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Sample records for additional water molecules

  1. Enantioselective Michael Addition of Water

    PubMed Central

    Chen, Bi-Shuang; Resch, Verena; Otten, Linda G; Hanefeld, Ulf

    2015-01-01

    The enantioselective Michael addition using water as both nucleophile and solvent has to date proved beyond the ability of synthetic chemists. Herein, the direct, enantioselective Michael addition of water in water to prepare important β-hydroxy carbonyl compounds using whole cells of Rhodococcus strains is described. Good yields and excellent enantioselectivities were achieved with this method. Deuterium labeling studies demonstrate that a Michael hydratase catalyzes the water addition exclusively with anti-stereochemistry. PMID:25529526

  2. Spectroscopic modeling of water molecule

    NASA Astrophysics Data System (ADS)

    Danylo, R. I.; Okhrimenko, B. A.

    2013-12-01

    This research is devoted to the vibrational spectroscopy inverse problem solution that gives a possibility to design a molecule and make conclusions about its geometry. The valence angle finding based on the usage of inverse spectral vibrational spectroscopy problem is a well-known task. 3N-matrix method was chosen to solve the proposed task. The usage of this method permits to make no assumptions about the molecule force field, besides it can be applied to molecules of matter in liquid state. Anharmonicity constants assessment is an important part of the valence angle finding. The reduction to zero vibrations is necessary because used matrix analytical expression were found in the harmonic approach. In order to find the single-valued inverse spectral problem of vibrational spectroscopy solution a shape parameter characterizing "mixing" of ω1 and ω2 vibrations forms must be found. The minimum of such a function Υ called a divergence parameter was found. This function characterizes method's accuracy. The valence angle assessment was reduced to the divergence parameter minimization. The β value concerning divergence parameter minimum was interpreted as the desired valence angle. The proposed method was applied for water molecule in liquid state: β = (88,8 ±1,7)° . The found angle fits the water molecule nearest surrounding tetrahedral model including hydrogen bond curvature in the first approximation.

  3. Water molecules orientation in surface layer

    NASA Astrophysics Data System (ADS)

    Klingo, V. V.

    2000-08-01

    The water molecules orientation has been investigated theoretically in the water surface layer. The surface molecule orientation is determined by the direction of a molecule dipole moment in relation to outward normal to the water surface. Entropy expressions of the superficial molecules in statistical meaning and from thermodynamical approach to a liquid surface tension have been found. The molecules share directed opposite to the outward normal that is hydrogen protons inside is equal 51.6%. 48.4% water molecules are directed along to surface outward normal that is by oxygen inside. A potential jump at the water surface layer amounts about 0.2 volts.

  4. Water based drilling mud additive

    SciTech Connect

    McCrary, J.L.

    1983-12-13

    A water based fluid additive useful in drilling mud used during drilling of an oil or gas well is disclosed, produced by reacting water at temperatures between 210/sup 0/-280/sup 0/ F. with a mixture comprising in percent by weight: gilsonite 25-30%, tannin 7-15%, lignite 25-35%, sulfonating compound 15-25%, water soluble base compound 5-15%, methylene-yielding compound 1-5%, and then removing substantially all of the remaining water to produce a dried product.

  5. Dynamics of water molecules in glucose solutions.

    SciTech Connect

    Talon, C.; Smith, L. J.; Brady, J. W.; Copley, J. R. D.; Price, D. L.; Saboungi, M. L.; Materials Science Division; Centre de Recherche sur la Matiyre Divisye; Cornell Univ.; NIST; Centre de Recherche sur les Matyriaux y Haute Tempyrature

    2004-04-22

    The effects of the solution of glucose molecules on the dynamics of solvent water have been studied by quasielastic neutron scattering (QENS) measurements on solutions of selectively deuterated glucose in natural water. The data are fitted to two Lorentzians ascribed to pure translational and mixed translational and rotational character, respectively. The addition of the glucose to the water causes a substantial slowing down, by a factor 10 for the translational diffusion and 3-4 for the rotational motion at the highest concentration studied, 1:11 C{sub 6}H{sub 12}O{sub 6}:H{sub 2}O. The values obtained for water diffusion constants are consistent with previous QENS and NMR experiments on monosaccharide solutions but an order of magnitude higher than those derived from a recent molecular dynamics simulation.

  6. Design of water molecule and its surrounding

    NASA Astrophysics Data System (ADS)

    Danylo, R. I.; Okhrimenko, B. A.; Yablochkova, K. S.

    2015-02-01

    Hydrogen bonds and their fluctuations are one of the factors that determine the unique properties of water [1]. Building models of formation and rupture of hydrogen bonds due to non-eigen vibrations of a molecule of water is to a large extent determined by the availability of accurate information on the geometric structure of the water molecule. Geometric parameters of the water molecule have been well studied for the gaseous state. This was aided by the possibility of an experimental study of the regularities in the rotational spectra of molecules. However, some questions about the geometry of the water molecule in the liquid state remain unanswered. For example, many sources state that the valence angle of the water molecule decreases during the transition into the liquid state [2]. Based on the experimental data of molecular vibration spectra in D2O and H2O molecules [3], the authors have estimated valence angle of water in the liquid state. Consequently, the value of the valence angle of water in liquid state was determined to be (89 +/-2)°. A question of determination of libration vibrations of water molecule, as well as the analysis of its consequent inversion doubling, based on the new information on the equilibrium angle of the water molecules in the liquid state, constitutes an interest and is discussed in the present paper.

  7. Effects of water molecules on photoluminescence from hierarchical peptide nanotubes and water probing capability.

    PubMed

    Wang, Minjie; Xiong, Shijie; Wu, Xinglong; Chu, Paul K

    2011-10-01

    Photoluminescence (PL) spectra reveal that deficiency of water molecules in the channel cores of bioinspired hierarchical diphenylalanine ( L -Phe- L -Phe, FF) peptide nanotubes (PNTs) not only modifies the bandgap of the subnanometer crystalline structure formed by the self-assembly process, but also induces a characteristic ultraviolet PL peak the position of which is linearly proportional to the number of water molecules in the PNTs. Addition or loss of water molecules gives rise to the UV PL redshift or blueshift. Density functional theory calculation also confirms that addition of water molecules to the PNTs causes splitting of the valence-band peak, which corresponds to the shift and splitting of the observed UV PL peak. Water molecules play an important role in the biological properties of FF PNTs and the results demonstrate that the PL spectra can be used to probe the number of water molecules bonded to the FF molecules. PMID:22049551

  8. Modelling water molecules inside cyclic peptide nanotubes

    NASA Astrophysics Data System (ADS)

    Tiangtrong, Prangsai; Thamwattana, Ngamta; Baowan, Duangkamon

    2016-03-01

    Cyclic peptide nanotubes occur during the self-assembly process of cyclic peptides. Due to the ease of synthesis and ability to control the properties of outer surface and inner diameter by manipulating the functional side chains and the number of amino acids, cyclic peptide nanotubes have attracted much interest from many research areas. A potential application of peptide nanotubes is their use as artificial transmembrane channels for transporting ions, biomolecules and waters into cells. Here, we use the Lennard-Jones potential and a continuum approach to study the interaction of a water molecule in a cyclo[(- D-Ala- L-Ala)_4-] peptide nanotube. Assuming that each unit of a nanotube comprises an inner and an outer tube and that a water molecule is made up of a sphere of two hydrogen atoms uniformly distributed over its surface and a single oxygen atom at the centre, we determine analytically the interaction energy of the water molecule and the peptide nanotube. Using this energy, we find that, independent of the number of peptide units, the water molecule will be accepted inside the nanotube. Once inside the nanotube, we show that a water molecule prefers to be off-axis, closer to the surface of the inner nanotube. Furthermore, our study of two water molecules inside the peptide nanotube supports the finding that water molecules form an array of a 1-2-1-2 file inside peptide nanotubes. The theoretical study presented here can facilitate thorough understanding of the behaviour of water molecules inside peptide nanotubes for applications, such as artificial transmembrane channels.

  9. Water molecule conformation outside a metal surface

    NASA Astrophysics Data System (ADS)

    Flores, F.; Gabbay, I.; March, N. H.

    1981-05-01

    The effect of a metal surface on the conformation of a water molecule has been analyzed by discussing two independent effects: (i) the screening of the proton-proton repulsion, (ii) the interaction of the lone-pair orbitals with the surface. Both effects tend to increase the HOH angle. However, the interaction between the lone-pairs with the surface is the dominant effect for a water molecule approaching the surface. In particular, for a chemisorbed state this interaction is responsible for the major part of the molecule deformation. We have estimated that for H 2O chemisorbed on Ru, the HOH angle must increase from the free molecule value of 104.5° by 3.1 ± 0.5° in good agreement with the experimental evidence.

  10. The Dipole Polarizability of a Water Molecule in Liquid Water

    NASA Astrophysics Data System (ADS)

    Distasio, Robert; Maitra, Rahul

    The dipole polarizability, α, provides a measure of the tendency of a molecule or material to deform (or polarize) in the presence of an electric field. Within the framework of density functional theory (DFT), we present a hierarchy of first principles based approaches for computing α of a molecule located in the condensed phase. This hierarchy includes a successive treatment of both short-range (hybridization, Pauli exchange-repulsion, etc.) and long-range (Coulomb) electrodynamical response screening in the computation of α, while simultaneously accounting for the surrounding condensed-phase environment. Utilizing highly accurate liquid water configurations generated from van der Waals inclusive hybrid DFT based ab initio molecular dynamics, we computed α for a given water molecule in liquid water as a first application of this approach. Our findings will be compared and contrasted with α computed for an isolated gas-phase water molecule.

  11. Clusters of mobile molecules in supercooled water

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas; Buldyrev, Sergey V.; Stanley, H. Eugene; Starr, Francis W.

    2005-07-01

    We study the spatially heterogeneous dynamics in water via molecular dynamics simulations using the extended simple point charge potential. We identify clusters formed by mobile molecules and study their properties. We find that these clusters grow in size and become more compact as temperature decreases. We analyze the probability density function of cluster size, and we study the cluster correlation length. We find that clusters appear to be characterized by a fractal dimension consistent with that of lattice animals. We relate the cluster size and correlation length to the configurational entropy, Sconf . We find that these quantities depend weakly on 1/Sconf . In particular, the linearity found between the cluster mass n* and 1/Sconf suggests that n* may be interpreted as the mass of the cooperatively rearranging regions that form the basis of the Adam-Gibbs approach to the dynamics of supercooled liquids. We study the motion of molecules within a cluster, and find that each molecule preferentially follows a neighboring molecule in the same cluster. Based on this finding we hypothesize that stringlike cooperative motion may be a general mechanism for molecular rearrangement of complex, as well as simple liquids. By mapping each equilibrium configuration onto its corresponding local potential energy minimum or inherent structure (IS), we are able to compare the mobile molecule clusters in the equilibrium system with the molecules forming the clusters identified in the transitions between IS. We find that (i) mobile molecule clusters obtained by comparing different system configurations and (ii) clusters obtained by comparing the corresponding IS are completely different for short time scales, but are the same on the longer time scales of diffusive motion.

  12. Unprecedentedly rapid transport of single-file rolling water molecules

    NASA Astrophysics Data System (ADS)

    Qiu, Tong; Huang, Ji-Ping

    2015-10-01

    The realization of rapid and unidirectional single-file water-molecule flow in nanochannels has posed a challenge to date. Here, we report unprecedentedly rapid unidirectional single-file water-molecule flow under a translational terahertz electric field, which is obtained by developing a Debye doublerelaxation theory. In addition, we demonstrate that all the single-file molecules undergo both stable translation and rotation, behaving like high-speed train wheels moving along a railway track. Independent molecular dynamics simulations help to confirm these theoretical results. The mechanism involves the resonant relaxation dynamics of H and O atoms. Further, an experimental demonstration is suggested and discussed. This work has implications for the design of high-efficiency nanochannels or smaller nanomachines in the field of nanotechnology, and the findings also aid in the understanding and control of water flow across biological nanochannels in biology-related research.

  13. Rotational motion of a single water molecule in a buckyball.

    PubMed

    Farimani, A Barati; Wu, Yanbin; Aluru, N R

    2013-11-01

    Encapsulation of a single water molecule in a buckyball (C60) can provide fundamental insights into the properties of water. Investigation of a single water molecule is feasible through its solitary confinement in C60. In this paper, we performed a detailed study of the properties and dynamics of a single water molecule in a buckyball using DFT and MD simulations. We report on the enhancement of rotational diffusion and entropy of a water molecule in C60, compared to a bulk water molecule. H2O@C60 has zero translational diffusion and terahertz revolution frequency. The harmonic, high amplitude rotation of a single water molecule in C60 is compared to stochastic behavior of bulk water molecules. The combination of large rotational and negligible translational motion of water in C60 creates new opportunities in nanotechnology applications. PMID:24061613

  14. Visualizing Water Molecules in Transmembrane Proteins Using Radiolytic Labeling Methods

    SciTech Connect

    Orban, T.; Gupta, S; Palczewski, K; Chance, M

    2010-01-01

    Essential to cells and their organelles, water is both shuttled to where it is needed and trapped within cellular compartments and structures. Moreover, ordered waters within protein structures often colocalize with strategically placed polar or charged groups critical for protein function, yet it is unclear if these ordered water molecules provide structural stabilization, mediate conformational changes in signaling, neutralize charged residues, or carry out a combination of all these functions. Structures of many integral membrane proteins, including G protein-coupled receptors (GPCRs), reveal the presence of ordered water molecules that may act like prosthetic groups in a manner quite unlike bulk water. Identification of 'ordered' waters within a crystalline protein structure requires sufficient occupancy of water to enable its detection in the protein's X-ray diffraction pattern, and thus, the observed waters likely represent a subset of tightly bound functional waters. In this review, we highlight recent studies that suggest the structures of ordered waters within GPCRs are as conserved (and thus as important) as conserved side chains. In addition, methods of radiolysis, coupled to structural mass spectrometry (protein footprinting), reveal dynamic changes in water structure that mediate transmembrane signaling. The idea of water as a prosthetic group mediating chemical reaction dynamics is not new in fields such as catalysis. However, the concept of water as a mediator of conformational dynamics in signaling is just emerging, because of advances in both crystallographic structure determination and new methods of protein footprinting. Although oil and water do not mix, understanding the roles of water is essential to understanding the function of membrane proteins.

  15. Quantum Tunneling of Water in Beryl: A New State of the Water Molecule

    NASA Astrophysics Data System (ADS)

    Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani; Prisk, Timothy R.; Mamontov, Eugene; Podlesnyak, Andrey; Ehlers, George; Seel, Andrew G.; Wesolowski, David J.; Anovitz, Lawrence M.

    2016-04-01

    Using neutron scattering and ab initio simulations, we document the discovery of a new "quantum tunneling state" of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. In addition, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

  16. Quantum behaviour of water molecule in gemstone: terahertz fingerprints

    NASA Astrophysics Data System (ADS)

    Zhukova, Elena S.; Gorshunov, Boris P.; Torgashev, Victor I.; Lebedev, Vladimir V.; Shakurov, Gil'man S.; Kremer, Reinhard K.; Pestrjakov, Efim V.; Thomas, Victor G.; Fursenko, Dimitry A.; Dressel, Martin

    2014-03-01

    We have shown that a weak interaction of a lone H2O molecule with the ''walls'' of nano-sized crystalline cage of gemstone (beryl) results in emergence of a rich set of molecular vibrational states. By analogy with translational and librational bands in liquid water and ice corresponding absorption bands are explained as due to translational (T) and librational (L) movements of the H2O molecule which is hydrogen bonded to the cage walls. In beryl crystal lattice, however, the six-fold symmetry of the cage brings about additional effect of splitting of the T and L bands into fine structure due to tunnelling within the six-well potential relief. The presented results will be of use for analysis of more complicated systems with confined water molecules like H2O chains in carbon nano-tubes, molecular clusters in e.g. zeolites, clays, silica gels and other natural or synthetic frameworks, as well as for interfacial water in biological systems.

  17. The large quadrupole of water molecules.

    PubMed

    Niu, Shuqiang; Tan, Ming-Liang; Ichiye, Toshiko

    2011-04-01

    Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical∕molecular mechanical (QM∕MM) calculations at the MP2∕aug-cc-pVQZ level on a B3LYP∕aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM∕MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM∕MM multipoles is much closer than that from the site models to the potential from the QM∕MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment. PMID:21476758

  18. The Large Quadrupole of Water Molecules

    SciTech Connect

    Niu, Shuqiang; Tan, Ming-Liang; Ichiye, Toshhiko

    2011-04-07

    Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical/molecular mechanical (QM/MM) calculations at the MP2/aug-cc-pVQZ level on a B3LYP/aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM/MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM/MM multipoles is much closer than that from the site models to the potential from the QM/MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment

  19. The large quadrupole of water molecules

    NASA Astrophysics Data System (ADS)

    Niu, Shuqiang; Tan, Ming-Liang; Ichiye, Toshiko

    2011-04-01

    Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical/molecular mechanical (QM/MM) calculations at the MP2/aug-cc-pVQZ level on a B3LYP/aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM/MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM/MM multipoles is much closer than that from the site models to the potential from the QM/MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment.

  20. Adsorption structure of water molecules on the Be(0001) surface

    SciTech Connect

    Yang, Yu; Li, Yanfang; Wang, Shuangxi; Zhang, Ping

    2014-06-07

    By using density functional theory calculations, we systematically investigate the adsorption of water molecules at different coverages on the Be(0001) surface. The coverage dependence of the prototype water structures and energetics for water adlayer growth are systematically studied. The structures, energetics, and electronic properties are calculated and compared with other available studies. Through our systematic investigations, we find that water molecules form clusters or chains on the Be(0001) surface at low coverages. When increasing the water coverage, water molecules tend to form a 2 × 2 hexagonal network on the Be(0001) surface.

  1. Electric Dipole Moments of Nanosolvated Acid Molecules in Water Clusters

    NASA Astrophysics Data System (ADS)

    Guggemos, Nicholas; Slavíček, Petr; Kresin, Vitaly V.

    2015-01-01

    The electric dipole moments of (H2O)nDCl (n =3 - 9 ) clusters have been measured by the beam-deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noticeable rise in the dipole moment occurring at n ≈5 - 6 . This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular-dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero-point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions.

  2. From single molecules to water networks: Dynamics of water adsorption on Pt(111).

    PubMed

    Naderian, Maryam; Groß, Axel

    2016-09-01

    The adsorption dynamics of water on Pt(111) was studied using ab initio molecular dynamics simulations based on density functional theory calculations including dispersion corrections. Sticking probabilities were derived as a function of initial kinetic energy and water coverage. In addition, the energy distribution upon adsorption was monitored in order to analyze the energy dissipation process. We find that on the water pre-covered surface the sticking probability is enhanced because of the attractive water-water interaction and the additional effective energy dissipation channels to the adsorbed water molecules. The water structures forming directly after the adsorption on the pre-covered surfaces do not necessarily correspond to energy minimum structures. PMID:27609006

  3. Water addition, evaporation and water holding capacity of poultry litter.

    PubMed

    Dunlop, Mark W; Blackall, Patrick J; Stuetz, Richard M

    2015-12-15

    Litter moisture content has been related to ammonia, dust and odour emissions as well as bird health and welfare. Improved understanding of the water holding properties of poultry litter as well as water additions to litter and evaporation from litter will contribute to improved litter moisture management during the meat chicken grow-out. The purpose of this paper is to demonstrate how management and environmental conditions over the course of a grow-out affect the volume of water A) applied to litter, B) able to be stored in litter, and C) evaporated from litter on a daily basis. The same unit of measurement has been used to enable direct comparison-litres of water per square metre of poultry shed floor area, L/m(2), assuming a litter depth of 5cm. An equation was developed to estimate the amount of water added to litter from bird excretion and drinking spillage, which are sources of regular water application to the litter. Using this equation showed that water applied to litter from these sources changes over the course of a grow-out, and can be as much as 3.2L/m(2)/day. Over a 56day grow-out, the total quantity of water added to the litter was estimated to be 104L/m(2). Litter porosity, water holding capacity and water evaporation rates from litter were measured experimentally. Litter porosity decreased and water holding capacity increased over the course of a grow-out due to manure addition. Water evaporation rates at 25°C and 50% relative humidity ranged from 0.5 to 10L/m(2)/day. Evaporation rates increased with litter moisture content and air speed. Maintaining dry litter at the peak of a grow-out is likely to be challenging because evaporation rates from dry litter may be insufficient to remove the quantity of water added to the litter on a daily basis. PMID:26367067

  4. High-harmonic generation in aligned water molecules

    NASA Astrophysics Data System (ADS)

    Wang, Song; Devin, Julien; Hoffmann, Matthias; Cryan, James; Kaldun, Andreas; Bucksbaum, Philip

    2016-05-01

    In recent years, the use of high harmonic generation (HHG) in aligned molecular vapors has become a powerful tool to study ultrafast dynamics of electronic and nuclear wave packets. In our new experimental setup, we are able to orient H2 O and D2 O molecules using a single cycle terahertz (THz) pulse. Aligning water is especially interesting as the highest occupied molecular orbital (HOMO) of water contains a node in the xz plane of the molecular frame, allowing us to perform HHG from second highest occupied molecular orbital (HOMO-1) only, by setting the polarization of the fundamental laser along the z-axis of the aligned water molecules. We are particularly interested in the HOMO-1 state, as there is fast motion of the H-O-H angle leading to sub-wavelength dynamics. On this poster we present our all-optical alignment setup where HHG and single-cycle THz generation take place in high-vacuum, where measurements with arbitrary polarization angles between the two are possible. In addition, we discuss the effects of the molecular orientation on HHG, including symmetry breaking that could produce even harmonics and isotope effects between H2 O and D2 O due to different vibrational energies. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.

  5. Single ionization of water molecules in collisions with bare ions

    NASA Astrophysics Data System (ADS)

    Mondal, A.; Mandal, C. R.; Purkait, M.

    2016-04-01

    We present the double differential cross sections (DDCSs) for the direct ionization of water molecules by impact of fully stripped helium, carbon and oxygen atoms, respectively. In the present formalism, we have represented the wavefunction in the entrance channel as the product of a plane wave for the projectile and an accurate one-center-molecular wavefunction of the water molecule by Moccia (1964 J. Chem. Phys. 40 2186). In the exit channel, we have expressed the total wavefunction as the product of pair-wise Coulomb wavefunctions among the ejected electron, projectile ion and the residual target ion, respectively. The contributions of DDCSs for five different molecular orbitals of water to the spectrum of angular distributions have been analyzed for several electron emission energies. The present results for DDCSs are compared with existing experimental and theoretical findings. We find an overall good agreement between our calculated results and the experimental findings for electron emission cross sections. In addition, DDCS results for ionization from different orbitals at a few electron emission energies are given in tabular form.

  6. Quantum Tunneling of Water in Beryl. A New State of the Water Molecule

    DOE PAGESBeta

    Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani; Prisk, Timothy R.; Mamontov, Eugene; Podlesnyak, Andrey; Ehlers, George; Seel, Andrew G.; Wesolowski, David J.; Anovitz, Lawrence M.

    2016-04-22

    When using neutron scattering and ab initio simulations, we document the discovery of a new “quantum tunneling state” of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. Additionally, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

  7. Quantum Tunneling of Water in Beryl: A New State of the Water Molecule.

    PubMed

    Kolesnikov, Alexander I; Reiter, George F; Choudhury, Narayani; Prisk, Timothy R; Mamontov, Eugene; Podlesnyak, Andrey; Ehlers, George; Seel, Andrew G; Wesolowski, David J; Anovitz, Lawrence M

    2016-04-22

    Using neutron scattering and ab initio simulations, we document the discovery of a new "quantum tunneling state" of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. In addition, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state. PMID:27152824

  8. EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions

    NASA Astrophysics Data System (ADS)

    Compernolle, S.; Ceulemans, K.; Müller, J.-F.

    2011-09-01

    We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects), a method to predict (subcooled) liquid pure compound vapour pressure p0 of organic molecules that requires only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T) is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: aldehydes, ketones, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA).

  9. Clusterization of water molecules as deduced from statistical mechanical approach

    NASA Astrophysics Data System (ADS)

    Krasnoholovets, Volodymyr

    2004-12-01

    Using the methods of statistical mechanics we have shown that a homogeneous water network is unstable and spontaneously disintegrates to the nonhomogeneous state (i.e. peculiar clusters), which can be treated as an ordinary state of liquid water. The major peculiarity of the concept is that it separates the paired potential into two independent components—the attractive potential and the repulsive one, which in turn should feature a very different dependence on the distance from the particle (a water molecule in the present case). We choose the interaction potential as a combination of the ionic crystal potential and the vibratory potential associated with the elastic properties of the water system as a whole. The number ℵ of water molecules that enters a cluster is calculated as a function of several parameters, such as the dielectric constant, the mass of a water molecule, the distance between nearest molecules, and the vibrations of nearest molecules in their nodes. The number of H2O molecules that comprise a cluster is estimated as about ℵ ≈ 900, which agrees with the available experimental data.

  10. On the Several Molecules and Nanostructures of Water

    PubMed Central

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called ‘Algebraic Chemistry’. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown’s gas, and cold fusion. PMID:22312305

  11. On the several molecules and nanostructures of water.

    PubMed

    Whitney, Cynthia Kolb

    2012-01-01

    This paper investigates the water molecule from a variety of viewpoints. Water can involve different isotopes of Hydrogen and Oxygen, it can form differently shaped isomer molecules, and, when frozen, it occupies space differently than most other substances do. The tool for conducting the investigation of all this is called 'Algebraic Chemistry'. This tool is a quantitative model for predicting the energy budget for all sorts of changes between different ionization states of atoms that are involved in chemical reactions and in changes of physical state. The model is based on consistent patterns seen in empirical data about ionization potentials, together with rational scaling laws that can interpolate and extrapolate for situations where no data are available. The results of the investigation of the water molecule include comments, both positive and negative, about technologies involving heavy water, poly water, Brown's gas, and cold fusion. PMID:22312305

  12. Quantum Behavior of Water Molecules Confined to Nanocavities in Gemstones.

    PubMed

    Gorshunov, Boris P; Zhukova, Elena S; Torgashev, Victor I; Lebedev, Vladimir V; Shakurov, Gil'man S; Kremer, Reinhard K; Pestrjakov, Efim V; Thomas, Victor G; Fursenko, Dimitry A; Dressel, Martin

    2013-06-20

    When water is confined to nanocavities, its quantum mechanical behavior can be revealed by terahertz spectroscopy. We place H2O molecules in the nanopores of a beryl crystal lattice and observe a rich and highly anisotropic set of absorption lines in the terahertz spectral range. Two bands can be identified, which originate from translational and librational motions of the water molecule isolated within the cage; they correspond to the analogous broad bands in liquid water and ice. In the present case of well-defined and highly symmetric nanocavities, the observed fine structure can be explained by macroscopic tunneling of the H2O molecules within a six-fold potential caused by the interaction of the molecule with the cavity walls. PMID:26283245

  13. THE FATE OF FLUOROSILICATE DRINKING WATER ADDITIVES

    EPA Science Inventory

    Periodically, the EPA reexamines its information on regulated drinking water contaminants to deterime if further study is required. Fluoride is one such contaminant undergoing review. The chemical literature indicates that some deficiencies exist in our understanding of the spe...

  14. Molecules to Materials for PEC Water Splitting

    SciTech Connect

    Neale, N. R.; Ruddy, D. A.; Lee, K.; Seabold, J. A.; Deutsch, T. G.; Dukovic, G.

    2013-01-01

    Advances in heterogeneous catalysis are driven by the formation of structure-property relationships at solid-liquid and solid-gaseous interfaces. The establishment of these relationships relies on cooperative research efforts on several fronts: prediction and analysis using high-level theoretical models, the development of new synthetic methods to prepare specific solid-state compositions and structures, new analytical methods to identify the active site and define interfacial properties, and mechanistic analysis of functioning catalysts. However, customized materials that allow for fine control of the interfacial properties at solid-liquid boundaries represent difficult synthetic targets. We have been investigating molecular synthons as precursors to advanced materials to address this challenge. In this presentation, we will discuss (1) the chemistry of molecular inorganic complexes, (2) their conversion to mixed-metal oxides, and (3) structure-property relationships of the resulting oxides relevant to PEC water splitting.

  15. Dynamics of Confined Water Molecules in Aqueous Salt Hydrates

    SciTech Connect

    Werhahn, Jasper C.; Pandelov, S.; Yoo, Soohaeng; Xantheas, Sotiris S.; Iglev, H.

    2011-04-01

    The unusual properties of water are largely dictated by the dynamics of the H bond network. A single water molecule has more H bonding sites than atoms, hence new experimental and theoretical investigations about this peculiar liquid have not ceased to appear. Confinement of water to nanodroplets or small molecular clusters drastically changes many of the liquid’s properties. Such confined water plays a major role in the solvation of macro molecules such as proteins and can even be essential to their properties. Despite the vast results available on bulk and confined water, discussions about the correlation between spectral and structural properties continue to this day. The fast relaxation of the OH stretching vibration in bulk water, and the variance of sample geometries in the experiments on confined water obfuscate definite interpretation of the spectroscopic results in terms of structural parameters. We present first time-resolved investigations on a new model system that is ideally suited to overcome many of the problems faced in spectroscopical investigation of the H bond network of water. Aqueous hydrates of inorganic salts provide water molecules in a crystal grid, that enables unambiguous correlations of spectroscopic and structural features. Furthermore, the confined water clusters are well isolated from each other in the crystal matrix, so different degrees of confinement can be achieved by selection of the appropriate salt.

  16. Theoretical study of impulsive orientation of asymmetric top water molecules

    NASA Astrophysics Data System (ADS)

    Rangan, Chitra; Senchuk, Andrew

    2008-05-01

    We theoretically study the orientation of a polar, asymmetric top molecule by a terahertz half-cycle pulse. This study is motivated by recent experimental results by C. Herne and P.H. Bucksbaum on the orientation of water molecule using terahertz half-cycle pulses. The half-cycle pulse is modelled as an impulse. The degree of orientation is calculated. Our aim is to characterize the calculated orientation curves in terms of rotational spectroscopy constants.

  17. How Many Water Molecules Does it Take to Dissociate HCl?

    PubMed

    Vargas-Caamal, Alba; Cabellos, Jose Luis; Ortiz-Chi, Filiberto; Rzepa, Henry S; Restrepo, Albeiro; Merino, Gabriel

    2016-02-18

    The potential energy surfaces of the HCl(H2O)n (n is the number of water molecules) clusters are systematically explored using density functional theory and high-level ab initio computations. On the basis of electronic energies, the number of water molecules needed for HCl dissociation is four as reported by some experimental groups. However, this number is five owing to the inclusion of entropic factors. Wiberg bond indices are calculated and analyzed, and the results provide a quadratic correlation and classification of clusters according to the nondissociated, partially dissociated, and fully dissociated character of the H-Cl bond. Our computations show that if temperature is not controlled during the experiment, the values obtained for the dipole moment (or for any measurable property) are susceptible to change, providing a different picture of the number of water molecules needed for HCl dissociation in a nanoscopic droplet. PMID:26774026

  18. Transport behavior of water molecules through two-dimensional nanopores

    SciTech Connect

    Zhu, Chongqin; Li, Hui; Meng, Sheng

    2014-11-14

    Water transport through a two-dimensional nanoporous membrane has attracted increasing attention in recent years thanks to great demands in water purification and desalination applications. However, few studies have been reported on the microscopic mechanisms of water transport through structured nanopores, especially at the atomistic scale. Here we investigate the microstructure of water flow through two-dimensional model graphene membrane containing a variety of nanopores of different size by using molecular dynamics simulations. Our results clearly indicate that the continuum flow transits to discrete molecular flow patterns with decreasing pore sizes. While for pores with a diameter ≥15 Å water flux exhibits a linear dependence on the pore area, a nonlinear relationship between water flux and pore area has been identified for smaller pores. We attribute this deviation from linear behavior to the presence of discrete water flow, which is strongly influenced by the water-membrane interaction and hydrogen bonding between water molecules.

  19. SPAM: A Simple Approach for Profiling Bound Water Molecules.

    PubMed

    Cui, Guanglei; Swails, Jason M; Manas, Eric S

    2013-12-10

    A method that identifies the hydration shell structure of proteins and estimates the relative free energies of water molecules within that hydration shell is described. The method, which we call "SPAM" (maps spelled in reverse), utilizes explicit solvent molecular dynamics (MD) simulations to capture discrete hydration sites at the water-protein interface and computes a local free energy measure from the distribution of interaction energies between water and the environment at a specific site. SPAM is able to provide a qualitative estimate of the thermodynamic profile of bound water molecules that correlates nicely with well-studied structure-activity relationships and observed binding "hot spots". This is demonstrated in retrospective analyses of HIV1 protease and hen egg white lysozyme, where the effects of water displacement and solvent binding have been studied extensively. The simplicity and effectiveness of SPAM allow for prospective application during the drug discovery process. PMID:26592287

  20. Structures of water molecules in carbon nanotubes under electric fields

    SciTech Connect

    Winarto,; Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-03-28

    Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electric field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.

  1. Structures of water molecules in carbon nanotubes under electric fields

    NASA Astrophysics Data System (ADS)

    Winarto, Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-03-01

    Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electric field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.

  2. [Investigation of membrane permeability of carp spermatozoa for water molecules].

    PubMed

    Pugovkin, A Iu; Kopeĭka, E F; Nardid, O A; Cherkashina, Ia O

    2014-01-01

    The fundamentals of a photometry method for determination of membrane permeability of some fish spermatozoa for water molecules are presented. Osmotic tolerance of carp spermatozoa membranes was studied using EPR-spectroscopy and photometric analysis methods. It was shown that carp spermatozoa look like the ideal osmometers in their reaction on media of different osmolarity. The value of membrane permeability of carp spermatozoa for water molecules was determined. Data obtained can be used in cryobiology for creating cryoprotective media and regimes of fish sperm cryopreservation. PMID:25715589

  3. Non-additivity of molecule-surface van der Waals potentials from force measurements

    NASA Astrophysics Data System (ADS)

    Wagner, Christian; Fournier, Norman; Ruiz, Victor G.; Li, Chen; Müllen, Klaus; Rohlfing, Michael; Tkatchenko, Alexandre; Temirov, Ruslan; Tautz, F. Stefan

    2014-11-01

    Van der Waals (vdW) forces act ubiquitously in condensed matter. Despite being weak on an atomic level, they substantially influence molecular and biological systems due to their long range and system-size scaling. The difficulty to isolate and measure vdW forces on a single-molecule level causes our present understanding to be strongly theory based. Here we show measurements of the attractive potential between differently sized organic molecules and a metal surface using an atomic force microscope. Our choice of molecules and the large molecule-surface separation cause this attraction to be purely of vdW type. The experiment allows testing the asymptotic vdW force law and its validity range. We find a superlinear growth of the vdW attraction with molecular size, originating from the increased deconfinement of electrons in the molecules. Because such non-additive vdW contributions are not accounted for in most first-principles or empirical calculations, we suggest further development in that direction.

  4. Non-additivity of molecule-surface van der Waals potentials from force measurements

    PubMed Central

    Wagner, Christian; Fournier, Norman; Ruiz, Victor G.; Li, Chen; Müllen, Klaus; Rohlfing, Michael; Tkatchenko, Alexandre; Temirov, Ruslan; Tautz, F. Stefan

    2014-01-01

    Van der Waals (vdW) forces act ubiquitously in condensed matter. Despite being weak on an atomic level, they substantially influence molecular and biological systems due to their long range and system-size scaling. The difficulty to isolate and measure vdW forces on a single-molecule level causes our present understanding to be strongly theory based. Here we show measurements of the attractive potential between differently sized organic molecules and a metal surface using an atomic force microscope. Our choice of molecules and the large molecule-surface separation cause this attraction to be purely of vdW type. The experiment allows testing the asymptotic vdW force law and its validity range. We find a superlinear growth of the vdW attraction with molecular size, originating from the increased deconfinement of electrons in the molecules. Because such non-additive vdW contributions are not accounted for in most first-principles or empirical calculations, we suggest further development in that direction. PMID:25424490

  5. Water-mediated influence of a crowded environment on internal vibrations of a protein molecule.

    PubMed

    Kuffel, Anna; Zielkiewicz, Jan

    2016-02-01

    The influence of crowding on the protein inner dynamics is examined by putting a single protein molecule close to one or two neighboring protein molecules. The presence of additional molecules influences the amplitudes of protein fluctuations. Also, a weak dynamical coupling of collective velocities of surface atoms of proteins separated by a layer of water is detected. The possible mechanisms of these phenomena are described. The cross-correlation function of the collective velocities of surface atoms of two proteins was decomposed into the Fourier series. The amplitude spectrum displays a peak at low frequencies. Also, the results of principal component analysis suggest that the close presence of an additional protein molecule influences the high-amplitude, low-frequency modes in the most prominent way. This part of the spectrum covers biologically important protein motions. The neighbor-induced changes in the inner dynamics of the protein may be connected with the changes in the velocity power spectrum of interfacial water. The additional protein molecule changes the properties of solvation water and in this way it can influence the dynamics of the second protein. It is suggested that this phenomenon may be described, at first approximation, by a damped oscillator driven by an external random force. This model was successfully applied to conformationally rigid Choristoneura fumiferana antifreeze protein molecules. PMID:26805932

  6. Non-additivity of molecule-surface van der Waals potentials from force measurements

    NASA Astrophysics Data System (ADS)

    Tautz, Stefan

    2014-03-01

    Van der Waals (vdW) forces act ubiquitously in condensed matter. Their description as an inherently quantum mechanical phenomenon was developed for single atoms and homogeneous macroscopic bodies by London, Casimir, and Lifshitz. For intermediate-sized objects like organic molecules an atomistic description is required, but explicit first principles calculations are very difficult since correlations between many interacting electrons have to be considered. Hence, semi-empirical correction schemes are often used that simplify the vdW interaction to a sum over atom-pair potentials. A similar gap exists between successful measurements of vdW and Casimir forces for single atoms on the one hand and macroscopic bodies on the other, as comparable experiments for molecules are absent. I will present experiments in which long-range vdW potentials between a series of related molecules and a metal surface have been determined experimentally. The experiments rely on the extremely sensitive force detection of an atomic force microscope in combination with its molecular manipulation capabilities. The results allow us to confirm the asymptotic force law and to quantify the non-additive part of the vdW interaction which is particularly challenging for theory. In the present case, cooperative effects account for 10% of the total interaction. This effect is of general validity in molecules and thus relevant at the intersection of chemistry, physics, biology, and materials science.

  7. Disulfuric acid dissociated by two water molecules: ab initio and density functional theory calculations.

    PubMed

    Kim, Seong Kyu; Lee, Han Myoung; Kim, Kwang S

    2015-11-21

    We have studied geometries, energies and vibrational spectra of disulfuric acid (H2S2O7) and its anion (HS2O7(-)) hydrated by a few water molecules, using density functional theory (M062X) and ab initio theory (SCS-MP2 and CCSD(T)). The most noteworthy result is found in H2S2O7(H2O)2 in which the lowest energy conformer shows deprotonated H2S2O7. Thus, H2S2O7 requires only two water molecules, the fewest number of water molecules for deprotonation among various hydrated monomeric acids reported so far. Even the second deprotonation of the first deprotonated species HS2O7(-) needs only four water molecules. The deprotonation is supported by vibration spectra, in which acid O-H stretching peaks disappear and specific three O-H stretching peaks for H3O(+) (eigen structure) appear. We have also kept track of variations in several geometrical parameters, atomic charges, and hybrid orbital characters upon addition of water. As the number of water molecules added increases, the S-O bond weakens in the case of H2S2O7, but strengthens in the case of HS2O7(-). It implies that the decomposition leading to H2SO4 and SO3 hardly occurs prior to the 2nd deprotonation at low temperatures. PMID:26400266

  8. 10. Water treatment plant, view to S. 1965 addition is ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    10. Water treatment plant, view to S. 1965 addition is in the foreground - Fort Benton Water Treatment Plant, Filtration Plant, Lots 9-13 of Block 7, Fort Benton Original Townsite at Missouri River, Fort Benton, Chouteau County, MT

  9. Oxidative addition of C--H bonds in organic molecules to transition metal centers

    SciTech Connect

    Bergman, R.G.

    1989-04-01

    Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs.

  10. The effect of switchable water additives on clay settling.

    PubMed

    Chen, Chien-Shun; Lau, Ying Yin; Mercer, Sean M; Robert, Tobias; Horton, J Hugh; Jessop, Philip G

    2013-01-01

    The recycling of process water from strip mining extractions is a very relevant task both industrially and environmentally. The sedimentation of fine tailings during such processes, however, can often require long periods of time and/or the addition of flocculants which make later water recycling difficult. We propose the use of switchable water additives as reversible flocculants for clay/water suspensions. Switchable water additives are compounds such as diamines that make it possible to reversibly control the ionic strength of an aqueous solution. Addition of CO(2) to such an aqueous solution causes the ionic strength to rise dramatically, and the change is reversed upon removal of the CO(2). These additives, while in the presence of CO(2), promote the aggregation of clay tailings, reduce settling times, and greatly increase the clarity of the liberated water. The removal of CO(2) from the liberated water regenerates a low ionic strength solution that does not promote clay aggregation and settling until CO(2) is added again. Such reversible behavior would be useful in applications such as oil sands separations in which the recycled water must not promote aggregation. When added to kaolinite and montmorillonite clay suspensions, switchable water provided process waters of lower turbidity than those additives from inorganic salts or by CO(2)-treatment alone. When recollected, the switchable water supernatant was shown to be recyclable over three cycles for enhanced settling of kaolinite. PMID:22945593

  11. Hadronic chemistry applied to hydrogen and water molecules

    NASA Astrophysics Data System (ADS)

    Tangde, Vijay M.

    2012-09-01

    The decades of research of R M Santilli resulted into the formulation of iso-, geno- and hyper- mathematics [1, 2] that helped in understanding numerous diversified problems and removing inadequacies in most of the established and celebrated theories of 20th century physics and chemistry, for example, the theories of relativity, quantum mechanics (chemistry), astrophysics, particle physics, and so on. This involves the isotopic, genotopic, etc. lifting of Lie algebra that generated Lie admissible mathematics to properly describe irreversible processes. The studies on Hadronic m Mechanics based on Santilli's mathematics for the first time has removed the very fundamental limitations of quantum chemistry [3, 4] [2, 3, 4]. Herein, we review a Santilli-Shillady model[3, 4, 5] of hydrogen and water molecules characterized by a bond at short distances of the two valance electrons into a singlet quasi-particle state called isoelectronium for hydrogen molecule and two isoelctronia (one per H-O dimer) in case of water molecule. We especially emphasis on: the numerically exact representation of binding energies from unadulterated first axiomatic principle, the reduction of the hydrogen molecule to a restricted three body problem that admits exact analytic solutions and the reduction of computer time by at least a factor of 1000 folds due to a much faster convergent series.

  12. Water and Small-Molecule Permeation of Dormant Bacillus subtilis Spores

    PubMed Central

    Cermak, Nathan; Feijó Delgado, Francisco; Setlow, Barbara; Setlow, Peter

    2015-01-01

    ABSTRACT We use a suspended microchannel resonator to characterize the water and small-molecule permeability of Bacillus subtilis spores based on spores' buoyant mass in different solutions. Consistent with previous results, we found that the spore coat is not a significant barrier to small molecules, and the extent to which small molecules may enter the spore is size dependent. We have developed a method to directly observe the exchange kinetics of intraspore water with deuterium oxide, and we applied this method to wild-type spores and a panel of congenic mutants with deficiencies in the assembly or structure of the coat. Compared to wild-type spores, which exchange in approximately 1 s, several coat mutant spores were found to have relatively high water permeability with exchange times below the ∼200-ms temporal resolution of our assay. In addition, we found that the water permeability of the spore correlates with the ability of spores to germinate with dodecylamine and with the ability of TbCl3 to inhibit germination with l-valine. These results suggest that the structure of the coat may be necessary for maintaining low water permeability. IMPORTANCE Spores of Bacillus species cause food spoilage and disease and are extremely resistant to standard decontamination methods. This hardiness is partly due to spores' extremely low permeability to chemicals, including water. We present a method to directly monitor the uptake of molecules into B. subtilis spores by weighing spores in fluid. The results demonstrate the exchange of core water with subsecond resolution and show a correlation between water permeability and the rate at which small molecules can initiate or inhibit germination in coat-damaged spores. The ability to directly measure the uptake of molecules in the context of spores with known structural or genetic deficiencies is expected to provide insight into the determinants of spores' extreme resistance. PMID:26483518

  13. The Effect of Small Molecule Additives on the Self-Assembly and Functionality of Protein-Polymer Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    Thomas, Carla; Xu, Liza; Olsen, Bradley

    2013-03-01

    Self-assembly of globular protein-polymer block copolymers into well-defined nanostructures provides a route towards the manufacture of protein-based materials which maintains protein fold and function. The model material mCherry-b-poly(N-isopropyl acrylamide) forms self-assembled nanostructures from aqueous solutions via solvent evaporation. To improve retention of protein functionality when dehydrated, small molecules such as trehalose and glycerol are added in solution prior to solvent removal. With as little as 10 wt% additive, improvements in retained functionality of 20-60% are observed in the solid-state as compared to samples in which no additive is present. Higher additive levels (up to 50%) continue to show improvement until approximately 100% of the protein function is retained. These large gains are hypothesized to originate from the ability of the additives to replace hydrogen bonds normally fulfilled by water. The addition of trehalose in the bulk material also improves the thermal stability of the protein by 15-20 °C, while glycerol decreases the thermal stability. Materials containing up to 50% additives remain microphase separated, and, upon incorporation of additives, nanostructure domain spacing tends to increase, accompanied by order-order transitions.

  14. Insight into water molecules bonding on 4d metal surfaces

    NASA Astrophysics Data System (ADS)

    Carrasco, Javier; Michaelides, Angelos; Scheffler, Matthias

    2008-03-01

    Water-metal interactions are of capital importance to a wide variety of phenomena in materials science, catalysis, corrosion, electrochemistry, etc. Here we address the nature of the bond between water molecules and metal surfaces through a careful systematic study. Specifically, the bonding of isolated water molecules to a series of close-packed transition metal surfaces - Ru(0001), Rh(111), Pd(111) and Ag(111) - has been examined in detail with density functional theory (DFT). Aiming to understand the origin behind energetic and structural trends along the 4d series we employ a range of analysis tools, such as decomposition of the density of states, electron density differences, electronic reactivity function and inspection of individual Kohn-Sham orbitals. The results obtained allow us to rationalize the bonding between water and transition metal surfaces as a balance of covalent and electrostatic interactions. A frontier orbital scheme based on so-called two-center four-electron interactions between molecular orbitals of water and d band states of the surface proves incisive in understanding these systems.

  15. Interaction Of Water Molecules With SiC(001) Surfaces

    SciTech Connect

    Cicero, G; Catellani, A; Galli, G

    2004-08-10

    We have investigated the interaction of water molecules with the polar Si- and C- terminated surfaces of cubic Silicon Carbide by means of ab initio molecular dynamics simulations at finite temperature. Different water coverages were considered, from {1/4} to a complete monolayer. Irrespective of coverage, we find that water dissociates on the silicon terminated surfaces, leading to important changes in both its structural and electronic properties. On the contrary, the carbon terminated surface remains inert when exposed to water. We propose experiments to reveal the ionic and electronic structure of wet Si-terminated surfaces predicted by our calculations, which at full coverage are notably different from those of hydrated Si(001) substrates. Finally, we discuss the implications of our results for SiC surface functionalization.

  16. Stereochemistry of enzymatic water addition to C=C bonds.

    PubMed

    Chen, Bi-Shuang; Otten, Linda G; Hanefeld, Ulf

    2015-01-01

    Water addition to carbon-carbon double bonds using hydratases is attracting great interest in biochemistry. Most of the known hydratases are involved in primary metabolism and to a lesser extent in secondary metabolism. New hydratases have recently been added to the toolbox, both from natural sources or artificial metalloenzymes. In order to comprehensively understand how the hydratases are able to catalyse the water addition to carbon-carbon double bonds, this review will highlight the mechanistic and stereochemical studies of the enzymatic water addition to carbon-carbon double bonds, focusing on the syn/anti-addition and stereochemistry of the reaction. PMID:25640045

  17. Radiation of nitrogen molecules in a dielectric barrier discharge with small additives of chlorine and bromine

    SciTech Connect

    Avtaeva, S. V.; Avdeev, S. M.; Sosnin, E. A.

    2010-08-15

    Spectral and energy characteristics of nitrogen molecule radiation in dielectric barrier discharges in Ar-N{sub 2}, Ar-N{sub 2}-Cl{sub 2}, and Ar-N{sub 2}-Br{sub 2} mixtures were investigated experimentally. Small additives of molecular chlorine or bromine to an Ar-N{sub 2} mixture are found to increase the radiation intensity of the second positive system of nitrogen. The conditions at which the radiation spectrum predominantly consists of vibronic bands of this system are determined. Using a numerical model of plasmachemical processes, it is shown that, at electron temperatures typical of gas discharges (2-4 eV), a minor additive of molecular chlorine to an Ar-N{sub 2} mixture leads to an increase in the concentrations of electrons, positive ions, and metastable argon atoms. In turn, collisional energy transfer from metastable argon atoms to nitrogen molecules results in the excitation of the N{sub 2}(C{sup 3{Pi}}{sub u}) state.

  18. Anomalous water molecules and mechanistic effects of water nanotube clusters confined to molecular porous crystals.

    PubMed

    Tadokoro, Makoto; Ohhara, Takashi; Ohhata, Yuhki; Suda, Takaaki; Miyasato, Yuji; Yamada, Takeshi; Kikuchi, Tatsuya; Tanaka, Ichiro; Kurihara, Kazuo; Oguni, Masaharu; Nakasuji, Kazuhiro; Yamamuro, Osamu; Ryota, Kuroki

    2010-02-18

    The movement of water molecules in the limited space present within nanoscale regions, which is different from the molecular motion of bulk water, is significantly affected by strong interfacial interactions with the surrounding outer walls. Hence, most of the water molecules that are confined to nanochannel spaces having widths less than ca. 2 nm can generally be classified together as "structural water". Since the motions of such water molecules are limited by interfacial interactions with the outer wall, the nature of structural water, which is strongly influenced by the interactions, will have different characteristics from normal water. For our investigations on the characteristics of structural water, we have developed a nanoporous crystal with a diameter of ca. 1.6 nm; it was constructed from 1-D hydrophilic channels by self-organization of the designed molecules. A tubelike three-layered water cluster, called a water nanotube (WNT), is formed in each internal channel space and is regulated by H-bonds with the outer wall. The WNT undergoes a glass transition (T(g) = 107 K) and behaves as a liquid; it freezes at 234 K and changes into an icelike nanotube cluster. In this study, the structure of the WNT is investigated through neutron structure analysis, and it is observed to stabilize by a mechanistic anchor effect of structural water. Furthermore, from neutron-scattering experiments, it is seen that a few water molecules around the center of the WNT move approximately with the same diffusion constant as those in bulk water; however, the residence time and average jump length are longer, despite the restrictions imposed by the H-bonding with structural water. The behavior of mobile water within a WNT is investigated; this can be used to elucidate the mechanism for the effect of structural water on vital functions on the cell surface. PMID:20102158

  19. The spontaneous synchronized dance of pairs of water molecules

    SciTech Connect

    Roncaratti, Luiz F.; Cappelletti, David Pirani, Fernando

    2014-03-28

    Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.

  20. Sticking of Molecules on Nonporous Amorphous Water Ice

    NASA Astrophysics Data System (ADS)

    He, Jiao; Acharyya, Kinsuk; Vidali, Gianfranco

    2016-05-01

    Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on nonporous amorphous solid water. The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King–Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas–grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.

  1. Fire extinct experiments with water mist by adding additives

    NASA Astrophysics Data System (ADS)

    Yang, Lijun; Zhao, Jianbo

    2011-12-01

    The effects of fire extinguishment with water mist by adding different additives were studied. Tens of chemical substances (including alkali metal salt, dilution agent and surface active agent) were selected as additives due to their different extinct mechanisms. At first the performance of fire extinguishment with single additive was studied, then the effects of the same kinds of chemical substances under the same mass fraction were compared to study their influences on the fire extinguishment factors, including extinct time, fire temperature and oxygen concentration from which the fire extinct mechanism with additives could be concluded. Based on this the experiments were conducted to study the cooperate effect of the complexity of different additives. It indicated the relations between different firefighting mechanisms and different additives were competitive. From a large number of experiments the extinct mechanism with water mist by adding additives was concluded and an optimal compounding additive was selected.

  2. Influence of Lithium Additives in Small Molecule Light-Emitting Electrochemical Cells.

    PubMed

    Lin, Kuo-Yao; Bastatas, Lyndon D; Suhr, Kristin J; Moore, Matthew D; Holliday, Bradley J; Minary-Jolandan, Majid; Slinker, Jason D

    2016-07-01

    Light-emitting electrochemical cells (LEECs) utilizing small molecule emitters such as iridium complexes have great potential as low-cost emissive devices. In these devices, ions rearrange during operation to facilitate carrier injection, bringing about efficient operation from simple, single layer devices. Recent work has shown that the luminance, efficiency, and responsiveness of iridium-based LEECs are greatly enhanced by the inclusion of small amounts of lithium salts (≤0.5%/wt) into the active layer. However, the origin of this enhancement has yet to be demonstrated experimentally. Furthermore, although iridium-based devices have been the longstanding leader among small molecule LEECs, fundamental understanding of the ionic distribution in these devices under operation is lacking. Herein, we use scanning Kelvin probe microscopy to measure the in situ potential profiles and electric field distributions of planar iridium-based LEECs and clarify the role of ionic lithium additives. In pristine devices, it is found that ions do not pack densely at the cathode, and ionic redistribution is slow. Inclusion of small amounts of Li[PF6] greatly increases ionic space charge near the cathode that doubles the peak electric fields and enhances electronic injection relative to pristine devices. This study confirms and clarifies a number of longstanding hypotheses regarding iridium LEECs and recent postulates concerning optimization of their operation. PMID:27299981

  3. Ionization of water molecules by fast charged projectiles

    SciTech Connect

    Dubois, A.; Carniato, S.; Fainstein, P. D.; Hansen, J. P.

    2011-07-15

    Single-ionization cross sections of water molecules colliding with fast protons are calculated from lowest-order perturbation theory by taking all electrons and molecular orientations consistently into account. Explicit analytical formulas based on the peaking approximation are obtained for differential ionization cross sections with the partial contribution from the various electron orbitals accounted for. The results, which are in very good agreement with total and partial cross sections at high electron and projectile energies, display a strong variation on molecular orientation and molecular orbitals.

  4. Estimating soil water retention using soil component additivity model

    NASA Astrophysics Data System (ADS)

    Zeiliger, A.; Ermolaeva, O.; Semenov, V.

    2009-04-01

    Soil water retention is a major soil hydraulic property that governs soil functioning in ecosystems and greatly affects soil management. Data on soil water retention are used in research and applications in hydrology, agronomy, meteorology, ecology, environmental protection, and many other soil-related fields. Soil organic matter content and composition affect both soil structure and adsorption properties; therefore water retention may be affected by changes in soil organic matter that occur because of both climate change and modifications of management practices. Thus, effects of organic matter on soil water retention should be understood and quantified. Measurement of soil water retention is relatively time-consuming, and become impractical when soil hydrologic estimates are needed for large areas. One approach to soil water retention estimation from readily available data is based on the hypothesis that soil water retention may be estimated as an additive function obtained by summing up water retention of pore subspaces associated with soil textural and/or structural components and organic matter. The additivity model and was tested with 550 soil samples from the international database UNSODA and 2667 soil samples from the European database HYPRES containing all textural soil classes after USDA soil texture classification. The root mean square errors (RMSEs) of the volumetric water content estimates for UNSODA vary from 0.021 m3m-3 for coarse sandy loam to 0.075 m3m-3 for sandy clay. Obtained RMSEs are at the lower end of the RMSE range for regression-based water retention estimates found in literature. Including retention estimates of organic matter significantly improved RMSEs. The attained accuracy warrants testing the 'additivity' model with additional soil data and improving this model to accommodate various types of soil structure. Keywords: soil water retention, soil components, additive model, soil texture, organic matter.

  5. An ab initio molecular dynamics study on hydrogen bonds between water molecules

    NASA Astrophysics Data System (ADS)

    Pan, Zhang; Chen, Jing; Lü, Gang; Geng, Yi-Zhao; Zhang, Hui; Ji, Qing

    2012-04-01

    The quantitative estimation of the total interaction energy of a molecular system containing hydrogen bonds (H bonds) depends largely on how to identify H bonding. The conventional geometric criteria of H bonding are simple and convenient in application, but a certain amount of non-H bonding cases are also identified as H bonding. In order to investigate the wrong identification, we carry out a systematic calculation on the interaction energy of two water molecules at various orientation angles and distances using ab initio molecular dynamics method with the dispersion correction for the Becke-Lee-Yang-Parr (BLYP) functionals. It is shown that, at many orientation angles and distances, the interaction energies of the two water molecules exceed the energy criterion of the H bond, but they are still identified as H-bonded by the conventional "distance-angle" criteria. It is found that in these non-H bonding cases the wrong identification is mainly caused by short-range interaction between the two neighbouring water molecules. We thus propose that, in addition to the conventional distance and angle criteria of H bonding, the distance dHṡṡṡH between the two neighbouring hydrogen atoms of the two water molecules should also be taken as a criterion, and the distance rOṡṡṡH between the hydrogen atom of the H-bond donor molecule and the oxygen atom of the acceptor molecule should be restricted by a lower limit. When dHṡṡṡH and rOṡṡṡH are small (e.g., dHṡṡṡH < 2.0 Å and rOṡṡṡH < 1.62 Å), the repulsion between the two neighbouring atoms increases the total energy of the two water molecules dramatically and apparently weakens the binding of the water dimer. A statistical analysis and comparison of the numbers of the H bonds identified by using different criteria have been conducted on a Car-Parrinello ab initio molecular dynamics simulation with dispersion correction for a system of 64 water molecules at near-ambient temperature. They

  6. [Utility of noise addition image made by using water phantom and image addition and subtraction software].

    PubMed

    Watanabe, Ryo; Ogawa, Masato; Mituzono, Hiroki; Aoki, Takahiro; Hayano, Mizuho; Watanabe, Yuka

    2010-08-20

    In optimizing exposures, it is very important to evaluate the impact of image noise on image quality. To realize this, there is a need to evaluate how much image noise will make the subject disease invisible. But generally it is very difficult to shoot images of different quality in a clinical examination. Thus, a method to create a noise addition image by adding the image noise to raw data has been reported. However, this approach requires a special system, so it is difficult to implement in many facilities. We have invented a method to easily create a noise addition image by using the water phantom and image add-subtract software that accompanies the device. To create a noise addition image, first we made a noise image by subtracting the water phantom with different SD. A noise addition image was then created by adding the noise image to the original image. By using this method, a simulation image with intergraded SD can be created from the original. Moreover, the noise frequency component of the created noise addition image is as same as the real image. Thus, the relationship of image quality to SD in the clinical image can be evaluated. Although this method is an easy method of LDSI creation on image data, a noise addition image can be easily created by using image addition and subtraction software and water phantom, and this can be implemented in many facilities. PMID:20953102

  7. Water-molecule dissociation by proton and hydrogen impact

    NASA Astrophysics Data System (ADS)

    Luna, H.; de Barros, A. L. F.; Wyer, J. A.; Scully, S. W. J.; Lecointre, J.; Garcia, P. M. Y.; Sigaud, G. M.; Santos, A. C. F.; Senthil, V.; Shah, M. B.; Latimer, C. J.; Montenegro, E. C.

    2007-04-01

    Time-of-flight-based mass analysis of charged water fragments have been used to measure the dissociative and the nondissociative reaction pathways of water formed during collisions with 15to100keV and 500to3500keV H+ projectiles and with 8to100keV H0 projectiles. The fragmentation pathways resulting from the ionization and the electron capture collisions with the incident H+ and H0 projectiles, as well as collisions involving projectile electron loss by the incident H0 projectiles, were separately recorded by detecting the target product ions in coincidence with either the ejected target electrons or the charge-analyzed projectiles. The fragmentation profile shows that at high collision energies the ionization of water arises mainly through outer shell processes. At lower energies valence electron capture and ionization dominate and transfer ionization leads to substantially different fragmentation patterns. H0 and H+ projectiles are found to be equally efficient at ionizing the water molecule. These results are of particular interest to workers in astrophysics and those involved in cancer therapy with heavy particle ion beams.

  8. Single-molecule redox blinking of perylene diimide derivatives in water.

    PubMed

    Cordes, Thorben; Vogelsang, Jan; Anaya, Milena; Spagnuolo, Carla; Gietl, Andreas; Summerer, Wolfram; Herrmann, Andreas; Müllen, Klaus; Tinnefeld, Philip

    2010-02-24

    Dynamic developments in ultrasensitive and superresolution fluorescence microscopy call for improved fluorescence markers with increased photostability and new functionalities. We used single-molecule spectroscopy to study water-soluble perylene dicarboximide fluorophores (PDI), which were immobilized in aqueous buffer by attaching the fluorophore to DNA. Under these conditions bright fluorescence, comparable to that of single-molecule compatible organic fluorophores, is observed with homogeneous spectral and fluorescence decay time distributions. We additionally show how the fluorescence of the PDI can be controlled through photoinduced electron-transfer reactions by using different concentrations of reductants and oxidants, yielding either blinking or stable emission. We explain these properties by the redox potentials of PDI and the recently introduced ROXS (reducing and oxidizing system) concept. Finally, we evaluate how this fluorescence control of PDIs can be used for superresolution "Blink-Microscopy" in aqueous or organic media and more generally for single-molecule spectroscopy. PMID:20121094

  9. Searching for Water and Other Molecules with JWST

    NASA Astrophysics Data System (ADS)

    Valenti, Jeff

    2015-08-01

    The James Webb Space Telescope (JWST) will be a powerful tool for measuring water and other molecules in transiting exoplanets, warm circumstellar disks, brown dwarfs, and cool stars. In early 2019 the observatory is scheduled to begin science operations near the Sun-Earth L2 Lagrange point. The sunshield will allow the telescope and science instrument module to cool passively to approximately 40 K. The segmented primary mirror has 25 square meters of collecting area, giving the observatory unprecedented sensitivity in the infrared. JWST has four science instruments that cover wavelengths from 0.6 to 28 microns at spectral resolutions up to about R=3000. I will summarize relevant observatory constraints, instrument capabilities, and observing templates. I will illustrate practical issues with examples from the Science Operations Design Reference Mission. Finally, I will discuss the Cycle 1 proposal process, which begins in 2017.

  10. Theoretical and experimental investigation of the interactions between [emim]Ac and water molecules

    NASA Astrophysics Data System (ADS)

    Ding, Zhen-Dong; Chi, Zhen; Gu, Wen-Xiu; Gu, Sheng-Ming; Wang, Hai-Jun

    2012-05-01

    Density functional theory (DFT) calculations, atom in molecules (AIM) theory, natural bond orbital (NBO) analysis and infrared (IR) spectroscopy were performed to investigate the interactions between water molecules and ionic liquid 1-ethyl-3-methylimidazolium acetate ([emim]Ac). It was found that [emim]Ac interacts with water molecules mainly via H-bonds, and the anionic part of [emim]Ac plays a major role in the interaction with H2O. The energies of H-bonds were estimated from spectral shifts of hydroxy antisymmetric stretching vibration. Moreover, the experimental results also indicated that hydroxy of water mainly interacts with the COO- of [emim]Ac. Further studies indicated that the intensity of hydroxy stretching vibrations tend to be stronger with the increase of the concentration of water. In addition, the frequency of hydroxy stretching vibrations showed clearly red-shift, and the COO- vibrational frequency gradually shifted to the lower wavenumber region, which were indicative of extended hydrogen bonded network.

  11. Roles of water molecules in bacteria and viruses

    NASA Astrophysics Data System (ADS)

    Cox, C. S.

    1993-02-01

    In addition to water, microbes mainly comprise lipids, carbohydrates, proteins and nucleic acids. Their structure and function singularly and conjointly is affected by water activity. Desiccation leads to dramatic lipid phase changes whereas carbohydrates, proteins and nucleic acids initially suffer spontaneous, reversible low activation energy Maillard reactions forming products that more slowly re-arrange, cross-link etc. to give non-native states. While initial products spontaneously may reverse to native states by raising water activity, later products only do so through energy consumption and enzymatic activity eg. repair. Yet, native states of lipid membranes and associated enzymes are required to generate energy. Consequently, good reserves of high energy compounds (e.g. ATP) and of membrane stabilisers (e.g. trehalose) may be expected to enhance survival following drying and rehydration (e.g. anhydrobiotic organisms).

  12. EVAPORATION: a new vapor pressure estimation method for organic molecules including non-additivity and intramolecular interactions

    NASA Astrophysics Data System (ADS)

    Compernolle, S.; Ceulemans, K.; Müller, J.-F.

    2011-04-01

    We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects), a method to predict vapour pressure p0 of organic molecules needing only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T) is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: carbonyls, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA).

  13. DNA--a molecule in search of additional functions: recipient of pool wave emissions? A hypothesis.

    PubMed

    Doerfler, Walter

    2010-09-01

    Almost the entire nucleotide sequence of human DNA is functionally unaccounted for, although large parts of the human genome are transcribed. The genes, as defined by current molecular biology, comprise about 1.5-2% of the DNA molecule. It is proposed that DNA encodes additional, hitherto unrecognized functions. In this discussion, the total information inside and outside the universe we live in is termed the pool or the sum total, known or unknown, of all laws, matter, energy, concepts and events. In a hypothetical model, a Gedankenexperiment, it is suggested that the total of all information emits pool waves of an unknown physical nature. They could be related to black energy or have completely different qualities. The designation pool waves should not imply any similarity to electromagnetism. Further, DNA is suggested to have the capability of interacting with the pool waves and thus permit humans - to some partly genetically determined and yet very limited extent - to perceive information from the pool. Pool emissions might be one of the forces that have been instrumental in and are still driving evolution from simple oligonucleotides to DNA with ever more complex recipient capacities. It will be a major challenge for researchers in the field to unravel these and less hypothetical undetected coding principles in DNA. It is uncertain whether the current trend to search the available DNA sequences with ever more refined computer technology on the basis of our present understanding of biology will detect unknown coding systems. For molecular medicine, research into the genetics of the most common human diseases could profit from the elucidation of presently still ephemeral codes in human DNA. Young scientists with a proven record of original research deserve support for the pursuit of unconventional ideas. This concept of granting priorities will be of the utmost importance in advancing the field beyond current concepts in molecular biology. PMID:20356684

  14. Influencing the structure of block copolymer micelles with small molecule additives

    NASA Astrophysics Data System (ADS)

    Robertson, Megan; Singh, Avantika; Cooksey, Tyler; Kidd, Bryce; Piemonte, Rachele; Wang, Shu; Mai Le, Kim; Madsen, Louis

    Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using small-angle scattering and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

  15. Distribution of binding energies of a water molecule in the water liquid-vapor interface

    SciTech Connect

    Chempath, Shaji; Pratt, Lawrence R

    2008-01-01

    Distributions of binding energies of a water molecule in the water liquid-vapor interface are obtained on the basis of molecular simulation with the SPC/E model of water. These binding energies together with the observed interfacial density profile are used to test a minimally conditioned Gaussian quasi-chemical statistical thermodynamic theory. Binding energy distributions for water molecules in that interfacial region clearly exhibit a composite structure. A minimally conditioned Gaussian quasi-chemical model that is accurate for the free energy of bulk liquid water breaks down for water molecules in the liquid-vapor interfacial region. This breakdown is associated with the fact that this minimally conditioned Gaussian model would be inaccurate for the statistical thermodynamics of a dilute gas. Aggressive conditioning greatly improves the performance of that Gaussian quasi-chemical model. The analogy between the Gaussian quasi-chemical model and dielectric models of hydration free energies suggests that naive dielectric models without the conditioning features of quasi-chemical theory will be unreliable for these interfacial problems. Multi-Gaussian models that address the composite nature of the binding energy distributions observed in the interfacial region might provide a mechanism for correcting dielectric models for practical applications.

  16. Disorder of Hydrofluorocarbon Molecules Entrapped in the Water Cages of Structure I Clathrate Hydrate.

    PubMed

    Takeya, Satoshi; Udachin, Konstantin A; Moudrakovski, Igor L; Ohmura, Ryo; Ripmeester, John A

    2016-05-23

    Water versus fluorine: Clathrate hydrates encaging hydrofluorocarbons as guests show both isotropic and anisotropic distributions within host water cages, depending on the number of fluorine atoms in the guest molecule; this is caused by changes in intermolecular interactions to host water molecules in the hydrates. PMID:27105807

  17. 21 CFR 173.310 - Boiler water additives.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...), pp. 744-745, which is incorporated by reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51... accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies are available from the National Academy Press, 2101... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Boiler water additives. 173.310 Section...

  18. 21 CFR 173.310 - Boiler water additives.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...), pp. 744-745, which is incorporated by reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51... accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies are available from the National Academy Press, 2101... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Boiler water additives. 173.310 Section...

  19. 21 CFR 173.310 - Boiler water additives.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...), pp. 744-745, which is incorporated by reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51... accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies are available from the National Academy Press, 2101... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Boiler water additives. 173.310 Section...

  20. 21 CFR 173.310 - Boiler water additives.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...), pp. 744-745, which is incorporated by reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51... accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies are available from the National Academy Press, 2101... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Boiler water additives. 173.310 Section...

  1. Electron capture by bare ions on water molecules

    NASA Astrophysics Data System (ADS)

    Rivarola, Roberto; Montenegro, Pablo; Monti, Juan; Fojón, Omar

    2016-05-01

    Single electron capture from water molecules by impact of bare ions is theoretically investigated at intermediate and high collision energies. This reaction is of fundamental importance to determine the deposition of energy in biological matter irradiated with ion beams (hadrontherapy), dominating other ionizing processes of the target at low-intermediate impact velocities and giving principal contributions to the energetic region where electronic stopping power maximizes. The dynamics of the interaction between the aggregates is described within the one active-electron continuum distorted wave-eikonal initial state theory. The orbitals of the target in the ground state are represented using the approximate self-consistent complete neglect of differential orbitals (SC-CNDO) model. The contribution of different molecular orbitals on the partial cross sections to selected n-principal quantum number projectile states is discriminated as well as the collaboration of these n-states on total cross sections. The latter ones are dominated by capture to n=1 states at high enough energies decreasing their contribution as n increases.

  2. Structure and dynamics of water and lipid molecules in charged anionic DMPG lipid bilayer membranes

    NASA Astrophysics Data System (ADS)

    Rønnest, A. K.; Peters, G. H.; Hansen, F. Y.; Taub, H.; Miskowiec, A.

    2016-04-01

    Molecular dynamics simulations have been used to investigate the influence of the valency of counter-ions on the structure of freestanding bilayer membranes of the anionic 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) lipid at 310 K and 1 atm. At this temperature, the membrane is in the fluid phase with a monovalent counter-ion and in the gel phase with a divalent counter-ion. The diffusion constant of water as a function of its depth in the membrane has been determined from mean-square-displacement calculations. Also, calculated incoherent quasielastic neutron scattering functions have been compared to experimental results and used to determine an average diffusion constant for all water molecules in the system. On extrapolating the diffusion constants inferred experimentally to a temperature of 310 K, reasonable agreement with the simulations is obtained. However, the experiments do not have the sensitivity to confirm the diffusion of a small component of water bound to the lipids as found in the simulations. In addition, the orientation of the dipole moment of the water molecules has been determined as a function of their depth in the membrane. Previous indirect estimates of the electrostatic potential within phospholipid membranes imply an enormous electric field of 108-109 V m-1, which is likely to have great significance in controlling the conformation of translocating membrane proteins and in the transfer of ions and molecules across the membrane. We have calculated the membrane potential for DMPG bilayers and found ˜1 V (˜2 ṡ 108 V m-1) when in the fluid phase with a monovalent counter-ion and ˜1.4 V (˜2.8 ṡ 108 V m-1) when in the gel phase with a divalent counter-ion. The number of water molecules for a fully hydrated DMPG membrane has been estimated to be 9.7 molecules per lipid in the gel phase and 17.5 molecules in the fluid phase, considerably smaller than inferred experimentally for 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC

  3. Study of water molecule decomposition in plasma by diode laser spectroscopy and optical actinometry methods

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Lagunov, V. V.; Ochkin, V. N.; Tskhai, S. N.

    2016-07-01

    The methods of diode laser radiation absorption at vibrational–rotational molecule transitions and optical actinometry with measurements of its electron emission spectra are used independently to study water molecule dissociation in glow discharge plasma in a mixture of water vapor and inert gases at reduced pressure. The methods yield close results. The dissociation reaches 98%.

  4. Key Role of Active-Site Water Molecules in Bacteriorhodopsin Proton-Transfer Reactions

    SciTech Connect

    Bondar, A.N.; Baudry, Jerome Y; Suhai, Sandor; Fischer, S.; Smith, Jeremy C

    2008-10-01

    The functional mechanism of the light-driven proton pump protein bacteriorhodopsin depends on the location of water molecules in the active site at various stages of the photocycle and on their roles in the proton-transfer steps. Here, free energy computations indicate that electrostatic interactions favor the presence of a cytoplasmic-side water molecule hydrogen bonding to the retinal Schiff base in the state preceding proton transfer from the retinal Schiff base to Asp85. However, the nonequilibrium nature of the pumping process means that the probability of occupancy of a water molecule in a given site depends both on the free energies of insertion of the water molecule in this and other sites during the preceding photocycle steps and on the kinetic accessibility of these sites on the time scale of the reaction steps. The presence of the cytoplasmic-side water molecule has a dramatic effect on the mechanism of proton transfer: the proton is channeled on the Thr89 side of the retinal, whereas the transfer on the Asp212 side is hindered. Reaction-path simulations and molecular dynamics simulations indicate that the presence of the cytoplasmic-side water molecule permits a low-energy bacteriorhodopsin conformer in which the water molecule bridges the twisted retinal Schiff base and the proton acceptor Asp85. From this low-energy conformer, proton transfer occurs via a concerted mechanism in which the water molecule participates as an intermediate proton carrier.

  5. Effect of addition of water-soluble chitin on amylose film.

    PubMed

    Suzuki, Shiho; Shimahashi, Katsumasa; Takahara, Junichi; Sunako, Michihiro; Takaha, Takeshi; Ogawa, Kozo; Kitamura, Shinichi

    2005-01-01

    Amylose films blended with chitosan, which were free from additives such as acid, salt, and plasticizer, were prepared by casting mixtures of an aqueous solution of an enzymatically synthesized amylose and that of water-soluble chitin (44.1% deacetylated). The presence of a small amount of chitin (less than 10%) increased significantly the permeability of gases (N2, O2, CO2, C2H4) and improved the mechanical parameters of amylose film; particularly, the elastic modulus and elongation of the blend films were larger than those of amylose or chitin films. No antibacterial activity was observed with either amylose or water-soluble chitin films. But amylose films having a small amount of chitin showed strong antibacterial action, suggesting a morphological change in water-soluble chitin on the film surface by blending with amylose molecule. These facts suggested the presence of a molecular complex of amylose and chitosan. PMID:16283751

  6. Adsorption of Small Molecules at Water--Hexane and Water--Membrane Interfaces

    NASA Astrophysics Data System (ADS)

    Wilson, Michael A.

    1996-03-01

    The interaction of solutes with aqueous interfaces plays a significant role in a variety of physical processes, including general anesthesia and atmospheric chemistry. We present molecular dynamics results for the transfer of several small solutes across water liquid--vapor, water--hexane and water--GMO bilayer membrane interfaces. (A. Pohorille and M. A. Wilson, J. Chem. Phys. (in press, 1995).)^, (A. Pohorille, P. CIeplak, and M. A. Wilson, Chem. Phys. (in press, 1995).) The free energies of transferring small polar molecules across the interface exhibit fairly deep minima while those of nonpolar molecules do not. This is due to a balance between nonelectrostatic contributions --- primarily the work required to create a cavity large enough to accommodate the solute --- and the solute--solvent electrostatic interactions.^1 The surface excess of solute is calculated and compared with experimental results from the Gibbs adsorption isotherm. The interfacial solubilities correlate with measured anesthetic potencies of these compounds, implying that the binding sites for anesthetics are located near the water--membrane interface.

  7. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  8. Chemical reactions of water molecules on Ru(0001) induced by selective excitation of vibrational modes

    SciTech Connect

    Mugarza, Aitor; Shimizu, Tomoko K.; Ogletree, D. Frank; Salmeron, Miquel

    2009-05-07

    Tunneling electrons in a scanning tunneling microscope were used to excite specific vibrational quantum states of adsorbed water and hydroxyl molecules on a Ru(0 0 0 1) surface. The excited molecules relaxed by transfer of energy to lower energy modes, resulting in diffusion, dissociation, desorption, and surface-tip transfer processes. Diffusion of H{sub 2}O molecules could be induced by excitation of the O-H stretch vibration mode at 445 meV. Isolated molecules required excitation of one single quantum while molecules bonded to a C atom required at least two quanta. Dissociation of single H{sub 2}O molecules into H and OH required electron energies of 1 eV or higher while dissociation of OH required at least 2 eV electrons. In contrast, water molecules forming part of a cluster could be dissociated with electron energies of 0.5 eV.

  9. Effects of a single water molecule on the OH + H2O2 reaction.

    PubMed

    Buszek, Robert J; Torrent-Sucarrat, Miquel; Anglada, Josep M; Francisco, Joseph S

    2012-06-21

    The effect of a single water molecule on the reaction between H(2)O(2) and HO has been investigated by employing MP2 and CCSD(T) theoretical approaches in connection with the aug-cc-PVDZ, aug-cc-PVTZ, and aug-cc-PVQZ basis sets and extrapolation to an ∞ basis set. The reaction without water has two elementary reaction paths that differ from each other in the orientation of the hydrogen atom of the hydroxyl radical moiety. Our computed rate constant, at 298 K, is 1.56 × 10(-12) cm(3) molecule(-1) s(-1), in excellent agreement with the suggested value by the NASA/JPL evaluation. The influence of water vapor has been investigated by considering either that H(2)O(2) first forms a complex with water that reacts with hydroxyl radical or that H(2)O(2) reacts with a previously formed H(2)O·OH complex. With the addition of water, the reaction mechanism becomes much more complex, yielding four different reaction paths. Two pathways do not undergo the oxidation reaction but an exchange reaction where there is an interchange between H(2)O(2)·H(2)O and H(2)O·OH complexes. The other two pathways oxidize H(2)O(2), with a computed total rate constant of 4.09 × 10(-12) cm(3) molecule(-1) s(-1) at 298 K, 2.6 times the value of the rate constant of the unassisted reaction. However, the true effect of water vapor requires taking into account the concentration of the prereactive bimolecular complex, namely, H(2)O(2)·H(2)O. With this consideration, water can actually slow down the oxidation of H(2)O(2) by OH between 1840 and 20.5 times in the 240-425 K temperature range. This is an example that demonstrates how water could be a catalyst in an atmospheric reaction in the laboratory but is slow under atmospheric conditions. PMID:22455374

  10. The local environment of the molecules in water-DMSO mixtures, as seen from computer simulations and Voronoi polyhedra analysis.

    PubMed

    Idrissi, Abdenacer; Marekha, B; Kiselev, M; Jedlovszky, Pál

    2015-02-01

    Molecular dynamics simulations of water-DMSO mixtures, containing 10, 20, 30, 40, 50, 60, 70, 80, and 90 mol% DMSO, respectively, have been performed on the isothermal-isobaric (N,p,T) ensemble at T = 298 K and at the pressure equal to the experimental vapor pressure at each mixture composition. In addition, simulations of the two neat systems have also been performed for reference. The potential models used in the simulations are known to excellently reproduce the mixing properties of these compounds. The simulation results have been analyzed in detail by means of the Voronoi polyhedra (VP) of the molecules. Distributions of the VP volume and the asphericity parameter as well as that of the radius of the spherical intermolecular voids have been calculated. Detailed analyses of these distributions have revealed that both molecules prefer to be in an environment consisting of both types of molecules, but the affinity of DMSO for mixing with water is clearly stronger than that of water for mixing with DMSO. As a consequence, the dilution of the two neat liquids by the other component has been found to follow different mechanisms: when DMSO is added to neat water small domains of neat-like water persist up to the equimolar composition, whereas no such domains are found when neat DMSO is diluted by water. The observed behaviour is also in line with the fact that the main thermodynamic driving force behind the full miscibility of water and DMSO is the energy change accompanying their mixing, and that the entropy change accompanying this mixing is negative in systems of low and positive in systems of high DMSO mole fractions. Finally, we have found a direct evidence for the existence of strong hydrogen bonded complexes formed by one DMSO and two water molecules, but it has also been shown that these complexes are in equilibrium with single (monomeric) water and DMSO molecules in the mixed systems. PMID:25533427

  11. Infrared Spectra of Water Bending Bands of Propylene Oxide-Water Complexes: Sequential Solvation of a Chiral Molecule in Water

    NASA Astrophysics Data System (ADS)

    Liu, Xunchen; Xu, Yunjie

    2011-06-01

    Sequential solvation of propylene oxide (C3H6O), an prototypical chiral molecule, with water has been investigated using high resolution infrared spectroscopy and ab initio methods. In a number of low resolution studies, the vibrational and vibrational circular dichroism spectral features at the water bending vibration region had been shown to be highly sensitive to the water solvation structures around propylene oxide in aqueous solution. The current study aims to provide quantitative information about solvation of a chiral molecule with water molecules at the molecular level and to provide the experimental benchmarks for calculations of vibrational frequencies in these larger molecular complexes. The high resolution infrared spectra of the propylene oxide-water complexes have been measured using a pulsed jet infrared spectrometer equipped with a room temperature external cavity quantum cascade laser and an astigmatic multi-pass cell. At least 6 bands have been observed from 1650 to 1680 Cm-1. Based on the previous microwave spectroscopic studies, these bands have been assigned to the blue-shifted water bending (ν_2) vibration modes associated with both the syn- and anti- conformers of the binary (C3H6O-H2O) and ternary (C3H6O-(H2O)2) complexes. This report shows the power of high resolution infrared spectroscopy to study multi-conformers of relatively large organic molecule complexes produced in a jet expansion. M. Losada, P. Nguyen, and Y .Xu, J. Phys. Chem. A, 112, 5621, (2008) Z. Su, Q. Wen, and Y. Xu, J. Am. Chem. Soc., 128, 6755, (2006) Z. Su and Y. Xu, Angew. Chem. Int. Ed., 46, 6163, (2007)

  12. Quasielastic neutron scattering from adsorbed water molecules on pyrogenic silica surfaces

    NASA Astrophysics Data System (ADS)

    Tumanov, A. A.; Zarko, V. I.

    1994-04-01

    Quasielastic neutron scattering (QNS) from hydrated samples of high dispersion (Aerosil) and of porous dioxide silicon was investigated. The broadening of the QNS peak analysis permits one to obtain the effective diffusion coefficient D of adsorbed water molecules. It was obtained that the D-value increases with silica hydration. The mean square displacement of the water molecules from equilibrium < x2> equals approximately 0.1 Å 2 and does not depend on the quantity of adsorbed water.

  13. Water disinfection: microbes versus molecules - an introduction of issues

    SciTech Connect

    Fowle, J.R. III, Kopfler, F.C.

    1986-11-01

    If the chemicals used to rid drinking water of disease-causing microbes are themselves potentially harmful, is drinking water safe. What trade-offs are acceptable with respect to microbial versus chemical water quality. This conference deals with current thinking about these topics. The subjects discussed reflect the evolution of thinking, both scientifically and socially, about how best to supply the public with safe, pure potable water. The goal of this paper is to introduce the issues associated with disinfectants and disinfectant by-products in water. This will be done by presenting a historical overview of the use of chemical disinfectants to purify drinking water and the subsequent awareness of potential health concerns. Historically, the major health issue associated with water has been the demonstrated role that water has played in spreading infectious disease. Waterborne infectious agents remain in the environment, and new ones emerge through evolution of humans and microorganisms and because of changing exposure patterns.

  14. Improved Growth Factor Directed Vascularization into Fibrin Constructs Through Inclusion of Additional Extracellular Molecules

    PubMed Central

    Smith, JD; Melhem, ME; Magge, KT; Waggoner, AS; Campbell, PG

    2009-01-01

    Using the chick chorioallantoic membrane assay (CAM) and a novel histological technique we investigated the ability of blood vessels to directly invade fibrin-based scaffolds. In our initial experiments utilizing vascular endothelial growth factor (VEGF165) we found no direct invasion. Instead, the fibrin was completely degraded and replaced with highly vascularized new tissue. Addition of fibroblast growth factor-2 (FGF-2), bone morphogenic protein-2 (BMP-2), or platelet-derived growth factor-BB (PDGF-BB) to the fibrin construct also did not result in construct vascularization. Because natural and regenerating tissues exhibit complex extracellular matrices (ECMs), we hypothesized that a more complex scaffold may improve blood vessel invasion. Addition of fibronectin, hyaluronic acid, and collagen type I within 20 mg/mL fibrin constructs resulted in no significant improvement. However, the same additive concentrations within 10 mg/mL fibrin constructs resulted in dramatic improvements, specifically with hyaluronic acid. Overall, we believe these results indicate the importance of structural and functional cues of not only in the initial scaffold but also as the construct is degraded and remodeled. Furthermore, the CAM assay may represent a useful model for understanding ECM interactions as well as for screening and designing tissue engineered scaffolds. PMID:17223139

  15. Implication of crystal water molecules in inhibitor binding at ALR2 active site.

    PubMed

    Hymavati; Kumar, Vivek; Sobhia, M Elizabeth

    2012-01-01

    Water molecules play a crucial role in mediating the interaction between a ligand and a macromolecule. The solvent environment around such biomolecule controls their structure and plays important role in protein-ligand interactions. An understanding of the nature and role of these water molecules in the active site of a protein could greatly increase the efficiency of rational drug design approaches. We have performed the comparative crystal structure analysis of aldose reductase to understand the role of crystal water in protein-ligand interaction. Molecular dynamics simulation has shown the versatile nature of water molecules in bridge H bonding during interaction. Occupancy and life time of water molecules depend on the type of cocrystallized ligand present in the structure. The information may be useful in rational approach to customize the ligand, and thereby longer occupancy and life time for bridge H-bonding. PMID:22649481

  16. Single-molecule analysis of ultradilute solutions with guided streams of 1-{mu}m water droplets

    SciTech Connect

    Kung, C.; Barnes, M.D.; Lermer, N.; Whitten, W.B.; Ramsey, J.M.

    1999-03-01

    We describe instrumentation for real-time detection of single-molecule fluorescence in guided streams of 1-{mu}m (nominal) water droplets. In this technique, target molecules were confined to droplets whose volumes were comparable with illumination volumes in diffraction-limited fluorescence microscopy and guided to the waist of a cw probe laser with an electrostatic potential. Concentration detection limits for Rhodamine 6G in water were determined to be {approximately}1 fM, roughly 3 orders of magnitude lower than corresponding limits determined recently with diffraction-limited microscopy techniques for a chemical separation of similar dyes. In addition to its utility as a vehicle for probing single molecules, instrumentation for producing and focusing stable streams of 1{endash}2-{mu}m-diameter droplets may have other important analytical applications as well. {copyright} 1999 Optical Society of America

  17. Conserved hydrogen bonds and water molecules in MDR HIV-1 protease substrate complexes

    SciTech Connect

    Liu, Zhigang; Wang, Yong; Yedidi, Ravikiran S.; Dewdney, Tamaria G.; Reiter, Samuel J.; Brunzelle, Joseph S.; Kovari, Iulia A.; Kovari, Ladislau C.

    2012-12-19

    Success of highly active antiretroviral therapy (HAART) in anti-HIV therapy is severely compromised by the rapidly developing drug resistance. HIV-1 protease inhibitors, part of HAART, are losing their potency and efficacy in inhibiting the target. Multi-drug resistant (MDR) 769 HIV-1 protease (resistant mutations at residues 10, 36, 46, 54, 62, 63, 71, 82, 84, 90) was selected for the present study to understand the binding to its natural substrates. The nine crystal structures of MDR769 HIV-1 protease substrate hepta-peptide complexes were analyzed in order to reveal the conserved structural elements for the purpose of drug design against MDR HIV-1 protease. Our structural studies demonstrated that highly conserved hydrogen bonds between the protease and substrate peptides, together with the conserved crystallographic water molecules, played a crucial role in the substrate recognition, substrate stabilization and protease stabilization. Additionally, the absence of the key flap-ligand bridging water molecule might imply a different catalytic mechanism of MDR769 HIV-1 protease compared to that of wild type (WT) HIV-1 protease.

  18. Quantifying the Entropy of Binding for Water Molecules in Protein Cavities by Computing Correlations

    PubMed Central

    Huggins, David J.

    2015-01-01

    Protein structural analysis demonstrates that water molecules are commonly found in the internal cavities of proteins. Analysis of experimental data on the entropies of inorganic crystals suggests that the entropic cost of transferring such a water molecule to a protein cavity will not typically be greater than 7.0 cal/mol/K per water molecule, corresponding to a contribution of approximately +2.0 kcal/mol to the free energy. In this study, we employ the statistical mechanical method of inhomogeneous fluid solvation theory to quantify the enthalpic and entropic contributions of individual water molecules in 19 protein cavities across five different proteins. We utilize information theory to develop a rigorous estimate of the total two-particle entropy, yielding a complete framework to calculate hydration free energies. We show that predictions from inhomogeneous fluid solvation theory are in excellent agreement with predictions from free energy perturbation (FEP) and that these predictions are consistent with experimental estimates. However, the results suggest that water molecules in protein cavities containing charged residues may be subject to entropy changes that contribute more than +2.0 kcal/mol to the free energy. In all cases, these unfavorable entropy changes are predicted to be dominated by highly favorable enthalpy changes. These findings are relevant to the study of bridging water molecules at protein-protein interfaces as well as in complexes with cognate ligands and small-molecule inhibitors. PMID:25692597

  19. Rapid recovery of cyanobacterial pigments in desiccated biological soil crusts following addition of water.

    PubMed

    Abed, Raeid M M; Polerecky, Lubos; Al-Habsi, Amal; Oetjen, Janina; Strous, Marc; de Beer, Dirk

    2014-01-01

    We examined soil surface colour change to green and hydrotaxis following addition of water to biological soil crusts using pigment extraction, hyperspectral imaging, microsensors and 13C labeling experiments coupled to matrix-assisted laser desorption and ionization time of flight-mass spectrometry (MALD-TOF MS). The topsoil colour turned green in less than 5 minutes following water addition. The concentrations of chlorophyll a (Chl a), scytonemin and echinenon rapidly increased in the top <1 mm layer while in the deeper layer, their concentrations remained low. Hyperspectral imaging showed that, in both wet and dehydrated crusts, cyanobacteria formed a layer at a depth of 0.2-0.4 mm and this layer did not move upward after wetting. 13C labeling experiments and MALDI TOF analysis showed that Chl a was already present in the desiccated crusts and de novo synthesis of this molecule started only after 2 days of wetting due to growth of cyanobacteria. Microsensor measurements showed that photosynthetic activity increased concomitantly with the increase of Chl a, and reached a maximum net rate of 92 µmol m-2 h-1 approximately 2 hours after wetting. We conclude that the colour change of soil crusts to green upon water addition was not due to hydrotaxis but rather to the quick recovery and reassembly of pigments. Cyanobacteria in crusts can maintain their photosynthetic apparatus intact even under prolonged periods of desiccation with the ability to resume their photosynthetic activities within minutes after wetting. PMID:25375172

  20. Fast transport of water molecules across carbon nanotubes induced by static electric fields

    NASA Astrophysics Data System (ADS)

    Zhang, Qi-Lin; Yang, Rong-Yao

    2016-01-01

    Water permeation across a single-walled carbon nanotube has been studied in the presence of static electric fields (SEFs) with different directions under hydrostatic pressures. With the angle between the SEF direction and tube axis increasing from 0∘ to 90∘, the water flux decreases gradually until almost vanishes, and the maximum value at 0∘ is approximately four times the case without SEFs. The phenomenon is attributed to the alignment of the polar water molecules along the SEF direction. We also show that water permeation properties are dependent on the field strength due mainly to thermal fluctuations of water molecules.

  1. Improving the performance of ammonia-water absorption cycles using salt additives and membranes

    SciTech Connect

    Ibrahim, O.M.; Barnett, S.M.; Balamuru, V.G.

    1997-12-31

    This paper proposes a new design of an ammonia-water absorption refrigeration cycle for low-temperature heat sources such as solar energy and waste heat. The proposed cycle uses a salt additive to shift the chemical equilibrium toward more effective separation of ammonia molecules from aqueous solution (i.e., salting out). Since salt additives can affect all aspects of the absorption cycle, membranes have been chosen to control the flow of ions in the cycle and limit their effects to the generation side. This paper describes an absorption cycle that uses membrane separation processes, such as reverse osmosis, dialysis, and electrodialysis. To optimize the performance of the cycle, however, the membranes and salts must be carefully chosen.

  2. Shape of a water molecule as function of OH separation

    NASA Astrophysics Data System (ADS)

    Gabbay, I.; March, N. H.

    1980-02-01

    For small O-H separation the water molecule becomes linear. The Murrell-Sorbie potential energy surface affords a basis to study the shape of the molecule for larger OH separation. The possible relevance to H 2O outside a metal surface is discussed.

  3. The putative role of some conserved water molecules in the structure and function of human transthyretin.

    PubMed

    Banerjee, Avik; Dasgupta, Subrata; Mukhopadhyay, Bishnu P; Sekar, Kanagaraj

    2015-11-01

    Human transthyretin (hTTR) is a multifunctional protein that is involved in several neurodegenerative diseases. Besides the transportation of thyroxin and vitamin A, it is also involved in the proteolysis of apolipoprotein A1 and Aβ peptide. Extensive analyses of 32 high-resolution X-ray and neutron diffraction structures of hTTR followed by molecular-dynamics simulation studies using a set of 15 selected structures affirmed the presence of 44 conserved water molecules in its dimeric structure. They are found to play several important roles in the structure and function of the protein. Eight water molecules stabilize the dimeric structure through an extensive hydrogen-bonding network. The absence of some of these water molecules in highly acidic conditions (pH ≤ 4.0) severely affects the interfacial hydrogen-bond network, which may destabilize the native tetrameric structure, leading to its dissociation. Three pairs of conserved water molecules contribute to maintaining the geometry of the ligand-binding cavities. Some other water molecules control the orientation and dynamics of different structural elements of hTTR. This systematic study of the location, absence, networking and interactions of the conserved water molecules may shed some light on various structural and functional aspects of the protein. The present study may also provide some rational clues about the conserved water-mediated architecture and stability of hTTR. PMID:26527142

  4. Unraveling the Sc(3+) Hydration Geometry: The Strange Case of the Far-Coordinated Water Molecule.

    PubMed

    Migliorati, Valentina; D'Angelo, Paola

    2016-07-01

    The hydration structure and dynamics of Sc(3+) in aqueous solution have been investigated using a combined approach based on quantum mechanical (QM) calculations, molecular dynamics (MD) simulations, and extended X-ray absorption fine structure (EXAFS) spectroscopy. An effective Sc-water two-body potential has been generated from QM calculations and then used in the MD simulation of Sc(3+) in water, and the reliability of the entire procedure has been assessed by comparing the theoretical structural results with the EXAFS experimental data. The outstanding outcome of this work is that the Sc(3+) ion forms a well-defined capped square antiprism (SAP) complex in aqueous solution, where the eight water molecules closest to the ion are located at the vertexes of a SAP polyhedron, while the ninth water molecule occupying the capping position is unusually found at a very long distance from the ion. This far-coordinated water molecule possesses a degree of structure comparable with the other first shell molecules surrounding the ion at much shorter distances, and its presence gave us the unique opportunity to easily identify the geometry of the Sc(3+) coordination polyhedron. Despite very strong ion-water interactions, the Sc(3+) hydration shell is very labile, as the far-coordinated ligand allows first shell water molecules to easily exchange their positions both inside the solvation shell and with the rest of the solvent molecules. PMID:27300102

  5. High physisorption affinity of water molecules to the hydroxylated aluminum oxide (001) surface.

    PubMed

    Kittaka, Shigeharu; Yamaguchi, Keisuke; Takahara, Shuichi

    2012-02-15

    The adsorption mechanism of water on the hydroxylated (001) plane of α-Al(2)O(3) was studied by measuring adsorption isotherms and GCMC simulations. The experimental adsorption isotherms for three α-Al(2)O(3) samples from different sources are typical type II, in which adsorption starts sharply at low pressures, suggesting a high affinity of water to the Al(2)O(3) surface. Water molecules are adsorbed in two registered forms (bilayer structure). In the first form, water is registered at the center of three surface hydroxyl groups by directing a proton of the water. In the second form, a water molecule is adsorbed by bridging two of the first-layer water molecules through hydrogen bonding, by which a hexagonal ring network is constructed over the hydroxylated surface. The network domains are spread over the surface, and their size decreases as the temperature increases. The simulated adsorption isotherms present a characteristic two-dimensional (2D) phase diagram including a 2D critical point at 365K, which is higher than that on the hydroxylated Cr(2)O(3) surface (319 K). This fact substantiates the high affinity of water molecules to the α-Al(2)O(3) surfaces, which enhances the adsorbability originating from higher heat of adsorption. The higher affinity of water molecules to the α-Al(2)O(3) (001) plane is ascribed to the high compatibility of the crystal plane to form a hexagonal ring network of (001) plane of ice Ih. PMID:22178567

  6. Relaxation dynamics of surface-adsorbed water molecules in nanoporous silica probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Ru; Liu, Kao-Hsiang; Mou, Chung-Yuan; Sun, Chi-Kuang

    2015-08-01

    Relaxation dynamics of an exclusively adsorbed water molecule in mesoporous silica MCM-41-S was studied by using terahertz spectroscopy. With the temperature controlled from 0 to 50 °C, we observed strongly frequency- and temperature-dependent dielectric relaxation responses, implying that, unlike ice, surface-adsorbed water molecules retained flourishing picosecond dynamics. Based on the Debye relaxation model, a relaxation time constant was found to increase from 1.77 to 4.83 ps when the water molecule was cooled from 50 to 0 °C. An activation energy of ˜15 kJ/mol, which was in close agreement with a hydrogen-bonding energy, was further extracted from the Arrhenius analysis. Combined with previous molecular dynamics simulations, our results indicate that the reorientation relaxation originated from the "flip-flop" rotation of a three hydrogen-bonded surface-adsorbed water molecule.

  7. Asymmetric self-diffusion with orientation-dependence of water molecule in finite timescale

    NASA Astrophysics Data System (ADS)

    Wei, Xu; Sheng, Nan; Wan, RongZheng; Hu, GuoHui; Fang, HaiPing

    2016-07-01

    Self-diffusion of water has been investigated by molecular dynamics simulations. It was found that the preference of the direction in self-diffusion of water is orientation dependent in a finite time. For a time of ~100 ps, there are more possibilities for water molecules moving along the initial dipole orientation than in the opposite direction. This reveals that self-diffusion of water molecules is asymmetric in a finite time. We tested four water models and found that they all show similar asymmetric diffusion, indicating that asymmetric diffusion of water is intrinsic behavior rather than induced by the water model. These results are important for understanding and application of asymmetric diffusion in research fields such as biological water and confined water in small dimensions.

  8. Free energy barriers for escape of water molecules from protein hydration layer.

    PubMed

    Roy, Susmita; Bagchi, Biman

    2012-03-01

    Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these "slow" water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface. PMID:22288939

  9. Computing the energy of a water molecule using multideterminants: A simple, efficient algorithm

    NASA Astrophysics Data System (ADS)

    Clark, Bryan K.; Morales, Miguel A.; McMinis, Jeremy; Kim, Jeongnim; Scuseria, Gustavo E.

    2011-12-01

    Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater-Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater determinants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily parallelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Additionally, we implement this method and use it to compute the ground state energy of a water molecule.

  10. Computing the energy of a water molecule using multideterminants: a simple, efficient algorithm.

    PubMed

    Clark, Bryan K; Morales, Miguel A; McMinis, Jeremy; Kim, Jeongnim; Scuseria, Gustavo E

    2011-12-28

    Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater-Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater determinants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily parallelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Additionally, we implement this method and use it to compute the ground state energy of a water molecule. PMID:22225142

  11. Analytical model for three-dimensional Mercedes-Benz water molecules.

    PubMed

    Urbic, T

    2012-06-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature. PMID:23005100

  12. Analytical model for three-dimensional Mercedes-Benz water molecules

    NASA Astrophysics Data System (ADS)

    Urbic, T.

    2012-06-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature.

  13. Analytical model for three-dimensional Mercedes-Benz water molecules

    PubMed Central

    Urbic, T.

    2013-01-01

    We developed a statistical model which describes the thermal and volumetric properties of water-like molecules. A molecule is presented as a three-dimensional sphere with four hydrogen-bonding arms. Each water molecule interacts with its neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of a model developed before for a two-dimensional Mercedes-Benz model of water. We explored properties such as molar volume, density, heat capacity, thermal expansion coefficient, and isothermal compressibility as a function of temperature and pressure. We found that the volumetric and thermal properties follow the same trends with temperature as in real water and are in good general agreement with Monte Carlo simulations, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds upon increasing the temperature. PMID:23005100

  14. Turbulent flow of oil-water emulsions with polymer additives

    NASA Astrophysics Data System (ADS)

    Manzhai, V. N.; Monkam Clovis Le Grand, Monkam; Abdousaliamov, A. V.

    2014-08-01

    The article outlines direct and reverse oil-water emulsions. Microphotography study of these emulsions was carried out. The effect of water-soluble and oil soluble polymers on the emulsion structure and their turbulent flow velocity in cylindrical channel was investigated. It has been experimentally proven that if the fluid being transported is not homogeneous, but a two-phase oil-water emulsion, only the polymer that is compatible with dispersion medium and capable of dissolving in this medium can reduce the hydrodynamic resistance of the fluid flow. Thus, the resistance in direct emulsions can be reduced by water- soluble polyacrylamide, while oil-soluble polyhexene can be applied for reverse emulsions.

  15. Exfoliated MoS2 in Water without Additives

    PubMed Central

    Forsberg, Viviane; Zhang, Renyun; Bäckström, Joakim; Dahlström, Christina; Andres, Britta; Norgren, Magnus; Andersson, Mattias; Hummelgård, Magnus; Olin, Håkan

    2016-01-01

    Many solution processing methods of exfoliation of layered materials have been studied during the last few years; most of them are based on organic solvents or rely on surfactants and other funtionalization agents. Pure water should be an ideal solvent, however, it is generally believed, based on solubility theories that stable dispersions of water could not be achieved and systematic studies are lacking. Here we describe the use of water as a solvent and the stabilization process involved therein. We introduce an exfoliation method of molybdenum disulfide (MoS2) in pure water at high concentration (i.e., 0.14 ± 0.01 g L−1). This was achieved by thinning the bulk MoS2 by mechanical exfoliation between sand papers and dispersing it by liquid exfoliation through probe sonication in water. We observed thin MoS2 nanosheets in water characterized by TEM, AFM and SEM images. The dimensions of the nanosheets were around 200 nm, the same range obtained in organic solvents. Electrophoretic mobility measurements indicated that electrical charges may be responsible for the stabilization of the dispersions. A probability decay equation was proposed to compare the stability of these dispersions with the ones reported in the literature. Water can be used as a solvent to disperse nanosheets and although the stability of the dispersions may not be as high as in organic solvents, the present method could be employed for a number of applications where the dispersions can be produced on site and organic solvents are not desirable. PMID:27120098

  16. Exfoliated MoS2 in Water without Additives.

    PubMed

    Forsberg, Viviane; Zhang, Renyun; Bäckström, Joakim; Dahlström, Christina; Andres, Britta; Norgren, Magnus; Andersson, Mattias; Hummelgård, Magnus; Olin, Håkan

    2016-01-01

    Many solution processing methods of exfoliation of layered materials have been studied during the last few years; most of them are based on organic solvents or rely on surfactants and other funtionalization agents. Pure water should be an ideal solvent, however, it is generally believed, based on solubility theories that stable dispersions of water could not be achieved and systematic studies are lacking. Here we describe the use of water as a solvent and the stabilization process involved therein. We introduce an exfoliation method of molybdenum disulfide (MoS2) in pure water at high concentration (i.e., 0.14 ± 0.01 g L-1). This was achieved by thinning the bulk MoS2 by mechanical exfoliation between sand papers and dispersing it by liquid exfoliation through probe sonication in water. We observed thin MoS2 nanosheets in water characterized by TEM, AFM and SEM images. The dimensions of the nanosheets were around 200 nm, the same range obtained in organic solvents. Electrophoretic mobility measurements indicated that electrical charges may be responsible for the stabilization of the dispersions. A probability decay equation was proposed to compare the stability of these dispersions with the ones reported in the literature. Water can be used as a solvent to disperse nanosheets and although the stability of the dispersions may not be as high as in organic solvents, the present method could be employed for a number of applications where the dispersions can be produced on site and organic solvents are not desirable. PMID:27120098

  17. Auger spectrum of a water molecule after single and double core ionization

    SciTech Connect

    Inhester, L.; Burmeister, C. F.; Groenhof, G.; Grubmueller, H.

    2012-04-14

    The high intensity of free electron lasers opens up the possibility to perform single-shot molecule scattering experiments. However, even for small molecules, radiation damage induced by absorption of high intense x-ray radiation is not yet fully understood. One of the striking effects which occurs under intense x-ray illumination is the creation of double core ionized molecules in considerable quantity. To provide insight into this process, we have studied the dynamics of water molecules in single and double core ionized states by means of electronic transition rate calculations and ab initio molecular dynamics (MD) simulations. From the MD trajectories, photoionization and Auger transition rates were computed based on electronic continuum wavefunctions obtained by explicit integration of the coupled radial Schroedinger equations. These rates served to solve the master equations for the populations of the relevant electronic states. To account for the nuclear dynamics during the core hole lifetime, the calculated electron emission spectra for different molecular geometries were incoherently accumulated according to the obtained time-dependent populations, thus neglecting possible interference effects between different decay pathways. We find that, in contrast to the single core ionized water molecule, the nuclear dynamics for the double core ionized water molecule during the core hole lifetime leaves a clear fingerprint in the resulting electron emission spectra. The lifetime of the double core ionized water was found to be significantly shorter than half of the single core hole lifetime.

  18. Fast phase transition of water molecules in a defective carbon nanotube under an electric field

    NASA Astrophysics Data System (ADS)

    Meng, Xianwen; Huang, Jiping

    2016-02-01

    We utilize molecular dynamics simulations to study the effect of an electric field on the permeation of water molecules through a defective single-walled carbon nanotube (DSWCNT). Compared with a perfect single-walled carbon nanotube (PSWCNT), the behaviors of water molecules respond more quickly under the same electric field in a DSWCNT. Wet-dry phase transition of water molecules occurs when the electric field reaches 0.32 V/nm, which is much lower than the case of the PSWCNT. Besides, the critical electric field is affected by the number of defects. These results pave a way for designing fast wet-dry transition devices and provide a new insight into water permeation through a defective nanochannel.

  19. Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice

    NASA Astrophysics Data System (ADS)

    Zhukova, Elena S.; Torgashev, Victor I.; Gorshunov, Boris P.; Lebedev, Vladimir V.; Shakurov, Gil'man S.; Kremer, Reinhard K.; Pestrjakov, Efim V.; Thomas, Victor G.; Fursenko, Dimitry A.; Prokhorov, Anatoly S.; Dressel, Martin

    2014-06-01

    Low-energy excitations of a single water molecule are studied when confined within a nano-size cavity formed by the ionic crystal lattice. Optical spectra are measured of manganese doped beryl single crystal Mn:Be3Al2Si6O18, that contains water molecules individually isolated in 0.51 nm diameter voids within the crystal lattice. Two types of orientation are distinguished: water-I molecules have their dipole moments aligned perpendicular to the c axis and dipole moments of water-II molecules are parallel to the c-axis. The optical conductivity σ(ν) and permittivity ɛ'(ν) spectra are recorded in terahertz and infrared ranges, at frequencies from several wavenumbers up to ν = 7000 cm-1, at temperatures 5-300 K and for two polarizations, when the electric vector E of the radiation is parallel and perpendicular to the c-axis. Comparative experiments on as-grown and on dehydrated samples allow to identify the spectra of σ(ν) and ɛ'(ν) caused exclusively by water molecules. In the infrared range, well-known internal modes ν1, ν2, and ν3 of the H2O molecule are observed for both polarizations, indicating the presence of water-I and water-II molecules in the crystal. Spectra recorded below 1000 cm-1 reveal a rich set of highly anisotropic features in the low-energy response of H2O molecule in a crystalline nano-cavity. While for E∥c only two absorption peaks are detected, at ˜90 cm-1 and ˜160 cm-1, several absorption bands are discovered for E⊥c, each consisting of narrower resonances. The bands are assigned to librational (400-500 cm-1) and translational (150-200 cm-1) vibrations of water-I molecule that is weakly coupled to the nano-cavity "walls." A model is presented that explains the "fine structure" of the bands by a splitting of the energy levels due to quantum tunneling between the minima in a six-well potential relief felt by a molecule within the cavity.

  20. Hydroxyl and water molecule orientations in trypsin: Comparison to molecular dynamics structures

    SciTech Connect

    McDowell, R.S.; Kossiakoff, A.A.

    1994-12-31

    A comparison is presented of experimentally observed hydroxyl and water hydrogens in trypsin determined from neutron density maps with the results of a 140ps molecular dynamics (MD) simulation. Experimental determination of hydrogen and deuterium atom positions in molecules as large as proteins is a unique capability of neutron diffraction. The comparison addresses the degree to which a standard force-field approach can adequately describe the local electrostatic and van der Waals forces that determine the orientations of these hydrogens. Neutron densities, derived from 2.1{Angstrom} D{sub 2}O-H{sub 2}O difference Fourier maps, provide a database of 27 well-ordered hydroxyl hydrogens. Most of the simulated hydroxyl orientations are within a standard deviation of the experimentally-observed positions, including several examples in which both the simulation and the neutron density indicate that a hydroxyl group is shifted from a {open_quote}standard{close_quote} rotamer. For the most highly ordered water molecules, the hydrogen distributions calculated from the trajectory were in good agreement with neutron density; simulated water molecules that displayed multiple hydrogen bonding networks had correspondingly broadened neutron density profiles. This comparison was facilitated by development of a method to construct a pseudo 2{Angstrom} density map based on the hydrogen atom distributions from the simulation. The degree of disorder of internal water molecules is shown to result primarily from the electrostatic environment surrounding that water molecule as opposed to the cavity size available to the molecule. A method is presented for comparing the discrete observations sampled in a dynamics trajectory with the time- averaged data obtained from X-ray or neutron diffraction studies. This method is particularly useful for statically-disordered water molecules, in which the average location assigned from a trajectory may represent a site of relatively low occupancy.

  1. Effects of atmospheric precipitation additions on phytoplankton photosynthesis in Lake Michigan water samples

    SciTech Connect

    Parker, J.I.; Tisue, G.T.; Kennedy, C.W.; Seils, C.A.

    1981-01-01

    The effects of incremental additions (0.1 to 50% v/v) of atmospheric precipitation on phytoplankton photosynthesis (/sup 14/C uptake) were tested in Lake Michigan water samples. Wet deposition was used in experiments I, III, and IV, and a melted snow core was used in experiment II. Additions of precipitation significantly reduced photosynthesis in the first three experiments, starting at about the 5 to 15% treatment level. No significant difference occurred in experiment IV, but photosynthesis was greater than in the control samples and this precipitation sample appeared to stimulate primary productivity. Soluble reactive phosphate, nitrate, and ammonia levels in the precipitation samples exceeded the lake water averages by factors of 10, 2, and 50, respectively. Silicon levels in precipitation reduced pH very little and no consistent relationship was observed with reduced photosynthesis. Alkalinity was greatly reduced in the treated samples and special precautions were required in ce, Ti, Be, Co, Cu, Mo, Ni, P,f the Pd crystals of about 30 A. Possible mechanisms are discussed for isotope exchange in CO molecules in these catalysts and for the promoting effect of Pd on the activity of CuO.

  2. Improving protein-ligand docking with flexible interfacial water molecules using SWRosettaLigand.

    PubMed

    Li, Linqing; Xu, Weiwei; Lü, Qiang

    2015-11-01

    Computational protein-ligand docking is of great importance in drug discovery and design. Conformational changes greatly affect the results of protein-ligand docking, especially when water molecules take part in mediating protein ligand interactions or when large conformational changes are observed in the receptor backbone interface. We have developed an improved protocol, SWRosettaLigand, based on the RosettaLigand protocol. This approach incorporates the flexibility of interfacial water molecules and modeling of the interface of the receptor into the original RosettaLigand. In a coarse sampling step, SWRosettaLigand pre-optimizes the initial position of the water molecules, docks the ligand to the receptor with explicit water molecules, and minimizes the predicted structure with water molecules. The receptor backbone interface is treated as a loop and perturbed and refined by kinematic closure, or cyclic coordinate descent algorithm, with the presence of the ligand. In two cross-docking test sets, it was identified that for 8 out of 14, and 16 out of 22, test instances, the top-ranked structures by SWRosettaLigand achieved better accuracy than other protocols. PMID:26515196

  3. Water molecules inside protein structure affect binding of monosaccharides with HIV-1 antibody 2G12.

    PubMed

    Ueno-Noto, Kaori; Takano, Keiko

    2016-10-01

    Water molecules inside biomolecules constitute integral parts of their structure and participate in the functions of the proteins. Some of the X-ray crystallographic data are insufficient for analyzing a series of ligand-protein complexes in the same condition. We theoretically investigated antibody binding abilities of saccharide ligands and the effects of the inner water molecules of ligand-antibody complexes. Classical molecular dynamics and quantum chemical simulations using a model with possible water molecules inside the protein were performed with saccharide ligands and Human Immunodeficiency Virus 1 neutralizing antibody 2G12 complexes to estimate how inner water molecules of the protein affect the dynamics of the complexes as well as the ligand-antibody interaction. Our results indicate the fact that d-fructose's strong affinity to the antibody was partly due to the good retentiveness of solvent water molecules of the ligand and its stability of the ligand's conformation and relative position in the active site. © 2016 Wiley Periodicals, Inc. PMID:27388036

  4. Enhanced permeation of single-file water molecules across a noncylindrical nanochannel

    NASA Astrophysics Data System (ADS)

    Meng, X. W.; Huang, J. P.

    2013-07-01

    We utilize molecular dynamics simulations to study the effect of noncylindrical shapes of a nanochannel (which are inspired from the shape of real biological water nanochannels) on the permeation of single-file water molecules across the nanochannel. Compared with the cylindrical shape that has been tremendously adopted in the literature, the noncylindrical shapes play a crucial role in enhancing water permeation. Remarkably, the maximal enhancement ratio reaches a value of 6.28 (enhancement behavior). Meanwhile, the enhancement becomes saturated when the volume of the noncylindrical shape continues to increase (saturation behavior). The analysis of average diffusivity of water molecules helps to reveal the mechanism underlying the two behaviors whereas Poiseuille's law fails to explain them. These results pave a way for designing high-flow nanochannels and provide insight into water permeation across biological water nanochannels.

  5. Giant pumping of single-file water molecules in a carbon nanotube.

    PubMed

    Wang, Y; Zhao, Y J; Huang, J P

    2011-11-17

    Achieving a fast, unidirectional flow of single-file water molecules (UFSWM) across nanochannels is important for membrane-based water purification or seawater desalination. For this purpose, electro-osmosis methods are recognized as a very promising approach and have been extensively discussed in the literature. Utilizing molecular dynamics simulations, here we propose a design for pumping water molecules in a single-walled carbon nanotube in the presence of a linearly gradient electric (GE) field. Such a GE field is inspired by GE fields generated from charged ions located adjacent to biological membrane water nanochannels that can conduct water in and out of cells and can be experimentally achieved by using the charged tip of an atomic force microscope. As a result, the maximum speed of the UFSWM can be 1 or 2 orders of magnitude larger than that in a uniform electric (UE) field. Also, inverse transportation of water molecules does not exist in case of the GE field but can appear for the UE field. Thus, the GE field yields a much more efficient UFSWM than the UE field. The giant pumping ability as revealed is attributed to the nonzero net electrostatic force acting on each water molecule confined in the nanotube. These observations have significance for the design of nanoscale devices for readily achieving controllable UFSWM at high speed. PMID:21977917

  6. Covalent Functionalization of Fluorinated Graphene and Subsequent Application as Water-based Lubricant Additive.

    PubMed

    Ye, Xiangyuan; Ma, Limin; Yang, Zhigang; Wang, Jinqing; Wang, Honggang; Yang, Shengrong

    2016-03-23

    Although the fluorinated graphene (FG) possesses numerous excellent properties, it can not be really applied in aqueous environments due to its high hydrophobicity. Therefore, how to achieve hydrophilic FG is a challenge. Here, a method of solvent-free urea melt synthesis is developed to prepare the hydrophilic urea-modified FG (UFG). Some characterizations via transmission electron microscopy (TEM), atomic force microscopy (AFM), Fourier transfer infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermo gravimetric analysis (TGA) demonstrate that the urea molecules can covalently functionalize the FG and the hydrophilic UFG can be prepared. According to the tribological tests run on an optimal-SRV-I reciprocation friction tester, it can be found that the antiwear ability of water can be largely improved by adding the appropriate UFG. When the concentration of UFG aqueous dispersion is 1 mg/mL, the sample of UFG-1 has the best antiwear ability with a 64.4% decrease of wear rate compared with that of the pure water (UFG-0), demonstrating the prepared UFG can be used as a novel and effective water-based lubricant additive. PMID:26923174

  7. Investigation of N-acyl homoserine lactone (AHL) molecule production in Gram-negative bacteria isolated from cooling tower water and biofilm samples.

    PubMed

    Haslan, Ezgi; Kimiran-Erdem, Ayten

    2013-09-01

    In this study, 99 Gram-negative rod bacteria were isolated from cooling tower water, and biofilm samples were examined for cell-to-cell signaling systems, N-acyl homoserine lactone (AHL) signal molecule types, and biofilm formation capacity. Four of 39 (10 %) strains isolated from water samples and 14 of 60 (23 %) strains isolated from biofilm samples were found to be producing a variety of AHL signal molecules. It was determined that the AHL signal molecule production ability and the biofilm formation capacity of sessile bacteria is higher than planktonic bacteria, and there was a statistically significant difference between the AHL signal molecule production of these two groups (p < 0.05). In addition, it was found that bacteria belonging to the same species isolated from cooling tower water and biofilm samples produced different types of AHL signal molecules and that there were different types of AHL signal molecules in an AHL extract of bacteria. In the present study, it was observed that different isolates of the same strains did not produce the same AHLs or did not produce AHL molecules, and bacteria known as AHL producers did not produce AHL. These findings suggest that detection of signal molecules in bacteria isolated from cooling towers may contribute to prevention of biofilm formation, elimination of communication among bacteria in water systems, and blockage of quorum-sensing controlled virulence of these bacteria. PMID:23250628

  8. Migration of additive molecules in a polymer filament obtained by melt spinning: Influence of the fiber processing steps

    NASA Astrophysics Data System (ADS)

    Gesta, E.; Skovmand, O.; Espuche, E.; Fulchiron, R.

    2015-12-01

    The purpose of this study is to understand the influence of the yarn processing on the migration of additives molecules, especially insecticide, within polyethylene (PE) yarns. Yarns were manufactured in the laboratory focusing on three key-steps (spinning, post-stretching and heat-setting). Influence of each step on yarn properties was investigated using tensile tests, differential scanning calorimetry and wide-angle X-ray diffraction. The post-stretching step was proved to be critical in defining yarn mechanical and structural properties. Although a first orientation of polyethylene crystals was induced during spinning, the optimal orientation was only reached by post-stretching. The results also showed that the heat-setting did not significantly change these properties. The presence of additives crystals at the yarn surface was evidenced by scanning-electron microscopy. These studies performed at each yarn production step allowed a detailed analysis of the additives' ability to migrate. It is concluded that while post-stretching decreased the migration rate, heat-setting seems to boost this migration.

  9. Formation of Organic Molecules and Water in Warm Disk Atmospheres

    NASA Astrophysics Data System (ADS)

    Najita, Joan R.; Ádámkovics, Máté; Glassgold, Alfred E.

    2011-12-01

    Observations from Spitzer and ground-based infrared spectroscopy reveal significant diversity in the molecular emission from the inner few AU of T Tauri disks. We explore theoretically the possible origin of this diversity by expanding on our earlier thermal-chemical model of disk atmospheres. We consider how variations in grain settling, X-ray irradiation, accretion-related mechanical heating, and the oxygen-to-carbon ratio can affect the thermal and chemical properties of the atmosphere at 0.25-40 AU. We find that these model parameters can account for many properties of the detected molecular emission. The column density of the warm (200-2000 K) molecular atmosphere is sensitive to grain settling and the efficiency of accretion-related heating, which may account, at least in part, for the large range in molecular emission fluxes that have been observed. The dependence of the atmospheric properties on the model parameters may also help to explain trends that have been reported in the literature between molecular emission strength and mid-infrared color, stellar accretion rate, and disk mass. We discuss whether some of the differences between our model results and the observations (e.g., for water) indicate a role for vertical transport and freezeout in the disk midplane. We also discuss how planetesimal formation in the outer disk (beyond the snowline) may imprint a chemical signature on the inner few AU of the disk and speculate on possible observational tracers of this process.

  10. Adsorption of a water molecule on the MgO(100) surface as described by cluster and slab models.

    PubMed

    Karalti, Ozan; Alfè, Dario; Gillan, Michael J; Jordan, Kenneth D

    2012-06-01

    The interaction of a water molecule with the (100) surface of MgO as described by cluster models is studied using MP2, coupled MP2 (MP2C) and symmetry-adapted perturbation theory (SAPT) methods. In addition, diffusion Monte Carlo (DMC) results are presented for several slab models as well as for the smallest, 2X2 cluster model. For the 2X2 model it is found that the MP2C, DMC, and CCSD(T) methods give nearly the same potential energy curve for the water-cluster interaction, whereas the potential energy curve from the SAPT calculations differs slightly from those of the other methods. The interaction of the water molecule with the cluster models of the MgO(100) surface is weakened upon expanding the number of layers from one to two and also upon expanding the description of the layers from 2X2 to 4X4 to 6X6. The SAPT calculations reveal that both these expansions of the cluster model are accompanied by reductions in the magnitudes of the induction and dispersion constributions. The best estimate of the energy for binding an isolated water molecule to the surface obtained from the cluster model calculations is in good agreement with that obtained from the DMC calculations using a 2-layer slab model with periodic boundary conditions. PMID:22535216

  11. How small polar molecules protect membrane systems against osmotic stress: the urea-water-phospholipid system.

    PubMed

    Costa-Balogh, Fátima O; Wennerström, Håkan; Wadsö, Lars; Sparr, Emma

    2006-11-30

    We investigate how a small polar molecule, urea, can act to protect a phospholipid bilayer system against osmotic stress. Osmotic stress can be caused by a dry environment, by freezing, or by exposure to aqueous systems with high osmotic pressure due to solutes like in saline water. A large number of organisms regularly experience osmotic stress, and it is a common response to produce small polar molecules intracellularly. We have selected a ternary system of urea-water-dimyristoyl phosphatidylcholine (DMPC) as a model to investigate the molecular mechanism behind this protective effect, in this case, of urea, and we put special emphasis on the applications of urea in skin care products. Using differential scanning calorimetry, X-ray diffraction, and sorption microbalance measurements, we studied the phase behavior of lipid systems exposed to an excess of solvent of varying compositions, as well as lipid systems exposed to water at reduced relative humidities. From this, we have arrived at a rather detailed thermodynamic characterization. The basic findings are as follows: (i) In excess solvent, the thermally induced lipid phase transitions are only marginally dependent on the urea content, with the exception being that the P(beta) phase is not observed in the presence of urea. (ii) For lipid systems with limited access to solvent, the phase behavior is basically determined by the amount (volume) of solvent irrespective of the urea content. (iii) The presence of urea has the effect of retaining the liquid crystalline phase at relative humidities down to 64% (at 27 degrees C), whereas, in the absence of urea, the transition to the gel phase occurs already at a relative humidity of 94%. This demonstrates the protective effect of urea against osmotic stress. (iv) In skin care products, urea is referred to as a moisturizer, which we find slightly misleading as it replaces the water while keeping the physical properties unaltered. (v) In other systems, urea is known to

  12. Rotation of water molecules in plastic phase at extreme conditions from first principles molecular dynamics method

    NASA Astrophysics Data System (ADS)

    Tasaka, Tomofumi; Tsumuraya, Kazuo

    2014-03-01

    Water has a variety of polymorphs in wide ranges of temperature and pressure. Ice VII phase transforms to ice X with increased pressure. However the ice VII transforms to a superionic phase at higher temperatures around 2000K and pressure 30GPa in which the protons migrate in the body centered cubic lattice of oxygens. The ice VII transforms into rotator phase (so called plastic phase at lower temperatures around 600K and 5 to 50GPa. The formation of the phase has been confirmed only with the empirical potentials, whereas the experimental confirmation has been postponed until now. The present study elucidates the mechanism of the rotation of the water molecules and the correlation between the molecules during the rotation with the first principles molecular dynamics method. The water molecules rotate around each oxygen atom to conserve the ice VII positions of the protons.

  13. Interaction of water molecules with hexagonal 2D systems. A DFT study

    NASA Astrophysics Data System (ADS)

    Rojas, Ángela; Rey, Rafael

    Over the years water sources have been contaminated with many chemical agents, becoming issues that affect health of the world population. The advances of the nanoscience and nanotechnology in the development new materials constitute an alternative for design molecular filters with great efficiencies and low cost for water treatment and purification. In the nanoscale, the process of filtration or separation of inorganic and organic pollutants from water requires to study interactions of these atoms or molecules with different nano-materials. Specifically, it is necessary to understand the role of these interactions in physical and chemical properties of the nano-materials. In this work, the main interest is to do a theoretical study of interaction between water molecules and 2D graphene-like systems, such as silicene (h-Si) or germanene (h-Ge). Using Density Functional Theory we calculate total energy curves as function of separation between of water molecules and 2D systems. Different spatial configurations of water molecules relative to 2D systems are considered. Structural relaxation effects and changes of electronic charge density also are reported. Universidad Nacional de Colombia.

  14. Solvation of a probe molecule by fluid supercooled water in a hydrogel at 200 K.

    PubMed

    Santangelo, Maria Grazia; Levantino, Matteo; Cupane, Antonio; Jeschke, Gunnar

    2008-12-11

    By combining electron paramagnetic resonance (EPR) measurements on a nitroxide probe and differential scanning calorimetry (DSC), we demonstrate existence of liquid supercooled water in a silica hydrogel with high hydration level down to temperatures of at least 198 K. Besides the major fraction of liquid supercooled water, a minor fraction crystallizes at about 236 K during cooling and melts at 246 K during heating. The liquid domains are of sufficient size to solvate the nearly spherical paramagnetic probe molecule TEMPO with a diameter of about 6 A. Analysis of EPR spectra provides the rotational correlation time of the probe that is further used to compare the viscosity of the supercooled water with the one of bulk water. In the temperature interval investigated, the supercooled water behaves as a fragile liquid and eventually solidifies at 120 K to a glass that incorporates the probe molecules. PMID:19053683

  15. Migration of additive molecules in a polymer filament obtained by melt spinning: Influence of the fiber processing steps

    SciTech Connect

    Gesta, E.; Skovmand, O.; Espuche, E. Fulchiron, R.

    2015-12-17

    The purpose of this study is to understand the influence of the yarn processing on the migration of additives molecules, especially insecticide, within polyethylene (PE) yarns. Yarns were manufactured in the laboratory focusing on three key-steps (spinning, post-stretching and heat-setting). Influence of each step on yarn properties was investigated using tensile tests, differential scanning calorimetry and wide-angle X-ray diffraction. The post-stretching step was proved to be critical in defining yarn mechanical and structural properties. Although a first orientation of polyethylene crystals was induced during spinning, the optimal orientation was only reached by post-stretching. The results also showed that the heat-setting did not significantly change these properties. The presence of additives crystals at the yarn surface was evidenced by scanning-electron microscopy. These studies performed at each yarn production step allowed a detailed analysis of the additives’ ability to migrate. It is concluded that while post-stretching decreased the migration rate, heat-setting seems to boost this migration.

  16. Characterization of Mechanics and Cytocompatibility of Fibrin-Genipin Annulus Fibrosus Sealant with the Addition of Cell Adhesion Molecules

    PubMed Central

    Guterl, Clare C.; Torre, Olivia M.; Purmessur, Devina; Dave, Khyati; Likhitpanichkul, Morakot; Hecht, Andrew C.; Nicoll, Steven B.

    2014-01-01

    There is an unmet clinical need for a biomaterial sealant capable of repairing small annulus fibrosus (AF) defects. Causes of these defects include painful intervertebral disc herniations, microdiscectomy procedures, morbidity associated with needle puncture injury from discography, and future nucleus replacement procedures. This study describes the enhancements of a fibrin gel through genipin crosslinking (FibGen) and the addition of the cell adhesion molecules (CAMs), fibronectin and collagen. The gel's performance as a potential AF sealant is assessed using a series of in vitro tests. FibGen gels with CAMs had equivalent adhesive strength, gene expression, cytomorphology, and cell proliferation as fibrin alone. However, FibGen gels had enhanced material behaviors that were tunable to higher shear stiffness values and approximated human annulus tissue as compared with fibrin alone, were more dimensionally stable, and had a slower in vitro degradation rate. Cytomorphology of human AF cells cultured on FibGen gels exhibited increased elongation compared with fibrin alone, and the addition of CAMs to FibGen did not significantly affect elongation. This FibGen gel offers the promise of being used as a sealant material to repair small AF defects or to be used in combination with other biomaterials as an adhesive for larger defects. PMID:24684314

  17. Crystallization of thin water films on graphite: Effects of n-hexane, formaldehyde, acetone, and methanol additives

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2015-12-01

    Interactions of molecular additives with amorphous solid water have been investigated using time-of-flight secondary ion mass spectrometry and temperature programmed desorption. The crystallization temperature of water on a clean graphite substrate decreases from the bulk value of 160 K to 150 K when water deposition temperature increases from 20 K to 100 K. This phenomenon is induced by the formation of a specifically oriented water layer at the interface, as evidenced by that a submonolayer of n-hexane adspecies on graphite quenches this behavior. Thermal desorption spectra of additives reflect their hydration forms. The n-hexane molecules are trapped in the interior of a porous water film via hydrophobic hydration and released explosively during crystallization. The thermal desorption spectra of methanol resemble those of water from multilayer films because methanol can enter the hydrogen-bond network of water via hydrophilic hydration. The hydration of formaldehyde is hydrophobic in nature despite the presence of the polar carbonyl group. Features of both hydrophilic and hydrophobic hydrations are identifiable in acetone-water interactions; the branching ratio depends on the water preparation method and substrate.

  18. Shear-stress-induced structural arrangement of water molecules in nanoscale Couette flow with slipping at wall boundary

    SciTech Connect

    Lin, Jau-Wen

    2014-08-07

    This study investigated the structuring of water molecules in a nanoscale Couette flow with the upper plate subjected to lateral forces with various magnitudes and water slipping against a metal wall. It was found that when the upper plate is subjected to a force, the water body deforms into a parallelepiped. Water molecules in the channel are then gradually arranged into lattice positions, creating a layered structure. The structural arrangement of water molecules is caused by the water molecules accommodating themselves to the increase in energy under the application of a lateral force on the moving plate. The ordering arrangement of water molecules increases the rotational degree of freedom, allowing the molecules to increase their Coulomb potential energy through polar rotation that accounts for the energy input through the upper plate. With a force continuously applied to the upper plate, the water molecules in contact with the upper plate move forward until slip between the water and upper plate occurs. The relation between the structural arrangement of water molecules, slip at the wall, and the shear force is studied. The relation between the slip and the locking/unlocking of water molecules to metal atoms is also studied.

  19. Dynamics of water molecules adsorbed by silica and resin SGK-7

    NASA Astrophysics Data System (ADS)

    Lisichkin, Yu. V.; Sakharova, L. A.; Tumanov, A. A.

    2014-01-01

    This paper has presented neutron spectroscopy data on the dynamics of light water molecules adsorbed in the cation exchanger (ion-exchange resin) SGK-7 and on the surface of aerosils (highly dispersed pyrogenic silica) with different levels of hydration. The measurements have been performed on a DIN-2PI spectrometer (Frank Laboratory of Neutron Physics of the Joint Institute for Nuclear Research, Dubna, Russia). The characteristics of the diffusive and vibrational motions of adsorbed water molecules have been determined from the experimental neutron scattering spectra. The data obtained in the quasi-elastic neutron scattering region have been analyzed using a model accounting for the effects of restricted translational and rotational diffusion. The results have demonstrated a significant decrease in the diffusion mobility of adsorbed water molecules as compared to conventional (bulk) water. In particular, the self-diffusion coefficient decreases several times, and the diffusion rate is the lower, the smaller is the thickness of the hydration layer. The dependences of the intensity and half-width of the quasi-elastic scattering peak on the magnitude of the neutron momentum transfer q in the scattering process exhibit a nonmonotonic character. This indicates manifestation of the effects of restricted translational diffusion, rotational diffusion, and jump diffusion. The partial distributions of vibrational frequencies of hydrogen atoms of water molecules adsorbed by the cation exchanger and aerosils have been obtained from the inelastic neutron scattering data.

  20. Ion hydration and associated defects in hydrogen bond network of water: Observation of reorientationally slow water molecules beyond first hydration shell in aqueous solutions of MgCl 2

    NASA Astrophysics Data System (ADS)

    Baul, Upayan; Vemparala, Satyavani

    2015-01-01

    Effects of the presence of ions, at moderate to high concentrations, on dynamical properties of water molecules are investigated through classical molecular dynamics simulations using two well-known nonpolarizable water models. Simulations reveal that the presence of magnesium chloride (MgCl2) induces perturbations in the hydrogen bond network of water leading to the formation of bulklike domains with ``defect sites'' on boundaries of such domains: water molecules at such defect sites have less number of hydrogen bonds than those in bulk water. Reorientational autocorrelation functions for dipole vectors of such defect water molecules are computed at different concentrations of ions and compared with system of pure water. Earlier experimental and simulation studies indicate significant differences in reorientational dynamics for water molecules in the first hydration shell of many dissolved ions. Results of this study suggest that defect water molecules, which are beyond the first hydration shells of ions, also experience significant slowing of reorientation times as a function of concentration in the case of MgCl2. However, addition of cesium chloride (CsCl) to water does not perturb the hydrogen bond network of water significantly even at higher concentrations. This difference in behavior between MgCl2 and CsCl is consistent with the well-known Hofmeister series.

  1. Local lateral environment of the molecules at the surface of DMSO-water mixtures.

    PubMed

    Fábián, Balázs; Idrissi, Abdenacer; Marekha, Bogdan; Jedlovszky, Pál

    2016-10-12

    Molecular dynamics simulations of the liquid-vapour interface of dimethyl sulphoxide (DMSO)-water mixtures of 11 different compositions, including two neat systems are performed on the canonical (N, V, T) ensemble at 298 K. The molecules constituting the surface layer of these systems are selected by means of the identification of the truly interfacial molecules (ITIM) method, and their local lateral environment at the liquid surface is investigated by performing Voronoi analysis. The obtained results reveal that both molecules prefer to be in a mixed local environment, consisting of both kinds of molecules, at the liquid surface, and this preference is even stronger here than in the bulk liquid phase. Neat-like patches, in which a molecule is surrounded by like neighbours, are not found. However, vacancies that are surrounded solely by water molecules are observed at the liquid surface. Our results show that strongly hydrogen bonded DMSO·H2O complexes, known to exist in the bulk phase of these mixtures, are absent from the liquid surface. PMID:27506283

  2. Vigorous Mold Growth in Soils After Addition of Water-Insoluble Fatty Substances

    PubMed Central

    Krause, Frank P.; Lange, Willy

    1965-01-01

    Various water-insoluble fatty compounds, when added to soil in finely divided form, will support as high-caloric nutrients a visible, vigorous growth of the molds, Fusarium solani Mart., F. diversisporum Sherb., and F. equiseti. n-Paraffins and olefins are most effective, because the effect of additives is reduced to the extent that oxygen atoms are introduced into the molecule. n-Fatty alcohols support growth in soil almost as well as the paraffins; however, growth is reduced when branched-chain compounds are added as nutrients. Compounds that will support mold growth when added to air-dried soil as finely powdered solids will not do so when incorporated at temperatures above their melting point, but will produce dense growth when applied to wet soil in this form. Mold growth is correlated with degradation of fatty matter. The rate of degradation is controlled by the availability of water, oxygen, and the basic inorganic nutrients. Images Fig. 1 Fig. 2 PMID:14325872

  3. DFTr optimization and DFTr-MD studies of glucose, ten explicit water molecules enclosed by an implicit solvent, COSMO

    Technology Transfer Automated Retrieval System (TEKTRAN)

    DFTr optimization studies are carried out on alpha/beta-glucose surrounded by ten explicit water molecules and the glucose/water super-molecule completely enclosed by an implicit solvation model, COSMO. Twenty one starting configurations of the explicit waters were first optimized empirically with t...

  4. Chemically accurate energy barriers of small gas molecules moving through hexagonal water rings.

    PubMed

    Hjertenæs, Eirik; Trinh, Thuat T; Koch, Henrik

    2016-07-21

    We present chemically accurate potential energy curves of CH4, CO2 and H2 moving through hexagonal water rings, calculated by CCSD(T)/aug-cc-pVTZ with counterpoise correction. The barriers are extracted from a potential energy surface obtained by allowing the water ring to expand while the gas molecule diffuses through. State-of-the-art XC-functionals are evaluated against the CCSD(T) potential energy surface. PMID:27345929

  5. Theoretical study of the decomposition of formamide in the presence of water molecules.

    PubMed

    Nguyen, Vinh Son; Orlando, Thomas M; Leszczynski, Jerzy; Nguyen, Minh Tho

    2013-03-28

    Formamide (NH2CHO, FM) has been considered an active key precursor in prebiotic chemistry on early Earth. Under certain conditions such as dry lagoons, FM can decompose to produce reactants that lead to formation of more complex biomolecules. Specifically, FM decomposition follows many reactive channels producing small molecules such as H2, CO, H2O, HCN, HNC, NH3, and HNCO with comparable energy barriers in the range of 73-82 kcal/mol. Due to the likely presence of water on prebiotic Earth and the intrinsic presence of water following FM decomposition, we explore the effects of water oligomers, (H2O)n with n = 1-3, on its dehydration, dehydrogenation, and decarbonylation reactions using quantum chemical computations. Geometries are optimized using MP2/aug-cc-pVxZ calculations (x = D,T), and relative energies are evaluated using coupled-cluster theory CCSD(T) with the aug-cc-pVxZ basis sets (x = D, T, Q). Where possible the coupled-cluster energies are extrapolated to the complete basis set limit (CBS). Water classically acts as an efficient bifunctional catalyst for decomposition. With the presence of one water molecule, the dehydration pathway leading to HCN is favored. When two and three water molecules are involved, dehydration remains energetically favored over other channels and attains an energy barrier of ~30 kcal/mol. PMID:23461351

  6. Size, separation, structural order, and mass density of molecules packing in water and ice

    PubMed Central

    Huang, Yongli; Zhang, Xi; Ma, Zengsheng; Li, Wen; Zhou, Yichun; Zhou, Ji; Zheng, Weitao; Sun, Chang Q.

    2013-01-01

    The structural symmetry and molecular separation in water and ice remain uncertain. We present herewith a solution to unifying the density, the structure order and symmetry, the size (H-O length dH), and the separation (dOO = dL + dH or the O:H length dL) of molecules packing in water and ice in terms of statistic mean. This solution reconciles: i) the dL and the dH symmetrization of the O:H-O bond in compressed ice, ii) the dOO relaxation of cooling water and ice and, iii) the dOO expansion of a dimer and between molecules at water surface. With any one of the dOO, the density ρ(g·cm−3), the dL, and the dH, as a known input, one can resolve the rest quantities using this solution that is probing conditions or methods independent. We clarified that: i) liquid water prefers statistically the mono-phase of tetrahedrally-coordinated structure with fluctuation, ii) the low-density phase (supersolid phase as it is strongly polarized with even lower density) exists only in regions consisting molecules with fewer than four neighbors and, iii) repulsion between electron pairs on adjacent oxygen atoms dictates the cooperative relaxation of the segmented O:H-O bond, which is responsible for the performance of water and ice. PMID:24141643

  7. Temperature dependence of the transport of single-file water molecules through a hydrophobic channel.

    PubMed

    Su, Jiaye; Yang, Keda

    2016-05-01

    Although great effort has been made on the transport properties of water molecules through nanometer channels, our understanding on the effect of some basic parameters are still rather poor. In this article, we use molecular dynamics simulations to study the temperature effect on the transport of single-file water molecules through a hydrophobic channel. Of particular interest is that the water flow and average translocation time both exhibit exponential relations with the temperature. Based on the continuous-time random-walk model and Arrhenius equation, we explore some new physical insights on these exponential behaviors. With the increase of temperature, the water dipoles flip more frequently, since the estimated flipping barrier is less than 2 kB T. Specifically, the flipping frequency also shows an exponential relation with the temperature. Furthermore, the water-water interaction and water occupancy demonstrate linear relations with the temperature, and the water density profiles along the channel axis can be slightly affected by the temperature. These results not only enhance our knowledge about the temperature effect on the single-file water transport, but also have potential implications for the design of controllable nanofluidic machines. © 2016 Wiley Periodicals, Inc. PMID:26777386

  8. The Dynamics, energetics and selectivity of water chain-containing aquapores created by the self-assembly of aquafoldamer molecules.

    PubMed

    Ma, Wenliang; Wang, Chunquan; Li, Juntong; Zhang, Kun; Lu, Yu-Jing; Huo, Yanping; Zeng, Huaqiang

    2015-11-21

    Through a series of crystallographic snapshots of water chain-containing aquapores formed from numerous one-dimensionally aligned aquafoldamer molecules 2, we demonstrated here (1) a preferential recognition of the water molecules over methanol molecules by the assembled cavity-containing aquapores with a selectivity factor of at least 17.7, (2) the dynamic nature of the water chains and the aquapores in response to varying external stimuli that exert the most influential impact on the aromatic π-π stacking in the aquapores and (3) the aquapores undergo a significant rearrangement in order to accommodate water, rather than methanol, molecules. PMID:26381358

  9. Computing the energy of a water molecule using multideterminants: A simple, efficient algorithm

    SciTech Connect

    Clark, Bryan K.; Morales, Miguel A; Mcminis, Jeremy; Kim, Jeongnim; Scuseria, Gustavo E

    2011-01-01

    Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater- Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater deter- minants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily par- allelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Addition- ally, we implement this method and use it to compute the ground state energy of a water molecule. 2011 American Institute of Physics. [doi:10.1063/1.3665391

  10. Density Functional Theory Study of the Complexation of the Uranyl Dication with Anionic Phosphate Ligands with and without Water Molecules

    SciTech Connect

    Jackson, Virgil E.; Gutowski, Keith E.; Dixon, David A.

    2013-08-01

    The structures, vibrational frequencies and energetics of anhydrous and hydrated complexes of UO2 2+ with the phosphate anions H2PO4 -, HPO4 2-, and PO4 3- were predicted at the density functional theory (DFT) and MP2 molecular orbital theory levels as isolated gas phase species and in aqueous solution by using self-consistent reaction field (SCRF) calculations with different solvation models. The geometries and vibrational frequencies of the major binding modes for these complexes are compared to experiment where possible and good agreement is found. The uranyl moiety is nonlinear in many of the complexes, and the coordination number (CN) 5 in the equatorial plane is the predominant binding motif. The phosphates are found to bind in both monodentate and bidentate binding modes depending on the charge and the number of water molecules. The SCRF calculations were done with a variety of approaches, and different SCRF approaches were found to be optimal for different reaction types. The acidities of HxPO4 3-x in HxPO4 3-x(H2O)4, x = 0-3 complexes were calculated with different SCRF models and compared to experiment. Phosphate anions can displace water molecules from the first solvation shell at the uranyl exothermically. The addition of water molecules can cause the bonding of H2PO4 - and HPO4 2- to change from bidentate to monodentate exothermically while maintaining CN 5. The addition of water can generate monodentate structures capable of cross-linking to other uranyl phosphates to form the types of structures found in the solid state. [UO2(HPO4)(H2O)3] is predicted to be a strong base in the gas phase and in aqueous solution. It is predicted to be a much weaker acid than H3PO4 in the gas phase and in solution.

  11. Trapped water molecule in the charge separation of a bacterial reaction center.

    PubMed

    Ivashin, Nikolai; Larsson, Sven

    2008-09-25

    Low-frequency oscillations in the absorption spectrum at 1020 nm, connected to the primary charge separation process in Rhodobacter sphaeroides, have been shown by Yakovlev et al. to be caused by rotational motion of an interstitial water molecule called "water-A". The same water molecule was shown by Potter et al. to increase the rate of charge separation by a factor of 8. We have carried out geometry optimization of water-A and its nearest atoms in the protein pocket, using density functional theory (DFT). There are strong hydrogen bonds to the axial imidazol group of the B part of the special pair (P=PAPB) and to the keto carbonyl group of ring V of the accessory chlorophyll (BA). Rotation of water-A is thus impossible in the electronic ground state. We have tried to support our speculations on other possible mechanisms by calculations. The P(+)BA(-) charge transfer state is stabilized by proton transfer from water-A and simultaneous proton transfer from the axial group of PB to water-A. After double proton transfer the hydrogen bond to the keto group disappears whereby a possibility opens up for almost free water rotation. The results therefore would explain the 32 cm(-1) oscillation of Yakovlev et al. The proposed mechanism assumes, however, that the general assumption that the activation energy disappears in the primary charge separation of bacterial photosynthesis, holds also for this special case. PMID:18761433

  12. Effects of water molecules on the chemical stability of MAGeI3 perovskite explored from a theoretical viewpoint.

    PubMed

    Sun, Ping-Ping; Chi, Wei-Jie; Li, Ze-Sheng

    2016-09-21

    The stability of perovskite in humid environments is one of the biggest obstacles for its potential applications in light harvesting and electroluminescent displays. Understanding the detailed degradation mechanism of MAGeI3 in moisture is a critical way to explore the practicability of MAGeI3 perovskite. In this study, we report a quantitative and systematic investigation of MAGeI3 degradation processes by exploring the effects of H2O molecules on the structural and electronic properties of the most stable MAGeI3(101) surface under various simulated environmental conditions with different water coverage based on first-principles calculations. The results show that H2O molecules can easily diffuse into the inner side of the perovskite and gradually corrode the structure as the number of H2O molecules increases. As a result of the interactions between perovskite and H2O molecules, a hydrated intermediate will be generated as the first step in the degradation mechanism; the perovskite will further decompose to HI and GeI2. In terms of one MAGeI3 molecule, it will be dissociated completely to GeI2 as a result of hydrolysis reactions with a minimum of 4H2O molecules. In addition, the degradation of the perovskite will also affect the electronic structure, causing a decrease in optical absorption across the visible region of the spectrum and a distinct deformation change in the crystal structure of the material. These findings further illustrate the degradation of the hydrolysis process of MAGeI3 perovskite in humid environments, which should be helpful to inspire experimentalists to take action to prolong the lifetimes of perovskite solar cells to achieve high conversion efficiency in their applications. PMID:27539944

  13. Trapping and desorption of complex organic molecules in water at 20 K

    NASA Astrophysics Data System (ADS)

    Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.; Viti, Serena; Slater, Ben; Brown, Wendy A.

    2015-10-01

    The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

  14. Disintegration of water molecules in a steam-plasma torch powered by microwaves

    SciTech Connect

    Uhm, Han S.; Kim, Jong H.; Hong, Yong C.

    2007-07-15

    A pure steam torch is generated by making use of 2.45 GHz microwave. Steam from a steam generator enters the discharge tube as a swirl gas at a temperature higher than 150 deg. C. This steam becomes a working gas and produces a stable steam torch. The torch volume is almost linearly proportional to the microwave power. The temperature of the torch flame is measured by making use of optical spectroscopy and a thermocouple device. Two distinctive regions are exhibited, a bright, whitish region of a high-temperature zone and a reddish, dimmer region of a relatively low-temperature zone. The bright, whitish region is a typical torch based on plasma species and the reddish, dimmer region is hydrogen burning in oxygen. Study of water molecule disintegration and gas temperature effects on the molecular fraction characteristics in steam-plasma of a microwave plasma torch at the atmospheric pressure is carried out. An analytical investigation of water disintegration indicates that a substantial fraction of water molecules disintegrate and form other compounds at high temperatures in the steam-plasma torch. Emission profiles of the hydroxide radical and water molecules confirm the theoretical predictions of water disintegration in the torch.

  15. Cardioprotective actions by a water-soluble carbon monoxide-releasing molecule.

    PubMed

    Clark, James E; Naughton, Patrick; Shurey, Sandra; Green, Colin J; Johnson, Tony R; Mann, Brian E; Foresti, Roberta; Motterlini, Roberto

    2003-07-25

    Carbon monoxide, which is generated in mammals during the degradation of heme by the enzyme heme oxygenase, is an important signaling mediator. Transition metal carbonyls have been recently shown to function as carbon monoxide-releasing molecules (CO-RMs) and to elicit distinct pharmacological activities in biological systems. In the present study, we report that a water-soluble form of CO-RM promotes cardioprotection in vitro and in vivo. Specifically, we found that tricarbonylchloro(glycinato)ruthenium(II) (CORM-3) is stable in water at acidic pH but in physiological buffers rapidly liberates CO in solution. Cardiac cells pretreated with CORM-3 (10 to 50 micromol/L) become more resistant to the damage caused by hypoxia-reoxygenation and oxidative stress. In addition, isolated hearts reperfused in the presence of CORM-3 (10 micromol/L) after an ischemic event displayed a significant recovery in myocardial performance and a marked and significant reduction in cardiac muscle damage and infarct size. The cardioprotective effects mediated by CORM-3 in cardiac cells and isolated hearts were totally abolished by 5-hydroxydecanoic acid, an inhibitor of mitochondrial ATP-dependent potassium channels. Predictably, cardioprotection is lost when CORM-3 is replaced by an inactive form (iCORM-3) that is incapable of liberating CO. Using a model of cardiac allograft rejection in mice, we also found that treatment of recipients with CORM-3 but not iCORM-3 considerably prolonged the survival rate of transplanted hearts. These data corroborate the notion that transition metal carbonyls could be used as carriers to deliver CO and highlight the bioactivity and potential therapeutic features of CO-RMs in the mitigation of cardiac dysfunction. The full text of this article is available online at http://www.circresaha.org. PMID:12842916

  16. A systematic method for studying the spatial distribution of water molecules around nucleic acid bases.

    PubMed Central

    Schneider, B; Cohen, D M; Schleifer, L; Srinivasan, A R; Olson, W K; Berman, H M

    1993-01-01

    A new method to analyze the distribution of water molecules around the bases in DNA is presented. This method relies on the notion of a "hydrated building block," which represents the joint observed hydration around all bases of a particular type, in structures of a particular conformation type. The hydrated building blocks were constructed using atomic coordinates from 40 structures contained in the Nucleic Acid Database. Pseudoelectron densities were calculated for water molecules in each hydrated building block using standard crystallographic procedures. The electron densities were fitted to obtain "average building blocks," which represent bases with waters only at average or probable positions. Both types of building blocks were used to construct models of hydrated DNA oligomers. The essential features of the solvent structure around d(CGCGAATTCGCG)2 in the B form and d(CGCGCG)2 in the Z form were reproduced. Images FIGURE 4 FIGURE 5 PMID:8312469

  17. Monte Carlo simulation of several biologically relevant molecules and zwitterions in water

    NASA Astrophysics Data System (ADS)

    Patuwo, Michael Y.; Bettens, Ryan P. A.

    2012-02-01

    In this work, we study the hydration free energies of butane, zwitterionic alanine, valine, serine, threonine, and asparagine, and two neuraminidase inhibitors by means of Monte Carlo (MC) simulation. The solute molecule, represented in the form of distributed multipoles and modified 6-12 potential, was varied from a non-interacting 'ghost' molecule to its full potential functions in TIP4P water. Intermediate systems with soft-core solute-solvent interaction potentials are simulated separately and then subjected to Bennett's Acceptance ratio (BAR) for the free energy calculation. Hydration shells surrounding the solute particles were used to assess the quality of potential functions.

  18. Structure detection in a libration vibration spectrum of water molecules by methods of nonlinear optics

    SciTech Connect

    Babenko, V A; Sychev, Andrei A

    2012-09-30

    In exciting water possessing an enhanced optical strength by the radiation of a YAG : Nd{sup 3+} laser with 20-ps pulses, nonlinear scattering of light was detected in the frequency range of the optical second harmonic. A relationship was established of the signal of the nonlinear scattering with a stimulated Raman scattering (SRS) of the laser radiation in water. Near the SRS threshold, the structure was observed in the spectrum of nonlinear scattering, which is related to intermolecular libration vibrations of water molecules. (laser applications and other topics in quantum electronics)

  19. Fast rotational motion of water molecules increases ordering of hydrophobes in solutions and may cause hydrophobic chains to collapse

    NASA Astrophysics Data System (ADS)

    Mohorič, Tomaž; Bren, Urban; Vlachy, Vojko

    2015-12-01

    Using the molecular dynamics simulations with separate thermostats for translational and rotational degrees of freedom, we investigate the effects of water's rotational motion on the interaction among Lennard-Jones solutes. The situation with rotational temperature higher than the translational one (TR > TT) is mimicking the effects of microwaves on model solutions. Molecular dynamics simulations suggest that solutions of Lennard-Jones solutes become increasingly more structured with the rise in TR, while keeping the TT constant. This is evidenced by an increase of the first and the second peak of the solute-solute radial distribution function. In addition, the first peak moves toward slightly larger distances; the effect seems to be caused by the destabilization of water molecules in the first hydration shell around hydrophobic solutes. More evidence of strong effects of the rotationally excited water is provided by the simulations of short hydrophobic polymers, which upon an increase in TR assume more compact conformations. In these simulations, we see the re-distribution of water molecules, which escape from hydrophobic "pockets" to better solvate the solvent exposed monomers.

  20. Effects of water molecules on tribological behavior and property measurements in nano-indentation processes - a numerical analysis

    PubMed Central

    2013-01-01

    Nano/micro-manufacturing under wet condition is an important consideration for various tool-based processes such as indentation, scratching, and machining. The existence of liquids adds complexity to the system, changes the tool/work interfacial condition, and affects material behaviors. For indentation, it may also affect material property measurements. However, little effort has been made to study this challenging issue at nano- or atomistic scale. In this study, we tackle this challenge by investigating nano-indentation processes submerged in water using the molecular dynamics (MD) simulation approach. Compared with dry indentation in which no water molecules are present, the existence of water molecules causes the increase of indentation force in initial penetration, but the decrease of indentation force in full penetration. It also reduces the sticking phenomenon between the work and tool atoms during indenter retraction, such that the indentation geometry can be better retained. Meanwhile, nano-indentation under wet condition exhibits the indentation size effect, while dry nano-indentation exhibits the reverse indentation size effect. The existence of water leads to higher computed hardness values at low indentation loads and a smaller value of Young's modulus. In addition, the friction along the tool/work interface is significantly reduced under wet indentation. PMID:24044504

  1. Fast rotational motion of water molecules increases ordering of hydrophobes in solutions and may cause hydrophobic chains to collapse.

    PubMed

    Mohorič, Tomaž; Bren, Urban; Vlachy, Vojko

    2015-12-28

    Using the molecular dynamics simulations with separate thermostats for translational and rotational degrees of freedom, we investigate the effects of water's rotational motion on the interaction among Lennard-Jones solutes. The situation with rotational temperature higher than the translational one (TR > TT) is mimicking the effects of microwaves on model solutions. Molecular dynamics simulations suggest that solutions of Lennard-Jones solutes become increasingly more structured with the rise in TR, while keeping the TT constant. This is evidenced by an increase of the first and the second peak of the solute-solute radial distribution function. In addition, the first peak moves toward slightly larger distances; the effect seems to be caused by the destabilization of water molecules in the first hydration shell around hydrophobic solutes. More evidence of strong effects of the rotationally excited water is provided by the simulations of short hydrophobic polymers, which upon an increase in TR assume more compact conformations. In these simulations, we see the re-distribution of water molecules, which escape from hydrophobic "pockets" to better solvate the solvent exposed monomers. PMID:26723695

  2. Water-inducing molecular self-assembly of amphiphilic molecules into nanofibers

    SciTech Connect

    Zhang, Weiguang; Zhao, Pusu; Song, Jie

    2011-12-15

    Graphical abstract: TPDP nanofibers with smooth surfaces can be obtained by reprecipitation method using ethanol as good solvent and water as poor solvent. In the self-assembly process, during the water adding to the amphiphilic molecules' saturated solution, the amphiphilic molecules firstly assembled into needle-like small rods. With an increase in the self-assembled time, a large number of the nanofibers are produced. The assembly behavior was revealed in the course of direct in situ monitoring of its growth with optical microscopy. Highlights: Black-Right-Pointing-Pointer 2,3,6,7-Tetramethoxy-9,10-di(4-pyridyl)-9,10-dihydroanthracen (TPDP) was synthesized. Black-Right-Pointing-Pointer TPDP nanofibers can be obtained by reprecipitation method. Black-Right-Pointing-Pointer The assembly behavior was revealed in situ monitoring with optical microscopy. -- Abstract: We present investigations on the microcosmic self-assembly process of new synthesized amphiphilic TPDP molecules. It can be seen that pure TPDP nanofibers with smooth surfaces can be obtained by reprecipitation method using ethanol as good solvent and water as poor solvent. In the self-assembly process, during the water adding to the amphiphilic molecules' saturated solution, the amphiphilic molecules firstly assembled into needle-like small rods. With an increase in the self-assembled time, a large number of the nanofibers are produced. The assembly behavior was revealed in the course of direct in situ monitoring of its growth with optical microscopy. Field emission scanning electron microscopy was adopted to characterize the morphologies of the products.

  3. Molecular mimicry of substrate oxygen atoms by water molecules in the beta-amylase active site.

    PubMed

    Pujadas, G; Palau, J

    2001-08-01

    Soybean beta-amylase (EC 3.2.1.2) has been crystallized both free and complexed with a variety of ligands. Four water molecules in the free-enzyme catalytic cleft form a multihydrogen-bond network with eight strategic residues involved in enzyme-ligand hydrogen bonds. We show here that the positions of these four water molecules are coincident with the positions of four potential oxygen atoms of the ligands within the complex. Some of these waters are displaced from the active site when the ligands bind to the enzyme. How many are displaced depends on the shape of the ligand. This means that when one of the four positions is not occupied by a ligand oxygen atom, the corresponding water remains. We studied the functional/structural role of these four waters and conclude that their presence means that the conformation of the eight side chains is fixed in all situations (free or complexed enzyme) and preserved from unwanted or forbidden conformational changes that could hamper the catalytic mechanism. The water structure at the active pocket of beta-amylase is therefore essential for providing the ligand recognition process with plasticity. It does not affect the protein active-site geometry and preserves the overall hydrogen-bonding network, irrespective of which ligand is bound to the enzyme. We also investigated whether other enzymes showed a similar role for water. Finally, we discuss the potential use of these results for predicting whether water molecules can mimic ligand atoms in the active center. PMID:11468361

  4. INTERSTELLAR ICES AS WITNESSES OF STAR FORMATION: SELECTIVE DEUTERATION OF WATER AND ORGANIC MOLECULES UNVEILED

    SciTech Connect

    Cazaux, S.; Spaans, M.; Caselli, P.

    2011-11-10

    Observations of star-forming environments revealed that the abundances of some deuterated interstellar molecules are markedly larger than the cosmic D/H ratio of 10{sup -5}. Possible reasons for this pointed to grain surface chemistry. However, organic molecules and water, which are both ice constituents, do not enjoy the same deuteration. For example, deuterated formaldehyde is very abundant in comets and star-forming regions, while deuterated water rarely is. In this paper, we explain this selective deuteration by following the formation of ices (using the rate equation method) in translucent clouds, as well as their evolution as the cloud collapses to form a star. Ices start with the deposition of gas-phase CO and O onto dust grains. While reaction of oxygen with atoms (H or D) or molecules (H{sub 2}) yields H{sub 2}O (HDO), CO only reacts with atoms (H and D) to form H{sub 2}CO (HDCO, D{sub 2}CO). As a result, the deuteration of formaldehyde is sensitive to the gas D/H ratio as the cloud undergoes gravitational collapse, while the deuteration of water strongly depends on the dust temperature at the time of ice formation. These results reproduce well the deuterium fractionation of formaldehyde observed in comets and star-forming regions and can explain the wide spread of deuterium fractionation of water observed in these environments.

  5. Bias-dependent local structure of water molecules at an electrochemical interface

    NASA Astrophysics Data System (ADS)

    Pedroza, Luana; Brandimarte, Pedro; Rocha, Alexandre R.; Fernandez-Serra, Marivi

    2015-03-01

    Following the need for new - and renewable - sources of energy worldwide, fuel cells using electrocatalysts can be thought of as a viable option. Understanding the local structure of water molecules at the interfaces of the metallic electrodes is a key problem. Notably the system is under an external potential bias, which makes the task of simulating this setup difficult. A first principle description of all components of the system is the most appropriate methodology in order to advance understanding of electrochemical processes. There, the metal is usually charged. To correctly compute the effect of an external bias potential applied to electrodes, we combine density functional theory (DFT) and non-equilibrium Green's functions methods (NEGF), with and without van der Waals interactions. In this work, we apply this methodology to study the electronic properties and forces of one water molecule and water monolayer at the interface of gold electrodes. We find that the water molecule has a different torque direction depending on the sign of the bias applied. We also show that it changes the position of the most stable configuration indicating that the external bias plays an important role in the structural properties of the interface. We acknowledge financial support from FAPESP.

  6. Grand canonical Monte Carlo simulation of the adsorption isotherms of water molecules on model soot particles

    NASA Astrophysics Data System (ADS)

    Moulin, F.; Picaud, S.; Hoang, P. N. M.; Jedlovszky, P.

    2007-10-01

    The grand canonical Monte Carlo method is used to simulate the adsorption isotherms of water molecules on different types of model soot particles. The soot particles are modeled by graphite-type layers arranged in an onionlike structure that contains randomly distributed hydrophilic sites, such as OH and COOH groups. The calculated water adsorption isotherm at 298K exhibits different characteristic shapes depending both on the type and the location of the hydrophilic sites and also on the size of the pores inside the soot particle. The different shapes of the adsorption isotherms result from different ways of water aggregation in or/and around the soot particle. The present results show the very weak influence of the OH sites on the water adsorption process when compared to the COOH sites. The results of these simulations can help in interpreting the experimental isotherms of water adsorbed on aircraft soot.

  7. Anomalous and anisotropic nanoscale diffusion of hydration water molecules in fluid lipid membranes.

    PubMed

    Toppozini, Laura; Roosen-Runge, Felix; Bewley, Robert I; Dalgliesh, Robert M; Perring, Toby; Seydel, Tilo; Glyde, Henry R; García Sakai, Victoria; Rheinstädter, Maikel C

    2015-11-14

    We have studied nanoscale diffusion of membrane hydration water in fluid-phase lipid bilayers made of 1,2-dimyristoyl-3-phosphocholine (DMPC) using incoherent quasi-elastic neutron scattering. Dynamics were fit directly in the energy domain using the Fourier transform of a stretched exponential. By using large, 2-dimensional detectors, lateral motions of water molecules and motions perpendicular to the membranes could be studied simultaneously, resulting in 2-dimensional maps of relaxation time, τ, and stretching exponent, β. We present experimental evidence for anomalous (sub-diffusive) and anisotropic diffusion of membrane hydration water molecules over nanometer distances. By combining molecular dynamics and Brownian dynamics simulations, the potential microscopic origins for the anomaly and anisotropy of hydration water were investigated. Bulk water was found to show intrinsic sub-diffusive motion at time scales of several picoseconds, likely related to caging effects. In membrane hydration water, however, the anisotropy of confinement and local dynamical environments leads to an anisotropy of relaxation times and stretched exponents, indicative of anomalous dynamics. PMID:26338138

  8. Versatile Small Molecule Motifs for Self-assembly in Water and Formation of Biofunctional Supramolecular Hydrogels

    PubMed Central

    Zhang, Ye; Kuang, Yi; Gao, Yuan; Xu, Bing

    2010-01-01

    This article introduces new structural motifs (referred as “samogen”) that serve as the building blocks of hydrogelators for molecular self-assembly in water to result in a series of supramolecular hydrogels. Using a compound that consists of two phenylalanine residues and a naphthyl group (also abbreviated as NapFF (1) in this text) as an example of the samogens, we demonstrated the ability of the samogens to convert bioactive molecules into molecular hydrogelators that self-assemble in water to result in nanofibers. By briefly summarizing the properties and applications (e.g., wound healing, drug delivery, controlling cell fate, typing bacteria, and catalysis) of these molecular hydrogelators derived from the samogens, we intend to illustrate the basic requirements and promises of the small molecule hydrogelators for applications in chemistry, materials science, and biomedicine. PMID:20608718

  9. Orientation and alignment effects in electron-induced ionization of a single oriented water molecule

    SciTech Connect

    Champion, C.; Rivarola, R. D.

    2010-10-15

    We here report a theoretical study about the orientation effect on the total ionization cross sections for a single oriented water molecule. The theoretical description of the ionization process is performed within the first Born framework with a collisional system including an initial state composed of a projectile and a water target molecule described by a plane wave and an accurate one-center molecular wave function, respectively, and a final state constituted by a slow ejected electron represented by a Coulomb wave and a scattered (fast) electron projectile described by a plane wave. Secondary electron energetic distributions as well as total cross sections are then compared for particular target configurations pointing out strong alignment and orientation effects on the description of the ionization process.

  10. Water molecule-enhanced CO{sub 2} insertion in lanthanide coordination polymers

    SciTech Connect

    Luo Liushan; Huang Xiaoyuan; Wang Ning; Wu Hongyan; Chen Wenbin; Feng Zihao; Zhu Huiping; Peng Xiaoling; Li Yongxian; Huang Ling; Yue Shantang; Liu Yingliang

    2009-08-15

    Two new lanthanide coordination polymers H{sub 2}N(CH{sub 3}){sub 2}.[Eu{sup III}{sub 2}(L{sub 1}){sub 3}(L{sub 2})] (1, L{sub 1}=isophthalic acid dianion, L{sub 2}=formic acid anion) and [La{sup III}(2,5-PDC)(L{sub 2})](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L{sub 2}) is not contained in the stating materials, but arises from the water molecule-enhanced CO{sub 2} insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks. - Graphical abstract: Two new lanthanide coordination polymers involving water molecule-enhanced CO{sub 2} insertion resulting in the formation of formic anion and dimethylammonium cation were synthesized under solvothermal conditions.

  11. Diagrammatic perturbation theory applied to the ground state of the water molecule

    NASA Technical Reports Server (NTRS)

    Silver, D. M.; Wilson, S.

    1977-01-01

    The diagrammatic many-body perturbation theory is applied to the ground state of the water molecule within the algebraic approximation. Using four different basis sets, the total energy, the equilibrium OH bond length, and the equilibrium HOH bond angle are examined. The latter is found to be a particularly sensitive test of the convergence of perturbation expansions. Certain third-order results, which incorporate all two-, three-, and four-body effects, show evidence of good convergence properties.

  12. Double ionization of single oriented water molecules by electron impact: Second-order Born description

    SciTech Connect

    Dal Cappello, C.; Champion, C.; Kada, I.; Mansouri, A.

    2011-06-15

    The double ionization of isolated water molecules fixed in space is investigated within a theoretical approach based on the second-order Born approximation. Electron angular distributions have been studied for specific kinematical conditions. The three usual mechanisms, the shake-off and the two two-step mechanisms, have been identified. A significant contribution of the two-step mechanism is clearly visible for some particular kinematics.

  13. Organic molecules and water in the planet formation region of young circumstellar disks.

    PubMed

    Carr, John S; Najita, Joan R

    2008-03-14

    The chemical composition of protoplanetary disks is expected to hold clues to the physical and chemical processes that influence the formation of planetary systems. However, characterizing the gas composition in the planet formation region of disks has been a challenge to date. We report here that the protoplanetary disk within 3 astronomical units of AA Tauri possesses a rich molecular emission spectrum in the mid-infrared, indicating a high abundance of simple organic molecules (HCN, C2H2, and CO2), water vapor, and OH. These results suggest that water is abundant throughout the inner disk and that the disk supports an active organic chemistry. PMID:18339932

  14. Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Fukutani, Katsuyuki

    2016-06-01

    Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13 K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n = 3-6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27 K yielded the formation of larger clusters, (H2O)n with n > 6 . We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

  15. Experimental Evaluation of Proposed Small-Molecule Inhibitors of Water Channel Aquaporin-1.

    PubMed

    Esteva-Font, Cristina; Jin, Byung-Ju; Lee, Sujin; Phuan, Puay-Wah; Anderson, Marc O; Verkman, A S

    2016-06-01

    The aquaporin-1 (AQP1) water channel is a potentially important drug target, as AQP1 inhibition is predicted to have therapeutic action in edema, tumor growth, glaucoma, and other conditions. Here, we measured the AQP1 inhibition efficacy of 12 putative small-molecule AQP1 inhibitors reported in six recent studies, and one AQP1 activator. Osmotic water permeability was measured by stopped-flow light scattering in human and rat erythrocytes that natively express AQP1, in hemoglobin-free membrane vesicles from rat and human erythrocytes, and in plasma membrane vesicles isolated from AQP1-transfected Chinese hamster ovary cell cultures. As a positive control, 0.3 mM HgCl2 inhibited AQP1 water permeability by >95%. We found that none of the tested compounds at 50 µM significantly inhibited or increased AQP1 water permeability in these assays. Identification of AQP1 inhibitors remains an important priority. PMID:26993802

  16. WScore: A Flexible and Accurate Treatment of Explicit Water Molecules in Ligand-Receptor Docking.

    PubMed

    Murphy, Robert B; Repasky, Matthew P; Greenwood, Jeremy R; Tubert-Brohman, Ivan; Jerome, Steven; Annabhimoju, Ramakrishna; Boyles, Nicholas A; Schmitz, Christopher D; Abel, Robert; Farid, Ramy; Friesner, Richard A

    2016-05-12

    We have developed a new methodology for protein-ligand docking and scoring, WScore, incorporating a flexible description of explicit water molecules. The locations and thermodynamics of the waters are derived from a WaterMap molecular dynamics simulation. The water structure is employed to provide an atomic level description of ligand and protein desolvation. WScore also contains a detailed model for localized ligand and protein strain energy and integrates an MM-GBSA scoring component with these terms to assess delocalized strain of the complex. Ensemble docking is used to take into account induced fit effects on the receptor conformation, and protein reorganization free energies are assigned via fitting to experimental data. The performance of the method is evaluated for pose prediction, rank ordering of self-docked complexes, and enrichment in virtual screening, using a large data set of PDB complexes and compared with the Glide SP and Glide XP models; significant improvements are obtained. PMID:27054459

  17. Ultrafast Raman-induced Kerr-effect of water: Single molecule versus collective motions

    NASA Astrophysics Data System (ADS)

    Winkler, Kathrin; Lindner, Jörg; Bürsing, Helge; Vöhringer, Peter

    2000-09-01

    The ultrafast optical Kerr-response of water and heavy water has been measured at 1 bar in the temperature range between 273 and 373 K. The nuclear Kerr response of the liquid exhibits a pronounced double exponential decay on longer time scales after dephasing of impulsively perturbed acoustic modes is completed. The time constant, τ2, characterizing the slowly decaying exponential component of the Kerr-response function is in quantitative agreement with rotational diffusion time constants of the water molecules obtained form nuclear magnetic resonance (NMR) spin-lattice relaxation rates. A detailed comparison with THz time domain spectroscopy demonstrates that the reorientational dynamics responsible for the long time tail of the Kerr response are due to single molecule as opposed to collective effects. Furthermore, a good agreement between the single molecule rotational diffusion and the Stokes-Einstein-Debye equation is found in the temperature range of thermodynamic stability of the liquid. The time constant, τ1, characterizing the fast exponential component of the Kerr-response of water is found to be in qualitative agreement with central Lorentzian linewidths obtained from frequency-domain, depolarized Raman scattering experiments. The temperature dependence of τ2 does not follow an Arrhenius-type behavior, which was previously taken as evidence for thermally activated crossing of a librational barrier with concomitant hydrogen-bond breakage. Instead, the temperature dependence of the fast relaxation time constant can be represented adequately by the Speedy-Angell relation which has been shown to accurately describe a number of transport parameters and thermodynamic properties of water.

  18. Single-Molecule Imaging of DNAs with Sticky Ends at Water/Fused Silica Interface

    SciTech Connect

    Slavica Isailovic

    2005-12-17

    Total internal reflection fluorescence microscopy (TIRFM) was used to study intermolecular interactions of DNAs with unpaired (sticky) ends of different lengths at water/fused silica interface at the single-molecule level. Evanescent field residence time, linear velocity and adsorption/desorption frequency were measured in a microchannel for individual DNA molecules from T7, Lambda, and PSP3 phages at various pH values. The longest residence times and the highest adsorption/desorption frequencies at the constant flow at pH 5.5 were found for PSP3 DNA, followed by lower values for Lambda DNA, and the lowest values for T7 DNA. Since T7, Lambda, and PSP3 DNA molecules contain none, twelve and nineteen unpaired bases, respectively, it was concluded that the affinity of DNAs for the surface increases with the length of the sticky ends. This confirms that hydrophobic and hydrogen-bonding interactions between sticky ends and fused-silica surface are driving forces for DNA adsorption at the fused-silica surface. Described single-molecule methodology and results therein can be valuable for investigation of interactions in liquid chromatography, as well as for design of DNA hybridization sensors and drug delivery systems.

  19. Atomic force microscopy study of nitrogen molecule self-assembly at the HOPG-water interface

    NASA Astrophysics Data System (ADS)

    Lu, Yi-Hsien; Yang, Chih-Wen; Hwang, Ing-Shouh

    2014-06-01

    In this work, we investigated the evolution of the graphite-water interface in a nitrogen atmosphere by using frequency-modulation atomic force microscopy (FM-AFM). A highly ordered pyrolytic graphite (HOPG) sample was immersed in pre-degassed water and subsequently placed in the nitrogen environment. The dissolved nitrogen molecules diffused in water and self-assembled into ordered row-like structural domains at the interface. Nucleation and growth processes of the domains were observed. When the coverage of the ordered structure surpassed 50%, small clusters began to appear on the ordered structure. The number density of the clusters increases as the coverage of the ordered structures increases and these clusters may hop on the ordered structures. A model is proposed to explain the evolution of the nitrogen molecule self-assembly process at the interface. The observation of nitrogen clusters may shed light on the nature and nucleation of the so-called nanobubbles at hydrophobic-water interfaces.

  20. CVRQD ab initio ground-state adiabatic potential energy surfaces for the water molecule.

    PubMed

    Barletta, Paolo; Shirin, Sergei V; Zobov, Nikolai F; Polyansky, Oleg L; Tennyson, Jonathan; Valeev, Edward F; Császár, Attila G

    2006-11-28

    The high accuracy ab initio adiabatic potential energy surfaces (PESs) of the ground electronic state of the water molecule, determined originally by Polyansky et al. [Science 299, 539 (2003)] and called CVRQD, are extended and carefully characterized and analyzed. The CVRQD potential energy surfaces are obtained from extrapolation to the complete basis set of nearly full configuration interaction valence-only electronic structure computations, augmented by core, relativistic, quantum electrodynamics, and diagonal Born-Oppenheimer corrections. We also report ab initio calculations of several quantities characterizing the CVRQD PESs, including equilibrium and vibrationally averaged (0 K) structures, harmonic and anharmonic force fields, harmonic vibrational frequencies, vibrational fundamentals, and zero-point energies. They can be considered as the best ab initio estimates of these quantities available today. Results of first-principles computations on the rovibrational energy levels of several isotopologues of the water molecule are also presented, based on the CVRQD PESs and the use of variational nuclear motion calculations employing an exact kinetic energy operator given in orthogonal internal coordinates. The variational nuclear motion calculations also include a simplified treatment of nonadiabatic effects. This sophisticated procedure to compute rovibrational energy levels reproduces all the known rovibrational levels of the water isotopologues considered, H(2) (16)O, H(2) (17)O, H(2) (18)O, and D(2) (16)O, to better than 1 cm(-1) on average. Finally, prospects for further improvement of the ground-state adiabatic ab initio PESs of water are discussed. PMID:17144700

  1. Vibrational spectra and molecular dynamics of hydrogen peroxide molecules at quartz/water interfaces

    NASA Astrophysics Data System (ADS)

    Lv, Ye-qing; Zheng, Shi-li; Wang, Shao-na; Yan, Wen-yi; Zhang, Yi; Du, Hao

    2016-06-01

    The influence of H2O2 on the water vibration at quartz interface was examined using sum-frequency generation (SFG) spectroscopy, and the effect of H2O2 concentration has been systematically studied. Further, the number density and radical distribution of water molecules, H2O2 molecules, and quartz surface silanol groups were calculated using molecular dynamics (MD) simulation to provide molecular level interpretation for the SFG spectra. It is concluded from this study that the hydrogen peroxide molecules prefers to donate H-bonds to the in-plane silanol groups rather than accepting H-bonds from out-of-plane silanol groups, as evidenced by the strengthening of the peak located at 3400 cm-1 assigned to "liquid-like" hydrogen-bonding network. The SFG results have been supported by the MD calculation results, which demonstrate that the relative intensity of the peak located at 3400 cm-1 to that of located at 3200 cm-1 increases monotonously with the increase in the number of hydrogen peroxide in the first hydration shell of silanol.

  2. Additional Reserve Recovery Using New Polymer Treatment on High Water Oil Ratio Wells in Alameda Field, Kingman County, Kansas

    SciTech Connect

    James Spillane

    2005-10-01

    The Chemical Flooding process, like a polymer treatment, as a tertiary (enhanced) oil recovery process can be a very good solution based on the condition of this field and its low cost compared to the drilling of new wells. It is an improved water flooding method in which high molecular-weight (macro-size molecules) and water-soluble polymers are added to the injection water to improve the mobility ratio by enhancing the viscosity of the water and by reducing permeability in invaded zones during the process. In other words, it can improve the sweep efficiency by reducing the water mobility. This polymer treatment can be performed on the same active oil producer well rather than on an injector well in the existence of strong water drive in the formation. Some parameters must be considered before any polymer job is performed such as: formation temperature, permeability, oil gravity and viscosity, location and formation thickness of the well, amount of remaining recoverable oil, fluid levels, well productivity, water oil ratio (WOR) and existence of water drive. This improved oil recovery technique has been used widely and has significant potential to extend reservoir life by increasing the oil production and decreasing the water cut. This new technology has the greatest potential in reservoirs that are moderately heterogeneous, contain moderately viscous oils, and have adverse water-oil mobility ratios. For example, many wells in Kansas's Arbuckle formation had similar treatments and we have seen very effective results. In addition, there were previous polymer treatments conducted by Texaco in Alameda Field on a number of wells throughout the Viola-Simpson formation in the early 70's. Most of the treatments proved to be very successful.

  3. Influence of water on the mobility of small molecules dispersed in a polymeric system.

    PubMed

    Le Meste, M; Voilley, A; Colas, B

    1991-01-01

    The rotational mobility of paramagnetic solutes dispersed in partially hydrated macromolecules (proteins, polysaccharides, synthetic polymers) was measured using Electron Spin Resonance. A critical minimum amount of water was observed to be necessary for these molecules to reach a level of mobility of the same order as in dilute solutions. This amount of water depended on the size of the diffusing solute and on the microporosity of the macromolecule. Above this critical moisture range, a progressive increase of the proportion of mobile solute occurred over a hydration range determined by the size of the diffusing solute. At the same time, the rotational diffusivity of the mobile solute increased linearly with water content. The mobilization pattern of spin-labelled side chains of caseinates was observed to be similar to that of the solute. Results are discussed with reference to free volume theory. PMID:1660672

  4. Interactions of water, methanol and diethyl ether molecules with the surface of oxidized activated carbon

    NASA Astrophysics Data System (ADS)

    Salame, Issa I.; Bandosz, Teresa J.

    Two samples of oxidized activated carbon of wood origin were used as adsorbents of water, methanol, and diethyl ether. Structural and chemical characteristics of the samples' surfaces were obtained using adsorption of nitrogen and Boehm titration. The adsorption isotherms of water and methanol were measured using a volumetric apparatus whereas the adsorption of diethyl ether was studied by means of inverse gas chromatography at finite concentration. Then the isotherms at three different temperatures were used to calculate the isosteric heats of adsorption. The results showed that the strength of interaction depends on the porosity of the sample and its surface chemistry. The effect of surface chemistry and the presence of oxygenated groups are predominant in the case of water and the least important in the case of diethyl ether. This is the result of the chemical nature of the molecules, their sizes, and the relative strengths of the dispersive interactions in small pores in comparison with hydrogen bonding to surface functional groups.

  5. Single molecule force spectroscopy by AFM indicates helical structure of poly(ethylene-glycol) in water

    NASA Astrophysics Data System (ADS)

    Oesterhelt, F.; Rief, M.; Gaub, H. E.

    1999-03-01

    We elongated individual poly(ethylene-glycol) (PEG) molecules tethered at one end to an AFM cantilever. We observed the resistive force as a function of elongation in different solvents. In all cases the molecular response was found to be fully reversible and thus in thermodynamic equilibrium. In hexadecane the stretched PEG acts like an ideal entropy spring and can be well described as a freely jointed chain. In water we observed marked deviations in the transition region from entropic to enthalpic elasticity, indicating the deformation of a supra-structure within the polymer. An analysis based on elastically coupled Markovian two-level systems agrees well with recent ab initio calculations predicting that PEG in water forms a non-planar supra-structure which is stabilized by water bridges. We obtained a binding free energy of 3.0+/-0.3 kT.

  6. Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

    USGS Publications Warehouse

    Lee, J.; Mortland, M.M.; Boyd, S.A.; Chiou, C.T.

    1989-01-01

    The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

  7. Influence of the water molecules near surface of viral protein on virus activation process

    NASA Astrophysics Data System (ADS)

    Shepelenko, S. O.; Salnikov, A. S.; Rak, S. V.; Goncharova, E. P.; Ryzhikov, A. B.

    2009-06-01

    The infection of a cell with influenza virus comprises the stages of receptor binding to the cell membrane, endocytosis of virus particle, and fusion of the virus envelope and cell endosome membrane, which is determined by the conformational changes in hemagglutinin, a virus envelope protein, caused by pH decrease within the endosome. The pH value that induces conformation rearrangements of hemagglutinin molecule considerably varies for different influenza virus strains, first and foremost, due to the differences in amino acid structure of the corresponding proteins. The main goal of this study was to construct a model making it possible to assess the critical pH value characterizing the fusogenic activity of influenza virus hemagglutinin from the data on hemagglutinin structure and experimental verification of this model. Under this model, we assume that when the electrostatic force between interacting hemagglutinin molecules in the virus envelop exceeds a certain value, the hemagglutinin HA1 subunits are arranged so that they form a cavity sufficient for penetration of water molecules. This event leads to an irreversible hydration of the inner fragments of hemagglutinin molecule in a trimer and to the completion of conformational changes. The geometry of electrostatic field in hemagglutinin trimer was calculated taking into account the polarization effects near the interface of two dielectrics, aqueous medium and protein macromolecule. The critical pH values for the conformational changes in hemagglutinin were measured by the erythrocyte hemolysis induced by influenza virus particles when decreasing pH. The critical pH value conditionally separating the pH range into the regions with and without the conformational changes was calculated for several influenza virus H1N1 and H3N2 strains based on the data on the amino acid structure of the corresponding hemagglutinin molecules. Comparison of the theoretical and experimental values of critical pH values for

  8. The Effect of Water Molecules on Mechanical Properties of Bamboo Microfibrils

    NASA Astrophysics Data System (ADS)

    Rahbar, Nima

    Bamboo fibers have higher strength-to-weight ratios than steel and concrete. The unique properties of bamboo fibers come from their natural composite structures that comprise mainly cellulose nanofibrils in a matrix of intertwined hemicellulose and lignin called lignin-carbohydrate complex (LCC). Here, we have utilized atomistic simulations to investigate the mechanical properties and mechanisms of interactions between these materials, in the presence of water molecules. Our results suggest that hemicellulose exhibits better mechanical properties and lignin shows greater tendency to adhere to cellulose nanofibrils. Consequently, the role of hemicellulose found to be enhancing the mechanical properties and lignin found to be providing the strength of bamboo fibers. The abundance of Hbonds in hemicellulose chains is responsible for improving the mechanical behavior of LCC. The strong van der Waals forces between lignin molecules and cellulose nanofibrils is responsible for higher adhesion energy between LCC/cellulose nanofibrils. We also found out that the amorphous regions of cellulose nanofibrils is the weakest interface in bamboo Microfibrils. In presence of water, the elastic modulus of lignin increases at low water content (less than 10 NSF CAREER Grant No. 1261284.

  9. Test conditions greatly influence permeation of water soluble molecules through the intestinal mucosa: need for standardisation.

    PubMed Central

    Peeters, M; Hiele, M; Ghoos, Y; Huysmans, V; Geboes, K; Vantrappen, G; Rutgeerts, P

    1994-01-01

    Permeability tests are widely used to investigate the pathogenesis of various gastrointestinal diseases including coeliac disease, infectious diarrhoea, and inflammatory bowel disease. In Crohn's disease they are used as activity parameters by some investigators. Lack of standardisation, however, makes it very difficult to compare data reported in different studies. The aim of this study was to gather permeation data in well controlled test conditions to standardise the methods. Nine healthy volunteers each received five consecutive permeability tests by mouth using polyethylene glycol-400 (PEG-400) and 51Cr-EDTA as probe molecules. The probes were dissolved in water, a glucose solution, a starch solution, a hyperosmolar lactulose-mannitol solution, and a liquid meal. A significantly decreased permeation for both probes was found when given with the hyperosmolar solution. The 51Cr-EDTA permeation was also decreased with water. The permeability index, 51Cr-EDTA/PEG-400, corrected for influencing factors, confirmed that the lactulose-mannitol solution and plain water yield lower values of macro-molecule permeation than starch, glucose or liquid meal. Hyperosmolarity was clearly accompanied by a decrease in permeability probably caused by reversed solvent drag. Interindividual variability of probe permeation and permeability index is very low with a standard liquid meal. It is proposed that for permeability studies a standard liquid meal is always used. PMID:7959195

  10. Test conditions greatly influence permeation of water soluble molecules through the intestinal mucosa: need for standardisation.

    PubMed

    Peeters, M; Hiele, M; Ghoos, Y; Huysmans, V; Geboes, K; Vantrappen, G; Rutgeerts, P

    1994-10-01

    Permeability tests are widely used to investigate the pathogenesis of various gastrointestinal diseases including coeliac disease, infectious diarrhoea, and inflammatory bowel disease. In Crohn's disease they are used as activity parameters by some investigators. Lack of standardisation, however, makes it very difficult to compare data reported in different studies. The aim of this study was to gather permeation data in well controlled test conditions to standardise the methods. Nine healthy volunteers each received five consecutive permeability tests by mouth using polyethylene glycol-400 (PEG-400) and 51Cr-EDTA as probe molecules. The probes were dissolved in water, a glucose solution, a starch solution, a hyperosmolar lactulose-mannitol solution, and a liquid meal. A significantly decreased permeation for both probes was found when given with the hyperosmolar solution. The 51Cr-EDTA permeation was also decreased with water. The permeability index, 51Cr-EDTA/PEG-400, corrected for influencing factors, confirmed that the lactulose-mannitol solution and plain water yield lower values of macro-molecule permeation than starch, glucose or liquid meal. Hyperosmolarity was clearly accompanied by a decrease in permeability probably caused by reversed solvent drag. Interindividual variability of probe permeation and permeability index is very low with a standard liquid meal. It is proposed that for permeability studies a standard liquid meal is always used. PMID:7959195

  11. Intramolecular cyclization of aspartic acid residues assisted by three water molecules: a density functional theory study

    NASA Astrophysics Data System (ADS)

    Takahashi, Ohgi; Kirikoshi, Ryota

    2014-01-01

    Aspartic acid (Asp) residues in peptides and proteins (l-Asp) are known to undergo spontaneous nonenzymatic reactions to form l-β-Asp, d-Asp, and d-β-Asp residues. The formation of these abnormal Asp residues in proteins may affect their three-dimensional structures and hence their properties and functions. Indeed, the reactions have been thought to contribute to aging and pathologies. Most of the above reactions of the l-Asp residues proceed via a cyclic succinimide intermediate. In this paper, a novel three-water-assisted mechanism is proposed for cyclization of an Asp residue (forming a gem-diol precursor of the succinimide) by the B3LYP/6-31 + G(d,p) density functional theory calculations carried out for an Asp-containing model compound (Ace-Asp-Nme, where Ace = acetyl and Nme = NHCH3). The three water molecules act as catalysts by mediating ‘long-range’ proton transfers. In the proposed mechanism, the amide group on the C-terminal side of the Asp residue is first converted to the tautomeric iminol form (iminolization). Then, reorientation of a water molecule and a conformational change occur successively, followed by the nucleophilic attack of the iminol nitrogen on the carboxyl carbon of the Asp side chain to form the gem-diol species. A satisfactory agreement was obtained between the calculated and experimental energetics.

  12. Thermodynamic properties of water molecules in the presence of cosolute depend on DNA structure: a study using grid inhomogeneous solvation theory.

    PubMed

    Nakano, Miki; Tateishi-Karimata, Hisae; Tanaka, Shigenori; Tama, Florence; Miyashita, Osamu; Nakano, Shu-Ichi; Sugimoto, Naoki

    2015-12-01

    In conditions that mimic those of the living cell, where various biomolecules and other components are present, DNA strands can adopt many structures in addition to the canonical B-form duplex. Previous studies in the presence of cosolutes that induce molecular crowding showed that thermal stabilities of DNA structures are associated with the properties of the water molecules around the DNAs. To understand how cosolutes, such as ethylene glycol, affect the thermal stability of DNA structures, we investigated the thermodynamic properties of water molecules around a hairpin duplex and a G-quadruplex using grid inhomogeneous solvation theory (GIST) with or without cosolutes. Our analysis indicated that (i) cosolutes increased the free energy of water molecules around DNA by disrupting water-water interactions, (ii) ethylene glycol more effectively disrupted water-water interactions around Watson-Crick base pairs than those around G-quartets or non-paired bases, (iii) due to the negative electrostatic potential there was a thicker hydration shell around G-quartets than around Watson-Crick-paired bases. Our findings suggest that the thermal stability of the hydration shell around DNAs is one factor that affects the thermal stabilities of DNA structures under the crowding conditions. PMID:26538600

  13. THE PERSISTENCE OF MYCOBACTERIUM AVIUM IN A DRINKING WATER SYSTEM AFTER THE ADDITION OF FILTRATION

    EPA Science Inventory

    Drinking water is increasingly recognized as a major source of pathogenic nontuberculous mycobacteria (NTM) associated with human infection. Our goal was to determine if the prevalence of NTM would decrease after the addition of filtration treatment to an unfiltered surface water...

  14. Dynamic Response of Forest Litter and Mineral Soil to Pulsed Water Additions

    NASA Astrophysics Data System (ADS)

    Boot, C. M.; Schaeffer, S. M.; Carbone, M. S.; Still, C. J.; Schimel, J.

    2010-12-01

    Quantifying microbial responses to drought and moisture pulses are essential to understanding terrestrial C cycling in a changing climate. Using laboratory incubations we sought to determine if water added in multiple consecutive pulses to pine forest litter and mineral soil resulted in different C dynamics than water added in a single event. Soils were collected from two sites on Santa Cruz Island located in Channel Islands National Park 40 km southwest of Santa Barbara, CA. Both sites are dominated by Bishop pine (Pinus muricata) mixed with chaparral shrubs, with a ~3-10 cm thick litter layer. The sites differ, however, in the frequency and amount of precipitation received. Following water additions as either one or three pulses (equal total volume) we measured respiration, dissolved organic carbon (DOC) and microbial biomass carbon (MBC) over twenty-two days after the first water addition. Three days after the initial water addition in the litter samples the DOC and MBC for both treatments were not different; however, the temporal dynamics varied by site with the high precipitation site responding more quickly and with a higher magnitude than the low precipitation site. In both the litter and mineral soil respiration rate correlated with soil moisture (r2=0.91 and 0.84 respectively). Our results suggest that the water history and other site-specific characteristics were more important in the response to pulsed water additions than how the water was introduced to the system.

  15. Enhancing water removal from whole stillage by enzyme addition during fermentation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The removal of water from coproducts in the fuel ethanol process requires a significant energy input. In this study, the addition of cell-wall-degrading enzymes was investigated to determine whether or not the enzymes could reduce the amount of water bound within the wet grains. This would have the ...

  16. Standard addition method for the determination of pharmaceutical residues in drinking water by SPE-LC-MS/MS.

    PubMed

    Cimetiere, Nicolas; Soutrel, Isabelle; Lemasle, Marguerite; Laplanche, Alain; Crocq, André

    2013-01-01

    The study of the occurrence and fate of pharmaceutical compounds in drinking or waste water processes has become very popular in recent years. Liquid chromatography with tandem mass spectrometry is a powerful analytical tool often used to determine pharmaceutical residues at trace level in water. However, many steps may disrupt the analytical procedure and bias the results. A list of 27 environmentally relevant molecules, including various therapeutic classes and (cardiovascular, veterinary and human antibiotics, neuroleptics, non-steroidal anti-inflammatory drugs, hormones and other miscellaneous pharmaceutical compounds), was selected. In this work, a method was developed using ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) and solid-phase extraction to determine the concentration of the 27 targeted pharmaceutical compounds at the nanogram per litre level. The matrix effect was evaluated from water sampled at different treatment stages. Conventional methods with external calibration and internal standard correction were compared with the standard addition method (SAM). An accurate determination of pharmaceutical compounds in drinking water was obtained by the SAM associated with UPLC-MS/MS. The developed method was used to evaluate the occurrence and fate of pharmaceutical compounds in some drinking water treatment plants in the west of France. PMID:24617062

  17. Two-dimensional interlocked pentagonal bilayer ice: how do water molecules form a hydrogen bonding network?

    PubMed

    Zhu, Weiduo; Zhao, Wen-Hui; Wang, Lu; Yin, Di; Jia, Min; Yang, Jinlong; Zeng, Xiao Cheng; Yuan, Lan-Feng

    2016-06-01

    The plethora of ice structures observed both in bulk and under nanoscale confinement reflects the extraordinary ability of water molecules to form diverse forms of hydrogen bonding networks. An ideal hydrogen bonding network of water should satisfy three requirements: (1) four hydrogen bonds connected with every water molecule, (2) nearly linear hydrogen bonds, and (3) tetrahedral configuration for the four hydrogen bonds around an O atom. However, under nanoscale confinement, some of the three requirements have to be unmet, and the selection of the specific requirement(s) leads to different types of hydrogen bonding structures. According to molecular dynamics (MD) simulations for water confined between two smooth hydrophobic walls, we obtain a phase diagram of three two-dimensional (2D) crystalline structures and a bilayer liquid. A new 2D bilayer ice is found and named the interlocked pentagonal bilayer ice (IPBI), because its side view comprises interlocked pentagonal channels. The basic motif in the top view of IPBI is a large hexagon composed of four small pentagons, resembling the top view of a previously reported "coffin" bilayer ice [Johnston, et al., J. Chem. Phys., 2010, 133, 154516]. First-principles optimizations suggest that both bilayer ices are stable. However, there are fundamental differences between the two bilayer structures due to the difference in the selection among the three requirements. The IPBI sacrifices the linearity of hydrogen bonds to retain locally tetrahedral configurations of the hydrogen bonds, whereas the coffin structure does the opposite. The tradeoff between the conditions of an ideal hydrogen bonding network can serve as a generic guidance to understand the rich phase behaviors of nanoconfined water. PMID:27063210

  18. Ammonia as a preferred additive in chiral and achiral applications of supercritical fluid chromatography for small, drug-like molecules.

    PubMed

    Ventura, Manuel; Murphy, Brent; Goetzinger, Wolfgang

    2012-01-13

    Supercritical fluid chromatography is routinely utilized by analytical separations groups in the pharmaceutical industry to efficiently handle separations for discovery medicinal chemistry purposes. Purifications are performed on samples ranging from a few milligrams up to hundreds of grams. Basic additives dissolved into the liquid component of the SFC mobile phase are commonly used to improve peak shape and efficiency in achiral and chiral separations. While for purposes of analysis there is minimal consequence to additive introduction in the mobile phase, for preparative separations one needs to consider the potential effect of an additive's presence when concentrated with the desired compound. Following an SFC purification using an additive-containing modifier, the resulting fractions will contain an easily evaporated modifier, and after its evaporation perhaps still significant levels of the less volatile additive. Depending on the aqueous solubility and basicity of the final product, the process of removing basic amine additives can be time-consuming and can result in reduced yields. NMR analysis following preparative isolation and evaporation often reveals the fact of insufficient removal of the chromatographic additive even after aqueous work up steps. In this study, ammonia is evaluated as an alternative additive to strong bases such as diethylamine (DEA) in SFC purification and analysis and to the authors' knowledge no previous publication has been written describing the application of methanolic ammonia as an additive for SFC separations. Dimethylethylamine (DMEA), a more volatile additive than DEA, is also evaluated relative to ammonia for its potential to simplify the isolation process after purification and in terms of chromatographic performance. The loss in concentration of ammonia in methanol modifier over time due to evaporation and effects of that loss are also described. Furthermore, for ammonia the analytical benefit is shown to extend to on

  19. Thermal behavior of water confined in micro porous of clay mineral at additional pressure.

    NASA Astrophysics Data System (ADS)

    Ito, Y.; Takemura, T.; Fujimori, H.; Nagoe, A.; Sugimoto, T.

    2014-12-01

    Water is the most familiar substance. However water has specific properties that has a crystal structure of a dozen and density of that is maximum at 277.15 K. Therefore it understands various natural phenomena to study physical properties of water. Oodo et al study physical properties of water confined in silica gel [1]. They indicate that melting point of water confined in silica gel decrease with decreasing pore size of silica gel. Also in case that pore size is less than 2 nm, water confined in silica gel is unfreezing water at low temperature. It is considered that effect of pore size prevent crystal growth of water. Therefore we are interested in water confined in clay minerals. Clay minerals have a number of water conditions. Also it is thought that water confined in clay minerals show different physical behavior to exist the domain where change with various effect. Therefore we studied a thermal properties and phase behavior of absorption water in clay minerals. In addition, we analyzed the changes in the thermal behavior of absorption water due to the effect of earth pressure that was an environmental factor in the ground. [1] Oodo & Fujimori, J. Non-Cryst. Solids, 357 (2011) 683.

  20. Calculating Partition Coefficients of Small Molecules in Octanol/Water and Cyclohexane/Water.

    PubMed

    Bannan, Caitlin C; Calabró, Gaetano; Kyu, Daisy Y; Mobley, David L

    2016-08-01

    Partition coefficients describe how a solute is distributed between two immiscible solvents. They are used in drug design as a measure of a solute's hydrophobicity and a proxy for its membrane permeability. We calculate partition coefficients from transfer free energies using molecular dynamics simulations in explicit solvent. Setup is done by our new Solvation Toolkit which automates the process of creating input files for any combination of solutes and solvents for many popular molecular dynamics software packages. We calculate partition coefficients between octanol/water and cyclohexane/water with the Generalized AMBER Force Field (GAFF) and the Dielectric Corrected GAFF (GAFF-DC). With similar methods in the past we found a root-mean-squared error (RMSE) of 6.3 kJ/mol in hydration free energies which would correspond to an error of around 1.6 log units in partition coefficients if solvation free energies in both solvents were estimated with comparable accuracy. Here we find an overall RMSE of about 1.2 log units with both force fields. Results from GAFF and GAFF-DC seem to exhibit systematic biases in opposite directions for calculated cyclohexane/water partition coefficients. PMID:27434695

  1. Explicit Consideration of Water Molecules to Study Vibrational Circular DICHROÎSM of Monosaccharide's

    NASA Astrophysics Data System (ADS)

    Moussi, Sofiane; Ouamerali, Ourida

    2014-06-01

    Carbohydrates have multiples roles in biological systems. It has been found that the glycoside bond is fundamentally important in many aspects of chemistry and biology and forms the basis of carbohydrate chemistry. That means the stereochemical information, namely, glycosidic linkages α or β, gives an significant features of the carbohydrate glycosidation position of the glycosylic acceptor. For these reasons, much effort was made for the synthesis and analysis of the glycoside bond. Vibrational circular dichroism VCD has some advantages over conventional electronic circular dichroism (ECD) due to the applicability to all organic molecules and the reliability of ab initio quantum calculation. However, for a molecule with many chiral centers such as carbohydrates, determination of the absolute configuration tends to be difficult because the information from each stereochemical center is mixed and averaged over the spectrum. In the CH stretching region, only two VCD studies on carbohydrates have been reported and spectra--structure correlation, as determined for the glycoside band, remains to be investigated. T. Taniguchi and collaborators report that methyl glycosides exhibit a characteristic VCD peak, the sign of which solely reflects the C-1 absolute configuration. This work is a theoretical contribution to study the behaviour of VCD spectrum's of the monosaccharides when the water molecules are taken explicitly. This study is focused on six different monosaccharides in theirs absolute configuration R and S. We used the method of density functional theory DFT by means of the B3LYP hybrid functional and 6-31G * basis set.

  2. Solvent-shared pairs of densely charged ions induce intense but short-range supra-additive slowdown of water rotation.

    PubMed

    Vila Verde, Ana; Santer, Mark; Lipowsky, Reinhard

    2016-01-21

    The question "Can ions exert supra-additive effects on water dynamics?" has had several opposing answers from both simulation and experiment. We address this ongoing controversy by investigating water reorientation in aqueous solutions of two salts with large (magnesium sulfate) and small (cesium chloride) effects on water dynamics using molecular dynamics simulations and classical, polarizable models. The salt models are reparameterized to reproduce properties of both dilute and concentrated solutions. We demonstrate that water rotation in concentrated MgSO4 solutions is unexpectedly slow, in agreement with experiment, and that the slowdown is supra-additive: the observed slowdown is larger than that predicted by assuming that the resultant of the extra forces induced by the ions on the rotating water molecules tilts the free energy landscape associated with water rotation. Supra-additive slow down is very intense but short-range, and is strongly ion-specific: in contrast to the long-range picture initially proposed based on experiment, we find that intense supra-additivity is limited to water molecules directly bridging two ions in solvent-shared ion pair configuration; in contrast to a non-ion-specific origin to supra-additive effects proposed from simulations, we find that the magnitude of supra-additive slowdown strongly depends on the identity of the cations and anions. Supra-additive slowdown of water dynamics requires long-lived solvent-shared ion pairs; long-lived ion pairs should be typical for salts of multivalent ions. We discuss the origin of the apparent disagreement between the various studies on this topic and show that the short-range cooperative slowdown scenario proposed here resolves the existing controversy. PMID:26687290

  3. Olefin Metathesis Reaction in Water and in Air Improved by Supramolecular Additives.

    PubMed

    Tomasek, Jasmine; Seßler, Miriam; Gröger, Harald; Schatz, Jürgen

    2015-01-01

    A range of water-immiscible commercially available Grubbs-type precatalysts can be used in ring-closing olefin metathesis reaction in high yields. The synthetic transformation is possible in pure water under ambient conditions. Sulfocalixarenes can help to boost the reactivity of the metathesis reaction by catalyst activation, improved mass transfer, and solubility of reactants in the aqueous reaction media. Additionally, the use of supramolecular additives allows lower catalyst loadings, but still high activity in pure water under aerobic conditions. PMID:26506329

  4. Interaction between water molecules and zinc sulfide nanoparticles studied by temperature-programmed desorption and molecular dynamics simulations.

    PubMed

    Zhang, Hengzhong; Rustad, James R; Banfield, Jillian F

    2007-06-14

    We have investigated the bonding of water molecules to the surfaces of ZnS nanoparticles (approximately 2-3 nm sphalerite) using temperature-programmed desorption (TPD). The activation energy for water desorption was derived as a function of the surface coverage through kinetic modeling of the experimental TPD curves. The binding energy of water equals the activation energy of desorption if it is assumed that the activation energy for adsorption is nearly zero. Molecular dynamics (MD) simulations of water adsorption on 3 and 5 nm sphalerite nanoparticles provided insights into the adsorption process and water binding at the atomic level. Water binds with the ZnS nanoparticle surface mainly via formation of Zn-O bonds. As compared with bulk ZnS crystals, ZnS nanoparticles can adsorb more water molecules per unit surface area due to the greatly increased curvature, which increases the distance between adjacent adsorbed molecules. Results from both TPD and MD show that the water binding energy increases with decreasing the water surface coverage. We attribute the increase in binding energy with decreasing surface water coverage to the increasing degree of surface under-coordination as removal of water molecules proceeds. MD also suggests that the water binding energy increases with decreasing particle size due to the further distance and hence lower interaction between adsorbed water molecules on highly curved smaller particle surfaces. Results also show that the binding energy, and thus the strength of interaction of water, is highest in isolated nanoparticles, lower in nanoparticle aggregates, and lowest in bulk crystals. Given that water binding is driven by surface energy reduction, we attribute the decreased binding energy for aggregated as compared to isolated particles to the decrease in surface energy that occurs as the result of inter-particle interactions. PMID:17518448

  5. Toward a mechanistic understanding of the effect of biochar addition on soil water retention

    NASA Astrophysics Data System (ADS)

    Yi, S.; Chang, N.; Guo, M.; Imhoff, P. T.

    2014-12-01

    Biochar (BC) is a carbon-rich product produced by thermal degradation of biomass in an oxygen-free environment, whose application to sediment is said to improve water retention. However, BC produced from different feedstocks and pyrolyzed at different temperatures have distinct properties, which may alter water retention in ways difficult to predict a priori. Our goal is to develop a mechanistic understanding of BC addition on water retention by examining the impact of BC from two feedstocks, poultry litter (PL) and hardwood (HW), on the soil-water retention curves (SWRC) of a uniform sand and a sandy loam (SL). For experiments with sand, BC and sand were sieved to the same particle size (~ 0.547 mm) to minimize effects of BC addition on particle size distribution. Experiments with SL contained the same sieved BC. PL and HW bicohars were added at 2 and 7% (w/w), and water retention was measured from 0 to -4.38 × 106 cm-H2O. Both BCs increased porosities for sand and SL, up to 39 and 13% for sand and SL, respectively, with 7% HW BC addition. The primary cause for these increases was the internal porosity of BC particles. While the matric potential for air-entry was unchanged with BC addition, BC amendment increased water retention for sand and SL in the capillary region (0 to -15,000 cm-H2O) by an average of 26 and 33 % for 7% PL and HW BC in sand, respectively, but only 7 and 14 % for 7% PL and HW BC in SL. The most dramatic influence of BC amendment on water retention occurred in the adsorption region (< -15,000 cm-H2O), where water retention increased by a factor of 11 and 22 for 7% PL and HW BC in sand, respectively, but by 140 and 190 % for 7% PL and HW BC in SL, respectively. The impact of BC on water retention in these sediments is explained primarily by the additional surface area and internal porosity of PL and HW BC particles. van Genuchten (VG) models were fitted to the water retention data. For SL where the impact of BC addition on water retention was

  6. Energy deposition model based on electron scattering cross section data from water molecules

    NASA Astrophysics Data System (ADS)

    Muñoz, A.; Oiler, J. C.; Blanco, F.; Gorfinkiel, J. D.; Limão-Vieira, P.; Maira-Vidal, A.; Borge, M. J. G.; Tengblad, O.; Huerga, C.; Téllez, M.; García, G.

    2008-10-01

    A complete set of electrons scattering cross sections by water molecules over a broad energy range, from the me V to the Me V ranges, is presented in this study. These data have been obtained by combining experiments and calculations and cover most relevant processes, both elastic and inelastic, which can take place in the considered energy range. A new Monte Carlo simulation programme has been developed using as input parameter these cross sectional data as well as experimental energy loss spectra. The simulation procedure has been applied to obtain electron tracks and energy deposition plots in water when irradiated by a Ru-106 plaque as those used for brachyteraphy of ocular tumours. Finally, the low energy electron tracks provided by the present model have been compared with those obtained with other codes available in the literature

  7. Dipole and quadrupole polarizabilities of the water molecule as a function of geometry.

    PubMed

    Loboda, Oleksandr; Ingrosso, Francesca; Ruiz-López, Manuel F; Reis, Heribert; Millot, Claude

    2016-09-01

    Dipolar, dipole-quadrupole and quadrupole-quadrupole static polarizabilities of the water molecule have been determined by ab initio calculations at coupled cluster level of theory with single, double and perturbative triple excitations CCSD(T) with an aug-cc-pVTZ basis set using a finite field and field-gradient method. The geometry dependence of polarizability tensor components has been explored and modeled by power series expansion in bond length and angle variations up to sum of powers equal to 4. The results provide a very detailed description of the static polarizability of water up to quadrupolar rank which can be used for the test and development of novel accurate polarizable interaction potentials for modeling aqueous solutions. © 2016 Wiley Periodicals, Inc. PMID:27354163

  8. Water and complex organic molecules in the warm inner regions of solar-type protostars

    NASA Astrophysics Data System (ADS)

    Coutens, A.; Jørgensen, J. K.; Persson, M. V.; Lykke, J. M.; Taquet, V.; van Dishoeck, E. F.; Vastel, C.; Wampfler, S. F.

    2015-12-01

    Water and complex organic molecules play an important role in the emergence of Life. They have been detected in different types of astrophysical environments (protostars, prestellar cores, outflows, protoplanetary disks, comets, etc). In particular, they show high abundances towards the warm inner regions of protostars, where the icy grain mantles thermally desorb. Can a part of the molecular content observed in these regions be preserved during the star formation process and incorporated into asteroids and comets, that can deliver it to planetary embryos through impacts? By comparison with cometary studies, interferometric observations of solar-type protostars can help to address this important question. We present recent results obtained with the Plateau de Bure interferometer about water deuteration, glycolaldehyde and ethylene glycol towards the low-mass protostar NGC 1333 IRAS2A.

  9. Role of additives in wood plastic composite of water soluble monomer

    NASA Astrophysics Data System (ADS)

    Ali, K. M. Idriss; Khan, Mubarak A.; Husain, M. M.

    1994-10-01

    Wood plastic composites are prepared under radiation of 60Co gamma source with simul, a low grade wood of Bangladesh using a water soluble monomer acrylamide (AM) mixed with a swelling solvent methanol, water or methanol/water (1:1) at different compositions in the presence of a number of additives and co-additives such as NVP ( N-vinylpyrrolidone), TPGDA (tripropylene glycol diacrylate), TMPTA (trimethylol propane triacrylate), sulfuric acid, urea and copper sulfate. Polymer loading (PL) and tensile strength (TS) of the composites are measured. The role of these additives on the composites is also discussed. It is observed that nitrogen-atom containing-materials like urea, NVP and AM produce composites with the highest mechanical strength, and incorporation of copper into this system provides additional property of protection and preservation of the composites against attacks by insects and microbes.

  10. Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    2016-04-01

    Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN doped graphene and C doped h-BN. We find that doped surfaces are considerably more reactive than their pristine counterparts and by comparing the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed.

  11. Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules.

    PubMed

    Al-Hamdani, Yasmine S; Alfè, Dario; von Lilienfeld, O Anatole; Michaelides, Angelos

    2016-04-21

    Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN dopedgraphene and C doped h-BN. We find that dopedsurfaces are considerably more reactive than their pristine counterparts and by comparing the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed. PMID:27389233

  12. The binding energies of one and two water molecules to the first transition-row metal positive ions. II

    NASA Technical Reports Server (NTRS)

    Rosi, Marzio; Bauschlicher, Charles W., Jr.

    1990-01-01

    The present investigation of H2O's binding energy to transition-metal ions proceeds from the D(2h) structure and bends the two water molecules out of plane. The molecule is constrained to have C(2v) symmetry, so that each water molecule and metal ion lies on a plane. The ground states are bent only for Mn(H2O)2(+) and Zn(H2O)2(+), where only 4s4p hybridization is energetically favorable; 4s4p hybridization reduces repulsion.

  13. Acceptor-donor-acceptor-based small molecules with varied crystallinity: processing additive-induced nanofibril in blend film for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Li, Chao; Chen, Yujin; Zhao, Yue; Wang, Huifang; Zhang, Wei; Li, Yaowen; Yang, Xiaoming; Ma, Changqi; Chen, Liwei; Zhu, Xiulin; Tu, Yingfeng

    2013-09-01

    A series of acceptor-donor-acceptor-based small molecules (SMs) with varied crystallinity were successfully synthesized. The processing additive can induce the SMs to self-organize as nanofibrils with higher crystallinity and controlled scales of nanofibrils, which have significant influence on the photovoltaic performance.A series of acceptor-donor-acceptor-based small molecules (SMs) with varied crystallinity were successfully synthesized. The processing additive can induce the SMs to self-organize as nanofibrils with higher crystallinity and controlled scales of nanofibrils, which have significant influence on the photovoltaic performance. Electronic supplementary information (ESI) available: Synthetic process and characterizations of SMs; TGA, electrochemical properties, molecular orbital surfaces of SMs; AFM images of SM:PC71BM blend films; EQE curves; optical, electrochemical properties and photovoltaic parameters. See DOI: 10.1039/c3nr03048b

  14. The effects of water molecules on the electronic and structural properties of peptide nanotubes.

    PubMed

    Andrade-Filho, T; Ferreira, Fabio Furlan; Alves, Wendel Andrade; Rocha, Alexandre Reily

    2013-05-28

    The self-assembly of short amino acid chains appears to be one of the most promising strategies for the fabrication of nanostructures. Their solubility in water and the possibility of chemical modification by targeting the amino or carboxyl terminus give peptide-based nanostructures several advantages over carbon nanotube nanostructures. However, because these systems are synthesized in aqueous solution, a deeper understanding is needed on the effects of water especially with respect to the electronic, structural and transport properties. In this work, the electronic properties of L-diphenylalanine nanotubes (FF-NTs) have been studied using the Self-Consistent Charge Density-Functional-based Tight-Binding method augmented with dispersion interaction. The presence of water molecules in the central hydrophilic channel and their interaction with the nanostructures are addressed. We demonstrate that the presence of water leads to significant changes in the electronic properties of these systems decreasing the band gap which can lead to an increase in the hopping probability and the conductivity. PMID:23588391

  15. Hydrodynamic and nonhydrodynamic contributions to the bimolecular collision rates of solute molecules in supercooled bulk water.

    PubMed

    Peric, Ida; Merunka, Dalibor; Bales, Barney L; Peric, Miroslav

    2014-06-26

    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, τ(R), the mean time between successive spin exchanges within a cage, τ(RE), and the long-time-averaged spin exchange rate constants, K(ex), of the same solute molecule may be measured independently. Thus, long- and short-time translational diffusion behavior may be inferred from K(ex) and τ(RE), respectively. In order to measure K(ex), 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, W(dd). We find that both K(ex) and W(dd) 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, τ(RE) 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

  16. 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

  17. ORGANIC MOLECULES AND WATER IN THE INNER DISKS OF T TAURI STARS

    SciTech Connect

    Carr, John S.; Najita, Joan R. E-mail: najita@noao.edu

    2011-06-01

    We report high signal-to-noise Spitzer Infrared Spectrograph spectra of a sample of 11 classical T Tauri stars. Molecular emission from rotational transitions of H{sub 2}O and OH and rovibrational bands of simple organic molecules (CO{sub 2}, HCN, C{sub 2}H{sub 2}) is common among the sources in the sample. The emission shows a range in both flux and line-to-continuum ratio for each molecule and in the flux ratios of different molecular species. The gas temperatures (200-800 K) and emitting areas we derive are consistent with the emission originating in a warm disk atmosphere in the inner planet formation region at radii <2 AU. The H{sub 2}O emission appears to form under a limited range of excitation conditions, as demonstrated by the similarity in relative strengths of H{sub 2}O features from star to star and the narrow range in derived temperature and column density. Emission from highly excited rotational levels of OH is present in all stars; the OH emission flux increases with the stellar accretion rate, and the OH/H{sub 2}O flux ratio shows a relatively small scatter. We interpret these results as evidence for OH production via FUV photodissociation of H{sub 2}O in the disk surface layers. No obvious explanation is found for the observed range in the relative emission strengths of different organic molecules or in their strength with respect to water. We put forward the possibility that these variations reflect a diversity in organic abundances due to star-to-star differences in the C/O ratio of the inner disk gas. Stars with the largest HCN/H{sub 2}O flux ratios in our sample have the largest disk masses. While larger samples are required to confirm this, we speculate that such a trend could result if higher mass disks are more efficient at planetesimal formation and sequestration of water in the outer disk, leading to enhanced C/O ratios and abundances of organic molecules in the inner disk. A comparison of our derived HCN-to-H{sub 2}O column density ratio

  18. Dynamic and Static Water Molecules Complement the TN16 Conformational Heterogeneity inside the Tubulin Cavity.

    PubMed

    Majumdar, Sarmistha; Maiti, Satyabrata; Ghosh Dastidar, Shubhra

    2016-01-19

    TN16 is one of the most promising inhibitors of α, β dimer of tubulin that occupies the cavity in the β-subunit located at the dimeric interface, known as the colchicine binding site. The experimentally determined structure of the complex (Protein Data Bank entry 3HKD) presents the conformation and position of the ligand based on the "best fit", keeping the controversy of other significant binding modes open for further investigation. Computation has already revealed that TN16 experiences fluctuations within the binding pocket, but the insight from that previous report was limited by the shorter windows of sampling and by the approximations on the surrounding environment by implicit solvation. This article reports that in most of the cases straightforward MMGBSA calculations of binding energy revealed a gradual loss of stabilization that was inconsistent with the structural observations, and thus, it indicated the lack of consideration of stabilizing factors with appropriate weightage. Consideration of the structurally packed water molecules in the space between the ligand and receptor successfully eliminated such discrepancies between the structure and stability, serving as the "litmus test" of the importance of explicit consideration of such structurally packed water in the calculations. Such consideration has further evidenced a quasi-degenerate character of the different binding modes of TN16 that has rationalized the observed intrinsic fluctuations of TN16 within the pocket, which is likely to be the most critical insight into its entropy-dominated binding. Quantum mechanical calculations have revealed a relay of electron density from TN16 to the protein via a water molecule in a concerted manner. PMID:26666704

  19. Vasoactive properties of CORM-3, a novel water-soluble carbon monoxide-releasing molecule.

    PubMed

    Foresti, Roberta; Hammad, Jehad; Clark, James E; Johnson, Tony R; Mann, Brian E; Friebe, Andreas; Green, Colin J; Motterlini, Roberto

    2004-06-01

    1 Carbon monoxide (CO), one of the end products of heme catabolism by heme oxygenase, possesses antihypertensive and vasodilatory characteristics. We have recently discovered that certain transition metal carbonyls are capable of releasing CO in biological fluids and modulate physiological functions via the delivery of CO. Because the initial compounds identified were not water soluble, we have synthesized new CO-releasing molecules that are chemically modified to allow solubility in water. The aim of this study was to assess the vasoactive properties of tricarbonylchloro(glycinato)ruthenium(II) (CORM-3) in vitro and in vivo. 2 CORM-3 produced a concentration-dependent relaxation in vessels precontracted with phenylephrine, exerting significant vasodilatation starting at concentrations of 25-50 microm. Inactive CORM-3, which does not release CO, did not affect vascular tone. 3 Blockers of ATP-dependent potassium channels (glibenclamide) or guanylate cyclase activity (ODQ) considerably reduced CORM-3-dependent relaxation, confirming that potassium channels activation and cGMP partly mediate the vasoactive properties of CO. In fact, increased levels of cGMP were detected in aortas following CORM-3 stimulation. 4 The in vitro and in vivo vasorelaxant activities of CORM-3 were further enhanced in the presence of YC-1, a benzylindazole derivative which is known to sensitize guanylate cyclase to activation by CO. Interestingly, inhibiting nitric oxide production or removing the endothelium significantly decreased vasodilatation by CORM-3, suggesting that factors produced by the endothelium influence CORM-3 vascular activities. 5 These results, together with our previous findings on the cardioprotective functions of CORM-3, indicate that this molecule is an excellent prototype of water-soluble CO carriers for studying the pharmacological and biological features of CO. PMID:15148243

  20. Vasoactive properties of CORM-3, a novel water-soluble carbon monoxide-releasing molecule

    PubMed Central

    Foresti, Roberta; Hammad, Jehad; Clark, James E; Johnson, Tony R; Mann, Brian E; Friebe, Andreas; Green, Colin J; Motterlini, Roberto

    2004-01-01

    Carbon monoxide (CO), one of the end products of heme catabolism by heme oxygenase, possesses antihypertensive and vasodilatory characteristics. We have recently discovered that certain transition metal carbonyls are capable of releasing CO in biological fluids and modulate physiological functions via the delivery of CO. Because the initial compounds identified were not water soluble, we have synthesized new CO-releasing molecules that are chemically modified to allow solubility in water. The aim of this study was to assess the vasoactive properties of tricarbonylchloro(glycinato)ruthenium(II) (CORM-3) in vitro and in vivo. CORM-3 produced a concentration-dependent relaxation in vessels precontracted with phenylephrine, exerting significant vasodilatation starting at concentrations of 25–50 μM. Inactive CORM-3, which does not release CO, did not affect vascular tone. Blockers of ATP-dependent potassium channels (glibenclamide) or guanylate cyclase activity (ODQ) considerably reduced CORM-3-dependent relaxation, confirming that potassium channels activation and cGMP partly mediate the vasoactive properties of CO. In fact, increased levels of cGMP were detected in aortas following CORM-3 stimulation. The in vitro and in vivo vasorelaxant activities of CORM-3 were further enhanced in the presence of YC-1, a benzylindazole derivative which is known to sensitize guanylate cyclase to activation by CO. Interestingly, inhibiting nitric oxide production or removing the endothelium significantly decreased vasodilatation by CORM-3, suggesting that factors produced by the endothelium influence CORM-3 vascular activities. These results, together with our previous findings on the cardioprotective functions of CORM-3, indicate that this molecule is an excellent prototype of water-soluble CO carriers for studying the pharmacological and biological features of CO. PMID:15148243

  1. Unintended consequences? Water molecules at biological and crystallographic protein-protein interfaces.

    PubMed

    Ahmed, Mostafa H; Habtemariam, Mesay; Safo, Martin K; Scarsdale, J Neel; Spyrakis, Francesca; Cozzini, Pietro; Mozzarelli, Andrea; Kellogg, Glen E

    2013-12-01

    The importance of protein-protein interactions (PPIs) is becoming increasingly appreciated, as these interactions lie at the core of virtually every biological process. Small molecule modulators that target PPIs are under exploration as new therapies. One of the greatest obstacles faced in crystallographically determining the 3D structures of proteins is coaxing the proteins to form "artificial" PPIs that lead to uniform crystals suitable for X-ray diffraction. This work compares interactions formed naturally, i.e., "biological", with those artificially formed under crystallization conditions or "non-biological". In particular, a detailed analysis of water molecules at the interfaces of high-resolution (≤2.30 Å) X-ray crystal structures of protein-protein complexes, where 140 are biological protein-protein complex structures and 112 include non-biological protein-protein interfaces, was carried out using modeling tools based on the HINT forcefield. Surprisingly few and relatively subtle differences were observed between the two types of interfaces: (i) non-biological interfaces are more polar than biological interfaces, yet there is better organized hydrogen bonding at the latter; (ii) biological associations rely more on water-mediated interactions with backbone atoms compared to non-biological associations; (iii) aromatic/planar residues play a larger role in biological associations with respect to water, and (iv) Lys has a particularly large role at non-biological interfaces. A support vector machines (SVMs) classifier using descriptors from this study was devised that was able to correctly classify 84% of the two interface types. PMID:24076743

  2. Orbiting Water Molecules Dance to Tune Of Galaxy's "Central Engine," Astronomers Say

    NASA Astrophysics Data System (ADS)

    2000-01-01

    A disk of water molecules orbiting a supermassive black hole at the core of a galaxy 60 million light-years away is "reverberating" in response to variations in the energy output from the galaxy's powerful "central engine" close to the black hole, astronomers say. The team of astronomers used the National Science Foundation's (NSF) Very Large Array (VLA) radio telescope in New Mexico and the 100-meter-diameter radio telescope of the Max Planck Institute for Radio Astronomy at Effelsberg, Germany, to observe the galaxy NGC 1068 in the constellation Cetus. They announced their findings today at the American Astronomical Society's meeting in Atlanta. The water molecules, in a disk some 5 light-years in diameter, are acting as a set of giant cosmic radio-wave amplifiers, called masers. Using energy radiated by the galaxy's "central engine," the molecules strengthen, or brighten, radio emission at a particular frequency as seen from Earth. "We have seen variations in the radio 'brightness' of these cosmic amplifiers that we believe were caused by variations in the energy output of the central engine," said Jack Gallimore, an astronomer at the National Radio Astronomy Observatory (NRAO) in Charlottesville, VA. "This could provide us with a valuable new tool for learning about the central engine itself," he added. Gallimore worked with Stefi Baum of the Space Telescope Science Institute in Baltimore, MD; Christian Henkel of the Max Planck Institute for Radio Astronomy in Bonn, Germany; Ian Glass of the South African Astronomical Observatory; Mark Claussen of the NRAO in Socorro, NM; and Almudena Prieto of the European Southern Observatory in Munich, Germany. "Our observations show that NGC 1068 is the second-known case of a giant disk of water molecules orbiting a supermassive black hole at a galaxy's core," Gallimore said. The first case was the galaxy NGC 4258 (Messier 106), whose disk of radio-amplifying water molecules was measured by the NSF's Very Long Baseline

  3. Effects of Water and Nitrogen Addition on Species Turnover in Temperate Grasslands in Northern China

    PubMed Central

    Xu, Zhuwen; Wan, Shiqiang; Ren, Haiyan; Han, Xingguo; Li, Mai-He; Cheng, Weixin; Jiang, Yong

    2012-01-01

    Global nitrogen (N) deposition and climate change have been identified as two of the most important causes of current plant diversity loss. However, temporal patterns of species turnover underlying diversity changes in response to changing precipitation regimes and atmospheric N deposition have received inadequate attention. We carried out a manipulation experiment in a steppe and an old-field in North China from 2005 to 2009, to test the hypothesis that water addition enhances plant species richness through increase in the rate of species gain and decrease in the rate of species loss, while N addition has opposite effects on species changes. Our results showed that water addition increased the rate of species gain in both the steppe and the old field but decreased the rates of species loss and turnover in the old field. In contrast, N addition increased the rates of species loss and turnover in the steppe but decreased the rate of species gain in the old field. The rate of species change was greater in the old field than in the steppe. Water interacted with N to affect species richness and species turnover, indicating that the impacts of N on semi-arid grasslands were largely mediated by water availability. The temporal stability of communities was negatively correlated with rates of species loss and turnover, suggesting that water addition might enhance, but N addition would reduce the compositional stability of grasslands. Experimental results support our initial hypothesis and demonstrate that water and N availabilities differed in the effects on rate of species change in the temperate grasslands, and these effects also depend on grassland types and/or land-use history. Species gain and loss together contribute to the dynamic change of species richness in semi-arid grasslands under future climate change. PMID:22768119

  4. Thermodynamic properties of water molecules in the presence of cosolute depend on DNA structure: a study using grid inhomogeneous solvation theory

    PubMed Central

    Nakano, Miki; Tateishi-Karimata, Hisae; Tanaka, Shigenori; Tama, Florence; Miyashita, Osamu; Nakano, Shu-ichi; Sugimoto, Naoki

    2015-01-01

    In conditions that mimic those of the living cell, where various biomolecules and other components are present, DNA strands can adopt many structures in addition to the canonical B-form duplex. Previous studies in the presence of cosolutes that induce molecular crowding showed that thermal stabilities of DNA structures are associated with the properties of the water molecules around the DNAs. To understand how cosolutes, such as ethylene glycol, affect the thermal stability of DNA structures, we investigated the thermodynamic properties of water molecules around a hairpin duplex and a G-quadruplex using grid inhomogeneous solvation theory (GIST) with or without cosolutes. Our analysis indicated that (i) cosolutes increased the free energy of water molecules around DNA by disrupting water–water interactions, (ii) ethylene glycol more effectively disrupted water–water interactions around Watson–Crick base pairs than those around G-quartets or non-paired bases, (iii) due to the negative electrostatic potential there was a thicker hydration shell around G-quartets than around Watson–Crick-paired bases. Our findings suggest that the thermal stability of the hydration shell around DNAs is one factor that affects the thermal stabilities of DNA structures under the crowding conditions. PMID:26538600

  5. Rotations and vibrations of water molecule inside the fullerene cage: infrared study of H2O@C60

    NASA Astrophysics Data System (ADS)

    Room, Toomas; Shugai, A.; Nagel, U.; Mamone, S.; Krachmalnicoff, A.; Whitby, R. J.; Levitt, M. H.; Nishida, T.; Murata, Y.; Lei, Xuegong; Li, Yongjun; Turro, N. J.

    2015-03-01

    Water is the second molecule after hydrogen what has been trapped inside the cage of a C60 molecule by the molucular surgery method. We studied isolated water molecule isotopologs H2O, D2O, and HDO in the solid phase at cryogenic temperatures using IR spectroscopy. The water molecule rotation transitions were observed in the THz and vibration-rotation transitions in the mid-IR range. The slow conversion between para and ortho water allowed us to record the time evolution of spectra and to separate ortho and para absorption lines of water. The similarity of the rotation spectrum of caged water to water in the gas phase indicates that water is free to rotate in the C60 cage even at temperature as low as 3 K. However, spectral lines show a splitting of about 0.5 meV what is not compatible with the icosahedral symmetry of C60. Different models (e.g. crystal field effects in solid C60, C60 cage distortions) will be discussed. This work was supported by institutional research funding IUT23-3 of the Estonian Ministry of Education and Research.

  6. Effects of Water and Nitrogen Addition on Ecosystem Carbon Exchange in a Meadow Steppe

    PubMed Central

    Wang, Yunbo; Jiang, Qi; Yang, Zhiming; Sun, Wei; Wang, Deli

    2015-01-01

    A changing precipitation regime and increasing nitrogen deposition are likely to have profound impacts on arid and semiarid ecosystem C cycling, which is often constrained by the timing and availability of water and nitrogen. However, little is known about the effects of altered precipitation and nitrogen addition on grassland ecosystem C exchange. We conducted a 3-year field experiment to assess the responses of vegetation composition, ecosystem productivity, and ecosystem C exchange to manipulative water and nitrogen addition in a meadow steppe. Nitrogen addition significantly stimulated aboveground biomass and net ecosystem CO2 exchange (NEE), which suggests that nitrogen availability is a primary limiting factor for ecosystem C cycling in the meadow steppe. Water addition had no significant impacts on either ecosystem C exchange or plant biomass, but ecosystem C fluxes showed a strong correlation with early growing season precipitation, rather than whole growing season precipitation, across the 3 experimental years. After we incorporated water addition into the calculation of precipitation regimes, we found that monthly average ecosystem C fluxes correlated more strongly with precipitation frequency than with precipitation amount. These results highlight the importance of precipitation distribution in regulating ecosystem C cycling. Overall, ecosystem C fluxes in the studied ecosystem are highly sensitive to nitrogen deposition, but less sensitive to increased precipitation. PMID:26010888

  7. Adsorption of apolar molecules at the water liquid-vapor interface: A Monte Carlo simulations study of the water-n-octane system

    NASA Astrophysics Data System (ADS)

    Jedlovszky, Pál; Varga, Imre; Gilányi, Tibor

    2003-07-01

    The adsorption of n-octane at the water liquid-vapor interface has been investigated by Monte Carlo computer simulation. For this purpose, simulation of five different water-apolar interfacial systems have been performed, in which the number of n-octane molecules has been varied. The results clearly show that the apolar n-octane molecules are adsorbed from the vapor phase at the interface. The adsorption is driven by the weak attraction due to the dispersion forces acting between the water molecules and the methyl and methylene groups of the octanes. This weak attraction is, however, amplified by the fact that it is added up for the CH2 and CH3 groups belonging to the same molecule. Consistently, the n-octane molecules located closest to the aqueous phase are found to prefer all-trans conformation and parallel alignment with the plane of the interface. On the other hand, entropic effects become more important among the molecules of the outer part of the adsorption layer. Hence, the preferred orientation of these molecules is perpendicular to the interface, as they can be extended toward the less dense region of the apolar phase; and gauche dihedrals appear more frequently here than among the molecules located next to the aqueous phase.

  8. CHARMM General Force Field (CGenFF): A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields

    PubMed Central

    Vanommeslaeghe, K.; Hatcher, E.; Acharya, C.; Kundu, S.; Zhong, S.; Shim, J.; Darian, E.; Guvench, O.; Lopes, P.; Vorobyov, I.; MacKerell, A. D.

    2010-01-01

    The widely used CHARMM additive all-atom force field includes parameters for proteins, nucleic acids, lipids and carbohydrates. In the present paper an extension of the CHARMM force field to drug-like molecules is presented. The resulting CHARMM General Force Field (CGenFF) covers a wide range of chemical groups present in biomolecules and drug-like molecules, including a large number of heterocyclic scaffolds. The parametrization philosophy behind the force field focuses on quality at the expense of transferability, with the implementation concentrating on an extensible force field. Statistics related to the quality of the parametrization with a focus on experimental validation are presented. Additionally, the parametrization procedure, described fully in the present paper in the context of the model systems, pyrrolidine, and 3-phenoxymethylpyrrolidine will allow users to readily extend the force field to chemical groups that are not explicitly covered in the force field as well as add functional groups to and link together molecules already available in the force field. CGenFF thus makes it possible to perform “all-CHARMM” simulations on drug-target interactions thereby extending the utility of CHARMM force fields to medicinally relevant systems. PMID:19575467

  9. Anisotropic conductivity tensor imaging in MREIT using directional diffusion rate of water molecules

    NASA Astrophysics Data System (ADS)

    In Kwon, Oh; Jeong, Woo Chul; Sajib, Saurav Z. K.; Kim, Hyung Joong; Woo, Eung Je

    2014-06-01

    Magnetic resonance electrical impedance tomography (MREIT) is an emerging method to visualize electrical conductivity and/or current density images at low frequencies (below 1 KHz). Injecting currents into an imaging object, one component of the induced magnetic flux density is acquired using an MRI scanner for isotropic conductivity image reconstructions. Diffusion tensor MRI (DT-MRI) measures the intrinsic three-dimensional diffusion property of water molecules within a tissue. It characterizes the anisotropic water transport by the effective diffusion tensor. Combining the DT-MRI and MREIT techniques, we propose a novel direct method for absolute conductivity tensor image reconstructions based on a linear relationship between the water diffusion tensor and the electrical conductivity tensor. We first recover the projected current density, which is the best approximation of the internal current density one can obtain from the measured single component of the induced magnetic flux density. This enables us to estimate a scale factor between the diffusion tensor and the conductivity tensor. Combining these values at all pixels with the acquired diffusion tensor map, we can quantitatively recover the anisotropic conductivity tensor map. From numerical simulations and experimental verifications using a biological tissue phantom, we found that the new method overcomes the limitations of each method and successfully reconstructs both the direction and magnitude of the conductivity tensor for both the anisotropic and isotropic regions.

  10. A DFT study of addition reaction between fragment ion (CH₂) units and fullerene (C₆₀) molecule.

    PubMed

    Zaragoza, Irineo Pedro; Vergara, Jaime; Pérez-Manríquez, Liliana; Salcedo, Roberto

    2011-05-01

    The theoretical study of the interaction between CH(2) and fullerene (C(60)) suggests the existence of an addition reaction mechanism; this feature is studied by applying an analysis of electronic properties. Several different effects are evident in this interaction as a consequence of the particular electronic transfer which occurs during the procedure. The addition or insertion of the methylene group results in a process, where the inclusion of CH(2) into a fullerene bond produces the formation of several geometric deformations. A simulation of these procedures was carried out, taking advantage of the dynamic semi-classical Born-Oppenheimer approximation. Dynamic aspects were analyzed at different speeds, for the interaction between the CH(2) group and the two bonds: CC (6, 6) and CC (6, 5) respectively on the fullerene (C(60)) rings. All calculations which involved electrons employed DFT as well as exchange and functional correlation. The results indicate a tendency for the CH(2) fragment to attack the CC (6, 5) bond. PMID:20658255

  11. Use of ready-mixed concrete plant sludge water in concrete containing an additive or admixture.

    PubMed

    Chatveera, B; Lertwattanaruk, P

    2009-04-01

    In this study, we investigated the feasibility of using sludge water from a ready-mixed concrete plant as mixing water in concrete containing either fly ash as an additive or a superplasticizer admixture based on sulfonated naphthalene-formaldehyde condensates (SNF). The chemical and physical properties of the sludge water and the dry sludge were investigated. Cement pastes were mixed using sludge water containing various levels of total solids content (0.5, 2.5, 5, 7.5, 10, 12.5, and 15%) in order to determine the optimum content in the sludge water. Increasing the total solids content beyond 5-6% tended to reduce the compressive strength and shorten the setting time. Concrete mixes were then prepared using sludge water containing 5-6% total solids content. The concrete samples were evaluated with regard to water required, setting time, slump, compressive strength, permeability, and resistance to acid attack. The use of sludge water in the concrete mix tended to reduce the effect of both fly ash and superplasticizer. Sludge water with a total solids content of less than 6% is suitable for use in the production of concrete with acceptable strength and durability. PMID:19231063

  12. Dynamic effect of sodium-water reaction in fast flux test facility power addition sodium pipes

    SciTech Connect

    Huang, S.N.; Anderson, M.J.

    1990-03-01

    The Fast Flux Facility (FFTF) is a demonstration and test facility of the sodium-cooled fast breeder reactor. A power addition'' to the facility is being considered to convert some of the dumped, unused heat into electricity generation. Components and piping systems to be added are sodium-water steam generators, sodium loop extensions from existing dump heat exchangers to sodium-water steam generators, and conventional water/steam loops. The sodium loops can be subjected to the dynamic loadings of pressure pulses that are caused by postulated sodium leaks and subsequent sodium-water reaction in the steam generator. The existing FFTF secondary pipes and the new power addition sodium loops were evaluated for exposure to the dynamic effect of the sodium-water reaction. Elastic and simplified inelastic dynamic analyses were used in this feasibility study. The results indicate that both the maximum strain and strain range are within the allowable limits. Several cycles of the sodium-water reaction can be sustained by the sodium pipes that are supported by ordinary pipe supports and seismic restraints. Expensive axial pipe restraints to withstand the sodium-water reaction loads are not needed, because the pressure-pulse-induced alternating bending stresses act as secondary stresses and the pressure pulse dynamic effect is a deformation-controlled quantity and is self-limiting. 14 refs., 7 figs., 3 tabs.

  13. The hydrolytic water molecule in trypsin, revealed by time-resolved Laue crystallography

    SciTech Connect

    Singer, P.T. ); Smalaas, A. ); Carty, R.P. ); Mangel, W.F.; Sweet, R.M. )

    1993-01-29

    Crystals of bovine trypsin were acylated at the reactive residue, serine 195, to form the transiently stable p-guanidinobenzoate. Hydrolysis of this species was triggered in the crystals by a jump in pH. The hydrolysis was monitored by three-dimensional Laue crystallography, resulting in three x-ray diffraction structures, all from the same crystal and each representing approximately 5 seconds of x-ray exposure. The structures were analyzed at a nominal resolution of 1.8 angstroms and were of sufficient quality to reproduce subtle features in the electron-density maps for each of the structures. Comparison of the structures before and after the pH jump reveals that a water molecule has positioned itself to attack the acyl group in the initial step of the hydrolysis of this transient intermediate. 12 refs., 3 figs., 2 tabs.

  14. Switching of the magnetocaloric effect of Mn(II) glycolate by water molecules.

    PubMed

    Chen, Yan-Cong; Guo, Fu-Sheng; Liu, Jun-Liang; Leng, Ji-Dong; Vrábel, Peter; Orendáč, Martin; Prokleška, Jan; Sechovský, Vladimír; Tong, Ming-Liang

    2014-03-10

    The transformation of Mn(II) glycolates (glc) between the three-dimensional coordination polymer [Mn(glc)2]n (1) and discrete mononuclear phase [Mn(glc)2 (H2O)2] (2) can be reversibly switched by water molecules, which dramatically change the magnetocaloric effect (MCE) of Mn(II) glycolates from the maximum of 6.9 J kg(-1)  K(-1) in 1 to 60.3 J kg(-1)  K(-1) in 2. This case example reveals that the effect of magnetic coupling on MCE plays a dominant role over that of other factors such as magnetic density for 3d-type magnetic refrigerants. PMID:24532426

  15. H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices - an extended view on complex organic molecule formation

    NASA Astrophysics Data System (ADS)

    Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

    2016-01-01

    Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high-mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules - methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO→H2CO→CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical-chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

  16. Measurements of the number density of water molecules in plasma by using a combined spectral-probe method

    NASA Astrophysics Data System (ADS)

    Bernatskiy, A. V.; Ochkin, V. N.; Afonin, O. N.; Antipenkov, A. B.

    2015-09-01

    A novel method for measuring the number density of water molecules in low-temperature plasma is developed. The absolute intensities of rotational lines of the (0,0) band of the OH( A 2Σ- X 2П) transition are used. Lines with sufficiently large rotational quantum numbers referring to the so-called "hot" group of molecules produced by electron-impact dissociative excitation of water molecules are chosen for measurements. The excitation rate of a process with a known cross section is determined by measuring the parameters of plasma electrons by means of the probe method. The measured number densities of molecules are compared with those in the initial plasma-forming mixture. The time evolution of the particle densities in plasma is investigated. The problems of the sensitivity and applicability of the absolute spectral method are considered.

  17. Measurements of the number density of water molecules in plasma by using a combined spectral−probe method

    SciTech Connect

    Bernatskiy, A. V. Ochkin, V. N.; Afonin, O. N.; Antipenkov, A. B.

    2015-09-15

    A novel method for measuring the number density of water molecules in low-temperature plasma is developed. The absolute intensities of rotational lines of the (0,0) band of the OH(A{sup 2}Σ–X{sup 2}Π) transition are used. Lines with sufficiently large rotational quantum numbers referring to the so-called “hot” group of molecules produced by electron-impact dissociative excitation of water molecules are chosen for measurements. The excitation rate of a process with a known cross section is determined by measuring the parameters of plasma electrons by means of the probe method. The measured number densities of molecules are compared with those in the initial plasma-forming mixture. The time evolution of the particle densities in plasma is investigated. The problems of the sensitivity and applicability of the absolute spectral method are considered.

  18. Effect of dilute polymer additives on the acoustic cavitation threshold of water

    SciTech Connect

    Crum, L.A.; Brosey, J.E.

    1984-02-01

    Measurements are presented of the variation of the acoustic cavitation threshold of water with concentration of the polymer additives polyethylene oxide and guar gum. It was found that small amounts of these additives could significantly increase the cavitation threshold. A theoretical model, based upon nucleation of a gas bubble from a Harvey-type crevice in a mote or solid particle, is developed that gives good agreement with the measurements. The applicability of this approach to an explanation of cavitation index reduction in flow-generated or confined jet cavitation, when polymer additives are introduced, is discussed.

  19. Releasing-addition method for the flame-photometric determination of calcium in thermal waters

    USGS Publications Warehouse

    Rowe, J.J.

    1963-01-01

    Study of the interferences of silica and sulfate in the flame-photometric determination of calcium in thermal waters has led to the development of a method requiring no prior chemical separations. The interference effects of silica, sulfate, potassium, sodium, aluminum, and phosphate are overcome by an addition technique coupled with the use of magnesium as a releasing agent. ?? 1963.

  20. Water sorption of CH3- and CF3-Bis-GMA based resins with additives

    PubMed Central

    PRAKKI, Anuradha; CILLI, Renato; VIEIRA, Ian Matos; DUDUMAS, Kristina; PEREIRA, José Carlos

    2012-01-01

    Objectives To evaluate the effect of additives on the water sorption characteristics of Bis-GMA based copolymers and composites containing TEGDMA, CH3Bis-GMA or CF3Bis-GMA. Material and methods Fifteen experimental copolymers and corresponding composites were prepared combining Bis-GMA and TEGDMA, CH3Bis-GMA or CF3Bis-GMA, with aldehyde or diketone (24 and 32 mol%) totaling 30 groups. For composites, barium aluminosilicate glass and pyrogenic silica was added to comonomer mixtures. Photopolymerization was effected by 0.2 wt% each of camphorquinone and N,N-dimethyl-p-toluidine. Specimen densities in dry and water saturated conditions were obtained by Archimedes' method. Water sorption and desorption were evaluated in a desorption-sorption-desorption cycle. Water uptake (%WU), water desorption (%WD), equilibrium solubility (ES; µg/mm3), swelling (f) and volume increase (%V) were calculated using appropriate equations. Results All resins with additives had increased %WU and ES. TEGDMA-containing systems presented higher %WU, %WD, ES, f and %V values, followed by resins based on CH3Bis-GMA and CF3Bis-GMA. Conclusions Aldehyde and diketone led to increases in the water sorption characteristics of experimental resins. PMID:23032211

  1. Burning of suspended coal-water slurry droplet with oil as combustion additive. Final report

    SciTech Connect

    Yao, S.C.

    1984-10-01

    The combustion of single coal-water slurry droplet with oil as combustion additive (CWOM) has been studied. In this study, the droplet is suspended on a fine quartz fiber and is exposed to the hot combustion product of propane (C/sub 3/H/sub 8/) and air. The results are documented in a movie series. The combustion of CWOM with various combinations of concentrations are compared with that of coal-water slurry and water-oil mixture droplets. The combustion of coal-water slurry is enhanced significantly due to the presence of emulsified kerosene. The enhancement is also dependent upon the mixing procedure during preparation of CWOM. The presence of emulsified kerosene induces local boil-off and combustion that coal particles are splashed as fire works during the early evaporation stage of droplet heat-up. After particle splashing, blow-holes appear on the droplet surface. The popcorn and swelling phenomena usually occurred in coal-water-slurry combustion is greatly reduced. Significant combustion enhancement occurs with the use of kerosene in an amount of about 15 percent of the overall CWOM. This process of using kerosene as combustion additive may provide obvious advantage for the combustion of bituminous coal-water slurry. 4 references, 6 figures.

  2. Effect of nanotube-length on the transport properties of single-file water molecules: Transition from bidirectional to unidirectional

    NASA Astrophysics Data System (ADS)

    Su, Jiaye; Guo, Hongxia

    2011-06-01

    We use molecular dynamics (MD) simulations to study the transport of single-file water molecules through carbon nanotubes (CNTs) with various lengths in an electric field. Most importantly, we find that even the water dipoles inside the CNT are maintained along the field direction, a large amount of water molecules can still transport against the field direction for short CNTs, leading to a low unidirectional transport efficiency (η). As the CNT length increases, the efficiency η will increase remarkably, and achieves the maximum value of 1.0 at or exceeding a critical CNT length. Consequently, the transition from bidirectional to unidirectional transport is observed and is found to be relevant to thermal fluctuations of the two reservoirs, which is explored by the interaction between water molecules inside and outside the CNT. We also find that the water flow vs CNT length follows an exponential decay of f ˜ exp ( - L/L0), and the average translocation time of individual water molecules yields to a power law of τtrans ˜ Lυ, where L0 and ν are constant and slightly depend on the field strength. We further compare our results with the continuous-time random-walk (CTRW) model and find that the water flow can also be described by a power law of f ˜ L-μ modified from CTRW. Our results provide some new physical insights into the biased transport of single-file water molecules, which show the feasibility of using CNTs with any length to pump water in an electric field. The mechanism is important for designing efficient nanofluidic apparatuses.

  3. Isomerization of the uncomplexed actinidin molecule: kinetic accessibility of additional steps in enzyme catalysis provided by solvent perturbation.

    PubMed Central

    Reid, James D; Hussain, Syeed; Bailey, Tamara S F; Sonkaria, Sanjiv; Sreedharan, Suneal K; Thomas, Emrys W; Resmini, Marina; Brocklehurst, Keith

    2004-01-01

    The effects of increasing the content of the aprotic dipolar organic co-solvent acetonitrile on the observed first-order rate constant (k(obs)) of the pre-steady state acylation phases of the hydrolysis of N-acetyl-Phe-Gly methyl thionester catalysed by the cysteine proteinase variants actinidin and papain in sodium acetate buffer, pH 5.3, were investigated by stopped-flow spectral analysis. With low acetonitrile content, plots of k(obs) against [S]0 for the actinidin reaction are linear with an ordinate intercept of magnitude consistent with a five-step mechanism involving a post-acylation conformational change. Increasing the acetonitrile content results in marked deviations of the plots from linearity with a rate minimum around [S]0=150 microM. The unusual negative dependence of k(obs) on [S]0 in the range 25-150 microM is characteristic of a rate-determining isomerization of the free enzyme before substrate binding, additional to the five-step mechanism. There was no evidence for this phenomenon nor for the post-acylation conformational change in the analogous reaction with papain. For this enzyme, however, acetonitrile acts as an inhibitor with approximately uncompetitive characteristics. Possible mechanistic consequences of the differential solvent-perturbed kinetics are indicated. The free enzyme isomerization of actinidin may provide an explanation for the marked difference in sensitivity between this enzyme and papain of binding site-catalytic site signalling in reactions of substrate-derived 2-pyridyl disulphide reactivity probes. PMID:14640975

  4. Free energy calculation of water addition coupled to reduction of aqueous RuO4-

    NASA Astrophysics Data System (ADS)

    Tateyama, Yoshitaka; Blumberger, Jochen; Ohno, Takahisa; Sprik, Michiel

    2007-05-01

    Free energy calculations were carried out for water addition coupled reduction of aqueous ruthenate, RuO4-+H2O +e-→[RuO3(OH)2]2-, using Car-Parrinello molecular dynamics simulations. The full reaction is divided into the reduction of the tetrahedral monoanion, RuO4-+e-→RuO42-, followed by water addition, RuO42-+H2O →[RuO3(OH)2]2-. The free energy of reduction is computed from the fluctuations of the vertical energy gap using the MnO4-+e -→MnO42- reaction as reference. The free energy for water addition is estimated using constrained molecular dynamics methods. While the description of this complex reaction, in principle, involves multiple reaction coordinates, we found that reversible transformation of the reactant into the product can be achieved by control of a single reaction coordinate consisting of a suitable linear combination of atomic distances. The free energy difference of the full reaction is computed to be -0.62eV relative to the normal hydrogen electrode. This is in good agreement with the experimental value of -0.59eV, lending further support to the hypothesis that, contrary to the ruthenate monoanion, the dianion is not tetrahedral but forms a trigonal-bipyramidal dihydroxo complex in aqueous solution. We construct an approximate two-dimensional free energy surface using the coupling parameter for reduction and the mechanical constraint for water addition as variables. Analyzing this surface we find that in the most favorable reaction pathway the reduction reaction precedes water addition. The latter takes place via the protonated complex [RuO3(OH)]- and subsequent transport of the created hydroxide ion to the fifth coordination site of Ru.

  5. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

    SciTech Connect

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-06-19

    Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII-(O2)-Zn(CF3SO3)2 (1-Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn2+. This further changes the reactivities of 1-Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn2+, whereas 1-Zn2+ coordinating two water molecules, (TMC)FeIII-(O2)-Zn(CF3SO3)2-(OH2)2 [1-Zn2+-(OH2)2], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn2+-(OH2)2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.

  6. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

    DOE PAGESBeta

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-06-19

    Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII-(O2)-Zn(CF3SO3)2 (1-Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn2+. This further changes the reactivities of 1-Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn2+, whereas 1-Zn2+ coordinatingmore » two water molecules, (TMC)FeIII-(O2)-Zn(CF3SO3)2-(OH2)2 [1-Zn2+-(OH2)2], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn2+-(OH2)2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.« less

  7. Tuning the Redox Properties of a Nonheme Iron(III)–Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

    PubMed Central

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-01-01

    Redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII-(O2)-Zn(CF3SO3)2 (1-Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn2+. This further changes the reactivities of 1-Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn2+, whereas 1-Zn2+ coordinating two water molecules, (TMC)FeIII-(O2)-Zn(CF3SO3)2-(OH2)2 [1-Zn2+-(OH2)2], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn2+-(OH2)2. The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates. PMID:26096281

  8. Transition energies of benzoquinone anions are immune to symmetry breaking by a single water molecule.

    PubMed

    Stockett, Mark H; Nielsen, Steen Brøndsted

    2016-03-14

    p-Benzoquinone is the prototypical member of the quinone class of molecules with a basic functionality relevant for the primary reactions of photosynthesis. As electronically excited quinone anions are formed in near-resonant electron transfer, key issues are how the local environment affects excited-state energy levels and deexcitation times. The former we address here with action spectroscopy of mass-selected bare radical anions (pBQ(-)) and one-water pBQ(-)·H2O complexes, isolated in vacuo. The complex represents a precursor for internal proton transfer to form the semiquinone free radical, the first chemical product in the light-driven electron transport chain. Both ions display bands in the visible and ultraviolet with, importantly, almost identical maxima. Despite localizing negative charge, thereby breaking the high orbital symmetries, water is surprisingly innocent. This finding implies that natural fluctuations in the quinone microenvironment cause only minor variations in excited-state energies and thus electron-transfer rates. Hence quinones are robust participants in electron transport. PMID:26490302

  9. A proactive role of water molecules in acceptor recognition by protein O-fucosyltransferase 2.

    PubMed

    Valero-González, Jessika; Leonhard-Melief, Christina; Lira-Navarrete, Erandi; Jiménez-Osés, Gonzalo; Hernández-Ruiz, Cristina; Pallarés, María Carmen; Yruela, Inmaculada; Vasudevan, Deepika; Lostao, Anabel; Corzana, Francisco; Takeuchi, Hideyuki; Haltiwanger, Robert S; Hurtado-Guerrero, Ramon

    2016-04-01

    Protein O-fucosyltransferase 2 (POFUT2) is an essential enzyme that fucosylates serine and threonine residues of folded thrombospondin type 1 repeats (TSRs). To date, the mechanism by which this enzyme recognizes very dissimilar TSRs has been unclear. By engineering a fusion protein, we report the crystal structure of Caenorhabditis elegans POFUT2 (CePOFUT2) in complex with GDP and human TSR1 that suggests an inverting mechanism for fucose transfer assisted by a catalytic base and shows that nearly half of the TSR1 is embraced by CePOFUT2. A small number of direct interactions and a large network of water molecules maintain the complex. Site-directed mutagenesis demonstrates that POFUT2 fucosylates threonine preferentially over serine and relies on folded TSRs containing the minimal consensus sequence C-X-X-S/T-C. Crystallographic and mutagenesis data, together with atomic-level simulations, uncover a binding mechanism by which POFUT2 promiscuously recognizes the structural fingerprint of poorly homologous TSRs through a dynamic network of water-mediated interactions. PMID:26854667

  10. The Use of Additional GPS Frequencies to Independently Determine Tropospheric Water Vapor Profiles

    NASA Technical Reports Server (NTRS)

    Herman, B.M.; Feng, D.; Flittner, D. E.; Kursinski, E. R.

    2000-01-01

    It is well known that the currently employed L1 and L2 GPS/MET frequencies (1.2 - 1.6) Ghz) do not allow for the separation of water vapor and density (or temperature) from active microwave occultation measurements in regions of the troposphere warmer than 240 K Therefore, additional information must be used, from other types of measurements and weather analyses, to recover water vapor (and temperature) profiles. Thus in data sparse regions, these inferred profiles can be subject to larger errors than would result in data rich regions. The use of properly selected additional GPS frequencies enables a direct, independent measurement of the absorption associated with the water vapor profile, which may then be used in the standard GPS/MET retrievals to obtain a more accurate determination of atmospheric temperature throughout the water vapor layer. This study looks at the use of microwave crosslinks in the region of the 22 Ghz water vapor absorption line for this purpose. An added advantage of using 22 Ghz frequencies is that they are only negligibly affected by the ionosphere in contrast to the large effect at the GPS frequencies. The retrieval algorithm uses both amplitude and phase measurements to obtain profiles of atmospheric pressure, temperature and water water vapor pressure with a vertical resolution of 1 km or better. This technique also provides the cloud liquid water content along the ray path, which is in itself an important element in climate monitoring. Advantages of this method include the ability to make measurements in the presence of clouds and the use of techniques and technology proven through the GPS/MET experiment and several of NASA's planetary exploration missions. Simulations demonstrating this method will be presented for both clear and cloudy sky conditions.

  11. State of Water Molecules and Silanol Groups in Opal Minerals: a Near Infrared Spectroscopic Study of Opals from Slovakia

    NASA Astrophysics Data System (ADS)

    Bobon, Miroslav; Christy, Alfred A.; Kluvanec, Daniel; Illasova, L'udmila

    2011-06-01

    Recently near infrared spectroscopy in combination with double derivative technique has been effectively used by Christy [1] to differentiate between free silanol groups and hydrogen bonded silanol groups on silica gel. The method has given some insight into the type of functionalities and their location in silica gel samples. The inportant information in this respect comes from the overtones of the OH groups of water molecules hydrogen bonded to free silanol groups, and hydrogen bonded silanol groups absorbing in the region 5500- 5100 Cm-1 region. The approach was adapted to study the state of water and silanol functionalities and their locations in opals from Slovakia. Twenty opal samples classified into CT and A classes and one quartz sample were used in this work. The samples were crushed using a hydrolic press and powderised. Each sample was then subjected to evacuation process to remove surface adsorbed water at 200°C and the near infrared spectrum of the sample was measured using a Perkin Elmer NTS near infrared spectrometer equipped with a transflectance accessory. The detailed analysis of the sample was carried out using the second derivative profile of the spectrum. The samples were also heated to 750°C to study the state of water molecules in Opal minerals. The results indicate that the opal samples contain 1) surface adsorbed water 2) free and hydrogen bonded silanol groups on the surface 3) Trapped water in the bulk 4) free and hydrogen bonded silanol groups in the cavity surfaces in the bulk. A part of the water molecules found in the bulk of opal minerals are free molecules and the rest are found in hydrogen bonded state to free and hydrogen bonded silanol groups. [1] A. A. Christy, New insights into the surface functionalities and adsorption evolution of water molecules on silica gel surface: A study by second derivative Near Infrared Spectroscopy, Vib. Spectrosc. 54 (2010) 42-49.

  12. Hyperfine coupling constants on inner-sphere water molecules of Gd(III)-based MRI contrast agents.

    PubMed

    Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Helm, Lothar; Platas-Iglesias, Carlos

    2012-11-12

    Herein we present a theoretical investigation of the hyperfine coupling constants (HFCCs) on the inner-sphere water molecules of [Gd(H(2)O)(8)](3+) and different Gd(III)-based magnetic resonance imaging contrast agents such as [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)]. DFT calculations performed on the [Gd(H(2)O)(8)](3+) model system show that both hybrid-GGA functionals (BH&HLYP, B3PW91 and PBE1PBE) and the hybrid meta-GGA functional TPSSh provide (17)O HFCCs in close agreement with the experimental data. The use of all-electron relativistic approaches based on the DKH2 approximation and the use of relativistic effective core potentials (RECP) provide results of essentially the same quality. The accurate calculation of HFCCs on the [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)] complexes requires an adequate description of solvent effects. This was achieved by using a mixed cluster/continuum approach that includes explicitly two second-sphere water molecules. The calculated isotropic (17)O HFCCs (A(iso)) fall within the range 0.40-0.56 MHz, and show deviations from the corresponding experimental values typically lower than 0.05 MHz. The A(iso) values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the Gd(III) ion, as well as by the orientation of the water molecule plane with respect to the Gd-O vector. (1)H HFCCs of coordinated water molecules and (17)O HFCCs of second-sphere water molecules take values close to zero. PMID:22927182

  13. Lithium Bromide/Water as Additives in Dearomatizing Samarium-Ketyl (Hetero)Arene Cyclizations.

    PubMed

    Rao, Chintada Nageswara; Bentz, Christoph; Reissig, Hans-Ulrich

    2015-11-01

    New conditions for dearomatizing samarium-ketyl (hetero)arene cyclizations are reported. In many examples of these samarium diiodide-mediated reactions, lithium bromide and water can be used as additives instead of the carcinogenic and mutagenic hexamethylphosphoramide (HMPA). The best results were obtained for the cyclizations of N-acylated indole derivatives delivering the expected indolines in good yields and excellent diastereoselectivities. A new type of cyclization delivering indolyl-substituted allene derivatives is also described. The scope and limitations of the lithium bromide/water system are discussed. PMID:26368916

  14. Acidification of East Siberian Arctic Shelf waters through addition of freshwater and terrestrial carbon

    NASA Astrophysics Data System (ADS)

    Semiletov, Igor; Pipko, Irina; Gustafsson, Örjan; Anderson, Leif G.; Sergienko, Valentin; Pugach, Svetlana; Dudarev, Oleg; Charkin, Alexander; Gukov, Alexander; Bröder, Lisa; Andersson, August; Spivak, Eduard; Shakhova, Natalia

    2016-05-01

    Ocean acidification affects marine ecosystems and carbon cycling, and is considered a direct effect of anthropogenic carbon dioxide uptake from the atmosphere. Accumulation of atmospheric CO2 in ocean surface waters is predicted to make the ocean twice as acidic by the end of this century. The Arctic Ocean is particularly sensitive to ocean acidification because more CO2 can dissolve in cold water. Here we present observations of the chemical and physical characteristics of East Siberian Arctic Shelf waters from 1999, 2000-2005, 2008 and 2011, and find extreme aragonite undersaturation that reflects acidity levels in excess of those projected in this region for 2100. Dissolved inorganic carbon isotopic data and Markov chain Monte Carlo simulations of water sources using salinity and δ18O data suggest that the persistent acidification is driven by the degradation of terrestrial organic matter and discharge of Arctic river water with elevated CO2 concentrations, rather than by uptake of atmospheric CO2. We suggest that East Siberian Arctic Shelf waters may become more acidic if thawing permafrost leads to enhanced terrestrial organic carbon inputs and if freshwater additions continue to increase, which may affect their efficiency as a source of CO2.

  15. Effect of Isopropyl Alcohol Addition in Ozonated Water on the Corrosion of Tungsten Film

    NASA Astrophysics Data System (ADS)

    Lee, Younghwan; Lee, June Young; Im, Kyung Taek; Lim, Sangwoo

    2009-05-01

    Acetic acid (HAc) or 2-propanol (IPA) was added to ozonated water vapor, and its ability to clean corroded Al and W surfaces was studied. No changes to the surface morphology or film thickness were observed on any of the Al films to which the ozonated water vapor cleaning process was applied, either with or without the addition of HAc and IPA. No change in the W surface was observed when it was exposed to either pure ozonated water vapor or that which had HAc-added. However, the surface morphology of the W film changed, and its thickness decreased, when it was exposed to the ozonated water vapor with added IPA. It was also noted that no corrosion occurred on the surface of W when only IPA and the water mixture vapor were injected. Given that the pH of the water with added IPA was unchanged, regardless of whether ozone feeding had occurred, it can be concluded that the main reason for the corrosion of the W film is the accelerated oxidation of W. This accelerated oxidation is a byproduct of ozone decomposition in the presence of a radical promoter, rather than the enhanced dissolution of oxidized W.

  16. Effect of AN Additive on Thermal Output during Electrolysis of Heavy Water with a Palladium Cathode

    NASA Astrophysics Data System (ADS)

    Wang, Q.; Dash, J.

    A titanium additive to a heavy water-sulfuric acid electrolyte has been found to increase the thermal output during electrolysis with a palladium foil cathode. Eight runs, about 6 h each, over a period of 16 days, gave an average of 1.8 W excess thermal power output compared with a light water control cell. This is about twice the excess obtained in co-deposition experiments. The excess thermal power output ranged from 0.5 ± 0.1 to 2.6 ± 0.1 W, which was an average of about 17% more than the input power. The additive apparently catalyzes heat-producing reactions on the surface of the palladium. After electrolysis, the Pd cathode contained localized surface concentrations of Ag, Ni, Fe, Ti, S, and Pt.

  17. Additional capabilities and benchmarking with the SPERT transients for heavy water application of the PARET code

    SciTech Connect

    Woodruff, W.L.

    1989-01-01

    The capabilities of the PARET code have been expanded to include the ability to compute steady-state and transient results for heavy water reactors. A comparison is provided between PARET and the SPERT II series of transients. Another significant improvement in the code is the addition of a restart capability. The current capabilities of the code are summarized. 7 refs., 12 figs., 3 tabs.

  18. [Clinical evaluation of an oxygen concentrator and humidifier that does not require additional reservoir water].

    PubMed

    Burioka, Naoto; Nakamoto, Sachiko; Fukuoka, Yasushi; Shimizu, Eiji

    2011-02-01

    A conventional humidifier with a reservoir of water for humidification can produce micro-aerosols contaminated with bacteria. The present study was undertaken to determine the clinical efficiency of a membrane humidifier that does not require additional reservoir water. We analyzed relative room air humidity and oxygen levels obtained from 2 pressure-swing adsorption (PSA)-type oxygen concentrators with membrane humidifiers. A significant correlation was found between relative room air humidity and that of oxygen moistened by a membrane humidifier. Several patients with chronic respiratory failure experienced improvements in subjectively reported nasal dryness using an oxygen concentrator with a membrane humidifier. This device avoids the need to change reservoir water, and may improve patient quality of life in the home. PMID:21400902

  19. Innovative additives can increase the drilling rates of water-based muds

    SciTech Connect

    Growcock, F.B.; Sinor, L.A.; Reece, A.R.; Powers, J.R.

    1994-12-31

    Several types of organic compounds were tested as rate of penetration (ROP) enhancers for a simple gel/water mud. Experiments conducted in a full-size drilling apparatus with both rollercone and PDC bits at wellbore pressures of 1,100 and 2,000 psi indicate that a paraffin/ester mixture, several terpenes and a mixture of insoluble poly(propylene glycols), or PPGs, can all increase the ROP by 5 to 20% when added at levels of 2--4% by volume. Complementary lubricity and shale recovery studies suggest that the paraffin and terpenes function by making the steel surfaces less water-wetting, thereby reducing the tendency of partially hydrated sticky shales to adhere. The PPG mixture, on the other hand, may function primarily by interacting directly with the shales to reduce their tendency to form a sticky mass. In either case, the additives increased ROP to levels comparable to the ROP observed with pure water.

  20. Nano-porous pottery using calcined waste sediment from tap water production as an additive.

    PubMed

    Sangsuk, Supin; Khunthon, Srichalai; Nilpairach, Siriphan

    2010-10-01

    A suspension of sediment from a lagoon in a tap water production plant was collected for this experiment. The suspension was spray dried and calcined at 700 °C for 1 h. After calcining, 30 wt.% of the sediment were mixed with pottery clay. Samples with and without calcined sediment were sintered at 900, 1000 and 1100 °C. The results show that calcined sediment can be used as an additive in pottery clay. The samples with calcined sediment show higher porosity, water absorption and flexural strength, especially for 900 and 1000 °C. At 900 °C, samples with calcined sediment show a porosity of 50% with an average pore size of 68 nm, water absorption of 31% and flexural strength of 12.61 MPa. PMID:19942644

  1. Growth control of nonionic reverse micelles by surfactant and solvent molecular architecture and water addition.

    PubMed

    Shrestha, Lok Kumar; Shrestha, Rekha Goswami; Aramaki, Kenji

    2011-06-01

    This paper describes a facile route to the shape, size, and structure control of reversed micelles by surfactant and solvent molecular architecture and water addition. Nonionic reverse micellar size is found to increase with increase in hydrophilic headgroup size of surfactant, whose scheme is understood in terms of decrease in the critical packing parameter (cpp). On the other hand, an opposite trend is observed with increase in lipophilicity of the surfactant. This is caused by the repulsive excluded volume interactions, which increases with the volume of lipophilic moiety of surfactant; as a result, the micelle interface tends to become more curved and micelles shrink. Solvent molecular structure has played a crucial role; increasing hydrocarbon chain length of alkanes favored one dimensional micellar growth. We note that long chain oil has a poor penetration tendency to lipophilic tail of surfactant and decreases the cpp. Solvent polarity is also crucial; globular micelles are formed in short chain oil cyclohexane. We note that decreasing chain length of oil mimic the decrease in the headgroup size of surfactant; rod-to-sphere type transition in the micellar structure. Addition of trace water favors micellar growth; maximum dimension and micellar cross section increases with increase in water concentration. The sizes of the water incorporated reverse micelles (or w/o microemulsion) are much bigger than the empty micelles. Micellar structure was confirmed by small angle X-ray scattering (SAXS) and supported by rheology. PMID:21770115

  2. Nitrification in lake sediment with addition of drinking water treatment residuals.

    PubMed

    Wang, Changhui; Liu, Juanfeng; Wang, Zhixin; Pei, Yuansheng

    2014-06-01

    Drinking water treatment residuals (WTRs), non-hazardous by-products generated during potable water production, can effectively reduce the lake internal phosphorus (P) loading and improve water quality in lakes. It stands to reason that special attention regarding the beneficial reuse of WTRs should be given not only to the effectiveness of P pollution control, but also to the effects on the migration and transformation of other nutrients (e.g., nitrogen (N)). In this work, based on laboratory enrichment tests, the effects of WTRs addition on nitrification in lake sediment were investigated using batch tests, fluorescence in situ hybridization, quantitative polymerase chain reaction and phylogenetic analysis techniques. The results indicated that WTRs addition had minor effects on the morphologies of AOB and NOB; however, the addition slightly enhanced the sediment nitrification potential from 12.8 to 13.2 μg-N g(-1)-dry sample h(-1) and also increased the ammonia oxidation bacteria (AOB) and nitrite oxidizing bacteria (NOB) abundances, particularly the AOB abundances (P < 0.05), which increased from 1.11 × 10(8) to 1.31 × 10(8) copies g(-1)-dry sample. Moreover, WTRs addition was beneficial to the enrichment of Nitrosomonas and Nitrosospira multiformis and promoted the emergence of a new Nitrospira cluster, causing the increase in AOB and NOB diversities. Further analysis showed that the variations of nitrification in lake sediment after WTRs addition were primarily due to the decrease of bioavailable P, the introduction of new nitrifiers and the increase of favorable carriers for microorganism attachment in sediments. Overall, these results suggested that WTRs reuse for the control of lake internal P loading would also lead to conditions that are beneficial to nitrification. PMID:24681379

  3. State of water molecules and silanol groups in opal minerals: a near infrared spectroscopic study of opals from Slovakia

    NASA Astrophysics Data System (ADS)

    Boboň, Miroslav; Christy, Alfred A.; Kluvanec, Daniel; Illášová, L'udmila

    2011-12-01

    Recently, near infrared spectroscopy in combination with double derivative technique has been effectively used by Christy (Vib Spectrosc 54:42-49, 2010) to study and differentiate between free and hydrogen bonded silanol groups on silica gel surface. The method has given some insight into the type of functionalities, their location in silica gel samples, and the way the water molecules bind onto the silanol groups. The important information in this respect comes from the overtones of the OH groups of water molecules hydrogen-bonded to free silanol groups, and hydrogen-bonded silanol groups absorbing in the region 5,500-5,100 cm-1. Chemically, opal minerals are hydrated silica and the same approach was adapted to study the state of water molecules, silanol functionalities, and their locations in opal samples from Slovakia. Twenty opal samples classified into CT and A classes and one quartz sample were used in this work. The samples were crushed using a hydraulic press and powderized. Each sample was then subjected to evacuation process to remove surface-adsorbed water at 200°C, and the near infrared spectrum of each sample was measured using a Perkin Elmer NTS FT-NIR spectrometer equipped with a transflectance accessory and a DTGS detector. The samples were also heated to 750°C to remove the hydrogen-bonded silanol groups on the surface to reveal their locality. Second derivative profiles of the near infrared reflectance spectra were obtained using the instrument's software and used in the detailed analysis of the samples. The analysis of the near infrared spectra and their second derivative profiles had the aim in finding relationships between the surface chemical structure and the classification of opal samples. The dry opal samples were also tested for their surface adsorption effectivity toward water molecules. The results indicate that the opal samples contain (1) surface-adsorbed water, (2) free and hydrogen-bonded silanol groups on the surface, (3) trapped

  4. Two-dimensional description of surface-bounded exospheres with application to the migration of water molecules on the Moon

    NASA Astrophysics Data System (ADS)

    Schorghofer, Norbert

    2015-05-01

    On the Moon, water molecules and other volatiles are thought to migrate along ballistic trajectories. Here, this migration process is described in terms of a two-dimensional partial differential equation for the surface concentration, based on the probability distribution of thermal ballistic hops. A random-walk model, a corresponding diffusion coefficient, and a continuum description are provided. In other words, a surface-bounded exosphere is described purely in terms of quantities on the surface, which can provide computational and conceptual advantages. The derived continuum equation can be used to calculate the steady-state distribution of the surface concentration of volatile water molecules. An analytic steady-state solution is obtained for an equatorial ring; it reveals the width and mass of the pileup of molecules at the morning terminator.

  5. Association of Catechin Molecules in Water: Quantitative Binding Study and Complex Structure Analysis.

    PubMed

    Ujihara, Tomomi; Hayashi, Nobuyuki

    2016-01-22

    Associations between catechin molecules were investigated by (1)H NMR titration experiments. Eight green tea catechins formed self-assembled dimers in water, and gallate-type catechins had a greater tendency to self-associate than non-gallate-type catechins. All eight catechins also associated as 1:1 heterodimer complexes. Investigation of complex formation of epigallocatechin-3-O-gallate (EGCg) and epigallocatechin (EGC) with the other catechins showed that the affinity between EGCg and 2,3-trans-gallate-type catechins was remarkably high, and the binding affinity of EGCg for ECg was also rather strong. In contrast, the non-gallate-type catechin EGC exhibited generally low binding affinity for other catechins. Structural analyses of the complexes by ROESY experiments and density functional theory calculations demonstrated that the higher binding abilities of gallate-type catechins are due to providing multiple intermolecular interactions that remain effective in an aqueous environment, such as aromatic/aromatic or CH/π interactions. PMID:26720794

  6. Preparation and tribological properties of water-soluble copper/silica nanocomposite as a water-based lubricant additive

    NASA Astrophysics Data System (ADS)

    Zhang, Chunli; Zhang, Shengmao; Yu, Laigui; Zhang, Zhijun; Wu, Zhishen; Zhang, Pingyu

    2012-10-01

    Cu/SiO2 nanocomposite was synthesized by sol-gel method. The size, morphology and phase structure of as-prepared Cu/SiO2 nanocomposite were analyzed by means of X-ray diffraction and transmission electron microscopy, and its ultraviolet-visible light spectrum was measured in relation to surface plasmon excitation of Cu particles. The tribological properties of as-synthesized Cu/SiO2 nanocomposite as an additive in distilled water were investigated with a four-ball machine, and the morphology and elemental composition of worn steel surfaces were examined with a scanning electron microscope and an X-ray photoelectron spectroscope. Results show that as-synthesized Cu/SiO2 nanocomposite as a lubricant additive is able to significantly improve the tribological properties of distilled water. A protective and lubricious film composed of Cu and a small amount of FeS, FeSO4 and SiO2 is formed on steel sliding surfaces lubricated by distilled water containing Cu/SiO2 nanocomposite. During friction process Cu nanoparticles can be released from Cu/SiO2 nanocomposite to fill up micro-pits and grooves of steel sliding surfaces, resulting in greatly reduced friction and wear of steel frictional pair via self-repairing. The state and thickness of the film formed on the worn surface is closely related to applied load; and Cu/SiO2 nanocomposite might be a promising water-based lubricant additive for steel-steel contact subjected to moderate load.

  7. Suppression of methane/air explosion by ultrafine water mist containing sodium chloride additive.

    PubMed

    Cao, Xingyan; Ren, Jingjie; Zhou, Yihui; Wang, Qiuju; Gao, Xuliang; Bi, Mingshu

    2015-03-21

    The suppression effect of ultrafine mists on methane/air explosions with methane concentrations of 6.5%, 8%, 9.5%, 11%, and 13.5% were experimentally studied in a closed visual vessel. Ultrafine water/NaCl solution mist as well as pure water mist was adopted and the droplet sizes of mists were measured by phase doppler particle analyzer (PDPA). A high speed camera was used to record the flame evolution processes. In contrast to pure water mist, the flame propagation speed, the maximum explosion overpressure (ΔP(max)), and the maximum pressure rising rate ((dP/dt)max) decreased significantly, with the "tulip" flame disappearing and the flame getting brighter. The results show that the suppressing effect on methane explosion by ultrafine water/NaCl solution mist is influenced by the mist amount and methane concentration. With the increase of the mist amount, the pressure, and the flame speed both descended significantly. And when the mist amount reached 74.08 g/m(3) and 37.04 g/m(3), the flames of 6.5% and 13.5% methane explosions can be absolutely suppressed, respectively. All of results indicate that addition of NaCl can improve the suppression effect of ultrafine pure water mist on the methane explosions, and the suppression effect is considered due to the combination effect of physical and chemical inhibitions. PMID:25528229

  8. Autotrophic nitrogen removal from black water: calcium addition as a requirement for settleability.

    PubMed

    de Graaff, M S; Temmink, H; Zeeman, G; van Loosdrecht, M C M; Buisman, C J N

    2011-01-01

    Black (toilet) water contains half of the organic load in the domestic wastewater, as well as the major fraction of the nutrients nitrogen and phosphorus. When collected with vacuum toilets, the black water is 25 times more concentrated than the total domestic wastewater stream, i.e. including grey water produced by laundry, showers etc. A two-stage nitritation-anammox process was successfully employed and removed 85%-89% of total nitrogen in anaerobically treated black water. The (free) calcium concentration in black water was too low (42 mg/L) to obtain sufficient granulation of anammox biomass. The granulation and retention of the biomass was improved considerably by the addition of 39 mg/L of extra calcium. This resulted in a volumetric nitrogen removal rate of 0.5 gN/L/d, irrespective of the two temperatures of 35 °C and 25 °C at which the anammox reactors were operated. Nitrous oxide, a very strong global warming gas, was produced in situations of an incomplete anammox conversion accompanied by elevated levels of nitrite. PMID:20822793

  9. Numerical study of the effect of water addition on gas explosion.

    PubMed

    Liang, Yuntao; Zeng, Wen

    2010-02-15

    Through amending the SENKIN code of CHEMKIN III chemical kinetics package, a computational model of gas explosion in a constant volume bomb was built, and the detailed reaction mechanism (GRI-Mech 3.0) was adopted. The mole fraction profiles of reactants, some selected free radicals and catastrophic gases in the process of gas explosion were analyzed by this model. Furthermore, through the sensitivity analysis of the reaction mechanism of gas explosion, the dominant reactions that affect gas explosion and the formation of catastrophic gases were found out. At the same time, the inhibition mechanisms of water on gas explosion and the formation of catastrophic gases were analyzed. The results show that the induced explosion time is prolonged, and the mole fractions of reactant species such as CH(4), O(2) and catastrophic gases such as CO, CO(2) and NO are decreased as water is added to the mixed gas. With the water fraction in the mixed gas increasing, the sensitivities of the dominant reactions contributing to CH(4), CO(2) are decreased and the sensitivity coefficients of CH(4), CO and NO mole fractions are also decreased. The inhibition of gas explosion with water addition can be ascribed to the significant decrease of H, O and OH in the process of gas explosion due to the water presence. PMID:19811873

  10. About Some Of The Properties Of A Guest Molecule Confined In A Water Network, In Order To Form A Clathrate

    NASA Astrophysics Data System (ADS)

    Pérez, G. Bravo; Cruz-Torres, A.; Romero-Martínez, A.

    2008-03-01

    At conditions of high pressure and or low temperature, like a sea bottom from even 1 Km deep, hydrates formation may take place. Its presence is facilitated at the water/oil interface inside conducting oil pipelines. Once formed, the hydrates nucleate further to agglomerations, sticking to the inner surface of the tube. This represents a big problem to flow assurance. We present results contributing to a better understanding of the interaction of a guest molecule with a water cage confining it, that give rise to a hydrate formation. The hydrate structure, its formation energy, and the role that the H bond and its cooperative effect in the water network play in the electrostatic dipole moment of the hydrate, are presented. Molecular calculations using the HF/6-311g(d, p), B3LYP/6-311g(d, p), and B3LYP/6-311++g(d,p) methods, have been applied to compare three different hydrates, each one confining one, two CH4 molecules, and a CO2 molecule, requiring respectively n = 14, 35, and 15 water molecules for the confinement.

  11. Infrared photodissociation of a water molecule from a flexible molecule-H{sub 2}O complex: Rates and conformational product yields following XH stretch excitation

    SciTech Connect

    Clarkson, Jasper R.; Herbert, John M.; Zwier, Timothy S.

    2007-04-07

    Infrared-ultraviolet hole-burning and hole-filling spectroscopies have been used to study IR-induced dissociation of the tryptamine{center_dot}H{sub 2}O and tryptamine{center_dot}D{sub 2}O complexes. Upon complexation of a single water molecule, the seven conformational isomers of tryptamine collapse to a single structure that retains the same ethylamine side chain conformation present in the most highly populated conformer of tryptamine monomer. Infrared excitation of the tryptamine{center_dot}H{sub 2}O complex was carried out using a series of infrared absorptions spanning the range of 2470-3715 cm{sup -1}. The authors have determined the conformational product yield over this range and the dissociation rate near threshold, where it is slow enough to be measured by our methods. The observed threshold for dissociation occurred at 2872 cm{sup -1} in tryptamine{center_dot}H{sub 2}O and at 2869 cm{sup -1} in tryptamine{center_dot}D{sub 2}O, with no dissociation occurring on the time scale of the experiment ({approx}2 {mu}s) at 2745 cm{sup -1}. The dissociation time constants varied from {approx}200 ns for the 2869 cm{sup -1} band of tryptamine{center_dot}D{sub 2}O to {approx}25 ns for the 2872 cm{sup -1} band of tryptamine{center_dot}H{sub 2}O. This large isotope dependence is associated with a zero-point energy effect that increases the binding energy of the deuterated complex by {approx}190 cm{sup -1}, thereby reducing the excess energy available at the same excitation energy. At all higher energies, the dissociation lifetime was shorter than the pulse duration of our lasers (8 ns). At all wavelengths, the observed products in the presence of collisions are dominated by conformers A and B of tryptamine monomer, with small contributions from the other minor conformers. In addition, right at threshold (2869 cm{sup -1}), tryptamine{center_dot}D{sub 2}O dissociates exclusively to conformer A in the absence of collisions with helium, while both A and B conformational

  12. A water soluble additive to suppress respirable dust from concrete-cutting chainsaws: a case study.

    PubMed

    Summers, Michael P; Parmigiani, John P

    2015-01-01

    Respirable dust is of particular concern in the construction industry because it contains crystalline silica. Respirable forms of silica are a severe health threat because they heighten the risk of numerous respirable diseases. Concrete cutting, a common work practice in the construction industry, is a major contributor to dust generation. No studies have been found that focus on the dust suppression of concrete-cutting chainsaws, presumably because, during normal operation water is supplied continuously and copiously to the dust generation points. However, there is a desire to better understand dust creation at low water flow rates. In this case study, a water-soluble surfactant additive was used in the chainsaw's water supply. Cutting was performed on a free-standing concrete wall in a covered outdoor lab with a hand-held, gas-powered, concrete-cutting chainsaw. Air was sampled at the operator's lapel, and around the concrete wall to simulate nearby personnel. Two additive concentrations were tested (2.0% and 0.2%), across a range of fluid flow rates (0.38-3.8 Lpm [0.1-1.0 gpm] at 0.38 Lpm [0.1 gpm] increments). Results indicate that when a lower concentration of additive is used exposure levels increase. However, all exposure levels, once adjusted for 3 hours of continuous cutting in an 8-hour work shift, are below the Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) of 5 mg/m(3). Estimates were made using trend lines to predict the fluid flow rates that would cause respirable dust exposure to exceed both the OSHA PEL and the American Conference of Governmental Industrial Hygienists (ACGIH®) threshold limit value (TLV). PMID:25714034

  13. Mono/bimetallic water-stable lanthanide coordination polymers as luminescent probes for detecting cations, anions and organic solvent molecules.

    PubMed

    Wang, Huarui; Qin, Jianhua; Huang, Chao; Han, Yanbing; Xu, Wenjuan; Hou, Hongwei

    2016-08-01

    Eleven water-stable isostructural mono/bimetallic lanthanide coordination polymers (Ln-CPs) {[EuxTb1-x (HL)(H2O)3]·H2O}n (x = 1.0 (1), 0.9 (3), 0.8 (4), 0.7 (5), 0.6 (6), 0.4 (7), 0.3 (8), 0.2 (9), 0.1 (10), 0.05 (11), 0 (2), H4L = 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) with uncoordinated Lewis basic triazole sites within the pores were prepared. The Ln-CPs represented by 1 showed a rapid and drastic emission quenching induced by external Fe(3+) and Cr(3+) cations and CrO4(2-) and CO3(2-) anions in aqueous solution. In addition, because of the comparable emission intensities of Eu(3+) and Tb(3+) ions, bimetallic CP 8 can be used as a ratiometric luminescent sensor for organic solvent molecules. Moreover, the luminescent color of the 8 sensor in pyridine and in other guest solvents undergoes obvious changes that can be clearly distinguished by the naked eye. PMID:27443408

  14. Improvement of pattern collapse issue by additive-added D.I. water rinse process

    NASA Astrophysics Data System (ADS)

    Tanaka, Keiichi; Naito, Ryoichiro; Kitada, Tomohiro; Kiba, Yukio; Yamada, Yoshiaki; Kobayashi, Masakazu; Ichikawa, Hiroyuki

    2003-06-01

    Reduction of critical dimension in lithography technology is aggressively promoted. At the same time, further resist thickness reduction is being pursued to increase the resolution capabilities of resist. However, thin film has its limitation because of etch requirements etc. As that result, the promotion of reduction results in increasing the aspect ratio, which leads to pattern collapse. It is well known that at drying step in developing process the capillary effect operates the photoresist pattern. If the force of the capillary effect is greater than the aggregation force of the resist pattern, the pattern collapse is generated. And the key parameters of the capillary effect are the space width between patterns, the aspect ratio, the contact angle of the D.I water rinse and the surface tension of rinse solution. Among these parameters the surface tension of rinse solution can be controlled by us. On the other hand, we've already reported that the penetration of TMAH and D.I water into the resist plays an important role on the lithographic latitude. For example, when we use the resist which TMA ion can be easily diffuse into, D.I water and TMA ion which are penetrated in the resist decreases the aggregation force of resist pattern and causes the pattern collapse even by the weak force against resist pattern. These results indicate that the swelling of photoresist by TMA ion and water is very important factor for controlling the pattern collapse. Currently, two methods are mainly tried to reduce the surface tension of rinse solution: SCF (Super Critical Fluid) and addition of additive to D.I water rinse. We used the latter method this time, because this technique has retrofittability and not special tool. And in this evaluation, we found that the degree of suppressing pattern collapse depends on the additive chemistry or formulation. With consideration given to process factors such as above, we investigated what factors contribute to suppressing pattern collapse

  15. Enhancement of nitrate removal at the sediment-water interface by carbon addition plus vertical mixing.

    PubMed

    Chen, Xuechu; He, Shengbing; Zhang, Yueping; Huang, Xiaobo; Huang, Yingying; Chen, Danyue; Huang, Xiaochen; Tang, Jianwu

    2015-10-01

    Wetlands and ponds are frequently used to remove nitrate from effluents or runoffs. However, the efficiency of this approach is limited. Based on the assumption that introducing vertical mixing to water column plus carbon addition would benefit the diffusion across the sediment-water interface, we conducted simulation experiments to identify a method for enhancing nitrate removal. The results suggested that the sediment-water interface has a great potential for nitrate removal, and the potential can be activated after several days of acclimation. Adding additional carbon plus mixing significantly increases the nitrate removal capacity, and the removal of total nitrogen (TN) and nitrate-nitrogen (NO3(-)-N) is well fitted to a first-order reaction model. Adding Hydrilla verticillata debris as a carbon source increased nitrate removal, whereas adding Eichhornia crassipe decreased it. Adding ethanol plus mixing greatly improved the removal performance, with the removal rate of NO3(-)-N and TN reaching 15.0-16.5 g m(-2) d(-1). The feasibility of this enhancement method was further confirmed with a wetland microcosm, and the NO3(-)-N removal rate maintained at 10.0-12.0 g m(-2) d(-1) at a hydraulic loading rate of 0.5 m d(-1). PMID:25556005

  16. Dendrite-Free Li Deposition Using Trace-Amounts of Water as an Electrolyte Additive

    SciTech Connect

    Qian, Jiangfeng; Xu, Wu; Bhattacharya, Priyanka; Engelhard, Mark H.; Henderson, Wesley A.; Zhang, Yaohui; Zhang, Jiguang

    2015-07-01

    Residual water presents in nonaqueous electrolytes has been widely regarded as a detrimental factor for lithium (Li) batteries. This is because water is highly reactive with the commonly used LiPF6 salt and leads to the formation of HF that corrodes battery materials. In this work, we demonstrate that a controlled trace-amount of water (25-100 ppm) can be an effective electrolyte additive for achieving dendrite-free Li metal deposition in LiPF6-based electrolytes and avoid its detrimental effect at the same time. Detailed analyses reveal that the trace amount of HF formed by the decomposition reaction of LiPF6 with water will be electrochemically reduced during initial Li deposition process to form a uniform and dense LiF-rich SEI layer on the surface of the substrate. This LiF-rich SEI layer leads to a uniform distribution of the electric field on the substrate surface and enables uniform and dendrite-free Li deposition. Meanwhile the detrimental effect of HF is diminished due to the consumption of HF in the LiF formation process. Microscopic analysis reveals that the as-deposited dendrite-free Li films exhibit a self-aligned and highly-compacted Li nanorods structure which is consistent with their charming blue color or known as structure color. These findings clearly demonstrate a novel approach to control the nucleation and grow process of Li metal films using well-controlled trace-amount of water. They also shine the light on the effect of water on other electrodeposition processes.

  17. Differential flexibility of the secondary structures of lysozyme and the structure and ordering of surrounding water molecules

    NASA Astrophysics Data System (ADS)

    Sinha, Sudipta Kumar; Bandyopadhyay, Sanjoy

    2011-03-01

    We have performed an atomistic molecular dynamics simulation of an aqueous solution of hen egg-white lysozyme at room temperature with explicit water molecules. Several analyses have been carried out to explore the differential flexibility of the secondary structural segments of the protein and the structure and ordering of water around them. It is found that the overall flexibility of the protein molecule is primarily controlled by few large-amplitude bistable motions exhibited by two coils; one connecting two α-helical segments in domain-1 and the other connecting a 310 helix and a β-sheet in domain-2 of the protein. The heterogeneous structuring of water around the segments of the protein has been found to depend on the degree of exposure of the segments to water. The ordering of water molecules around the protein segments and their tagged potential energies have been found to be anticorrelated with each other. Some of these findings can be verified by suitable experimental studies.

  18. Label-Free Fluctuation Spectroscopy Based on Coherent Anti-Stokes Raman Scattering from Bulk Water Molecules.

    PubMed

    Rabasovic, M D; Sisamakis, E; Wennmalm, S; Widengren, J

    2016-04-01

    Nanoparticles (NPs) and molecules can be analyzed by inverse fluorescence correlation spectroscopy (iFCS) as they pass through an open detection volume, displacing fractions of the fluorescence-emitting solution in which they are dissolved. iFCS does not require the NPs or molecules to be labeled. However, fluorophores in μm-mm concentrations are needed for the solution signal. Here, we instead use coherent anti-Stokes Raman scattering (CARS) from plain water molecules as the signal from the solution. By this fully label-free approach, termed inverse CARS-based correlation spectroscopy (iCARS-CS), NPs that are a few tenths of nm in diameter and at pM concentrations can be analyzed, and their absolute volumes/concentrations can be determined. Likewise, lipid vesicles can be analyzed as they diffuse/flow through the detection volume by using CARS fluctuations from the surrounding water molecules. iCARS-CS could likely offer a broadly applicable, label-free characterization technique of, for example, NPs, small lipid exosomes, or microparticles in biomolecular diagnostics and screening, and can also utilize CARS signals from biologically relevant media other than water. PMID:26819085

  19. The Formation of Oxygen-Containing Molecules in Liquid Water Environments on the Surface of Titan (Invited)

    NASA Astrophysics Data System (ADS)

    Neish, C.

    2010-12-01

    Saturn’s moon Titan represents a unique locale for studying prebiotic chemistry. Reactions occurring in its thick nitrogen - methane atmosphere produce a wide variety of organic molecules. Observations by the Voyager spacecraft found evidence for six gas-phase hydrocarbons and three nitriles, along with an enveloping haze layer shrouding the surface of the moon (Hanel et al., 1981; Kunde et al., 1981; Maguire et al., 1981). More recently, the INMS instrument on the Cassini spacecraft has found evidence for organic molecules up to its mass limit of 100 Da at altitudes as high as 1200 km (Waite et al., 2005; Vuitton et al. 2007). Laboratory experiments that simulate the reactions occurring in Titan’s atmosphere produce many of the same organic molecules observed by Voyager and Cassini, along with organic precipitates known as tholins. Tholins have the general formula CxHyNz and are spectrally similar to Titan’s haze (Khare et al., 1984). Though interesting from the point of view of organic chemistry, the molecules found in Titan’s atmosphere stop short of addressing questions related to the origins of life. Oxygen - a key element for most known biological molecules - is generally lacking in Titan’s atmosphere. The most abundant oxygenated molecule, CO, is present at only ~50 ppm (de Kok et al., 2007). However, if Titan’s atmospheric organic molecules mix with water found in cryovolcanic lavas or impact melts, they may react to produce oxygen-containing, prebiotic species. In this paper, I will show that reactions between Titan tholins and low temperature aqueous solutions produce a wide variety of oxygen-containing species. These reactions display first-order kinetic behaviour with half-lives between 0.4 to 7 days at 273 K (in water) and between 0.3 and 14 days at 253 K (in 13 wt. % ammonia-water). Tholin hydrolysis is thus very fast compared to the freezing timescales of impact melts and volcanic sites on Titan, which take hundreds to thousands of years

  20. Extraction of Organic Molecules from Terrestrial Material: Quantitative Yields from Heat and Water Extractions

    NASA Technical Reports Server (NTRS)

    Beegle, L. W.; Abbey, W. A.; Tsapin, A. T.; Dragoi, D.; Kanik, I.

    2004-01-01

    In the robotic search for life on Mars, different proposed missions will analyze the chemical and biological signatures of life using different platforms. The analysis of samples via analytical instrumentation on the surface of Mars has thus far only been attempted by the two Viking missions. Robotic arms scooped relogith material into a pyrolysis oven attached to a GC/MS. No trace of organic material was found on any of the two different samples at either of the two different landing sites. This null result puts an upper limit on the amount of organics that might be present in Martian soil/rocks, although the level of detection for each individual molecular species is still debated. Determining the absolute limit of detection for each analytical instrument is essential so that null results can be understood. This includes investigating the trade off of using pyrolysis versus liquid solvent extraction to release organic materials (in terms of extraction efficiencies and the complexity of the sample extraction process.) Extraction of organics from field samples can be accomplished by a variety of methods such utilizing various solvents including HCl, pure water, supercritical fluid and Soxhelt extraction. Utilizing 6N HCl is one of the most commonly used method and frequently utilized for extraction of organics from meteorites but it is probably infeasible for robotic exploration due to difficulty of storage and transport. Extraction utilizing H2O is promising, but it could be less efficient than 6N HCl. Both supercritical fluid and Soxhelt extraction methods require bulky hardware and require complex steps, inappropriate for inclusion on rover spacecraft. This investigation reports the efficiencies of pyrolysis and solvent extraction methods for amino acids for different terrestrial samples. The samples studied here, initially created in aqueous environments, are sedimentary in nature. These particular samples were chosen because they possibly represent one of the

  1. Kinetic modeling of the oxidative degradation of additive free PE in bleach disinfected water

    NASA Astrophysics Data System (ADS)

    Mikdam, Aïcha; Colin, Xavier; Billon, Noëlle; Minard, Gaëlle

    2016-05-01

    The chemical interactions between PE and bleach were studied at 60°C in immersion in bleach solutions kept at a free chlorine concentration of 100 ppm and a pH of 5 or 7.2. It was found that the polymer undergoes a severe oxidation from the earliest weeks of exposure, in a superficial layer whose thickness (of about 50-70 µm) is almost independent of the pH value, although the superficial oxidation rate is faster in acidic than in neutral medium. Oxidation leads to the formation and accumulation of a large variety of carbonyl products (mostly ketones and carboxylic acids) and, after a few weeks, to a decrease in the average molar mass due to the large predominance of chain scissions over crosslinking. A scenario was elaborated for explaining such unexpected results. According to this scenario, the non-ionic molecules (Cl2 and ClOH) formed from the disinfectant in the water phase, would migrate deeply into PE and dissociate into highly reactive radicals (Cl• and HO•) in order to initiate a radical chain oxidation. A kinetic model was derived from this scenario for predicting the general trends of the oxidation kinetics and its dependence on environmental factors such as temperature, free chlorine concentration and pH. The validity of this model was successfully checked by comparing the numerical simulations with experimental data.

  2. Cold crystallisation behaviour of water molecules in ionic liquids as a screening method to evaluate biocompatibility of the hydrated ionic liquids.

    PubMed

    Fujita, Kyoko; Nikawa, Yohsuke; Ohno, Hiroyuki

    2013-04-21

    Hydrated ionic liquids, exhibiting cold crystallisation behaviour of water molecules in a certain range of water contents, successfully dissolved cytochrome c maintaining the original spin state of heme. PMID:23486783

  3. Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO2(110)

    SciTech Connect

    Petrik, Nikolay G.; Kimmel, Gregory A.

    2015-09-16

    The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO2(110) surfaces is studied using infrared reflection-absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IRAS peaks at 2737 cm-1 and 3711 cm-1 are observed for stretching vibrations of ODb and OHb on TiO2(110), respectively. IRAS measurements with s- and p-polarized light demonstrate that the bridging hydroxyls are oriented normal to the (110) surface. The IR peaks disappear after the sample is exposed to O2 or annealed in the temperature range of 400 – 600 K (correlating with the temperature at which pairs of OHb’s reform water and then desorb), which is consistent with their identification as bridging hydroxyls. We have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls (using IRAS) as a function of the annealing temperature for a small amount of water initially dosed on the TiO2(110) at low temperature. Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions largely complete for T > 250 K. The temperature-dependent water-VO reaction kinetics are consistent with a Gaussian distribution of activation energies with Ea = 0.545 eV, ΔEa(FWHM) = 0.125 eV, and a “normal” prefactor, v = 1012 s-1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti5c rows on the reduced TiO2

  4. Tertiary and quaternary structures of photoreactive Fe-type nitrile hydratase from Rhodococcus sp. N-771: roles of hydration water molecules in stabilizing the structures and the structural origin of the substrate specificity of the enzyme.

    PubMed

    Nakasako, M; Odaka, M; Yohda, M; Dohmae, N; Takio, K; Kamiya, N; Endo, I

    1999-08-01

    The crystal structure analysis of the Fe-type nitrile hydratase from Rhodococcus sp. N-771 revealed the unique structure of the enzyme composed of the alpha- and beta-subunits and the unprecedented structure of the non-heme iron active center [Nagashima, S., et al. (1998) Nat. Struct. Biol. 5, 347-351]. A number of hydration water molecules were identified both in the interior and at the exterior of the enzyme. The study presented here investigated the roles of the hydration water molecules in stabilizing the tertiary and the quaternary structures of the enzyme, based on the crystal structure and the results from a laser light scattering experiment for the enzyme in solution. Seventy-six hydration water molecules between the two subunits significantly contribute to the alphabeta heterodimer formation by making up the surface shape, forming extensive networks of hydrogen bonds, and moderating the surface charge of the beta-subunit. In particular, 20 hydration water molecules form the extensive networks of hydrogen bonds stabilizing the unique structure of the active center. The amino acid residues hydrogen-bonded to those hydration water molecules are highly conserved among all known nitrile hydratases and even in the homologous enzyme, thiocyanate hydrolase, suggesting the structural conservation of the water molecules in the NHase family. The crystallographic asymmetric unit contained two heterodimers connected by 50 hydration water molecules. The heterotetramer formation in crystallization was clearly explained by the concentration-dependent aggregation state of NHase found in the light scattering measurement. The measurement proved that the dimer-tetramer equilibrium shifted toward the heterotetramer dominant state in the concentration range of 10(-2)-1.0 mg/mL. In the tetramer dominant state, 50 water molecules likely glue the two heterodimers together as observed in the crystal structure. Because NHase exhibits a high abundance in bacterial cells, the result

  5. Effect of PAC addition on immersed ultrafiltration for the treatment of algal-rich water.

    PubMed

    Zhang, Yan; Tian, Jiayu; Nan, Jun; Gao, ShanShan; Liang, Heng; Wang, Meilian; Li, Guibai

    2011-02-28

    The aim of this study was to evaluate the effect of powdered activated carbon (PAC) addition on the treatment of algal-rich water by immersed ultrafiltration (UF), in terms of permeate quality and membrane fouling. Experiments were performed with a hollow-fiber polyvinyl chloride ultrafiltration membrane at a laboratory scale, 20-25°C and 10 L/(m(2) h) constant permeate flux. UF could achieve an absolute removal of Microcystis aeruginosa cells, but a poor removal of algogenic organic matter (AOM) released into water, contaminants responsible for severe membrane fouling. The addition of 4 g/L PAC to the immersed UF reactor significantly alleviated the development of trans-membrane pressure and enhanced the removal of dissovled organic carbon (by 10.9±1.7%), UV(254) (by 27.1±1.7%), and microcystins (expressed as MC-LR(eq), by 40.8±4.2%). However, PAC had little effect on the rejection of hydrophilic high molecular weight AOM such as carbohydrates and proteins. It was also identified that PAC reduced the concentrations of carbohydrates and proteins in the reactor due to decreased light intensity, as well as the MC-LR(eq) concentration by PAC adsorption. PMID:21216530

  6. Properties of Poloxamer Molecules and Poloxamer Micelles Dissolved in Water and Next to Lipid Bilayers: Results from Computer Simulations.

    PubMed

    Adhikari, Upendra; Goliaei, Ardeshir; Tsereteli, Levan; Berkowitz, Max L

    2016-07-01

    To study the properties of poloxamer molecules P85 and P188 and micelles containing these poloxamers in bulk water and also next to lipid bilayers, we performed coarse-grained molecular dynamics computer simulations. We used MARTINI force-field and adjusted Lennard-Jones nonbonded interaction strength parameters for poloxamer beads to take into account the presence of polarizable water. Simulations of systems containing poloxamer molecules or micelles solvated in bulk water showed that structural properties, such as radii of gyration of the molecules and micelles, agree with the ones inferred from experiments. We observed that P85 micelle is almost spherical in shape, whereas the P188 micelle is distorted from being spherical. Simulations containing systems with the water-lipid bilayer interface showed that hydrophilic blocks of poloxamers interact with lipid headgroups of the bilayer and remain at the interface, whereas hydrophobic blocks prefer to insert into the central hydrophobic region of the bilayer. Simulations containing poloxamer micelles next to lipid bilayer showed no permeation of these micelles into the bilayer. To study the "healing" properties of P188 poloxamer, we performed simulations on a system containing a P188 micelle next to "damaged" lipid bilayer containing a pore. We observed that hydrophobic chains of poloxamers got inserted into the bilayer through the pore region, ultimately closing the pore. PMID:26719970

  7. Additive and interaction effects at three amino acid positions in HLA-DQ and HLA-DR molecules drive type 1 diabetes risk

    PubMed Central

    Hu, Xinli; Deutsch, Aaron J; Lenz, Tobias L; Onengut-Gumuscu, Suna; Han, Buhm; Chen, Wei-Min; Howson, Joanna M M; Todd, John A; de Bakker, Paul I W; Rich, Stephen S; Raychaudhuri, Soumya

    2016-01-01

    Variation in the human leukocyte antigen (HLA) genes accounts for one-half of the genetic risk in type 1 diabetes (T1D). Amino acid changes in the HLA-DR and HLA-DQ molecules mediate most of the risk, but extensive linkage disequilibrium complicates the localization of independent effects. Using 18,832 case-control samples, we localized the signal to 3 amino acid positions in HLA-DQ and HLA-DR. HLA-DQβ1 position 57 (previously known; P = 1 × 10−1,355) by itself explained 15.2% of the total phenotypic variance. Independent effects at HLA-DRβ1 positions 13 (P = 1 × 10−721) and 71 (P = 1 × 10−95) increased the proportion of variance explained to 26.9%. The three positions together explained 90% of the phenotypic variance in the HLA-DRB1–HLA-DQA1–HLA-DQB1 locus. Additionally, we observed significant interactions for 11 of 21 pairs of common HLA-DRB1–HLA-DQA1–HLA-DQB1 haplotypes (P = 1.6 × 10−64). HLA-DRβ1 positions 13 and 71 implicate the P4 pocket in the antigen-binding groove, thus pointing to another critical protein structure for T1D risk, in addition to the HLA-DQ P9 pocket. PMID:26168013

  8. Additive method for the prediction of protein-peptide binding affinity. Application to the MHC class I molecule HLA-A*0201.

    PubMed

    Doytchinova, Irini A; Blythe, Martin J; Flower, Darren R

    2002-01-01

    A method has been developed for prediction of binding affinities between proteins and peptides. We exemplify the method through its application to binding predictions of peptides with affinity to major histocompatibility complex class I molecule HLA-A*0201. The method is named "additive" because it is based on the assumption that the binding affinity of a peptide could be presented as a sum of the contributions of the amino acids at each position and the interactions between them. The amino acid contributions and the contributions of the interactions between adjacent side chains and every second side chain were derived using a partial least squares (PLS) statistical methodology using a training set of 420 experimental IC50 values. The predictive power of the method was assessed using rigorous cross-validation and using an independent test set of 89 peptides. The mean value of the residuals between the experimental and predicted pIC50 values was 0.508 for this test set. The additive method was implemented in a program for rapid T-cell epitope search. It is universal and can be applied to any peptide-protein interaction where binding data is known. PMID:12645903

  9. Diesel engine experiments with oxygen enrichment, water addition and lower-grade fuel

    SciTech Connect

    Sekar, R.R.; Marr, W.W.; Cole, R.L.; Marciniak, T.J. ); Schaus, J.E. )

    1990-01-01

    The concept of oxygen enriched air applied to reciprocating engines is getting renewed attention in the context of the progress made in the enrichment methods and the tougher emissions regulations imposed on diesel and gasoline engines. An experimental project was completed in which a direct injection diesel engine was tested with intake oxygen levels of 21% -- 35%. Since an earlier study indicated that it is necessary to use a cheaper fuel to make the concept economically attractive, a less refined fuel was included in the test series. Since a major objection to the use of oxygen enriched combustion air had been the increase in NO{sub x} emissions, a method must be found to reduce NO{sub x}. Introduction of water into the engine combustion process was included in the tests for this purpose. Fuel emulsification with water was the means used here even though other methods could also be used. The teat data indicated a large increase in engine power density, slight improvement in thermal efficiency, significant reductions in smoke and particulate emissions and NO{sub x} emissions controllable with the addition of water. 15 refs., 10 figs., 2 tabs.

  10. Radical-Molecule Reaction C3H + H2O on Amorphous Water Ice: A Promising Route for Interstellar Propynal

    NASA Astrophysics Data System (ADS)

    Xie, Hong-bin; Shao, Chang-bin; Ding, Yi-hong

    2007-11-01

    Intriguing propynal (HCCCHO) has been attracting chemist's attention since 1955. However, to date, no satisfying conclusion concerning its formation mechanism in the interstellar medium (ISM) has been reached, although a variety of gas-reaction models, including ion-molecule, radical-molecule, and molecule-molecule, have been postulated. In this paper, we consider for the first time the gas-grain interaction model that involves heterogeneous reaction at the surface of dust grain or in the icy mantles to account for the propynal's formation. Based on the detailed density functional theory (DFT) and Gaussian-3 potential energy surface studies, we found that although the gaseous process C3H+H2O-->propynal+H must surmount a considerable entrance barrier (around 10 kcal mol-1), amorphous water ice can significantly catalyze the propynal's formation to be barrierless. So, this model should be a more reasonable one for propynal's formation in the low-temperature interstellar space. This result may also represent one rare case of the water-catalyzed reaction associated with a molecular radical in space. Future experimental studies are greatly desired to probe such interesting processes.

  11. Heat transfer characteristics for some coolant additives used for water cooled engines

    SciTech Connect

    Abou-Ziyan, H.Z.; Helali, A.H.B.

    1996-12-31

    Engine coolants contain certain additives to prevent engine overheating or coolant freezing in cold environments. Coolants, also, contain corrosion and rust inhibitors, among other additives. As most engines are using engine cooling solutions, it is of interest to evaluate the effect of engine coolants on the boiling heat transfer coefficient. This has its direct impact on radiator size and environment. This paper describes the apparatus and the measurement techniques. Also, it presents the obtained boiling heat transfer results at different parameters. Three types of engine coolants and their mixtures in distilled water are evaluated, under sub-cooled and saturated boiling conditions. A profound effect of the presence of additives in the coolant, on heat transfer, was clear since changes of heat transfer for different coolants were likely to occur. The results showed that up to 180% improvement of boiling heat transfer coefficient is experienced with some types of coolants. However, at certain concentrations other coolants provide deterioration or not enhancement in the boiling heat transfer characteristics. This investigation proved that there are limitations, which are to be taken into consideration, for the composition of engine coolants in different environments. In warm climates, ethylene glycol should be kept at the minimum concentration required for dissolving other components, whereas borax is beneficial to the enhancement of the heat transfer characteristics.

  12. How water molecules affect the catalytic activity of hydrolases - A XANES study of the local structures of peptide deformylase

    NASA Astrophysics Data System (ADS)

    Cui, Peixin; Wang, Yu; Chu, Wangsheng; Guo, Xiaoyun; Yang, Feifei; Yu, Meijuan; Zhao, Haifeng; Dong, Yuhui; Xie, Yaning; Gong, Weimin; Wu, Ziyu

    2014-12-01

    Peptide deformylase (PDF) is a prokaryotic enzyme that catalyzes the deformylation of nascent peptides generated during protein synthesis and water molecules play a key role in these hydrolases. Using X-ray absorption near edge spectroscopy (XANES) and ab initio calculations we accurately probe the local atomic environment of the metal ion binding in the active site of PDF at different pH values and with different metal ions. This new approach is an effective way to monitor existing correlations among functions and structural changes. We show for the first time that the enzymatic activity depends on pH values and metal ions via the bond length of the nearest coordinating water (Wat1) to the metal ion. Combining experimental and theoretical data we may claim that PDF exhibits an enhanced enzymatic activity only when the distance of the Wat1 molecule with the metal ion falls in the limited range from 2.15 to 2.55 Å.

  13. Molecular orientation effect on the differential cross sections for the electron-impact double ionization of oriented water molecules

    SciTech Connect

    Champion, C.; Dal Cappello, C.; Oubaziz, D.; Aouchiche, H.; Popov, Yu. V.

    2010-03-15

    Double ionization of isolated water molecules fixed in space is here investigated in a theoretical approach based on the first Born approximation. Secondary electron angular distributions are reported for particular (e,3e) kinematical conditions and compared in terms of shape and magnitude. Strong dependence of the fivefold differential cross sections on the molecular target orientation is clearly observed in (e,3-1e) as well as (e,3e) channels. Furthermore, for the major part of the kinematics considered, we identified the different mechanisms involved in the double ionization of water molecule, namely, the direct shake-off process as well as the two-step1 process. They are both discussed and analyzed with respect to the molecular target orientation.

  14. Observing the water molecule in macromolecules using infrared spectrometry: structure of the hydrogen bond network and hydration mechanism

    NASA Astrophysics Data System (ADS)

    Maréchal, Y.

    2004-08-01

    The power and precision of IR spectrometry, or IR quantitative spectroscopy, to observe water molecules embedded in macromolecules, is illustrated, taking as examples the determination of the structures of the hydrogen-bond network of a dried polysaccharide, hyaluronan, of a dried protein, bovine serum albumine, and of a dried polymer, a sulfonated polyimide. We also indicate how IR spectrometry conveys original and precise information from which their hydration mechanisms can be precisely determined in terms of chemical reactions.

  15. Velocity of a Molecule Evaporated from a Water Nanodroplet: Maxwell-Boltzmann Statistics versus Non-Ergodic Events.

    PubMed

    Abdoul-Carime, Hassan; Berthias, Francis; Feketeová, Linda; Marciante, Mathieu; Calvo, Florent; Forquet, Valérian; Chermette, Henry; Farizon, Bernadette; Farizon, Michel; Märk, Tilmann D

    2015-12-01

    The velocity of a molecule evaporated from a mass-selected protonated water nanodroplet is measured by velocity map imaging in combination with a recently developed mass spectrometry technique. The measured velocity distributions allow probing statistical energy redistribution in ultimately small water nanodroplets after ultrafast electronic excitation. As the droplet size increases, the velocity distribution rapidly approaches the behavior expected for macroscopic droplets. However, a distinct high-velocity contribution provides evidence of molecular evaporation before complete energy redistribution, corresponding to non-ergodic events. PMID:26473406

  16. Velocity of a Molecule Evaporated from a Water Nanodroplet: Maxwell–Boltzmann Statistics versus Non-Ergodic Events

    PubMed Central

    Abdoul-Carime, Hassan; Berthias, Francis; Feketeová, Linda; Marciante, Mathieu; Calvo, Florent; Forquet, Valérian; Chermette, Henry; Farizon, Bernadette; Farizon, Michel; Märk, Tilmann D

    2015-01-01

    The velocity of a molecule evaporated from a mass-selected protonated water nanodroplet is measured by velocity map imaging in combination with a recently developed mass spectrometry technique. The measured velocity distributions allow probing statistical energy redistribution in ultimately small water nanodroplets after ultrafast electronic excitation. As the droplet size increases, the velocity distribution rapidly approaches the behavior expected for macroscopic droplets. However, a distinct high-velocity contribution provides evidence of molecular evaporation before complete energy redistribution, corresponding to non-ergodic events. PMID:26473406

  17. Reduction of Local Stress Concentration on Nanosheet in Layered Nanoparticles with Water Molecules

    NASA Astrophysics Data System (ADS)

    Sato, Kiminori; Numata, Kazuomi; Fujimoto, Koichiro

    2014-01-01

    The local stress concentration on 2D nanosheets is investigated for saponite layered nanoparticles by means of X-ray diffraction (XRD) and positronium (Ps) annihilation spectroscopy. XRD experiments indicated that the layered structure for the mechanochemically milled sample is maintained in the presence of H2O molecules. Ps annihilation studies of self-assembly revealed that the 2D nanosheets are well in-plane ordered after uniaxial pressure compaction without H2O molecules due to the efficient propagation of stress concentration. The present results of both XRD and Ps lifetime spectroscopy clearly demonstrates that the stress concentration on the 2D nanosheets can be reduced in the presence of H2O molecules.

  18. Polymer growth rate in a wire chamber with oxygen, water, or alcohol gas additives

    NASA Astrophysics Data System (ADS)

    Boyarski, Adam M.

    2009-06-01

    The rate of polymer growth on wires was measured in a wire chamber while the chamber was aged initially with helium:isobutane (80:20) gas, and then with either oxygen, water, or alcohol added to the gas. At the completion of the aging process for each gas mixture, the carbon content on the wires was measured in a scanning electron microscope/energy dispersive X-ray (SEM/EDX) instrument. The same physical wires were used in all the gas mixtures, allowing measurement of polymer build-up or polymer depletion by each gas additive. It is found that the rate of polymer growth is not changed by the presence of oxygen, water, or alcohol. Conjecture that oxygen reduces breakdown by removing polymer deposits on field wires is negated by these measurements. Instead, it appears that the reduced breakdown is due to lower resistance in the polymer from oxygen ions being transported into the polymer. It is also observed that field wires bombarded by the electrons in the SEM and then placed back into the chamber show an abundance of single electrons being emitted, indicating that electron charge is trapped in the polymer layer and that a high electric field is necessary to remove the charge.

  19. Polymer Growth Rate in a Wire Chamber with Oxygen,Water, or Alcohol Gas Additives

    SciTech Connect

    Boyarski, Adam; /SLAC

    2008-07-02

    The rate of polymer growth on wires was measured in a wire chamber while the chamber was aged initially with helium-isobutane (80:20) gas, and then with either oxygen, water, or alcohol added to the gas. At the completion of the aging process for each gas mixture, the carbon content on the wires was measured in a SEM/EDX instrument. The same physical wires were used in all the gas mixtures, allowing measurement of polymer build up or polymer depletion by each gas additive. It is found that the rate of polymer growth is not changed by the presence of oxygen, water or alcohol. Conjecture that oxygen reduces breakdown by removing polymer deposits on field wires is negated by these measurements. Instead, it appears that the reduced breakdown is due to lower resistance in the polymer from oxygen ions being transported into the polymer. It is also observed that field wires bombarded by the electrons in the SEM and then placed back into the chamber show an abundance of single electrons being emitted, indicating that electron charge is stored in the polymer layer and that a high electric field is necessary to remove the charge.

  20. [Distribution of Phosphorus Forms in the Overlying Water Under Disturbance with the Addition of Algae].

    PubMed

    Chen, Jun; Li, Yong; Li, Da-peng; Huang, Yong; Zhu, Pei-ying

    2016-04-15

    Distribution of different phosphorus (P) forms in the overlying water and the contribution of different algae to the P disappearance were investigated under disturbance with the addition of algae (Microcystis aeruginosa and Selenastrum capricornutum, respectively). The sediments and overlying water were taken from Meiliang Bay in Taihu Lake. The results showed that the concentrations of total P (TP), dissolved total P (DTP), dissolved inorganic P (DIP) and biavailable P (BAP) decreased with and without disturbance. The uptake of DTP and DIP by Microcystis aeruginosa was better than that of Selenastrum capricornutum under the disturbance, but it was the opposite without the disturbance. The disappearance of P in the overlying water was attributed completely to the physico-chemical adsorption of the suspended solids and the uptake of algae. But the contribution of suspended solids and algae depended on the disturbance. The contribution of Microcystis aeruginosa and Selenastrum capricornutum to DTP and DIP absorption was about 60% without disturbance. However, the value was reduced to 40% (Microcystis aeruginosa) and 25% ( Selenastrum capricornutum) under the disturbance. Under the disturbance and the action of algae, the distribution of sedimentary P forms changed. NH4 Cl-P and Ca-P release and Fe/Al-P increase were observed with and without disturbance. The decrease of NH4 Cl-P and Ca-P and the increase of Fe/Al-P were more obvious with disturbance than without disturbance. Selenastrum capricornutum was favor of the release of Ca-P and the formation of Fe/Al-P. PMID:27548963

  1. Long-term nitrogen additions and the intrinsic water-use efficiency of boreal Scots pine.

    NASA Astrophysics Data System (ADS)

    Marshall, John; Wallin, Göran; Linder, Sune; Lundmark, Tomas; Näsholm, Torgny

    2015-04-01

    Nitrogen fertilization nearly always increases productivity in boreal forests, at least in terms of wood production, but it is unclear how. In a mature (80 yrs. old) Scots pine forest in northern Sweden, we tested the extent to which nitrogen fertilization increased intrinsic photosynthetic water-use efficiency. We measured δ13C both discretely, in biweekly phloem sampling, and continuously, by monitoring of bole respiration. The original experiment was designed as a test of eddy covariance methods and is not therefore strictly replicated. Nonetheless, we compared phloem contents among fifteen trees from each plot and stem respiration from four per plot. The treatments included addition of 100 kg N/ha for eight years and a control. Phloem contents have the advantage of integrating over the whole canopy and undergoing complete and rapid turnover. Their disadvantage is that some have observed isotopic drift with transport down the length of the stem, presumably as a result of preferential export and/or reloading. We also measured the isotopic composition of stem respiration from four trees on each plot using a Picarro G1101-I CRDS attached to the vent flow from a continuous gas-exchange system. We detected consistent differences in δ13C between the treatments in phloem contents. Within each treatment, the phloem δ13C was negatively correlated with antecedent temperature (R2= 0.65) and no other measured climate variable. The isotopic composition of stem CO2 efflux will be compared to that of phloem contents. However, when converted to intrinsic water-use efficiency, the increase amounted to only about 4%. This is a small relative to the near doubling in wood production. Although we were able to detect a clear and consistent increase in water-use efficiency with N-fertilization, it constitutes but a minor cause of the observed increase in wood production.

  2. Segmentation and additive approach: A reliable technique to study noncovalent interactions of large molecules at the surface of single-wall carbon nanotubes.

    PubMed

    Torres, Ana M; Scheiner, Steve; Roy, Ajit K; Garay-Tapia, Andrés M; Bustamante, John; Kar, Tapas

    2016-08-01

    This investigation explores a new protocol, named Segmentation and Additive approach (SAA), to study exohedral noncovalent functionalization of single-walled carbon nanotubes with large molecules, such as polymers and biomolecules, by segmenting the entire system into smaller units to reduce computational cost. A key criterion of the segmentation process is the preservation of the molecular structure responsible for stabilization of the entire system in smaller segments. Noncovalent interaction of linoleic acid (LA, C18 H32 O2 ), a fatty acid, at the surface of a (10,0) zigzag nanotube is considered for test purposes. Three smaller segmented models have been created from the full (10,0)-LA system and interaction energies were calculated for these models and compared with the full system at different levels of theory, namely ωB97XD, LDA. The success of this SAA is confirmed as the sum of the interaction energies is in very good agreement with the total interaction energy. Besides reducing computational cost, another merit of SAA is an estimation of the contributions from different sections of the large system to the total interaction energy which can be studied in-depth using a higher level of theory to estimate several properties of each segment. On the negative side, bulk properties, such as HOMO-LUMO (highest occupied molecular orbital - lowest occupied molecular orbital) gap, of the entire system cannot be estimated by adding results from segment models. © 2016 Wiley Periodicals, Inc. PMID:27241227

  3. Effects of Additives, Photodegradation, and Water-tree Degradation on the Photoluminescence in Polyethylene and Polypropylene

    NASA Astrophysics Data System (ADS)

    Ito, Toshihide; Fuse, Norikazu; Ohki, Yoshimichi

    Photoluminescence (PL) spectra induced by irradiation of ultraviolet photons are compared among low-density polyethylene (LDPE), crosslinked polyethylene (XLPE), and polypropylene (PP). Three PL bands appear around 4.2, 3.6, and 3.1 eV in LDPE and XLPE, while similar three PL bands are observed at similar energies in PP. The PL spectra and their decay profiles are independent of the presence of additives and are also independent of whether the samples were crosslinked or not. These results indicate that neither the additives nor the crosslinking has any significant effects on the respective three PLs in PE and PP. When the sample was pre-irradiated by the ultraviolet photons under different atmospheres (air, O2, and vacuum), all the PL intensities decrease with the progress of the pre-irradiation regardless of whether the sample is PE or PP. Therefore, all the PLs are considered to result from impurities. In all the pre-irradiated samples, a new PL band appears at 2.9 eV, of which intensity is stronger when the oxygen partial pressure during the pre-irradiation was lower. This PL is considered to be due to photo-induced conjugated double bonds. It has also been confirmed that water-tree degradation in LDPE or in XLPE does not contribute to PL.

  4. Control of water molecule aggregations in copper 1,4-cyclohexanedicarboxylate coordination polymers containing pyridyl-piperazine type ligands

    NASA Astrophysics Data System (ADS)

    Qiblawi, Sultan H.; LaDuca, Robert L.

    2014-01-01

    A series of layered divalent copper coordination polymers containing 1,4-cyclohexanedicarboxylate and long-spanning pyridyl-piperazine type ligands exhibits greatly different co-crystallized water molecule aggregations depending on the specific ligands used. Both [Cu(t-14cdc)(4-bpmp)]n (1, t-14cdc = trans-1,4-cyclohexanedicarboxylate, 4-bpmp = bis(4-pyridylmethyl)piperazine) and {[Cu(t-14cdc)(4-bpfp)(H2O)2]·6H2O}n (2, 4-bpfp = bis(4-pyridylformyl)piperazine) possess 2D (4,4) coordination polymer grids. However 1 lacks any co-crystallized water and has pinched grid apertures, while 2 manifests infinite water tapes with T6(2)4(2) classification and rectangular grid apertures. {[Cu2(c-14cdc)2(4-bpmp)]·2H2O}n (3, c-14cdc = cis-1,4-cyclohexanedicarboxylate) has [Cu2(c-14cdc)]2 ribbons with paddlewheel dimeric units linked into 2D slabs by 4-bpmp tethers, along with isolated water molecule pairs. In contrast, {[Cu2(c-14cdc)2(4-bpfp)]·10H2O}n (4) shows a very similar underlying coordination polymer topology but entrains unique decameric water molecule clusters. The minor product {[Cu2(c-14cdcH)2(t-1,4-cdc)(4-bpfp)2(H2O)2]·2H2O}n (5) was isolated along with 4; this compound underwent some in situ cis to trans cyclohexane-dicarboxylate ligand isomerization and exhibits a ladder polymer motif.

  5. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers.

    PubMed

    Guo, Pan; Tu, Yusong; Yang, Jinrong; Wang, Chunlei; Sheng, Nan; Fang, Haiping

    2015-10-30

    By combining molecular dynamics simulations and quantum mechanics calculations, we show the formation of a composite structure composed of embedded water molecules and the COOH matrix on carboxyl-terminated self-assembled monolayers (COOH SAMs) with appropriate packing densities. This composite structure with an integrated hydrogen bond network inside reduces the hydrogen bonds with the water above. This explains the seeming contradiction on the stability of the surface water on COOH SAMs observed in experiments. The existence of the composite structure at appropriate packing densities results in the two-step distribution of contact angles of water droplets on COOH SAMs, around 0° and 35°, which compares favorably to the experimental measurements of contact angles collected from forty research articles over the past 25 years. These findings provide a molecular-level understanding of water on surfaces (including surfaces on biomolecules) with hydrophilic functional groups. PMID:26565476

  6. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Guo, Pan; Tu, Yusong; Yang, Jinrong; Wang, Chunlei; Sheng, Nan; Fang, Haiping

    2015-10-01

    By combining molecular dynamics simulations and quantum mechanics calculations, we show the formation of a composite structure composed of embedded water molecules and the COOH matrix on carboxyl-terminated self-assembled monolayers (COOH SAMs) with appropriate packing densities. This composite structure with an integrated hydrogen bond network inside reduces the hydrogen bonds with the water above. This explains the seeming contradiction on the stability of the surface water on COOH SAMs observed in experiments. The existence of the composite structure at appropriate packing densities results in the two-step distribution of contact angles of water droplets on COOH SAMs, around 0° and 35°, which compares favorably to the experimental measurements of contact angles collected from forty research articles over the past 25 years. These findings provide a molecular-level understanding of water on surfaces (including surfaces on biomolecules) with hydrophilic functional groups.

  7. Ion condensation behavior and dynamics of water molecules surrounding the sodium poly(methacrylic acid) chain in water: a molecular dynamics study.

    PubMed

    Chung, Yung-Ting; Huang, Ching-I

    2012-03-28

    All-atom molecular dynamics simulations are used to study the condensation behavior of monovalent (Na(+)) and multivalent (Ca(2+)) salt counterions associated with the co-ions (Cl(-)) surrounding the charged poly(methacrylic acid) (PMAA) chain in water. The study is extended to the influences on chain conformation, local arrangement, and dynamics of water in the highly diluted aqueous solutions. We find that even when the salt ions are monovalent, they attract more than one charged monomer and act as a bridging agent within the chain, as the multivalent salt ions. In principle, the salt ions bridge between not only the "non-adjacent" but also the "adjacent" charged monomers, leading to a more coil-like and a locally stretched conformation, respectively. With an increase in the salt concentration, the amount of coiled-type condensed ions increase and reach a maximum when the chain conformation becomes the most collapsed; whereas, the stretched-type shows an opposite trend. Our results show that the attractive interactions through the condensed salt ions between the non-adjacent monomers are responsible for the conformational collapse. When the salt concentration increases high enough, a significant increase for the stretched-type condensed ions makes an expansion effect on the chain. These stretched-type salt ions, followed by the adsorption of the co-ions and water molecules, tend to form a multilayer organization outside surrounding the PMAA chain. Thus, the expansion degree of the chain conformation is greatly limited. When only the monovalent Na(+) ions are present in the solutions, water molecules are primarily adsorbed into either the condensed Na(+) ions or the COO(-) groups. These adsorbed water molecules form hydrogen bonds with each other and enhance the local bridging behavior associated with the Na(+) condensation on the resultant chain conformation. With an increase in the amount of multivalent Ca(2+) salt ions, more water molecules are bonded directly

  8. All-electron scalar relativistic calculation of water molecule adsorption onto small gold clusters.

    PubMed

    Kuang, Xiang-Jun; Wang, Xin-Qiang; Liu, Gao-Bin

    2011-08-01

    An all-electron scalar relativistic calculation was performed on Au( n )H(2)O (n = 1-13) clusters using density functional theory (DFT) with the generalized gradient approximation at PW91 level. The calculation results reveal that, after adsorption, the small gold cluster would like to bond with oxygen and the H(2)O molecule prefers to occupy the single fold coordination site. Reflecting the strong scalar relativistic effect, Au( n ) geometries are distorted slightly but still maintain a planar structure. The Au-Au bond is strengthened and the H-O bond is weakened, as manifested by the shortening of the Au-Au bond-length and the lengthening of the H-O bond-length. The H-O-H bond angle becomes slightly larger. The enhancement of reactivity of the H(2)O molecule is obvious. The Au-O bond-lengths, adsorption energies, VIPs, HLGs, HOMO (LUMO) energy levels, charge transfers and the highest vibrational frequencies of the Au-O mode for Au( n )H(2)O clusters exhibit an obvious odd-even oscillation. The most favorable adsorption between small gold clusters and the H(2)O molecule takes place when the H(2)O molecule is adsorbed onto an even-numbered Au( n ) cluster and becomes an Au( n )H(2)O cluster with an even number of valence electrons. The odd-even alteration of magnetic moments is observed in Au( n )H(2)O clusters and may serve as material with a tunable code capacity of "0" and "1" by adsorbing a H(2)O molecule onto an odd or even-numbered small gold cluster. PMID:21140279

  9. Nucleation of Mixed Nitric Acid-Water Ice Nanoparticles in Molecular Beams that Starts with a HNO3 Molecule.

    PubMed

    Lengyel, Jozef; Pysanenko, Andriy; Kočišek, Jaroslav; Poterya, Viktoriya; Pradzynski, Christoph C; Zeuch, Thomas; Slavíček, Petr; Fárník, Michal

    2012-11-01

    Mixed (HNO3)m(H2O)n clusters generated in supersonic expansion of nitric acid vapor are investigated in two different experiments, (1) time-of-flight mass spectrometry after electron ionization and (2) Na doping and photoionization. This combination of complementary methods reveals that only clusters containing at least one acid molecule are generated, that is, the acid molecule serves as the nucleation center in the expansion. The experiments also suggest that at least four water molecules are needed for HNO3 acidic dissociation. The clusters are undoubtedly generated, as proved by electron ionization; however, they are not detected by the Na doping due to a fast charge-transfer reaction between the Na atom and HNO3. This points to limitations of the Na doping recently advocated as a general method for atmospheric aerosol detection. On the other hand, the combination of the two methods introduces a tool for detecting molecules with sizable electron affinity in clusters. PMID:26296012

  10. Tailoring 1H spin dynamics in small molecules via supercooled water: a promising approach for metabolite identification and validation.

    PubMed

    Farooq, Hashim; Soong, Ronald; Courtier-Murias, Denis; Anklin, Clemens; Simpson, André

    2012-08-01

    Metabolic mixtures are often analyzed via NMR spectroscopy as it provides a metabolic profile without sample alteration in a noninvasive manner. These mixtures however tend to be very complex and demonstrate considerable spectral overlap resulting in assignments that are sometimes ambiguous given the range of current NMR methods available. De novo molecular identification in these mixtures is generally accomplished using chemical shift information and J-coupling based experiments to determine spin connectivity information, but these techniques fall short when a molecule of interest contains nonrelaying centers. A method is presented here that enhances intramolecular spatial interactions via supercooled water and uses the resulting spatial correlations to edit mixtures. This is accomplished by utilizing nuclear Overhauser effect spectroscopy (NOESY) at subzero temperatures in capillaries to enhance NOE and provide more complete spin systems. This technique is applied to a standard mixture of three known molecules in D(2)O with overlapping resonances and is further demonstrated to assign molecules in a worm tissue extract. The current method proves to be a powerful complement to existing methods such as total correlation spectroscopy (TOCSY) to expand the range of molecules that can be assigned in situ without physical separation of mixtures. PMID:22788933

  11. [Dynamics of Irreversible Evaporation of a Water-Protein Droplet and a Problem of Structural and Dynamical Experiments with Single Molecules].

    PubMed

    Shaitan, K V; Armeev, G A; Shaytan, A K

    2016-01-01

    We discuss the effect of isothermal and adiabatic evaporation of water on the state of a water-protein droplet. The discussed problem is of current importance due to development of techniques to perform single molecule experiments using free electron lasers. In such structure-dynamic experiments the delivery of a sample into the X-ray beam is performed using the microdroplet injector. The time between the injection and delivery is in the order of microseconds. In this paper we developed a specialized variant of all-atom molecular dynamics simulations for the study of irreversible isothermal evaporation of the droplet. Using in silico experiments we determined the parameters of isothermal evaporation of the water-protein droplet with the sodium and chloride ions in the concentration range of 0.3 M at different temperatures. The energy of irreversible evaporation determined from in silico experiments at the initial stages of evaporation virtually coincides with the specific heat of evaporation for water. For the kinetics of irreversible adiabatic evaporation an exact analytical solution was obtained in the limit of high thermal conductivity of the droplet (or up to the droplet size of -100 Å). This analytical solution incorporates parameters that are determined using in silico. experiments on isothermal droplet evaporation. We show that the kinetics of adiabatic evaporation and cooling of the droplet scales with the droplet size. Our estimates of the water-protemi droplet. freezing rate in the adiabatic regime in a vacuum chamber show that additional techniques for stabilizing the temperature inside the droplet should be used in order to study the conformational transitions of the protein in single molecules. Isothermal and quasi-isothermal conditions are most suitable for studying the conformational transitions upon object functioning. However, in this case it is necessary to take into account the effects of dehydration and rapid increase of ionic strength in an

  12. SET7/9 Catalytic Mutants Reveal the Role of Active Site Water Molecules in Lysine Multiple Methylation

    SciTech Connect

    Del Rizzo, Paul A.; Couture, Jean-François; Dirk, Lynnette M.A.; Strunk, Bethany S.; Roiko, Marijo S.; Brunzelle, Joseph S.; Houtz, Robert L.; Trievel, Raymond C.

    2010-11-15

    SET domain lysine methyltransferases (KMTs) methylate specific lysine residues in histone and non-histone substrates. These enzymes also display product specificity by catalyzing distinct degrees of methylation of the lysine {epsilon}-amino group. To elucidate the molecular mechanism underlying this specificity, we have characterized the Y245A and Y305F mutants of the human KMT SET7/9 (also known as KMT7) that alter its product specificity from a monomethyltransferase to a di- and a trimethyltransferase, respectively. Crystal structures of these mutants in complex with peptides bearing unmodified, mono-, di-, and trimethylated lysines illustrate the roles of active site water molecules in aligning the lysine {epsilon}-amino group for methyl transfer with S-adenosylmethionine. Displacement or dissociation of these solvent molecules enlarges the diameter of the active site, accommodating the increasing size of the methylated {epsilon}-amino group during successive methyl transfer reactions. Together, these results furnish new insights into the roles of active site water molecules in modulating lysine multiple methylation by SET domain KMTs and provide the first molecular snapshots of the mono-, di-, and trimethyl transfer reactions catalyzed by these enzymes.

  13. 2-haloacrylate hydratase, a new class of flavoenzyme that catalyzes the addition of water to the substrate for dehalogenation.

    PubMed

    Mowafy, Amr M; Kurihara, Tatsuo; Kurata, Atsushi; Uemura, Tadashi; Esaki, Nobuyoshi

    2010-09-01

    Enzymes catalyzing the conversion of organohalogen compounds are useful in the chemical industry and environmental technology. Here we report the occurrence of a new reduced flavin adenine dinucleotide (FAD) (FADH(2))-dependent enzyme that catalyzes the removal of a halogen atom from an unsaturated aliphatic organohalogen compound by the addition of a water molecule to the substrate. A soil bacterium, Pseudomonas sp. strain YL, inducibly produced a protein named Caa67(YL) when the cells were grown on 2-chloroacrylate (2-CAA). The caa67(YL) gene encoded a protein of 547 amino acid residues (M(r) of 59,301), which shared weak but significant sequence similarity with various flavoenzymes and contained a nucleotide-binding motif. We found that 2-CAA is converted into pyruvate when the reaction was carried out with purified Caa67(YL) in the presence of FAD and a reducing agent [NAD(P)H or sodium dithionite] under anaerobic conditions. The reducing agent was not stoichiometrically consumed during this reaction, suggesting that FADH(2) is conserved by regeneration in the catalytic cycle. When the reaction was carried out in the presence of H(2)(18)O, [(18)O]pyruvate was produced. These results indicate that Caa67(YL) catalyzes the hydration of 2-CAA to form 2-chloro-2-hydroxypropionate, which is chemically unstable and probably spontaneously dechlorinated to form pyruvate. 2-Bromoacrylate, but not other 2-CAA analogs such as acrylate and methacrylate, served as the substrate of Caa67(YL). Thus, we named this new enzyme 2-haloacrylate hydratase. The enzyme is very unusual in that it requires the reduced form of FAD for hydration, which involves no net change in the redox state of the coenzyme or substrate. PMID:20656877

  14. Relationships between membrane water molecules and Patman equilibration kinetics at temperatures far above the phosphatidylcholine melting point.

    PubMed

    Vaughn, Alexandra R; Bell, Thomas A; Gibbons, Elizabeth; Askew, Caitlin; Franchino, Hannabeth; Hirsche, Kelsey; Kemsley, Linea; Melchor, Stephanie; Moulton, Emma; Schwab, Morgan; Nelson, Jennifer; Bell, John D

    2015-04-01

    The naphthalene-based fluorescent probes Patman and Laurdan detect bilayer polarity at the level of the phospholipid glycerol backbone. This polarity increases with temperature in the liquid-crystalline phase of phosphatidylcholines and was observed even 90°C above the melting temperature. This study explores mechanisms associated with this phenomenon. Measurements of probe anisotropy and experiments conducted at 1M NaCl or KCl (to reduce water permittivity) revealed that this effect represents interactions of water molecules with the probes without proportional increases in probe mobility. Furthermore, comparison of emission spectra to Monte Carlo simulations indicated that the increased polarity represents elevation in probe access to water molecules rather than increased mobility of relevant bilayer waters. Equilibration of these probes with the membrane involves at least two steps which were distinguished by the membrane microenvironment reported by the probe. The difference in those microenvironments also changed with temperature in the liquid-crystalline phase in that the equilibrium state was less polar than the initial environment detected by Patman at temperatures near the melting point, more polar at higher temperatures, and again less polar as temperature was raised further. Laurdan also displayed this level of complexity during equilibration, although the relationship to temperature differed quantitatively from that experienced by Patman. This kinetic approach provides a novel way to study in molecular detail basic principles of what happens to the membrane environment around an individual amphipathic molecule as it penetrates the bilayer. Moreover, it provides evidence of unexpected and interesting membrane behaviors far from the phase transition. PMID:25559316

  15. Fermentation Quality of Ensiled Water Hyacinth (Eichhornia crassipes) as Affected by Additives

    PubMed Central

    Tham, Ho Thanh; Van Man, Ngo; Pauly, Thomas

    2013-01-01

    A lab-scale ensiling study was carried out to investigate the fermentation quality of water hyacinth (WH) supplemented with molasses, rice bran, as an absorbent, and an inoculant in the form of fermented vegetable juice and their combinations. After wilting the water hyacinths for 7 h to a dry matter (DM) content of 240 to 250 g/kg, the following treatments were applied: i) Control (C), WH only; ii) WH with sugarcane molasses at 40 g/kg WH (CM); iii) WH inoculated with fermented vegetable juice at 10 ml/kg WH (CI); iv) CM and CI (CMI) combined; v) WH with 150 g rice bran/kg WH (CA); vi) CA and CI combined (CAI); vii) CA and CM combined (CAM); and viii) CA, CM and CI combined (CAMI). After application of additives, the differently treated forages were mixed and ensiled in triplicates in 1,500-ml polyethylene jars. After ensiling for 3 d, pH values in all treatments, except C and CI, had decreased to approximately 4.0 and remained low till 14 d. After 56 d, pH had increased between 0.4 to 0.9 pH-units compared to those at 14 d. The ammonia nitrogen (NH3-N) concentration ranged from an acceptable level in treatment CM (8 g/kg N) to a high NH3-N value in treatment CMI (16 g/kg N). Lactic acid formation was higher in CI than in all other treatments. Butyric acid contents, which indicate badly fermented silages, were low in all silages (<2 g/kg DM). There were two-way interactions (p-values from <0.001 to 0.045) for almost all fermentation end-products and pH, except for the molasses×inoculant interaction on NH3-N (p = 0.26). Significant 3-way interactions were found on all observed variables except for weight losses of silages. It is concluded that conserving wilted WH as silage for ruminants may be improved by the addition of molasses or rice bran. PMID:25049776

  16. ADDITIONAL STRESS AND FRACTURE MECHANICS ANALYSES OF PRESSURIZED WATER REACTOR PRESSURE VESSEL NOZZLES

    SciTech Connect

    Walter, Matthew; Yin, Shengjun; Stevens, Gary; Sommerville, Daniel; Palm, Nathan; Heinecke, Carol

    2012-01-01

    In past years, the authors have undertaken various studies of nozzles in both boiling water reactors (BWRs) and pressurized water reactors (PWRs) located in the reactor pressure vessel (RPV) adjacent to the core beltline region. Those studies described stress and fracture mechanics analyses performed to assess various RPV nozzle geometries, which were selected based on their proximity to the core beltline region, i.e., those nozzle configurations that are located close enough to the core region such that they may receive sufficient fluence prior to end-of-life (EOL) to require evaluation of embrittlement as part of the RPV analyses associated with pressure-temperature (P-T) limits. In this paper, additional stress and fracture analyses are summarized that were performed for additional PWR nozzles with the following objectives: To expand the population of PWR nozzle configurations evaluated, which was limited in the previous work to just two nozzles (one inlet and one outlet nozzle). To model and understand differences in stress results obtained for an internal pressure load case using a two-dimensional (2-D) axi-symmetric finite element model (FEM) vs. a three-dimensional (3-D) FEM for these PWR nozzles. In particular, the ovalization (stress concentration) effect of two intersecting cylinders, which is typical of RPV nozzle configurations, was investigated. To investigate the applicability of previously recommended linear elastic fracture mechanics (LEFM) hand solutions for calculating the Mode I stress intensity factor for a postulated nozzle corner crack for pressure loading for these PWR nozzles. These analyses were performed to further expand earlier work completed to support potential revision and refinement of Title 10 to the U.S. Code of Federal Regulations (CFR), Part 50, Appendix G, Fracture Toughness Requirements, and are intended to supplement similar evaluation of nozzles presented at the 2008, 2009, and 2011 Pressure Vessels and Piping (PVP

  17. Subpicosecond energy transfer from a highly intense THz pulse to water: A computational study based on the TIP4P/2005 rigid-water-molecule model

    NASA Astrophysics Data System (ADS)

    Mishra, Pankaj Kr.; Vendrell, Oriol; Santra, Robin

    2016-03-01

    The dynamics of ultrafast energy transfer to water clusters and to bulk water by a highly intense, subcycle THz pulse of duration ≈150 fs is investigated in the context of force-field molecular dynamics simulations. We focus our attention on the mechanisms by which rotational and translational degrees of freedom of the water monomers gain energy from these subcycle pulses with an electric field amplitude of up to about 0.6 V/Å. It has been recently shown that pulses with these characteristics can be generated in the laboratory [C. Vicario, B. Monoszlai, and C. P. Hauri, Phys. Rev. Lett. 112, 213901 (2014), 10.1103/PhysRevLett.112.213901]. Through their permanent dipole moment, water molecules are acted upon by the electric field and forced off their preferred hydrogen-bond network conformation. This immediately sets them in motion with respect to one another as energy quickly transfers to their relative center of mass displacements. We find that, in the bulk, the operation of these mechanisms is strongly dependent on the initial temperature and density of the system. In low density systems, the equilibration between rotational and translational modes is slow due to the lack of collisions between monomers. As the initial density of the system approaches 1 g/cm3 , equilibration between rotational and translational modes after the pulse becomes more efficient. In turn, low temperatures hinder the direct energy transfer from the pulse to rotational motion owing to the resulting stiffness of the hydrogen bond network. For small clusters of just a few water molecules we find that fragmentation due to the interaction with the pulse is faster than equilibration between rotations and translations, meaning that the latter remain colder than the former after the pulse. In contrast, clusters with more than a few tens of water molecules already display energy gain dynamics similar to water in condensed phases owing to inertial confinement of the internal water molecules by

  18. Soy Protein Isolate As Fluid Loss Additive in Bentonite-Water-Based Drilling Fluids.

    PubMed

    Li, Mei-Chun; Wu, Qinglin; Song, Kunlin; Lee, Sunyoung; Jin, Chunde; Ren, Suxia; Lei, Tingzhou

    2015-11-11

    Wellbore instability and formation collapse caused by lost circulation are vital issues during well excavation in the oil industry. This study reports the novel utilization of soy protein isolate (SPI) as fluid loss additive in bentonite-water based drilling fluids (BT-WDFs) and describes how its particle size and concentration influence on the filtration property of SPI/BT-WDFs. It was found that high pressure homogenization (HPH)-treated SPI had superior filtration property over that of native SPI due to the improved ability for the plugging pore throat. HPH treatment also caused a significant change in the surface characteristic of SPI, leading to a considerable surface interaction with BT in aqueous solution. The concentration of SPI had a significant impact on the dispersion state of SPI/BT mixtures in aquesous solution. At low SPI concentrations, strong aggregations were created, resulting in the formation of thick, loose, high-porosity and high-permeability filter cakes and high fluid loss. At high SPI concentrations, intercatlated/exfoliated structures were generated, resulting in the formation of thin, compact, low-porosity and low-permeability filter cakes and low fluid loss. The SPI/BT-WDFs exhibited superior filtration property than pure BT-WDFs at the same solid concentraion, demonstrating the potential utilization of SPI as an effective, renewable, and biodegradable fluid loss reducer in well excavation applications. PMID:26492498

  19. Preparations and properties of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials.

    PubMed

    Watanabe, Shoji

    2008-01-01

    This short review describes various types of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials. It is concerned with synthetic additives classified according to their functional groups; silicone compounds, carboxylic acids and dibasic acids, esters, Diels-Alder adducts, various polymers, nitrogen compounds, phosphoric esters, phosphonic acids, and others. Testing methods for water-soluble metal working fluids for aluminum alloy materials are described for a practical application in a laboratory. PMID:18075217

  20. 78 FR 35929 - Proposed Listing of Additional Waters To Be Included on Indiana's 2010 List of Impaired Waters...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-14

    ... decision identifying water quality limited segments and associated pollutants in Indiana to be listed... pollution controls are not stringent enough to attain or maintain state water quality standards and for... certain water quality limited segments and associated pollutants (Table 1 in Appendix A1 of EPA's...

  1. 78 FR 56695 - Proposed Listing of Additional Waters To Be Included on Indiana's 2010 List of Impaired Waters...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-09-13

    ... EPA's proposed decision identifying water quality limited segments and associated pollutants in Indiana to be listed pursuant to the Clean Water Act Section 303(d)(2), and requests public comment. For... Under the Clean Water Act AGENCY: Environmental Protection Agency (EPA). ACTION: Reopening of...

  2. An aspartate and a water molecule mediate efficient acid-base catalysis in a tailored antibody pocket

    SciTech Connect

    Debler, Erik W.; Müller, Roger; Hilvert, Donald; Wilson, Ian A.

    2009-12-01

    Design of catalysts featuring multiple functional groups is a desirable, yet formidable goal. Antibody 13G5, which accelerates the cleavage of unactivated benzisoxazoles, is one of few artificial enzymes that harness an acid and a base to achieve efficient proton transfer. X-ray structures of the Fab-hapten complexes of wild-type 13G5 and active-site variants now afford detailed insights into its mechanism. The parent antibody preorganizes Asp{sup H35} and Glu{sup L34} to abstract a proton from substrate and to orient a water molecule for leaving group stabilization, respectively. Remodeling the environment of the hydrogen bond donor with a compensatory network of ordered waters, as seen in the Glu{sup L34} to alanine mutant, leads to an impressive 10{sup 9}-fold rate acceleration over the nonenzymatic reaction with acetate, illustrating the utility of buried water molecules in bifunctional catalysis. Generalization of these design principles may aid in creation of catalysts for other important chemical transformations.

  3. Binding site identification and role of permanent water molecule of PIM-3 kinase: A molecular dynamics study.

    PubMed

    Ul-Haq, Zaheer; Gul, Sana; Usmani, Saman; Wadood, Abdul; Khan, Waqasuddin

    2015-11-01

    The kinome is a protein kinase complement of the human genome, categorized as serine/threonine and tyrosine kinases. These kinases catalyze phosphorylation reaction by using ATP as phosphoryl donor. Proviral Integration Site for Moloney Murine Leukemia Virus (PIM) kinase encodes serine/threonine protein kinases that recognized as proto-oncogene, responsible for rapid growth of cancerous cells. It is implicated in cell survival and function via cell cycle progression and its metabolism. PIM-3, sub-member of PIM kinases is a proto-oncogene, its overexpression inhibits apoptosis, and results in progression of hepatocellular carcinoma. PIM-3 is considered as a promising drug target but attempts to develop its specific inhibitors is slowed down due to the lack of 3D structure by any experimental technique. In silico techniques generally facilitate scientist to explore hidden structural features in order to improve drug discovery. In the present study, homology modeling, molecular docking and MD simulation techniques were utilized to explore the structure and dynamics of PIM-3 kinase. Induction of water molecules during molecular docking simulation explored differences in the hinge region between PIM-1 and PIM-3 kinases that may be responsible for specificity. Furthermore, role of water molecules in the active site was also explored via radial distribution function (RDF) after a 10 ns molecular dynamics (MD) simulations. Generated RDF plots exhibited the importance of water for inhibitor binding through their bridging capability that links the ligand with binding site residues. PMID:26529487

  4. THE COMBINED CARCINOGENIC RISK FOR EXPOSURE TO MIXTURES OF DRINKING WATER DISINFECTION BY-PRODUCTS MAY BE LESS THAN ADDITIVE

    EPA Science Inventory

    The Combined Carcinogenic Risk for Exposure to Mixtures of Drinking Water Disinfection By-Products May be Less Than Additive

    Risk assessment methods for chemical mixtures in drinking water are not well defined. Current default risk assessments for chemical mixtures assume...

  5. H-bonding networks of the distal residues and water molecules in the active site of Thermobifida fusca hemoglobin.

    PubMed

    Nicoletti, Francesco P; Droghetti, Enrica; Howes, Barry D; Bustamante, Juan P; Bonamore, Alessandra; Sciamanna, Natascia; Estrin, Darío A; Feis, Alessandro; Boffi, Alberto; Smulevich, Giulietta

    2013-09-01

    The ferric form of truncated hemoglobin II from Thermobifida fusca (Tf-trHb) and its triple mutant WG8F-YB10F-YCD1F at neutral and alkaline pH, and in the presence of CN(-) have been characterized by resonance Raman spectroscopy, electron paramagnetic resonance spectroscopy, and molecular dynamics simulations. Tf-trHb contains three polar residues in the distal site, namely TrpG8, TyrCD1 and TyrB10. Whereas TrpG8 can act as a potential hydrogen-bond donor, the tyrosines can act as donors or acceptors. Ligand binding in heme-containing proteins is determined by a number of factors, including the nature and conformation of the distal residues and their capability to stabilize the heme-bound ligand via hydrogen-bonding and electrostatic interactions. Since both the RR Fe-OH(-) and Fe-CN(-) frequencies are very sensitive to the distal environment, detailed information on structural variations has been obtained. The hydroxyl ligand binds only the WT protein giving rise to two different conformers. In form 1 the anion is stabilized by H-bonds with TrpG8, TyrCD1 and a water molecule, in turn H-bonded to TyrB10. In form 2, H-bonding with TyrCD1 is mediated by a water molecule. Unlike the OH(-) ligand, CN(-) binds both WT and the triple mutant giving rise to two forms with similar spectroscopic characteristics. The overall results clearly indicate that H-bonding interactions both with distal residues and water molecules are important structural determinants in the active site of Tf-trHb. This article is part of a Special Issue entitled: Oxygen Binding and Sensing Proteins. PMID:23467007

  6. Water-soluble carbon monoxide-releasing molecules: helping to elucidate the vascular activity of the 'silent killer'.

    PubMed

    Chatterjee, Prabal Kumar

    2004-06-01

    Carbon monoxide (CO) is formed during the degradation of haeme by haeme oxygenase (HO). As well as being an important signalling molecule and vasodilator, CO also possesses antihypertensive, anti-inflammatory and antiapoptotic qualities and protects against ischaemic tissue injury. Several approaches have been used to investigate the therapeutic potential of CO, ranging from direct administration of CO gas to the use of prodrugs, which generate CO upon metabolism. A novel approach involves the use of specific CO carriers, which will release measurable, controllable and effective amounts of CO into biological systems. Transitional metal carbonyls based around iron, manganese or ruthenium have recently been developed as CO-releasing molecules (CO-RMs) that, under appropriate conditions, will release CO. Such molecules have been shown to provide cardioprotection in both ex vivo and in vivo experiments. To date, CO-RMs have been largely incompatible with biological systems in that they are only soluble in organic solvents or have to be preactivated either by physical or chemical stimuli. However, the recent development of water-soluble CO-RMs has provided new opportunities to investigate the pharmacological and biological features of CO without such confounding influences. CORM-3, a novel water-soluble CO-RM, has recently been used to confirm the cardioprotective actions of CO. In this issue of British Journal of Pharmacology, Foresti and co-workers report that CORM-3 delivers CO, produces aortic vasodilation ex vivo and reduces blood pressure in vivo via modulation of the same cGMP and potassium channels utilised by endogenous and exogenous CO. These findings suggest that CORM-3 has the potential for use as a modulator of vascular function and hypertension. However, the use of water-soluble CO-RMs raises several questions of their own which will need to be addressed if CO-RMs are to be of future use therapeutically. PMID:15148242

  7. Water-soluble carbon monoxide-releasing molecules: helping to elucidate the vascular activity of the ‘silent killer'

    PubMed Central

    Chatterjee, Prabal Kumar

    2004-01-01

    Carbon monoxide (CO) is formed during the degradation of haeme by haeme oxygenase (HO). As well as being an important signalling molecule and vasodilator, CO also possesses antihypertensive, anti-inflammatory and antiapoptotic qualities and protects against ischaemic tissue injury. Several approaches have been used to investigate the therapeutic potential of CO, ranging from direct administration of CO gas to the use of prodrugs, which generate CO upon metabolism. A novel approach involves the use of specific CO carriers, which will release measurable, controllable and effective amounts of CO into biological systems. Transitional metal carbonyls based around iron, manganese or ruthenium have recently been developed as CO-releasing molecules (CO-RMs) that, under appropriate conditions, will release CO. Such molecules have been shown to provide cardioprotection in both ex vivo and in vivo experiments. To date, CO-RMs have been largely incompatible with biological systems in that they are only soluble in organic solvents or have to be preactivated either by physical or chemical stimuli. However, the recent development of water-soluble CO-RMs has provided new opportunities to investigate the pharmacological and biological features of CO without such confounding influences. CORM-3, a novel water-soluble CO-RM, has recently been used to confirm the cardioprotective actions of CO. In this issue of British Journal of Pharmacology, Foresti and co-workers report that CORM-3 delivers CO, produces aortic vasodilation ex vivo and reduces blood pressure in vivo via modulation of the same cGMP and potassium channels utilised by endogenous and exogenous CO. These findings suggest that CORM-3 has the potential for use as a modulator of vascular function and hypertension. However, the use of water-soluble CO-RMs raises several questions of their own which will need to be addressed if CO-RMs are to be of future use therapeutically. PMID:15148242

  8. DFT studies of carbohydrate solvation: II. MD-DFTr of a super-molecule complex of glucose, explicit waters, and an implicit solvent (COSMO)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    MD-DFTr studies are carried out on the super-molecule solvated complexes of glucose described in paper I. Included were ten explicit water molecules and an implicit solvation model, COSMO, superimposed upon the complex. Starting configurations were taken from DFTr optimized complexes resulting from ...

  9. Structure and function of residue 104 and water molecules in the xenobiotic substrate-binding site in human glutathione S-transferase P1-1.

    PubMed

    Ji, X; Blaszczyk, J; Xiao, B; O'Donnell, R; Hu, X; Herzog, C; Singh, S V; Zimniak, P

    1999-08-10

    Two variants of human class pi glutathione (GSH) S-transferase 1-1 with either isoleucine or valine in position 104 (hGSTP1-1[I104] and hGSTP1-1[V104]) have distinct activity toward (+)-anti-7, 8-dihydroxy-9,10-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene [(+)-anti-BPDE]. To elucidate their structure-function relationship, we determined the crystal structures of the two variants in complex with GSBpd, the GSH conjugate of (+)-anti-BPDE, at 2.1 and 2.0 A resolution, respectively. The crystal structures reveal that residue 104 in the xenobiotic substrate-binding site (H-site) dictates the binding modes of the product molecule GSBpd with the following three consequences. First, the distance between the hydroxyl group of Y7 and the sulfur atom of GSBpd is 5.9 A in the hGSTP1-1[I104].GSBpd complex versus 3.2 A in the V104 variant. Second, one of the hydroxyl groups of GSBpd forms a direct hydrogen bond with R13 in hGSTP1-1[V104].GSBpd; in contrast, this hydrogen bond is not observed in the I104 complex. Third, in the hydrophilic portion of the H-site of the I104 complex, five H-site water molecules [Ji, X., et al. (1997) Biochemistry 36, 9690-9702] are observed, whereas in the V104 complex, two of the five have been displaced by the Bpd moiety of GSBpd. Although there is no direct hydrogen bond between Y108 (OH) and the hydroxyl groups of GSBpd, indirect hydrogen bonds mediated by water molecules are observed in both complexes, supporting the previously suggested role of the hydroxyl group of Y108 as an electrophilic participant in the addition of GSH to epoxides. PMID:10441116

  10. Possible interstellar formation of glycine from the reaction of CH2=NH, CO and H2O: catalysis by extra water molecules through the hydrogen relay transport.

    PubMed

    Nhlabatsi, Zanele P; Bhasi, Priya; Sitha, Sanyasi

    2016-01-01

    "How the fundamental life elements are created in the interstellar medium (ISM)?" is one of the intriguing questions related to the genesis of life. Using computational calculations, we have discussed the reaction of CH2=NH, CO and H2O for the formation of glycine, the simplest life element. This reaction proceeds through a concerted mechanism with reasonably large barriers for the cases with one and two water molecules as reactants. For the two water case we found that the extra water molecule exhibits some catalytic role through the hydrogen transport relay effect and the barrier height is reduced substantially compared to the case with one water molecule. These two cases can be treated as ideal cases for the hot-core formation of the interstellar glycine. With an increasing number of water molecules as the reactants, we found that when the numbers of water molecules are three or more than three, the barrier height reduced so drastically that the transition states were more stable than the reactants. Such a situation gives a clear indication that with excess water molecules as the reactants, this reaction will be feasible even under the low temperature conditions existing in the cold interstellar clouds and the exothermic nature of the reaction will be the driving force. PMID:26616741

  11. Product distributions and rate constants for ion-molecule reactions in water, hydrogen sulfide, ammonia, and methane

    NASA Technical Reports Server (NTRS)

    Huntress, W. T., Jr.; Pinizzotto, R. F., Jr.

    1973-01-01

    The thermal energy, bimolecular ion-molecule reactions occurring in gaseous water, hydrogen sulfide, ammonia, and methane have been identified and their rate constants determined using ion cyclotron resonance methods. Absolute rate constants were determined for the disappearance of the primary ions by using the trapped ion method, and product distributions were determined for these reactions by using the cyclotron ejection method. Previous measurements are reviewed and compared with the results using the present methods. The relative rate constants for hydrogen-atom abstraction, proton transfer, and charge transfer are also determined for reactions of the parent ions.

  12. Double ionization of the water molecule: Influence of the target orientation on the secondary-electron angular distributions

    SciTech Connect

    Oubaziz, D.; Aouchiche, H.; Champion, C.

    2011-01-15

    Fivefold differential cross sections for electron-induced double ionization of isolated oriented water molecules are reported. The theoretical investigation is performed within the first Born approximation by describing the initial molecular state by means of single-center wave functions. The contributions of each final state to the double-ionization process, i.e., with target electrons ejected from similar and/or different molecular subshells, are studied and compared in terms of shape and magnitude. Furthermore, for the particular target orientations investigated, we identify clearly the signature of the main scenarios involved in (e,3e) reactions, namely, the shake-off and the two-step 1 mechanisms.

  13. Quantum-chemical study of the interactions between cyanide ions and water molecules

    SciTech Connect

    Baranovskii, V.I.; Fomicheva, V.P.; Ivanova, N.V.; Sizova, O.V.

    1986-05-01

    Nonempirical MO SCF calculations have been performed in the 4-31 G basis to examine the interactions of CN/sup -/ ions with H/sub 2/O molecules. The most stable geometrical configurations have been used in calculating the force constants of the C-N and hydrogen-bond stretching vibrations and of the deformation vibration for the H...N-C (H...C-N) angle. The frequencies of the corresponding vibrations have been determined. The results are compared with data obtained for the uncharged HCN x H/sub 2/O system.

  14. Rearrangements of a Water Molecule in Both Directions between Two Hydrogen-Bonding Sites of 5-Hydroxyindole Cation: Experimental Determination of the Energy Threshold for the Rearrangement.

    PubMed

    Ikeda, Takamasa; Sakota, Kenji; Sekiya, Hiroshi

    2016-03-24

    Rearrangements of a water molecule in both directions between two hydrogen-bonding (H-bonding) sites of the 5-hydroxyindole (5HI) cation was investigated in the gas phase. IR-dip spectra of jet-cooled 5HI-(H2O)1 revealed that two structural isomers, 5HI(OH)-(H2O)1 and 5HI(NH)-(H2O)1, in which a water molecule is bound to either the OH group or the NH group of 5HI, were formed in the S0 state. The IR photodissociation spectrum of [5HI-(H2O)1](+) generated by two-color resonant two-photon ionization (2C-R2PI) via the S1-S0 origin of 5HI(NH)-(H2O)1 clearly showed that [5HI(OH)-(H2O)1](+) and [5HI(NH)-(H2O)1](+) coexist in the D0 state. The appearance of [5HI(OH)-(H2O)1](+) after R2PI via the S1-S0 origin of 5HI(NH)-(H2O)1 is explained by isomerization of [5HI(NH)-(H2O)1](+) to [5HI(OH)-(H2O)1](+), which corresponds to the rearrangement of the water. In addition, isomerization in the opposite direction was also observed when [5HI-(H2O)1](+) was generated via the S1-S0 origin of 5HI(OH)-(H2O)1. The upper limit of the energy threshold for the rearrangement of the water in [5HI(NH)-(H2O)1](+) was experimentally determined to be 2127 ± 30 cm(-1) from the adiabatic ionization energy of 5HI(NH)-(H2O)1. Above the energy threshold, the water molecule in [5HI-(H2O)1](+) may fluctuate between the two preferential H-bonding sites of 5HI(+). PMID:26950041

  15. THE CARCINOGENIC RESPONSE TO A MIXTURE OF DRINKING WATER DISINFECTION BY-PRODUCTS (DBP) WAS LESS THAN ADDITIVE

    EPA Science Inventory

    THE CARCINOGENIC RESPONSE TO A MIXTURE OF DRINKING WATER DISINFECTION BY -PRODUCTS (DBP) W AS LESS THAN ADDITIVE.

    Current default risk assessments for chemical mixtures assume additivity of carcinogenic effects but this may under or over represent the actual biological res...

  16. Water soluble graphene as electrolyte additive in magnesium-air battery system

    NASA Astrophysics Data System (ADS)

    Mayilvel Dinesh, M.; Saminathan, K.; Selvam, M.; Srither, S. R.; Rajendran, V.; Kaler, Karan V. I. S.

    2015-02-01

    Magnesium-air (Mg-air) batteries are an important energy source used to power electronic equipment and automobiles. Metal-air batteries give more energy density due to surplus air involved in reduction reaction at air cathode. In this study, the scope of improvements in the efficiency of Metal-air batteries is investigated through addition of water soluble graphene (WSG) as inhibitor in NaCl electrolyte. The discharge performance, corrosion behaviour and electrochemical impedance are studied for (i) the conventional Mg-air battery using 3.5% NaCl and (ii) Mg-air battery with WSG-based 3.5% NaCl electrolyte. X-ray diffraction analysis for WSG is carried out and it shows the crystalline nature of WSG by an intense sharp peak at 26.3°. Scanning electron microscope study is also performed and shows the flake-like structure of WSG denoted by thin layers of carbon. The immersion of WSG in 3.5% NaCl electrolyte increased the current density from 13.24 to 19.33 mA cm-2. Meanwhile, the WSG-based Mg-air battery was found to hold specific discharge capacity of 1030.71 mAh g-1, which was higher than that obtained in 3.5% NaCl electrolyte (i.e., 822.85 mAh g-1). The WSG-based Mg-air battery shows good self-discharge capacity and higher electrochemical activity during discharge.

  17. Water soluble graphene as electrolyte additive in magnesium-air battery system

    NASA Astrophysics Data System (ADS)

    Saminathan, K.; Mayilvel Dinesh, M.; Selvam, M.; Srither, S. R.; Rajendran, V.; Kaler, Karan V. I. S.

    2015-02-01

    Magnesium-air (Mg-air) batteries are an important energy source used to power electronic equipment and automobiles. Metal-air batteries give more energy density due to surplus air involved in reduction reaction at air cathode. In this study, the scope of improvements in the efficiency of Metal-air batteries is investigated through addition of water soluble graphene (WSG) as inhibitor in NaCl electrolyte. The discharge performance, corrosion behaviour and electrochemical impedance are studied for (i) the conventional Mg-air battery using 3.5% NaCl and (ii) Mg-air battery with WSG-based 3.5% NaCl electrolyte. X-ray diffraction analysis for WSG is carried out and it shows the crystalline nature of WSG by an intense sharp peak at 26.3°. Scanning electron microscope study is also performed and shows the flake-like structure of WSG denoted by thin layers of carbon. The immersion of WSG in 3.5% NaCl electrolyte increased the current density from 13.24 to 19.33 mA cm-2. Meanwhile, the WSG-based Mg-air battery was found to hold specific discharge capacity of 1030.71 mAh g-1, which was higher than that obtained in 3.5% NaCl electrolyte (i.e., 822.85 mAh g-1). The WSG-based Mg-air battery shows good self-discharge capacity and higher electrochemical activity during discharge.

  18. Boltzmann equation analysis of electron-molecule collision cross sections in water vapor and ammonia

    SciTech Connect

    Yousfi, M.; Benabdessadok, M.D.

    1996-12-01

    Sets of electron-molecule collision cross sections for H{sub 2}O and NH{sub 3} have been determined from a classical technique of electron swarm parameter unfolding. This deconvolution method is based on a simplex algorithm using a powerful multiterm Boltzmann equation analysis established in the framework of the classical hydrodynamic approximation. It is well adapted for the simulation of the different classes of swarm experiments (i.e., time resolved, time of flight, and steady state experiments). The sets of collision cross sections that exist in the literature are reviewed and analyzed. Fitted sets of cross sections are determined for H{sub 2}O and NH{sub 3} which exhibit features characteristic of polar molecules such as high rotational excitation collision cross sections. The hydrodynamic swarm parameters (i.e., drift velocity, longitudinal and transverse diffusion coefficients, ionization and attachment coefficients) calculated from the fitted sets are in excellent agreement with the measured ones. These sets are finally used to calculate the transport and reaction coefficients needed for discharge modeling in two cases of typical gas mixtures for which experimental swarm data are very sparse or nonexistent (i.e., flue gas mixtures and gas mixtures for rf plasma surface treatment). {copyright} {ital 1996 American Institute of Physics.}

  19. Rotational dynamics of water molecules near biological surfaces with implications for nuclear quadrupole relaxation.

    PubMed

    Braun, Daniel; Schmollngruber, Michael; Steinhauser, Othmar

    2016-09-21

    Based on Molecular Dynamics simulations of two different systems, the protein ubiquitin dissolved in water and an AOT reverse micelle, we present a broad analysis of the single particle rotational dynamics of water. A comprehensive connection to NQR, which is a prominent experimental method in this field, is developed, based on a reformulation of its theoretical framework. Interpretation of experimental NQR results requires a model which usually assumes that the NQR experiences retardation only in the first hydration shell. Indeed, the present study shows that this first-shell model is correct. Moreover, previous experimental retardation factors are quantitatively reproduced. All of this is seemingly contradicted by results of other methods, e.g., dielectric spectroscopy, responsible for a long-standing debate in this field. Our detailed analysis shows that NQR omits important information contained in overall water dynamics, most notably, the retardation of the water dipole axis in the electric field exerted by a biological surface. PMID:27546227

  20. Energy and water additions give rise to simple responses in plant canopy and soil microclimates of a high arctic ecosystem

    NASA Astrophysics Data System (ADS)

    Sullivan, Patrick F.; Welker, Jeffrey M.; Steltzer, Heidi; Sletten, Ronald S.; Hagedorn, Birgit; Arens, Seth J. T.; Horwath, Jennifer L.

    2008-09-01

    Energy and water inputs were increased during the snow-free season to test the sensitivity of a cold, dry ecosystem to climate change. Infrared radiators were used to provide two levels of supplemental radiation (T1 and T2) to prostrate dwarf-shrub, herb tundra in northwest Greenland. The higher radiation addition was combined with supplemental water in a factorial design. Radiation additions increased midday canopy temperatures by up to 4.0°C and 6.0°C and growing season mean shallow soil temperatures by 1.3°C and 2.4°C in T1 and T2 plots, respectively. Soil warming was measured at and probably exceeded 10 cm in depth. There was no evidence of soil drying in plots that received additional radiation, in contrast with other studies, nor was there evidence that supplemental water interacted with radiation additions to affect soil temperatures. Water additions were generally undetectable against a background of large seasonal changes in soil water content. We suggest that well-drained soils and strong seasonal controls on soil water contents (e.g., soil thaw and evapotranspiration) limit the system's sensitivity to changes in precipitation during the brief growing season. In general, multifactor changes in climate gave rise to simple changes in the vegetation microclimate of this cold, dry ecosystem.

  1. Experimental evaluation of water mist with metal chloride additives for suppressing CH4/air cup-burner flames

    NASA Astrophysics Data System (ADS)

    Liu, Jianghong; Cong, Beihua

    2013-06-01

    In order to investigate the fire suppression effectiveness of water mist with metal chloride additives, ultrafine water mists of these salts with diameters about 10μm were introduced into CH4/air non-premixed flame in the cup burner. Results showed that these droplets hard to make itself to the flame front under the cup burner flow conditions functioned as a carrier of the vaporized solid particles or its decomposed materials. The metal chloride improved fire suppression efficacy of water mist which were affected by the type and concentration of metal chloride. On a mass basis, there is a fire suppression effectiveness relationship of MgCl2water solution/metal chlorides improves as the concentration of metal chlorides increase. However, upper additive limits exist due to the associated limiting vapour pressure of the additive.

  2. Burning of suspended coal-water slurry droplet with oil as combustion additive

    SciTech Connect

    Yao, S.C.; Manwani, P.

    1986-10-01

    Coal-water slurries have been regarded as a potential substitute for heavy fuel oil. Various demonstrations of coal-water slurry combustion have been performed; however, a fundamental understanding of how the combustion process of a slurry fuel is enhanced is still not adequate. The combustion of coal-water mixture droplets suspended on microthermocouples has been investigated. It was found that droplets of lignite coal (which is a noncaking coal) burn effectively; however, droplets of bituminous coal (which is a caking coal) are relatively difficult to burn. During the heat-up of bituminous coal-water slurry droplets may turn to ''popcorn'' and show significant agglomeration. The incomplete combustion of coal-water slurry droplets in furnaces has been reported, and this is a drawback of this process. The objective of the present study is to explore the possibility of enhancing the combustion of coal-water slurry droplets with the use of a combustible emulsified oil.

  3. Size-dependent molecule-like to plasmonic transition in water-soluble glutathione stabilized gold nanomolecules

    NASA Astrophysics Data System (ADS)

    Kothalawala, Nuwan; Lee West, James, IV; Dass, Amala

    2013-12-01

    A size-dependent transition from molecule-like to plasmonic behaviour is demonstrated in the case of water soluble Au:SG nanomolecules. This was achieved using PAGE separation of smaller and larger nanomolecules, resulting in an unprecedented 26 bands, in a wide-range from 10's to 1000's of Au-atoms. PAGE separation of larger plasmonic nanomolecules is demonstrated for the first time. High resolution ESI-MS, with isotopic resolution, of smaller nanoparticles is reported, including the first time report of Au43(SG)26. This report will aid in the fundamental understanding of size-dependent properties of nanomolecules. The synthetic procedure employs a green approach with non-toxic chemicals and processes. The water solubility, non-toxicity and biocompatibility will lead to applications in biomedicine.A size-dependent transition from molecule-like to plasmonic behaviour is demonstrated in the case of water soluble Au:SG nanomolecules. This was achieved using PAGE separation of smaller and larger nanomolecules, resulting in an unprecedented 26 bands, in a wide-range from 10's to 1000's of Au-atoms. PAGE separation of larger plasmonic nanomolecules is demonstrated for the first time. High resolution ESI-MS, with isotopic resolution, of smaller nanoparticles is reported, including the first time report of Au43(SG)26. This report will aid in the fundamental understanding of size-dependent properties of nanomolecules. The synthetic procedure employs a green approach with non-toxic chemicals and processes. The water solubility, non-toxicity and biocompatibility will lead to applications in biomedicine. Electronic supplementary information (ESI) available: Detailed synthetic conditions, expanded MS, and optical spectra. This material is available free of charge via the Internet at http://pubs.acs.org. See DOI: 10.1039/c3nr03657j

  4. What interactions can distort the orientational distribution of interfacial water molecules as probed by second harmonic and sum frequency generation?

    NASA Astrophysics Data System (ADS)

    de Beer, Alex G. F.; Roke, Sylvie

    2016-07-01

    Aqueous interfaces are omnipresent in nature. Nonlinear optical methods such as second harmonic and sum frequency generation (SHG/SFG) are valuable techniques to access molecular level information from these interfaces. In the interpretation of SHG and SFG data for both scattering and reflection mode experiments, the relation between the second-order hyperpolarizability tensor β(2), a molecular property, and the surface second-order susceptibility (" separators=" χ(2), a surface averaged property, plays a central role. To correctly describe the molecular details of the interface, it needs to be determined how molecules are oriented, and what the influence is of interfacial electrostatic fields and H-bonding on the orientational distribution. Here, we revisit the relations between β(2) and χ(2) and show, by means of a Boltzmann average, that significant energy differences are needed to generate measurable changes in the molecular orientational distribution at the interface. In practice, H-bonding and surface pressure such as applied in a Langmuir trough can be strong enough to alter the shape of the orientational distribution function of water. In contrast, electrostatic fields, such as those present in the Stern layer, will not have a significant impact on the shape of the orientational distribution function of water molecules.

  5. Hydrogen-bonding changes of internal water molecules upon the actions of microbial rhodopsins studied by FTIR spectroscopy.

    PubMed

    Furutani, Yuji; Kandori, Hideki

    2014-05-01

    Microbial rhodopsins are classified into type-I rhodopsins, which utilize light energy to perform wide varieties of function, such as proton pumping, ion pumping, light sensing, cation channels, and so on. The crystal structures of several type-I rhodopsins were solved and the molecular mechanisms have been investigated based on the atomic structures. However, the crystal structures of proteins of interest are not always available and the basic architectures are sometimes quite similar, which obscures how the proteins achieve different functions. Stimulus-induced difference FTIR spectroscopy is a powerful tool to detect minute structural changes providing a clue for elucidating the molecular mechanisms. In this review, the studies on type-I rhodopsins from fungi and marine bacteria, whose crystal structures have not been solved yet, were summarized. Neurospora rhodopsin and Leptosphaeria rhodopsin found from Fungi have sequence similarity. The former has no proton pumping function, while the latter has. Proteorhodopsin is another example, whose proton pumping machinery is altered at alkaline and acidic conditions. We described how the structural changes of protein were different and how water molecules were involved in them. We reviewed the results on dynamics of the internal water molecules in pharaonis halorhodopsin as well. This article is part of a Special Issue entitled: Retinal Proteins - You can teach an old dog new tricks. PMID:24041645

  6. How water molecules affect the catalytic activity of hydrolases--a XANES study of the local structures of peptide deformylase.

    PubMed

    Cui, Peixin; Wang, Yu; Chu, Wangsheng; Guo, Xiaoyun; Yang, Feifei; Yu, Meijuan; Zhao, Haifeng; Dong, Yuhui; Xie, Yaning; Gong, Weimin; Wu, Ziyu

    2014-01-01

    Peptide deformylase (PDF) is a prokaryotic enzyme that catalyzes the deformylation of nascent peptides generated during protein synthesis and water molecules play a key role in these hydrolases. Using X-ray absorption near edge spectroscopy (XANES) and ab initio calculations we accurately probe the local atomic environment of the metal ion binding in the active site of PDF at different pH values and with different metal ions. This new approach is an effective way to monitor existing correlations among functions and structural changes. We show for the first time that the enzymatic activity depends on pH values and metal ions via the bond length of the nearest coordinating water (Wat1) to the metal ion. Combining experimental and theoretical data we may claim that PDF exhibits an enhanced enzymatic activity only when the distance of the Wat1 molecule with the metal ion falls in the limited range from 2.15 to 2.55 Å. PMID:25503313

  7. What interactions can distort the orientational distribution of interfacial water molecules as probed by second harmonic and sum frequency generation?

    PubMed

    de Beer, Alex G F; Roke, Sylvie

    2016-07-28

    Aqueous interfaces are omnipresent in nature. Nonlinear optical methods such as second harmonic and sum frequency generation (SHG/SFG) are valuable techniques to access molecular level information from these interfaces. In the interpretation of SHG and SFG data for both scattering and reflection mode experiments, the relation between the second-order hyperpolarizability tensor β(2), a molecular property, and the surface second-order susceptibility χ(2), a surface averaged property, plays a central role. To correctly describe the molecular details of the interface, it needs to be determined how molecules are oriented, and what the influence is of interfacial electrostatic fields and H-bonding on the orientational distribution. Here, we revisit the relations between β(2) and χ(2) and show, by means of a Boltzmann average, that significant energy differences are needed to generate measurable changes in the molecular orientational distribution at the interface. In practice, H-bonding and surface pressure such as applied in a Langmuir trough can be strong enough to alter the shape of the orientational distribution function of water. In contrast, electrostatic fields, such as those present in the Stern layer, will not have a significant impact on the shape of the orientational distribution function of water molecules. PMID:27475384

  8. Ligand uptake in Mycobacterium tuberculosis truncated hemoglobins is controlled by both internal tunnels and active site water molecules

    PubMed Central

    Davidge, Kelly S; Singh, Sandip; Bowman, Lesley AH; Tinajero-Trejo, Mariana; Carballal, Sebastián; Radi, Rafael; Poole, Robert K; Dikshit, Kanak; Estrin, Dario A; Marti, Marcelo A; Boechi, Leonardo

    2015-01-01

    Mycobacterium tuberculosis, the causative agent of human tuberculosis, has two proteins belonging to the truncated hemoglobin (trHb) family. Mt-trHbN presents well-defined internal hydrophobic tunnels that allow O 2 and •NO to migrate easily from the solvent to the active site, whereas Mt-trHbO possesses tunnels that are partially blocked by a few bulky residues, particularly a tryptophan at position G8. Differential ligand migration rates allow Mt-trHbN to detoxify •NO, a crucial step for pathogen survival once under attack by the immune system, much more efficiently than Mt-trHbO. In order to investigate the differences between these proteins, we performed experimental kinetic measurements, •NO decomposition, as well as molecular dynamics simulations of the wild type Mt-trHbN and two mutants, VG8F and VG8W. These mutations introduce modifications in both tunnel topologies and affect the incoming ligand capacity to displace retained water molecules at the active site. We found that a single mutation allows Mt-trHbN to acquire ligand migration rates comparable to those observed for Mt-trHbO, confirming that ligand migration is regulated by the internal tunnel architecture as well as by water molecules stabilized in the active site. PMID:26478812

  9. Ligand uptake in Mycobacterium tuberculosis truncated hemoglobins is controlled by both internal tunnels and active site water molecules.

    PubMed

    Boron, Ignacio; Bustamante, Juan Pablo; Davidge, Kelly S; Singh, Sandip; Bowman, Lesley Ah; Tinajero-Trejo, Mariana; Carballal, Sebastián; Radi, Rafael; Poole, Robert K; Dikshit, Kanak; Estrin, Dario A; Marti, Marcelo A; Boechi, Leonardo

    2015-01-01

    Mycobacterium tuberculosis, the causative agent of human tuberculosis, has two proteins belonging to the truncated hemoglobin (trHb) family. Mt-trHbN presents well-defined internal hydrophobic tunnels that allow O 2 and (•)NO to migrate easily from the solvent to the active site, whereas Mt-trHbO possesses tunnels that are partially blocked by a few bulky residues, particularly a tryptophan at position G8. Differential ligand migration rates allow Mt-trHbN to detoxify (•)NO, a crucial step for pathogen survival once under attack by the immune system, much more efficiently than Mt-trHbO. In order to investigate the differences between these proteins, we performed experimental kinetic measurements, (•)NO decomposition, as well as molecular dynamics simulations of the wild type Mt-trHbN and two mutants, VG8F and VG8W. These mutations introduce modifications in both tunnel topologies and affect the incoming ligand capacity to displace retained water molecules at the active site. We found that a single mutation allows Mt-trHbN to acquire ligand migration rates comparable to those observed for Mt-trHbO, confirming that ligand migration is regulated by the internal tunnel architecture as well as by water molecules stabilized in the active site. PMID:26478812

  10. Prototropic tautomerism of 4-Methyl 1,2,4-Triazole-3-Thione molecule in solvent water medium: DFT and Car-Parrinello molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Dutta, Bipan; De, Rina; Chowdhury, Joydeep

    2015-12-01

    The ground state prototropic tautomerism of 4-Methyl 1,2,4-Triazole-3-Thione molecule in solvent water medium has been investigated with the aid of DFT and Car-Parrinello molecular dynamics (CPMD) simulation studies. The CPMD simulations envisage the possibility of proton transfer reactions of the molecule through the solvent water medium. Probable proton transfer pathways have been predicted from the DFT calculations which are substantiated by the natural bond orbital analyses. The evolution and breaking of the concerned bonds of the molecule for different proton transfer reaction pathways are also estimated.

  11. Dynamics of molecules in a supercooled water nanoparticle during the ice accretion on the aircraft surface

    NASA Astrophysics Data System (ADS)

    Amelyushkin, I. A.; Stasenko, A. L.

    2015-06-01

    The principal aim of this work is to elaborate a robust physical model and the corresponding numerical code for prediction of the icing startup due to numerous water nanoparticles in the supercooled humid air. For this purpose, a scientified approach was used which is based not on the quantum-mechanics considerations but on the information about intermolecular potentials (especially, Lennard-Jones (LJ), etc.) tightly connected with the state equations of the corresponding specie (e. g., van der Waals for air and water and Mie-Grünaisen for circumfluent body). u In other words, the principal idea of this work is to adequately ascribe certain macroscopic characteristics of a water nanoparticle which may significantly differ from those indicated in physical reference books for bulk materials.

  12. Effect of anodizing voltage on the sorption of water molecules on porous alumina

    NASA Astrophysics Data System (ADS)

    Vrublevsky, I.; Chernyakova, K.; Bund, A.; Ispas, A.; Schmidt, U.

    2012-05-01

    The amount of water adsorbed on different centers on the surface of oxalic acid alumina films is a function of the anodizing voltage. It is decreased with increasing the anodizing voltage from 20 up to 50 V, came up to maximum value at 20-30 V and slightly increased at voltages above 50 V. Water adsorption by oxide films formed at voltages below 50 V can be due to the negative surface charge that is present on the alumina surface. The negative surface charge disappears in the films formed at voltages higher than 50 V, and thus, the water is adsorbed on aluminum ions in a tetrahedral and octahedral environment. The correlation between anodizing conditions of aluminum in oxalic acid and the structure and composition of anodic alumina was established by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), thermogravimetric and differential thermal analyses (TG/DTA).

  13. Mercedes–Benz water molecules near hydrophobic wall: Integral equation theories vs Monte Carlo simulations

    PubMed Central

    Urbic, T.; Holovko, M. F.

    2011-01-01

    Associative version of Henderson-Abraham-Barker theory is applied for the study of Mercedes–Benz model of water near hydrophobic surface. We calculated density profiles and adsorption coefficients using Percus-Yevick and soft mean spherical associative approximations. The results are compared with Monte Carlo simulation data. It is shown that at higher temperatures both approximations satisfactory reproduce the simulation data. For lower temperatures, soft mean spherical approximation gives good agreement at low and at high densities while in at mid range densities, the prediction is only qualitative. The formation of a depletion layer between water and hydrophobic surface was also demonstrated and studied. PMID:21992334

  14. Mercedes-Benz water molecules near hydrophobic wall: Integral equation theories vs Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Urbic, T.; Holovko, M. F.

    2011-10-01

    Associative version of Henderson-Abraham-Barker theory is applied for the study of Mercedes-Benz model of water near hydrophobic surface. We calculated density profiles and adsorption coefficients using Percus-Yevick and soft mean spherical associative approximations. The results are compared with Monte Carlo simulation data. It is shown that at higher temperatures both approximations satisfactory reproduce the simulation data. For lower temperatures, soft mean spherical approximation gives good agreement at low and at high densities while in at mid range densities, the prediction is only qualitative. The formation of a depletion layer between water and hydrophobic surface was also demonstrated and studied.

  15. Mercedes-Benz water molecules near hydrophobic wall: integral equation theories vs Monte Carlo simulations.

    PubMed

    Urbic, T; Holovko, M F

    2011-10-01

    Associative version of Henderson-Abraham-Barker theory is applied for the study of Mercedes-Benz model of water near hydrophobic surface. We calculated density profiles and adsorption coefficients using Percus-Yevick and soft mean spherical associative approximations. The results are compared with Monte Carlo simulation data. It is shown that at higher temperatures both approximations satisfactory reproduce the simulation data. For lower temperatures, soft mean spherical approximation gives good agreement at low and at high densities while in at mid range densities, the prediction is only qualitative. The formation of a depletion layer between water and hydrophobic surface was also demonstrated and studied. PMID:21992334

  16. Supramolecular polymerisation in water; elucidating the role of hydrophobic and hydrogen-bond interactions† †Electronic supplementary information (ESI) available: Experimental details, characterization by IR and UV spectroscopy and dynamic light scattering, video files of optical microscopy imaging. See DOI: 10.1039/c5sm02843d Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file.

    PubMed Central

    Leenders, Christianus M. A.; Baker, Matthew B.; Pijpers, Imke A. B.; Lafleur, René P. M.; Albertazzi, Lorenzo

    2016-01-01

    Understanding the self-assembly of small molecules in water is crucial for the development of responsive, biocompatible soft materials. Here, a family of benzene-1,3,5-tricarboxamide (BTA) derivatives that comprise a BTA moiety connected to an amphiphilic chain is synthesised with the aim to elucidate the role of hydrophobic and hydrogen-bonding interactions in the self-assembly of these BTAs. The amphiphilic chain consists of an alkyl chain with a length of 10, 11, or 12 methylene units, connected to a tetraethylene glycol (at the periphery). The results show that an undecyl spacer is the minimum length required for these BTAs to self-assemble into supramolecular polymers. Interestingly, exchange studies reveal only minor differences in exchange rates between BTAs containing undecyl or dodecyl spacers. Additionally, IR spectroscopy provides the first experimental evidence that hydrogen-bonding is operative and contributes to the stabilisation of the supramolecular polymers in water. PMID:26892482

  17. Addition of nucleophiles on cyanoacetylene N≡CCH=CH-X (X = NH2, OH, SH, …). Synthesis and Physico-chemical Properties of Potential Prebiotic Compounds or Interstellar Molecules.

    NASA Astrophysics Data System (ADS)

    Guillemin, Jean-Claude

    Among the molecules detected to date in the interstellar medium (ISM), cyanopolyynes constitute a rich and important subset. These robust compounds exhibit special properties with respect to their reactivity and kinetic stability, and some have been found in other astrochemical environments, such as comets or in lab simulations of planetary atmospheres.[1] These systems are supposed to be good starting materials for the formation of new, more complex, astrochemical species, or amino acids on primitive Earth. The formal addition of water, hydrogen sulfur or ammonia on cyanoacetylene (H-C≡C-C≡N) gives the corresponding heterosubstitued acrylonitriles. We have extensively investigated the study of such adducts. With water, the formed cyanovinylalcohol (NC-CH=CH-OH) is in a tautomeric equilibrium with the kinetically more stable cyanoacetaldehyde (NC-CH2 CH(=O)). Isolation of these compounds in pure form is challenging but the gas phase infrared spectrum has been recorded. Reaction of ammonia with cyanoacetylene gives aminoacrylonitrile (H2 N-CH=CH-CN), a stable enamine; microwave and infrared spectra were obtained.[2] Similarly the MW spectrum of 3-mercapto-2-propenenitrile (HS-CH=CH-CN) has been recorded.[3] Attempts to detect both species in the ISM have been performed. A combined experimental and theoretical study on the gas-phase basicity and acidity of a series of cyanovinyl derivatives is also presented.[4] We will demonstrate that many particular physicochemical properties are associated to these simple adducts of cyanoacetylene, compounds often proposed as prebiotic molecules or components of the ISM. 1] S. W. Fow, K. Dose, Molecular Evolution and the Origin of Life, Marcel Dekker, Stateplace- New York, metricconverterProductID1977. A1977. A. Coustenis, T. Encrenaz, B. BJzard, B. Bjoraker, G. Graner, G. Dang-Nhu, E. AriJ, Icarus 1993, 102, 240 - 269. [2] Benidar, A. ; Guillemin, J.-C. ; M—, O. ; Y‡-ez, M. J. Phys. Chem. A. 2005, 109, 4705-4712. E

  18. Recombination time of an RF discharge plasma in the presence of water molecules

    SciTech Connect

    Protasevich, E.T.

    1986-05-01

    The authors show that the introduction of water vapor into an electrodeless rf discharge noticeably reduces the excitation temperature and substantially increases the recombination time of the plasma. An attempt is made to explain the physical processes associated with these phenomena.

  19. Addition of a Magnetite Layer onto a Polysulfone Water Treatment Membrane to Enhance Virus Removal

    NASA Astrophysics Data System (ADS)

    Raciny, Isabel

    The applicability of low-pressure membranes systems in distributed (point of use) water treatment is hindered by, among other things, their inability to remove potentially harmful viruses and ions via size exclusion. According to the USEPA and the Safe Drinking Water Act, drinking water treatment processes must be designed for 4-log virus removal. Batch experiments using magnetite nanoparticle (nano-Fe3O4) suspensions and water filtration experiments with Polysulfone (PSf) membranes coated with nano-Fe3O 4 were conducted to assess the removal of a model virus (bacteriophage MS2). The membranes were coated via a simple filtration protocol. Unmodified membranes were a poor adsorbent for MS2 bacteriophage with less than 0.5-log removal, whereas membranes coated with magnetite nanoparticles exhibited a removal efficiency exceeding 99.99% (4-log). Thus, a cartridge of PSf membranes coated with nano-Fe3O4 particles could be used to remove viruses from water. Such membranes showed negligible iron leaching into the filtrate, thus obviating concern about colored water. Further research is needed to reduce the loss of water flux caused by coating.

  20. Hierarchical assembly of an achiral pi-conjugated molecule into a chiral nanotube through the air/water interface.

    PubMed

    Yao, Pingping; Wang, Haifeng; Chen, Penglei; Zhan, Xiaowei; Kuang, Xun; Zhu, Daoben; Liu, Minghua

    2009-06-16

    An achiral pi-conjugated fluorinated fused pyrazine derivative has been spread at the air/water interface, and its assembling property is investigated. It has been found that the compound, although without any long alkyl chain, could be spread as a floating film on water surface, the surface pressure of which can be compressed up to ca. 70 mN/m. An inflection point has been observed in the isotherm of the floating film on water surface. The atomic force microscope (AFM), scanning electron microscope (SEM) as well as the transmission electron microscope (TEM) observations revealed that the floating film first formed a multilayer structure and then was compressed into nanotubes after the inflection region as a result of the rolling of the ultrathin film. Interestingly, the rolled nanotubes show circular dichroism although the molecule itself is an achiral species, suggesting the chiral nanotube is predominantly produced on the water surface. The investigation provides an effective way to fabricate supramolecular-based organic chiral nanotubes through an interfacial supramolecular assembly process. PMID:19459675

  1. Structural and atoms-in-molecules analysis of hydrogen-bond network around nitroxides in liquid water.

    PubMed

    Houriez, Céline; Masella, Michel; Ferré, Nicolas

    2010-09-28

    In this study, we investigated the hydrogen-bond network patterns involving the NO moieties of five small nitroxides in liquid water by analyzing nanosecond scale molecular dynamics trajectories. To this end, we implemented two types of hydrogen-bond definitions, based on electronic structure, using Bader's atoms-in-molecules analysis and based on geometric criteria. In each definition framework, the nitroxide/water hydrogen-bond networks appear very variable from a nitroxide to another. Moreover, each definition clearly leads to a different picture of nitroxide hydration. For instance, the electronic structure-based definition predicts a number of hydrogen bonds around the nitroxide NO moiety usually larger than geometric structure-based ones. One particularly interesting result is that the strength of a nitroxide/water hydrogen bond does not depend on its linearity, leading us to question the relevance of geometric definition based on angular cutoffs to study this type of hydrogen bond. Moreover, none of the hydrogen-bond definitions we consider in the present study is able to quantitatively correlate the strength of nitroxide/water hydrogen-bond networks with the aqueous nitroxide spin properties. This clearly exhibits that the hydrogen-bonding concept is not reliable enough to draw quantitative conclusions concerning such properties. PMID:20886951

  2. Structural and atoms-in-molecules analysis of hydrogen-bond network around nitroxides in liquid water

    NASA Astrophysics Data System (ADS)

    Houriez, Céline; Masella, Michel; Ferré, Nicolas

    2010-09-01

    In this study, we investigated the hydrogen-bond network patterns involving the NO moieties of five small nitroxides in liquid water by analyzing nanosecond scale molecular dynamics trajectories. To this end, we implemented two types of hydrogen-bond definitions, based on electronic structure, using Bader's atoms-in-molecules analysis and based on geometric criteria. In each definition framework, the nitroxide/water hydrogen-bond networks appear very variable from a nitroxide to another. Moreover, each definition clearly leads to a different picture of nitroxide hydration. For instance, the electronic structure-based definition predicts a number of hydrogen bonds around the nitroxide NO moiety usually larger than geometric structure-based ones. One particularly interesting result is that the strength of a nitroxide/water hydrogen bond does not depend on its linearity, leading us to question the relevance of geometric definition based on angular cutoffs to study this type of hydrogen bond. Moreover, none of the hydrogen-bond definitions we consider in the present study is able to quantitatively correlate the strength of nitroxide/water hydrogen-bond networks with the aqueous nitroxide spin properties. This clearly exhibits that the hydrogen-bonding concept is not reliable enough to draw quantitative conclusions concerning such properties.

  3. 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.

  4. [DOTA-bis(amide)]lanthanide complexes: NMR evidence for differences in water-molecule exchange rates for coordination isomers.

    PubMed

    Zhang, S; Kovacs, Z; Burgess, S; Aime, S; Terreno, E; Sherry, A D

    2001-01-01

    Two derivatives of 1,4,7,10-tetraazacyclododecane with trans-acetate and trans-amide side-chain ligating groups have been prepared and their complexes with lanthanide cations examined by multinuclear NMR spectroscopy. These lanthanide complexes exist in aqueous solution as a mixture of slowly interconverting coordination isomers with 1H chemical shifts similar to those reported previously for the major (M) and minor (m) forms of the tetraacetate ([Ln(dota)]-) and tetraamide ([Ln(dtma)]3+) complexes. As in the [Ln(dota)]- and [Ln(dtma)]3+ complexes, the m/M ratio proved to be a sensitive function of lanthanide size and temperature. An analysis of 1H hyperfine shifts in spectra of the Yb3+ complexes revealed significant differences between the axial (D1) and non-axial (D2) components of the magnetic susceptibility tensor anisotropy in the m and M coordination isomers and the energetics of ring inversion and m <==> M isomerization as determined by two-dimensional exchange spectroscopy (EXSY). (17)O shift data for the Dy3+ complexes showed that both have one inner-sphere water molecule. A temperature-dependent (17)O NMR study of bulk water linewidths for solutions of the Gd3+ complexes provided direct evidence for differences in water exchange rates for the two coordination isomers. The bound-water lifetimes (tauM298) in the M and m isomers of the Gd3+ complexes ranged from 1.4-2.4 micros and 3-14 ns, respectively. This indicates that 1) the inner-sphere water lifetimes for the complexes with a single positive charge reported here are considerably shorter for both coordination isomers than the corresponding values for the [Gd(dtma)]3+ complex with three positive charges, and 2) the difference in water lifetimes for M and m isomers in these two series is magnified in the [Gd[dota-bis(amide)

  5. The reaction of clean Li surfaces with small molecules in ultrahigh vacuum. 2: Water

    SciTech Connect

    Zhuang, G.; Ross, P.N. Jr.; Kong, F.P.; McLarnon, F. |

    1998-01-01

    Reactions at the Li/H{sub 2}O interface were studied at 160 to 290 K in ultrahigh vacuum by a combination of spectroscopic ellipsometry and Auger electron spectroscopy. Ice multilayers, ca. 100 ML thick, were deposited on clean Li at 160 K. The evaporation rate of water at 160 K is sufficiently slow that the ice layer remains on the surface for about 1 h. After 10 min at 160 k, a pure LiOH layer ca. 70 {angstrom} thick is produced, and after 1 h there is evidence of a slow conversion to LiOH to Li{sub 2}O in the layer, probably at the Li/LiOH interface. Raising the temperature to 240 K results in desorption of the adsorbed water and conversion of all the LiOH to a porous (60% void) layer composed mostly of Li{sub 2}O (35%) with some metallic Li mixed in. Raising the temperature further to 290 K results in densification of the layer by both collapse of the voids and by diffusion of Li into the interstices of the Li{sub 2}O, increasing the Li content to 27% and shrinking the film thickness to 26 {angstrom}. Based on these results, a model for the behavior of small amounts of water in Li battery electrolyte is presented.

  6. Proposed photosynthesis method for producing hydrogen from dissociated water molecules using incident near-infrared light.

    PubMed

    Li, Xingxing; Li, Zhenyu; Yang, Jinlong

    2014-01-10

    Highly efficient solar energy utilization is very desirable in photocatalytic water splitting. However, until now, the infrared part of the solar spectrum, which constitutes almost half of the solar energy, has not been used, resulting in significant loss in the efficiency of solar energy utilization. Here, we propose a new mechanism for water splitting in which near-infrared light can be used to produce hydrogen. This ability is a result of the unique electronic structure of the photocatalyst, in which the valence band and conduction band are distributed on two opposite surfaces with a large electrostatic potential difference produced by the intrinsic dipole of the photocatalyst. This surface potential difference, acting as an auxiliary booster for photoexcited electrons, can effectively reduce the photocatalyst's band gap required for water splitting in the infrared region. Our electronic structure and optical property calculations on a surface-functionalized hexagonal boron-nitride bilayer confirm the existence of such photocatalysts and verify the reaction mechanism. PMID:24483934

  7. 75 FR 41725 - Food Additives Permitted in Feed and Drinking Water of Animals; Ammonium Formate

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-19

    .... Background In a notice published in the Federal Register of January 11, 2008 (73 FR 2055), FDA announced that... ammonium formate as an acidifying agent in swine feed. This action is in response to a food additive... exceed 1.2 percent in swine feed. Subsequently, it was determined that the food additive is...

  8. Synthesis of DHA/EPA-rich phosphatidylcholine by immobilized phospholipase A1: effect of water addition and vacuum condition.

    PubMed

    Li, Daoming; Qin, Xiaoli; Wang, Weifei; Li, Zhigang; Yang, Bo; Wang, Yonghua

    2016-08-01

    DHA/EPA-rich phosphatidylcholine (PC) was successfully synthesized by immobilized phospholipase A1 (PLA1)-catalyzed transesterification of PC and DHA/EPA-rich ethyl esters in a solvent-free system. Effects of reaction temperature, water addition and substrate mass ratio on the incorporation of DHA/EPA were evaluated using response surface methods (RSM). Water addition had most significant effect on the incorporation. Reaction temperature and substrate mass ratio, however, had no significant effect on the incorporation. The maximal incorporation was 19.09 % (24 h) under the following conditions: temperature 55.7 °C, water addition 1.1 wt % and substrate mass ratio (ethyl esters/PC) 6.8:1. Furthermore, effects of water addition (from 0 to 1.25 wt %) on DHA/EPA incorporation and the composition of products were further investigated. The immobilized PLA1 was more active when water addition was above 0.5 wt %. By monitoring the reaction processes with different water addition, a possible reaction scheme was proposed for transesterification of PC with DHA/EPA-rich ethyl esters. In summary, PC and sn2-lysophosphatidylocholine (LPC) were predominant in the mixtures at early stages of reaction, whereas sn1-LPC and glycerophosphocholine (GPC) predominant at later stages. The vacuum employed after 24 h significantly increased the incorporation of DHA/EPA and the composition of PC, and the highest incorporation (30.31 %) of DHA/EPA was obtained at 72 h and the yield of PC was 47.2 %. PMID:27108109

  9. Effect of enzyme concentration, addition of water and incubation time on increase in yield of starch from potato.

    PubMed

    Sit, Nandan; Agrawal, U S; Deka, Sankar C

    2014-05-01

    Enzymatic treatment process for starch extraction from potato was investigated using cellulase enzyme and compared with conventional process. The effects of three parameters, cellulase enzyme concentration, incubation time and addition of water were evaluated for increase in starch yield as compared to the conventional process i.e., without using enzyme. A two-level full factorial design was used to study the process. The results indicated that all the main parameters and their interactions are statistically significant. Enzyme concentration and incubation time had a positive effect on the increase in starch yield while addition of water had a negative effect. The increase in starch yield ranged from 1.9% at low enzyme concentration and incubation time and high addition of water to a maximum of 70% increase from conventional process in starch yield was achieved when enzyme concentration and incubation time were high and addition of water was low suggesting water present in the ground potato meal is sufficient for access to the enzyme with in the slurry ensuring adequate contact with the substrate. PMID:24803713

  10. Optimizing electrostatic field calculations with the Adaptive Poisson-Boltzmann Solver to predict electric fields at protein-protein interfaces II: explicit near-probe and hydrogen-bonding water molecules.

    PubMed

    Ritchie, Andrew W; Webb, Lauren J

    2014-07-17

    We have examined the effects of including explicit, near-probe solvent molecules in a continuum electrostatics strategy using the linear Poisson-Boltzmann equation with the Adaptive Poisson-Boltzmann Solver (APBS) to calculate electric fields at the midpoint of a nitrile bond both at the surface of a monomeric protein and when docked at a protein-protein interface. Results were compared to experimental vibrational absorption energy measurements of the nitrile oscillator. We examined three methods for selecting explicit water molecules: (1) all water molecules within 5 Å of the nitrile nitrogen; (2) the water molecule closest to the nitrile nitrogen; and (3) any single water molecule hydrogen-bonding to the nitrile. The correlation between absolute field strengths with experimental absorption energies were calculated and it was observed that method 1 was only an improvement for the monomer calculations, while methods 2 and 3 were not significantly different from the purely implicit solvent calculations for all protein systems examined. Upon taking the difference in calculated electrostatic fields and comparing to the difference in absorption frequencies, we typically observed an increase in experimental correlation for all methods, with method 1 showing the largest gain, likely due to the improved absolute monomer correlations using that method. These results suggest that, unlike with quantum mechanical methods, when calculating absolute fields using entirely classical models, implicit solvent is typically sufficient and additional work to identify hydrogen-bonding or nearest waters does not significantly impact the results. Although we observed that a sphere of solvent near the field of interest improved results for relative field calculations, it should not be consider a panacea for all situations. PMID:24446740

  11. Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives

    PubMed Central

    Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

    2016-01-01

    High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application. PMID:26951794

  12. Effect of water and nitrogen additions on free-living nitrogen fixer populations in desert grass root zones.

    PubMed Central

    Herman, R P; Provencio, K R; Torrez, R J; Seager, G M

    1993-01-01

    In this study we measured changes in population levels of free-living N2-fixing bacteria in the root zones of potted Bouteloua eriopoda and Sporobolus flexuosus plants as well as the photosynthetic indices of the plants in response to added nitrogen, added water, and added water plus nitrogen treatments. In addition, N2 fixer population changes in response to added carbon source and nitrogen were measured in plant-free soil columns. There were significant increases in the numbers of N2 fixers associated with both plant species in the water and the water plus nitrogen treatments. Both treatments increased the photosynthetic index, suggesting that plant exudates were driving N2 fixer population changes. Population increases were greatest in the water plus nitrogen treatments, indicating that added nitrogen was synergistic with added water and suggesting that nitrogen addition spared bacteria the metabolic cost of N2 fixation, allowing greater reproduction. Plant-free column studies demonstrated a synergistic carbon-nitrogen effect when carbon levels were limiting (low malate addition) but not when carbon was abundant (high malate), further supporting this hypothesis. The results of this study indicate the presence of N2 fixer populations which interact with plants and which may play a role in the nitrogen balance of desert grasslands. PMID:8215373

  13. Numerical study of water entry supercavitating flow around a vertical circular cylinder influenced by turbulent drag-reducing additives

    NASA Astrophysics Data System (ADS)

    Jiang, C. X.; Cheng, J. P.; Li, F. C.

    2015-01-01

    This paper attempts to introduce a numerical simulation procedure to simulate water-entry problems influenced by turbulent drag-reducing additives in a viscous incompressible medium. Firstly we performed a numerical investigation on water-entry supercavities in water and turbulent drag-reducing solution at the impact velocity of 28.4 m/s to confirm the accuracy of the numerical method. Based on the verification, projectile entering water and turbulent drag-reducing solution at relatively high velocity of 142.7 m/s (phase transition is considered) is simulated. The cross viscosity equation was adopted to represent the shear-thinning characteristic of aqueous solution of drag-reducing additives. The configuration and dynamic characteristics of water entry supercavity, flow resistance were discussed respectively. It was obtained that the numerical simulation results are in consistence with experimental data. Numerical results show that the supercavity length in drag-reducing solution is larger than one in water and the velocity attenuates faster at high velocity than at low velocity; the influence of drag-reducing solution is more obvious at high impact velocity. Turbulent drag-reducing additives have the great potential for enhancement of supercavity.

  14. Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives.

    PubMed

    Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

    2016-01-01

    High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application. PMID:26951794

  15. Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives

    NASA Astrophysics Data System (ADS)

    Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

    2016-03-01

    High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application.

  16. Geohydrology of the Central Oahu, Hawaii, Ground-Water Flow System and Numerical Simulation of the Effects of Additional Pumping

    USGS Publications Warehouse

    Oki, Delwyn S.

    1998-01-01

    -calculated freshwater-saltwater interface location for the future recharge and pumping conditions. Model results indicate that an additional 10 million gallons per day (beyond the 1995-allocated rates) of freshwater can potentially be developed from northern Oahu. Various distributions of pumping can be used to obtain the additional 10 million gallons per day of water. The quality of the water pumped will be dependent on site-specific factors and cannot be predicted on the basis of model results. If the additional 10 million gallons per day pumpage is restricted to the Kawailoa and Waialua areas, model results indicate that a regional drawdown (relative to the water-level distribution associated with the 1995-allocated pumping rates) of less than 0.6 foot can be maintained in these two areas. The additional pumping, however, would cause salinity increases in water pumped by existing deep wells. In addition, increases in salinity may occur at other wells in areas where the model indicates no significant problem with upconing.

  17. Water reuse: >90% water yield in MBR/RO through concentrate recycling and CO2 addition as scaling control.

    PubMed

    Joss, Adriano; Baenninger, Claudia; Foa, Paolo; Koepke, Stephan; Krauss, Martin; McArdell, Christa S; Rottermann, Karin; Wei, Yuansong; Zapata, Ana; Siegrist, Hansruedi

    2011-11-15

    Over 1.5 years continuous piloting of a municipal wastewater plant upgraded with a double membrane system (ca. 0.6 m(3) d(-1) of product water produced) have demonstrated the feasibility of achieving high water quality with a water yield of 90% by combining a membrane bioreactor (MBR) with a submerged ultrafiltration membrane followed by a reverse osmosis membrane (RO). The novelty of the proposed treatment scheme consists of the appropriate conditioning of MBR effluent prior to the RO and in recycling the RO concentrates back to the biological unit. All the 15 pharmaceuticals measured in the influent municipal sewage were retained below 100 ng L(-1), a proposed quality parameter, and mostly below detection limits of 10 ng L(-1). The mass balance of the micropollutants shows that these are either degraded or discharged with the excess concentrate, while only minor quantities were found in the excess sludge. The micropollutant load in the concentrate can be significantly reduced by ozonation. A low treated water salinity (<10 mM inorganic salts; 280 ± 70 μS cm(-1)) also confirms that the resulting product has a high water quality. Solids precipitation and inorganic scaling are effectively mitigated by lowering the pH in the RO feed water with CO(2) conditioning, while the concentrate from the RO is recycled to the biological unit where CO(2) is stripped by aeration. This causes precipitation to occur in the bioreactor bulk, where it is much less of a process issue. SiO(2) is the sole exception. Equilibrium modeling of precipitation reactions confirms the effectiveness of this scaling-mitigation approach for CaCO(3) precipitation, calcium phosphate and sulfate minerals. PMID:21959090

  18. Passive nutrient addition for the biodegradation of ethylene glycol in storm water.

    PubMed

    Safferman, Steven I; Azar, Roger A; Sigler, Stephanie

    2002-01-01

    This laboratory proof-of-concept research examined the feasibility of adding solid, slow-release macronutrients to a biofilm reactor system to achieve the effective biodegradation of a predominately organic polluted storm water. The target scenario was treating ethylene glycol in storm water, representing the runoff of airport deicing and anti-icing fluids. However, the results can also be generalized for any water polluted with a predominately carbonaceous material. The use of a solid, slow-release nutrient source, compared to amending with a soluble solution in proportion to influent flow, would be ideal for storm water applications and other specialized wastewater flows when maintenance requirements and operational support must be minimized. Several commercially available fertilizers were preliminarily examined to determine which had the best potential to provide the required amount of nutrients. A time-released, polymer-coated granular fertilizer was ultimately selected. Based on laboratory studies, it was found that this fertilizer could provide a controllable source of macronutrients that enabled treatment to a similar degree as if the macronutrients had been dissolved in the influent. The only major operational problem was reduced nutrient delivery from the fertilizer after it became coated with a thick biofilm. However, the inherent intermittent nature of storm water production resulting in wet/dry cycles may minimize the development of a thick biofilm. PMID:12049128

  19. Atmospheric transport and deposition, an additional input pathway for triazine herbicides to surface waters

    SciTech Connect

    Muir, D.C.G.; Rawn, D.F.

    1996-10-01

    Although surface runoff from treated fields is regarded as the major route of entry of triazine herbicides to surface waters, other pathways such as deposition via precipitation, gas absorption and dryfall may also be important. Triazine herbicides have been detected in precipitation but there has been only a very limited amount of work on gas phase and aerosols. To examine the importance of atmospheric inputs concentrations of atrazine, cyanazine and terbuthylazine in gas phase/aerosols, precipitation, and surface waters were determined (along with other herbicides) using selected ion GC-MS. Atrazine was detected at low ng/L concentrations in surface waters (<0.04-5.3 ng/L) and precipitation (0.1-53 ng/L), and at 0.02-0.1 ng/m{sup 3} in air. Cyanazine and terbuthylazine were detected in air and infrequently in water. Highest atrazine concentrations in air were found during June each year on both gas phase and particles. Concentrations of atrazine in surface waters at both locations increased during June, even in the absence of precipitation or overland flow, presumably due to inputs from dryfall and to gas areas and boreal forest lakes due to transport and deposition. Ecological risk assessment of triazines, especially for pristine aquatic environments should include consideration of this atmospheric pathway.

  20. An Insoluble Copper(II) Acetylacetonate-Chiral Bipyridine Complex that Catalyzes Asymmetric Silyl Conjugate Addition in Water.

    PubMed

    Kitanosono, Taku; Zhu, Lei; Liu, Chang; Xu, Pengyu; Kobayashi, Shū

    2015-12-16

    Acicular purplish crystals were obtained from Cu(acac)2 and a chiral bipyridine ligand. Although the crystals were not soluble, they nevertheless catalyzed asymmetric silyl conjugate addition of lipophilic substrates in water. Indeed, the reactions proceeded efficiently only in water; they did not proceed well either in organic solvents or in mixed water/organic solvents in which the catalyst/substrates were soluble. This is in pronounced contrast to conventional organic reactions wherein the catalyst/substrates tend to be in solution. Several advantages of the chiral Cu(II) catalysis in water over previously reported catalyst systems have been demonstrated. Water is expected to play a prominent role in constructing and stabilizing sterically confined transition states and accelerating subsequent protonation to achieve high yields and enantioselectivities. PMID:26646601

  1. Photo-electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation.

    PubMed

    Reichert, Robert; Zambrzycki, Christian; Jusys, Zenonas; Behm, R Jürgen

    2015-11-01

    To better understand organic-molecule-assisted photo-electrochemical water splitting, photo-electrochemistry and on-line mass spectrometry measurements are used to investigate the photo-electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2 (+) and CO2 (+) ion currents show that water oxidation is strongly suppressed by the organic species. Photo-electro-oxidation of formic acid is dominated by formation of CO2 , whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo-electro-oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed. PMID:26382643

  2. Binding Energy of Molecules on Water Ice: Laboratory Measurements and Modeling

    NASA Astrophysics Data System (ADS)

    He, Jiao; Acharyya, Kinsuk; Vidali, Gianfranco

    2016-07-01

    We measured the binding energy of N2, CO, O2, CH4, and CO2 on non-porous (compact) amorphous solid water (np-ASW), of N2 and CO on porous ASW, and of NH3 on crystalline water ice. We were able to measure binding energies down to a fraction of 1% of a layer, thus making these measurements more appropriate for astrochemistry than the existing values. We found that CO2 forms clusters on the np-ASW surface even at very low coverages. The binding energies of N2, CO, O2, and CH4 decrease with coverage in the submonolayer regime. Their values at the low coverage limit are much higher than what is commonly used in gas-grain models. An empirical formula was used to describe the coverage dependence of the binding energies. We used the newly determined binding energy distributions in a simulation of gas-grain chemistry for cold cloud and hot-core models. We found that owing to the higher value of binding energy in the submonolayer regime, a fraction of all these ices remains for much longer and up to higher temperatures on the grain surface compared to the single value energies currently used in the astrochemical models.

  3. Confined Water Determines Transport Properties of Guest Molecules in Narrow Pores.

    PubMed

    Phan, Anh; Cole, David R; Weiß, R Gregor; Dzubiella, Joachim; Striolo, Alberto

    2016-08-23

    We computed the transport of methane through 1 nm wide slit-shaped pores carved out of solid substrates. Models for silica, magnesium oxide, and alumina were used as solid substrates. The pores were filled with water. The results show that the methane permeability through the hydrated pores is strongly dependent on the solid substrate. Detailed analysis of the simulated systems reveals that local properties of confined water, including its structure, and more importantly, evolution of solvation free energy and hydrogen bond structure are responsible for the pronounced differences observed. The simulations are extended to multicomponent systems representative of natural gas, containing methane, ethane, and H2S. The results show that all pores considered have high affinity for H2S, moderate affinity for methane, and low affinity for ethane. The H2S/methane transport selectivity through the hydrated alumina pore is comparable, or superior, to that reported for existing commercial membranes. A multiscale approach was then implemented to demonstrate that a Smoluchowski one-dimensional model is able to reproduce the molecular-level results for short pores when appropriate values for the local self-diffusion coefficients are used as input parameters. We propose that the model can be extended to predict methane transport through uniform hydrated pores of macroscopic length. When verified by experiments, our simulation results could have important implications in applications such as natural gas sweetening and predictions of methane migration through hydraulically fractured shale formations. PMID:27490280

  4. Theoretical investigation of hydrogen bonding between water and platinum(II): an atom in molecule (AIM) study

    NASA Astrophysics Data System (ADS)

    Li, Yan; Zhang, Guiqiu; Chen, Dezhan

    2012-02-01

    Recently, Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] [1] reported a hydrogen-bonding-like interaction between a water molecule and a d8 metal ion (PtII) based on neutron diffraction, and provided the first crystallographic evidence for this interaction. We studied the hydrogen bonding of the O-H ... Pt interaction theoretically using atoms in molecule (AIM) and natural bond orbital analysis (NBO) in the crystallographic geometries. The method used density functional theory (DFT) with the hybrid B3LYP function. For platinum atoms, we used the Los Alamos National Laboratory 2-Double-Zeta (LANL2DZ) basis set, and for the other atoms we used 6-311++G(d,p) basis sets. Criteria based on a topological analysis of the electron density were used in order to characterize the nature of interactions in the complexes. The main purpose of the present work is to provide an answer to the following questions: Why can a filled d orbital of square-planar d8 metal ions such as platinum(II) also act as hydrogen-bond acceptors? Can a study based on the electron charge density answer this question? A good correlation between the density at the intermolecular bond critical point and the energy interaction was found. The interaction is mainly closed-shell and there is some charge transfer in this system.

  5. Open challenges in structure-based virtual screening: Receptor modeling, target flexibility consideration and active site water molecules description.

    PubMed

    Spyrakis, Francesca; Cavasotto, Claudio N

    2015-10-01

    Structure-based virtual screening is currently an established tool in drug lead discovery projects. Although in the last years the field saw an impressive progress in terms of algorithm development, computational performance, and retrospective and prospective applications in ligand identification, there are still long-standing challenges where further improvement is needed. In this review, we consider the conceptual frame, state-of-the-art and recent developments of three critical "structural" issues in structure-based drug lead discovery: the use of homology modeling to accurately model the binding site when no experimental structures are available, the necessity of accounting for the dynamics of intrinsically flexible systems as proteins, and the importance of considering active site water molecules in lead identification and optimization campaigns. PMID:26271444

  6. Rotationally resolved photoelectron spectroscopy of a triatomic molecule: Photoionization of the C (0.0.0) state of water

    SciTech Connect

    Glab, W.L.; Glynn, P.T.; Dehmer, P.M.; Dehmer, J.L.

    1996-05-01

    The authors have used a magnetic bottle photoelectron spectrometer to study the distribution of ion rotational states following photoionization of selected rotational states of the {tilde C}(0,0,0) state of water by 355 nm light. The spectrometer`s kinetic energy resolution of about 4 meV was sufficient to yield rotationally resolved time-of-flight photoelectron spectra. Comparison of the measured and calculated photoelectron spectra is encouraging and reveals unusual photoionization dynamics due to very nonatomic-like behavior in the photoionization continuum and to the presence of Cooper minima. This is the first time that such a test of photoionization theory for a polyatomic molecule at finite kinetic energy has been possible.

  7. Internal water molecules and H-bonding in biological macromolecules: a review of structural features with functional implications.

    PubMed Central

    Meyer, E.

    1992-01-01

    Conserved structural patterns of internal water molecules and/or H-bond chains were observed and are here correlated in this review, which then describes two functional properties: equilibration of hydrostatic pressure and proton transport. Available evidence in support of these hypotheses is presented, together with suggested experiments to test them. High-resolution crystal structures of a variety of proteins were studied with interactive computer graphics. Conserved H-bonding linkages may be used as a paradigm for a rationalization of proton transport in membranes. The concept of the "proton wire," which links buried active-site amino acids with the surface of the protein raises the more general question of the functional role of the various molecular components. PMID:1304887

  8. CO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and water.

    PubMed

    Devlin, J Paul; Balcı, F Mine; Maşlakcı, Zafer; Uras-Aytemiz, Nevin

    2014-11-14

    Recent demonstrations of subsecond and microsecond timescales for formation of clathrate hydrate nanocrystals hint at future methods of control of environmental and industrial gases such as CO2 and methane. Combined results from cold-chamber and supersonic-nozzle [A. S. Bhabhe, "Experimental study of condensation and freezing in a supersonic nozzle," Ph.D. thesis (Ohio State University, 2012), Chap. 7] experiments indicate extremely rapid encagement of components of all-vapor pre-mixtures. The extreme rates are derived from (a) the all-vapor premixing of the gas-hydrate components and (b) catalytic activity of certain oxygenated organic large-cage guests. Premixing presents no obvious barrier to large-scale conditions of formation. Further, from sequential efforts of the groups of Trout and Buch, a credible defect-based model of the catalysis mechanism exists for guidance. Since the catalyst-generated defects are both mobile and abundant, it is often unnecessary for a high percentage of the cages to be occupied by a molecular catalyst. Droplets represent the liquid phase that bridges the premixed vapor and clathrate hydrate phases but few data exist for the droplets themselves. Here we describe a focused computational and FTIR spectroscopic effort to characterize the aerosol droplets of the all-vapor cold-chamber methodology. Computational data for CO2 and C2H2, hetero-dimerized with each of the organic catalysts and water, closely match spectroscopic redshift patterns in both magnitude and direction. Though vibrational frequency shifts are an order of magnitude greater for the acetylene stretch mode, both CO2 and C2H2 experience redshift values that increase from that for an 80% water-methanol solvent through the solvent series to approximately doubled values for tetrahydrofuran and trimethylene oxide (TMO) droplets. The TMO solvent properties extend to a 50 mol.% solution of CO2, more than an order of magnitude greater than for the water-methanol solvent mixture

  9. CO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and water

    NASA Astrophysics Data System (ADS)

    Devlin, J. Paul; Balcı, F. Mine; Maşlakcı, Zafer; Uras-Aytemiz, Nevin

    2014-11-01

    Recent demonstrations of subsecond and microsecond timescales for formation of clathrate hydrate nanocrystals hint at future methods of control of environmental and industrial gases such as CO2 and methane. Combined results from cold-chamber and supersonic-nozzle [A. S. Bhabhe, "Experimental study of condensation and freezing in a supersonic nozzle," Ph.D. thesis (Ohio State University, 2012), Chap. 7] experiments indicate extremely rapid encagement of components of all-vapor pre-mixtures. The extreme rates are derived from (a) the all-vapor premixing of the gas-hydrate components and (b) catalytic activity of certain oxygenated organic large-cage guests. Premixing presents no obvious barrier to large-scale conditions of formation. Further, from sequential efforts of the groups of Trout and Buch, a credible defect-based model of the catalysis mechanism exists for guidance. Since the catalyst-generated defects are both mobile and abundant, it is often unnecessary for a high percentage of the cages to be occupied by a molecular catalyst. Droplets represent the liquid phase that bridges the premixed vapor and clathrate hydrate phases but few data exist for the droplets themselves. Here we describe a focused computational and FTIR spectroscopic effort to characterize the aerosol droplets of the all-vapor cold-chamber methodology. Computational data for CO2 and C2H2, hetero-dimerized with each of the organic catalysts and water, closely match spectroscopic redshift patterns in both magnitude and direction. Though vibrational frequency shifts are an order of magnitude greater for the acetylene stretch mode, both CO2 and C2H2 experience redshift values that increase from that for an 80% water-methanol solvent through the solvent series to approximately doubled values for tetrahydrofuran and trimethylene oxide (TMO) droplets. The TMO solvent properties extend to a 50 mol.% solution of CO2, more than an order of magnitude greater than for the water-methanol solvent mixture

  10. Ubiquitous Water-Soluble Molecules in Aquatic Plant Exudates Determine Specific Insect Attraction

    PubMed Central

    Sérandour, Julien; Reynaud, Stéphane; Willison, John; Patouraux, Joëlle; Gaude, Thierry; Ravanel, Patrick; Lempérière, Guy; Raveton, Muriel

    2008-01-01

    Plants produce semio-chemicals that directly influence insect attraction and/or repulsion. Generally, this attraction is closely associated with herbivory and has been studied mainly under atmospheric conditions. On the other hand, the relationship between aquatic plants and insects has been little studied. To determine whether the roots of aquatic macrophytes release attractive chemical mixtures into the water, we studied the behaviour of mosquito larvae using olfactory experiments with root exudates. After testing the attraction on Culex and Aedes mosquito larvae, we chose to work with Coquillettidia species, which have a complex behaviour in nature and need to be attached to plant roots in order to obtain oxygen. This relationship is non-destructive and can be described as commensal behaviour. Commonly found compounds seemed to be involved in insect attraction since root exudates from different plants were all attractive. Moreover, chemical analysis allowed us to identify a certain number of commonly found, highly water-soluble, low-molecular-weight compounds, several of which (glycerol, uracil, thymine, uridine, thymidine) were able to induce attraction when tested individually but at concentrations substantially higher than those found in nature. However, our principal findings demonstrated that these compounds appeared to act synergistically, since a mixture of these five compounds attracted larvae at natural concentrations (0.7 nM glycerol, <0.5 nM uracil, 0.6 nM thymine, 2.8 nM uridine, 86 nM thymidine), much lower than those found for each compound tested individually. These results provide strong evidence that a mixture of polyols (glycerol), pyrimidines (uracil, thymine), and nucleosides (uridine, thymidine) functions as an efficient attractive signal in nature for Coquillettidia larvae. We therefore show for the first time, that such commonly found compounds may play an important role in plant-insect relationships in aquatic eco-systems. PMID:18841203

  11. Crystal Structure of Fatty Acid Amide Hydrolase Bound to the Carbamate Inhibitor URB597: Discovery of a Deacylating Water Molecule and Insight into Enzyme Inactivation

    SciTech Connect

    Mileni, Mauro; Kamtekar, Satwik; Wood, David C.; Benson, Timothy E.; Cravatt, Benjamin F.; Stevens, Raymond C.

    2010-08-12

    The endocannabinoid system regulates a wide range of physiological processes including pain, inflammation, and cognitive/emotional states. URB597 is one of the best characterized covalent inhibitors of the endocannabinoid-degrading enzyme fatty acid amide hydrolase (FAAH). Here, we report the structure of the FAAH-URB597 complex at 2.3 {angstrom} resolution. The structure provides insights into mechanistic details of enzyme inactivation and experimental evidence of a previously uncharacterized active site water molecule that likely is involved in substrate deacylation. This water molecule is part of an extensive hydrogen-bonding network and is coordinated indirectly to residues lining the cytosolic port of the enzyme. In order to corroborate our hypothesis concerning the role of this water molecule in FAAH's catalytic mechanism, we determined the structure of FAAH conjugated to a urea-based inhibitor, PF-3845, to a higher resolution (2.4 {angstrom}) than previously reported. The higher-resolution structure confirms the presence of the water molecule in a virtually identical location in the active site. Examination of the structures of serine hydrolases that are non-homologous to FAAH, such as elastase, trypsin, or chymotrypsin, shows a similarly positioned hydrolytic water molecule and suggests a functional convergence between the amidase signature enzymes and serine proteases.

  12. Dynamics of water around the complex structures formed between the KH domains of far upstream element binding protein and single-stranded DNA molecules

    SciTech Connect

    Chakraborty, Kaushik; Bandyopadhyay, Sanjoy

    2015-07-28

    Single-stranded DNA (ss-DNA) binding proteins specifically bind to the single-stranded regions of the DNA and protect it from premature annealing, thereby stabilizing the DNA structure. We have carried out atomistic molecular dynamics simulations of the aqueous solutions of two DNA binding K homology (KH) domains (KH3 and KH4) of the far upstream element binding protein complexed with two short ss-DNA segments. Attempts have been made to explore the influence of the formation of such complex structures on the microscopic dynamics and hydrogen bond properties of the interfacial water molecules. It is found that the water molecules involved in bridging the ss-DNA segments and the protein domains form a highly constrained thin layer with extremely retarded mobility. These water molecules play important roles in freezing the conformational oscillations of the ss-DNA oligomers and thereby forming rigid complex structures. Further, it is demonstrated that the effect of complexation on the slow long-time relaxations of hydrogen bonds at the interface is correlated with hindered motions of the surrounding water molecules. Importantly, it is observed that the highly restricted motions of the water molecules bridging the protein and the DNA components in the complexed forms originate from more frequent hydrogen bond reformations.

  13. Dynamics of water around the complex structures formed between the KH domains of far upstream element binding protein and single-stranded DNA molecules

    NASA Astrophysics Data System (ADS)

    Chakraborty, Kaushik; Bandyopadhyay, Sanjoy

    2015-07-01

    Single-stranded DNA (ss-DNA) binding proteins specifically bind to the single-stranded regions of the DNA and protect it from premature annealing, thereby stabilizing the DNA structure. We have carried out atomistic molecular dynamics simulations of the aqueous solutions of two DNA binding K homology (KH) domains (KH3 and KH4) of the far upstream element binding protein complexed with two short ss-DNA segments. Attempts have been made to explore the influence of the formation of such complex structures on the microscopic dynamics and hydrogen bond properties of the interfacial water molecules. It is found that the water molecules involved in bridging the ss-DNA segments and the protein domains form a highly constrained thin layer with extremely retarded mobility. These water molecules play important roles in freezing the conformational oscillations of the ss-DNA oligomers and thereby forming rigid complex structures. Further, it is demonstrated that the effect of complexation on the slow long-time relaxations of hydrogen bonds at the interface is correlated with hindered motions of the surrounding water molecules. Importantly, it is observed that the highly restricted motions of the water molecules bridging the protein and the DNA components in the complexed forms originate from more frequent hydrogen bond reformations.

  14. Availability of Additional Water for Chiricahua National Monument, Cochise County, Arizona

    USGS Publications Warehouse

    Johnson, Phillip W.

    1962-01-01

    The Chiricahua National Monument is in the eastern part of Cochise County, Ariz. The monument is about 35 miles southeast of Wilicox in the north end of the Chiricahua Mountains which border Sulphur Springs Valley on the west. The area is drained by two intermittent washes, one in Bonita and the other in Rhyolite Canyons. Shake Spring is the present source of water for the monument. It ranges in rate of flow from 2 to 12 gpm (gallons per minute) and during dry periods It is not adequate to support the requirements of the monument. Ample water to meet the present and future needs of the Chiricahua National Monument is available from a combination of several sources - undeveloped springs or seeps, capture of runoff out of the canyons, and wells drilled in the alluvium.

  15. Corrosion and Heat Transfer Characteristics of Water Dispersed with Carboxylate Additives and Multi Walled Carbon Nano Tubes

    NASA Astrophysics Data System (ADS)

    Moorthy, Chellapilla V. K. N. S. N.; Srinivas, Vadapalli

    2016-02-01

    This paper summarizes a recent work on anti-corrosive properties and enhanced heat transfer properties of carboxylated water based nanofluids. Water mixed with sebacic acid as carboxylate additive found to be resistant to corrosion and suitable for automotive environment. The carboxylated water is dispersed with very low mass concentration of carbon nano tubes at 0.025, 0.05 and 0.1 %. The stability of nanofluids in terms of zeta potential is found to be good with carboxylated water compared to normal water. The heat transfer performance of nanofluids is carried out on an air cooled heat exchanger similar to an automotive radiator with incoming air velocities across radiator at 5, 10 and 15 m/s. The flow Reynolds number of water is in the range of 2500-6000 indicating developing flow regime. The corrosion resistance of nanofluids is found to be good indicating its suitability to automotive environment. There is a slight increase in viscosity and marginal decrease in the specific heat of nanofluids with addition of carboxylate as well as CNTs. Significant improvement is observed in the thermal conductivity of nanofluids dispersed with CNTs. During heat transfer experimentation, the inside heat transfer coefficient and overall heat transfer coefficient has also improved markedly. It is also found that the velocity of air and flow rate of coolant plays an important role in enhancement of the heat transfer coefficient and overall heat transfer coefficient.

  16. Addition of a Worm Leachate as Source of Humic Substances in the Drinking Water of Broiler Chickens

    PubMed Central

    Gomez-Rosales, S.; de L. Angeles, M.

    2015-01-01

    The objective of this research was to evaluate the growth performance, the apparent ileal digestibility of nitrogen and energy, the retention of nutrients and the apparent metabolizable energy corrected to zero nitrogen retention (AMEn) in broiler chickens supplemented with increasing doses of a worm leachate (WL) as a source of humic substances (HS) in the drinking water. In Exp. 1, 140 male broilers were penned individually and assigned to four WL levels (0%, 10%, 20%, and 30%) mixed in the drinking water from 21 to 49 days of age. Water was offered in plastic bottles tied to the cage. In Exp. 2, 600 male broilers from 21 to 49 days of age housed in floor pens were assigned to three levels of WL (0%, 10%, and 20%) mixed in the drinking water. The WL was mixed with tap water in plastic containers connected by plastic tubing to bell drinkers. The results of both experiments were subjected to analysis of variance and polynomial contrasts. In Exp. 1, the daily water consumption was similar among treatments but the consumption of humic, fulvic, and total humic acids increased linearly (p<0.01) as the WL increased in the drinking water. The feed conversion (p<0.01) and the ileal digestibility of energy, the excretion of dry matter and energy, the retention of dry matter, ash and nitrogen and the AMEn showed quadratic responses (p<0.05) relative to the WL levels in drinking water. In Exp. 2, the increasing level of WL in the drinking water had quadratic effects on the final body weight, daily weight gain and feed conversion ratio (p<0.05). The addition of WL as a source of HS in the drinking water had beneficial effects on the growth performance, ileal digestibility of energy, the retention of nutrients as well on the AMEn in broiler chickens; the best results were observed when the WL was mixed at levels of 20% to 30% in the drinking water. PMID:25557817

  17. Loss in CD4 T-cell responses to multiple epitopes in influenza due to expression of one additional MHC class II molecule in the host

    PubMed Central

    Nayak, Jennifer L; Sant, Andrea J

    2012-01-01

    An understanding of factors controlling CD4 T-cell immunodominance is needed to pursue CD4 T-cell epitope-driven vaccine design, yet our understanding of this in humans is limited by the complexity of potential MHC class II molecule expression. In the studies described here, we took advantage of genetically restricted, well-defined mouse strains to better understand the effect of increasing MHC class II molecule diversity on the CD4 T-cell repertoire and the resulting anti-influenza immunodominance hierarchy. Interferon-γ ELISPOT assays were implemented to directly quantify CD4 T-cell responses to I-Ab and I-As restricted peptide epitopes following primary influenza virus infection in parental and F1 hybrid strains. We found striking and asymmetric declines in the magnitude of many peptide-specific responses in F1 animals. These declines could not be accounted for by the lower surface density of MHC class II on the cell or by antigen-presenting cells failing to stimulate T cells with lower avidity T-cell receptors. Given the large diversity of MHC class II expressed in humans, these findings have important implications for the rational design of peptide-based vaccines that are based on the premise that CD4 T-cell epitope specificity can be predicted by a simple cataloguing of an individual’s MHC class II genotype. PMID:22747522

  18. Water Splitting: Strongly Coupled Nafion Molecules and Ordered Porous CdS Networks for Enhanced Visible-Light Photoelectrochemical Hydrogen Evolution (Adv. Mater. 24/2016).

    PubMed

    Zheng, Xue-Li; Song, Ji-Peng; Ling, Tao; Hu, Zhen Peng; Yin, Peng-Fei; Davey, Kenneth; Du, Xi-Wen; Qiao, Shi-Zhang

    2016-06-01

    T. Ling, X.-W. Du, S. Z. Qiao, and co-workers report strongly coupled Nafion molecules and ordered-porous CdS networks for visible-light water splitting. The image conceptually shows how the three-dimensional ordered structure effectively harvests incoming light. As described on page 4935, the inorganic CdS skeleton is homogeneously passivated by the organic Nafion molecules to facilitate hydrogen generation. PMID:27311095

  19. Interactions between organic additives and active powders in water-based lithium iron phosphate electrode slurries

    NASA Astrophysics Data System (ADS)

    Li, Chia-Chen; Lin, Yu-Sheng

    2012-12-01

    The interactions of organic additives with active powders are investigated and are found to have great influence on the determination of the mixing process for preparing electrode slurries with good dispersion and electrochemical properties of lithium iron phosphate (LiFePO4) electrodes. Based on the analyses of zeta potential, sedimentation, and rheology, it is shown that LiFePO4 prefers to interact with styrene-butadiene rubber (SBR) relative to other organic additives such as sodium carboxymethyl cellulose (SCMC), and thus shows preferential adsorption by SBR, whereas SBR has much lower efficiency than SCMC in dispersing LiFePO4. Therefore, for SCMC to interact with and disperse LiFePO4 before the interaction of LiFePO4 with SBR, it is suggested to mix SCMC with LiFePO4 prior to the addition of SBR during the slurry preparation process. For the electrode prepared via the suggested process, i.e., the sequenced adding process in which SCMC is mixed with active powders prior to the addition of SBR, a much better electrochemical performance is obtained than that of the one prepared via the process referred as the simultaneous adding process, in which mixing of SCMC and SBR with active powders in simultaneous.

  20. Additive Effects on Si3n4 Oxidation/Volatilization in Water Vapor

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.; Robinson, R. Craig; Fox, Dennis S.; Wenglarz, Richard A.; Ferber, Mattison K.

    2002-01-01

    Two commercially available additive-containing silicon nitride materials were exposed in four environments which range in severity from dry oxygen at 1 atm pressure, and low gas velocity to an actual turbine engine. Oxidation and volatilization kinetics were monitored at temperatures ranging from 1066 to 1400 C. The main purpose of this paper is to examine the surface oxide morphology resulting from the exposures. It was found that the material surface was enriched in rare earth silicate phases in combustion environments when compared to the oxides formed on materials exposed in dry oxygen. However, the in situ formation of rare earth disilicate phases offered little additional protection from the volatilization of silica observed in combustion environments. It was concluded that externally applied environmental barrier coatings are needed to protect additive-containing silicon nitride materials from volatilization reactions in combustion environments. Introduction Si3N4 is proposed for use as components, such as vanes, in turbine applications. Tens of thousands of hours of life are needed for both land-based turbines and aeropropulsion applications. Additive-containing SisN4 materials are

  1. 76 FR 7106 - Food Additives Permitted in Feed and Drinking Water of Animals; Formic Acid

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-09

    ... notice published in the Federal Register of December 7, 2009 (74 FR 64091), FDA announced that a food... agent in swine feed. This action is in response to a food additive petition filed by Kemira Oyj of... safe use of formic acid as an acidifying agent at levels not to exceed 1.2 percent in swine feed....

  2. Chill water additive controls transfer of Salmonella and Campylobacter by improved chlorine efficacy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In earlier work, we showed that a proprietary additive (T-128) maintains chlorine activity in the presence of organic material such as broiler parts. T-128 improves the efficacy of chlorine to control transfer of Campylobacter and Salmonella from inoculated wings to un-inoculated wings during immer...

  3. Reflections on Small Molecule Manganese Models that Seek to Mimic Photosynthetic Water Oxidation Chemistry

    PubMed Central

    Mullins, Christopher S.

    2008-01-01

    Recent advances in the study of the Oxygen Evolving Complex (OEC) of Photosystem II (PSII) include structural information attained from several X-ray crystallographic (XRD) and spectroscopic (XANES and EXAFS) investigations. The possible structural features gleaned from these studies have enabled synthetic chemists to design more accurate model complexes, which in turn, offer better insight into the possible pathways used by PSII to drive photosynthetic water oxidation catalysis. Mononuclear model compounds have been used to advance the knowledge base regarding the physical properties and reactivity of high-valent (MnIV or MnV) complexes. Such investigations have been especially important in regard to the manganyl (MnIV=O or MnV≡O) species, as there are no reports, to date, of any structural characterized multinuclear model compounds that incorporate such a functionality. Dinuclear and trinuclear model compounds have also been thoroughly studied in attempts to draw further comparison to the physical properties observed in the natural system and to design systems of catalytic relevance. As the reactive center of the OEC has been shown to contain an oxo-Mn4Ca cluster, exact structural models necessitate a tetranuclear Mn core. The number of models that make use of Mn4 clusters has risen substantially in recent years, and these models have provided evidence to support and refute certain mechanistic proposals. Further work is needed to adequately address the rationale for Ca (and Cl) in the OEC and to determine the sequence of events that lead to O2 evolution. PMID:19081816

  4. The 1:2:1 adduct of DABCO dication, hydrogen squarate and water molecules studied by X-ray diffraction and FTIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Barczyński, P.; Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.

    2011-07-01

    The molecular structure of 1:2:1 adduct of diprotonated 1,4-diazabicyclo[2.2.2]octane, (DABCO), hydrogen squarates (HSQ -) and water ( 1) has been characterized by single-crystal X-ray diffraction and infrared spectroscopy. The crystals of 1 are orthorhombic, space group Pnma. The non-equivalent HSQ - anions are bonded into zigzag chains (α-chain) by two short O sbnd H⋯O hydrogen bonds of 2.485(2) and 2.509(2) Å, and additionally H-bonded by water molecules linking the zigzag chains into ribbons. The diprotonated DABCO cations are located between the ribbons and interact with HSQ - anions by the N sbnd H⋯O trifurcated hydrogen bonds. The FTIR spectrum shows a very broad absorption in the 1740-550 cm -1 region, typical of short hydrogen bonds and it is attributed to the ν(OHO) and γ(OHO) vibrations. The second derivative spectrum distinguishes the νC sbnd O and γC sbnd C modes assigned to the π-delocalized squaric acid ring.

  5. The rates of exchange of water molecules from Al(III)-methylmalonate complexes: The effect of chelate ring size

    SciTech Connect

    Casey, W.H.; Phillips, B.L.; Nordin, J.P.; Sullivan, D.J.

    1998-08-01

    Rate coefficients are reported for exchange of hydration waters in the inner-coordination-sphere of Al(III)-methylmalonate complexes with bulk solution as determined via {sup 17}O-NMR. Surprisingly, water molecules in the thermodynamically less-stable complexes containing six-membered chelates are much more labile than those in five-membered oxalate-A(III) complexes. The surprising trend in reactivity is attributable either to differences in the Lewis basicities of oxygens in bidentate oxalate and methylmalonate ligands, or to rapid dissociation/reassociation of one of the acetate groups to the metal center. These results identify a useful case where trends in the apparent labilities of dissolved and presumed surface complexes deviate sharply. This deviation could be usefully exploited to probe surfaces if ligand-promoted dissolution rates could be compared at conditions where inner-sphere and outer-sphere chelate complexes could be distinguished spectroscopically. The authors expect inner-sphere oxalate to have a smaller labilizing effect than malonate or methylmalonate. A contrary result would indicate structural dissimilarity between complexes on the surface and in solution, or perhaps steric hindrance.

  6. Double differential distribution of electron emission in the ionization of water molecules by fast bare oxygen ions

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, Shamik; Biswas, Shubhadeep; Bagdia, Chandan; Roychowdhury, Madhusree; Nandi, Saikat; Misra, Deepankar; Monti, J. M.; Tachino, C. A.; Rivarola, R. D.; Champion, C.; Tribedi, Lokesh C.

    2016-03-01

    The doubly differential distributions of low-energy electron emission in the ionization of water molecules under the impact of fast bare oxygen ions with energy of 48 MeV are measured. The measured data are compared with two quantum-mechanical models, i.e. the post and prior versions of the continuum distorted wave-eikonal initial state (CDW-EIS) approximation, and the first-order Born approximation with initial and final wavefunctions verifying correct boundary conditions (CB1). An overall excellent qualitative agreement is found between the data and the CDW-EIS models whereas the CB1 model showed substantial deviation. However, the detailed angular distributions display some discrepancies with both CDW-EIS models. The single differential and total cross-sections exhibit good agreement with the CDW-EIS models. The present detailed data set could also be used as an input for modeling highly charged ion induced radiation damage in living tissues, whose most abundant component is water. Similar measurements are also carried out for a projectile energy of 60 MeV. However, since the double differential cross-section data show similar results the details are not provided here, except for the total ionization cross-sections results.

  7. Theoretical predictions of the spectroscopic parameters in noble-gas molecules: HXeOH and its complex with water.

    PubMed

    Cukras, Janusz; Sadlej, Joanna

    2011-09-14

    We employ state-of-the-art methods and basis sets to study the effect of inserting the Xe atom into the water molecule and the water dimer on their NMR parameters. Our aim is to obtain predictions for the future experimental investigation of novel xenon complexes by NMR spectroscopy. Properties such as molecular structure and energetics have been studied by supermolecular approaches using HF, MP2, CCSD, CCSD(T) and MP4 methods. The bonding in HXeOH···H(2)O complexes has been analyzed by Symmetry-Adapted Perturbation Theory to provide the intricate insight into the nature of the interaction. We focus on vibrational spectra, NMR shielding and spin-spin coupling constants-experimental signals that reflect the electronic structures of the compounds. The parameters have been calculated at electron-correlated and Dirac-Hartree-Fock relativistic levels. This study has elucidated that the insertion of the Xe atom greatly modifies the NMR properties, including both the electron correlation and relativistic effects, the (129)Xe shielding constants decrease in HXeOH and HXeOH···H(2)O in comparison to Xe atom; the (17)O, as a neighbour of Xe, is deshielded too. The HXeOH···H(2)O complex in its most stable form is stabilized mainly by induction and dispersion energies. PMID:21804992

  8. The dynamics of some metal-organic and organic molecules in water solution studied by molecular mechanical and molecular dynamical methods

    NASA Astrophysics Data System (ADS)

    Broo, Anders

    1993-07-01

    A force field is developed to reproduce geometries and vibration spectra of rutheniumhexaamine(III) and rutheniumhexamine(II) complexes. The force constants for ruthenium were then used in molecular dynamics simulation of a Ru 2+ ion, a Ru 3+ ion and Ru(NH 3) 5-pyrazine 2+ in water solution. Simulations of pyrazine and 1,3-dimethyluracile in water solution were also performed. A comparison of different ways of how to include solvation effects in quantum chemical calculations is discussed using the results from the simulations. The MD simulations show that the solvent surrounding a small charged ion, such as a Ru 2+ ion, have a pronounced shell structure and the first layer of solvent molecules is stable during a 61 ps simulation. For a metal-organic molecule as Ru(NH 3) 5-pyrazine the solvent shows shell structure, but the water molecules are exchanged frequently. In the relatively charge-symmetric pyrazine the solvent is not polarized around the molecule. In a molecule like 1,3-dimethyluracile, which is non-symmetric in the charge distribution, the water is strongly polarized.

  9. Generalizing the Concept of Specific Compound Formulation Additives towards Non-Fluorescent Drugs: A Solubilization Study on Potential Anti-Alzheimer-Active Small-Molecule Compounds.

    PubMed

    Lawatscheck, Carmen; Pickhardt, Marcus; Wieczorek, Sebastian; Grafmüller, Andrea; Mandelkow, Eckhard; Börner, Hans G

    2016-07-18

    Tailor-made compound formulation additives enable the testing of potential drugs with undesirable pharmacological profiles. A combinatorial approach using Raman microscopy as the readout method is presented to select peptide sequences from large one-bead-one-compound libraries. The resulting peptide-PEG conjugates solubilize potential prophylactic and therapeutic anti-Alzheimer compounds and can be used as specific additives not only for fluorescent but also for non-fluorescent compounds. PMID:27282127

  10. A first screening and risk assessment of pharmaceuticals and additives in personal care products in waste water, sludge, recipient water and sediment from Faroe Islands, Iceland and Greenland.

    PubMed

    Huber, Sandra; Remberger, Mikael; Kaj, Lennart; Schlabach, Martin; Jörundsdóttir, Hrönn Ó; Vester, Jette; Arnórsson, Mímir; Mortensen, Inge; Schwartson, Richard; Dam, Maria

    2016-08-15

    A screening of a broad range of pharmaceuticals and additives in personal care products (PPCPs) in sub-arctic locations of the Faroe Islands (FO), Iceland (IS) and Greenland (GL) was conducted. In total 36 pharmaceuticals including some metabolites, and seven additives in personal care products were investigated in influent and effluent waters as well as sludge of waste water treatment plants (WWTPs) and in water and sediment of recipients. Concentrations and distribution patterns for PPCPs discharged via sewage lines (SLs) to the marine environment were assessed. Of the 36 pharmaceuticals or metabolites analysed 33 were found close to or above the limit of detection (LOD) in all or a part of the samples. All of the seven investigated additives in personal care products were detected above the LOD. Some of the analysed PPCPs occurred in every or almost every sample. Among these were diclofenac, ibuprofen, lidocaine, naproxen, metformin, citalopram, venlafaxine, amiloride, furosemide, metoprolol, sodium dodecyl sulphate (SDS) and cetrimonium salt (ATAC-C16). Additionally, the study encompasses ecotoxicological risk assessment of 2/3 of the analysed PPCPs in recipient and diluted effluent waters. For candesartan only a small margin to levels with inacceptable risks was observed in diluted effluent waters at two locations (FO). Chronical risks for aquatic organisms staying and/or living around WWTP effluent pipe-outlets were indicated for 17β-estradiol and estriol in the three countries. Additives in PCPs were found to pose the largest risk to the aquatic environment. The surfactants CAPB and ATAC-C16 were found in concentrations resulting in risk factors up to 375 for CAPB and 165 for ATAC-C16 in recipients for diluted effluents from Iggia, Nuuk (GL) and Torshavn (FO) respectively. These results demonstrates a potentially high ecological risk stemming from discharge of surfactants as used in household and industrial detergents as well as additives in personal care

  11. Translational and rotational energy measurements of desorbed water molecules in their vibrational ground state following 157 nm irradiation of amorphous solid water

    NASA Astrophysics Data System (ADS)

    Hama, Tetsuya; Yokoyama, Masaaki; Yabushita, Akihiro; Kawasaki, Masahiro; Watanabe, Naoki

    2011-05-01

    Water ice is the major solid component in a variety of astrophysical environments, e.g., cold and dense molecular clouds. Photodesorption plays a dominant role in consuming ice in such cold regions. In this study, photodesorption of vibrationally ground-state H 2O( v = 0) from amorphous solid water has been investigated at 157 nm. Using a resonance-enhanced multiphoton ionization technique, the translational and rotational energy distributions of photodesorbed H 2O( v = 0) were measured, i.e., Boltzmann distributions at 1800 and 300 K, respectively. These energies are in good accordance with those predicted by classical molecular calculations for water photodesorption due to a kick-out mechanism following absorption of a single photon; hot H atom released by photodissociation of H 2O in ice transfers enough momentum to another H 2O molecule to kick it off the surface. Desorption of D 2O( v = 0) following 193 nm photoirradiation of a D 2O/H 2S mixed ice was investigated to provide further direct evidence for the operation of a kick-out mechanism. The other desorption mechanisms were also discussed in the context of possible photodesorption of vibrationally excited H 2O.

  12. Mixed-metal molecular complexes: Single-molecule nanomagnets and bioinorganic models of the water oxidizing complex of photosystem II

    NASA Astrophysics Data System (ADS)

    Mishra, Abhudaya

    2006-12-01

    The current burgeoning research in high nuclearity manganese-containing carboxylate clusters is primarily due to their relevance in areas as diverse as magnetic materials and bioinorganic chemistry. In the former, the ability of single molecules to retain, below a critical temperature (T B), their magnetization vector, resulting in the observation of bulk magnetization in the absence of a field and without long-range ordering of the spins, has termed such molecules as Single-Molecule Magnets (SMMs), or molecular nanomagnets. These molecules display superparamagnet like slow magnetization relaxation arising from the combination of a large molecular spin, S, and a large and negative magnetoanisotropy, D. Traditionally, these nanomagnets have been Mn containing species. An out of the box approach towards synthesizing SMMs is engineering mixed-metal Mn-containing compounds. An attractive choice towards this end is the use of Lanthanides (Ln), which possess both a high spin, S, and a large D. A family of related MnIII8Ce IV SMMs has been synthesized. However, the Ce ion of these complexes is diamagnetic (CeIV). Thus, further investigation has led to the isolation of a family of MnIII11Ln III4 complexes in which all but the Ln = Eu complex function as single-molecule nanomagnets. The mixed-metal synthetic effort has been extended to include actinides with the successful isolation of a Mn IV10ThIV6 complex, albeit this homovalent complex is not a SMM. In the bioinorganic research, the Water Oxidizing Complex (WOC) in Photosystem II (PS II) catalyzes the oxidation of H2O to O2 in green plants, algae and cyanobacteria. Recent crystal structures of the WOC confirm it to be a Mn4CaOx cluster with primarily carboxylate ligation. To date, various multinuclear Mn complexes have been synthesized as putative models of the WOC. On the contrary, there have been no synthetic MnCa(Sr) mixed-metal complexes. Thus, in this bioinorganic modeling research of the WOC, various synthetic

  13. Methemoglobinemia attributable to nitrite contamination of potable water through boiler fluid additives--New Jersey, 1992 and 1996.

    PubMed

    1997-03-01

    Nitrite and nitrate ions are naturally occurring forms of nitrogen that can be present in ground and surface water and can be used as a food preservative because they inhibit the growth of Clostridium botulinum. Exposure to excessive levels of nitrite or nitrate may result in the acute syndrome of methemoglobinemia (MetHb), in which nitrite binds to hemoglobin. This report summarizes the findings of investigations of two incidents in which unintentional exposure to high doses of nitrite occurred through drinking potable water contaminated with additives to boiler conditioning fluids. PMID:9072681

  14. The influence of additives on coal-water mixtures prepared with beneficiated coal

    SciTech Connect

    Ekmann, J.M.; Wildman, D.J.

    1986-01-01

    Use of coal-water mixtures (CWM) as fuels for utility and industrial applications is currently constrained by a number of factors, including the cost of compliance with environmental quality regulations. From a utilization standpoint, limiting ash and sulfur contents to levels comparable to those for residual fuel oil produces an attractive alternate fuel provided the unit cost is equal to that for the fuel oil. Reduction in the mineral matter content of the coal has been identified as a target for continued development of CWM. Changes in coal type or in the characteristics of a single coal have been shown to affect CWM properties. It appears worthwhile to examine the impact that beneficiation might have on CWM properties.

  15. Chemical interaction of water molecules with framework Al in acid zeolites: a periodic ab initio study on H-clinoptilolite.

    PubMed

    Valdiviés-Cruz, Karell; Lam, Anabel; Zicovich-Wilson, Claudio M

    2015-09-28

    Periodic quantum-chemistry methods as implemented in the CRYSTAL14 code were considered to analyse the interaction of acid clinoptilolite with water. Initially adsorbed molecules hydrolyse the Al-O bonds, giving rise to defective dealuminated materials. A suitable and representative periodic model of the partially disordered hydrated H-zeolite is the primitive cell (18 T sites) of a decahydrated trialuminated structure of HEU topology. The water distribution inside the material cavities was initially investigated. The model considered for further dealumination was the most stable one from those generated through a combined force field Monte Carlo and ab initio optimization strategy. Optimizations and energy estimations were made at the hybrid DFT level of theory (PBE0 functional) with an atomic basis set of VDZP quality. The energetics of the different pathways involved in the dealumination process was addressed by considering the Gibbs free energy with thermal and zero-point corrections through phonon analysis. It arises that hydrated models exhibit protonated water clusters stabilized by different kinds of H-bonds. The first Al extraction is slightly more energetically favourable from T3 than T2 sites, but at the same time the latter is more probable owing to its larger Al population. However, concerning the second dealumination step, it is more favourable removing the Al atom from both remaining sites after a starting abstraction from T2 rather than T3. These facts determine that the most probable overall pathways go through a first Al removal from T2. The agreement with experimental results is discussed. PMID:26299763

  16. Study of stability and thermodynamic properties of water-in-diesel nanoemulsion fuels with nano-Al additive

    NASA Astrophysics Data System (ADS)

    Mehta, Rakhi N.; More, Utkarsh; Malek, Naved; Chakraborty, Mousumi; Parikh, Parimal A.

    2015-11-01

    The present work addresses the formation of water-in-diesel (W/D) nanoemulsion by blending different percentages of water along with nano-Al additive in various propositions to enhance the combustion characteristics. The roles of various surfactants such as Sorbitan monooleate (Span 80), Triton X-100, Tetradecyltrimethylammonium bromide, and newly synthesized and characterized dicationic surfactants were discussed based upon their ability to stabilize the nanoemulsions. Surface active properties of the surfactants were determined by measuring their interfacial tension and subsequently by measuring the critical micelle concentration of the surfactants. Triton X-100 was found to be the most efficient surfactant for the current water-in-diesel nanoemulsion as it stabilized the suspensions for more than 8 h. Particle size analysis proved emulsion size to be in the order of nanometer, and zeta potential values were found to have neutral behavior at water-diesel interface. Experimental studies confirmed that that blends W/D [1 % (vol.) water] and W/DA [1 % (vol.) water, 0.1 % (wt.) nano-Al] were thermodynamically stable.

  17. A Novel Lipase as Aquafeed Additive for Warm-Water Aquaculture

    PubMed Central

    Yang, Yalin; Huang, Lu; Zhou, Zhigang

    2015-01-01

    A novel Acinetobacter lipase gene lipG1was cloned from DNA extracted from intestinal sample of common carp (Cyprinus carpio), and expressed in E. coli BL21. The encoded protein was 406 amino acids in length. Phylogenetic analysis indicated that LipG1 and its relatives comprised a novel group of true lipases produced by Gram-negative bacteria. LipG1 showed maximal activity at 40℃ and pH 8.0 when pNP decanoate (C10) was used as the substrate, and remained high activity between 20℃ and 35℃. Activity of the lipase was promoted by Ca2+ and Mg2+, and inhibited by Zn2+ and Cu2+. Moreover, LipG1 is stable with proteases, most commercial detergents and organic solvents. Substrate specificity test indicated that LipG1can hydrolyse pNP esters with acyl chain length from C2 to C16, with preference for medium-chain pNP esters (C8, C10). Lastly, LipG1was evaluated as an aquafeed additive for juvenile common carp (Cyprinus carpio). Results showed that supplementation of LipG1significantly improved the gut and heptaopancreas lipase activity of fish fed with palm oil diet. Consistently, improved feed conversion ratio and growth performance were recorded in the LipG1 feeding group, to levels comparable to the group of fish fed with soybean oil diet. Collectively, LipG1 exhibited good potential as an aquafeed additive enzyme, and deserves further characterization as the representative of a novel group of lipases. PMID:26147311

  18. Longevity and effectiveness of aluminum addition to reduce sediment phosphorus release and restore lake water quality.

    PubMed

    Huser, Brian J; Egemose, Sara; Harper, Harvey; Hupfer, Michael; Jensen, Henning; Pilgrim, Keith M; Reitzel, Kasper; Rydin, Emil; Futter, Martyn

    2016-06-15

    114 lakes treated with aluminum (Al) salts to reduce internal phosphorus (P) loading were analyzed to identify factors driving longevity of post-treatment water quality improvements. Lakes varied greatly in morphology, applied Al dose, and other factors that may have affected overall treatment effectiveness. Treatment longevity based on declines in epilimnetic total P (TP) concentration averaged 11 years for all lakes (range of 0-45 years). When longevity estimates were used for lakes with improved conditions through the end of measurements, average longevity increased to 15 years. Significant differences in treatment longevity between deeper, stratified lakes (mean 21 years) and shallow, polymictic lakes (mean 5.7 years) were detected, indicating factors related to lake morphology are important for treatment success. A decision tree developed using a partition model suggested Al dose, Osgood index (OI, a morphological index), and watershed to lake area ratio (related to hydraulic residence time, WA:LA) were the most important variables determining treatment longevity. Multiple linear regression showed that Al dose, WA:LA, and OI explained 47, 32 and 3% respectively of the variation in treatment longevity. Other variables (too data limited to include in the analysis) also appeared to be of importance, including sediment P content to Al dose ratios and the presence of benthic feeding fish in shallow, polymictic lakes. PMID:26250754

  19. Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

    NASA Astrophysics Data System (ADS)

    Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

    2015-03-01

    Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES

  20. THE USE OF DI WATER TO MITIGATE DUSTING FOR ADDITION OF DWPF FRIT TO THE SLURRY MIX EVAPORATOR

    SciTech Connect

    Hansen, E.

    2010-07-21

    The Defense Waste Processing Facility (DPWF) presently is in the process to determine means to reduce water utilization in the Slurry Mix Evaporator (SME) process, thus reducing effluent and processing times. The frit slurry addition system mixes the dry frit with water, yielding approximately a 50 weight percent slurry containing frit and the other fraction water. This slurry is discharged into the SME and excess water is removed via boiling. To reduce this water load to the SME, DWPF has proposed using a pneumatic system in conveying the frit to the SME, in essence a dry delivery system. The problem associated with utilizing a dry delivery system with the existing frit is the generation of dust when discharged into the SME. The use of water has been shown to be effective in the mining industry as well in the DOE complex to mitigate dusting. The method employed by SRNL to determine the quantity of water to mitigate dusting in dry powders was effective, between a lab and bench scale tests. In those tests, it was shown that as high as five weight percent (wt%) of water addition was required to mitigate dust from batches of glass forming minerals used by the Waste Treatment Plant at Hanford, Washington. The same method used to determine the quantity of water to mitigate dusting was used in this task to determine the quantity of water to mitigate this dusting using as-received frit. The ability for water to mitigate dusting is due to its adhesive properties as shown in Figure 1-1. Wetting the frit particles allows for the smaller frit particles (including dust) to adhere to the larger frit particles or to agglomerate into large particles. Fluids other than water can also be used, but their adhesive properties are different than water and the quantity required to mitigate dusting is different, as was observed in reference 1. Excessive water, a few weight percentages greater than that required to mitigate dusting can cause the resulting material not to flow. The primary

  1. Effects of Solvent and Residual Water on Enhancing the Reactivity of Six-Membered Silyloxyallyl Cations toward Nucleophilic Addition.

    PubMed

    Malone, Joshua A; Cleveland, Alexander H; Fronczek, Frank R; Kartika, Rendy

    2016-09-01

    A new strategy for the generation of six-membered unsymmetrical silyloxyallyl cations using catalytic mild Brønsted acid is reported. These reactive intermediates were found to readily undergo direct nucleophilic addition with a broad range of nucleophiles to produce various α,α'-disubstituted silyl enol ether structural motifs. The findings also highlight the significance of the solvent effect and residual water in enhancing the reaction rate. PMID:27538538

  2. C-C Bond Formation via Copper-Catalyzed Conjugate Addition Reactions to Enones in Water at Room Temperature

    PubMed Central

    Lipshutz, Bruce H.; Huang, Shenlin; Leong, Wendy Wen Yi; Isley, Nicholas A.

    2013-01-01

    Conjugate addition reactions to enones can now be done in water at room temperature with in situ-generated organocopper reagents. Mixing an enone, zinc powder, TMEDA, and an alkyl halide in a micellar environemnt containing catalytic amounts of Cu(I), Ag(I), and Au(III), leads to 1,4-adducts in good isolated yields: no organometallic precursor is involved. PMID:23190029

  3. Moisture effects in low-slope roofs: Drying rates after water addition with various vapor retarders

    SciTech Connect

    Pedersen, C.R. ); Petrie, T.W. . Dept. of Mechanical Engineering); Courville, G.E.; Desjarlais, A.O.; Childs, P.W.; Wilkes, K.E. )

    1992-10-01

    Tests have been conducted in the Large Scale Climate Simulator (LSCS) of the US. Building Envelope Research Center at the Oak Ridge National Laboratory (ORNL) to investigate downward drying rates of various unvented, low-slope roof systems. A secondary objective was to study heat flow patterns so as to understand how to control latent heat effects on impermeable heat flux transducers. Nine test sections were tested simultaneously. The sections had a p deck above fibrous-glass insulation and were examples of cold-deck systems. These five sections had various vapor retarder systems on a gypsum board ceiling below the insulation. The other four sections had a lightweight insulating concrete deck below expanded polystyrene insulation and the same vapor retarder systems, and were examples of warm-deck systems. The cold-deck systems had materials that were relatively permeable to water vapor, while the materials in the warm-deck systems were less permeable. All test sections were topped by an impermeable roofing membrane. The test sections were instrumented with thermocouples between all layers and with small heat flux transducers at the bottom and top of the fibrous-glass insulation and in the middle of the expanded polystyrene insulation. Two different kinds of moisture probes were used to qualitatively monitor the movement of the moisture. The heat flux measurements showed that heat conduction dominates the system using impermeable insulation materials, with only a slight increase due to increased thermal conductivity of wet expanded polystyrene. There was significant transfer of latent heat in the test sections with permeable insulation, causing the peak heat fluxes to increase by as much as a factor of two. With temperatures imposed that are typical of summer days, latent heat transfer associated with condensation and evaporation of moisture in the test sections was measured to be as important as the heat transfer by conduction.

  4. Tracking all-vapor instant gas-hydrate formation and guest molecule populations: a possible probe for molecules trapped in water nanodroplets.

    PubMed

    Uras-Aytemiz, Nevin; Cwiklik, Lukasz; Paul Devlin, J

    2012-11-28

    Quantitative Fourier-transform infrared spectra for low-temperature (160-200 K) aerosols of clathrate-hydrate nanoparticles that contain large-cage catalysts and small-cage nonpolar guests have been extended to a broad range of vapor compositions and sampling conditions. The data better reveal the stages by which room-temperature vapor mixtures, when cooled below ∼220 K, instantly generate aerosols with particles composed exclusively of the corresponding clathrate hydrates. In particular the quantitative data help relate the nature of the hydrates that form to the composition of the aqueous nanodroplets of the first stages of the rapid transition from the all-vapor mixture. The overall transition from an all-vapor mixture to "gas"-hydrate nanocrystals is a multistage one that has been characterized as homogeneous nucleation and growth of solution nanodroplets (∼240 K) followed by nucleation and growth of the gas-hydrate particles (∼220 K); all occurring within a subsecond that follows pulsing of the warm vapor into a sampling cold chamber. This may serve well as a general description of the instantaneous generation of the gas-hydrate aerosols, but closer consideration of the nature of the sampling method, in context with recent computation-based insights to (a) gas-hydrate nucleation stages∕rates and (b) the lifetimes of trapped small nonpolar molecules in cold aqueous nanodroplets, suggests a more complex multistage transition. The simulated lifetimes and extensive new quantitative infrared data significantly broaden the knowledge base in which the instantaneous transition from vapor to crystalline hydrate particles is viewed. The apparent need for a high occupancy of large-cage catalytic guest molecules currently limits the practical value of the all-vapor method. Only through greater clarity in the molecular-level description of the transition will the ultimate limits be defined. PMID:23206013

  5. Tracking all-vapor instant gas-hydrate formation and guest molecule populations: A possible probe for molecules trapped in water nanodroplets

    NASA Astrophysics Data System (ADS)

    Uras-Aytemiz, Nevin; Cwiklik, Lukasz; Paul Devlin, J.

    2012-11-01

    Quantitative Fourier-transform infrared spectra for low-temperature (160-200 K) aerosols of clathrate-hydrate nanoparticles that contain large-cage catalysts and small-cage nonpolar guests have been extended to a broad range of vapor compositions and sampling conditions. The data better reveal the stages by which room-temperature vapor mixtures, when cooled below ˜220 K, instantly generate aerosols with particles composed exclusively of the corresponding clathrate hydrates. In particular the quantitative data help relate the nature of the hydrates that form to the composition of the aqueous nanodroplets of the first stages of the rapid transition from the all-vapor mixture. The overall transition from an all-vapor mixture to "gas"-hydrate nanocrystals is a multistage one that has been characterized as homogeneous nucleation and growth of solution nanodroplets (˜240 K) followed by nucleation and growth of the gas-hydrate particles (˜220 K); all occurring within a subsecond that follows pulsing of the warm vapor into a sampling cold chamber. This may serve well as a general description of the instantaneous generation of the gas-hydrate aerosols, but closer consideration of the nature of the sampling method, in context with recent computation-based insights to (a) gas-hydrate nucleation stages/rates and (b) the lifetimes of trapped small nonpolar molecules in cold aqueous nanodroplets, suggests a more complex multistage transition. The simulated lifetimes and extensive new quantitative infrared data significantly broaden the knowledge base in which the instantaneous transition from vapor to crystalline hydrate particles is viewed. The apparent need for a high occupancy of large-cage catalytic guest molecules currently limits the practical value of the all-vapor method. Only through greater clarity in the molecular-level description of the transition will the ultimate limits be defined.

  6. A new Gaussian MCTDH program : implementation and validation on the levels of the water and glycine molecules

    PubMed Central

    Skouteris, D.; Barone, V.

    2015-01-01

    We report the main features of a new general implementation of the Gaussian Multi-Configuration Time-Dependent Hartree (G-MCTDH) model. The code allows effective computations of time-dependent phenomena, including calculation of vibronic spectra (in one or more electronic states), relative state populations etc. Moreover, by expressing the Dirac-Frenkel variational principle in terms of an effective Hamiltonian we are able to provide a new reliable estimate of the representation error. After validating the code on simple one-dimensional systems, we analyze the harmonic and anharmonic vibrational spectra of water and glycine showing that reliable and converged energy levels can be obtained with reasonable computing resources. The data obtained on water and glycine are compared with results of previous calculations using the vibrational second-order perturbation theory (VPT2) method. Additional features and perspectives are also shortly discussed. PMID:24985615

  7. 1H NMR detection of immobilized water molecules within a strong distal hydrogen-bonding network of substrate-bound human heme oxygenase-1.

    PubMed

    Syvitski, Ray T; Li, Yiming; Auclair, Karine; Ortiz De Montellano, Paul R; La Mar, Gerd N

    2002-12-01

    Solution 1H NMR is used to probe the environments of the donor protons of eight strong hydrogen bonds on the distal side of the heme substrate in the cyanide-inhibited, substrate-bound complex of human heme oxygenase, hHO. It is demonstrated that significant magnetization transfer from the bulk water signal to the eight labile protons does not result from chemical exchange, but from direct nuclear Overhauser effect due to the dipolar interaction of these labile protons with "ordered" water molecules. The enzyme labile proton to water proton distances are estimated at approximately 3 A. It is proposed that the role of the strong hydrogen-bonding network is to immobilize numerous water molecules which both stabilize the activated hydroperoxy species and funnel protons to the active site. PMID:12452690

  8. Effect of two-stage coagulant addition on coagulation-ultrafiltration process for treatment of humic-rich water.

    PubMed

    Liu, Ting; Chen, Zhong-lin; Yu, Wen-zheng; Shen, Ji-min; Gregory, John

    2011-08-01

    A novel two-stage coagulant addition strategy applied in a coagulation-ultrafiltration (UF) process for treatment of humic-rich water at neutral pH was investigated in this study. When aluminum sulfate (alum) doses were set at a ratio of 3:1 added during rapid mix stage and half way through flocculation stage, the integrated process of two-stage alum addition achieved almost the same organic matter removal as that of conventional one-stage alum addition at the same overall dose. Whereas membrane fouling could be effectively mitigated by the two-stage addition exhibited by trans-membrane pressure (TMP) developments. The TMP developments were found to be primarily attributed to external fouling on membrane surface, which was closely associated with floc characteristics. The results of jar tests indicated that the average size of flocs formed in two-stage addition mode roughly reached one half larger than that in one-stage addition mode, which implied a beneficial effect on membrane fouling reduction. Moreover, the flocs with more irregular structure and lower effective density resulted from the two-stage alum addition, which caused higher porosity of cake layer formed by such flocs on membrane surface. Microscopic observations of membrane surface demonstrated that internal fouling in membrane pores could be also remarkably limited by two-stage alum addition. It is likely that the freshly formed hydroxide precipitates were distinct in surface characteristics from the aged precipitates due to formation of more active groups or adsorption of more labile aluminum species. Consequently, the flocs could further connect and aggregate to contribute to preferable properties for filtration performance of the coagulation-UF process. As a simple and efficient approach, two-stage coagulant addition strategy could have great practical significance in coagulation-membrane processes. PMID:21704354

  9. Maximizing T2-exchange in Dy3+DOTA-(amide)X chelates: Fine-tuning the water molecule exchange rate for enhanced T2 contrast in MRI

    PubMed Central

    Soesbe, Todd C.; Ratnakar, S. James; Milne, Mark; Zhang, Shanrong; Do, Quyen N.; Kovacs, Zoltan; Sherry, A. Dean

    2014-01-01

    Purpose The water molecule exchange rates in a series of DyDOTA-(amide)X chelates were fine-tuned to maximize the effects of T2-exchange line broadening and improve T2 contrast. Methods Four DyDOTA-(amide)X chelates having a variable number of glycinate side-arms were prepared and characterized as T2-exchange agents. The non-exchanging DyTETA chelate was also used to measure the bulk water T2 reduction due solely to T2*. The total transverse relaxivity (r2tot) at 22, 37, and 52 °C for each chelate was measured in vitro at 9.4 T (400 MHz) by fitting plots of total T2−1 versus concentration. The water molecule exchange rates for each complex were measured by fitting 17O line-width versus temperature data taken at 9.4 T (54.3 MHz). Results The measured transverse relaxivities due to water molecule exchange (r2ex) and bound water lifetimes (τM) were in excellent agreement with Swift-Connick theory, with DyDOTA-(gly)3 giving the largest r2ex = 11.8 s−1 mM−1 at 37 °C. Conclusion By fine-tuning the water molecule exchange rate at 37 °C, the transverse relaxivity has been increased by 2 to 30 times compared to previously studied Dy3+-based chelates. Polymerization or dendrimerization of the optimal chelate could yield a highly sensitive, molecule-sized T2 contrast agent for improved molecular imaging applications. PMID:24390729

  10. Effect of nonionic surfactant addition on Pyrex glass ablation using water-assisted CO2 laser processing

    NASA Astrophysics Data System (ADS)

    Chung, C. K.; Liao, M. W.; Lin, S. L.

    2010-04-01

    Pyrex glass etching using laser ablation is an important technology for the microfluid application to lab-on-a-chip devices but suffers from the formation of surface crack. In this article, the addition of nonionic surfactant to water for glass ablation using water-assisted CO2 laser processing (WACLAP) has been investigated to enhance ablation rate and to eliminate conventional surface defects of cracks in air. WACLAP for Pyrex glass ablation can reduce thermal-stress-induced crack with water cooling and hydrophilic nonionic surfactant to water can enhance ablation performance. Compared to pure water, the 15% weight percent Lauramidopropyl Betaine surfactant solutions for WACLAP can enhance ablation rate from 13.6 to 25 μm/pass of Pyrex glass ablation at a linear laser energy density of 2.11 J/cm, i.e., 24 W power, 114 mm/s scanning speed, and obtain through-wafer etching at 3.16 J/cm for 20 passes without cracks on the surface. Effect of surfactant concentration and linear energy density on WACLAP was also examined. The possible mechanism of surfactant-enhanced phenomenon was discussed by the Newton’s law of viscosity of surfactant solution.

  11. Improved Estimation of Protein-Ligand Binding Free Energy by Using the Ligand-Entropy and Mobility of Water Molecules

    PubMed Central

    Fukunishi, Yoshifumi; Nakamura, Haruki

    2013-01-01

    We previously developed the direct interaction approximation (DIA) method to estimate the protein-ligand binding free energy (ΔG). The DIA method estimates the ΔG value based on the direct van der Waals and electrostatic interaction energies between the protein and the ligand. In the current study, the effect of the entropy of the ligand was introduced with protein dynamic properties by molecular dynamics simulations, and the interaction between each residue of the protein and the ligand was also weighted considering the hydration of each residue. The molecular dynamics simulation of the apo target protein gave the hydration effect of each residue, under the assumption that the residues, which strongly bind the water molecules, are important in the protein-ligand binding. These two effects improved the reliability of the DIA method. In fact, the parameters used in the DIA became independent of the target protein. The averaged error of ΔG estimation was 1.3 kcal/mol and the correlation coefficient between the experimental ΔG value and the calculated ΔG value was 0.75. PMID:24276169

  12. Interactions of carbon nanotubes with the nitromethane-water mixture governing selective adsorption of energetic molecules from aqueous solution.

    PubMed

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

    2015-03-14

    The structure and dynamics of the nitromethane-water (NM-WT) binary mixture surrounding single walled carbon nanotubes (SWNTs) have been investigated by molecular dynamics simulations. The simulation trajectories show that the NM molecules can be selectively adsorbed both outside the surface and inside the cavity of SWNTs mainly dominated by van der Waals attractions because SWNTs have a higher binding affinity for NM than WT. The binding energies of SWNTs with NM and WT obtained from electronic structure calculations at the M06-2X/6-31+G* level are 15.31 and 5.51 kcal mol(-1), respectively. Compared with the SWNT exterior, the selective adsorption of NM is preferentially occurred in the SWNT interior due to the hydrophobic interactions and the dipole-dipole interactions, which induces the decrease of the hydrogen-bond number of NM with WT and ordered structures of NM with preferred intermolecular orientation in the SWNT cavity. Furthermore, the selective adsorption dynamics of NM from the aqueous solution is regardless of the chirality and radius of SWNTs. The SWNT radius plays a negligible role in the mass density distributions of NM outside the SWNTs, while the mass density of NM in the SWNT interior decreases gradually as the SWNT radius increases. The structural arrangements and intermolecular orientations of NM in the SWNT cavity are greatly dependent on the SWNT radius due to the size effect. PMID:25684688

  13. Heterogeneous versus homogeneous copper(II) catalysis in enantioselective conjugate-addition reactions of boron in water.

    PubMed

    Kitanosono, Taku; Xu, Pengyu; Kobayashi, Shū

    2014-01-01

    We have developed Cu(II)-catalyzed enantioselective conjugate-addition reactions of boron to α,β-unsaturated carbonyl compounds and α,β,γ,δ-unsaturated carbonyl compounds in water. In contrast to the previously reported Cu(I) catalysis that required organic solvents, chiral Cu(II) catalysis was found to proceed efficiently in water. Three catalyst systems have been exploited: cat. 1: Cu(OH)2 with chiral ligand L1; cat. 2: Cu(OH)2 and acetic acid with ligand L1; and cat. 3: Cu(OAc)2 with ligand L1. Whereas cat. 1 is a heterogeneous system, cat. 2 and cat. 3 are homogeneous systems. We tested 27 α,β-unsaturated carbonyl compounds and an α,β-unsaturated nitrile compound, including acyclic and cyclic α,β-unsaturated ketones, acyclic and cyclic β,β-disubstituted enones, acyclic and cyclic α,β-unsaturated esters (including their β,β-disubstituted forms), and acyclic α,β-unsaturated amides (including their β,β-disubstituted forms). We found that cat. 2 and cat. 3 showed high yields and enantioselectivities for almost all substrates. Notably, no catalysts that can tolerate all of these substrates with high yields and high enantioselectivities have been reported for the conjugate addition of boron. Heterogeneous cat. 1 also gave high yields and enantioselectivities with some substrates and also gave the highest TOF (43,200 h(-1) ) for an asymmetric conjugate-addition reaction of boron. In addition, the catalyst systems were also applicable to the conjugate addition of boron to α,β,γ,δ-unsaturated carbonyl compounds, although such reactions have previously been very limited in the literature, even in organic solvents. 1,4-Addition products were obtained in high yields and enantioselectivities in the reactions of acyclic α,β,γ,δ-unsaturated carbonyl compounds with diboron 2 by using cat. 1, cat. 2, or cat. 3. On the other hand, in the reactions of cyclic α,β,γ,δ-unsaturated carbonyl compounds with compound 2, whereas 1,4-addition products

  14. Linkages Between Biotic and Abiotic Belowground Processes in a Mojave Desert Ecosystem: Responses to Experimental Nitrogen and Water Additions

    NASA Astrophysics Data System (ADS)

    Verburg, P. S.; Marion, G. M.; Young, A. C.; Glanzmann, I.; Stevenson, B.; Arnone, J. A.; Nowak, R. S.

    2007-05-01

    Fine roots play a critical role in nutrient acquisition and water uptake. Yet it is unclear how fine roots in arid environments respond to increased nitrogen deposition and rainfall, two important global change factors in arid lands in the southwestern United States. In addition it is unclear how changes in root activity may impact soil CO2 concentrations, an important parameter affecting carbonate dynamics. We measured fine root length density (RLD) and soil CO2 concentrations for two years in experimentally manipulated plots in a Mojave Desert ecosystem. The study was conducted at the Mojave Global Change Facility located at the Nevada Test Site 60 miles northwest of Las Vegas. The treatments included: 1) three 25 mm water additions during the summer, 2) one nitrogen addition in the fall equivalent to 40 kg per hectare per year, 3) a combined water and nitrogen addition and, 4) untreated controls. Root data were collected using minirhizotron imaging approximately every 90 days underneath shrubs and intershrub areas. Soil CO2 concentrations were collected at the same sampling times and locations at 10, 40 and 90 cm depth using gas wells. The RLD showed clear seasonal patterns with the fastest increase in RLD occurring between February and April. During the winter the increase in RLD was higher underneath shrubs than in intershrub areas but during the summer months increases in RLD were similar under shrubs and in intershrub areas. Water additions slightly increased root mortality during the summer but this increase in mortality was not large enough to cause consistent differences in RLD between control and irrigated plots. Nitrogen addition had no effect on root dynamics in any of the plots. In contrast to RLD, irrigation consistently increased soil CO2 concentrations at all depths during the summer even when roots were not actively growing anymore. We speculate that the increased mortality under irrigation causes increased heterotrophic respiration which may

  15. The role of water molecules in the binding of class I and II peptides to the SH3 domain of the Fyn tyrosine kinase.

    PubMed

    Camara-Artigas, Ana; Ortiz-Salmeron, Emilia; Andujar-Sánchez, Montserrrat; Bacarizo, Julio; Martin-Garcia, Jose Manuel

    2016-09-01

    Interactions of proline-rich motifs with SH3 domains are present in signal transduction and other important cell processes. Analysis of structural and thermodynamic data suggest a relevant role of water molecules in these protein-protein interactions. To determine whether or not the SH3 domain of the Fyn tyrosine kinase shows the same behaviour, the crystal structures of its complexes with two high-affinity synthetic peptides, VSL12 and APP12, which are class I and II peptides, respectively, have been solved. In the class I complexes two water molecules were found at the binding interface that were not present in the class II complexes. The structures suggest a role of these water molecules in facilitating conformational changes in the SH3 domain to allow the binding of the class I or II peptides. In the third binding pocket these changes modify the cation-π and salt-bridge interactions that determine the affinity of the binding. Comparison of the water molecules involved in the binding of the peptides with previous reported hydration spots suggests a different pattern for the SH3 domains of the Src tyrosine kinase family. PMID:27599862

  16. Dissecting the Influence of Protein Flexibility on the Location and Thermodynamic Profile of Explicit Water Molecules in Protein-Ligand Binding.

    PubMed

    Yang, Ying; Lill, Markus A

    2016-09-13

    Explicit water molecules in the binding site of proteins play a crucial role for protein-ligand association. Recent advances in computer-aided drug discovery methodology allow for an accurate prediction of the localized position and thermodynamic profile of water molecules (i.e., hydration sites) in the binding site. The underlying calculations are based on MD simulations of explicit water molecules in a restrained protein structure. However, the ligand-binding process is typically associated with protein conformational change that influences the position and thermodynamic properties of the hydration site. In this manuscript, we present the developments of two methods to incorporate the influence of protein conformational change on hydration sites either by following the conformational transition step-by-step (method I) or to match the hydration sites of the two transition end states using local coordinate systems (method II). Using these methods, we highlight the difference in the estimated protein desolvation free energy with and without inclusion of protein flexibility. To the best of our knowledge, this is the first study that explicitly studies the influence of protein conformational change on the position and thermodynamic profiles of water molecules and provides methodology to incorporate protein flexibility into the estimation of the desolvation free energy. PMID:27494046

  17. Decrease of droplet size of the reverse microemulsion 1-butyl-3-methylimidazolium tetrafluoroborate/Triton X-100/cyclohexane by addition of water.

    PubMed

    Gao, Yanan; Hilfert, Liane; Voigt, Andreas; Sundmacher, Kai

    2008-03-27

    In the present contribution, results concerning the role of small amounts of water in the 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4)-in-cyclohexane ionic liquid (IL) reverse microemulsions are reported. Dynamic light scattering (DLS) revealed that the size of microemulsion droplets decreased remarkably with increasing water content although water is often used as a polar component to swell reverse microemulsions. It was thus deduced that the number of microemulsion droplets was increased which was confirmed by conductivity measurements. The states of dissolved water were investigated by Fourier transform IR (FTIR) spectroscopic analysis showing that water molecules mainly act as bound water. 1H NMR along with two-dimensional rotating frame nuclear Overhauser effect (NOE) experiments (ROESY) further revealed that water molecules were mainly located in the periphery of the polar core of the microemulsion droplets and behave like a chock being inserted in the palisade layer of the droplet. This increased the curvature of the surfactant film at the IL/cyclohexane interface and thus led to the decrease of the microemulsion droplet size. The order of surfactant molecules arranged in the interface film was increased and thus induced a loss of entropy. Isothermal titration calorimetry (ITC) indicated that an enthalpy increase compensates for the loss of entropy during the process of microstructural transition. PMID:18318531

  18. Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes

    NASA Astrophysics Data System (ADS)

    Smejtek, Pavel; Word, Robert C.

    2004-01-01

    We studied the effect of segmented solvent molecules on the free energy of transfer of small molecules from water into alkanes (hexane, heptane, octane, decane, dodecane, tetradecane, and hexadecane). For these alkanes we measured partition coefficients of benzene, 3-methylindole (3MI), 2,3,4,6-tetrachlorophenol (TeCP), and 2,4,6-tribromophenol (TriBP) at 3, 11, 20, 3, and 47 °C. For 3MI, TeCP, and TriBP the dependence of free energy of transfer on length of alkane chains was found to be very different from that for benzene. In contrast to benzene, the energy of transfer for 3MI, TeCP, and TriBP was independent of the number of carbons in alkanes. To interpret data, we used the classic Flory-Huggins (FH) theory of concentrated polymer solutions for the alkane phase. For benzene, the measured dependence of energy of transfer on the number of carbons in alkanes agreed well with predictions based on FH model in which the size of alkane segments was obtained from the ratio of molar volumes of alkanes and the solute. We show that for benzene, the energy of transfer can be divided into two components, one called environmental swap energy (ESE), and one representing the contribution of configurational entropy of alkane chains. For 3MI, TeCP, and TriBP the contribution of configurational entropy was not measurable even though the magnitude of the effect predicted from the FH model for short chain alkanes was as much as 20 times greater than experimental uncertainties. From the temperature dependence of ESE we obtained enthalpy and entropy of transfer for benzene, 3MI, TeCP, and TriBP. Experimental results are discussed in terms of a thermodynamic cycle considering creation of cavity, insertion of solute, and activation of solute-medium attractive interactions. Our results suggest that correcting experimental free energy of transfer by Flory-Huggins configurational entropy term is not generally appropriate and cannot be applied indiscriminately.

  19. Addition of hydrogen peroxide for the simultaneous control of bromate and odor during advanced drinking water treatment using ozone.

    PubMed

    Wang, Yongjing; Yu, Jianwei; Zhang, Dong; Yang, Min

    2014-03-01

    Complete removal of the characteristic septic/swampy odor from Huangpu River source water could only be achieved under an ozone dose as high as 4.0 mg/L in an ozone-biological activated carbon (O3-BAC) process, which would lead to the production of high concentrations of carcinogenic bromate due to the high bromide content. This study investigated the possibility of simultaneous control of bromate and the septic/swampy odor by adding H2O2 prior to the O3-BAC process for the treatment of Huangpu River water. H2O2 addition could reduce the bromate concentration effectively at an H2O2/O3 (g/g) ratio of 0.5 or higher. At the same time, the septic/swampy odor removal was enhanced by the addition of H2O2, although optimization of the H2O2/O3 ratio was required for each ozone dose. At an ozone dose of 2.0 mg/L, the odor was removed completely at an H2O2/O3 ratio of 0.5. The results indicated that H2O2 application at a suitable dose could enhance the removal of the septic/swampy odor while suppressing the formation of bromate during ozonation of Huangpu River source water. PMID:25079267

  20. Effects of protonation state of Asp181 and position of active site water molecules on the conformation of PTP1B.

    PubMed

    Ozcan, Ahmet; Olmez, Elif Ozkirimli; Alakent, Burak

    2013-05-01

    In protein tyrosine phosphatase 1B (PTP1B), the flexible WPD loop adopts a closed conformation (WPDclosed ) in the active state of PTP1B, bringing the catalytic Asp181 close to the active site pocket, while WPD loop is in an open conformation (WPDopen ) in the inactive state. Previous studies showed that Asp181 may be protonated at physiological pH, and ordered water molecules exist in the active site. In the current study, molecular dynamics simulations are employed at different Asp181 protonation states and initial positions of active site water molecules, and compared with the existing crystallographic data of PTP1B. In WPDclosed conformation, the active site is found to maintain its conformation only in the protonated state of Asp181 in both free and liganded states, while Asp181 is likely to be deprotonated in WPDopen conformation. When the active site water molecule network that is a part of the free WPDclosed crystal structure is disrupted, intermediate WPD loop conformations, similar to that in the PTPRR crystal structure, are sampled in the MD simulations. In liganded PTP1B, one active site water molecule is found to be important for facilitating the orientation of Cys215 and the phosphate ion, thus may play a role in the reaction. In conclusion, conformational stability of WPD loop, and possibly catalytic activity of PTP1B, is significantly affected by the protonation state of Asp181 and position of active site water molecules, showing that these aspects should be taken into consideration both in MD simulations and inhibitor design. PMID:23239271

  1. Modified TEWL in vitro measurements on transdermal patches with different additives with regard to water vapour permeability kinetics.

    PubMed

    Fokuhl, Joana; Müller-Goymann, Christel C

    2013-02-28

    Water vapour permeability (WVP) and water absorption capacity (WAC) influence physicochemical properties and wearability of transdermal patches considerably. For determination of WVP, a modified transepidermal water loss (TEWL) measurement was developed. These measurements continuously measure WVP of transdermal patches in vitro along with time required to reach steady state, and its magnitude according to the type of polymer used. Additionally, WAC of the patches was examined and related to WVP. According to literature in the field of WVP determination, usually selected points are taken from the evaporation time curve and averaged over a given time span without knowing whether steady state has already been reached or not. The latter causes errors upon averaging. The advantage of the in vitro TEWL measurement presented includes reproducibly adjustable conditions for every time span desired, thus providing information on the kinetics of the experiment and avoiding biased results from averaging. Knowing the shape of the evaporation time curve and thus the kinetics of the experiment allows for focusing on the relevant part of the measurement, i.e. the determination of the steady state level and the time to reach it. Four different polymers (P1-P4) based on sugar-modified polyacrylates were investigated with regard to WVP and WAC of the matrices prepared thereof along with the influence of drug loading and the incorporation of a variety of additives commonly used for transdermal patches. A clear correlation between WVP and the hydrophilicity in terms of the number of free hydroxyl groups of the polymer was elaborated. Additives of higher hydrophilicity compared to that of the polymer itself led to higher WVPs and vice versa. The combination of the model drug lidocaine in its free base form together with the additive succinic acid (Suc) resulted in ionization of the drug and thus in substantially increased WVPs. Addition of α-tocopherol acetate (Toc) into P3 and P4 and

  2. Effect of plasticizers (water and glycerol) on the diffusion of a small molecule in iota-carrageenan biopolymer films for edible coating application.

    PubMed

    Karbowiak, Thomas; Hervet, Hubert; Léger, Liliane; Champion, Dominique; Debeaufort, Frédéric; Voilley, Andrée

    2006-06-01

    Translational diffusion of a fluorescein probe has been measured in iota-carrageenan edible films containing different amounts of glycerol (0, 15, 30, and 45%), using fluorescence recovery after photobleaching (FRAP) experiments. The effects of this plasticizer as well as the plasticizing effect of water on the diffusion of fluorescein have been studied in this edible coating mainly composed of natural biopolymer. Diffusion coefficients of about 10(-13) m2 s(-1) have been measured in these films for water activity (aw) lower than 0.7. Above this water content threshold, fluorescein translational diffusion coefficient increases up to 10(-12) m2 s(-1). Another interesting information obtained from FRAP experiments on this system is the ratio of the diffusing molecules which are immobilized in the carrageenan matrix at aw lower than 0.98. Moreover, films containing more than 30% glycerol (w/w carrageenan) present a huge increase of the diffusion coefficient of fluorescein at high water activity (about 2 orders of magnitude), this effect being less pronounced at low water activity. The increase of diffusion seems to be only related to the water content, and glycerol only acts through the enhancement of water adsorption. Therefore, in biopolymer films containing polyol plasticizers, the gain in mobility could be devoted to the effect of the ubiquitous plasticizing molecule, water, whose adsorption is increased by the plasticizer. PMID:16768427

  3. Effect of water treatment additives on lime softening residual trace chemical composition--implications for disposal and reuse.

    PubMed

    Cheng, Weizhi; Roessler, Justin; Blaisi, Nawaf I; Townsend, Timothy G

    2014-12-01

    Drinking water treatment residues (WTR) offer potential benefits when recycled through land application. The current guidance in Florida, US allows for unrestricted land application of lime softening WTR; alum and ferric WTR require additional evaluation of total and leachable concentrations of select trace metals prior to land application. In some cases a mixed WTR is produced when lime softening is accompanied by the addition of a coagulant or other treatment chemical; applicability of the current guidance is unclear. The objective of this research was to characterize the total and leachable chemical content of WTR from Florida facilities that utilize multiple treatment chemicals. Lime and mixed lime WTR samples were collected from 18 water treatment facilities in Florida. Total and leachable concentrations of the WTR were measured. To assess the potential for disposal of mixed WTR as clean fill below the water table, leaching tests were conducted at multiple liquid to solid ratios and under reducing conditions. The results were compared to risk-based soil and groundwater contamination thresholds. Total metal concentrations of WTR were found to be below Florida soil contaminant thresholds with Fe found in the highest abundance at a concentration of 3600 mg/kg-dry. Aluminum was the only element that exceeded the Florida groundwater contaminant thresholds using SPLP (95% UCL = 0.23 mg/L; risk threshold = 0.2 mg/L). Tests under reducing conditions showed elevated concentrations of Fe and Mn, ranging from 1 to 3 orders of magnitude higher than SPLP leachates. Mixed lime WTR concentrations (total and leachable) were lower than the ferric and alum WTR concentrations, supporting that mixed WTR are appropriately represented as lime WTR. Testing of WTR under reducing conditions demonstrated the potential for release of certain trace metals (Fe, Al, Mn) above applicable regulatory thresholds; additional evaluation is needed to assess management options where

  4. Photoinduced conversion of carbon dioxide and water molecules to methanol on the surface of molybdenum oxide MoO x ( x < 2)

    NASA Astrophysics Data System (ADS)

    Silaev, I. V.; Khubezhov, S. A.; Ramonova, A. G.; Grigorkina, G. S.; Kaloeva, A. G.; Demeev, Z. S.; Bliev, A. P.; Sekiba, D.; Ogura, S.; Fukutani, K.; Magkoev, T. T.

    2016-03-01

    X-ray and UV photoelectron spectroscopic data are used to demonstrate that, when pulsed laser light with a photon energy of 6.4 eV acts on the surface of nonstoichiometric molybdenum oxide MoO x ( x < 2), methanol is effectively formed from adsorbed molecules of carbon dioxide and water. The processes in which CO2 and H2O molecules are adsorbed on substrate surface defects and their bonds are activated, enhanced under the effect of photons, should be regarded as the key factors.

  5. PbnI4n+2(2n+2)- ribbons (n = 3, 5) as dimensional reductions of 2D perovskite layers in cystamine cation based hybrids, also incorporating iodine molecules or reversible guest water molecules.

    PubMed

    Louvain, Nicolas; Bi, Wenhua; Mercier, Nicolas; Buzaré, Jean-Yves; Legein, Christophe; Corbel, Gwenaël

    2007-03-01

    Pb(n)I(4n+2)((2n+2)-) (n = 3, 5) ribbons, which can be regarded as dimensional reductions of 2D perovskite layers, are stabilized by diprotonated cystamine cations in (NH(3)(CH(2))(2)SS(CH(2))(2)NH(3))(4)Pb(3)I(14),I(2) (1) and (NH(3)(CH(2))(2)SS(CH(2))(2)NH(3))(6)Pb(5)I(22).4H(2)O (2). Both 1 and 2 have interesting structural characteristics; it is unprecedented that the ribbons are linked via I(2) molecules incorporated in the lattice of 1, while tetrameric water clusters are trapped in the structure of 2. 2 undergoes a (reversible) water desorption process at 310 K leading to (NH(3)(CH(2))(2)SS(CH(2))(2)NH(3))(6)Pb(5)I(22).2H(2)O (3). The electrical behavior of 2 and 3 has been investigated in the ranges 293-310 K and 310-358 K respectively. Above 310 K, the electronic contribution remains constant while the ionic transference number tends towards unity showing almost pure ionic transport at 360 K (6 x 10(-7) S cm(-1) at 330 K) originating probably from the migration of protons through the hydrogen bonds connecting the water molecules to the cystamine counter cations. PMID:17308677

  6. Effects of Ethanol Addition on the Efficiency of Subcritical Water Extraction of Proteins and Amino Acids from Porcine Placenta

    PubMed Central

    2015-01-01

    In a previous study, hydrolysates of porcine placenta were obtained and the extraction efficiency for proteins and amino acids was compared between sub- and super-critical water extraction systems; optimum efficiency was found to be achieved using subcritical water (170℃, 10 bar). In this study, the effects of adding ethanol to the subcritical water system were investigated. The lowest-molecular-weight extraction product detected weighed 434 Da, and the efficiency of extraction for low-molecular-weight products was increased when either the concentration of ethanol was decreased, or the extraction time was lengthened from 10 min to 30 min. The highest concentration of free amino acids (approximately 8 mM) was observed following 30 min extraction using pure distilled water. The concentration of free amino acids was significantly lower when ethanol was added or a shorter extraction time was used (p<0.05). Color change of the solution following extraction was measured. There were no significant differences in color between lysates produced with different extraction times when using distilled water (p>0.05); however, using different extraction times produced significant differences in color when using 20% or 50% ethanol solution for subcritical extraction (p<0.05). The range of pH for the hydrolysate solutions was 6.4-7.5. In conclusion, the investigated extraction system was successful in the extraction of ≤ 500 Da hydrolysates from porcine placenta, but addition of ethanol did not yield higher production of low-molecular-weight hydrolysates than that achieved by DW alone. PMID:26761837

  7. Inorganics in Organics: Tracking down the Intrinsic Equilibriums between Organic Molecules and Trace Elements in Oceanic Waters

    NASA Astrophysics Data System (ADS)

    Lechtenfeld, O. J.; Koch, B. P.; Kattner, G.

    2010-12-01

    Recent developments in analytical instrumentation enable to describe biogeochemical processes in oceanic waters on a molecular level. This is the prerequisite to integrate biological and geochemical parameters and to develop chemical cycles on a global perspective. The state-of-the-art Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) applications for dissolved organic matter (DOM) focus mainly on carbon, hydrogen, oxygen and nitrogen isotopes. Implementation of sulfur and especially phosphorus in the molecular formula assignment has been questionable because of ambiguous calculated elemental formulas. On the other hand, many compounds bearing these elements are well known to occur in the dissolved state as part of the permanent recycling processes (e.g. phospholipids, phosphonates) but analytics of dissolved organic phosphorus (DOP) and sulfur (DOS) are often hampered by the large inorganic P and S pools. Even less is known about complexation characteristics of the DOM moieties. Although electrochemical methods provide some information about trace metal speciation, the high amount of organic molecules and its insufficient description as chemical functional classes prevent the assignment of trace metals to ligand classes. Nevertheless, it is undoubtful that a varying but extensive amount of transition metals is bond in form of organic complexes. Hyphenation of reversed phase high performance liquid chromatography (RP-HPLC) with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) is a valuable tool to study these metal-organic interactions in a qualitative and quantitative approach. We established a desolvation method that allows direct transfer of high organic solvent loads into the plasma. Thus, in combination with internal standardization and external calibration, the investigation of a broad polarity scale was possible. This approach overcomes previous restrictions to non-organic solvent separation techniques like size

  8. DNA origami based Au–Ag-core–shell nanoparticle dimers with single-molecule SERS sensitivity† †Electronic supplementary information (ESI) available: Additional information about materials and methods, designs of DNA origami templates, height profiles, additional SERS spectra, assignment of DNA bands, SEM images, additional AFM images, FDTD simulations, additional reference spectra for Cy3 and detailed description of EF estimation, simulated absorption and scattering spectra. See DOI: 10.1039/c5nr08674d Click here for additional data file.

    PubMed Central

    Prinz, J.; Heck, C.; Ellerik, L.; Merk, V.

    2016-01-01

    DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled. PMID:26892770

  9. Additions of nutrients and major ions by the atmosphere and tributaries to nearshore waters of northwestern Lake Huron

    USGS Publications Warehouse

    Manny, Bruce A.; Owens, R.W.

    1983-01-01

    Nutrient additions by the atmosphere and six tributaries to nearshore waters of northwestern Lake Huron were measured at weekly intervals from August 1975 to July 1976. The atmosphere contributed 43% of the nitrogen (N) and 10% of the phosphorus (P) that was added during the year. The 1975–76 atmospheric loading rate of total N to this area (11 kg/ha/yr) was one of the highest found to date in the United States. N was conserved more efficiently than P in the tributary drainage basins. Of the N and P that fell annually on the watersheds under study, 2 to 37% of the N and 31 to 84% of the P was carried with runoff to the lake. From a basin where ditching and clear-cutting occurred, water, P, silica (SiO2), N, and sodium were lost at higher rates than from five other basins. Most of the N in bulk atmospheric samples (23%) and tributary waters (56%) was dissolved organic N, a form of N not often measured.

  10. An FTIR study on the catalytic effect of water molecules on the reaction of CO successive hydrogenation at 3 and 10K

    NASA Astrophysics Data System (ADS)

    Pirim, C.; Krim, L.

    2011-05-01

    The ubiquitous presence of water and the relative high abundance of H2, H and CO molecules in the interstellar medium motivated numerous studies on their potential interaction. The reaction of successive hydrogenation of CO is of large interest in astrochemistry because of its implication in the formation of formaldehyde and methanol in interstellar grains and in comets. The catalytic effect of water on the successive hydrogenation of CO has been investigated by two methods. The first is the hydrogenation of a CO/H2O surface. The second is a co-injection of (CO/H2O) mixtures and H atoms. Both methods have been performed at 3 and 10 K. When the hydrogenation of a CO surface is performed at 3 K, no products are observed. In fact, the presence of solid hydrogen screens the hydrogenation process. However, when performed at 10 K, the experiment shows that water molecules increase the concentration of the H2CO and CH3OH species. At 3 and 10K, [(CO/H2O)+H] co-depositions confirm a subtantial impact on by-products formation. We show that water molecules increase the probability of reactive to encounter H atoms either physically, or chemically, by raising the number of chemical pathways. A coordinated theoretical study of the possible chemical pathways is currently under way.

  11. Changes in the hydrogen-bonding strength of internal water molecules and cysteine residues in the conductive state of channelrhodopsin-1

    NASA Astrophysics Data System (ADS)

    Lórenz-Fonfría, Víctor A.; Muders, Vera; Schlesinger, Ramona; Heberle, Joachim

    2014-12-01

    Water plays an essential role in the structure and function of proteins, particularly in the less understood class of membrane proteins. As the first of its kind, channelrhodopsin is a light-gated cation channel and paved the way for the new and vibrant field of optogenetics, where nerve cells are activated by light. Still, the molecular mechanism of channelrhodopsin is not understood. Here, we applied time-resolved FT-IR difference spectroscopy to channelrhodopsin-1 from Chlamydomonas augustae. It is shown that the (conductive) P2380 intermediate decays with τ ≈ 40 ms and 200 ms after pulsed excitation. The vibrational changes between the closed and the conductive states were analyzed in the X-H stretching region (X = O, S, N), comprising vibrational changes of water molecules, sulfhydryl groups of cysteine side chains and changes of the amide A of the protein backbone. The O-H stretching vibrations of "dangling" water molecules were detected in two different states of the protein using H218O exchange. Uncoupling experiments with a 1:1 mixture of H2O:D2O provided the natural uncoupled frequencies of the four O-H (and O-D) stretches of these water molecules, each with a very weakly hydrogen-bonded O-H group (3639 and 3628 cm-1) and with the other O-H group medium (3440 cm-1) to moderately strongly (3300 cm-1) hydrogen-bonded. Changes in amide A and thiol vibrations report on global and local changes, respectively, associated with the formation of the conductive state. Future studies will aim at assigning the respective cysteine group(s) and at localizing the "dangling" water molecules within the protein, providing a better understanding of their functional relevance in CaChR1.

  12. Changes in the hydrogen-bonding strength of internal water molecules and cysteine residues in the conductive state of channelrhodopsin-1.

    PubMed

    Lórenz-Fonfría, Víctor A; Muders, Vera; Schlesinger, Ramona; Heberle, Joachim

    2014-12-14

    Water plays an essential role in the structure and function of proteins, particularly in the less understood class of membrane proteins. As the first of its kind, channelrhodopsin is a light-gated cation channel and paved the way for the new and vibrant field of optogenetics, where nerve cells are activated by light. Still, the molecular mechanism of channelrhodopsin is not understood. Here, we applied time-resolved FT-IR difference spectroscopy to channelrhodopsin-1 from Chlamydomonas augustae. It is shown that the (conductive) P2(380) intermediate decays with τ ≈ 40 ms and 200 ms after pulsed excitation. The vibrational changes between the closed and the conductive states were analyzed in the X-H stretching region (X = O, S, N), comprising vibrational changes of water molecules, sulfhydryl groups of cysteine side chains and changes of the amide A of the protein backbone. The O-H stretching vibrations of "dangling" water molecules were detected in two different states of the protein using H2 (18)O exchange. Uncoupling experiments with a 1:1 mixture of H2O:D2O provided the natural uncoupled frequencies of the four O-H (and O-D) stretches of these water molecules, each with a very weakly hydrogen-bonded O-H group (3639 and 3628 cm(-1)) and with the other O-H group medium (3440 cm(-1)) to moderately strongly (3300 cm(-1)) hydrogen-bonded. Changes in amide A and thiol vibrations report on global and local changes, respectively, associated with the formation of the conductive state. Future studies will aim at assigning the respective cysteine group(s) and at localizing the "dangling" water molecules within the protein, providing a better understanding of their functional relevance in CaChR1. PMID:25494778

  13. Zinc oxide nanoparticle growth from homogenous solution: Influence of Zn:OH, water concentration, and surfactant additives

    SciTech Connect

    Ratkovich, Anthony; Penn, R. Lee

    2009-05-06

    Zinc oxide particle growth from homogeneous solution was monitored using in situ UV-vis spectroscopy. Final particle size and overall growth rate increased with increasing zinc to hydroxide concentration ratio and were both sensitive to the surfactant added. Particle growth was fit using two models: (1) the classic coarsening model and (2) the simultaneous coarsening and oriented aggregation model. Results demonstrate that using adamantane carboxylic acid as a surfactant additive inhibits ZnO nanoparticle growth both by coarsening and oriented aggregation as compared to using other monocarboxylates (e.g., acetate and tribromoacetate). In addition, ZnO nanoparticle growth was independent of water concentration within the range of 40-100 mM for the conditions studied here (1 mM zinc perchlorate, 1.6 mM hydroxide, and 0.38 mM adamantane carboxylic acid). High-resolution transmission electron micrographs confirm inhibited growth by oriented aggregation for ZnO grown with adamantane carboxylic acid. Results are compared to previous work and generally show that ZnO growth by coarsening and oriented aggregation can be selectively inhibited or promoted by judicious selection of the surfactant additive.

  14. Superposition-additive approach: thermodynamic parameters of clusterization of monosubstituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Fainerman, V B; Aksenenko, E V; Vollhardt, D; Miller, R

    2011-12-21

    The applicability of the superposition-additive approach for the calculation of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole electric polarisabilities, molecular diamagnetic susceptibilities, π-electron circular currents, as well as for the estimation of the thermodynamic parameters of substituted alkanes, was demonstrated earlier. Now the applicability of the superposition-additive approach for the description of clusterization of fatty alcohols, thioalcohols, amines, carboxylic acids at the air/water interface is studied. Two superposition-additive schemes are used that ensure the maximum superimposition of the graphs of the considered molecular structures including the intermolecular CH-HC interactions within the clusters. The thermodynamic parameters of clusterization are calculated for dimers, trimers and tetramers. The calculations are based on the values of enthalpy, entropy and Gibbs' energy of clusterization calculated earlier using the semiempirical quantum chemical PM3 method. It is shown that the proposed approach is capable of the reproduction with sufficiently enough accuracy of the values calculated previously. PMID:22042000

  15. The mobility of single-file water molecules is governed by the number of H-bonds they may form with channel-lining residues

    PubMed Central

    Horner, Andreas; Zocher, Florian; Preiner, Johannes; Ollinger, Nicole; Siligan, Christine; Akimov, Sergey A.; Pohl, Peter

    2015-01-01

    Channel geometry governs the unitary osmotic water channel permeability, pf, according to classical hydrodynamics. Yet, pf varies by several orders of magnitude for membrane channels with a constriction zone that is one water molecule in width and four to eight molecules in length. We show that both the pf of those channels and the diffusion coefficient of the single-file waters within them are determined by the number NH of residues in the channel wall that may form a hydrogen bond with the single-file waters. The logarithmic dependence of water diffusivity on NH is in line with the multiplicity of binding options at higher NH densities. We obtained high-precision pf values by (i) having measured the abundance of the reconstituted aquaporins in the vesicular membrane via fluorescence correlation spectroscopy and via high-speed atomic force microscopy, and (ii) having acquired the vesicular water efflux from scattered light intensities via our new adaptation of the Rayleigh-Gans-Debye equation. PMID:26167541

  16. Natural Hazard Mitigation thru Water Augmentation Strategies to Provide Additional Snow Pack for Water Supply and Hydropower Generation in Drought Stressed Alps/Mountains

    NASA Astrophysics Data System (ADS)

    Matthews, D.; Brilly, M.

    2009-12-01

    .08 million acre feet (1.33 x 10**9 m3) of additional water could be captured by seeding efficiently and effectively in just 10 storms. Recent projects sponsored by the National Science Foundation, NOAA, and the States of Wyoming, Utah and Nevada, and conducted by the National Center for Atmospheric Research will be discussed briefly. Examples of conditions in extreme droughts of the Western United States will be presented that show potential to mitigate droughts in these regions through cloud seeding. Implications for American and European hydropower generation and sustainable water supplies will be discussed.

  17. A structurally stable 3D supramolecular framework with 4.0% guest-accessible void spaces that are reversibly occupied by guest water molecules

    NASA Astrophysics Data System (ADS)

    Luo, Feng; Che, Yun-Xia; Zheng, Ji-min

    2008-02-01

    A new Cd(II)-Cu(II)-containing coordination compound, namely Cu(bpy)Cd(ip) 2(μ-OH 2) · (H 2O) 2 ( 1, bpy = 2,2 '-bipyridine, H 2ip = m-phthalic acid), has been synthesized hydrothermally by the reaction of CdCl 2, CuCl 2, bpy, and H 2ip. In 1, Cd(II) and Cu(II) ions are in turn connected by ip 2- ligands to generate the 2D (4, 4) nets. Further, these 2D sheets are linked together via π-π, C-H…O, and O-H…O contacts, thus resulting in the 3D supramolecular frameworks with the irregular 1D channels occupied by water molecules. Remarkably, the investigation by using IR, TG, and PXRD (powder X-ray diffraction) shows that the uptake and release of guest water molecules will not influence the structural integrity.

  18. Radio searches for additional interstellar molecules

    NASA Technical Reports Server (NTRS)

    Hollis, J. M.; Suenram, R. D.; Lovas, F. J.; Snyder, L. E.

    1983-01-01

    Observations in the 2-mm wavelength range are reported which yield new interstellar molecular transitions of NH2CHO, SO2, H2CCO, U150820.5, and U150850.0 toward Sgr B2, and SO2, CH2CHCN, HCOOCH3, and U153513.0 toward Orion A. The first interstellar searches for HOCl, CH3CH2CCH, and CH3SiH3 were conducted, but these species were not detected. During these observations limits were also obtained on 2-mm wave transitions of N2O and NaOH toward several galactic sources of molecular emission.

  19. Transitional liquid crystalline phases between the hexagonal and lamellar phases in ternary cesium N-tetradecanoate-water-additive mixtures

    SciTech Connect

    Blackburn, J.C.; Kilpatrick, P.K. )

    1993-04-01

    The effects of added salt (CsOH, CsCl), long-chain carboxylic acid, and long-chain alcohol on the lyotropic liquid crystalline phase behavior in the cesium n-tetradecanoate (CsTD)-water system is reported. The transitional region between the hexagonal (H) and lamellar (L) phases was the compositional range of focus. Three transitional phases were observed: (i) the ribbon (R) phase, a biaxial phase consisting of cylinders of ellipsoidal cross section; (ii) the viscous isotropic (VI) phase, an isotropic phase thought to consist of interconnected rods on an Ia3d lattice; and (iii) the intermediate (Int) phase, a uniaxial anisotropic phase thought to consist of interconnected rods on a planar lattice. The effect of the additives was to decrease the interfacial curvature of the surfactant head group layer by varying head group repulsion and by varying the surfactant tail volume relative to the surfactant head group area. These changes resulted in formation of transitional phases seeming to possess curvature between that of the cylindrical H phase and the planar L phase. The ionic repulsion between carboxylate head groups was reduced by the addition of CsOH or CsCl, and resulted in destabilization of the VI phase and the formation of the anisotropic Int phase. With the addition of cosurfactants, n-tetradecanoic acid (TDA) and 1-tetradecanol (TDOH), no Int phase was observed. With 7 wt% added TDA the R phase was stabilized up to temperatures of 336 K, above the 330 K temperature limit in the binary CsTD-D[sub 2]O system. In all four systems, sufficient additive (5-10 wt%) resulted in a transition to the L phase, which was stable over a large portion of the compositional range. In order of apparently decreasing mean curvature, the phase sequence is: hexagonal, ribbon, viscous isotropic, intermediate, and lamellar.

  20. The advantage of polymer addition to a non-ionic oil in water microemulsion for the dermal delivery of progesterone.

    PubMed

    Biruss, Babette; Valenta, Claudia

    2008-02-12

    The influence of progesterone on the physicochemical behaviour of the o/w microemulsion consisting of the non-ionic surfactant polyoxyethylene-10-dodecyl ether, tributyrin and water was investigated. Thereby no significant influence could be detected in terms of droplet size, zeta potential, conductivity and pH by progesterone. However the chemical stability of progesterone was insufficient during the storage of 6 months. Therefore, two different polymeric agents, named silicon dioxide and polymeric emulsifier, were added to the progesterone containing microemulsions. These polymers increased the chemical stability of progesterone significantly. Moreover the polymeric additives improved the skin permeation 1.24- and 1.63-fold and decreased the skin retention in relation to the pure microemulsion. The polymer-stabilized progesterone microemulsions are interesting vehicles for skin application of progesterone. PMID:17869457

  1. Structure of hydrated clusters of dibenzo-18-crown-6-ether in a supersonic jet--encapsulation of water molecules in the crown cavity.

    PubMed

    Kusaka, Ryoji; Inokuchi, Yoshiya; Ebata, Takayuki

    2008-11-01

    The structure of dibenzo-18-crown-6-ether (DB18C6) and its hydrated clusters has been investigated in a supersonic jet. Two conformers of bare DB18C6 and six hydrated clusters (DB18C6-(H(2)O)(n)) were identified by laser-induced fluorescence, fluorescence-detected UV-UV hole-burning and IR-UV double-resonance spectroscopy. The IR-UV double resonance spectra were compared with the IR spectra obtained by quantum chemical calculations at the B3LYP/6-31+G* level. The two conformers of bare DB18C6 are assigned to "boat" and "chair I" forms, respectively, among which the boat form is dominant. All the six DB18C6-(H(2)O)(n) clusters with n = 1-4 have a boat conformation in the DB18C6 part. The water molecules form a variety of hydration networks in the boat-DB18C6 cavity. In DB18C6-(H(2)O)(1), a water molecule forms the bidentate hydrogen bond with the O atoms adjacent to the benzene rings. In this cluster, the water molecule is preferentially hydrogen bonded from the bottom of boat-DB18C6. In the larger clusters, the hydration networks are developed on the basis of the DB18C6-(H(2)O)(1) cluster. PMID:18936847

  2. The effect on the lanthanide luminescence of structurally simple Eu(III) cyclen complexes upon deprotonation of metal bound water molecules and amide based pendant arms.

    PubMed

    Plush, Sally E; Clear, Naomi A; Leonard, Joseph P; Fanning, Ann-Marie; Gunnlaugsson, Thorfinnur

    2010-04-21

    A series of substituted 1,4,7,10-tetraazacylcododecane ligands 1-4, possessing sensitizing nitrobenzene or naphthalene antennae, as one of the amide pendant arms, and their complexes with europium(III) were synthesised. The protonation constants and the metal ion stability constants of two of these ligands were determined by potentiometric titration. The pK(a) of the water molecules coordinated to the complexed metal ion were determined by both luminescent and potentiometric measurements. The luminescence pH dependence of a further three Eu(III) complexes, 5-7, which lack any antennae, were also studied with the aim of gaining a better understanding of the role of the metal bound water molecules in the luminescence properties of such complexes upon direct excitation of the lanthanide ion. The results from these luminescent measurements demonstrate that the Eu(III) emission was significantly modulated as a function of pH for all the complexes, which we assigned to changes occurring in the coordination environment of the ion within the cyclen system, caused by deprotonation of metal bound water molecules and/or deprotonation of pendent amide arms. PMID:20354617

  3. Influence of Anthropogenic Nutrient Additions on Greenhouse Gas Production Rates at Water-soil Interfaces in an Urban Dominated Estuary

    NASA Astrophysics Data System (ADS)

    Brigham, B. A.; O'Mullan, G. D.; Bird, J. A.

    2014-12-01

    The tidal Hudson River Estuary (HRE) receives significant inputs of readily dissolvable carbon (C) and nitrogen (N) from incomplete wastewater treatment and sewer overflow during storm events associated with NYC and other urban centers. Nutrient deposition may alter C utilization in the estuarine water column, associated sediments and surrounding wetlands. In these anaerobic systems, we hypothesize that microbial activity is limited by the availability of easily-degradable C (not electron acceptors), which acts as a co-metabolite and provides energy for organic matter decomposition. Sporadic transport of highly C enriched storm derived runoff may substantially enhance greenhouse gas (GHG) production rates through the utilization of stored C pools. To test our hypothesis carbon dioxide (CO2) and methane (CH4) process rates (1) were evaluated from soil cores removed from three distinct HRE wetland sites (Saw Mill Creek, Piermont, and Iona Island Marsh(s)) across a salinity gradient and incubated under varying nutrient treatments. Further, CO2 and CH4 surface water effluxes (2) were quantified from multiple river cruises spanning two years at varying distance from nutrient sources associated with NYC. Incubation experiments from wetland soil core experiments demonstrated that readily degradable C but not inorganic N additions stimulated GHG production (200 - 350 ug C g-1 of dry soil day-1) threefold compared to negative controls. The HRE was found to be both a CO2 and CH4 source under all conditions. The greatest GHG efflux (300 - 3000 nmoles C m-2 day-1) was quantified in mid-channel, tributary, and near shore sites in close proximity to NYC which following precipitation events demonstrated 2-20X increased GHG efflux. These results demonstrate that anthropogenic C additions associated with dense urban centers have the potential to enhance anaerobic microbial degradation of organic matter and subsequent GHG production.

  4. Intercomparison of stratospheric water vapor observed by satellite experiments - Stratospheric Aerosol and Gas Experiment II versus Limb Infrared Monitor of the Stratosphere and Atmospheric Trace Molecule Spectroscopy

    NASA Technical Reports Server (NTRS)

    Chiou, E. W.; Mccormick, M. P.; Mcmaster, L. R.; Chu, W. P.; Larsen, J. C.; Rind, D.; Oltmans, S.

    1993-01-01

    A comparison is made of the stratospheric water vapor measurements made by the satellite sensors of the Stratospheric Aerosol and Gas Experiment II (SAGE II), the Nimbus-7 LIMS, and the Spacelab 3 Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment. It was found that, despite differences in the measurement techniques, sampling bias, and observational periods, the three experiments have disclosed a generally consistent pattern of stratospheric water vapor distribution. The only significant difference occurs at high southern altitudes in May below 18 km, where LIMS measurements were 2-3 ppmv greater than those of SAGE II and ATMOS.

  5. Effects of organic and inorganic additives on flotation recovery of washed cells of Saccharomyces cerevisiae resuspended in water.

    PubMed

    DeSousa, Sandro Rogério; Laluce, Cecilia; Jafelicci, Miguel

    2006-03-01

    Separation of microbial cells by flotation recovery is usually carried out in industrial reactors or wastewater treatment systems, which contain a complex mixture of microbial nutrients and excretion products. In the present study, the separation of yeast cells by flotation recovery was carried out using a simple flotation recovery systems containing washed yeast cells resuspended in water in order to elucidate the effects of additives (defined amounts of organic and inorganic acids, ethanol, surfactants and sodium chloride) on the cellular interactions at interfaces (cell/aqueous phase and cell/air bubble). When sodium chloride, organic acids (notably propionic, succinic and acetic acids) and organic surfactants (sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB) and Nonidet P40) were added to the flotation recovery system, significant increases in the cell recovery of yeast hydrophobic cells (Saccharomyces cerevisiae, strain FLT-01) were observed. The association of ethanol to acetic acid solution (a minor by-product of alcoholic fermentation) in the flotation recovery system, containing washed cells of strain FLT-01 resuspended in water, leading to an increased flotation recovery at pH 5.5. Thus, the association among products of the cellular metabolism (e.g., ethanol and acetic acid) can improve yeast cell recovery by flotation recovery. PMID:16500092

  6. Model assessment of additional contamination of water bodies as a result of wildfires in the Chernobyl exclusion zone.

    PubMed

    Bondar, Yu I; Navumau, A D; Nikitin, A N; Brown, J; Dowdall, M

    2014-12-01

    Forest fires and wild fires are recognized as a possible cause of resuspension and redistribution of radioactive substances when occurring on lands contaminated with such materials, and as such are a matter of concern within the regions of Belarus and the Ukraine which were contaminated by the Chernobyl accident in 1986. Modelling the effects of such fires on radioactive contaminants is a complex matter given the number of variables involved. In this paper, a probabilistic model was developed using empirical data drawn from the Polessie State Radiation-Ecological Reserve (PSRER), Belarus, and the Maximum Entropy Method. Using the model, it was possible to derive estimates of the contribution of fire events to overall variability in the levels of (137)Cs and (239,240)Pu in ground air as well as estimates of the deposition of these radionuclides to specific water bodies within the contaminated areas of Belarus. Results indicate that fire events are potentially significant redistributors of radioactive contaminants within the study area and may result in additional contamination being introduced to water bodies. PMID:25240987

  7. Multiple Stressors in Agricultural Streams: A Mesocosm Study of Interactions among Raised Water Temperature, Sediment Addition and Nutrient Enrichment

    PubMed Central

    Piggott, Jeremy J.; Lange, Katharina; Townsend, Colin R.; Matthaei, Christoph D.

    2012-01-01

    Changes to land use affect streams through nutrient enrichment, increased inputs of sediment and, where riparian vegetation has been removed, raised water temperature. We manipulated all three stressors in experimental streamside channels for 30 days and determined the individual and pair-wise combined effects on benthic invertebrate and algal communities and on leaf decay, a measure of ecosystem functioning. We added nutrients (phosphorus+nitrogen; high, intermediate, natural) and/or sediment (grain size 0.2 mm; high, intermediate, natural) to 18 channels supplied with water from a nearby stream. Temperature was increased by 1.4°C in half the channels, simulating the loss of upstream and adjacent riparian shade. Sediment affected 93% of all biological response variables (either as an individual effect or via an interaction with another stressor) generally in a negative manner, while nutrient enrichment affected 59% (mostly positive) and raised temperature 59% (mostly positive). More of the algal components of the community responded to stressors acting individually than did invertebrate components, whereas pair-wise stressor interactions were more common in the invertebrate community. Stressors interacted often and in a complex manner, with interactions between sediment and temperature most common. Thus, the negative impact of high sediment on taxon richness of both algae and invertebrates was stronger at raised temperature, further reducing biodiversity. In addition, the decay rate of leaf material (strength loss) accelerated with nutrient enrichment at ambient but not at raised temperature. A key implication of our findings for resource managers is that the removal of riparian shading from streams already subjected to high sediment inputs, or land-use changes that increase erosion or nutrient runoff in a landscape without riparian buffers, may have unexpected effects on stream health. We highlight the likely importance of intact or restored buffer strips, both

  8. Graphene oxide as a high-performance fluid-loss-control additive in water-based drilling fluids.

    PubMed

    Kosynkin, Dmitry V; Ceriotti, Gabriel; Wilson, Kurt C; Lomeda, Jay R; Scorsone, Jason T; Patel, Arvind D; Friedheim, James E; Tour, James M

    2012-01-01

    Graphene oxide (GO) performs well as a filtration additive in water-based drilling fluids at concentrations as low as 0.2 % (w/w) by carbon content. Standard American Petroleum Institute (API) filtration tests were conducted on pH-adjusted, aqueous dispersions of GO and xanthan gum. It was found that a combination of large-flake GO and powdered GO in a 3:1 ratio performed best in the API tests, allowing an average fluid loss of 6.1 mL over 30 min and leaving a filter cake ~20 μm thick. In comparison, a standard suspension (~12 g/L) of clays and polymers used in the oil industry gave an average fluid loss of 7.2 mL and a filter cake ~280 μm thick. Scanning electron microscopy imaging revealed the extreme pliability of well-exfoliated GO, as the pressure due to filtration crumpled single GO sheets, forcing them to slide through pores with diameters much smaller than the flake's flattened size. GO solutions also exhibited greater shear thinning and higher temperature stability compared to clay-based fluid-loss additives, demonstrating potential for high-temperature well applications. PMID:22136134

  9. Evaluation of a water-soluble adjuvant for the development of monoclonal antibodies against small-molecule compounds*

    PubMed Central

    Liu, Rui; Liu, Ying; Lan, Mei-jing; Taheri, Niusha; Cheng, Jing-li; Guo, Yi-rong; Zhu, Guo-nian

    2016-01-01

    A water-soluble adjuvant named QuickAntibody (QA) was introduced into the procedure of mouse immunization for the development of hapten-specific monoclonal antibodies (mAbs), using four kinds of pesticides as model compounds. Compared with conventional Freund’s adjuvants, QA treatments offered relatively low but acceptable antiserum titers after three inoculations, gave little adverse effects to the experimental animals, and were preferable in harvesting splenocytes during the steps of cell fusion. Afterwards, hybridomas from the QA group were prepared and screened by both non-competitive and competitive indirect enzyme-linked immunosorbent assays (ELISAs). The efficiency of gaining immune-positive hybridomas was satisfactory, and the resultant mAbs showed sensitivities (half maximal inhibitory concentration (IC50)) of 0.91, 2.46, 3.72, and 6.22 ng/ml to triazophos, parathion, chlorpyrifos, and fenpropathrin, respectively. Additionally, the performance of QA adjuvant was further confirmed by acquiring a high-affinity mAb against okadaic acid (IC50 of 0.36 ng/ml) after three immunizations. These newly developed mAbs showed similar or even better sensitivities compared with previously reported mAbs specific to the corresponding analytes. This study suggested that the easy-to-use adjuvant could be applicable to the efficient generation of highly sensitive mAbs against small compounds.

  10. Librational modes of the water molecules in barium and strontium halide monohydrates, MX 2 · 1H 2O (M = Ba, Sr; X = Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Lutz, H. D.; Christian, H.

    1983-09-01

    The IR and Raman spectra of the isotypic alkaline earth halide monohydrates, MX 2 · 1H 2O, with M = Sr, Ba and X = Cl, Br, I, and of deuterated samples are presented for the range 200-700 cm -1 and discussed in terms of normal modes, assignment, coupling, correlation with structure data, and temperature dependence of both the H 2O (D 2O) and the HDO librational modes. The normal modes of the out-of-plane librations of HDO molecules are of the wagging and twisting type rather than H and D out-of-plane vibrations [4], at least for water molecules with C2v or nearly C2v symmetry. Thus the observed H 2O/HDO isotopic shifts can be used as a criterion for assigning the H 2O librations. The librational modes of the halide monohydrates (with tetrahedrally coordinated water oxygen atoms) are found in the order ν Rγ ≫ ν Rt ≫ ν Rr. The intensities of the IR and Raman spectra are in the order Rγ ≫ Rr ≫ Rt (or ˜ Rt in the case of strongly distorted H 2O molecules) and Rt ≫ Rr ≫ Rγ, respectively. Correlations of the H 2O librational modes with structural or bonding data are restricted by frequency shifts due to vibrational coupling and by the fact that the oxygen and the hydrogen atoms of the water molecules are generally affected in a different manner by bond interactions. However, in the case of the twisting vibrations, there are clear correlations with both the size of the metal ions, i.e. increase of ν Rt with decreasing size, and the intermolecular bonding of the hydrogen atoms, as shown by the OH stretching frequencies, i.e. increase of ν Rt with decreasing ν OH.

  11. Molecule nanoweaver

    DOEpatents

    Gerald, II; Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2009-03-10

    A method, apparatus, and system for constructing uniform macroscopic films with tailored geometric assemblies of molecules on the nanometer scale. The method, apparatus, and system include providing starting molecules of selected character, applying one or more force fields to the molecules to cause them to order and condense with NMR spectra and images being used to monitor progress in creating the desired geometrical assembly and functionality of molecules that comprise the films.

  12. Processes at the sediment water interface after addition of organic matter and lime to an acid mine pit lake mesocosm

    SciTech Connect

    Matthias Koschorreck; Elke Bozau; Rene Froemmichen; Walter Geller; Peter Herzsprung; Katrin Wendt-Potthoff

    2007-03-01

    A strategy to neutralize acidic pit lakes was tested in a field mesocosm of 4500 m{sup 3} volume in the Acidic Pit Mine Lake 111 in the Koyne-Plessa lignite mining district of Lusatia, Germany. Carbokalk, a byproduct from sugar production, and wheat straw was applied near to the sediment surface to stimulate in lake microbial alkalinity generation by sulfate and iron reduction. The biogeochemical processes at the sediment-water interface were studied over 3 years by geochemical monitoring and an in situ microprofiler. Substrate addition generated a reactive zone at the sediment surface where sulfate and iron reduction proceeded. Gross sulfate reduction reached values up to 10 mmol m{sup -2} d{sup -1}. The neutralization rates between 27 and 0 meq m{sup -2} d{sup -1} were considerably lower than in previous laboratory experiments. The precipitation of ferric iron minerals resulted in a growing acidic sediment layer on top of the neutral sediment. In this layer sulfate reduction was observed but iron sulfides could not precipitate. In the anoxic sediment H{sub 2}S was oxidized by ferric iron minerals. H{sub 2}S partly diffused to the water column where it was oxidized. As a result the net formation of iron sulfides decreased after 1 year although gross sulfate reduction rates continued to be high. The rate of iron reduction exceeded the sulfate reduction rate, which resulted in high fluxes of ferrous iron out of the sediment. 46 refs., 6 figs., 1 tab.

  13. Modulation of the interbilayer hydration pressure by the addition of dipoles at the hydrocarbon/water interface.

    PubMed Central

    Simon, S A; McIntosh, T J; Magid, A D; Needham, D

    1992-01-01

    The effects of the cholesterol analog 5 alpha-cholestan-3 beta-ol-6-one (6-ketocholestanol) on bilayer structure, bilayer cohesive properties, and interbilayer repulsive pressures have been studied by a combination of x-ray diffraction, pipette aspiration, and dipole potential experiments. It is found that 6-ketocholestanol, which has a similar structure to cholesterol except with a keto moiety at the 6 position of the B ring, has quite different effects than cholesterol on bilayer organization and cohesive properties. Unlike cholesterol, 6-ketocholestanol does not appreciably modify the thickness of liquid-crystalline egg phosphatidylcholine (EPC) bilayers, and causes a much smaller increase in bilayer compressibility modulus than does cholesterol. These data imply that 6-ketocholestanol has both its hydroxyl and keto moieties situated near the water-hydrocarbon interface, thus making its orientation in the bilayer different from cholesterol's. The addition of equimolar 6-ketocholestanol into EPC bilayers increases the magnitude, but not the decay length, of the exponentially decaying repulsive hydration pressure between adjacent bilayers. Incorporation of equimolar 6-ketocholestanol into EPC monolayers increases the dipole potential by approximately 300 mV. These data are consistent with our previous observation that the magnitude of the hydration pressure is proportional to the square of the dipole potential. These results mean that 6-ketocholestanol, despite its location in the bilayer hydrocarbon region, approximately 10 A from the physical edge of the bilayer, modifies the organization of interlamellar water. We argue that the incorporation of 6-ketocholestanol into EPC bilayers increases the hydration pressure, at least in part, by increasing the electric field strength in the polar head group region. PMID:1504249

  14. THE CARCINOGENIC RESPONSE OF TSC2 MUTANT LONG EVANS (EKER) RATS TO A MIXTURE OF DRINKING WATER DISINFECTION BY-PRODUCTS WAS LESS THAN ADDITIVE

    EPA Science Inventory

    Cancer risk assessment methods for chemical mixtures in drinking water are not well defined. Current default risk assessments for chemical mixtures assume additivity of carcinogenic effects but this may not represent the actual biological response. A rodent model of hereditary ...

  15. Investigation on the eco-toxicity of lake sediments with the addition of drinking water treatment residuals.

    PubMed

    Yuan, Nannan; Wang, Changhui; Pei, Yuansheng

    2016-08-01

    Drinking water treatment residuals (WTRs) have a potential to realize eutrophication control objectives by reducing the internal phosphorus (P) load of lake sediments. Information regarding the ecological risk of dewatered WTR reuse in aquatic environments is generally lacking, however. In this study, we analyzed the eco-toxicity of leachates from sediments with or without dewatered WTRs toward algae Chlorella vulgaris via algal growth inhibition testing with algal cell density, chlorophyll content, malondialdehyde content, antioxidant enzyme superoxide dismutase activity, and subcellular structure indices. The results suggested that leachates from sediments unanimously inhibited algal growth, with or without the addition of different WTR doses (10% or 50% of the sediment in dry weight) at different pH values (8-9), as well as from sediments treated for different durations (10 or 180days). The inhibition was primarily the result of P deficiency in the leachates owing to WTR P adsorption, however, our results suggest that the dewatered WTRs were considered as a favorable potential material for internal P loading control in lake restoration projects, as it shows acceptably low risk toward aquatic plants. PMID:27521931

  16. Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

    SciTech Connect

    Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin

    2015-12-14

    In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics.

  17. Site-specific vibrational spectral signatures of water molecules in the magic H3O+(H2O)20 and Cs+(H2O)20 clusters

    PubMed Central

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Christopher J.; Johnson, Mark A.; Heine, Nadja; Gewinner, Sandy; Schöllkopf, Wieland; Esser, Tim K.; Fagiani, Matias R.; Knorke, Harald; Asmis, Knut R.

    2014-01-01

    Theoretical models of proton hydration with tens of water molecules indicate that the excess proton is embedded on the surface of clathrate-like cage structures with one or two water molecules in the interior. The evidence for these structures has been indirect, however, because the experimental spectra in the critical H-bonding region of the OH stretching vibrations have been too diffuse to provide band patterns that distinguish between candidate structures predicted theoretically. Here we exploit the slow cooling afforded by cryogenic ion trapping, along with isotopic substitution, to quench water clusters attached to the H3O+ and Cs+ ions into structures that yield well-resolved vibrational bands over the entire 215- to 3,800-cm−1 range. The magic H3O+(H2O)20 cluster yields particularly clear spectral signatures that can, with the aid of ab initio predictions, be traced to specific classes of network sites in the predicted pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the surface. PMID:25489068

  18. Effects of water addition on OH radical generation and plasma properties in an atmospheric argon microwave plasma jet

    SciTech Connect

    Srivastava, Nimisha; Wang Chuji

    2011-09-01

    Water vapor was added to the feeding gas of a continuous atmospheric argon (Ar) microwave plasma jet to study its influence on plasma shape, plasma gas temperature, and OH radical concentrations. The plasma jet was created by a 2.45 GHz microwave plasma source operating at constant power of 104 W with H{sub 2}O-Ar mixture flow rate of 1.7 standard liter per minute (slm). With an increase in the H{sub 2}O/Ar ratio from 0.0 to 1.9%, the plasma jet column length decreased from 11 mm to 4 mm, and the plasma jet became unstable when the ratio was higher than 1.9%; elevation of plasma gas temperature up to 330 K was observed in the plasma temperature range of 420-910 K. Optical emission spectroscopy showed that the dominant plasma emissions changed from N{sub 2} in the pure Ar plasma jet to OH with the addition of water vapor, and simulations of emission spectra suggested non-Boltzmann distribution of the rotational levels in the OH A-state (v'=0). Spatially resolved absolute OH number densities along the plasma jet axis were measured using UV cavity ringdown spectroscopy of the OH (A-X) (0-0) band in the H{sub 2}O/Ar ratio range of 0.0-1.9%. The highest OH number density is consistently located in the vicinity of the plasma jet tip, regardless of the H{sub 2}O/Ar ratio. OH number density in the post-tip region follows approximately an exponential decay along the jet axis with the fastest decay constant of 3.0 mm in the H{sub 2}O/Ar ratio of 1.5%. Given the low gas temperature of 420-910 K and low electron temperature of 0.5-5 eV along the jet axis, formation of the OH radical is predominantly due to electron impact induced dissociation of H{sub 2}O and dissociative recombination of H{sub 2}O{sup +} resulting from the Penning ionization process.

  19. Isolated monohydrates of a model peptide chain: effect of a first water molecule on the secondary structure of a capped phenylalanine.

    PubMed

    Biswal, Himansu S; Loquais, Yohan; Tardivel, Benjamin; Gloaguen, Eric; Mons, Michel

    2011-03-23

    The formation of monohydrates of capped phenylalanine model peptides, CH(3)-CO-Phe-NH(2) and CH(3)-CO-Phe-NH-CH(3), in a supersonic expansion has been investigated using laser spectroscopy and quantum chemistry methods. Conformational distributions of the monohydrates have been revealed by IR/UV double-resonance spectroscopy and their structures assigned by comparison with DFT-D calculations. A careful analysis of the final hydrate distribution together with a detailed theoretical investigation of the potential energy surface of the monohydrates demonstrates that solvation occurs from the conformational distribution of the isolated peptide monomers. The distribution of the monohydrates appears to be strongly dependent on both the initial monomer conformation (extended or folded backbone) and the solvation site initially occupied by the water molecule. The solvation processes taking place during the cooling can be categorized as follows: (a) solvation without significant structural changes of the peptide, (b) solvation inducing significant distortions of the backbone but retaining the secondary structure, and (c) solvation triggering backbone isomerizations, leading to a modification of the peptide secondary structure. It is observed that solvation by a single water molecule can fold a β-strand into a γ-turn structure (type c) or induce a significant opening of a γ-turn characterized by an elongated C(7) hydrogen bond (type b). These structural changes can be considered as a first step toward the polyproline II condensed-phase structure, illustrating the role played by the very first water molecule in the solvation process. PMID:21361380

  20. Enhancement of the anaerobic hydrolysis and fermentation of municipal solid waste in leachbed reactors by varying flow direction during water addition and leachate recycle

    SciTech Connect

    Uke, Matthew N.; Stentiford, Edward

    2013-06-15

    Highlights: ► Combined downflow and upflow water addition improved hydraulic conductivity. ► Upflow water addition unclogged perforated screen leading to more leachate flow. ► The volume of water added and transmitted positively correlated with hydrolysis process. ► Combined downflow and upflow water addition increased COD production and yield. ► Combined downflow and upflow leachate recycle improved leachate and COD production. - Abstract: Poor performance of leachbed reactors (LBRs) is attributed to channelling, compaction from waste loading, unidirectional water addition and leachate flow causing reduced hydraulic conductivity and leachate flow blockage. Performance enhancement was evaluated in three LBRs M, D and U at 22 ± 3 °C using three water addition and leachate recycle strategies; water addition was downflow in D throughout, intermittently upflow and downflow in M and U with 77% volume downflow in M, 54% volume downflow in U while the rest were upflow. Leachate recycle was downflow in D, alternately downflow and upflow in M and upflow in U. The strategy adopted in U led to more water addition (30.3%), leachate production (33%) and chemical oxygen demand (COD) solubilisation (33%; 1609 g against 1210 g) compared to D (control). The total and volatile solids (TS and VS) reductions were similar but the highest COD yield (g-COD/g-TS and g-COD/g-VS removed) was in U (1.6 and 1.9); the values were 1.33 and 1.57 for M, and 1.18 and 1.41 for D respectively. The strategy adopted in U showed superior performance with more COD and leachate production compared to reactors M and D.

  1. A Model of Ball Lightning as a Formation of Water Molecules Confining an Electric Charge and the Classical Theory of the Electron

    NASA Astrophysics Data System (ADS)

    Tennakone, K.

    2012-04-01

    Ball lightning or faintly luminous floating spheres with radii of the order of ten centimeters appearing transiently in air notably during stormy weather continue to remain an unresolved phenomenon. It is suggested that these objects are organized structures constituted of an electrically charged spherical thin shell of electro-frozen dipole oriented water molecules carrying an electric charge, balanced by the internal negative pressure and outward electrostatic stress. A model presented, resembling the classical theory of the electron with Poincare stresses explain almost all observed attributes of this phenomenon. The possibility of realizing macroscopic spherical surface charge distributions in the vacuum and their implication on the problem of electron are commented.

  2. Water- and Plant-Mediated Responses of Ecosystem Carbon Fluxes to Warming and Nitrogen Addition on the Songnen Grassland in Northeast China

    PubMed Central

    Jiang, Li; Guo, Rui; Zhu, Tingcheng; Niu, Xuedun; Guo, Jixun; Sun, Wei

    2012-01-01

    Background Understanding how grasslands are affected by a long-term increase in temperature is crucial to predict the future impact of global climate change on terrestrial ecosystems. Additionally, it is not clear how the effects of global warming on grassland productivity are going to be altered by increased N deposition and N addition. Methodology/Principal Findings In-situ canopy CO2 exchange rates were measured in a meadow steppe subjected to 4-year warming and nitrogen addition treatments. Warming treatment reduced net ecosystem CO2 exchange (NEE) and increased ecosystem respiration (ER); but had no significant impacts on gross ecosystem productivity (GEP). N addition increased NEE, ER and GEP. However, there were no significant interactions between N addition and warming. The variation of NEE during the four experimental years was correlated with soil water content, particularly during early spring, suggesting that water availability is a primary driver of carbon fluxes in the studied semi-arid grassland. Conclusion/Significance Ecosystem carbon fluxes in grassland ecosystems are sensitive to warming and N addition. In the studied water-limited grassland, both warming and N addition influence ecosystem carbon fluxes by affecting water availability, which is the primary driver in many arid and semiarid ecosystems. It remains unknown to what extent the long-term N addition would affect the turn-over of soil organic matter and the C sink size of this grassland. PMID:23028848

  3. Ionic liquids as mobile phase additives for the high-performance liquid chromatographic analysis of fluoroquinolone antibiotics in water samples.

    PubMed

    Herrera-Herrera, Antonio V; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Angel

    2008-12-01

    In this work, four ionic liquids differing in the length of the alkyl chain on the imidazolium cation and one ionic liquid containing tetraethylammonium, all with the same counterion, (i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIm-BF(4)), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIm-BF(4)), 1-hexyl-3-methylimidazolium tetrafluoroborate (HMIm-BF(4)), 1-methyl-3-octylimidazolium tetrafluoroborate (MOIm-BF(4)), and tetraethylammonium tetrafluroborate (Et(4)N-BF(4))) were tested as mobile phase additives for HPLC separation of a group of seven basic fluoroquinolone (FQ) antibiotics for human and veterinary use (i.e. fleroxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, sarafloxacin, and difloxacin) using a conventional reversed-phase Nova-Pak C(18) column. Fluorescence detection was used. Among the ionic liquids selected, use of BMIm-BF(4) enabled effective separation of these compounds with relatively low analysis time (14 min). The best separation was achieved by isocratic elution at 1 mL min(-1) with 5 mmol L(-1) BMIm-BF(4) and 10 mmol L(-1) ammonium acetate at pH 3.0 with 13% (v/v) acetonitrile. Limits of detection (LODs) for fluorescence detection were in the range 0.5-11 microg L(-1). The method was tested by analyzing several water samples after the optimization of a suitable solid-phase extraction (SPE) procedure using Oasis HLB cartridges. Mean recovery values were above 84% for all analytes with LODs in the range 1-29 ng L(-1). PMID:18854988

  4. Effects of dust additions on phytoplankton growth and DMS production in high CO2 northeast Pacific HNLC waters

    NASA Astrophysics Data System (ADS)

    Mélançon, J.; Levasseur, M.; Lizotte, M.; Scarratt, M.; Tremblay, J.-É.; Tortell, P.; Yang, G.-P.; Shi, G.-Y.; Gao, H.-W.; Semeniuk, D. M.; Robert, M.; Arychuk, M.; Johnson, K.; Sutherland, N.; Davelaar, M.; Nemcek, N.; Peña, A.; Richardson, W.

    2015-08-01

    Ocean acidification (OA) is likely to have an effect on the fertilizing potential of desert dust in high-nutrient, low-chlorophyll oceanic regions, either by modifying Fe speciation and bioavailability, or by altering phytoplankton Fe requirements and acquisition. To address this issue, short incubations (4 days) of northeast subarctic Pacific waters enriched with either FeSO4 or dust, and set at pH 8.0 (in situ) and 7.8 were conducted in August 2010. We assessed the impact of a decrease in pH on dissolved Fe concentration, phytoplankton biomass, taxonomy and productivity, and the production of dimethylsulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP). Chlorophyll a (chl a) remained unchanged in the controls and doubled in both the FeSO4-enriched and dust-enriched incubations, confirming the Fe-limited status of the plankton assemblage during the experiment. In the acidified treatments, a significant reduction (by 16-38 %) of the final concentration of chl a was measured compared to their non-acidified counterparts, and a 15 % reduction in particulate organic carbon (POC) concentration was measured in the dust-enriched acidified treatment compared to the dust-enriched non-acidified treatment. FeSO4 and dust additions had a fertilizing effect mainly on diatoms and cyanobacteria. Lowering the pH affected mostly the haptophytes, but pelagophyte concentrations were also reduced in some acidified treatments. Acidification did not significantly alter DMSP and DMS concentrations. These results show that dust deposition events in a low-pH iron-limited Northeast subarctic Pacific are likely to stimulate phytoplankton growth to a lesser extent than in today's ocean during the few days following fertilization and point to a low initial sensitivity of the DMSP and DMS dynamics to OA.

  5. Percent recoveries of anthropogenic organic compounds with and without the addition of ascorbic acid to preserve finished-water samples containing free chlorine, 2004-10

    USGS Publications Warehouse

    Valder, Joshua F.; Delzer, Gregory C.; Bender, David A.; Price, Curtis V.

    2011-01-01

    This report presents finished-water matrix-spike recoveries of 270 anthropogenic organic compounds with and without the addition of ascorbic acid to preserve water samples containing free chlorine. Percent recoveries were calculated using analytical results from a study conducted during 2004-10 for the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey (USGS). The study was intended to characterize the effect of quenching on finished-water matrix-spike recoveries and to better understand the potential oxidation and transformation of 270 anthropogenic organic compounds. The anthropogenic organic compounds studied include those on analytical schedules 1433, 2003, 2033, 2060, 2020, and 4024 of the USGS National Water Quality Laboratory. Three types of samples were collected from 34 NAWQA locations across the Nation: (1) quenched finished-water samples (not spiked), (2) quenched finished-water matrix-spike samples, and (3) nonquenched finished-water matrix-spike samples. Percent recoveries of anthropogenic organic compounds in quenched and nonquenched finished-water matrix-spike samples are presented. Comparisons of percent recoveries between quenched and nonquenched spiked samples can be used to show how quenching affects finished-water samples. A maximum of 18 surface-water and 34 groundwater quenched finished-water matrix-spike samples paired with nonquenched finished-water matrix-spike samples were analyzed. Percent recoveries for the study are presented in two ways: (1) finished-water matrix-spike samples supplied by surface-water or groundwater, and (2) by use (or source) group category for surface-water and groundwater supplies. Graphical representations of percent recoveries for the quenched and nonquenched finished-water matrix-spike samples also are presented.

  6. Addition of water, methanol, and ammonia to Al3O3- clusters: Reaction products, transition states, and electron detachment energies

    NASA Astrophysics Data System (ADS)

    Guevara-García, Alfredo; Martínez, Ana; Ortiz, J. V.

    2005-06-01

    Products of reactions between the book and kite isomers of Al3O3- and three important molecules are studied with electronic structure calculations. Dissociative adsorption of H2O or CH3OH is highly exothermic and proton-transfer barriers between anion-molecule complexes and the products of these reactions are low. For NH3, the reaction energies are less exothermic and the corresponding barriers are higher. Depending on experimental conditions, Al3O3- (NH3) coordination complexes or products of dissociative adsorption may be prepared. Vertical electron detachment energies of stable anions are predicted with ab initio electron propagator calculations and are in close agreement with experiments on Al3O3- and its products with H2O and CH3OH. Changes in the localization properties of two Al-centered Dyson orbitals account for the differences between the photoelectron spectra of Al3O3- and those of the product anions.

  7. The binding energies of one and two water molecules to the first transition-row metal positive ions

    NASA Technical Reports Server (NTRS)

    Rosi, Marzio; Bauschlicher, Charles W., Jr.

    1989-01-01

    The bonding of water to the transition metal positive ions is electrostatic in origin. The electrostatic bonding is enhanced by a variety of mechanisms: mixing in 4p character, 4s-3d hybridization, and 4s promotion into the compact 3d orbital. The importance of these effects varies between the different metal ions due to changes in the separation of the metal ion atomic states. Furthermore, the change in the metal-water repulsion when a second water is added also changes the relative importance of the different metal asymptotes. The second water binding energy varies from being 11 kcal/mol smaller than the first for Mn(+) to 3 kcal/mol larger for V(+) and Fe(+).

  8. Study Design and Percent Recoveries of Anthropogenic Organic Compounds With and Without the Addition of Ascorbic Acid to Preserve Water Samples Containing Free Chlorine, 2004-06

    USGS Publications Warehouse

    Valder, Joshua F.; Delzer, Gregory C.; Price, Curtis V.; Sandstrom, Mark W.

    2008-01-01

    The National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey (USGS) began implementing Source Water-Quality Assessments (SWQAs) in 2002 that focus on characterizing the quality of source water and finished water of aquifers and major rivers used by some of the larger community water systems in the United States. As used for SWQA studies, source water is the raw (ambient) water collected at the supply well prior to water treatment (for ground water) or the raw (ambient) water collected from the river near the intake (for surface water). Finished water is the water that is treated, which typically involves, in part, the addition of chlorine or other disinfection chemicals to remove pathogens, and is ready to be delivered to consumers. Finished water is collected before the water enters the distribution system. This report describes the study design and percent recoveries of anthropogenic organic compounds (AOCs) with and without the addition of ascorbic acid to preserve water samples containing free chlorine. The percent recoveries were determined by using analytical results from a laboratory study conducted in 2004 by the USGS's National Water Quality Laboratory (NWQL) and from data collected during 2004-06 for a field study currently (2008) being conducted by the USGS's NAWQA Program. The laboratory study was designed to determine if preserving samples with ascorbic acid (quenching samples) adversely affects analytical performance under controlled conditions. During the laboratory study, eight samples of reagent water were spiked for each of five analytical schedules evaluated. Percent recoveries from these samples were then compared in two ways: (1) four quenched reagent spiked samples analyzed on day 0 were compared with four quenched reagent spiked samples analyzed on day 7 or 14, and (2) the combined eight quenched reagent spiked samples analyzed on day 0, 7, or 14 were compared with eight laboratory reagent spikes (LRSs). Percent

  9. Iridium-mediated Bond Activation and Water Oxidation as an Exemplary Case of CARISMA, A European Network for the Development of Catalytic Routines for Small Molecule Activation.

    PubMed

    Licini, Giulia; Albrecht, Martin

    2015-01-01

    CARISMA is a currently running COST Action that pools leading European experts in computational and experimental chemistry to foster synergies for developing new catalytic processes for the transformation of abundant small molecules such as water, carbon dioxide, or ammonia into high-value chemicals and energy-relevant products. CARISMA promotes new collaborations, exchange of knowledge and skills, frontier training to young as well as established researchers, and a platform for the advancement of theoretical and experimental research in an iterative process, comprised of expertise in various connate domains including synthesis, catalysis, spectroscopy, kinetics, and computational chemistry. These interactions stimulate the discovery of new and efficient catalytic processes, illustrated in the second part of this contribution with the collaborative development of powerful iridium-based complexes for bond activation and water oxidation catalysis. PMID:26507475

  10. Effects of addition of supramolecular assembly on the anatase nanocrystalline precipitation of sol-gel derived SiO2-TiO2 coating films by hot-water treatment.

    PubMed

    Katagiri, Kiyofumi; Harada, Genki; Matsuda, Atsunori; Kogure, Toshihiro; Muto, Hiroyuki; Sakai, Mototsugu

    2006-06-01

    Effects of the addition of a supramolecular assembly of cetyltrimethylammonium bromide in SiO2-TiO2 gel films on the formation of anatase type TiO2 nanocrystals with hot-water treatment were investigated. Anatase nanocrystals were formed in the whole SiO2-TiO2 gel films with the addition of cetyltrimethylammonium bromide by the treatment, whereas the nanocrystals were formed only on the film surface in the case of gel films without cetyltrimethylammonium bromide. Cetyltrimethylammonium bromide molecules in the SiO2-TiO2 gel films were completely removed by the hot-water treatment and the following UV irradiation. In the usual procedure for preparation of porous materials, the removal of template molecular assemblies required high temperature treatment over 400 degrees C. In this system, all the processes were performed at temperatures less than 100 degrees C. Additionally, the porous structure produced by the removal of micellar assembly allowed anatase nanocrystals to be formed inside the films. Therefore, the method presented in this work provides us with the novel photocatalyst coatings of porous membrane with highly-dispersed TiO2 nanocrystals via low temperature process. PMID:17025087

  11. The structures of RNase A complexed with 3'-CMP and d(CpA): active site conformation and conserved water molecules.

    PubMed Central

    Zegers, I.; Maes, D.; Dao-Thi, M. H.; Poortmans, F.; Palmer, R.; Wyns, L.

    1994-01-01

    The interactions of RNase A with cytidine 3'-monophosphate (3'-CMP) and deoxycytidyl-3',5'-deoxyadenosine (d(CpA)) were analyzed by X-ray crystallography. The 3'-CMP complex and the native structure were determined from trigonal crystals, and the d(CpA) complex from monoclinic crystals. The differences between the overall structures are concentrated in loop regions and are relatively small. The protein-inhibitor contacts are interpreted in terms of the catalytic mechanism. The general base His 12 interacts with the 2' oxygen, as does the electrostatic catalyst Lys 41. The general acid His 119 has 2 conformations (A and B) in the native structure and is found in, respectively, the A and the B conformation in the d(CpA) and the 3'-CMP complex. From the present structures and from a comparison with RNase T1, we propose that His 119 is active in the A conformation. The structure of the d(CpA) complex permits a detailed analysis of the downstream binding site, which includes His 119 and Asn 71. The comparison of the present RNase A structures with an inhibitor complex of RNase T1 shows that there are important similarities in the active sites of these 2 enzymes, despite the absence of any sequence homology. The water molecules were analyzed in order to identify conserved wate