of a water molecule at the interface and in the bulk. Using the homogeneous liquid as an example, we show that the solvation free energy for growing a water molecule can be estimated by applying UWHAM to the simulation data generated from the initial and final states (i.e., "the end points") instead of multistate free energy perturbation simulations because of the possible overlaps of the configurations sampled at the end points. Then end point simulations are used to estimate the solvation free energy of water at the interface with a protein in solution. The estimate of the solvation free energy at the interface from two simulations at the end points agrees with the benchmark using 32 states within a 95% confidence interval for most interfacial locations. The ability to accurately estimate the excess chemical potential of water from end point simulations facilitates the statistical thermodynamic analysis of diverse interfacial phenomena. Our focus is on analyzing the excess chemical potential of water at protein receptor binding sites with the goal of using this information to assist in the design of tight binding ligands.

Moisture variation associated with water input and evaporation during sewage sludge bio-drying.

PubMed

Cai, Lu; Gao, Ding; Chen, Tong-Bin; Liu, Hong-Tao; Zheng, Guo-Di; Yang, Qi-Wei

2012-08-01

The variation of moisture during sewage sludge bio-drying was investigated. In situ measurements were conducted to monitor the bulk moisture and water vapor, while the moisture content, water generation, water evaporation and aeration water input of the bio-drying bulk were calculated based on the water mass balance. The moisture in the sewage sludge bio-drying material decreased from 66% to 54% in response to control technology for bio-drying. During the temperature increasing and thermophilic phases of sewage sludge bio-drying, the moisture content, water generation and water evaporation of the bulk initially increased and then decreased. The peak water generation and evaporation occurred during the thermophilic phase. During the bio-drying, water evaporation was much greater than water generation, and aeration facilitated the water evaporation. Copyright © 2012. Published by Elsevier Ltd.

Mutual Influence of Mannitol and Trehalose on Crystallization Behavior in Frozen Solutions.

PubMed

Jena, Sampreeti; Suryanarayanan, Raj; Aksan, Alptekin

2016-06-01

Phase separation of trehalose during freeze-drying could render it ineffective as a lyoprotectant. The bulking agent, mannitol, on the other hand, should crystallize readily upon freezing. It is therefore imperative to understand the mutual interaction of these sugars during freezing to ensure preservation of the API during freeze-drying. We investigated the effect of mannitol to trehalose ratio (R) on the crystallization behavior of both solutes using Differential Scanning Calorimetry, X-Ray Crystallography and FTIR Spectrosopy during controlled freezing and annealing. When R = 1, crystallization of both mannitol (as hemihydrate) and trehalose (as α-anhydrate) were observed. When R ≥ 1, extent of mannitol crystallization was directly proportional to the value of R. When R < 1, trehalose completely suppressed mannitol crystallization. At R > 1, the freeze concentrate was heterogeneous and characterized by two glass transitions - the lower temperature transition (Tg") attributed to systems containing "extra" unfrozen water. When heated above Tg", crystallization of mannitol and the associated unfrozen water resulted in Tg' (glass transition temperature of the freeze-concentrate). R and not the total solute concentration, dictates the composition of the freeze concentrate as well as the physical stability of the excipients.

Charge Behaviors around Oxide Device/Pseudo-Physiological Solution Interface with Molecular Dynamic Simulations

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Shibuta, Yasushi; Sakata, Toshiya

2013-12-01

In this study, we investigated the charge behaviors of ions and water molecules at the oxide device/pseudo-physiological solution interface by use of molecular dynamics (MD) simulations because the detection principle of semiconductor-based biosensors is based on the detection of charge density changes at the oxide sensing surface in physiological environments. In particular, we designed an alpha-quartz (100) surface with some charges corresponding to pH=5.5 so that the ionic behaviors for 500 mM each of Na+ and Cl- around the interface were calculated under the surface condition with charges, considering a real system. As a result of the simulation, we defined the region of Debye length from the calculated potential distribution, in which some parameters such as diffusion coefficient and the vibration of water molecules around the interface differed from those of the bulk solution. The elucidation of the solid/liquid interfacial behaviors by the simulation technique should deepen our understanding of the detection principle of semiconductor-based biosensors and will give guidelines for the design of a bio-interface in the field of biosensing technology, because they cannot be demonstrated experimentally.

Does an electronic continuum correction improve effective short-range ion-ion interactions in aqueous solution?

NASA Astrophysics Data System (ADS)

Bruce, Ellen E.; van der Vegt, Nico F. A.

2018-06-01

Non-polarizable force fields for hydrated ions not always accurately describe short-range ion-ion interactions, frequently leading to artificial ion clustering in bulk aqueous solutions. This can be avoided by adjusting the nonbonded anion-cation or cation-water Lennard-Jones parameters. This approach has been successfully applied to different systems, but the parameterization is demanding owing to the necessity of separate investigations of each ion pair. Alternatively, polarization effects may effectively be accounted for using the electronic continuum correction (ECC) of Leontyev et al. [J. Chem. Phys. 119, 8024 (2003)], which involves scaling the ionic charges with the inverse square-root of the water high-frequency dielectric permittivity. ECC has proven to perform well for monovalent salts as well as for divalent salts in water. Its performance, however, for multivalent salts with higher valency remains unexplored. The present work illustrates the applicability of the ECC model to trivalent K3PO4 and divalent K2HPO4 in water. We demonstrate that the ECC models, without additional tuning of force field parameters, provide an accurate description of water-mediated interactions between salt ions. This results in predictions of the osmotic coefficients of aqueous K3PO4 and K2HPO4 solutions in good agreement with experimental data. Analysis of ion pairing thermodynamics in terms of contact ion pair (CIP), solvent-separated ion pair, and double solvent-separated ion pair contributions shows that potassium-phosphate CIP formation is stronger with trivalent than with divalent phosphate ions.

Plexcitonics: Coupled and Plasmon-Exciton Systems with Tailorable Properties

DTIC Science & Technology

2013-11-14

demonstrated efficient steam generation from aqueous nanoparticles solutions without heating the bulk volume of the liquid. Application in ethanol ...solutions without heating the bulk volume of the liquid. Applications in ethanol distillation and sanitation have been demonstrated. Key Accomplishments...nanoparticle surface. This state-selective population of adsorbate resonances could be exploited to prepare reactants in specific states on nanoparticle

Formation and Stability of Bulk Nanobubbles Generated by Ethanol-Water Exchange.

PubMed

Qiu, Jie; Zou, Zhenglei; Wang, Shuo; Wang, Xingya; Wang, Lei; Dong, Yaming; Zhao, Hongwei; Zhang, Lijuan; Hu, Jun

2017-05-19

Bulk nanobubbles have unique properties and find potential applications in many important processes. However, their stability or long lifetime still needs to be understood and has attracted much attention from researchers. Bulk nanobubbles are generated based on ethanol-water exchange, a method that is generally used in the study of surface nanobubbles. Their formation and stability is further studied by using a new type of dynamic light scattering known as NanoSight. The results show that the concentration of the bulk nanobubbles produced by this method is about five times greater than that in the degassed group, which indicates the existence of bulk gas nanobubbles. The effects of ethanol/water ratios and temperature on the stability of the bulk nanobubbles have also been studied and their numbers reach a maximum at a ratio of about 1:10 (v/v). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental Observation of Bulk Liquid Water Structure in ``No Man's Land''

NASA Astrophysics Data System (ADS)

Sellberg, Jonas; McQueen, Trevor; Huang, Congcong; Loh, Duane; Laksmono, Hartawan; Sierra, Raymond; Hampton, Christina; Starodub, Dmitri; Deponte, Daniel; Martin, Andrew; Barty, Anton; Wikfeldt, Thor; Schlesinger, Daniel; Pettersson, Lars; Beye, Martin; Nordlund, Dennis; Weiss, Thomas; Feldkamp, Jan; Caronna, Chiara; Seibert, Marvin; Messerschmidt, Marc; Williams, Garth; Boutet, Sebastien; Bogan, Michael; Nilsson, Anders

2013-03-01

Experiments on pure bulk water below about 235 K have so far been difficult: water crystallization occurs very rapidly below the homogeneous nucleation temperature of 232 K and above 160 K, leading to a ``no man's land'' devoid of experimental results regarding the structure. Here, we demonstrate a new, general experimental approach to study the structure of liquid states at supercooled conditions below their limit of homogeneous nucleation. We use femtosecond x-ray pulses generated by the LCLS x-ray laser to probe evaporatively cooled droplets of supercooled bulk water and find experimental evidence for the existence of metastable bulk liquid water down to temperatures of 223 K in the previously largely unexplored ``no man's land''. We acknoweledge NSF (CHE-0809324), Office of Basic Energy Sciences, and the Swedish Research Council for financial support.

The structure of aqueous sodium hydroxide solutions: a combined solution x-ray diffraction and simulation study.

PubMed

Megyes, Tünde; Bálint, Szabolcs; Grósz, Tamás; Radnai, Tamás; Bakó, Imre; Sipos, Pál

2008-01-28

To determine the structure of aqueous sodium hydroxide solutions, results obtained from x-ray diffraction and computer simulation (molecular dynamics and Car-Parrinello) have been compared. The capabilities and limitations of the methods in describing the solution structure are discussed. For the solutions studied, diffraction methods were found to perform very well in describing the hydration spheres of the sodium ion and yield structural information on the anion's hydration structure. Classical molecular dynamics simulations were not able to correctly describe the bulk structure of these solutions. However, Car-Parrinello simulation proved to be a suitable tool in the detailed interpretation of the hydration sphere of ions and bulk structure of solutions. The results of Car-Parrinello simulations were compared with the findings of diffraction experiments.

Entropy and enthalpy of interaction between amino acid side chains in nanopores

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

Vaitheeswaran, S., E-mail: vaithee05@gmail.com; Thirumalai, D.; Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742

2014-12-14

Understanding the stabilities of proteins in nanopores requires a quantitative description of confinement induced interactions between amino acid side chains. We use molecular dynamics simulations to study the nature of interactions between the side chain pairs ALA-PHE, SER-ASN, and LYS-GLU in bulk water and in water-filled nanopores. The temperature dependence of the bulk solvent potentials of mean force and the interaction free energies in cylindrical and spherical nanopores is used to identify the corresponding entropic and enthalpic components. The entropically stabilized hydrophobic interaction between ALA and PHE in bulk water is enthalpically dominated upon confinement depending on the relative orientationsmore » between the side chains. In the case of SER-ASN, hydrogen bonded configurations that are similar in bulk water are thermodynamically distinct in a cylindrical pore, thus making rotamer distributions different from those in the bulk. Remarkably, salt bridge formation between LYS-GLU is stabilized by entropy in contrast to the bulk. Implications of our findings for confinement-induced alterations in protein stability are briefly outlined.« less

EFFECTIVE POROSITY IMPLIES EFFECTIVE BULK DENSITY IN SORBING SOLUTE TRANSPORT

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

Flach, G.

2012-02-27

The concept of an effective porosity is widely used in solute transport modeling to account for the presence of a fraction of the medium that effectively does not influence solute migration, apart from taking up space. This non-participating volume or ineffective porosity plays the same role as the gas phase in single-phase liquid unsaturated transport: it increases pore velocity, which is useful towards reproducing observed solute travel times. The prevalent use of the effective porosity concept is reflected by its prominent inclusion in popular texts, e.g., de Marsily (1986), Fetter (1988, 1993) and Zheng and Bennett (2002). The purpose ofmore » this commentary is to point out that proper application of the concept for sorbing solutes requires more than simply reducing porosity while leaving other material properties unchanged. More specifically, effective porosity implies the corresponding need for an effective bulk density in a conventional single-porosity model. The reason is that the designated non-participating volume is composed of both solid and fluid phases, both of which must be neglected for consistency. Said another way, if solute does not enter the ineffective porosity then it also cannot contact the adjoining solid. Conceptually neglecting the fluid portion of the non-participating volume leads to a lower (effective) porosity. Likewise, discarding the solid portion of the non-participating volume inherently leads to a lower or effective bulk density. In the author's experience, practitioners virtually never adjust bulk density when adopting the effective porosity approach.« less

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

Design and development of guar gum based novel, superabsorbent and moisture retaining hydrogels for agricultural applications.

PubMed

Thombare, Nandkishore; Mishra, Sumit; Siddiqui, M Z; Jha, Usha; Singh, Deodhari; Mahajan, Gopal R

2018-04-01

The novel hydrogels were synthesized by grafting guar gum with acrylic acid and cross-linking with ethylene glycol di methacrylic acid (EGDMA). The synthesis of hydrogel was confirmed by characterization through 13 C NMR, FTIR spectroscopy, SEM micrography, thermo-gravimetric analysis and water absorption studies under different solutions. Synthesized hydrogel (GG-AA-EGDMA) was confirmed to be biodegradable with half-life period of 77 days through soil burial biodegradation studies. The effects of hydrogel treatment on soil were evaluated by studying various physico-chemical properties of soil like bulk density, porosity, water absorption and retention capacity etc. The hydrogel which could absorb up to 800 ml water per gram, after addition to soil, improved its porosity, moisture absorption and retention capacity significantly. Water holding capacity of water increased up to 54% of its original and porosity also increased up to 9% of its original. The synthesized hydrogel revealed tremendous potential as soil conditioning material for agricultural applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

From solid to liquid: Assessing the release of carbon from soil into solution in response to forest management

NASA Astrophysics Data System (ADS)

James, J. N.; Gross, C. D.; Butman, D. E.; Harrison, R. B.

2016-12-01

Dissolved organic matter (DOM) is a crucial conduit for internal cycling of carbon within soils as well as for the transfer of organic matter out of soil and into aquatic systems. Little is known about how the quantity, quality, lability and chemical characteristics of DOM changes in response to human management of forest soils. To examine the processes that release soil organic matter (SOM) into solution, we gathered samples from adjacent native and industrially managed Eucalyptus grandis plantation forests across Sao Paulo State, Brazil and from adjacent old-growth and Douglas-fir (Pseudotsuga menzisii) plantation forests in the coastal Pacific Northwest. Samples from each soil horizon were taken from soil profiles excavated to at least 1.5 m at each site. Water extractable organic matter (WEOM) was extracted twice from each sample using 0.5 M K2SO4 and Milli-Q water to quantify both dissolved and exchange phase organic matter. These extracts were measured for total organic carbon (TOC), 13C and 14C, and chemical characteristics were assessed by fluorescence spectroscopy (EEMs and SUVA254). At the same time, solid phase characteristics of the soil samples were quantified, including bulk density, pH, total carbon and nitrogen, microbial biomass, and 13C and 14C. Characterization of bulk SOM was undertaken by Fourier Transform Infrared Spectroscopy (FTIR) by subtracting mineral matrix spectra of each sample from the bulk spectra. Organic matter lability was assessed by incubations using difference in TOC for WEOM extracts and repeated measurement of CO2 efflux for bulk SOM. All together, these analyses permit a unique snapshot of the natural separation of organic matter from solid into liquid phase through the entire soil profile. Initial results reveal that small but measureable quantities of WEOM may be released from deep B and C horizons in soil, and that this material is labile to microbial decomposition. By identifying differences in SOM and DOM cycling due to forest management, this study aims to connect human management of terrestrial forest ecosystems to the transport of organic matter from surface and subsurface horizons to freshwater ecosystems, where it forms a major component of aquatic food webs.

Theoretical and Simulations-Based Modeling of Micellization in Linear and Branched Surfactant Systems

NASA Astrophysics Data System (ADS)

Mendenhall, Jonathan D.

Surfactants are chemically-heterogeneous molecules possessing hydrophilic (head) and hydrophobic (tail) moieties. This dual nature of surfactants leads to interesting phase behavior in aqueous solution as a function of surfactant concentration, including: (i) formation of surfactant monolayers at surfaces and interfaces, and (ii) self-assembly into finite aggregates (micelles) in the bulk solution beyond the critical micelle concentration (cmc). This concentration-dependent phase behavior induces changes in solution properties. For example, the surface activity of surfactants can decrease the surface tension, and self-assembly in bulk solution can lead to changes in viscosity, equivalent conductivity, solubilization capacity, and other bulk properties. These effects make surfactants quite attractive and unique for use in product formulations, where they are utilized as detergents, dispersants, emulsifiers, solubilizers, surface and interfacial tension modifiers, and in other contexts. The specific chemical structure of the surfactant head and tail is essential in determining the overall performance properties of a surfactant in aqueous media. The surfactant tail drives the self-assembly process through the hydrophobic effect, while the surfactant head imparts a certain extent of solubility to the surfactant in aqueous solution through preferential interactions with the hydrogen-bonding network of water. The interplay between these two effects gives rise to the particular phase diagram of a surfactant, including the specific cmc at which micelles begin to form. In addition to serving as a quantitative indicator of micelle formation, the cmc represents a limit to surface monolayer formation, and hence to surface and interfacial tension reduction, because surfactant adsorption at interfaces remains approximately constant beyond the cmc. In addition, the cmc represents the onset of changes in bulk solution properties. This Thesis is concerned with the prediction of cmc's and other micellization properties for a variety of linear and branched surfactant chemical architectures which are commonly encountered in practice. Single-component surfactant solutions are investigated, in order to clarify the specific contributions of the surfactant head and tail to the free energy of micellization, a quantity which determines the cmc and all other aspects of micellization. First, a molecular-thermodynamic (MT) theory is presented which makes use of bulk-phase thermodynamics and a phenomenological thought process to describe the energetics related to the formation of a micelle from its constituent surfactant monomers. Second, a combined computer-simulation/molecular-thermodynamic (CSMT) framework is discussed which provides a more detailed quantification of the hydrophobic effect using molecular dynamics simulations. A novel computational strategy to identify surfactant head and tail using an iterative dividing surface approach, along with simulated micelle results, is proposed. Force-field development for novel surfactant structures is also discussed. Third, a statistical-thermodynamic, single-chain, mean-field theory for linear and branched tail packing is formulated, which enables quantification of the specific energetic penalties related to confinement and constraint of surfactant tails within micelles. Finally, these theoretical and simulations-based strategies are used to predict the micellization behavior of 55 linear surfactants and 28 branched surfactants. Critical micelle concentration and optimal micelle properties are reported and compared with experiment, demonstrating good agreement across a range of surfactant head and tail types. In particular, the CSMT framework is found to provide improved agreement with experimental cmc's for the branched surfactants considered. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

Dehydration process in NaCl solutions under various external electric fields

NASA Astrophysics Data System (ADS)

Kadota, Kazunori; Shimosaka, Atsuko; Shirakawa, Yoshiyuki; Hidaka, Jusuke

2007-06-01

Ionic motions at solid-liquid interface in supersaturated NaCl solutions have been investigated by molecular dynamics (MD) simulation for understanding crystal growth processes. The density profile in the vicinity of the interfaces between NaCl(100) and the supersaturated NaCl solution was calculated. Diffusion coefficients of water molecules in the solution were estimated as a function of distance from the crystal interface. It turned out that the structure and dynamics of the solution in the interfaces was different from those of bulk solution owing to electric fields depending on the surface charge. Therefore, the electric field was applied to the supersaturated solutions and dehydration phenomenon occurring in the process of the crystal growth was discussed. As the electric field increased, it was observed that the Na+ keeping strongly hydration structure broke out by the electric force. In supersaturated concentration, the solution structure is significantly different from that of dilution and has a complicated structure with hydration ions and clusters of NaCl. If the electric fields were applied to the solutions, the breakout of hydration structure was not affected with increasing the supersaturated ratio. This reason is that the cluster structures are destroyed by the electric force. The situation depends on the electric field or crystal surface structure.

Probing the conformational dynamics of photosystem I in unconfined and confined spaces.

PubMed

Das, Gaurav; Chattoraj, Shyamtanu; Nandi, Somen; Mondal, Prasenjit; Saha, Abhijit; Bhattacharyya, Kankan; Ghosh, Surajit

2017-12-20

The fluorescence dynamics of Photosystem I (PSI) in bulk water and inside a confined environment like a liposome have been investigated using time resolved confocal microscopy. In bulk water, PSI exhibits a major emission peak at ∼680 nm, while in the liposome it exhibits a markedly blue shifted emission maximum at ∼485 nm. This is indicative of conformational changes due to entrapment and emergence of a stressed conformation of PSI inside the liposome. The observed time constants for the fluorescence lifetime of PSI inside the liposome are significantly high as opposed to PSI in bulk water. More interestingly, the fluorescence intensity of PSI in bulk water exhibits strong fluctuations with many high intensity jumps and these are anti-correlated with the fluorescence lifetime of PSI. In contrast, inside the liposome, no such anti-correlated behaviour is observed. We further demonstrated that PSI exhibits at least two conformational states in bulk water, whereas a single conformation is observed inside the liposome, indicating the conformational rigidity and locking of the PSI complex inside a liposome.

Effects of Water on Structure and Dynamics of Trehalose Glasses at Low Water Contents and its Relationship to Preservation Outcomes

NASA Astrophysics Data System (ADS)

Weng, Lindong; Ziaei, Shima; Elliott, Gloria D.

2016-07-01

Dry preservation of biologics in sugar glasses is regarded as a promising alternative to conventional cryopreservation. Evidence from various studies has suggested that there is a critical range of water content beyond which the viability of preserved biologics can be greatly compromised. In this study the viability of T-cells was determined as a function of end water content after microwave-assisted drying in trehalose solutions. Hydrogen-bonding and clustering phenomena in trehalose solutions of the same moisture content were also evaluated using molecular dynamics simulation. Post-rehydration viability decreased dramatically within the range of 0.1-1 gH2O/gdw. Molecular modeling revealed that as the water content approached 0.1 gH2O/gdw the matrix formed a large interconnected trehalose skeleton with a minimal number of bound water molecules scattered in the bulk. The diffusion coefficients of trehalose oxygen atoms most distant from the glycosidic linkage fluctuated around 7.5 × 10-14 m2/s within the range of 0.02-0.1 gH2O/gdw and increased again to ~1.13 × 10-13 m2/s at 0.01 gH2O/gdw and below due to the loss of water in the free volume between trehalose molecules. These insights can guide the optimal selection of final moisture contents to advance dry preservation methods.

Effects of Water on Structure and Dynamics of Trehalose Glasses at Low Water Contents and its Relationship to Preservation Outcomes.

PubMed

Weng, Lindong; Ziaei, Shima; Elliott, Gloria D

2016-07-08

Dry preservation of biologics in sugar glasses is regarded as a promising alternative to conventional cryopreservation. Evidence from various studies has suggested that there is a critical range of water content beyond which the viability of preserved biologics can be greatly compromised. In this study the viability of T-cells was determined as a function of end water content after microwave-assisted drying in trehalose solutions. Hydrogen-bonding and clustering phenomena in trehalose solutions of the same moisture content were also evaluated using molecular dynamics simulation. Post-rehydration viability decreased dramatically within the range of 0.1-1 gH2O/gdw. Molecular modeling revealed that as the water content approached 0.1 gH2O/gdw the matrix formed a large interconnected trehalose skeleton with a minimal number of bound water molecules scattered in the bulk. The diffusion coefficients of trehalose oxygen atoms most distant from the glycosidic linkage fluctuated around 7.5 × 10(-14) m(2)/s within the range of 0.02-0.1 gH2O/gdw and increased again to ~1.13 × 10(-13) m(2)/s at 0.01 gH2O/gdw and below due to the loss of water in the free volume between trehalose molecules. These insights can guide the optimal selection of final moisture contents to advance dry preservation methods.

Ion Diffusion Within Water Films in Unsaturated Porous Media.

PubMed

Tokunaga, Tetsu K; Finsterle, Stefan; Kim, Yongman; Wan, Jiamin; Lanzirotti, Antonio; Newville, Matthew

2017-04-18

Diffusion is important in controlling local solute transport and reactions in unsaturated soils and geologic formations. Although it is commonly assumed that thinning of water films controls solute diffusion at low water contents, transport under these conditions is not well understood. We conducted experiments in quartz sands at low volumetric water contents (θ) to quantify ion diffusion within adsorbed films. At the lowest water contents, we employed fixed relative humidities to control water films at nm thicknesses. Diffusion profiles for Rb + and Br - in unsaturated sand packs were measured with a synchrotron X-ray microprobe, and inverse modeling was used to determine effective diffusion coefficients, D e, as low as ∼9 × 10 -15 m 2 s -1 at θ = 1.0 × 10 -4 m 3 m -3 , where the film thickness = 0.9 nm. Given that the diffusion coefficients (D o ) of Rb + and Br - in bulk water (30 °C) are both ∼2.4 × 10 -9 m 2 s -1 , we found the impedance factor f = D e /(θD o ) is equal to 0.03 ± 0.02 at this very low saturation, in agreement with the predicted influence of interface tortuosity (τ a ) for diffusion along grain surfaces. Thus, reduced cross-sectional area (θ) and tortuosity largely accounted for the more than 5 orders of magnitude decrease in D e relative to D o as desaturation progressed down to nanoscale films.

In-situ suspended aggregate microextraction of gold nanoparticles from water samples and determination by electrothermal atomic absorption spectrometry.

PubMed

Choleva, Tatiana G; Kappi, Foteini A; Tsogas, George Z; Vlessidis, Athanasios G; Giokas, Dimosthenis L

2016-05-01

This work describes a new method for the extraction and determination of gold nanoparticles in environmental samples by means of in-situ suspended aggregate microextraction and electrothermal atomic absorption spectrometry. The method relies on the in-situ formation of a supramolecular aggregate phase through ion-association between a cationic surfactant and a benzene sulfonic acid derivative. Gold nanoparticles are physically entrapped into the aggregate phase which is separated from the bulk aqueous solution by vacuum filtration on the surface of a cellulose filter in the form of a thin film. The film is removed from the filter surface and is dissociated into an acidified methanolic solution which is used for analysis. Under the optimized experimental conditions, gold nanoparticles can be efficiently extracted from water samples with recovery rates between 81.0-93.3%, precision 5.4-12.0% and detection limits as low as 75femtomolL(-1) using only 20mL of sample volume. The satisfactory analytical features of the method along with the simplicity indicate the efficiency of this new approach to adequately collect and extract gold nanoparticle species from water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

On the localisation of four-dimensional brane-world black holes: II. The general case

NASA Astrophysics Data System (ADS)

Kanti, P.; Pappas, N.; Pappas, T.

2016-01-01

We perform a comprehensive analysis of a number of scalar field theories in an attempt to find analytically five-dimensional, localised-on-the-brane, black-hole solutions. Extending a previous analysis, we assume a generalised Vaidya ansatz for the five-dimensional metric tensor that allows for a time-dependent, non-trivial profile of the mass function in terms of the bulk coordinate and a deviation from the over-restricting Schwarzschild-type solution on the brane. In order to support such a solution, we study a variety of theories including single or multiple scalar fields, with canonical or non-canonical kinetic terms, minimally or non-minimally coupled to gravity. We demonstrate that for such a metric ansatz and for a carefully chosen energy-momentum tensor which is non-isotropic in five dimensions, solutions that have the form of a Schwarzschild-(anti)de Sitter or Reissner-Nordstrom type of solution do emerge. However, the resulting profile of the mass function along the bulk coordinate, when allowed, is not the correct one for eliminating bulk singularities.

Dynamics of glycerine and water transport across human skin from binary mixtures.

PubMed

Ventura, S A; Kasting, G B

2017-04-01

Skin transport properties of glycerine and water from binary mixtures contacting human skin were determined to better understand the mechanism of skin moisturization by aqueous glycerine formulations. Steady-state permeation for 3 H 2 O and 14 C-glycerine across split-thickness human skin in vitro and desorption dynamics of the same permeants in isolated human stratum corneum (HSC) were experimentally determined under near equilibrium conditions. These data were compared to a priori values developed in the context of a thermodynamic model for binary mixtures of glycerine and water and a previously determined water sorption isotherm for HSC. This allowed the estimation of diffusion and partition coefficients for each permeant in the HSC, as well as HSC thickness, as a function of composition of the contacting solution. These data may be used to estimate water retention and associated HSC swelling related to the absorption and slow release of glycerine from the skin. It took 6+ days for glycerine to completely desorb from HSC immersed in glycerine/water binary solutions. Desorption of both 3 H 2 O and 14 C-glycerine from HSC was slower in pure water than from binary mixtures, a result that is largely explained by the greater swelling of HSC in water. Parametric relationships were developed for water and glycerine intradiffusivities in HSC as functions of HSC water content, and a mutual diffusion coefficient was estimated by analogy with glycerine/water binary solutions. The intradiffusivity of 14 C-glycerine in HSC as inferred from sorption/desorption experiments was shown to be approximately 10-fold less than that inferred from permeation experiments, whereas the corresponding values for 3 H 2 O were comparable. These studies confirm that glycerine enters HSC in substantial quantities and has a long residence time therein. The coupling between bulk water and glycerine transport projected from binary solution data suggests the net effect of glycerine is to slow water loss from the skin. The data support the concept of glycerine as a humectant with an excellent balance of skin penetration and retention characteristics; however, they do not rule out the possibility of an additional biological effect on skin barrier homoeostasis. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Aggregation of concentrated monoclonal antibody solutions studied by rheology and neutron scattering

NASA Astrophysics Data System (ADS)

Castellanos, Maria Monica; Pathak, Jai; Colby, Ralph

2013-03-01

Protein solutions are studied using rheology and scattering techniques to investigate aggregation. Here we present a monoclonal antibody (mAb) that aggregates after incubation at 40 °C (below its unfolding temperature), with a decrease in monomer purity of 6% in 10 days. The mAb solution contains surfactant and behaves as a Newtonian fluid when reconstituted into solution from the lyophilized form (before incubation at 40 °C). In contrast, mAb solutions incubated at 40 °C for 1 month exhibit shear yielding in torsional bulk rheometers. Interfacial rheology reveals that interfacial properties are controlled by the surfactant, producing a negligible surface contribution to the bulk yield stress. These results provide evidence that protein aggregates formed in the bulk are responsible for the yield stress. Small-angle neutron scattering (SANS) measurements show an increase in intensity at low wavevectors (q < 4*10-2 nm-1) that we attribute to protein aggregation, and is not observed in solutions stored at 4 °C for 3 days before the measurement. This work suggests a correlation between the aggregated state of the protein (stability) and the yield stress from rheology. Research funded by MedImmune

Novel Fluorinated Tensioactive Extractant Combined with Flotation for Decontamination of Extractant Residual during Solvent Extraction

NASA Astrophysics Data System (ADS)

Wu, Xue; Chang, Zhidong; Liu, Yao; Choe, Chol Ryong

2017-12-01

Solvent-extraction is widely used in chemical industry. Due to the amphiphilic character, a large amount of extractant remains in water phase, which causes not only loss of reagent, but also secondary contamination in water phase. Novel fluorinated extractants with ultra-low solubility in water were regarded as effective choice to reduce extractant loss in aqueous phase. However, trace amount of extractant still remained in water. Based on the high tensioactive aptitude of fluorinated solvent, flotation was applied to separate fluorinated extractant remaining in raffinate. According to the data of surface tension measurement, the surface tension of solution was obviously decreased with the addition of fluorinated extractant tris(2,2,3,3,4,4,5,5-octafluoropentyl) phosphate (FTAP). After flotation, the FTAP dissolved in water can be removed as much as 70%, which proved the feasibility of this key idea. The effects of operation time, gas velocity, pH and salinity of bulk solution on flotation performance were discussed. The optimum operating parameters were determined as gas velocity of 12ml/min, operating time of 15min, pH of 8.7, and NaCl volume concentration of 1.5%, respectively. Moreover, adsorption process of FTAP on bubble surface was simulated by ANSYS VOF model using SIMPLE algorithm. The dynamic mechanism of flotation was also theoretically investigated, which can be considered as supplement to the experimental results.

Facile and Green Production of Impurity-Free Aqueous Solutions of WS2 Nanosheets by Direct Exfoliation in Water.

PubMed

Pan, Long; Liu, Yi-Tao; Xie, Xu-Ming; Ye, Xiong-Ying

2016-12-01

To obtain 2D materials with large quantity, low cost, and little pollution, liquid-phase exfoliation of their bulk form in water is a particularly fascinating concept. However, the current strategies for water-borne exfoliation exclusively employ stabilizers, such as surfactants, polymers, or inorganic salts, to minimize the extremely high surface energy of these nanosheets and stabilize them by steric repulsion. It is worth noting, however, that the remaining impurities inevitably bring about adverse effects to the ultimate performances of 2D materials. Here, a facile and green route to large-scale production of impurity-free aqueous solutions of WS 2 nanosheets is reported by direct exfoliation in water. Crucial parameters such as initial concentration, sonication time, centrifugation speed, and centrifugation time are systematically evaluated to screen out an optimized condition for scaling up. Statistics based on morphological characterization prove that substantial fraction (66%) of the obtained WS 2 nanosheets are one to five layers. X-ray diffraction and Raman characterizations reveal a high quality with few, if any, structural distortions. The water-borne exfoliation route opens up new opportunities for easy, clean processing of WS 2 -based film devices that may shine in the fields of, e.g., energy storage and functional nanocomposites owing to their excellent electrochemical, mechanical, and thermal properties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterotrophic bacteria in drinking water distribution system: a review.

PubMed

Chowdhury, Shakhawat

2012-10-01

The microbiological quality of drinking water in municipal water distribution systems (WDS) depends on several factors. Free residual chlorine and/or chloramines are typically used to minimize bacterial recontamination and/or regrowth in WDS. Despite such preventive measures, regrowth of heterotrophic (HPC) and opportunistic bacteria in bulk water and biofilms has yet to be controlled completely. No approach has shown complete success in eliminating biofilms or HPC bacteria from bulk water and pipe surfaces. Biofilms can provide shelter for pathogenic bacteria and protect these bacteria from disinfectants. Some HPC bacteria may be associated with aesthetic and non-life threatening diseases. Research to date has achieved important success in understanding occurrence and regrowth of bacteria in bulk water and biofilms in WDS. To achieve comprehensive understanding and to provide efficient control against bacteria regrowth, future research on bacteria regrowth dynamics and their implications is warranted. In this study, a review was performed on the literature published in this area. The findings and limitations of these papers are summarized. Occurrences of bacteria in WDS, factors affecting bacteria regrowth in bulk water and biofilms, bacteria control strategies, sources of nutrients, human health risks from bacterial exposure, modelling of bacteria regrowth and methods of bacteria sampling and detection and quantification are investigated. Advances to date are noted, and future research needs are identified. Finally, research directions are proposed to effectively control HPC and opportunistic bacteria in bulk water and biofilms in WDS.

On the molecular origin of the cooperative coil-to-globule transition of poly(N-isopropylacrylamide) in water† †Electronic supplementary information (ESI) available: Stereochemistry and initial conformation of PNIPAM 30-mer; pair distribution functions of PNIPAM methyl groups; average time of transitions of dihedral angles; distribution of methyl dihedral angles; temperature dependence of average number of hydration water molecules; correlation between hydrogen bonding of water molecules per repeating unit in the FHS and end to end distance and correlation between PNIPAM–water hydrogen bonding and end to end distance. Time evolution of PNIPAM with the first hydration shell: movie FHSpnipam.avi. See DOI: 10.1039/c8cp00537k

PubMed Central

Zaccarelli, E.

2018-01-01

By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the water soluble states of PNIPAM we detect a correlation between polymer segmental dynamics and diffusion motion of bound water, occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently, the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in the proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in the bulk displays a decreased structuring of solvent at the hydrophobic polymer–water interface across the transition temperature, as expected because of the topological extension along the chain of such interface. No evidence of an upper critical solution temperature behaviour, postulated in theoretical and thermodynamics studies of PNIPAM aqueous solution, is observed in the low temperature domain. PMID:29619464

Where's the Water in (Salty) Ice?

NASA Astrophysics Data System (ADS)

Kahan, T.; Malley, P.

2017-12-01

Solutes can have large effects on reactivity in ice and at ice surfaces. Freeze concentration ("the salting out effect") forms liquid regions containing high solute concentrations surrounded by relatively solute-free ice. Thermodynamics can predict the fraction of ice that is liquid for a given temperature and (pre-frozen) solute concentration, as well as the solute concentration within these liquid regions, but they do not inform on the spatial distribution of the solutes and the liquid regions within the ice. This leads to significant uncertainty in predictions of reaction kinetics in ice and at ice surfaces. We have used Raman microscopy to determine the location of liquid regions within ice and at ice surface in the presence of sodium chloride (NaCl). Under most conditions, liquid channels are observed at the ice surface and throughout the ice bulk. The fraction of the ice that is liquid, as well as the widths of these channels, increases with increasing temperature. Below the eutectic temperature (-21.1 oC), no liquid is observed. Patches of NaCl.2H2O ("hydrohalite") are observed at the ice surface under these conditions. These results will improve predictions of reaction kinetics in ice and at ice surfaces.

Complex Behavior of Aqueous α-Cyclodextrin Solutions. Interfacial Morphologies Resulting from Bulk Aggregation.

PubMed

Hernandez-Pascacio, Jorge; Piñeiro, Ángel; Ruso, Juan M; Hassan, Natalia; Campbell, Richard A; Campos-Terán, José; Costas, Miguel

2016-07-05

The spontaneous aggregation of α-cyclodextrin (α-CD) molecules in the bulk aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K using a battery of techniques: transmission electron microscopy, dynamic light scattering, dynamic surface tensiometry, Brewster angle microscopy, neutron reflectometry, and ellipsometry. We show that α-CD molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to the liquid/air interface with their size in the bulk determining the adsorption rate. The material that reaches the interface coalesces laterally to form two-dimensional domains on the micrometer scale with a layer thickness on the nanometer scale. These processes are affected by the ages of both the bulk and the interface. The interfacial layer formed is not in fast dynamic equilibrium with the subphase as the resulting morphology is locked in a kinetically trapped state. These results reveal a surprising complexity of the parallel physical processes taking place in the bulk and at the interface of what might have seemed initially like a simple system.

Microbiological Tests Performed During the Design of the International Space Station ECLSS: Part 1, Bulk Phase Water and Wastewater

NASA Technical Reports Server (NTRS)

Roman, Monsi C.; Mittelman, Marc W.

2010-01-01

This slide presentation summarizes the studies performed to assess the bulk phase microbial community during the Space Station Water Recover Tests (WRT) from 1990-1998. These tests show that it is possible to recycle water from different sources including urine, and produce water that can exceed the quality of municpally produced tap water.

Tritium migration to the surfaces of Type 316 stainless steel; aluminum 6061; and oxygen-free, high-conductivity copper

DOE PAGES

Sharpe, M.; Shmayda, W. T.; Schroder, W. U.

2016-05-25

The migration of tritium to the surfaces of aluminum 6061, oxygen-free, high-conductivity copper (OFHC), and stainless-steel 316 from the bulk metal was studied using low-pressure Tonks–Langmuir argon plasma. The plasma is shown to be effective at removing tritium from metal surfaces in a controlled manner. Tritium is removed in decreasing quantities with successive plasma exposures, which suggests a depletion of the surface and near-surface tritium inventories. A diffusion model was developed to predict tritium migration from the bulk and its accumulation in the water layers present on the metal surface. The model reproduces the rate of tritium re-growth on themore » surface for all three metals and can be used to calculate the triton solubility in the water layers present on metal surfaces. The ratio of surface-to-bulk solubilities at the water-layer/bulk-metal interface uniquely determines the concentration ratio between these two media. Removing the tritium-rich water layers induces tritium to migrate from the bulk to the surface. Furthermore, this process is driven by a concentration gradient that develops in the bulk because of the perturbation on the surface.« less

Poly(vinyl methyl ether) hydrogels at temperatures below the freezing point of water-molecular interactions and states of water.

PubMed

Pastorczak, Marcin; Dominguez-Espinosa, Gustavo; Okrasa, Lidia; Pyda, Marek; Kozanecki, Marcin; Kadlubowski, Slawomir; Rosiak, Janusz M; Ulanski, Jacek

2014-01-01

Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the pre-melting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above -60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting.

Aspects of the zero Λ limit in the AdS/CFT correspondence

NASA Astrophysics Data System (ADS)

Caldeira Costa, R. N.

2014-11-01

We examine the correspondence between QFT observables and bulk solutions in the context of AdS/CFT in the limit as the cosmological constant Λ →0 . We focus specifically on the spacetime metric and a nonbackreacting scalar in the bulk, compute the one-point functions of the dual operators, and determine the necessary conditions for the correspondence to admit a well-behaved zero-Λ limit. We discuss holographic renormalization in this limit and find that it requires schemes that partially break diffeomorphism invariance of the bulk theory. In the specific case of three bulk dimensions, we compute the zero-Λ limit of the holographic Weyl anomaly and reproduce the central charge that arises in the central extension of bms3 . We compute holographically the energy and momentum of those QFT states dual to flat cosmological solutions and to the Kerr solution and find an agreement with the bulk theory. We also compute holographically the renormalized two-point function of a scalar operator in the zero-Λ limit and find it to be consistent with that of a conformal operator in two dimensions fewer. Finally, our results can be used in a new definition of asymptotic Ricci flatness at null infinity based on the zero-Λ limit of asymptotically Einstein manifolds.

Effect of mixing, concentration and temperature on the formation of mesostructured solutions and their role in the nucleation of DL-valine crystals.

PubMed

Jawor-Baczynska, Anna; Moore, Barry D; Sefcik, Jan

2015-01-01

We report investigations on the formation of mesostructured solutions in DL-valine-water-2-propanol mixtures, and the crystallization of DL-valine from these solutions. Mesostructured liquid phases, similar to those previously observed in aqueous solutions of glycine and DL-alanine, were observed using Dynamic Light Scattering and Brownian microscopy, in both undersaturated and supersaturated solutions below a certain transition temperature. Careful experimentation was used to demonstrate that the optically clear mesostructured liquid phase, comprising colloidal mesoscale clusters dispersed within bulk solution, is thermodynamically stable and present in equilibrium with the solid phase at saturation conditions. Solutions prepared by slow cooling contained mesoscale clusters with a narrow size distribution and a mean hydrodynamic diameter of around 200 nm. Solutions of identical composition prepared by rapid isothermal mixing of valine aqueous solutions with 2-propanol contained mesoscale clusters which were significantly larger than those observed in slowly cooled solutions. The presence of larger mesoscale clusters was found to correspond to faster nucleation. Observed induction times were strongly dependent on the rapid initial mixing step, although solutions were left undisturbed afterwards and the induction times observed were up to two orders of magnitude longer than the initial mixing period. We propose that mesoscale clusters above a certain critical size are likely to be the location of productive nucleation events.

Structure and dynamics of water near the interface with oligo(ethylene oxide) self-assembled monolayers

NASA Astrophysics Data System (ADS)

Ismail, Ahmed E.; Grest, Gary S.; Stevens, Mark J.

2007-03-01

Oligo(ethylene oxide) self-assembled monolayers (OEO SAM's) deposited on Au are the prototypical materials used to study protein resistance. Recently, protein resistance has been shown to vary as a function of surface coverage and to be maximal at about two-thirds coverage, not complete coverage. We use molecular dynamics simulations to study the nature of the interface between water and the OEO SAM for a range of SAM coverages. As SAM coverage decreases, the amount of water within the OEO monolayer increases monotonically; however, the penetration depth of the water shows a maximum near the experimentally-found maximal coverage. As the water content increases, the SAM-water mixture becomes harder to distinguish from bulk water. Since the oxygen atoms of OEO are hydrogen bond acceptors, a hydrogen bond network forms within the SAM-water mixture. The water molecules diffuse freely within the monolayer and exchange with the bulk water. Because the monolayer becomes increasingly like bulk water as the coverage decreases, proteins stay in their bulk soluble conformation and do not adsorb. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract No. DE-AC04-94AL85000.

Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

PubMed

Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

2016-11-17

A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

Faecal bulking efficacy of Australasian breakfast cereals.

PubMed

Monro, John A

2002-01-01

Faecal bulk may play an important role in preventing a range of disorders of the large bowel, but as yet there is little information available on the relative faecal bulking capacities of various foods. Breakfast cereals are often promoted as a good source of potential bulk for 'inner health' because they provide dietary fibre, but their relative abilities to provide faecal bulk per se have not been described. The faecal bulking efficacy of 28 representative Australasian breakfast cereals was therefore measured. A rat model developed for the purpose, and shown to give similar responses as humans to cereal fibres, was used to measure faecal bulking efficacy as increases in fully hydrated faecal weight/100 g diet, based on precise measurements of food intake, faecal dry matter output and faecal water-holding capacity (g water held without stress/g faecal dry matter). Compared to a baseline diet containing 50% sucrose, increments in hydrated faecal weight due to 50% breakfast cereal ranged from slightly negative (Cornflakes, -2 g/100 g diet) to about 80 g/100 g diet (San Bran). Most breakfast cereals increased hydrated faecal weight by between 10 and 20 g/100 g diet from a baseline of 21 +/- 1.5 g/100 g diet, but four products containing high levels of wheat bran had an exceptionally large impact on hydrated faecal weight (increment > 20 g/100 g diet), and the changes resulted more from relative changes in dry matter output than in faecal water retention/gram. However, as faecal water retention was about 2.5 g water/g faecal dry matter on average, increases in dry matter represented large increases in faecal water load. Faecal bulking indices (FBI) for most of the breakfast cereals were less than 20 (wheat bran = 100). The content of wheat bran equivalents for faecal bulk (WBE(fb)) in the breakfast cereals was calculated from FBI. Most breakfast cereals contributed, per serve, less than 10% of a theoretical daily reference value for faecal bulk (DRV(fb) = 63 WBE(fb)/day), which was based on data from human clinical trials and dietary fibre recommendations. Based on the WBE(fb) contribution/serving that would be required to meet the DRV(fb) from the number of servings of dietary fibre sources in the CSIRO 12345+ food and nutrition plan, the results suggest that although some high bran breakfast cereals may contribute substantially to, and many are reasonable sources of, faecal bulk, for most of them, one or two servings at breakfast cannot be relied on to effectively redress shortfalls in faecal bulk elsewhere in the diet.

Assessment of groundwater quality by unsaturated zone study due to migration of leachate from Abloradjei waste disposal site, Ghana

NASA Astrophysics Data System (ADS)

Egbi, Courage Davidson; Akiti, Tetteh Thomas; Osae, Shiloh; Dampare, Samuel Boakye; Abass, Gibrilla; Adomako, Dickson

2017-05-01

Leachate generated by open solid waste disposal sites contains substances likely to contaminate groundwater. The impact of potential contaminants migrating from leachate on groundwater can be quantified by monitoring their concentration and soil properties at specific points in the unsaturated zone. In this study, physical and chemical analyses were carried out on leachate, soil and water samples within the vicinity of the municipal solid waste disposal site at Abloradjei, a suburb of Accra, Ghana. The area has seen a massive increase in population and the residents depend on groundwater as the main source of water supply. Results obtained indicate alkaline pH for leachate and acidic conditions for unsaturated zone water. High EC values were recorded for leachate and unsaturated zone water. Major ions (Ca2+, Na+, Mg2+, K+, NO3 -, SO4 2-, Cl-, PO4 3- were analysed in leachate, unsaturated zone water, soil solution and groundwater while trace metals (Al, Fe, Cu, Zn, Pb) were analysed in both soil and extracted soil solution. Concentrations of major ions were high in all samples indicating possible anthropogenic origin. Mean % gravel, % sand, % clay, bulk density, volumetric water content and porosity were 28.8, 63.93, 6.6, 1 g cm-3, 35 and 62.7 %, respectively. Distribution of trace elements showed Kd variation of Al > Cu > Fe > Pb > Zn in the order of sequential increasing solubility. It was observed that the quality of groundwater is not suitable for drinking.

Protein Conformation and Supercharging with DMSO from Aqueous Solution

NASA Astrophysics Data System (ADS)

Sterling, Harry J.; Prell, James S.; Cassou, Catherine A.; Williams, Evan R.

2011-07-01

The efficacy of dimethyl sulfoxide (DMSO) as a supercharging reagent for protein ions formed by electrospray ionization from aqueous solution and the mechanism for supercharging were investigated. Addition of small amounts of DMSO to aqueous solutions containing hen egg white lysozyme or equine myoglobin results in a lowering of charge, whereas a significant increase in charge occurs at higher concentrations. Results from both near-UV circular dichroism spectroscopy and solution-phase hydrogen/deuterium exchange mass spectrometry indicate that DMSO causes a compaction of the native structure of these proteins at low concentration, but significant unfolding occurs at ~63% and ~43% DMSO for lysozyme and myoglobin, respectively. The DMSO concentrations required to denature these two proteins in bulk solution are ~3-5 times higher than the concentrations required for the onset of supercharging, consistent with a significantly increased concentration of this high boiling point supercharging reagent in the ESI droplet as preferential evaporation of water occurs. DMSO is slightly more basic than m-nitrobenzyl alcohol and sulfolane, two other supercharging reagents, based on calculated proton affinity and gas-phase basicity values both at the B3LYP and MP2 levels of theory, and all three of these supercharging reagents are significantly more basic than water. These results provide additional evidence that the origin of supercharging from aqueous solution is the result of chemical and/or thermal denaturation that occurs in the ESI droplet as the concentration of these supercharging reagents increases, and that proton transfer reactivity does not play a significant role in the charge enhancement observed.

Origins of protein denatured state compactness and hydrophobic clustering in aqueous urea: inferences from nonpolar potentials of mean force.

PubMed

Shimizu, Seishi; Chan, Hue Sun

2002-12-01

Free energies of pairwise hydrophobic association are simulated in aqueous solutions of urea at concentrations ranging from 0-8 M. Consistent with the expectation that hydrophobic interactions are weakened by urea, the association of relatively large nonpolar solutes is destabilized by urea. However, the association of two small methane-sized nonpolar solutes in water has the opposite tendency of being slightly strengthened by the addition of urea. Such size effects and the dependence of urea-induced stability changes on the configuration of nonpolar solutes are not predicted by solvent accessible surface area approaches based on energetic parameters derived from bulk-phase solubilities of model compounds. Thus, to understand hydrophobic interactions in proteins, it is not sufficient to rely solely on transfer experiment data that effectively characterize a single nonpolar solute in an aqueous environment but not the solvent-mediated interactions among two or more nonpolar solutes. We find that the m-values for the rate of change of two-methane association free energy with respect to urea concentration is a dramatically nonmonotonic function of the spatial separation between the two methanes, with a distance-dependent profile similar to the corresponding two-methane heat capacity of association in pure water. Our results rationalize the persistence of residual hydrophobic contacts in some proteins at high urea concentrations and explain why the heat capacity signature (DeltaC(P)) of a compact denatured state can be similar to DeltaC(P) values calculated by assuming an open random-coil-like unfolded state. Copyright 2002 Wiley-Liss, Inc.

Sample preparation of metal alloys by electric discharge machining

NASA Technical Reports Server (NTRS)

Chapman, G. B., II; Gordon, W. A.

1976-01-01

Electric discharge machining was investigated as a noncontaminating method of comminuting alloys for subsequent chemical analysis. Particulate dispersions in water were produced from bulk alloys at a rate of about 5 mg/min by using a commercially available machining instrument. The utility of this approach was demonstrated by results obtained when acidified dispersions were substituted for true acid solutions in an established spectrochemical method. The analysis results were not significantly different for the two sample forms. Particle size measurements and preliminary results from other spectrochemical methods which require direct aspiration of liquid into flame or plasma sources are reported.

In situ hydride formation in titanium during focused ion milling.

PubMed

Ding, Rengen; Jones, Ian P

2011-01-01

It is well known that titanium and its alloys are sensitive to electrolytes and thus hydrides are commonly observed in electropolished foils. In this study, focused ion beam (FIB) milling was used to prepare thin foils of titanium and its alloys for transmission electron microscopy. The results show the following: (i) titanium hydrides were observed in pure titanium, (ii) the preparation of a bulk sample in water or acid solution resulted in the formation of more hydrides and (iii) FIB milling aids the precipitation of hydrides, but there were never any hydrides in Ti64 and Ti5553.

The effect of dissolution of volcanic glass on the water chemistry in a tuffaceous aquifer, Rainier Mesa, Nevada

USGS Publications Warehouse

White, Art F.; Claassen, H.C.; Benson, Larry V.

1980-01-01

Geochemistry of ground water associated with the Tertiary tuffs within Rainier Mesa, southern Nevada, was investigated to determine the relative importance of glass dissolution in controlling water chemistry. Water samples were obtained both from interstitial pores in core sections and from free-flowing fractures. Cation com- positions showed that calcium and magnesium decreased as a function of depth in the mesa, as sodium increased. The maximum effect occurs within alteration zones containing clinoptilolite and montmorillonite, suggesting these minerals effectively remove bivalent cations from the system. Comparisons are made between compositions of ground waters found within Rainier Mesa that apparently have not reacted with secondary minerals and compositions of waters produced by experimental dissolution of vitric and crystalline tufts which comprise the principal aquifers in the area. The two tuff phases have the same bulk chemistry but produce aqueous solutions of different chemistry. Rapid parabolic dissolution of sodium and silica from, and the retention of, potassium within the vitric phase verify previous predictions concerning water compositions associated with vitric volcanic rocks. Parabolic dissolution of the crystalline phase results in solutions high in calcium and magnesium and low in silica. Extrapolation of the parabolic dissolution mechanism for the vitric tuff to long times successfully reproduces, at com- parable pH, cation ratios existing in Rainier Mesa ground water. Comparison of mass- transfer rates of the vitric and crystalline tuffs indicates that the apparent higher glass-surface to aqueous-volume ratio associated with the vitric rocks may account for dominance of the glass reaction.

Characterization of protein hydration by solution NMR spectroscopy

NASA Astrophysics Data System (ADS)

Wand, Joshua

A comprehensive understanding of the interactions between protein molecules and hydration water remains elusive. Solution nuclear magnetic resonance (NMR) spectroscopy has been proposed as a means to characterize these interactions but is plagued with artifacts when employed in bulk aqueous solution. Encapsulation of proteins in reverse micelles prepared in short chain alkane solvents can overcome these technical limitations. Application of this approach has revealed that the interaction of water with the surface of protein molecules is quite heterogeneous with some regions of the protein having long-lived interactions while other regions show relatively transient hydration. Results from several proteins will be presented including ubiquitin, staphylococcal nuclease, interleukin 1beta, hen egg white lysozyme (HEWL) and T4 lysozyme. Ubiquitin and interleukin 1beta are signaling proteins and interact with other proteins through formation of dry protein-protein interfaces. Interestingly, the protein surfaces of the free proteins show relatively slowed (restricted) motion at the surface, which is indicative of low residual entropy. Other regions of the protein surface have relatively high mobility water. These results are consistent with the idea that proteins have evolved to maximize the hydrophobic effect in optimization of binding with protein partners. As predicted by simulation and theory, we find that hydration of internal hydrophobic cavities of interleukin 1beta and T4 lysozyme is highly disfavored. In contrast, the hydrophilic polar cavity of HEWL is occupied by water. Initial structural correlations suggest that hydration of alpha helical structure is characterized by relatively mobile water while those of beta strands and loops are more ordered and slowed. These and other results from this set of proteins reveals that the dynamical and structural character of hydration of proteins is heterogeneous and complex. Supported by the National Science Foundation.

Sulfadiazine/ciprofloxacin promote opportunistic pathogens occurrence in bulk water of drinking water distribution systems.

PubMed

Wang, Haibo; Shen, Yi; Hu, Chun; Xing, Xueci; Zhao, Dan

2018-03-01

Effects of sulfadiazine and ciprofloxacin on the occurrence of free-living and particle-associated opportunistic pathogens in bulk water of simulated drinking water distribution systems (DWDSs) were investigated. It was found that sulfadiazine and ciprofloxacin greatly promoted the occurrence of opportunistic pathogens including Pseudomonas aeruginosa, Legionella pneumophila, Mycobacterium avium and its broader genus Mycobacterium spp., as well as the amoebae Acanthamoeba spp. and Hartmanella vermiformis, in bulk water of DWDSs. Moreover, sulfadiazine and ciprofloxacin exhibited much stronger combined effects on the increase of these opportunistic pathogens. Based on the analysis of the antibiotic resistance genes (ARGs) and extracellular polymeric substances (EPS), it was verified that EPS production was increased by the antibiotic resistant bacteria arising from the effects of sulfadiazine/ciprofloxacin. The combined effects of sulfadiazine and ciprofloxacin induced the greatest increase of EPS production in DWDSs. Furthermore, the increased EPS with higher contents of proteins and secondary structure β-sheet led to greater bacterial aggregation and adsorption. Meanwhile, large numbers of suspended particles were formed, increasing the chlorine-resistance capability, which was responsible for the enhancement of the particle-associated opportunistic pathogens in bulk water of DWDSs with sulfadiazine/ciprofloxacin. Therefore, sulfadiazine and ciprofloxacin promoted the occurrence of particle-associated opportunistic pathogens in bulk water of DWDSs due to the role of EPS produced by the bacteria with ARGs. Copyright © 2017 Elsevier Ltd. All rights reserved.

The interaction of NO2 with BaO: from cooperative adsorption to Ba(NO3)2 formation

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

Yi, Cheol-Woo W.; Kwak, Ja Hun; Szanyi, Janos

2007-10-25

The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. The conversion of surface to bulk Ba-nitrates is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation ofmore » nitrites and bulk nitrates exclusively, i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.« less

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS.

PubMed

Eklund, Lars; Hofer, Tomas S; Persson, Ingmar

2015-01-28

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2(-), chlorate, ClO3(-), and perchlorate, ClO4(-). In addition, the structures of the hydrated hypochlorite, ClO(-), bromate, BrO3(-), iodate, IO3(-) and metaperiodate, IO4(-), ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO6(3-), ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01-0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

PubMed Central

Eklund, Lars; Hofer, Tomas S.

2014-01-01

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2−, chlorate, ClO3−, and perchlorate, ClO4−. In addition, the structures of the hydrated hypochlorite, ClO−, bromate, BrO3−, iodate, IO3− and metaperiodate, IO4−, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO63−, ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5=1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5=2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions. PMID:25473816

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

DOE PAGES

Eklund, Lars; Hofer, Tomas S.; Persson, Ingmar

2014-11-26

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO 2 –, chlorate, ClO 3 –, and perchlorate, ClO 4 –. In addition, the structures of the hydrated hypochlorite, ClO –, bromate, BrO 3 –, iodate, IO 3 – and metaperiodate, IO 4 –, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H 2IO 6 3–, ions have been determinedmore » by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl–O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. Here, the water exchange rate for the perchlorate ion is significantly faster, τ 0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ 0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.« less

Examining the structural evolution of bicarbonate–water clusters: insights from photoelectron spectroscopy, basin-hopping structural search, and comparison with available IR spectral studies

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

Wen, Hui; Hou, Gao-Lei; Liu, Yi-Rong

2016-05-31

Bicarbonate serves a crucial biochemical role in the physiological pH buffering system and also has important atmospheric implications. In the current study, HCO 3 $-$(H 2O) n (n = 0-13) clusters were successfully produced via electrospray ionization of corresponding bulk salt solution, and were characterized by combining negative ion photoelectron spectroscopy and theoretical calculations. The photoelectron spectra reveal that the electron binding energy monotonically increases with the cluster size up to n = 10 and remains largely the same after n > 10. The photo-detaching feature of the solute HCO3$-$itself, which dominates in the small clusters, diminishes with increase ofmore » water coverage. Based on the charge distribution and molecular orbital analyses, the universal high electron binding energy tail that dominates in the larger clusters can be attributed to ionization of water. Thus, the transition of ionization from solute to solvent at the size larger than n=10 has been observed. Extensive theoretical structural search based on the Basin-Hopping unbiased method was carried out, and a plethora of low energy isomers have been obtained for each medium and large size. By comparing the simulated photoelectron spectra and calculated electron binding energies with the experiments, as well as by comparing the simulated infrared spectra with previously reported IR spectra, the probable global minima and the structural evolutionary routes are presented. The nature of bicarbonate-water interactions are mainly electrostatic as implied by the electron localization function (ELF) analysis.« less

Encapsulation of organic light emitting diodes

NASA Astrophysics Data System (ADS)

Visweswaran, Bhadri

Organic Light Emitting Diodes (OLEDs) are extremely attractive candidates for flexible display and lighting panels due to their high contrast ratio, light weight and flexible nature. However, the materials in an OLED get oxidized by extremely small quantities of atmospheric moisture and oxygen. To obtain a flexible OLED device, a flexible thin-film barrier encapsulation with low permeability for water is necessary. Water permeates through a thin-film barrier by 4 modes: microcracks, contaminant particles, along interfaces, and through the bulk of the material. We have developed a flexible barrier film made by Plasma Enhanced Chemical Vapor Deposition (PECVD) that is devoid of any microcracks. In this work we have systematically reduced the permeation from the other three modes to come up with a barrier film design for an operating lifetime of over 10 years. To provide quantitative feedback during barrier material development, techniques for measuring low diffusion coefficient and solubility of water in a barrier material have been developed. The mechanism of water diffusion in the barrier has been identified. From the measurements, we have created a model for predicting the operating lifetime from accelerated tests when the lifetime is limited by bulk diffusion. To prevent the particle induced water permeation, we have encapsulated artificial particles and have studied their cross section. A three layer thin-film that can coat a particle at thicknesses smaller than the particle diameter is identified. It is demonstrated to protect a bottom emission OLED device that was contaminated with standard sized glass beads. The photoresist and the organic layers below the barrier film causes sideways permeation that can reduce the lifetime set by permeation through the bulk of the barrier. To prevent the sideways permeation, an impermeable inorganic grid made of the same barrier material is designed. The reduction in sideways permeation due to the impermeable inorganic grid is demonstrated in an encapsulated OLED. In this work, we have dealt with three permeation mechanisms and shown solution to each of them. These steps give us reliable flexible encapsulation that has a lifetime of greater than 10 years.

Nano-composites for water remediation: a review.

PubMed

Tesh, Sarah J; Scott, Thomas B

2014-09-17

As global populations continue to increase, the pressure on water supplies will inevitably intensify. Consequently the international need for more efficient and cost effective water remediation technologies will also rise. The introduction of nano-technology into the industry may represent a significant advancement and zero-valent iron nano-particles (INPs) have been thoroughly studied for potential remediation applications. However, the application of water dispersed INP suspensions is limited and somewhat contentious on the grounds of safety, whilst INP reaction mechanisms, transport properties and ecotoxicity are areas still under investigation. Theoretically, the development of nano-composites containing INPs to overcome these issues provides the logical next step for developing nano-materials that are better suited to wide application across the water industry. This review provides an overview of the range of static, bulk nano-composites containing INPs being developed, whilst highlighting the limitations of individual solutions, overall classes of technology, and lack of comparative testing for nano-composites. The review discusses what further developments are needed to optimize nano-composite water remediation systems to subsequently achieve commercial maturity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning the tetrahedrality of the hydrogen-bonded network of water: Comparison of the effects of pressure and added salts

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

Prasad, Saurav, E-mail: saurav7188@gmail.com, E-mail: cyz118212@chemistry.iitd.ac.in; Chakravarty, Charusita

Experiments and simulations demonstrate some intriguing equivalences in the effect of pressure and electrolytes on the hydrogen-bonded network of water. Here, we examine the extent and nature of equivalence effects between pressure and salt concentration using relationships between structure, entropy, and transport properties based on two key ideas: first, the approximation of the excess entropy of the fluid by the contribution due to the atom-atom pair correlation functions and second, Rosenfeld-type excess entropy scaling relations for transport properties. We perform molecular dynamics simulations of LiCl–H{sub 2}O and bulk SPC/E water spanning the concentration range 0.025–0.300 molefraction of LiCl at 1more » atm and pressure range from 0 to 7 GPa, respectively. The temperature range considered was from 225 to 350 K for both the systems. To establish that the time-temperature-transformation behaviour of electrolyte solutions and water is equivalent, we use the additional observation based on our simulations that the pair entropy behaves as a near-linear function of pressure in bulk water and of composition in LiCl–H{sub 2}O. This allows for the alignment of pair entropy isotherms and allows for a simple mapping of pressure onto composition. Rosenfeld-scaling implies that pair entropy is semiquantitatively related to the transport properties. At a given temperature, equivalent state points in bulk H{sub 2}O and LiCl–H{sub 2}O (at 1 atm) are defined as those for which the pair entropy, diffusivity, and viscosity are nearly identical. The microscopic basis for this equivalence lies in the ability of both pressure and ions to convert the liquid phase into a pair-dominated fluid, as demonstrated by the O–O–O angular distribution within the first coordination shell of a water molecule. There are, however, sharp differences in local order and mechanisms for the breakdown of tetrahedral order by pressure and electrolytes. Increasing pressure increases orientational disorder within the first neighbour shell while addition of ions shifts local orientational order from tetrahedral to close-packed as water molecules get incorporated in ionic hydration shells. The variations in local order within the first hydration shell may underlie ion-specific effects, such as the Hofmeister series.« less

Tuning the tetrahedrality of the hydrogen-bonded network of water: Comparison of the effects of pressure and added salts

NASA Astrophysics Data System (ADS)

Prasad, Saurav; Chakravarty, Charusita

2016-06-01

Experiments and simulations demonstrate some intriguing equivalences in the effect of pressure and electrolytes on the hydrogen-bonded network of water. Here, we examine the extent and nature of equivalence effects between pressure and salt concentration using relationships between structure, entropy, and transport properties based on two key ideas: first, the approximation of the excess entropy of the fluid by the contribution due to the atom-atom pair correlation functions and second, Rosenfeld-type excess entropy scaling relations for transport properties. We perform molecular dynamics simulations of LiCl-H2O and bulk SPC/E water spanning the concentration range 0.025-0.300 molefraction of LiCl at 1 atm and pressure range from 0 to 7 GPa, respectively. The temperature range considered was from 225 to 350 K for both the systems. To establish that the time-temperature-transformation behaviour of electrolyte solutions and water is equivalent, we use the additional observation based on our simulations that the pair entropy behaves as a near-linear function of pressure in bulk water and of composition in LiCl-H2O. This allows for the alignment of pair entropy isotherms and allows for a simple mapping of pressure onto composition. Rosenfeld-scaling implies that pair entropy is semiquantitatively related to the transport properties. At a given temperature, equivalent state points in bulk H2O and LiCl-H2O (at 1 atm) are defined as those for which the pair entropy, diffusivity, and viscosity are nearly identical. The microscopic basis for this equivalence lies in the ability of both pressure and ions to convert the liquid phase into a pair-dominated fluid, as demonstrated by the O-O-O angular distribution within the first coordination shell of a water molecule. There are, however, sharp differences in local order and mechanisms for the breakdown of tetrahedral order by pressure and electrolytes. Increasing pressure increases orientational disorder within the first neighbour shell while addition of ions shifts local orientational order from tetrahedral to close-packed as water molecules get incorporated in ionic hydration shells. The variations in local order within the first hydration shell may underlie ion-specific effects, such as the Hofmeister series.

Water-Induced Morphology Changes in BaO/gamma-Al2O3 NOx Storage Materials: an FTIR, TPD, and Time-Resolved Synchrotron XRD Study

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

Szanyi,J.; Kwak, J.; Kim, D.

2007-01-01

The effect of water on the morphology of BaO/Al{sub 2}O{sub 3}-based NO{sub x} storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multispectroscopy study reveal that in the presence of water surface Ba-nitrates convert to bulk nitrates and water facilitates the formation of large Ba(NO{sub 3}){sub 2} particles. The conversion of surface to bulk Ba-nitrates is completely reversible (i.e., after the removal of water from the storage material a significant fraction of the bulk nitrates reconverts to surface nitrates). NO{sub 2} exposure of a H{sub 2}O-containing (wet)more » BaO/Al{sub 2}O{sub 3} sample results in the formation of nitrites and bulk nitrates exclusively (i.e., no surface nitrates form). After further exposure to NO{sub 2}, the nitrites completely convert to bulk nitrates. The amount of NO{sub x} taken up by the storage material, however, is essentially unaffected by the presence of water regardless of whether the water was dosed prior to or after NO{sub 2} exposure. On the basis of the results of this study, we are now able to explain most of the observations reported in the literature on the effect of water on NO{sub x} uptake on similar storage materials.« less

Experimentally quantifying anion polarizability at the air/water interface.

PubMed

Tong, Yujin; Zhang, Igor Ying; Campen, R Kramer

2018-04-03

The adsorption of large, polarizable anions from aqueous solution on the air/water interface controls important atmospheric chemistry and is thought to resemble anion adsorption at hydrophobic interfaces generally. While the favourability of adsorption of such ions is clear, quantifying adsorption thermodynamics has proven challenging because it requires accurate description of the structure of the anion and its solvation shell at the interface. In principle anion polarizability offers a structural window, but to the best of our knowledge there has so far been no experimental technique that allowed its characterization with interfacial specificity. Here, we meet this challenge using interface-specific vibrational spectroscopy of Cl-O vibrations of the [Formula: see text] anion at the air/water interface and report that the interface breaks the symmetry of the anion, the anisotropy of [Formula: see text]'s polarizability tensor is more than two times larger than in bulk water and concentration dependent, and concentration-dependent polarizability changes are consistent with correlated changes in surface tension.

Ice-surface adsorption enhanced colligative effect of antifreeze proteins in ice growth inhibition

NASA Astrophysics Data System (ADS)

Mao, Yougang; Ba, Yong

2006-09-01

This Communication describes a mechanism to explain antifreeze protein's function to inhibit the growth of ice crystals. We propose that the adsorption of antifreeze protein (AFP) molecules on an ice surface induces a dense AFP-water layer, which can significantly decrease the mole fraction of the interfacial water and, thus, lower the temperature for a seed ice crystal to grow in a super-cooled AFP solution. This mechanism can also explain the nearly unchanged melting point for the ice crystal due to the AFP's ice-surface adsorption. A mathematical model combining the Langmuir theory of adsorption and the colligative effect of thermodynamics has been proposed to find the equilibrium constants of the ice-surface adsorptions, and the interfacial concentrations of AFPs through fitting the theoretical curves to the experimental thermal hysteresis data. This model has been demonstrated by using the experimental data of serial size-mutated beetle Tenebrio molitor (Tm) AFPs. It was found that the AFP's ice-surface adsorptions could increase the interfacial AFP's concentrations by 3 to 4 orders compared with those in the bulk AFP solutions.

Optical label-free and model-free probe of the surface potential of nanoscale and microscopic objects in aqueous solution

NASA Astrophysics Data System (ADS)

Lütgebaucks, Cornelis; Gonella, Grazia; Roke, Sylvie

2016-11-01

The electrostatic environment of aqueous systems is an essential ingredient for the function of any living system. To understand the electrostatic properties and their molecular foundation in soft, living, and three-dimensional systems, we developed a table-top model-free method to determine the surface potential of nano- and microscopic objects in aqueous solutions. Angle-resolved nonresonant second harmonic (SH) scattering measurements contain enough information to determine the surface potential unambiguously, without making assumptions on the structure of the interfacial region. The scattered SH light that is emitted from both the particle interface and the diffuse double layer can be detected in two different polarization states that have independent scattering patterns. The angular shape and intensity are determined by the surface potential and the second-order surface susceptibility. Calibrating the response with the SH intensity of bulk water, a single, unique surface potential value can be extracted. We demonstrate the method with 80 nm bare oil droplets in water and ˜50 nm dioleoylphosphatidylcholine (DOPC) and dioleoylphosphatidylserine (DOPS) liposomes at various ionic strengths.

The dynamical crossover phenomenon in bulk water, confined water and protein hydration water.

PubMed

Mallamace, Francesco; Corsaro, Carmelo; Baglioni, Piero; Fratini, Emiliano; Chen, Sow-Hsin

2012-02-15

We discuss a phenomenon regarding water that was until recently a subject of scientific controversy, i.e. the dynamical crossover from fragile-to-strong glass-forming material, for both bulk and protein hydration water. Such a crossover is characterized by a temperature T(L) at which significant dynamical changes occur, such as violation of the Stokes-Einstein relation and changes of behaviour of homologous transport parameters such as the density relaxation time and the viscosity. In this respect we will consider carefully the dynamic properties of water-protein systems. More precisely, we will study proteins and their hydration water as far as bulk and confined water. In order to clarify the controversy we will discuss in a comparative way many previous and new experimental data that have emerged using different techniques and molecular dynamic simulation (MD). We point out the reasons for the different dynamical findings from the use of different experimental techniques.

Thermal Conductivity of Diamond Packed Electrospun PAN-Based Carbon Fibers Incorporated with Multi Wall Carbon Nanotubes.

PubMed

Dong, Qi; Lu, Chunyuan; Tulugan, Kelimu; Jin, Chunzi; Yoon, Soo Jong; Park, Yeong Min; Kim, Tae Gyu

2016-02-01

Multi wall carbon nanotubes (MWCNTs) and diamond are renowned as superlative material due to their relatively high thermal conductivity and hardness while comparing with any bulk materials. In this research, polyacrylonitrile (PAN) solution incorporated with MWCNTs at an alteration of mass fractions (0 wt%, 0.6 wt%, 1 wt%, 2 wt%) were fabricated via electrospinning under optimized parameters. Dried composite nanofibers were stabilized and carbonized, after which water base polytrafluorethylene (PTFE) mixed with nano diamond powder solution was spin coated on them. Scanning electron microscopy, Raman spectroscopy, X-ray scattering and Laserflash thermal conductivity were used to characterize the composite nanofiber sheets. The result shows that the thermal conductivity increased to 4.825 W/m K from 2.061 W/mK. The improvement of thermal conductivities is suggesting the incorporation of MWCNTs.

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

PubMed

Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

2016-08-25

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules of arbitrary structure.

21 CFR 1250.67 - Watering equipment.

Code of Federal Regulations, 2014 CFR

2014-04-01

... permanent signs warning that the water is unfit for drinking. (c) Ice. If bulk ice is used for the cooling..., washing, handling, and delivery to conveyances of such bulk ice, and such equipment shall be used for no...

21 CFR 1250.67 - Watering equipment.

Code of Federal Regulations, 2012 CFR

2012-04-01

... permanent signs warning that the water is unfit for drinking. (c) Ice. If bulk ice is used for the cooling..., washing, handling, and delivery to conveyances of such bulk ice, and such equipment shall be used for no...

21 CFR 1250.67 - Watering equipment.

Code of Federal Regulations, 2011 CFR

2011-04-01

... permanent signs warning that the water is unfit for drinking. (c) Ice. If bulk ice is used for the cooling..., washing, handling, and delivery to conveyances of such bulk ice, and such equipment shall be used for no...

21 CFR 1250.67 - Watering equipment.

Code of Federal Regulations, 2013 CFR

2013-04-01

... permanent signs warning that the water is unfit for drinking. (c) Ice. If bulk ice is used for the cooling..., washing, handling, and delivery to conveyances of such bulk ice, and such equipment shall be used for no...

Strong Dependence of Hydration State of F-Actin on the Bound Mg(2+)/Ca(2+) Ions.

PubMed

Suzuki, Makoto; Imao, Asato; Mogami, George; Chishima, Ryotaro; Watanabe, Takahiro; Yamaguchi, Takaya; Morimoto, Nobuyuki; Wazawa, Tetsuichi

2016-07-21

Understanding of the hydration state is an important issue in the chemomechanical energetics of versatile biological functions of polymerized actin (F-actin). In this study, hydration-state differences of F-actin by the bound divalent cations are revealed through precision microwave dielectric relaxation (DR) spectroscopy. G- and F-actin in Ca- and Mg-containing buffer solutions exhibit dual hydration components comprising restrained water with DR frequency f2 (fw). The hydration state of F-actin is strongly dependent on the ionic composition. In every buffer tested, the HMW signal Dhyme (≡ (f1 - fw)δ1/(fwδw)) of F-actin is stronger than that of G-actin, where δw is DR-amplitude of bulk solvent and δ1 is that of HMW in a fixed-volume ellipsoid containing an F-actin and surrounding water in solution. Dhyme value of F-actin in Ca2.0-buffer (containing 2 mM Ca(2+)) is markedly higher than in Mg2.0-buffer (containing 2 mM Mg(2+)). Moreover, in the presence of 2 mM Mg(2+), the hydration state of F-actin is changed by adding a small fraction of Ca(2+) (∼0.1 mM) and becomes closer to that of the Ca-bound form in Ca2.0-buffer. This is consistent with the results of the partial specific volume and the Cotton effect around 290 nm in the CD spectra, indicating a change in the tertiary structure and less apparent change in the secondary structure of actin. The number of restrained water molecules per actin (N2) is estimated to be 1600-2100 for Ca2.0- and F-buffer and ∼2500 for Mg2.0-buffer at 10-15 °C. These numbers are comparable to those estimated from the available F-actin atomic structures as in the first water layer. The number of HMW molecules is roughly explained by the volume between the equipotential surface of -kT/2e and the first water layer of the actin surface by solving the Poisson-Boltzmann equation using UCSF Chimera.

Soil water retention of a bare soil with changing bulk densities

USDA-ARS?s Scientific Manuscript database

Tillage changes the bulk density of the soil, lowering the density initially after which it increases as the soil settles. Implications of this for soil water content and soil water potential are obvious, but limited efforts have been made to monitor these changes continuously. We present in-situ me...

Eco-friendly synthesis of metal dichalcogenides nanosheets and their environmental remediation potential driven by visible light

PubMed Central

Mishra, Ashish Kumar; Lakshmi, K. V.; Huang, Liping

2015-01-01

Exfoliated transition metal dichalcogenides (TMDs) such as WS2 and MoS2 have shown exciting potential for energy storage, catalysis and optoelectronics. So far, solution based methods for scalable production of few-layer TMDs usually involve the use of organic solvents or dangerous chemicals. Here, we report an eco-friendly method for facile synthesis of few-layer WS2 and MoS2 nanosheets using dilute aqueous solution of household detergent. Short time sonication of varying amount of bulk samples in soapy water was used to scale up the production of nanosheets. Thermal stability, optical absorption and Raman spectra of as-synthesized WS2 and MoS2 nanosheets are in close agreement with those from other synthesis techniques. Efficient photocatalytic activity of TMDs nanosheets was demonstrated by decomposing Brilliant Green dye in aqueous solution under visible light irradiation. Our study shows the great potential of TMDs nanosheets for environmental remediation by degrading toxic industrial chemicals in wastewater using sunlight. PMID:26503125

Eco-friendly synthesis of metal dichalcogenides nanosheets and their environmental remediation potential driven by visible light

NASA Astrophysics Data System (ADS)

Mishra, Ashish Kumar; Lakshmi, K. V.; Huang, Liping

2015-10-01

Exfoliated transition metal dichalcogenides (TMDs) such as WS2 and MoS2 have shown exciting potential for energy storage, catalysis and optoelectronics. So far, solution based methods for scalable production of few-layer TMDs usually involve the use of organic solvents or dangerous chemicals. Here, we report an eco-friendly method for facile synthesis of few-layer WS2 and MoS2 nanosheets using dilute aqueous solution of household detergent. Short time sonication of varying amount of bulk samples in soapy water was used to scale up the production of nanosheets. Thermal stability, optical absorption and Raman spectra of as-synthesized WS2 and MoS2 nanosheets are in close agreement with those from other synthesis techniques. Efficient photocatalytic activity of TMDs nanosheets was demonstrated by decomposing Brilliant Green dye in aqueous solution under visible light irradiation. Our study shows the great potential of TMDs nanosheets for environmental remediation by degrading toxic industrial chemicals in wastewater using sunlight.

Spherically symmetric solutions and gravitational collapse in brane-worlds

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

Heydari-Fard, Malihe; Sepangi, Hamid R., E-mail: heydarifard@qom.ac.ir, E-mail: hr-sepangi@sbu.ac.ir

2009-02-15

We consider spherically symmetric solutions within the context of brane-world theory without mirror symmetry or any form of junction conditions. For a constant curvature bulk, we obtain the modified Tolman-Oppenheimer-Volkoff (TOV) interior solutions in two cases where one is matched to a schwarzschild-de Sitter exterior while the other is consistent with an exterior solution whose structure can be used to explain the galaxy rotation curves without postulating dark matter. We also find the upper bound to the mass of a static brane-world star and show that the influence of the bulk effects on the interior solutions is small. Finally, wemore » investigate the gravitational collapse on the brane and show that the exterior of a collapsing star can be static in this scenario.« less

Evaluation and quantification of reprocessing modification in single-use devices in interventional cardiology

NASA Astrophysics Data System (ADS)

Tessarolo, Francesco; Ferrari, Paolo; Silvia, Bortoluzzi; Motta, Antonella; Migliaresi, Claudio; Zennaro, Lucio; Rigo, Adelio; Guarrera, Giovanni Maria; Nollo, Giandomenico

2004-11-01

The increasing demand in interventional cardiology urges for reprocessing of single-use-labelled medical devices. To fulfil this aim, accurate and validated regeneration protocols are mandatory to guarantee sterility, functionality and safeness. The reprocessing protocol was realized by decontamination with chloro-donors, cleaning with enzymatic solutions and hydrogen peroxide gas plasma sterilization. Reprocessing effects on ablation and electrophysiology catheters were evaluated by assessing physical-chemical changes on surfaces and bulks, as a function of the reprocessing cycles number. Conventional optical microscopy and environmental scanning electron microscopy (ESEM) underlined the presence of micro-scratches on the polyurethane shaft surface. A clear correlation was found between surface damages and number of reprocessing cycles. Atomic force microscopy (AFM) confirmed the occurrence of physical-chemical etching of the polyurethane shaft caused by the hydrogen peroxide plasma sterilization, with increasing of nano-roughness at increasing number of the reprocessing cycles. UV-Vis spectra performed on the incubation solution of polymeric shaft sample, showed an absorbance increase at about 208 nm. This fact could be attributed to the water elution from the polymer of low molecular weight oligomers. The presence of hydrolysis products of the polymeric shaft after incubation demands both the characterization of the products released in the solution and the chemical characterization of the water exposed surface.

Deliquescence and efflorescence of small particles.

PubMed

McGraw, Robert; Lewis, Ernie R

2009-11-21

We examine size-dependent deliquescence/efflorescence phase transformation for particles down to several nanometers in size. Thermodynamic properties of inorganic salt particles, coated with aqueous solution layers of varying thickness and surrounded by vapor, are analyzed. A thin layer criterion (TLC) is introduced to define a limiting deliquescence relative humidity (RH(D)) for small particles. This requires: (1) equality of chemical potentials between salt in an undissolved core, and thin adsorbed solution layer, and (2) equality of chemical potentials between water in the thin layer and vapor phase. The usual bulk deliquescence conditions are recovered in the limit of large dry particle size. Nanosize particles are found to deliquesce at relative humidity just below the RH(D) on crossing a nucleation barrier, located at a critical solution layer thickness. This barrier vanishes precisely at the RH(D) defined by the TLC. Concepts and methods from nucleation theory including the kinetic potential, self-consistent nucleation theory, nucleation theorems, and the Gibbs dividing surface provide theoretical foundation and point to unifying features of small particle deliquescence/efflorescence processes. These include common thermodynamic area constructions, useful for interpretation of small particle water uptake measurements, and a common free-energy surface, with constant RH cross sections describing deliquescence and efflorescence related through the nucleation theorem.

Effects of CO2 injection and Kerogen Maturation on Low-Field Nuclear Magnetic Resonance Response

NASA Astrophysics Data System (ADS)

Prasad, M.; Livo, K.

2017-12-01

Low-field Nuclear Magnetic Resonance (NMR) is commonly used in petrophysical analysis of petroleum reservoir rocks. NMR experiments record the relaxation and polarization of in-situ hydrogen protons present in gaseous phases such as free-gas intervals and solution gas fluids, bulk fluid phases such as oil and aquifer intervals, and immovable fractions of kerogen and bitumen. Analysis of NMR relaxation spectra is performed to record how fluid composition, maturity, and viscosity change NMR experimental results. We present T1-T2 maps as thermal maturity of a water-saturated, sub-mature Woodford shale is increased at temperatures from 125 to 400 degrees Celsius. Experiments with applied fluid pressure in paraffinic mineral oil and DI water with varying fluid pH have been performed to mimic reservoir conditions in analysis of the relaxation of bulk fluid phases. We have recorded NMR spectra, T1-T2 maps, and fluid diffusion coefficients using a low-field (2 MHz) MagritekTM NMR. CO2 was injected at a pressure of 900 psi in an in house developed NMR pressure vessel made of torlon plastic. Observable 2D NMR shifts in immature kerogen formations as thermal maturity is increased show generation of lighter oils with increased maturity. CO2 injection leads to a decrease in bulk fluid relaxation time that is attributed to viscosity modification with gas presence. pH variation with increased CO2 presence were shown to not effect NMR spectra. From this, fluid properties have been shown to greatly affect NMR readings and must be taken into account for more accurate NMR reservoir characterization.

Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

PubMed Central

Qin, Chunling; Zhao, Weimin; Inoue, Akihisa

2011-01-01

This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni) and Cu–Zr–Ag–Al–(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance. PMID:21731441

Surface versus bulk activity of lysozyme deposited on hydrogel contact lens materials in vitro.

PubMed

Omali, Negar Babaei; Subbaraman, Lakshman N; Heynen, Miriam; Ng, Alan; Coles-Brennan, Chantal; Fadli, Zohra; Jones, Lyndon

2018-04-30

To determine and compare the levels of surface versus bulk active lysozyme deposited on several commercially available hydrogel contact lens materials. Hydrogel contact lens materials [polymacon, omafilcon A, nelfilcon A, nesofilcon A, ocufilcon and etafilcon A with polyvinylpyrrolidone (PVP)] were incubated in an artificial tear solution for 16 h. Total activity was determined using a standard turbidity assay. The surface activity of the deposited lysozyme was determined using a modified turbidity assay. The amount of active lysozyme present within the bulk of the lens material was calculated by determining the difference between the total and surface active lysozyme. The etafilcon A materials showed the highest amount of total lysozyme activity (519 ± 8 μg/lens, average of Moist and Define), followed by the ocufilcon material (200 ± 5 μg/lens) and these two were significantly different from each other (p < 0.05). The amount of surface active lysozyme on etafilcon and ocufilcon lens materials was significantly higher than that found on all other lenses (p < 0.05). There was no active lysozyme quantified in the bulk of the nelfilcon material, as all of the active lysozyme was found on the surface (1.7 ± 0.3 μg/lens). In contrast, no active lysozyme was quantified on the surface of polymacon, with all of the active lysozyme found in the bulk of the lens material (0.6 ± 0.6 μg/lens). The surface and bulk activity of lysozyme deposited on contact lenses is material dependent. Lysozyme deposited on ionic, high water content lens materials such as etafilcon A show significantly higher surface and bulk activity than many other hydrogel lens materials. Copyright © 2018 British Contact Lens Association. Published by Elsevier Ltd. All rights reserved.

Molecular modeling the microstructure and phase behavior of bulk and inhomogeneous complex fluids

NASA Astrophysics Data System (ADS)

Bymaster, Adam

Accurate prediction of the thermodynamics and microstructure of complex fluids is contingent upon a model's ability to capture the molecular architecture and the specific intermolecular and intramolecular interactions that govern fluid behavior. This dissertation makes key contributions to improving the understanding and molecular modeling of complex bulk and inhomogeneous fluids, with an emphasis on associating and macromolecular molecules (water, hydrocarbons, polymers, surfactants, and colloids). Such developments apply broadly to fields ranging from biology and medicine, to high performance soft materials and energy. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's thermodynamic perturbation theory (TPT1), is extended to include a crossover correction that significantly improves the predicted phase behavior in the critical region. In addition, PC-SAFT is used to investigate the vapor-liquid equilibrium of sour gas mixtures, to improve the understanding of mercaptan/sulfide removal via gas treating. For inhomogeneous fluids, a density functional theory (DFT) based on TPT1 is extended to problems that exhibit radially symmetric inhomogeneities. First, the influence of model solutes on the structure and interfacial properties of water are investigated. The DFT successfully describes the hydrophobic phenomena on microscopic and macroscopic length scales, capturing structural changes as a function of solute size and temperature. The DFT is used to investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. A comprehensive study is conducted characterizing the role of polymer concentration and particle/polymer size ratio on the structure, polymer induced depletion forces, and tendency towards colloidal aggregation. The inhomogeneous form of the association functional is used, for the first time, to extend the DFT to associating polymer systems, applicable to any association scheme. Theoretical results elucidate how reversible bonding governs the structure of a fluid near a surface and in confined environments, the molecular connectivity (formation of supramolecules, star polymers, etc.) and the phase behavior of the system. Finally, the DFT is extended to predict the inter- and intramolecular correlation functions of polymeric fluids. A theory capable of providing such local structure is important to understanding how local chemistry, branching, and bond flexibility affect the thermodynamic properties of polymers.

Temperature Dependence of Nonelectrolyte Permeation across Red Cell Membranes

PubMed Central

Galey, W. R.; Owen, J. D.; Solomon, A. K.

1973-01-01

The temperature dependence of permeation across human red cell membranes has been determined for a series of hydrophilic and lipophilic solutes, including urea and two methyl substituted derivatives, all the straight-chain amides from formamide through valeramide and the two isomers, isobutyramide and isovaleramide. The temperature coefficient for permeation by all the hydrophilic solutes is 12 kcal mol-1 or less, whereas that for all the lipophilic solutes is 19 kcal mol-1 or greater. This difference is consonant with the view that hydrophilic molecules cross the membrane by a path different from that taken by the lipophilic ones. The thermodynamic parameters associated with lipophile permeation have been studied in detail. ΔG is negative for adsorption of lipophilic amides onto an oil-water interface, whereas it is positive for transfer of the polar head from the aqueous medium to bulk lipid solvent. Application of absolute reaction rate theory makes it possible to make a clear distinction between diffusion across the water-red cell membrane interface and diffusion within the membrane. Diffusion coefficients and apparent activation enthalpies and entropies have been computed for each process. Transfer of the polar head from the solvent into the interface is characterized by ΔG ‡ = 0 kcal mol-1 and ΔS ‡ negative, whereas both of these parameters have large positive values for diffusion within the membrane. Diffusion within the membrane is similar to what is expected for diffusion through a highly associated viscous fluid. PMID:4708405

Comparative exploration of hydrogen sulfide and water transmembrane free energy surfaces via orthogonal space tempering free energy sampling

DOE PAGES

Lv, Chao; Aitchison, Erick W.; Wu, Dongsheng; ...

2015-06-29

Hydrogen sulfide (H 2S), a commonly known toxic gas compound, possesses unique chemical features that allow this small solute molecule to quickly diffuse through cell membranes. Taking advantage of the recent orthogonal space tempering (OST) method, we comparatively mapped the transmembrane free energy landscapes of H 2S and its structural analogue, water (H 2O), seeking to decipher the molecular determinants that govern their drastically different permeabilities. Here, as revealed by our OST sampling results, in contrast to the highly polar water solute, hydrogen sulfide is evidently amphipathic, and thus inside membrane is favorably localized at the interfacial region, that is,more » the interface between the polar head-group and nonpolar acyl chain regions. Because the membrane binding affinity of H 2S is mainly governed by its small hydrophobic moiety and the barrier height inbetween the interfacial region and the membrane center is largely determined by its moderate polarity, the transmembrane free energy barriers to encounter by this toxic molecule are very small. Moreover when H2S diffuses from the bulk solution to the membrane center, the above two effects nearly cancel each other, so as to lead to a negligible free energy difference. Lastly, this study not only explains why H 2S can quickly pass through cell membranes but also provides a practical illustration on how to use the OST free energy sampling method to conveniently analyze complex molecular processes.« less

Comparative exploration of hydrogen sulfide and water transmembrane free energy surfaces via orthogonal space tempering free energy sampling.

PubMed

Lv, Chao; Aitchison, Erick W; Wu, Dongsheng; Zheng, Lianqing; Cheng, Xiaolin; Yang, Wei

2016-03-05

Hydrogen sulfide (H2 S), a commonly known toxic gas compound, possesses unique chemical features that allow this small solute molecule to quickly diffuse through cell membranes. Taking advantage of the recent orthogonal space tempering (OST) method, we comparatively mapped the transmembrane free energy landscapes of H2 S and its structural analogue, water (H2 O), seeking to decipher the molecular determinants that govern their drastically different permeabilities. As revealed by our OST sampling results, in contrast to the highly polar water solute, hydrogen sulfide is evidently amphipathic, and thus inside membrane is favorably localized at the interfacial region, that is, the interface between the polar head-group and nonpolar acyl chain regions. Because the membrane binding affinity of H2 S is mainly governed by its small hydrophobic moiety and the barrier height inbetween the interfacial region and the membrane center is largely determined by its moderate polarity, the transmembrane free energy barriers to encounter by this toxic molecule are very small. Moreover when H2 S diffuses from the bulk solution to the membrane center, the above two effects nearly cancel each other, so as to lead to a negligible free energy difference. This study not only explains why H2 S can quickly pass through cell membranes but also provides a practical illustration on how to use the OST free energy sampling method to conveniently analyze complex molecular processes. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Dipolar response of hydrated proteins

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2012-02-01

The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins in solution. We calculate the effective dielectric constant representing the average dipole moment induced at the protein by a uniform external field. The dielectric constant shows a remarkable variation among the proteins, changing from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility, that is a dia-electric dipolar response and negative dielectrophoresis. It means that ubiquitin, carrying an average dipole of ≃240 D, is expected to repel from the region of a stronger electric field. This outcome is the result of a negative cross-correlation between the protein and water dipoles, compensating for the positive variance of the intrinsic protein dipole in the overall dipolar susceptibility. In contrast to the neutral ubiquitin, charged proteins studied here show para-electric dipolar response and positive dielectrophoresis. The study suggests that the dipolar response of proteins in solution is strongly affected by the coupling of the protein surface charge to the hydration water. The protein-water dipolar cross-correlations are long-ranged, extending ˜2 nm from the protein surface into the bulk. A similar correlation length of about 1 nm is seen for the electrostatic potential produced by the hydration water inside the protein. The analysis of numerical simulations suggests that the polarization of the protein-water interface is highly heterogeneous and does not follow the standard dielectric results for cavities carved in dielectrics. The polarization of the water shell gains in importance, relative to the intrinsic protein dipole, at high frequencies, above the protein Debye peak. The induced interfacial dipole can be either parallel or antiparallel to the protein dipole, depending on the distribution of the protein surface charge. As a result, the high-frequency absorption of the protein solution can be either higher or lower than the absorption of water. Both scenarios have been experimentally observed in the THz window of radiation.

Dipolar response of hydrated proteins.

PubMed

Matyushov, Dmitry V

2012-02-28

The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins in solution. We calculate the effective dielectric constant representing the average dipole moment induced at the protein by a uniform external field. The dielectric constant shows a remarkable variation among the proteins, changing from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility, that is a dia-electric dipolar response and negative dielectrophoresis. It means that ubiquitin, carrying an average dipole of ≃240 D, is expected to repel from the region of a stronger electric field. This outcome is the result of a negative cross-correlation between the protein and water dipoles, compensating for the positive variance of the intrinsic protein dipole in the overall dipolar susceptibility. In contrast to the neutral ubiquitin, charged proteins studied here show para-electric dipolar response and positive dielectrophoresis. The study suggests that the dipolar response of proteins in solution is strongly affected by the coupling of the protein surface charge to the hydration water. The protein-water dipolar cross-correlations are long-ranged, extending ~2 nm from the protein surface into the bulk. A similar correlation length of about 1 nm is seen for the electrostatic potential produced by the hydration water inside the protein. The analysis of numerical simulations suggests that the polarization of the protein-water interface is highly heterogeneous and does not follow the standard dielectric results for cavities carved in dielectrics. The polarization of the water shell gains in importance, relative to the intrinsic protein dipole, at high frequencies, above the protein Debye peak. The induced interfacial dipole can be either parallel or antiparallel to the protein dipole, depending on the distribution of the protein surface charge. As a result, the high-frequency absorption of the protein solution can be either higher or lower than the absorption of water. Both scenarios have been experimentally observed in the THz window of radiation.

Hollow Polycaprolactone Microspheres with/without a Single Surface Hole by Co-Electrospraying

PubMed Central

2017-01-01

We describe the co-electrospraying of hollow microspheres from a polycaprolactone (PCL) shell solution and various core solutions including water, cyclohexane, poly(ethylene oxide) (PEO), and polyethylene glycol (PEG), using different collectors. The morphologies of the resultant microspheres were characterized by scanning electron microscopy (SEM), confocal microscopy, and nano-X-ray computed tomography (nano-XCT). The core/shell solution miscibility played an important role in the co-electrospraying process and the formation of microsphere structures. Spherical particles were more likely to be produced from miscible combinations of core/shell solutions than from immiscible ones. Hollow PCL microspheres with a single hole in their surfaces were produced when an ethanol bath was used as the collector. The mechanism by which the core/shell structure is transformed into single-hole hollow microspheres is proposed to be primarily based on the evaporation through the shell and extraction by ethanol of the core solution and is described in detail. Additionally, we present a 3D macroscopic tubular structure composed of hollow PCL microspheres, directly assembled on a copper wire collector during co-electrospraying. SEM and nano-XCT confirm that microspheres in the 3D bulk structure remain hollow. PMID:28901145

Lower Critical Solubility Temperature Behavior in Membranes Formed from a 2-(2-Methoxyethoxy)ethoxy-Containing Polyphosphazene

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

Stewart, F.F.; Lash, R.P.

A phosphazene polymer with three pendant groups was synthesized and characterized as a membrane material. Substitution of the phosphazene with 64% 2-(2-methoxyethoxy)ethanol (MEE), 27% 4-methoxyphenol, and 9% 2-allyphenol yielded a hydrophilic elastomer with considerable flow at room temperature. Solution behavior showed significant aging effects where, using fresh solutions, membranes could not cast on porous ceramic supports (0.2-micron pore size) without significant polymer penetration into the pores. Solutions aged for two weeks were found to readily penetrate into the pores of the ceramic support. Analysis of fresh and aged solutions by laser light scattering showed significant loss in molecular weight withmore » time. Pervaporation of water-dye solutions using dimensionally stabilized membranes revealed in inverse correlation between flux and temperature, suggesting thermally induced morphological changes within the polymer. This polymer was found to exhibit, in the bulk state, lower critical solubility temperature (LCST) behavior where the material becomes less hydrophilic with increasing temperature. LCST behavior was probed thermally and gravimetrically and has been attributed to the anomalous pervaporation results. The degree to which LCST effects membrane transport was influenced by changes in the crosslink density and permeate side pressure.« less

Relation of bulk precipitation and evapotranspiration to water quality and water resources, St. Thomas, Virgin Islands

USGS Publications Warehouse

Jordan, Donald George; Fisher, Donald W.

1977-01-01

St. Thomas, Virgin Islands, lies in what can be considered a true maritime regime, being 600 miles (1000 kilometers) from the nearest continental landmass. The island is composed almost entirely of volcanic rocks mantled by a thin soil seldom more than 2 feet (60 centimeters) thick. Rainfall, averaging about 40 inches (1020 millimeters) annually, has an orographic distribution related to the central ridge of the island, altitude 600 to 1500 feet (180 to 405 meters), and the easterly to northeasterly trade winds. The mineral content of bulk precipitation falling on the island is derived principally from the sea although soil dust contributes much of the calcium, sodium, and bicarbonate. Two-thirds of the sulfate in the precipitation is provided by sea salts; the remainder is derived from other sources. The concentration of the constituents of bulk precipitation fluctuates widely month to month, but the load of the constituents shows little monthly variation. Bulk precipitation is concentrated on the land surface and in the soil zone. From there it is carried into the ground water during recharge or is removed by storm-water runoff. It is the principal source of minerals in the waters of the island. Soil-moisture demand and evaporation limits recharge to 1 to 2 inches (25 to 50 millimeters) annually for the greater part of the island. Evapotranspiration also occurs directly from the aquifer. The salts left further increase the mineralization of the ground water. Water loss from the aquifer by evapotranspiration ranges from 40 to 80 percent of the recharge. Recharge to the aquifers and evapotranspiration of ground water determined by ratios of chloride concentrations in bulk precipitation, surface water, and subsurface water agree favorably with recharge and groundwater loss computed by other means.

Fiber lubrication: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Liu, Hongyi

Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.

Modeling the soil water retention curves of soil-gravel mixtures with regression method on the Loess Plateau of China.

PubMed

Wang, Huifang; Xiao, Bo; Wang, Mingyu; Shao, Ming'an

2013-01-01

Soil water retention parameters are critical to quantify flow and solute transport in vadose zone, while the presence of rock fragments remarkably increases their variability. Therefore a novel method for determining water retention parameters of soil-gravel mixtures is required. The procedure to generate such a model is based firstly on the determination of the quantitative relationship between the content of rock fragments and the effective saturation of soil-gravel mixtures, and then on the integration of this relationship with former analytical equations of water retention curves (WRCs). In order to find such relationships, laboratory experiments were conducted to determine WRCs of soil-gravel mixtures obtained with a clay loam soil mixed with shale clasts or pebbles in three size groups with various gravel contents. Data showed that the effective saturation of the soil-gravel mixtures with the same kind of gravels within one size group had a linear relation with gravel contents, and had a power relation with the bulk density of samples at any pressure head. Revised formulas for water retention properties of the soil-gravel mixtures are proposed to establish the water retention curved surface models of the power-linear functions and power functions. The analysis of the parameters obtained by regression and validation of the empirical models showed that they were acceptable by using either the measured data of separate gravel size group or those of all the three gravel size groups having a large size range. Furthermore, the regression parameters of the curved surfaces for the soil-gravel mixtures with a large range of gravel content could be determined from the water retention data of the soil-gravel mixtures with two representative gravel contents or bulk densities. Such revised water retention models are potentially applicable in regional or large scale field investigations of significantly heterogeneous media, where various gravel sizes and different gravel contents are present.

Modeling the Soil Water Retention Curves of Soil-Gravel Mixtures with Regression Method on the Loess Plateau of China

PubMed Central

Wang, Huifang; Xiao, Bo; Wang, Mingyu; Shao, Ming'an

2013-01-01

Soil water retention parameters are critical to quantify flow and solute transport in vadose zone, while the presence of rock fragments remarkably increases their variability. Therefore a novel method for determining water retention parameters of soil-gravel mixtures is required. The procedure to generate such a model is based firstly on the determination of the quantitative relationship between the content of rock fragments and the effective saturation of soil-gravel mixtures, and then on the integration of this relationship with former analytical equations of water retention curves (WRCs). In order to find such relationships, laboratory experiments were conducted to determine WRCs of soil-gravel mixtures obtained with a clay loam soil mixed with shale clasts or pebbles in three size groups with various gravel contents. Data showed that the effective saturation of the soil-gravel mixtures with the same kind of gravels within one size group had a linear relation with gravel contents, and had a power relation with the bulk density of samples at any pressure head. Revised formulas for water retention properties of the soil-gravel mixtures are proposed to establish the water retention curved surface models of the power-linear functions and power functions. The analysis of the parameters obtained by regression and validation of the empirical models showed that they were acceptable by using either the measured data of separate gravel size group or those of all the three gravel size groups having a large size range. Furthermore, the regression parameters of the curved surfaces for the soil-gravel mixtures with a large range of gravel content could be determined from the water retention data of the soil-gravel mixtures with two representative gravel contents or bulk densities. Such revised water retention models are potentially applicable in regional or large scale field investigations of significantly heterogeneous media, where various gravel sizes and different gravel contents are present. PMID:23555040

Photochemical oxidation of water and reduction of polyoxometalate anions at interfaces of water with ionic liquids or diethylether

PubMed Central

Bernardini, Gianluca; Wedd, Anthony G.; Zhao, Chuan; Bond, Alan M.

2012-01-01

Photoreduction of [P2W18O62]6-, [S2Mo18O62]4-, and [S2W18O62]4- polyoxometalate anions (POMs) and oxidation of water occurs when water–ionic liquid and water–diethylether interfaces are irradiated with white light (275–750 nm) or sunlight. The ionic liquids (ILs) employed were aprotic ([Bmim]X; Bmim = (1-butyl-3-methylimidazolium,X = BF4,PF6) and protic (DEAS = diethanolamine hydrogen sulphate; DEAP = diethanolamine hydrogen phosphate). Photochemical formation of reduced POMs at both thermodynamically stable and unstable water–IL interfaces led to their initial diffusion into the aqueous phase and subsequent extraction into the IL phase. The mass transport was monitored visually by color change and by steady-state voltammetry at microelectrodes placed near the interface and in the bulk solution phases. However, no diffusion into the organic phase was observed when [P2W18O62]6- was photo-reduced at the water–diethylether interface. In all cases, water acted as the electron donor to give the overall process: 4POM + 2H2O + hν → 4POM- + 4H+ + O2. However, more highly reduced POM species are likely to be generated as intermediates. The rate of diffusion of photo-generated POM- was dependent on the initial concentration of oxidized POM and the viscosity of the IL (or mixed phase system produced in cases in which the interface is thermodynamically unstable). In the water-DEAS system, the evolution of dioxygen was monitored in situ in the aqueous phase by using a Clark-type oxygen sensor. Differences in the structures of bulk and interfacial water are implicated in the activation of water. An analogous series of reactions occurred upon irradiation of solid POM salts in the presence of water vapor. PMID:22753501

Ultrasonic degradation, mineralization and detoxification of diclofenac in water: optimization of operating parameters.

PubMed

Naddeo, V; Belgiorno, V; Kassinos, D; Mantzavinos, D; Meric, S

2010-01-01

The 20 kHz ultrasound-induced degradation of non-steroidal, anti-inflammatory drug diclofenac (DCF) was investigated. Several operating conditions, such as power density (25-100 W/L), substrate concentration (2.5-80 mg/L), initial solution pH (3.5-11), liquid bulk temperature and the type of sparging gas (air, oxygen, argon), were tested concerning their effect on DCF degradation (as assessed measuring absorbance at 276 nm) and hydroxyl radicals generation (as assessed measuring H(2)O(2) concentration). Sample mineralization (in terms of TOC and COD removal), aerobic biodegradability (as assessed by the BOD(5)/COD ratio) and ecotoxicity to Daphnia magna and Artemia salina were followed too. DCF conversion is enhanced at increased applied power densities and liquid bulk temperatures, acidic conditions and in the presence of dissolved air or oxygen. The reaction rate increases with increasing DCF concentration in the range 2.5-5mg/L but it remains constant in the range 40-80 mg/L, indicating different kinetic regimes (i.e. first and zero order, respectively). H(2)O(2) production rates in pure water are higher than those in DCF solutions, implying that decomposition basically proceeds through hydroxyl radical reactions. Mineralization is a slow process as reaction by-products are more stable than DCF to total oxidation; nonetheless, they are also more readily biodegradable. Toxicity to D. magna increases during the early stages of the reaction and then decreases progressively upon degradation of reaction by-products; nevertheless, complete toxicity elimination cannot be achieved at the conditions in question. Neither the original nor the treated DCF samples are toxic to A. salina.

Waterflow visualized by tracer transport in root-soil-systems using MRI

NASA Astrophysics Data System (ADS)

Haber-Pohlmeier, S.; van Dusschoten, D.; Stapf, S.

2009-04-01

Water supply for root and plant growth is one of the most important soil functions, which is mainly controlled by water fluxes in this unsaturated porous medium. Here, the rhizosphere i.e. the region directly between the rhizoplane and bulk soil is of special interest, since in this area the immediate root water uptake takes place. Using MRI as a powerful non-invasive method the water content can be visualized, but the water flow velocities themselves are too slow to be monitored directly by MRI flow imaging. Therefore indirect methods like monitoring the flux of paramagnetic tracers must be applied. Using infiltration experiments we have investigated for the first time the behaviour of a Gd-DTPA tracer solution in an unsaturated, heterogenous model soil that held maize and lupin plants, respectively. The tracer content was imaged by a fast spin echo sequence over a period of 60 minutes and a resolution of 0.4 mm. The infiltration process can be divided in several stages: i) While the plume moves homogeneously into the bulk soil, the tracer does not get into the im-mediate surrounding of the roots during the first three minutes. ii) After this initial period a con-tinuously increasing enrichment of tracer in this region is observed for about 12 minutes. This means that the tracer moves from the environment towards the root-soil interface. iii) However, there are no hints that tracer is taken up by the root-system. So we can conclude that this nega-tively charged paramagnetic Gd-complex behaves conservatively. The studies show that Gd-DTPA is a very convenient tracer for monitoring flow processes in soil - root systems and the investigations will be extended in future to natural soil cores.

Radical re-appraisal of water structure in hydrophilic confinement.

PubMed

Soper, Alan K

2013-12-18

The structure of water confined in MCM41 silica cylindrical pores is studied to determine whether confined water is simply a version of the bulk liquid which can be substantially supercooled without crystallisation. A combination of total neutron scattering from the porous silica, both wet and dry, and computer simulation using a realistic model of the scattering substrate is used. The water in the pore is divided into three regions: core, interfacial and overlap. The average local densities of water in these simulations are found to be about 20% lower than bulk water density, while the density in the core region is below, but closer to, the bulk density. There is a decrease in both local and core densities when the temperature is lowered from 298 K to 210 K. The radical proposal is made here that water in hydrophilic confinement is under significant tension, around -100 MPa, inside the pore.

Explicit parametric solutions of lattice structures with proper generalized decomposition (PGD) - Applications to the design of 3D-printed architectured materials

NASA Astrophysics Data System (ADS)

Sibileau, Alberto; Auricchio, Ferdinando; Morganti, Simone; Díez, Pedro

2018-01-01

Architectured materials (or metamaterials) are constituted by a unit-cell with a complex structural design repeated periodically forming a bulk material with emergent mechanical properties. One may obtain specific macro-scale (or bulk) properties in the resulting architectured material by properly designing the unit-cell. Typically, this is stated as an optimal design problem in which the parameters describing the shape and mechanical properties of the unit-cell are selected in order to produce the desired bulk characteristics. This is especially pertinent due to the ease manufacturing of these complex structures with 3D printers. The proper generalized decomposition provides explicit parametic solutions of parametric PDEs. Here, the same ideas are used to obtain parametric solutions of the algebraic equations arising from lattice structural models. Once the explicit parametric solution is available, the optimal design problem is a simple post-process. The same strategy is applied in the numerical illustrations, first to a unit-cell (and then homogenized with periodicity conditions), and in a second phase to the complete structure of a lattice material specimen.

Inflationary solutions in the brane world and their geometrical interpretation

NASA Astrophysics Data System (ADS)

Khoury, Justin; Steinhardt, Paul J.; Waldram, Daniel

2001-05-01

We consider the cosmology of a pair of domain walls bounding a five-dimensional bulk space-time with a negative cosmological constant, in which the distance between the branes is not fixed in time. Although there are strong arguments to suggest that this distance should be stabilized in the present epoch, no such constraints exist for the early universe and thus non-static solutions might provide relevant inflationary scenarios. We find the general solution for the standard ansatz where the bulk is foliated by planar-symmetric hypersurfaces. We show that in all cases the bulk geometry is that of anti-de Sitter (AdS5) space. We then present a geometrical interpretation for the solutions as embeddings of two de Sitter (dS4) surfaces in AdS5, which provide a simple interpretation of the physical properties of the solutions. A notable feature explained in the analysis is that two-way communication between branes expanding away from one another is possible for a finite amount of time, after which communication can proceed in one direction only. The geometrical picture also shows that our class of solutions (and related solutions in the literature) is not completely general, contrary to some claims. We then derive the most general solution for two walls in AdS5. This includes novel cosmologies where the brane tensions are not constrained to have opposite signs. The construction naturally generalizes to arbitrary FRW cosmologies on the branes.

Molecular density functional theory of water describing hydrophobicity at short and long length scales

NASA Astrophysics Data System (ADS)

Jeanmairet, Guillaume; Levesque, Maximilien; Borgis, Daniel

2013-10-01

We present an extension of our recently introduced molecular density functional theory of water [G. Jeanmairet et al., J. Phys. Chem. Lett. 4, 619 (2013)] to the solvation of hydrophobic solutes of various sizes, going from angstroms to nanometers. The theory is based on the quadratic expansion of the excess free energy in terms of two classical density fields: the particle density and the multipolar polarization density. Its implementation requires as input a molecular model of water and three measurable bulk properties, namely, the structure factor and the k-dependent longitudinal and transverse dielectric susceptibilities. The fine three-dimensional water structure around small hydrophobic molecules is found to be well reproduced. In contrast, the computed solvation free-energies appear overestimated and do not exhibit the correct qualitative behavior when the hydrophobic solute is grown in size. These shortcomings are corrected, in the spirit of the Lum-Chandler-Weeks theory, by complementing the functional with a truncated hard-sphere functional acting beyond quadratic order in density, and making the resulting functional compatible with the Van-der-Waals theory of liquid-vapor coexistence at long range. Compared to available molecular simulations, the approach yields reasonable solvation structure and free energy of hard or soft spheres of increasing size, with a correct qualitative transition from a volume-driven to a surface-driven regime at the nanometer scale.

Spherical nitroguanidine process

DOEpatents

Sanchez, John A.; Roemer, Edward L.; Stretz, Lawrence A.

1990-01-01

A process of preparing spherical high bulk density nitroguanidine by dissing low bulk density nitroguanidine in N-methyl pyrrolidone at elevated temperatures and then cooling the solution to lower temperatures as a liquid characterized as a nonsolvent for the nitroguanidine is provided. The process is enhanced by inclusion in the solution of from about 1 ppm up to about 250 ppm of a metal salt such as nickel nitrate, zinc nitrate or chromium nitrate, preferably from about 20 to about 50 ppm.

To what extent is water responsible for the maintenance of the life for warm-blooded organisms?

PubMed

Fisenko, Anatoliy I; Malomuzh, Nikolay P

2009-05-22

In this work, attention is mainly focused on those properties of water which are essentially changed in the physiological temperature range of warm-blooded organisms. Studying in detail the half-width of the diffusion peak in the quasi-elastic incoherent neutron scattering, the behavior of the entropy and the kinematic shear viscosity, it is shown that the character of the translational and rotational thermal motions in water radically change near T(H) ~ 315 K, which can be interpreted as the temperature of the smeared dynamic phase transition. These results for bulk pure water are completed by the analysis of the isothermic compressibility and the NMR-spectra for water-glycerol solutions. It was noted that the non-monotone temperature dependence of the isothermic compressibility (beta(T)) takes also place for the water-glycerol solutions until the concentration of glycerol does not exceed 30 mol%. At that, the minimum of beta(T) shifts at left when the concentration increases. All these facts give us some reasons to assume that the properties of the intracellular and extracellular fluids are close to ones for pure water. Namely therefore, we suppose that the upper temperature limit for the life of warm-blooded organisms [T(D) = (315 +/- 3) K] is tightly connected with the temperature of the dynamic phase transition in water. This supposition is equivalent to the assertion that the denaturation of proteins at T > or = T(H) is mainly provoked by the rebuilding of the H-bond network in the intracellular and extracellular fluids, which takes place at T > or = T(H). A question why the heavy water cannot be a matrix for the intracellular and extracellular fluids is considered. The lower physiological pH limit for the life of warm-blooded organisms is discussed.

Effect of water on nanomechanics of bone is different between tension and compression

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

Samuel, Jitin; Park, Jun-Sang; Almer, Jonathan

Water, an important constituent in bone, resides in different compartments in bone matrix and may impose significant effects on its bulk mechanical properties. However, a clear understanding of the mechanistic role of water in toughening bone is yet to emerge. To address this issue, this study used a progressive loading protocol, coupled with measurements of in situ mineral and collagen fibril deformations using synchrotron X-ray diffraction techniques. Using this unique approach, the contribution of water to the ultrastructural behavior of bone was examined by testing bone specimens in different loading modes (tension and compression) and hydration states (wet and dehydrated).more » The results indicated that the effect of water on the mechanical behavior of mineral and collagen phases at the ultrastructural level was loading mode dependent and correlated with the bulk behavior of bone. Tensile loading elicited a transitional drop followed by an increase in load bearing by the mineral phase at the ultrastructural level, which was correlated with a strain hardening behavior of bone at the bulk level. Compression loading caused a continuous loss of load bearing by the mineral phase, which was reflected at the bulk level as a strain softening behavior. In addition, viscous strain relaxation and pre-strain reduction were observed in the mineral phase in the presence of water. Taken together, the results of this study suggest that water dictates the bulk behavior of bone by altering the interaction between mineral crystals and their surrounding matrix.« less

Coarse-Grain Molecular Dynamics Simulations To Investigate the Bulk Viscosity and Critical Micelle Concentration of the Ionic Surfactant Sodium Dodecyl Sulfate (SDS) in Aqueous Solution.

PubMed

Ruiz-Morales, Yosadara; Romero-Martínez, Ascención

2018-04-12

The first critical micelle concentration (CMC) of the ionic surfactant sodium dodecyl sulfate (SDS) in diluted aqueous solution has been determined at room temperature from the investigation of the bulk viscosity, at several concentrations of SDS, by means of coarse-grain molecular dynamics simulations. The coarse-grained model molecules at the mesoscale level are adopted. The bulk viscosity of SDS was calculated at several millimolar concentrations of SDS in water using the MARTINI force field by means of NVT shear Mesocite molecular dynamics. The definition of each bead in the MARTINI force field is established, as well as their radius, volume, and mass. The effect of the size of the simulation box on the obtained CMC has been investigated, as well as the effect of the number of SDS molecules, in the simulations, on the formation of aggregates. The CMC, which was obtained from a graph of the calculated viscosities versus concentration, is in good agreement with the reported experimental data and does not depend on the size of the box used in the simulation. The formation of a spherical micelle-like aggregate is observed, where the dodecyl sulfate tails point inward and the heads point outward the aggregation micelle, in accordance with experimental observations. The advantage of using coarse-grain molecular dynamics is the possibility of treating explicitly charged beads, applying a shear flow for viscosity calculation, and processing much larger spatial and temporal scales than atomistic molecular dynamics can. Furthermore, the CMC of SDS obtained with the coarse-grained model is in much better agreement with the experimental value than the value obtained with atomistic simulations.

Comparing Classical Water Models Using Molecular Dynamics to Find Bulk Properties

ERIC Educational Resources Information Center

Kinnaman, Laura J.; Roller, Rachel M.; Miller, Carrie S.

2018-01-01

A computational chemistry exercise for the undergraduate physical chemistry laboratory is described. In this exercise, students use the molecular dynamics package Amber to generate trajectories of bulk liquid water for 4 different water models (TIP3P, OPC, SPC/E, and TIP4Pew). Students then process the trajectory to calculate structural (radial…

Silver-modified mobile phase for normal-phase liquid chromatographic determination of prostaglandins and their 5,6-trans isomers in prostaglandin bulk drugs and triacetin solutions.

PubMed

Kissinger, L D; Robins, R H

1985-03-15

A silver-modified, normal-phase, high-performance liquid chromatographic system has been developed for prostaglanding bulk drugs and triacetin solutions. Silver nitrate present in the mobile phase results in high selectivity for cis/trans isomers with conventional silica columns. Prostaglandins were esterified with alpha-bromo-2'-acetonaphthone prior to chromatography to provide high detectability at 254 nm. For dilute triacetin solutions, a sample preparation scheme based on gravity-flow chromatography with silica columns was developed to isolate the prostaglandin from triacetin prior to derivatization. The analytical technique was applied to triacetin solutions containing as little as 10 micrograms/ml arbaprostil [15-(R)-methyl-PGE2].

A new approach to the problem of bulk-mediated surface diffusion.

PubMed

Berezhkovskii, Alexander M; Dagdug, Leonardo; Bezrukov, Sergey M

2015-08-28

This paper is devoted to bulk-mediated surface diffusion of a particle which can diffuse both on a flat surface and in the bulk layer above the surface. It is assumed that the particle is on the surface initially (at t = 0) and at time t, while in between it may escape from the surface and come back any number of times. We propose a new approach to the problem, which reduces its solution to that of a two-state problem of the particle transitions between the surface and the bulk layer, focusing on the cumulative residence times spent by the particle in the two states. These times are random variables, the sum of which is equal to the total observation time t. The advantage of the proposed approach is that it allows for a simple exact analytical solution for the double Laplace transform of the conditional probability density of the cumulative residence time spent on the surface by the particle observed for time t. This solution is used to find the Laplace transform of the particle mean square displacement and to analyze the peculiarities of its time behavior over the entire range of time. We also establish a relation between the double Laplace transform of the conditional probability density and the Fourier-Laplace transform of the particle propagator over the surface. The proposed approach treats the cases of both finite and infinite bulk layer thicknesses (where bulk-mediated surface diffusion is normal and anomalous at asymptotically long times, respectively) on equal footing.

Assessing the influence of the rhizosphere on soil hydraulic properties using X-ray computed tomography and numerical modelling

PubMed Central

Daly, Keith R.; Mooney, Sacha J.; Bennett, Malcolm J.; Crout, Neil M. J.; Roose, Tiina; Tracy, Saoirse R.

2015-01-01

Understanding the dynamics of water distribution in soil is crucial for enhancing our knowledge of managing soil and water resources. The application of X-ray computed tomography (CT) to the plant and soil sciences is now well established. However, few studies have utilized the technique for visualizing water in soil pore spaces. Here this method is utilized to visualize the water in soil in situ and in three-dimensions at successive reductive matric potentials in bulk and rhizosphere soil. The measurements are combined with numerical modelling to determine the unsaturated hydraulic conductivity, providing a complete picture of the hydraulic properties of the soil. The technique was performed on soil cores that were sampled adjacent to established roots (rhizosphere soil) and from soil that had not been influenced by roots (bulk soil). A water release curve was obtained for the different soil types using measurements of their pore geometries derived from CT imaging and verified using conventional methods, such as pressure plates. The water, soil, and air phases from the images were segmented and quantified using image analysis. The water release characteristics obtained for the contrasting soils showed clear differences in hydraulic properties between rhizosphere and bulk soil, especially in clay soil. The data suggest that soils influenced by roots (rhizosphere soil) are less porous due to increased aggregation when compared with bulk soil. The information and insights obtained on the hydraulic properties of rhizosphere and bulk soil will enhance our understanding of rhizosphere biophysics and improve current water uptake models. PMID:25740922

Fractionation of aquatic natural organic matter upon sorption to goethite and kaolinite

USGS Publications Warehouse

Meier, M.; Namjesnik-Dejanovic, K.; Maurice, P.A.; Chin, Y.-P.; Aiken, G.R.

1999-01-01

Natural organic matter (NOM) consists of a complex mixture of organic molecules; previous studies have suggested that preferential sorption of higher molecular weight, more hydrophobic, and more aromatic components may lead to fractionation of the NOM pool upon passage through porous media. Our work expands upon previous studies by quantifying the change in solution-phase weight average molecular weight (M(w)) upon sorption of bulk (rather than isolated) surface water NOM from the Suwannee River (SR) and the Great Dismal Swamp (GDS) to goethite and kaolinite at different sorption densities and at pH 4, 22??C. High pressure size exclusion chromatography (HPSEC) was used to quantify changes in M(w) upon sorption, and molar absorptivities at ?? = 280 nm were used to approximate changes in solution NOM aromaticity. Two SR water samples were used, with M(w) = 2320 and 2200 Da; a single GDS sample was used, with M(w) = 1890 Da. The SR NOM was slightly more hydrophobic and aromatic. These differences were reflected in greater sorption of SR NOM than GDS NOM. Both surface water NOMs showed a much greater affinity for goethite than for kaolinite. HPSEC analysis of the NOM remaining in solution after 24 h reaction time with geothite revealed that the largest changes in solution phase M(w)s (decreases by 900-1700 Da) occurred at relatively low equilibrium sorbate concentrations (approximately 5-20 mg C 1-1); the decrease in solution M(w) suggested that reactive surface sites were occupied disproportionately by large and intermediate size NOM moieties. At higher equilibrium NOM concentrations (>20 mg C 1-1), as percent adsorption decreased, M(w) in solution was similar to original samples. A smaller decrease in solution NOM M(w) (300-500 Da at 10-20 mg C 1-1 ~ 100 Da at > 20 mg) also occurred upon sorption to kaolinite. Overall, our results showed that factors (as related to NOM composition, clay mineral surface properties, and position along the sorption isotherm) which promote a higher percent sorption lead to the most pronounced decreases in solution M(w).

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2012 CFR

2012-10-01

... Category 2-Amino-2-hydroxymethyl-1,3-propanediol solution III Ammonium hydrogen phosphate solution D...) D Ammonium phosphate, Urea solution, see also Urea, Ammonium phosphate solution D Ammonium..., Magnesium nitrate, Potassium chloride solution III Caramel solutions III Chlorinated paraffins (C14-C17...

Oscillatory fluid flow in deformable tubes: Implications for pore-scale hydromechanics from comparing experimental observations with theoretical predictions.

PubMed

Kurzeja, Patrick; Steeb, Holger; Strutz, Marc A; Renner, Jörg

2016-12-01

Oscillatory flow of four fluids (air, water, two aqueous sodium-tungstate solutions) was excited at frequencies up to 250 Hz in tubes of two materials (steel, silicone) covering a wide range in length, diameter, and thickness. The hydrodynamical response was characterized by phase shift and amplitude ratio between pressures in an upstream (pressure excitation) and a downstream reservoir connected by the tubes. The resulting standing flow waves reflect viscosity-controlled diffusive behavior and inertia-controlled wave behavior for oscillation frequencies relatively low and high compared to Biot's critical frequency, respectively. Rigid-tube theories correspond well with the experimental results for steel tubes filled with air or water. The wave modes observed for silicone tubes filled with the rather incompressible liquids or air, however, require accounting for the solid's shear and bulk modulus to correctly predict speed of pressure propagation and deformation mode. The shear mode may be responsible for significant macroscopic attenuation in porous materials with effective frame-shear moduli lower than the bulk modulus of the pore fluid. Despite notable effects of the ratio of densities and of acoustic and shear velocity of fluid and solid, Biot's frequency remains an approximate indicator of the transition from the viscosity to the inertia controlled regime.

A new insight on the dynamics of sodium dodecyl sulfate aqueous micellar solutions by dielectric spectroscopy.

PubMed

Lanzi, Leandro; Carlà, Marcello; Lanzi, Leonardo; Gambi, Cecilia M C

2009-02-01

Aqueous sodium dodecyl sulfate micellar solutions were investigated by a recently developed double-differential dielectric spectroscopy technique in the frequency range 100 MHz-3 GHz at 22 degrees C, in the surfactant concentration range 29.8-524 mM, explored for the first time above 104 mM. The micellar contribution to dielectric spectra was analyzed according to three models containing, respectively, a single Debye relaxation, a Cole-Cole relaxation and a double Debye relaxation. The single Debye model is not accurate enough. Both Cole-Cole and double Debye models fit well the experimental dielectric spectra. With the double Debye model, two characteristic relaxation times were identified: the slower one, in the range 400-900 ps, is due to the motion of counterions bound to the micellar surface (lateral motion); the faster one, in the range 100-130 ps, is due to interfacial bound water. Time constants and amplitudes of both processes are in fair agreement with Grosse's theoretical model, except at the largest concentration values, where interactions between micelles increase. For each sample, the volume fraction of bulk water and the effect of bound water as well as the conductivity in the low frequency limit were computed. The bound water increases as the surfactant concentration increases, in quantitative agreement with the micellar properties. The number of water molecules per surfactant molecule was also computed. The conductivity values are in agreement with Kallay's model over the whole surfactant concentration range.

Influence of organic solvent on optical and structural properties of ultra-small silicon dots synthesized by UV laser ablation in liquid.

PubMed

Intartaglia, Romuald; Bagga, Komal; Genovese, Alessandro; Athanassiou, Athanassia; Cingolani, Roberto; Diaspro, Alberto; Brandi, Fernando

2012-11-28

Ultra small silicon nanoparticles (Si-NPs) with narrow size distribution are prepared in a one step process by UV picosecond laser ablation of silicon bulk in liquid. Characterization by electron microscopy and absorption spectroscopy proves Si-NPs generation with an average size of 2 nm resulting from an in situ photofragmentation effect. In this context, the current work aims to explore the liquid medium (water and toluene) effect on the Si-NPs structure and on the optical properties of the colloidal solution. Si-NPs with high pressure structure (s.g. Fm3m) and diamond-like structure (s.g. Fd3m), in water, and SiC moissanite 3C phase (s.g. F4[combining macron]3m) in toluene are revealed by the means of High-Resolution TEM and HAADF-STEM measurements. Optical investigations show that water-synthesized Si-NPs have blue-green photoluminescence emission characterized by signal modulation at a frequency of 673 cm(-1) related to electron-phonon coupling. The synthesis in toluene leads to generation of Si-NPs embedded in the graphitic carbon-polymer composite which has intrinsic optical properties at the origin of the optical absorption and luminescence of the obtained colloidal solution.

Efficient Removal of Cationic and Anionic Radioactive Pollutants from Water Using Hydrotalcite-Based Getters.

PubMed

Bo, Arixin; Sarina, Sarina; Liu, Hongwei; Zheng, Zhanfeng; Xiao, Qi; Gu, Yuantong; Ayoko, Godwin A; Zhu, Huaiyong

2016-06-29

Hydrotalcite (HT)-based materials are usually applied to capture anionic pollutants in aqueous solutions. Generally considered anion exchangers, their ability to capture radioactive cations is rarely exploited. In the present work, we explored the ability of pristine and calcined HT getters to effectively capture radioactive cations (Sr(2+) and Ba(2+)) which can be securely stabilized at the getter surface. It is found that calcined HT outperforms its pristine counterpart in cation removal ability. Meanwhile, a novel anion removal mechanism targeting radioactive I(-) is demonstrated. This approach involves HT surface modification with silver species, namely, Ag2CO3 nanoparticles, which can attach firmly on HT surface by forming coherent interface. This HT-based anion getter can be further used to capture I(-) in aqueous solution. The observed I(-) uptake mechanism is distinctly different from the widely reported ion exchange mechanism of HT and much more efficient. As a result of the high local concentrations of precipitants on the getters, radioactive ions in water can be readily immobilized onto the getter surface by forming precipitates. The secured ionic pollutants can be subsequently removed from water by filtration or sedimentation for safe disposal. Overall, these stable, inexpensive getters are the materials of choice for removal of trace ionic pollutants from bulk radioactive liquids, especially during episodic environmental crisis.

Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Benjamin, Ilan

1993-01-01

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2013 CFR

2013-10-01

...-ethylamino-6-isopropylamino-5-triazine solution # Choline chloride solution D Clay slurry III Coal slurry III... acid, dimethylamine salt solution * Y Choline chloride solutions Z Clay slurry OS Coal slurry OS...

Pore Scale Dynamics of Microemulsion Formation.

PubMed

Unsal, Evren; Broens, Marc; Armstrong, Ryan T

2016-07-19

Experiments in various porous media have shown that multiple parameters come into play when an oleic phase is displaced by an aqueous solution of surfactant. In general, the displacement efficiency is improved when the fluids become quasi-miscible. Understanding the phase behavior oil/water/surfactant systems is important because microemulsion has the ability to generate ultralow interfacial tension (<10(-2) mN m(-1)) that is required for miscibility to occur. Many studies focus on microemulsion formation and the resulting properties under equilibrium conditions. However, the majority of applications where microemulsion is present also involve flow, which has received relatively less attention. It is commonly assumed that the characteristics of an oil/water/surfactant system under flowing conditions are identical to the one under equilibrium conditions. Here, we show that this is not necessarily the case. We studied the equilibrium phase behavior of a model system consisting of n-decane and an aqueous solution of olefin sulfonate surfactant, which has practical applications for enhanced oil recovery. The salt content of the aqueous solution was varied to provide a range of different microemulsion compositions and oil-water interfacial tensions. We then performed microfluidic flow experiments to study the dynamic in situ formation of microemulsion by coinjecting bulk fluids of n-decane and surfactant solution into a T-junction capillary geometry. A solvatochromatic fluorescent dye was used to obtain spatially resolved compositional information. In this way, we visualized the microemulsion formation and the flow of it along with the excess phases. A complex interaction between the flow patterns and the microemulsion properties was observed. The formation of microemulsion influenced the flow regimes, and the flow regimes affected the characteristics of the microemulsion formation. In particular, at low flow rates, slug flow was observed, which had profound consequences on the pore scale mixing behavior and resulting microemulsion properties.

Seasonal variations in water relations in current-year leaves of evergreen trees with delayed greening.

PubMed

Harayama, Hisanori; Ikeda, Takefumi; Ishida, Atsushi; Yamamoto, Shin-Ichi

2006-08-01

We investigated seasonal patterns of water relations in current-year leaves of three evergreen broad-leaved trees (Ilex pedunculosa Miq., Ligustrum japonicum Thunb., and Eurya japonica Thunb.) with delayed greening in a warm-temperate forest in Japan. We used the pressure-volume method to: (1) assess the extent to which seasonal variation in leaf water relations is attributable to leaf development processes in delayed greening leaves versus seasonal variation in environmental variables; and (2) investigate variation in leaf water relations during the transition from the sapling to the adult tree stage. Leaf mass per unit leaf area was generally lowest just after completion of leaf expansion in May (late spring), and increased gradually throughout the year. Osmotic potential at full turgor (Psi(o) (ft)) and leaf water potential at the turgor loss point (Psi(w) (tlp)) were highest in May, and lowest in midwinter in all species. In response to decreasing air temperature, Psi(o) (ft) dropped at the rate of 0.037 MPa degrees C(-1). Dry-mass-based water content of leaves and the symplastic water fraction of total leaf water content gradually decreased throughout the year in all species. These results indicate that reductions in the symplastic water fraction during leaf development contributed to the passive concentration of solutes in cells and the resulting drop in winter Psi(o) (ft). The ratio of solutes to water volume increased in winter in current-year leaves of L. japonicum and E. japonica, indicating that osmotic adjustment (active accumulation of solutes) also contributed to the drop in winter in Psi(o) (ft). Bulk modulus of elasticity in cell walls fluctuated seasonally, but no general trend was found across species. Over the growing season, Psi(o) (ft) and Psi(w) (tlp) were lower in adult trees than in saplings especially in the case of I. pedunculosa, suggesting that adult-tree leaves are more drought and cold tolerant than sapling leaves. The ontogenetic increase in the stress resistance of I. pedunculosa may be related to its characteristic life form because I. pedunculosa grows taller than the other species studied.

Compositional data for Bengal delta sediment collected from boreholes at Srirampur, Kachua, Bangladesh

USGS Publications Warehouse

Breit, George N.; Yount, James C.; Uddin, Md. Nehal; Muneem, Ad. Atual; Lowers, Heather; Driscoll, Rhonda L.; Whitney, John W.

2006-01-01

Processes active within sediment of the Bengal delta have attracted world concern because of the locally high content of arsenic dissolved in ground water drawn from that sediment. Sediment samples were collected from two boreholes in Srirampur village, Kachua upazila, Chandphur district, Bangladesh, to investigate the processes contributing to arsenic contamination. The samples were mineralogically and chemically analyzed to determine compositional variations related to the arsenic content of the sediment. Mineralogy of the sediments was determined using powder X-ray diffraction. Bulk chemical composition was measured by Combustion, Inductively Coupled Plasma Atomic Emission Spectroscopy, Energy Dispersive X-ray Fluorescence, and Hydride Generation Atomic Absorption Spectrophotometry. Solutions produced by four chemical extractions-0.1 molar strontium chloride, 0.5 normal hydrochloric acid, titanium(III)-EDTA, and a solution of hydrogen peroxide and hydrochloric acid-were analyzed to evaluate the chemical reactivity of the sediment with an emphasis on arsenic residence. Acid-volatile sulfide, acid-soluble sulfate, and reducible sulfide were also measured. Sediment sampled at Srirampur is typically unlithified, gray, micaceous, feldspathic, arenaceous silt and sand. Arsenic content of the sediment ranges from <1 to 210 ppm, with the highest contents measured in sediment collected at a depth of 320 meters. Samples with high arsenic contents typically contain high concentrations of sulfur. The greatest amount of arsenic was extracted using the oxidative hydrogen peroxide and hydrochloric acid extraction solution. The extraction results are consistent with the apparent association of arsenic in sulfur in the bulk chemical analyses. Pyrite is typically the most abundant form of sulfur in the sediment and is dissolved by the oxidative extraction.

Sequential water molecule binding enthalpies for aqueous nanodrops containing a mono-, di- or trivalent ion and between 20 and 500 water molecules† †Electronic supplementary information (ESI) available: Detailed description of the experimental and computational modeling methods. Isolation, BIRD and UVPD sequence for [Ru(NH3)6]3+·(H2O)169–171, nanoESI spectra for 2+ and 3+ ions. Detailed description of the isotope distribution simulation program. Comparison between experimental and simulated 1+, 2+ and 3+ ion isotope distributions. Wavelength dependence of the deduced sequential binding enthalpies. Comparison of experimental UVPD binding enthalpies to the liquid drop model at different temperatures. Complete list of binding enthalpies and average number of water molecules lost upon UVPD. See DOI: 10.1039/c6sc04957e Click here for additional data file.

PubMed Central

Heiles, Sven; Cooper, Richard J.; DiTucci, Matthew J.

2017-01-01

Sequential water molecule binding enthalpies, ΔH n,n–1, are important for a detailed understanding of competitive interactions between ions, water and solute molecules, and how these interactions affect physical properties of ion-containing nanodrops that are important in aerosol chemistry. Water molecule binding enthalpies have been measured for small clusters of many different ions, but these values for ion-containing nanodrops containing more than 20 water molecules are scarce. Here, ΔH n,n–1 values are deduced from high-precision ultraviolet photodissociation (UVPD) measurements as a function of ion identity, charge state and cluster size between 20–500 water molecules and for ions with +1, +2 and +3 charges. The ΔH n,n–1 values are obtained from the number of water molecules lost upon photoexcitation at a known wavelength, and modeling of the release of energy into the translational, rotational and vibrational motions of the products. The ΔH n,n–1 values range from 36.82 to 50.21 kJ mol–1. For clusters containing more than ∼250 water molecules, the binding enthalpies are between the bulk heat of vaporization (44.8 kJ mol–1) and the sublimation enthalpy of bulk ice (51.0 kJ mol–1). These values depend on ion charge state for clusters with fewer than 150 water molecules, but there is a negligible dependence at larger size. There is a minimum in the ΔH n,n–1 values that depends on the cluster size and ion charge state, which can be attributed to the competing effects of ion solvation and surface energy. The experimental ΔH n,n–1 values can be fit to the Thomson liquid drop model (TLDM) using bulk ice parameters. By optimizing the surface tension and temperature change of the logarithmic partial pressure for the TLDM, the experimental sequential water molecule binding enthalpies can be fit with an accuracy of ±3.3 kJ mol–1 over the entire range of cluster sizes. PMID:28451364

46 CFR 154.1105 - Exterior water spray system: General.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 154.1105 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SAFETY STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Firefighting § 154.1105 Exterior water spray system: General. Each liquefied flammable gas vessel...

46 CFR 154.1105 - Exterior water spray system: General.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 154.1105 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SAFETY STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Firefighting § 154.1105 Exterior water spray system: General. Each liquefied flammable gas vessel...

46 CFR 154.1105 - Exterior water spray system: General.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 154.1105 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SAFETY STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Firefighting § 154.1105 Exterior water spray system: General. Each liquefied flammable gas vessel...

Mineralogy and geochemistry of efflorescent minerals on mine tailings and their potential impact on water chemistry.

PubMed

Grover, B P C; Johnson, R H; Billing, D G; Weiersbye, I M G; Tutu, H

2016-04-01

In the gold mining Witwatersrand Basin of South Africa, efflorescent mineral crusts are a common occurrence on and nearby tailings dumps during the dry season. The crusts are readily soluble and generate acidic, metal- and sulphate-rich solutions on dissolution. In this study, the metal content of efflorescent crusts at an abandoned gold mine tailings dump was used to characterise surface and groundwater discharges from the site. Geochemical modelling of the pH of the solution resulting from the dissolution of the crusts was used to better understand the crusts' potential impact on water chemistry. The study involved two approaches: (i) conducting leaching experiments on oxidised and unoxidised tailings using artificial rainwater and dilute sulphuric acid and correlating the composition of crusts to these leachates and (ii) modelling the dissolution of the crusts in order to gain insight into their mineralogy and their potential impact on receiving waters. The findings suggested that there were two chemically distinct discharges from the site, namely an aluminium- and magnesium-rich surface water plume and an iron-rich groundwater plume. The first plume was observed to originate from the oxidised tailings following leaching with rainwater while the second plume originated from the underlying unoxidised tailings with leaching by sulphuric acid. Both groups of minerals forming from the respective plumes were found to significantly lower the pH of the receiving water with simulations of their dissolution found to be within 0.2 pH units of experimental values. It was observed that metals in a low abundance within the crust (for example, iron) had a stronger influence on the pH of the resulting solutions than metals in a greater abundance (aluminium or magnesium). Techniques such as powder X-ray diffraction (PXRD) and in situ mineral determination techniques such as remote sensing can effectively determine the dominant mineralogy. However, the minerals or metals incorporated through solid solution into bulk mineralogy that dominates the chemistry of the solutions upon their dissolution may occur in minor quantities that can only be predicted using chemical analysis. Their mineralogy can be predicted using geochemical modelling and can provide a set of hypothetical minerals that upon dissolution yield a solution similar to that of the actual crusts. This realisation has a bearing on decision-making such as in risk assessment and designing pollutant mitigation strategies.

Groundwater hydrochemistry in the active layer of the proglacial zone, Finsterwalderbreen, Svalbard

USGS Publications Warehouse

Cooper, R.J.; Wadham, J.L.; Tranter, M.; Hodgkins, R.; Peters, N.E.

2002-01-01

Glacial bulk meltwaters and active-layer groundwaters were sampled from the proglacial zone of Finsterwalderbreen during a single melt season in 1999, in order to determine the geochemical processes that maintain high chemical weathering rates in the proglacial zone of this glacier. Results demonstrate that the principle means of solute acquisition is the weathering of highly reactive moraine and fluvial active-layer sediments by supra-permafrost groundwaters. Active-layer groundwater derives from the thaw of the proglacial snowpack, buried ice and glacial bulk meltwaters. Groundwater evolves by sulphide oxidation and carbonate dissolution. Evaporation- and freeze-concentration of groundwater in summer and winter, respectively produce Mg-Ca-sulphate salts on the proglacial surface. Re-dissolution of these salts in early summer produces groundwaters that are supersaturated with respect to calcite. There is a pronounced spatial pattern to the geochemical evolution of groundwater. Close to the main proglacial channel, active layer sediments are flushed diurnally by bulk meltwaters. Here, Mg-Ca-sulphate deposits become exhausted in the early season and geochemical evolution proceeds by a combination of sulphide oxidation and carbonate dissolution. At greater distances from the channel, the dissolution of Mg-Ca-sulphate salts is a major influence and dilution by the bulk meltwaters is relatively minor. The influence of sulphate salt dissolution decreases during the sampling season, as these salts are exhausted and waters become increasingly routed by subsurface flowpaths. ?? 2002 Elsevier Science B.V. All rights reserved.

Isotope effects in liquid water by infrared spectroscopy. IV. No free OH groups in liquid water.

PubMed

Max, Jean-Joseph; Chapados, Camille

2010-10-28

The presence of free OH (OH not H-bonded) in bulk water is a key element for the determination of its molecular structure. The OH covalent bond infrared (IR) absorption is highly sensitive to the molecular environment. For this reason, IR spectroscopy is used for the determination of free OH. A workable definition of this is obtained with methanol (MeOH) in hexane where minute quantities of free OH are present. These absorb at 3654 cm(-1) (a 27 cm(-1) redshift from the gas position) with a full width at half height of 35 cm(-1). The IR spectrum of water between room temperature and 95 °C does not display such a band near 3650 cm(-1). This indicates that we do not see, in the IR spectra, the "free" OH group. From this we conclude that it is not present in liquid water at least down to the 1000 ppm level which is the limit of detectivity of our spectrometer. Other spectroscopic considerations of methanol and water in acetonitrile solutions indicate that weak H-bonds are also not present in liquid water.

Numerical study of underwater dispersion of dilute and dense sediment-water mixtures

NASA Astrophysics Data System (ADS)

Chan, Ziying; Dao, Ho-Minh; Tan, Danielle S.

2018-05-01

As part of the nodule-harvesting process, sediment tailings are released underwater. Due to the long period of clouding in the water during the settling process, this presents a significant environmental and ecological concern. One possible solution is to release a mixture of sediment tailings and seawater, with the aim of reducing the settling duration as well as the amount of spreading. In this paper, we present some results of numerical simulations using the smoothed particle hydrodynamics (SPH) method to model the release of a fixed volume of pre-mixed sediment-water mixture into a larger body of quiescent water. Both the sediment-water mixture and the “clean” water are modeled as two different fluids, with concentration-dependent bulk properties of the sediment-water mixture adjusted according to the initial solids concentration. This numerical model was validated in a previous study, which indicated significant differences in the dispersion and settling process between dilute and dense mixtures, and that a dense mixture may be preferable. For this study, we investigate a wider range of volumetric concentration with the aim of determining the optimum volumetric concentration, as well as its overall effectiveness compared to the original process (100% sediment).

Self-assembled pentacenequinone derivative for trace detection of picric acid.

PubMed

Bhalla, Vandana; Gupta, Ankush; Kumar, Manoj; Rao, D S Shankar; Prasad, S Krishna

2013-02-01

Pentacenequinone derivative 3 forms luminescent supramolecular aggregates both in bulk as well as in solution phase. In bulk phase at high temperature, long-range stacking of columns leads to formation of stable and ordered columnar mesophase. Further, derivative 3 works as sensitive chemosensor for picric acid (PA) and gel-coated paper strips detect PA at nanomolar level and provide a simple, portable, and low-cost method for detection of PA in aqueous solution, vapor phase, and in contact mode.

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

Lawrence, G.B.; Fernandez, I.J.; Goltz, S.M.

To provide information needed to assess the current and future status of spruce-fir forests in Maine, the Howland Integrated Forest Study (HIFS) was initiated in 1987 as part of the USDA Forest Service Forest Response Program, in conjunction with the establishment of a Mountain Cloud Chemistry Program (MCCP) monitoring site. Through this project, bulk and wet-only precipitation, dry deposition, throughfall and soil solution chemistry has been determined. This paper will focus on soil solution collected between May, 1988 and bulk precipitation collected from June through November, 1988.

Using 87Sr/86Sr ratios to investigate changes in stream chemistry during snowmelt in the Provo River, Utah, USA

NASA Astrophysics Data System (ADS)

Hale, C. A.; Carling, G. T.; Fernandez, D. P.; Nelson, S.; Aanderud, Z.; Tingey, D. G.; Dastrup, D.

2017-12-01

Water chemistry in mountain streams is variable during spring snowmelt as shallow groundwater flow paths are activated in the watershed, introducing solutes derived from soil water. Sr isotopes and other tracers can be used to differentiate waters that have interacted with soils and dust (shallow groundwater) and bedrock (deep groundwater). To investigate processes controlling water chemistry during snowmelt, we analyzed 87Sr/86Sr ratios, Sr and other trace element concentrations in bulk snowpack, dust, soil, soil water, ephemeral channels, and river water during snowmelt runoff in the upper Provo River watershed in northern Utah, USA, over four years (2014-2017). Strontium concentrations in the river averaged 20 ppb during base flow and decreased to 10 ppb during snowmelt runoff. 87Sr/86Sr ratios were around 0.717 during base flow and decreased to 0.715 in 2014 and 0.713 in 2015 and 2016 during snowmelt, trending towards less radiogenic values of mineral dust inputs in the Uinta Mountain soils. Ephemeral channels, representing shallow flow paths with soil water inputs, had Sr concentrations between 7-20 ppb and 87Sr/86Sr ratios between 0.713-0.716. Snowpack Sr concentrations were generally <2 ppb with 87Sr/86Sr ratios between 0.710-711, similar to atmospheric dust inputs. The less radiogenic 87Sr/86Sr ratios and lower Sr concentrations in the river during snowmelt are likely a result of activating shallow groundwater flow paths, which allows melt water to interact with shallow soils that contain accumulated dust deposits with a less radiogenic 87Sr/86Sr ratio. These results suggest that flow paths and atmospheric dust are important to consider when investigating variable solute loads in mountain streams.

Controls on soil solution nitrogen along an altitudinal gradient in the Scottish uplands

NASA Astrophysics Data System (ADS)

Jackson-Blake, L.; Helliwell, R. C.; Britton, A. J.; Gibbs, S.; Coull, M. C.; Dawson, L.

2012-04-01

Nitrogen (N) deposition continues to threaten upland ecosystems, contributing to acidification, eutrophication and biodiversity loss. We present results from a monitoring study aimed at investigating the fate of this deposited N within a relatively pristine catchment in the Cairngorm Mountains (Scotland). Six sites were established along an elevation gradient (486 - 908 m) spanning the key habitats of temperate maritime uplands. Bulk deposition chemistry, soil carbon content, soil solution chemistry, soil temperature and soil moisture content were monitored over a 5 year period, making this the first study of its kind in a maritime Alpine environment. Results were used to assess spatial variability in soil solution N and to investigate the factors and processes driving this variability. Highest soil solution inorganic N concentrations were found in the alpine soils at the top of the hillslope. Soil carbon stock, dissolved organic carbon concentration and factors representing site hydrology were the best predictors of nitrate concentration. These factors act as proxies for changing net biological uptake and soil/water contact time, and support the hypothesis that spatial variations in soil solution nitrate are controlled by habitat N retention capacity. Soil percent carbon was a better predictor of soil solution N concentration than mass of carbon. Ammonium was less affected by soil hydrology than nitrate and showed the effects of net mineralization inputs, particularly at Racomitrium heath and peaty sites. We hypothesize that high ammonium concentrations at the Racomitrium heath are related to the mineralization of microbial cell tissue during times of stress, largely in the absence of plant uptake. Due to the spatial heterogeneity in N leaching potential, a fine-scale approach to assessing surface water vulnerability to N leaching is recommended over the broad scale, critical loads approach currently in use, particularly for sensitive areas.

Exact solutions of bulk viscous with string cloud attached to strange quark matter for higher dimensional FRW universe in Lyra geometry

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

Çağlar, Halife, E-mail: hlfcglr@gmail.com; Aygün, Sezgin, E-mail: saygun@comu.edu.tr

In this study, we have investigated bulk viscous with strange quark matter attached to the string cloud for higher dimensional Friedman-Robertson-Walker (FRW) universe in Lyra geometry. By using varying deceleration parameter and conservation equations we have solved Einstein Field Equations (EFE’s) and obtained generalized exact solutions for our model. Also we have found that string is not survived for bulk viscous with strange quark matter attached to the string cloud in framework higher dimensional FRW universe in Lyra geometry. This result agrees with Kiran and Reddy, Krori et al, Sahoo and Mishra and Mohanty et al. in four and fivemore » dimensions.« less

Aqueous heterogeneity at the air/water interface revealed by 2D-HD-SFG spectroscopy.

PubMed

Hsieh, Cho-Shuen; Okuno, Masanari; Hunger, Johannes; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

2014-07-28

Water molecules interact strongly with each other through hydrogen bonds. This efficient intermolecular coupling causes strong delocalization of molecular vibrations in bulk water. We study intermolecular coupling at the air/water interface and find intermolecular coupling 1) to be significantly reduced and 2) to vary strongly for different water molecules at the interface--whereas in bulk water the coupling is homogeneous. For strongly hydrogen-bonded OH groups, coupling is roughly half of that of bulk water, due to the lower density in the near-surface region. For weakly hydrogen-bonded OH groups that absorb around 3500 cm(-1), which are assigned to the outermost, yet hydrogen-bonded OH groups pointing towards the liquid, coupling is further reduced by an additional factor of 2. Remarkably, despite the reduced structural constraints imposed by the interfacial hydrogen-bond environment, the structural relaxation is slow and the intermolecular coupling of these water molecules is weak. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Retardation of Bulk Water Dynamics by Disaccharide Osmolytes

NASA Astrophysics Data System (ADS)

Shukla, Nimesh; Chen, Lee; Pomarico, Enrico; Chergui, Majed; Othon, Christina

Bioprotective nature of disaccharides is hypothesized to derive from the modification of the hydrogen bonding network of water which protects biomolecules through lowered water activity at the protein interface. Using ultrafast fluorescence spectroscopy, we measured the relaxation of bulk water dynamics around the induced dipole moment of two fluorescent probes (Lucifer Yellow Ethylenediamine and Tryptophan). Our results indicate a reduction in bulk water reorganization rate of approximately 30%. We observe this retardation in the low concentration regime measured at 0.1 and 0.25 M, far below the onset of glassy dynamics. This water structuring should be significant in crowded biological systems, contributing to a global change in protein energy landscape, resulting in a significant enhancement of protein stability under environmental stress. We observed similar dynamic reduction for two disaccharide osmolytes, sucrose and trehalose, with trehalose being the more effective in reducing solvation dynamics.