Conserved water molecules in bacterial serine hydroxymethyltransferases.

Science.gov (United States)

Milano, Teresa; Di Salvo, Martino Luigi; Angelaccio, Sebastiana; Pascarella, Stefano

2015-10-01

Water molecules occurring in the interior of protein structures often are endowed with key structural and functional roles. We report the results of a systematic analysis of conserved water molecules in bacterial serine hydroxymethyltransferases (SHMTs). SHMTs are an important group of pyridoxal-5'-phosphate-dependent enzymes that catalyze the reversible conversion of l-serine and tetrahydropteroylglutamate to glycine and 5,10-methylenetetrahydropteroylglutamate. The approach utilized in this study relies on two programs, ProACT2 and WatCH. The first software is able to categorize water molecules in a protein crystallographic structure as buried, positioned in clefts or at the surface. The other program finds, in a set of superposed homologous proteins, water molecules that occur approximately in equivalent position in each of the considered structures. These groups of molecules are referred to as 'clusters' and represent structurally conserved water molecules. Several conserved clusters of buried or cleft water molecules were found in the set of 11 bacterial SHMTs we took into account for this work. The majority of these clusters were not described previously. Possible structural and functional roles for the conserved water molecules are envisaged. This work provides a map of the conserved water molecules helpful for deciphering SHMT mechanism and for rational design of molecular engineering experiments. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Instantaneous, parameter-free methods to define a solute’s hydration shell

International Nuclear Information System (INIS)

Chatterjee, Anupam; Higham, Jonathan; Henchman, Richard H.

2015-01-01

A range of methods are presented to calculate a solute’s hydration shell from computer simulations of dilute solutions of monatomic ions and noble gas atoms. The methods are designed to be parameter-free and instantaneous so as to make them more general, accurate, and consequently applicable to disordered systems. One method is a modified nearest-neighbor method, another considers solute-water Lennard-Jones overlap followed by hydrogen-bond rearrangement, while three methods compare various combinations of water-solute and water-water forces. The methods are tested on a series of monatomic ions and solutes and compared with the values from cutoffs in the radial distribution function, the nearest-neighbor distribution functions, and the strongest-acceptor hydrogen bond definition for anions. The Lennard-Jones overlap method and one of the force-comparison methods are found to give a hydration shell for cations which is in reasonable agreement with that using a cutoff in the radial distribution function. Further modifications would be required, though, to make them capture the neighboring water molecules of noble-gas solutes if these weakly interacting molecules are considered to constitute the hydration shell

Effect of supercritical water shell on cavitation bubble dynamics

International Nuclear Information System (INIS)

Shao Wei-Hang; Chen Wei-Zhong

2015-01-01

Based on reported experimental data, a new model for single cavitation bubble dynamics is proposed considering a supercritical water (SCW) shell surrounding the bubble. Theoretical investigations show that the SCW shell apparently slows down the oscillation of the bubble and cools the gas temperature inside the collapsing bubble. Furthermore, the model is simplified to a Rayleigh–Plesset-like equation for a thin SCW shell. The dependence of the bubble dynamics on the thickness and density of the SCW shell is studied. The results show the bubble dynamics depends on the thickness but is insensitive to the density of the SCW shell. The thicker the SCW shell is, the smaller are the wall velocity and the gas temperature in the bubble. In the authors’ opinion, the SCW shell works as a buffering agent. In collapsing, it is compressed to absorb a good deal of the work transformed into the bubble internal energy during bubble collapse so that it weakens the bubble oscillations. (paper)

Optical oscillator strengths of the valence-shell excitations of atoms and molecules determined by the dipole ( γ,γ) method

Science.gov (United States)

Xu, Long-Quan; Liu, Ya-Wei; Xu, Xin; Ni, Dong-Dong; Yang, Ke; Zhu, Lin-Fan

2017-07-01

The dipole (γ,γ) method, which is the inelastic X-ray scattering operated at a negligibly small momentum transfer, has been developed to determine the absolute optical oscillator strengths of the valence-shell excitations of atoms and molecules. This new method is free from the line saturation effect, and its Bethe-Born conversion factor varies much more slowly with the excitation energy than that of the dipole (e, e) method. Thus the dipole (γ,γ) method provides a reliable approach to obtain the benchmark optical oscillator strengths of the valence-shell excitations for gaseous atoms and molecules. In this paper, we give a review of the dipole (γ,γ) method and some recent measurements of absolute optical oscillator strengths of gaseous atoms and molecules. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Development of magnetic luminescent core/shell nanocomplex particles with fluorescence using Rhodamine 6G

Energy Technology Data Exchange (ETDEWEB)

Lee, Hee Uk; Song, Yoon Seok [Department of Chemical and Biological Engineering, Korea University, 5 Ga, Anam-Dong, Sungbuk-Gu, Seoul 136-701 (Korea, Republic of); Park, Chulhwan [Department of Chemical Engineering, Kwangwoon University, 447-1 Wolgye-Dong, Nowon-Gu, Seoul 139-701 (Korea, Republic of); Kim, Seung Wook, E-mail: kimsw@korea.ac.kr [Department of Chemical and Biological Engineering, Korea University, 5 Ga, Anam-Dong, Sungbuk-Gu, Seoul 136-701 (Korea, Republic of)

2012-12-15

Graphical abstract: Display Omitted Highlights: ► A simple method was developed to synthesize Co-B/SiO{sub 2}/dye/SiO{sub 2} composite particles. ► The magnetic particle shows that highly luminescent and core/shell particles are formed. ► Such core/shell particles can be easily suspended in water. ► The magnetic particles could detect fluorescence for the application of biosensor. -- Abstract: A simple and reproducible method was developed to synthesize a novel class of Co-B/SiO{sub 2}/dye/SiO{sub 2} composite core/shell particles. Using a single cobalt core, Rhodamine 6G of organic dye molecules was entrapped in a silica shell, resulting in core/shell particles of ∼200 nm diameter. Analyses using a variety of techniques such as transmission electron microscopy, X-ray photoelectron spectroscopy, vibration sample magnetometry, confocal laser scanning microscopy, and fluorescence intensity demonstrated that dye molecules were trapped inside the core/shell particles. A photoluminescence investigation showed that highly luminescent and photostable core/shell particles were formed. Such core/shell particles can be easily suspended in water. The synthesized magnetic particles could be used to detect fluorescence on glass substrate arrays for bioassay and biosensor applications.

Vibration experiment of the semi-spherical shell fixed in water; Suichu ni koteisareta hankyu shell no sessui shindo jikken

Energy Technology Data Exchange (ETDEWEB)

Toyoda, K; Yasuzawa, Y; Kagawa, K; Sugimoto, S [Kyushu University, Fukuoka (Japan). Faculty of Engineering

1997-10-01

Vibration characteristics of the semi-spherical shell fixed in water with bidirectional curvatures were studied experimentally. Various marine structures have been devised as relay station for life spaces or submarine resource excavation. As compared with land structures, marine structures are constantly under a severe condition subjected to hydrostatic pressure, and requires advanced technologies. The experimental result, numerical computation result by analytical code DASOR (Dynamic Analysis of Shell of Revolution) and theoretical analysis result were compared with each other. FEM and BEM were used in DASOR computation for the axisymmetric thin semi-spherical shell and circumferential liquid, respectively. Due to an added mass effect, the natural frequency decreased with an increase in water level regardless of mode orders. However, the water level over the top of the semi-spherical shell caused the nearly constant natural frequencies of 30-40% of that in the air. The computation result by DASOR well agreed with the experimental result demonstrating its validity. 4 refs., 13 figs., 1 tab.

An extension of the fenske-hall LCAO method for approximate calculations of inner-shell binding energies of molecules

Science.gov (United States)

Zwanziger, Ch.; Reinhold, J.

1980-02-01

The approximate LCAO MO method of Fenske and Hall has been extended to an all-election method allowing the calculation of inner-shell binding energies of molecules and their chemical shifts. Preliminary results are given.

Water-assisted dehalogenation of thionyl chloride in the presence of water molecules.

Science.gov (United States)

Yeung, Chi Shun; Ng, Ping Leung; Guan, Xiangguo; Phillips, David Lee

2010-04-01

A second-order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT) investigation of the dehalogenation reactions of thionyl chloride is reported, in which water molecules (up to seven) were explicitly involved in the reaction complex. The dehalogenation processes of thionyl chloride were found to be dramatically catalyzed by water molecules. The reaction rate became significantly faster as more water molecules became involved in the reaction complex. The dehalogenation processes can be reasonably simulated by the gas-phase water cluster models, which reveals that water molecules can help to solvate the thionyl chloride molecules and activate the release of the Cl(-) leaving group. The computed activation energies were used to compare the calculations to available experimental data.

Rotating shell eggs immersed in hot water for the purpose of pasteurization

Science.gov (United States)

Pasteurization of shell eggs for inactivation of Salmonella using hot water immersion can be used to improve their safety. The rotation of a shell egg immersed in hot water has previously been simulated by computational fluid dynamics (CFD); however, experimental data to verify the results do not ex...

High-resolution inner-shell spectroscopies of free atoms and molecules using soft-x-ray beamlines at the third-generation synchrotron radiation sources

International Nuclear Information System (INIS)

Ueda, Kiyoshi

2003-01-01

This article reviews the current status of inner-shell spectroscopies of free atoms and molecules using high-resolution soft-x-ray monochromators installed in the soft-x-ray beamlines at the third-generation synchrotron radiation facilities. Beamlines and endstations devoted to atomic and molecular inner-shell spectroscopies and various types of experimental techniques, such as ion yield spectroscopy, resonant photoemission spectroscopy and multiple-coincidence momentum imaging, are described. Experimental results for K-shell excitation of Ne, O K-shell excitation of H 2 O and CO 2 , C K-shell excitation and ionization of CO 2 and B K-shell excitation of BF 3 , obtained at beamline 27SU of SPring-8 in Japan, are discussed as examples of atomic and molecular inner-shell spectroscopies using the third-generation synchrotron radiation sources. (topical review)

Effect of the shell on the transport properties of poly(glycerol) and Poly(ethylene imine) nanoparticles

International Nuclear Information System (INIS)

Adeli, M.; Haag, R.; Zarnegar, Z.

2007-01-01

Dendritic core-shell architectures containing poly (glycerol) and poly (ethylene imine) cores and poly(lactide) shell (PG-PLA and PEI-PLA respectively) were synthesized. Analogous of these core-shell architectures containing the same cores but poly (L-lactide) shell (PG-PLLA and PEI-PLLA, respectively) were also synthesized. In this work PG and PEI were used as macroinitiator for ring opening polymerization of the lactid and L-lactide monomers. Different molar ratios of monomer to end functional groups of PG ([LA]/[OH]) and PEI ([LA]/[NHn] (n = 1 or 2)) were used to prepare the core-shell architectures with different shell thickness. These core-shell architectures were able to encapsulate and transport the small guest molecules. Their transport capacity (TC) depended on the type and thickness of the shells. TC of core-shell architectures containing PLLA shell was higher than that for their analogs containing PLA shell. The diameter of core-shell architectures was between 20-80 nm. The rate of release of guest molecules from chloroform solution of nanocarriers to water phase was investigated and it depended on the type of the core, shell and solvent

Vibrationally resolved photoionization of the 1σg and 1σu shells of N2 molecule

International Nuclear Information System (INIS)

Semenov, S K; Cherepkov, N A; Matsumoto, M; Fujiwara, K; Ueda, K; Kukk, E; Tahara, F; Sunami, T; Yoshida, H; Tanaka, T; Nakagawa, K; Kitajima, M; Tanaka, H; De Fanis, A

2006-01-01

Theoretical and experimental study of vibrationally resolved partial photoionization cross sections and angular asymmetry parameter β for the 1σ g and 1σ u shells of N 2 molecule in the region of the σ* shape resonance is reported. The measurements were made at the synchrotron radiation facility SPring-8 in Japan. The calculations in the random phase approximation have been performed using the relaxed core Hartree-Fock wavefunctions with the fractional charge of the ion core equal to 0.7. With its help, the role of interchannel coupling between the closely spaced 1σ g and 1σ u shells was studied. The experiment demonstrates the existence of a correlational maximum in the 1σ u shell photoionization cross section induced by the σ* shape resonance in the 1σ g shell. This maximum reveals itself even more clearly in the angular asymmetry parameter β for the v' = 0 and v' = 1 vibrational states of the ion. The calculation in the random phase approximation gives a consistent interpretation of the experimental data

Nonlinear thermo-optical properties of two-layered spherical system of gold nanoparticle core and water vapor shell during initial stage of shell expansion

Directory of Open Access Journals (Sweden)

Astafyeva Liudmila

2011-01-01

Full Text Available Abstract Nonlinear thermo-optical properties of two-layered spherical system of gold nanoparticle core and water vapor shell, created under laser heating of nanoparticle in water, were theoretically investigated. Vapor shell expansion leads to decreasing up to one to two orders of magnitude in comparison with initial values of scattering and extinction of the radiation with wavelengths 532 and 633 nm by system while shell radius is increased up to value of about two radii of nanoparticle. Subsequent increasing of shell radius more than two radii of nanoparticle leads to rise of scattering and extinction properties of system over initial values. The significant decrease of radiation scattering and extinction by system of nanoparticle-vapor shell can be used for experimental detection of the energy threshold of vapor shell formation and investigation of the first stages of its expansion. PACS: 42.62.BE. 78.67. BF

Enhancing photocatalytic activity by using TiO2-MgO core-shell-structured nanoparticles

International Nuclear Information System (INIS)

Jung, Hyun Suk; Lee, Jung-Kun; Nastasi, Michael; Kim, Jeong-Ryeol; Lee, Sang-Wook; Kim, Jin Young; Park, Jong-Sung; Hong, Kug Sun; Shin, Hyunho

2006-01-01

Hygroscopic Mg(OH) 2 gel was topotactically decomposed on TiO 2 particle surfaces, resulting in highly nanoporous MgO-coated TiO 2 particles. The highly hygroscopic and nanoporous MgO shell absorbed more water molecules and hydroxyl groups from the environment to yield an improved photocatalytic property of the core-shell particles as compared to the uncoated TiO 2 counterpart

Nondipole effects in the angular distribution of photoelectrons from the C K shell of the CO molecule

International Nuclear Information System (INIS)

Hosaka, K.; Teramoto, T.; Adachi, J.; Yagishita, A.; Golovin, A. V.; Takahashi, M.; Watanabe, N.; Jahnke, T.; Weber, Th.; Schoeffler, M.; Schmidt, L.; Jagutzki, O.; Schmidt-Boecking, H.; Doerner, R.; Osipov, T.; Prior, M. H.; Landers, A. L.; Semenov, S. K.; Cherepkov, N. A.

2006-01-01

Measurements and calculations of a contribution of the nondipole terms in the angular distribution of photoelectrons from the C K shell of randomly oriented CO molecules are reported. In two sets of measurements, the angular distribution in the plane containing the photon polarization and the photon momentum vectors of linearly polarized radiation and the full three-dimensional photoelectron momentum distribution after absorption of circularly polarized light have been measured. Calculations have been performed in the relaxed core Hartree-Fock approximation with a fractional charge. Both theory and experiment show that the nondipole terms are very small in the photon energy region from the ionization threshold of the K shell up to about 70 eV above it

Induced Orbital Paramagnetism and Paratropism in Closed-Shell Molecules

Science.gov (United States)

Pelloni, Stefano; Lazzeretti, Paolo; Zanasi, Riccardo

2009-07-01

Three-dimensional models of the quantum-mechanical current density induced by a uniform magnetic field in the electron cloud have been obtained for closed-shell systems BeH-, BH, and CH+, characterized by induced orbital paramagnetism, and in planar unsaturated hydrocarbons C4H4 and clamped C8H8, exhibiting π paramagnetism. It is shown that, even for these paramagnetic systems, the paramagnetic contributions to magnetic susceptibilities and nuclear magnetic shielding, customarily taken into account in perturbation theory approaches, can formally be eliminated via the procedure of continuous transformation of the origin of the current density-paramagnetic zero. The definition of magnetic response properties can therefore be recast as a sum of two formally "diamagnetic" terms for any molecule, including systems showing strong induced orbital paramagnetism. It is shown that the paramagnetism in the compounds studied arises from the nodal topology of the electronic wave function. In particular, paratropic vortices circulate about stagnation lines at the intersection of nodal surfaces of the highest-occupied zero-order molecular orbital and corresponding first-order orbital.

Towards ligand docking including explicit interface water molecules.

Directory of Open Access Journals (Sweden)

Gordon Lemmon

Full Text Available Small molecule docking predicts the interaction of a small molecule ligand with a protein at atomic-detail accuracy including position and conformation the ligand but also conformational changes of the protein upon ligand binding. While successful in the majority of cases, docking algorithms including RosettaLigand fail in some cases to predict the correct protein/ligand complex structure. In this study we show that simultaneous docking of explicit interface water molecules greatly improves Rosetta's ability to distinguish correct from incorrect ligand poses. This result holds true for both protein-centric water docking wherein waters are located relative to the protein binding site and ligand-centric water docking wherein waters move with the ligand during docking. Protein-centric docking is used to model 99 HIV-1 protease/protease inhibitor structures. We find protease inhibitor placement improving at a ratio of 9:1 when one critical interface water molecule is included in the docking simulation. Ligand-centric docking is applied to 341 structures from the CSAR benchmark of diverse protein/ligand complexes [1]. Across this diverse dataset we see up to 56% recovery of failed docking studies, when waters are included in the docking simulation.

Molecular dynamics study of water molecule diffusion in oil-paper insulation materials

International Nuclear Information System (INIS)

Liao Ruijin; Zhu Mengzhao; Yang Lijun; Zhou Xin; Gong Chunyan

2011-01-01

Moisture is an important factor that influences the safe operation of transformers. In this study, molecular dynamics was employed to investigate the diffusion behavior of water molecules in the oil-paper insulation materials of transformers. Two oil-cellulose models were built. In the first model, water molecules were initially distributed in oil, and in the second model, water molecules were distributed in cellulose. The non-bonding energies of interaction between water molecules and oil, and between water molecules and cellulose, were calculated by the Dreiding force field. The interaction energy was found to play a dominant role in influencing the equilibrium distribution of water molecules. The radial direction functions of water molecules toward oil and cellulose indicate that the hydrogen bonds between water molecules and cellulose are sufficiently strong to withstand the operating temperature of the transformer. Mean-square displacement analysis of water molecules diffusion suggests that water molecules initially distributed in oil showed anisotropic diffusion; they tended to diffuse toward cellulose. Water molecules initially distributed in cellulose diffused isotropically. This study provides a theoretical contribution for improvements in online monitoring of water in transformers, and for subsequent research on new insulation materials.

Molecular dynamics study of water molecule diffusion in oil-paper insulation materials

Energy Technology Data Exchange (ETDEWEB)

Liao Ruijin [State Key Laboratory of Power Transmission Equipment and System Security and New Technology, Chongqing University, Chongqing 400044 (China); Zhu Mengzhao, E-mail: xiaozhupost@163.co [State Key Laboratory of Power Transmission Equipment and System Security and New Technology, Chongqing University, Chongqing 400044 (China); Yang Lijun; Zhou Xin; Gong Chunyan [State Key Laboratory of Power Transmission Equipment and System Security and New Technology, Chongqing University, Chongqing 400044 (China)

2011-03-01

Moisture is an important factor that influences the safe operation of transformers. In this study, molecular dynamics was employed to investigate the diffusion behavior of water molecules in the oil-paper insulation materials of transformers. Two oil-cellulose models were built. In the first model, water molecules were initially distributed in oil, and in the second model, water molecules were distributed in cellulose. The non-bonding energies of interaction between water molecules and oil, and between water molecules and cellulose, were calculated by the Dreiding force field. The interaction energy was found to play a dominant role in influencing the equilibrium distribution of water molecules. The radial direction functions of water molecules toward oil and cellulose indicate that the hydrogen bonds between water molecules and cellulose are sufficiently strong to withstand the operating temperature of the transformer. Mean-square displacement analysis of water molecules diffusion suggests that water molecules initially distributed in oil showed anisotropic diffusion; they tended to diffuse toward cellulose. Water molecules initially distributed in cellulose diffused isotropically. This study provides a theoretical contribution for improvements in online monitoring of water in transformers, and for subsequent research on new insulation materials.

Multinuclear NMR characterization of CTAB-hexanol-water, sodium oleate-butanol-water and triton X-100-decanol-water microemulsions

International Nuclear Information System (INIS)

Nagy, J.B.; Bodart-Ravet, I.; Derouane, E.G.; Gourgue, A.; Verfaillie, J.P.

1989-01-01

Multinuclear NMR is a very valuable tool to characterize micellar systems or microemulsions. It allows one to determine c.m.c. values, to study the dissolution of organic molecules, the solvation of cations and anions, the structural changes occurring in a ternary diagram, the mobility of the molecules, etc. This review paper essentially deals with the characterization of cationic (CTAB-hexanol-water), anionic (sodium oleate-butanol-water) and neutral (Triton X-100-decanol-water) reversed micelles. The use of paramagnetic ions [Ni(II), CO(II), Fe(III), etc.] is particularly emphasized to characterize the site of solubilization and their interaction with surfactant and cosurfactant molecules 13 C-NMR). It is concluded, that the metallic ions are basically solvated in the inner water cores and one or more hexanol molecules are included in their first coordination shells in the CTAB-hexanol-water microemulsions. In the Triton X-100-decanol-water microemulsions, both decanol and Triton X-100 molecules enter the first coordination shell of Co(II) ions which are dissolved in both aqeous water cores and the organic medium. 19 F-NMR of a fluorinated probe molecule is particularly useful to study the size of the inner water cores. The method is based on the partition of the molecules between the interface and the organic medium. However, this method has to be applied with great care, and the computed data have to be compared to other physico-chemical results. Both 19 F- and 23 Na-NMR results show a great variation of the behaviour of the sodium oleate-butanol-water system in the so-called bicontinuous region. The Na + ions are oriented independently on a hypothetical inverse micellar droplet. (author). 43 refs.; 18 figs.; 7 tabs

Vibrational and orientational dynamics of water in aqueous hydroxide solutions.

Science.gov (United States)

Hunger, Johannes; Liu, Liyuan; Tielrooij, Klaas-Jan; Bonn, Mischa; Bakker, Huib

2011-09-28

We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH(-) from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H(2)O. For the O-H vibration of HDO molecules outside the first hydration shell of OD(-), we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D(2)O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ~7 surrounding water molecules, considerably less than previously reported for the proton. © 2011 American Institute of Physics

Transfer of energy between a pair of molecules near a plasmonic core-shell nanoparticle: Tunability and sensing

Energy Technology Data Exchange (ETDEWEB)

Daneshfar, Nader, E-mail: ndaneshfar@gmail.com, E-mail: ndaneshfar@razi.ac.ir; Yavari, Asghar [Department of Physics, Razi University, Kermanshah (Iran, Islamic Republic of)

2016-05-15

Our model is applied to the calculation of interaction energy between a pair of dipolar molecules (point dipoles) in the vicinity of a nanoshell monomer with core-shell structure, based on the dipole quasi-electrostatic theory of classical electrodynamics and using the Drude and Maxwell-Garnett model. In other words, this work discusses the intermolecular energy transfer from a donor molecule to an acceptor molecule near a spherical nanoparticle that is important for practical applications like sensing. It is shown that the proximity of plasmonic nanoparticles can have a strong effect on the energy transfer between molecules. In addition to the influence of the size, composition, embedding medium, and the filling fraction of doped particles on the interaction energy, the contribution of the dipolar, quadrupolar, octupolar, hexadecapolar, triakontadipolar, and higher order multipole interactions is presented and analyzed. Briefly, we will show that it is possible to achieve enhanced energy transfer by manipulation of different parameters as mentioned above.

Structural and energetic properties of La3+ in water/DMSO mixtures

Science.gov (United States)

Montagna, Maria; Spezia, Riccardo; Bodo, Enrico

2017-11-01

By using molecular dynamics based on a custom polarizable force field, we have studied the solvation of La3+ in an equimolar mixture of dimethylsulfoxide (DMSO) with water. An extended structural analysis has been performed to provide a complete picture of the physical properties at the basis of the interaction of La3+ with both solvents. Through our simulations we found that, very likely, the first solvation shell in the mixture is not unlike the one found in pure water or pure DMSO and contains 9 solvent molecules. We have also found that the solvation is preferentially due to DMSO molecules with the water initially present in first shell quickly leaving to the bulk. The dehydration process of the first shell has been analyzed by both plain MD simulations and a constrained dynamics approach; the free energy profiles for the extraction of water from first shell have also been computed.

On the Several Molecules and Nanostructures of Water

Directory of Open Access Journals (Sweden)

Cynthia Kolb Whitney

2012-01-01

Full Text Available 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.

Hydrogeology and water quality of the Shell Valley Aquifer, Rolette County, North Dakota

Science.gov (United States)

Strobel, M.L.

1997-01-01

The Shell Valley aquifer is the sole source of water for the city of Belcourt and the primary source of water for most of the Turtle Mountain Indian Reservation. The Turtle Mountain Band of Chippewa Indians is concerned about the quantity and quality of water in the Shell Valley aquifer, which underlies about 56 square miles in central Rolette County and has an average saturated thickness of about 35 feet. Water levels across most of the Shell Valley aquifer fluctuate with variations in precipitation but generally are stable. Withdrawals from the north well field decreased slightly during 1976-95, but withdrawals from the south well field increased during 1983-95. Water levels in the south well field declined as withdrawals increased. The average decline during the last 8 years was about 1.75 feet per year. The water level has reached the well screen in at least one of the production wells. Most of the water in the aquifer is a bicarbonate type and has dissolved-solids concentrations ranging from 479 to 1,510 milligrams per liter. None of the samples analyzed had detectable concentrations of pesticides, but hydrocarbons were detected in both ground- and surfacewater samples. Polycyclic aromatic hydrocarbons (PAH) were the most frequently detected hydrocarbons. Benzene, toluene, ethylbenzene, and xylene (BTEX), polychlorinated biphenyls (PCB), and pentachlorophenol (PCP) also were detected.Generally, the Shell Valley aquifer is an adequate source of water for current needs, but evaluation of withdrawals in relation to a knowledge of aquifer hydrology would be important in quantifying sustainable water supplies. Water quality in the aquifer generally is good; the Turtle Mountain Band of Chippewa Indians filters the water to reduce concentrations of dissolved constituents. Hydrocarbons, although present in the aquifer, have not been quantified and may not pose a general health risk. Further analysis of the quantity and distribution of the hydrocarbons would be useful

Coordination geometries of Zn(II) and Cd(II) in phosphotriesterase: Influence of water molecules in the active site

DEFF Research Database (Denmark)

Krauss, M; Olsen, Lars; Antony, J

2002-01-01

Models of the metal ion binding sites of native ZnZn and of cadmium-substituted ZnCd and CdCd phosphotriesterase, including full amino acid side chains, were geometry optimized with quantum mechanical methods, with effective fragment potentials (EFP) representing the protein environment surroundi...... to the Od1 of the carboxylate of the first-shell aspartate designated M 1, but the energy difference between Cd1Zn2 and the lowest energy Zn1Cd2 structure is only about 2 kcal/mol and decreasing with the addition of water molecules. The Zn1Cd2 arrangement is found experimentally....

The synthesis of four-layer gold-silver-polymer-silver core-shell nanomushroom with inbuilt Raman molecule for surface-enhanced Raman scattering

Science.gov (United States)

Jiang, Tao; Wang, Xiaolong; Zhou, Jun

2017-12-01

A facial two-step reduction method was proposed to synthesize four-layer gold-silver-polymer-silver (Au@Ag@PSPAA@Ag) core-shell nanomushrooms (NMs) with inbuilt Raman molecule. The surface-enhanced Raman scattering (SERS) intensity of 4MBA adhered on the surface of Au core gradually increased with the modification of middle Ag shell and then Ag mushroom cap due to the formation of two kinds of ultra-small interior nanogap. Compared with the initial Au nanoparticles, the SERS enhancement ratio of the Au@Ag@PSPAA@Ag NMs approached to nearly 40. The novel core-shell NMs also exhibited homogeneous SERS signals for only one sample and reproducible signals for 10 different samples, certified by the low relative standard deviation values of less than 10% and 15% for the character peaks of 4-mercaptobenzoic acid, respectively. Such a novel four-layer core-shell nanostructure with reliable SERS performance has great potential application in quantitative SERS-based immunoassay.

Core-shell microspheres with porous nanostructured shells for liquid chromatography.

Science.gov (United States)

Ahmed, Adham; Skinley, Kevin; Herodotou, Stephanie; Zhang, Haifei

2018-01-01

The development of new stationary phases has been the key aspect for fast and efficient high-performance liquid chromatography separation with relatively low backpressure. Core-shell particles, with a solid core and porous shell, have been extensively investigated and commercially manufactured in the last decade. The excellent performance of core-shell particles columns has been recorded for a wide range of analytes, covering small and large molecules, neutral and ionic (acidic and basic), biomolecules and metabolites. In this review, we first introduce the advance and advantages of core-shell particles (or more widely known as superficially porous particles) against non-porous particles and fully porous particles. This is followed by the detailed description of various methods used to fabricate core-shell particles. We then discuss the applications of common silica core-shell particles (mostly commercially manufactured), spheres-on-sphere particles and core-shell particles with a non-silica shell. This review concludes with a summary and perspective on the development of stationary phase materials for high-performance liquid chromatography applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of sub- and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation.

Science.gov (United States)

Osada, Mitsumasa; Miura, Chika; Nakagawa, Yuko S; Kaihara, Mikio; Nikaido, Mitsuru; Totani, Kazuhide

2015-12-10

This study examined the effects of sub- and supercritical water pretreatments on the physicochemical properties of crab shell α-chitin and its enzymatic degradation to obtain N,N'-diacetylchitobiose (GlcNAc)2. Following sub- and supercritical water pretreatments, the protein in the crab shell was removed and the residue of crab shell contained α-chitin and CaCO3. Prolonged pretreatment led to α-chitin decomposition. The reaction of pure α-chitin in sub- and supercritical water pretreatments was investigated separately; we observed lower mean molecular weight and weaker hydrogen bonds compared with untreated α-chitin. (GlcNAc)2 yields from enzymatic degradation of subcritical (350 °C, 7 min) and supercritical water (400 °C, 2.5 min) pretreated crab shell were 8% and 6%, compared with 0% without any pretreatment. This study shows that sub- and supercritical water pretreatments of crab shell provide to an alternative method to the use of acid and base for decalcification and deproteinization of crab shell required for (GlcNAc)2 production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Autodissociation of a water molecule in liquid water

Energy Technology Data Exchange (ETDEWEB)

Geissler, Phillip L.; Dellago, Christoph; Chandler, David; Hutter, Jurg; Parrinello, Michele

2000-04-01

The dissociation of a water molecule in liquid water is the fundamental event in acid-base chemistry, determining the pH of water.Because the microscopic dynamics of this autodissociation are difficult to probe, both by experiment and by computer simulation, its mechanism has been unknown. Here we report several autodissociation trajectories generated by ab initio molecular dynamics [1]. These trajectories, which were harvested using transition path sampling [2-4], reveal the mechanism for the first time. Rare fluctuations in solvation energies destabilize an oxygen-hydrogen bond. Through the transfer of one or more protons along a hydrogen bond.

Developmental plasticity of shell morphology of quagga mussels from shallow and deep-water habitats of the Great Lakes.

Science.gov (United States)

Peyer, Suzanne M; Hermanson, John C; Lee, Carol Eunmi

2010-08-01

The invasive zebra mussel (Dreissena polymorpha) has quickly colonized shallow-water habitats in the North American Great Lakes since the 1980s but the quagga mussel (Dreissena bugensis) is becoming dominant in both shallow and deep-water habitats. While quagga mussel shell morphology differs between shallow and deep habitats, functional causes and consequences of such difference are unknown. We examined whether quagga mussel shell morphology could be induced by three environmental variables through developmental plasticity. We predicted that shallow-water conditions (high temperature, food quantity, water motion) would yield a morphotype typical of wild quagga mussels from shallow habitats, while deep-water conditions (low temperature, food quantity, water motion) would yield a morphotype present in deep habitats. We tested this prediction by examining shell morphology and growth rate of quagga mussels collected from shallow and deep habitats and reared under common-garden treatments that manipulated the three variables. Shell morphology was quantified using the polar moment of inertia. Of the variables tested, temperature had the greatest effect on shell morphology. Higher temperature (approximately 18-20 degrees C) yielded a morphotype typical of wild shallow mussels regardless of the levels of food quantity or water motion. In contrast, lower temperature (approximately 6-8 degrees C) yielded a morphotype approaching that of wild deep mussels. If shell morphology has functional consequences in particular habitats, a plastic response might confer quagga mussels with a greater ability than zebra mussels to colonize a wider range of habitats within the Great Lakes.

Rapid and accurate prediction and scoring of water molecules in protein binding sites.

Directory of Open Access Journals (Sweden)

Gregory A Ross

Full Text Available Water plays a critical role in ligand-protein interactions. However, it is still challenging to predict accurately not only where water molecules prefer to bind, but also which of those water molecules might be displaceable. The latter is often seen as a route to optimizing affinity of potential drug candidates. Using a protocol we call WaterDock, we show that the freely available AutoDock Vina tool can be used to predict accurately the binding sites of water molecules. WaterDock was validated using data from X-ray crystallography, neutron diffraction and molecular dynamics simulations and correctly predicted 97% of the water molecules in the test set. In addition, we combined data-mining, heuristic and machine learning techniques to develop probabilistic water molecule classifiers. When applied to WaterDock predictions in the Astex Diverse Set of protein ligand complexes, we could identify whether a water molecule was conserved or displaced to an accuracy of 75%. A second model predicted whether water molecules were displaced by polar groups or by non-polar groups to an accuracy of 80%. These results should prove useful for anyone wishing to undertake rational design of new compounds where the displacement of water molecules is being considered as a route to improved affinity.

Effect of hydration on the organo-noble gas molecule HKrCCH: role of krypton in the stabilization of hydrated HKrCCH complexes.

Science.gov (United States)

Biswas, Biswajit; Singh, Prashant Chandra

2015-11-11

The effect of hydration on the fluorine free organo-noble gas compound HKrCCH and the role of krypton in the stabilization of the hydrated HKrCCH complexes have been investigated using the quantum chemical calculations on the HKrCCH-(H2O)n=1-6 clusters. Structure and energetics calculations show that water stabilizes HKrCCH through the π hydrogen bond in which the OH group of water interacts with the C[triple bond, length as m-dash]C group of HKrCCH. A maximum of four water molecules can directly interact with the C[triple bond, length as m-dash]C of HKrCCH and after that only inter-hydrogen bonding takes place between the water molecules indicating that the primary hydration shell contains four water molecules. Atom in molecule analysis depicts that π hydrogen bonded complexes of the hydrated HKrCCH are cyclic structures in which the OKr interaction cooperates in the formation of strong O-HC[triple bond, length as m-dash]C interaction. Structure, energetics and charge analysis clearly established that krypton plays an important role in the stabilization as well as the formation of the primary hydration shell of hydrated HKrCCH complexes.

Charge-Dipole Acceleration of Polar Gas Molecules towards Charged Nanoparticles: Involvement in Powerful Charge-Induced Catalysis of Heterophase Chemical Reactions and Ball Lightning Phenomenon

Directory of Open Access Journals (Sweden)

Oleg Meshcheryakov

2010-01-01

Full Text Available In humid air, the substantial charge-dipole attraction and electrostatic acceleration of surrounding water vapour molecules towards charged combustible nanoparticles cause intense electrostatic hydration and preferential oxidation of these nanoparticles by electrostatically accelerated polar water vapour molecules rather than nonaccelerated nonpolar oxygen gas molecules. Intense electrostatic hydration of charged combustible nanoparticles converts the nanoparticle's oxide-based shells into the hydroxide-based electrolyte shells, transforming these nanoparticles into reductant/air core-shell nanobatteries, periodically short-circuited by intraparticle field and thermionic emission. Partially synchronized electron emission breakdowns within trillions of nanoparticles-nanobatteries turn a cloud of charged nanoparticles-nanobatteries into a powerful radiofrequency aerosol generator. Electrostatic oxidative hydration and charge-catalyzed oxidation of charged combustible nanoparticles also contribute to a self-oscillating thermocycling process of evolution and periodic autoignition of inflammable gases near to the nanoparticle's surface. The described effects might be of interest for the improvement of certain nanotechnological heterophase processes and to better understand ball lightning phenomenon.

Facile synthesis of terminal-alkyne bioorthogonal molecules for live -cell surface-enhanced Raman scattering imaging through Au-core and silver/dopamine-shell nanotags.

Science.gov (United States)

Chen, Meng; Zhang, Ling; Yang, Bo; Gao, Mingxia; Zhang, Xiangmin

2018-03-01

Alkyne is unique, specific and biocompatible in the Raman-silent region of the cell, but there still remains a challenge to achieve ultrasensitive detection in living systems due to its weak Raman scattering. Herein, a terminal alkyne ((E)-2-[4-(ethynylbenzylidene)amino]ethane-1-thiol (EBAE)) with surface-enhanced Raman scattering is synthesized. The EBAE molecule possesses S- and C-termini, which can be directly bonded to gold nanoparticles and dopamine/silver by forming the Au-S chemical bond and the carbon-metal bond, respectively. The distance between Raman reporter and AuNPs/AgNPs can be reduced, contributing to forming hot-spot-based SERS substrate. The alkyne functionalized nanoparticles are based on Au core and encapsulating polydopamine shell, defined as Au-core and dopamine/Ag-shell (ACDS). The bimetallic ACDS induce strong SERS signals for molecular imaging that arise from the strong electromagnetic field. Furthermore, the EBAE provides a distinct peak in the cellular Raman-silent region with nearly zero background interference. The EBAE Raman signals could be tremendously enhanced when the Raman reporter is located at the middle of the Au-core and dopamine/Ag-shell. Therefore, this work could have huge potential benefits for the highly sensitive detection of intercellular information delivery by connecting the recognition molecules in biomedical diagnostics. Graphical abstract Terminal-alkyne-functionalized Au-core and silver/dopamine-shell nanotags for live-cell surface-enhanced Raman scattering imaging.

The role of water molecules in computational drug design.

Science.gov (United States)

de Beer, Stephanie B A; Vermeulen, Nico P E; Oostenbrink, Chris

2010-01-01

Although water molecules are small and only consist of two different atom types, they play various roles in cellular systems. This review discusses their influence on the binding process between biomacromolecular targets and small molecule ligands and how this influence can be modeled in computational drug design approaches. Both the structure and the thermodynamics of active site waters will be discussed as these influence the binding process significantly. Structurally conserved waters cannot always be determined experimentally and if observed, it is not clear if they will be replaced upon ligand binding, even if sufficient space is available. Methods to predict the presence of water in protein-ligand complexes will be reviewed. Subsequently, we will discuss methods to include water in computational drug research. Either as an additional factor in automated docking experiments, or explicitly in detailed molecular dynamics simulations, the effect of water on the quality of the simulations is significant, but not easily predicted. The most detailed calculations involve estimates of the free energy contribution of water molecules to protein-ligand complexes. These calculations are computationally demanding, but give insight in the versatility and importance of water in ligand binding.

Quantum Behavior of Water Molecules Confined to Nanocavities in Gemstones.

Science.gov (United States)

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.

Core-shell architectures as nano-size transporters

International Nuclear Information System (INIS)

Adeli, M.; Zarnegar, Z.; Kabiri, R.; Salimi, F.; Dadkah, A.

2006-01-01

Core-shell architectures containing poly (ethylene imine) (PEI) as a core and poly (lactide) (PLA) as arms were prepared. PEI was used as macro initiator for ring opening polymerization of lactide. PEI-PLA core-shell architectures were able to encapsulate guest molecules. Size of the core-shell architectures was between 10- 100 nm, hence they can be considered as nano carriers to transport the guest molecules. Transport capacity of nano carriers depends on their nano-environments and type of self-assembly in solvent. In solid state nano carriers self-assemble as long structures with nano-size diameter or they form network structures. Aggregations type depends on the concentration of nano carriers in solution. Effect of the shell thickness and aggregation type on the release rate are also investigated

Adaptive resolution simulation of an atomistic DNA molecule in MARTINI salt solution

NARCIS (Netherlands)

Zavadlav, J.; Podgornik, R.; Melo, M.n.; Marrink, S.j.; Praprotnik, M.

2016-01-01

We present a dual-resolution model of a deoxyribonucleic acid (DNA) molecule in a bathing solution, where we concurrently couple atomistic bundled water and ions with the coarse-grained MAR- TINI model of the solvent. We use our fine-grained salt solution model as a solvent in the inner shell

Core-shell designed scaffolds for drug delivery and tissue engineering.

Science.gov (United States)

Perez, Roman A; Kim, Hae-Won

2015-07-01

Scaffolds that secure and deliver therapeutic ingredients like signaling molecules and stem cells hold great promise for drug delivery and tissue engineering. Employing a core-shell design for scaffolds provides a promising solution. Some unique methods, such as co-concentric nozzle extrusion, microfluidics generation, and chemical confinement reactions, have been successful in producing core-shelled nano/microfibers and nano/microspheres. Signaling molecules and drugs, spatially allocated to the core and/or shell part, can be delivered in a controllable and sequential manner for optimal therapeutic effects. Stem cells can be loaded within the core part on-demand, safely protected from the environments, which ultimately affords ex vivo culture and in vivo tissue engineering. The encapsulated cells experience three-dimensional tissue-mimic microenvironments in which therapeutic molecules are secreted to the surrounding tissues through the semi-permeable shell. Tuning the material properties of the core and shell, changing the geometrical parameters, and shaping them into proper forms significantly influence the release behaviors of biomolecules and the fate of the cells. This topical issue highlights the immense usefulness of core-shell designs for the therapeutic actions of scaffolds in the delivery of signaling molecules and stem cells for tissue regeneration and disease treatment. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Lake Water Quality Improvement by Using Waste Mussel Shell Powder as an Adsorbent

Science.gov (United States)

Zukri, N. I.; Khamidun, M. H.; Sapiren, M. S.; Abdullah, S.; Rahman, M. A. A.

2018-04-01

Lake water in UTHM was slightly greenish in color indicating the eutrophication process. Eutrophication problem is due to excessive amount of nutrient in the lake water which causes nuisance growth of algae and other aquatic plant. The improvement of lake water quality should be conducted wisely in preventing from eutrophication problem by using a suitable water treatment method. Natural materials, agricultural wastes and industrial wastes are locally available sources can be utilized as low-cost adsorbents. The natural abundant source of waste mussel’s shells is advantages to use as basis material to produce the low cost adsorbent for water treatment. Batch experiments were carried out with the preparation 500 ml volume of lake water sample with the dosage of 2.5g, 7.5g and 12.5g. Then the solution shaking in an incubator with 200 rpm shaking speed. The various dosage of mussel shell greatly affected pollutants removal. Both of NH4+ and PO43- have a higher percentage removal with 31.28% and 21.74% at the 7.5g of sample dosage. Other parameters such as COD and TSS also shown good percentage of removal at 7.5g of dosage sample with 44.45% and 25% respectively. While, dosage at 2.5g was performed as a good adsorption capacity of NH4+, PO43-, COD and TSS as high as 0.142, 0.234, 7.6 and 20 mg/g, respectively. These experimental results suggested that the use of mussel shell powder as good basis material in removing pollutants from lake water.

Superficial shell insulation in resting and exercising men in cold water.

Science.gov (United States)

Veicsteinas, A; Ferretti, G; Rennie, D W

1982-06-01

From measurements of subcutaneous fat temperature (Tsf) at known depths below the surface, skin surface temperature (Tsk), and direct skin heat flux (H), the superficial shell isulation (Iss) of the thigh (fat + skin) was calculated as Iss (degrees C.m2.w-1) = (Tsf - Tsk)/H in nine male subjects immersed head out in a well-stirred water bath. Also, at critical water temperature (CWT = 28-33 degrees C), eight of the subjects rested for 3 h, enabling overall maximal tissue insulation (It,max) to be calculated as It,max (degrees C.m2.W-1) = (Tre - Tw)/(0.92 M +/- delta S), where Tre is rectal temperature, Tw is water temperature, M is metabolic rate, and s is loss or gain of body heat. Five subjects performed up to 2 h of mild leg cycling, preceded and followed by 60 min of rest, and both thigh Iss and overall It were measured during exercise. Iss increased from minimal values in Tw greater than 33 degrees C to maximal values (Iss,max) at CWT or below. Iss,max was linearly related to tissue thickness (d) in millimeters of fat plus skin, Iss,max (degrees C.m2.W-1) = 0.0048d-0.0052; r = 0.95, n = 37, and was not influenced by leg exercise up to a metabolic rate of 150 W.m-2 in CWT despite large increases in Tsf and H and large decreases in overall It. The slope of Iss,max vs. depth, 0.0048 degrees C.m2.W-1.mm-1, is almost identical to thermal resistivity of fat in vitro, suggesting that the superficial shell is unperfused in CWT at rest or during mild exercise. When maximal superficial shell insulation (It,ss,max) for the whole body was calculated with allowance for differing fat thicknesses and surface areas of body regions, it could account for only 10-15% of overall It,max at rest and 35-40% of overall It in mild exercise. We suggest that the poorly perfused muscle shell plays a more important role as a defense against cooling at CWT than does the superficial shell (fat + skin), particularly at rest.

Effect of the sulphur atom on geometry and spectra of the biomolecule 2-thiouracil and in the WC base pair 2-thiouridine-adenosine. Influence of water in the first hydration shell.

Science.gov (United States)

Alcolea Palafox, M; Rastogi, V K; Singh, S P

2018-04-01

The effect of the sulphur atom on 2-thiouracil (2TU) and 2-thiouridine molecules, as compared with uracil and uridine molecules, respectively, was carried out in several environments. The predicted IR spectrum of 2TU in the isolated state was compared with that obtained for uracil molecule and with those reported experimentally in matrix isolation. Its crystal unit cell in the solid state was simulated through a tetramer form using DFT methods for the first time. The calculated Raman spectrum was compared to the experimental ones in the solid state. A linear scaling procedure was used for this task. The first hydration shell was simulated by explicit number of water molecules surrounding 2TU up to 30 and was compared with that obtained in uracil molecule. Water molecules 'distributed' around 2TU was preferred over that 'clustering', because it can better reproduce the hydration and their effects on different parameters of the molecular structure of 2TU and uracil. The total atomic charges and several calculated thermodynamic parameters were discussed. The effect of the sulphur atom on the Watson-Crick (WC) and reverse WC base pair uridine-adenosine was estimated, and the CP corrected interaction energies were calculated. 2-thiouridine has a weaker WC pair than that with uridine, although its slight higher dipole moment (μ) facilitates the interaction with the water molecules. Several helical parameters were determined.

Utilization of wasted cockle shell as a natural coagulant and a neutralizer of polluted water in Bangka Belitung islands, Indonesia

Science.gov (United States)

Tiandho, Y.; Aldila, H.; Mustari; Megiyo; Afriani, F.

2018-05-01

Bangka Belitung Islands is the largest tin producer in Indonesia. The high activity of tin mining caused the environmental damage which had an impact on the emergence of clean water crisis in some areas in this province. In this paper, a simple water quality improvement method based on wasted cockle shell was developed. Based on x-ray diffraction analysis it is known that calcination of cockle shell powder at 700°C will decompose the powder into calcium oxide compound. The addition of calcined cockle shell powder into acidic water from Merawang Sub-district will increase the pH of water through the process of forming hydroxide groups in the water. The calcined cockle shell powder can also coagulate pollutants in some polluted water from Koba Sub-district. The coagulation results were analyzed using SEM/EDS.

Density, distribution, and orientation of water molecules inside and outside carbon nanotubes.

Science.gov (United States)

Thomas, J A; McGaughey, A J H

2008-02-28

The behavior of water molecules inside and outside 1.1, 2.8, 6.9, and 10.4 nm diameter armchair carbon nanotubes (CNTs) is predicted using molecular dynamics simulations. The effects of CNT diameter on mass density, molecular distribution, and molecular orientation are identified for both the confined and unconfined fluids. Within 1 nm of the CNT surface, unconfined water molecules assume a spatially varying density profile. The molecules distribute nonuniformly around the carbon surface and have preferred orientations. The behavior of the unconfined water molecules is invariant with CNT diameter. The behavior of the confined water, however, can be correlated to tube diameter. Inside the 10.4 nm CNT, the molecular behavior is indistinguishable from that of the unconfined fluid. Within the smaller CNTs, surface curvature effects reduce the equilibrium water density and force water molecules away from the surface. This effect changes both the molecular distribution and preferred molecular orientations.

Structures of water molecules in carbon nanotubes under electric fields

International Nuclear Information System (INIS)

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

2015-01-01

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

Approximative Krieger-Nelkin orientation averaging and anisotropy of water molecules vibrations

International Nuclear Information System (INIS)

Markovic, M.I.

1974-01-01

Quantum-mechanics approach of water molecules dynamics should be taken into account for precise theoretical calculation of differential scattering cross sections of neutrons. Krieger and Nelkin have proposed an approximate method for averaging orientation of molecules regarding directions of incoming and scattered neutron. This paper shows that this approach can be successfully applied for general shape of water molecule vibration anisotropy

Quantum Electric Dipole Lattice - Water Molecules Confined to Nanocavities in Beryl

Science.gov (United States)

Dressel, Martin; Zhukova, Elena S.; Thomas, Victor G.; Gorshunov, Boris P.

2018-02-01

Water is subject to intense investigations due to its importance in biological matter but keeps many of its secrets. Here, we unveil an even other aspect by confining H2O molecules to nanosize cages. Our THz and infrared spectra of water in the gemstone beryl evidence quantum tunneling of H2O molecules in the crystal lattice. The water molecules are spread out when confined in a nanocage. In combination with low-frequency dielectric measurements, we were also able to show that dipolar coupling among the H2O molecules leads towards a ferroelectric state at low temperatures. Upon cooling, a ferroelectric soft mode shifts through the THz range. Only quantum fluctuations prevent perfect macroscopic order to be fully achieved. Beside the significance to life science and possible application, nanoconfined water may become the prime example of a quantum electric dipolar lattice.

Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

Science.gov (United States)

Wang, Xu; Le, Anh-Thu; Yu, Chao; Lucchese, R. R.; Lin, C. D.

2016-01-01

We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. A simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method. PMID:27025410

Double containment shell for nuclear power plants

International Nuclear Information System (INIS)

Sykora, D.

1977-01-01

A double containment shell is proposed for nuclear power plants, especially those equipped with pressurized water reactors. The shell offers increased environmental protection from primary circuit accidents. The inner shell is built of steel or concrete while the outer shell is always built of concrete. The space between the two shells is filled with water and is provided with several manholes and with stiffeners designed for compensation for load due to the water hydrostatic pressure. Water serves the airtight separation of the containment shell inside from the environment and the absorption of heat released in a primary circuit accident. In case the inner shell is made of concrete, it is provided with heat-removal tubes in-built in its walls ensuring rapid heat transfer from the inside of the containment to the water in the interwall space. (Z.M.)

Bifunctional Au@TiO_2 core–shell nanoparticle films for clean water generation by photocatalysis and solar evaporation

International Nuclear Information System (INIS)

Huang, Jian; He, Yurong; Wang, Li; Huang, Yimin; Jiang, Baocheng

2017-01-01

Highlights: • Au@TiO_2 core-shell nanoparticles were prepared in this study. • Bifunctional films for photocatalysis and solar evaporation were designed. • The evaporation and photodegradation with core-shell structures were investigated. - Abstract: With water scarcity becoming an increasingly critical issue for modern society, solar seawater desalination represents a promising approach to mitigating water shortage. In addition, solar seawater desalination shows great potential for mitigating the energy crisis due to its high photo-thermal conversion efficiency. However, the increasing contamination of seawater makes it difficult to generate clean water through simple desalination processes. In this work, clean water is generated by a newly designed bifunctional Au@TiO_2 core-shell nanoparticle film with a high photo-thermal conversion efficiency that is capable of photocatalysis and solar evaporation for seawater desalination. Bifunctional films of Au@TiO_2 core-shell nanoparticles with good stability were prepared. It was found that the formation of the core-shell structures played a key role in promoting the photo-thermal conversion efficiency and the evaporation of seawater, while the photocatalytic function demonstrated herein could contribute to the purification of polluted seawater. Furthermore, the film structure can serve to concentrate the NPs for the photo-reaction, as well as heat for water evaporation, improving both the photo-reaction efficiency and photo-thermal conversion efficiency. This efficient approach to solar seawater desalination, which combines evaporation with the photodegradation of pollutants, could help to address the dual issues of water scarcity and water pollution.

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

Energy Technology Data Exchange (ETDEWEB)

Chempath, Shaji [Los Alamos National Laboratory; Pratt, Lawrence R [TULANE UNIV

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.

Stabilities of protonated water-ammonia clusters

Science.gov (United States)

Sundén, A. E. K.; Støchkel, K.; Hvelplund, P.; Brøndsted Nielsen, S.; Dynefors, B.; Hansen, K.

2018-05-01

Branching ratios of water and ammonia evaporation have been measured for spontaneous evaporation from protonated mixed clusters H+(H2O)n(NH3)m in the size range 0 ≤ n ≤ 11 and 0 ≤ m ≤ 7. Mixed clusters evaporate water except for clusters containing six or more ammonia molecules, indicating the formation of a stable core of one ammonium ion surrounded by four ammonia molecules and a second shell consisting predominantly of water. We relate evaporative branching ratios to free energy differences between the products of competing channels and determine the free energy differences for clusters with up to seven ammonia molecules. Clusters containing up to five ammonia molecules show a very strong scaling of these free energy differences.

Preparation and characterization of water-soluble ZnSe:Cu/ZnS core/shell quantum dots

Energy Technology Data Exchange (ETDEWEB)

Wang, Lei; Cao, Lixin, E-mail: caolixin@ouc.edu.cn; Su, Ge; Liu, Wei; Xia, Chenghui; Zhou, Huajian

2013-09-01

The synthesis and luminescent properties of water-soluble ZnSe:Cu/ZnS core/shell quantum dots (QDs) with different shell thickness are reported in this paper. X-ray powder diffraction (XRD) studies present that the ZnSe:Cu/ZnS core/shell QDs with different shell thickness have a cubic zinc-blende structure. The tests of transmission electron microscope (TEM) pictures exhibit that the QDs obtained are spherical-shaped particles and the average grain size increased from 2.7 to 3.8 nm with the growth of ZnS shell. The emission peak position of QDs has a small redshift from 461 to 475 nm with the growth of ZnS shell within the blue spectral window. The photoluminescence (PL) emission intensity and stability of the ZnSe:Cu core d-dots are both enhanced by coating ZnS shell on the surface of core d-dots. The largest PL intensity of the core/shell QDs is almost 3 times larger than that of Cu doped ZnSe quantum dots (ZnSe:Cu d-dots). The redshift of core/shell QDs compared with the core QDs are observed in both the absorption and the photoluminescence excitation spectra.

Effects of Soil Water Deficit on Insecticidal Protein Expression in Boll Shells of Transgenic Bt Cotton and the Mechanism

Directory of Open Access Journals (Sweden)

Xiang Zhang

2017-12-01

Full Text Available This study was conducted to investigate the effects of soil water deficit on insecticidal protein expression in boll shells of cotton transgenic for a Bt gene. In 2014, Bt cotton cultivars Sikang 1 (a conventional cultivar and Sikang 3 (a hybrid cultivar were planted in pots and five soil water content treatments were imposed at peak boll stage: 15% (G1, 35% (G2, 40% (G3, 60% (G4, and 75% field capacity (CK, respectively. Four treatments (G2, G3, G4, and CK were repeated in 2015 in the field. Results showed that the insecticidal protein content of boll shells decreased with increasing water deficit. Compared with CK, boll shell insecticidal protein content decreased significantly when soil water content was below 60% of maximum water holding capacity for Sikang 1 and Sikang 3. However, increased Bt gene expression was observed when boll shell insecticidal protein content was significantly reduced. Activity assays of key enzymes in nitrogen metabolism showed that boll shell protease and peptidase increased but nitrogen reductase and glutamic-pyruvic transaminase (GPT decreased. Insecticidal protein content exhibited significant positive correlation with nitrogen reductase and GPT activities; and significant negative correlation with protease and peptidase activities. These findings suggest that the decrease of insecticidal protein content associated with increasing water deficit was a net result of decreased synthesis and increased decomposition.

Efficient tungsten oxide/bismuth oxyiodide core/shell photoanode for photoelectrochemical water splitting

Science.gov (United States)

Ma, Haipeng; Zhang, Jing; Liu, Zhifeng

2017-11-01

The novel WO3 nanorods (NRs)/BiOI core/shell structure composite is used as an efficient photoanode applied in photoelectrochemical (PEC) water splitting for the first time. It is synthesized via facile hydrothermal method and, successive ionic layer adsorption and reaction (SILAR) process. This facile synthesis route can achieve uniform WO3/BiOI core/shell composite nanostructures and obtain varied BiOI morphologies simultaneously. The WO3 NRs/BiOI-20 composite exhibits enhanced PEC activity compared to pristine WO3 with a photocurrent density of 0.79 mA cm-2 measured at 0.8 V vs. RHE under AM 1.5G. This excellent performance benefits from the broader absorption spectrum and suppressed electron-hole recombination. This novel core/shell composite may provide insight in developing more efficient solar driven photoelectrodes.

Preparation and characterisation of core-shell CNTs@MIPs nanocomposites and selective removal of estrone from water samples.

Science.gov (United States)

Gao, Ruixia; Su, Xiaoqian; He, Xiwen; Chen, Langxing; Zhang, Yukui

2011-01-15

This paper reports the preparation of carbon nanotubes (CNTs) functionalized with molecularly imprinted polymers (MIPs) for advanced removal of estrone. CNTs@Est-MIPs nanocomposites with a well-defined core-shell structure were obtained using a semi-covalent imprinting strategy, which employed a thermally reversible covalent bond at the surface of silica-coated CNTs for a large-scale production. The morphology and structure of the products were characterised by transmission electron microscopy and Fourier transform infrared spectroscopy. The adsorption properties were demonstrated by equilibrium rebinding experiments and Scatchard analysis. The results demonstrate that the imprinted nanocomposites possess favourable selectivity, high capacity and fast kinetics for template molecule uptake, yielding an adsorption capacity of 113.5 μmol/g. The synthetic process is quite simple, and the different batches of synthesized CNTs@Est-MIPs nanocomposites showed good reproducibility in template binding. The feasibility of removing estrogenic compounds from environmental water using the CNTs@Est-MIPs nanocomposites was demonstrated using water samples spiked with estrone. Copyright © 2010 Elsevier B.V. All rights reserved.

Hydrology and water quality of Shell Lake, Washburn County, Wisconsin, with special emphasis on the effects of diversion and changes in water level on the water quality of a shallow terminal lake

Science.gov (United States)

Juckem, Paul F.; Robertson, Dale M.

2013-01-01

Shell Lake is a relatively shallow terminal lake (tributaries but no outlets) in northwestern Wisconsin that has experienced approximately 10 feet (ft) of water-level fluctuation over more than 70 years of record and extensive flooding of nearshore areas starting in the early 2000s. The City of Shell Lake (City) received a permit from the Wisconsin Department of Natural Resources in 2002 to divert water from the lake to a nearby river in order to lower water levels and reduce flooding. Previous studies suggested that water-level fluctuations were driven by long-term cycles in precipitation, evaporation, and runoff, although questions about the lake’s connection with the groundwater system remained. The permit required that the City evaluate assumptions about lake/groundwater interactions made in previous studies and evaluate the effects of the water diversion on water levels in Shell Lake and other nearby lakes. Therefore, a cooperative study between the City and U.S. Geological Survey (USGS) was initiated to improve the understanding of the hydrogeology of the area and evaluate potential effects of the diversion on water levels in Shell Lake, the surrounding groundwater system, and nearby lakes. Concerns over deteriorating water quality in the lake, possibly associated with changes in water level, prompted an additional cooperative project between the City and the USGS to evaluate efeffects of changes in nutrient loading associated with changes in water levels on the water quality of Shell Lake. Numerical models were used to evaluate how the hydrology and water quality responded to diversion of water from the lake and historical changes in the watershed. The groundwater-flow model MODFLOW was used to simulate groundwater movement in the area around Shell Lake, including groundwater/surface-water interactions. Simulated results from the MODFLOW model indicate that groundwater flows generally northward in the area around Shell Lake, with flow locally converging

Dynamics of water molecules in the active-site cavity of human cytochromes P450

DEFF Research Database (Denmark)

Rydberg, Patrik; Rod, Thomas Holm; Olsen, Lars

2007-01-01

We have studied the dynamics of water molecules in six crystal structures of four human cytochromes P450, 2A6, 2C8, 2C9, and 3A4, with molecular dynamics simulations. In the crystal structures, only a few water molecules are seen and the reported sizes of the active-site cavity vary a lot....... In the simulations, the cavities are completely filled with water molecules, although with approximately 20% lower density than in bulk water. The 2A6 protein differs from the other three in that it has a very small cavity with only two water molecules and no exchange with the surroundings. The other three proteins...... channels, through which there is a quite frequent exchange of water molecules (one molecule is exchanged every 30-200 ps), except in 2A6. Most of the channels are observed also in the crystal structures, but two to three channels in each protein open only during the simulations. There are no water...

Quantum Chemistry on Quantum Computers: A Polynomial-Time Quantum Algorithm for Constructing the Wave Functions of Open-Shell Molecules.

Science.gov (United States)

Sugisaki, Kenji; Yamamoto, Satoru; Nakazawa, Shigeaki; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Takui, Takeji

2016-08-18

Quantum computers are capable to efficiently perform full configuration interaction (FCI) calculations of atoms and molecules by using the quantum phase estimation (QPE) algorithm. Because the success probability of the QPE depends on the overlap between approximate and exact wave functions, efficient methods to prepare accurate initial guess wave functions enough to have sufficiently large overlap with the exact ones are highly desired. Here, we propose a quantum algorithm to construct the wave function consisting of one configuration state function, which is suitable for the initial guess wave function in QPE-based FCI calculations of open-shell molecules, based on the addition theorem of angular momentum. The proposed quantum algorithm enables us to prepare the wave function consisting of an exponential number of Slater determinants only by a polynomial number of quantum operations.

Photocatalytic hydrogen generation from water under visible light using core/shell nano-catalysts.

Science.gov (United States)

Wang, X; Shih, K; Li, X Y

2010-01-01

A microemulsion technique was employed to synthesize nano-sized photocatalysts with a core (CdS)/shell (ZnS) structure. The primary particles of the photocatalysts were around 10 nm, and the mean size of the catalyst clusters in water was about 100 nm. The band gaps of the catalysts ranged from 2.25 to 2.46 eV. The experiments of photocatalytic H(2) generation showed that the catalysts (CdS)(x)/(ZnS)(1-x) with x ranging from 0.1 to 1 were able to produce hydrogen from water photolysis under visible light. The catalyst with x=0.9 had the highest rate of hydrogen production. The catalyst loading density also influenced the photo-hydrogen production rate, and the best catalyst concentration in water was 1 g L(-1). The stability of the nano-catalysts in terms of size, morphology and activity was satisfactory during an extended test period for a specific hydrogen production rate of 2.38 mmol g(-1) L(-1) h(-1) and a quantum yield of 16.1% under visible light (165 W Xe lamp, lambda>420 nm). The results demonstrate that the (CdS)/(ZnS) core/shell nano-particles are a novel photo-catalyst for renewable hydrogen generation from water under visible light. This is attributable to the large band-gap ZnS shell that separates the electron/hole pairs generated by the CdS core and hence reduces their recombinations.

Structural Arrangement of Water Molecules around Highly Charged Nanoparticles: Molecular Dynamics Simulation

International Nuclear Information System (INIS)

Kim, Eunae; Yeom, Min Sun

2014-01-01

Molecular dynamics simulations were performed to understand the structural arrangement of water molecules around highly charged nanoparticles under aqueous conditions. The effect of two highly charged nanoparticles on the solvation charge asymmetry has been examined. We calculated the radial distribution functions of the components of water molecules around nanoparticles which have four charge types at two different salt concentrations. Even though the distributions of water molecules surrounding a sodium ion and a chloride ion are hardly affected by the charges of nanoparticles and the salt concentrations, those around highly charged nanoparticles are strongly influenced by the charges of nanoparticles, but hardly by the charges of nanoparticles and salt concentrations. We find that the distributions of hydrogen atoms in water molecules around one highly charged nanoparticle are dependent on the magnitude of the nanoparticle charge

High-temperature stability of the hydrate shell of a Na+ cation in a flat nanopore with hydrophobic walls

Science.gov (United States)

Shevkunov, S. V.

2017-11-01

The effect of elevated temperature has on the hydrate shell of a singly charged sodium cation inside a flat nanopore with smooth walls is studied using the Monte Carlo method. The free energy and the entropy of vapor molecule attachment are calculated by means of a bicanonical statistical ensemble using a detailed model of interactions. The nanopore has a stabilizing effect on the hydrate shell with respect to fluctuations and a destabilizing effect with respect to complete evaporation. At the boiling point of water, behavior is observed that is qualitatively similar to behavior at room temperature, but with a substantial shift in the vapor pressure and shell size.

Vibrational properties of water molecules adsorbed in different zeolitic frameworks

International Nuclear Information System (INIS)

Crupi, V; Longo, F; Majolino, D; Venuti, V

2006-01-01

The perturbation of water 'sorbed' in samples of zeolites of different structural type, genesis, and cation composition (K-, Na-, Mg- and Ca-rich zeolites), namely the CHA framework of a synthetic K-chabazite, the LTA framework of synthetic Na-A and Mg50-A zeolites, and the NAT framework of a natural scolecite, has been studied by FTIR-ATR spectroscopy, in the -10 to +80 o C temperature range. The aim was to show how differences in the chemical composition and/or in the topology of the zeolite framework and, in particular, the possibility for the guest water molecules to develop guest-guest and/or host-guest interactions, lead to substantial differences in their vibrational dynamical properties. The spectra, collected in the O-H stretching and H 2 O bending mode regions, are complex, with multiple bands being observed. As far as water in the CHA and LTA frameworks is concerned, whose behaviour is governed by the balance of water-water, water-framework and water-extra-framework cations interactions, the assignment of the resolved components of the O-H stretching band has been discussed by fitting the band shapes into individual components attributed to H 2 O molecules engaged in different degrees of hydrogen bonding. A detailed quantitative picture of the connectivity pattern of water, as a function of temperature and according to the chemical and topological properties of the environment, is furnished. The H 2 O bending vibrational bands give additional information that perfectly agrees with the results obtained from the analysis of the O-H stretching spectral region. In the case of scolecite, a small-pored zeolite where water-water interactions are eliminated, the increased complexity observed in the infrared spectra in the O-H stretching and H 2 O bending regions was explained as due to the hydrogen bonding between the water molecules and the network, and also with the extra-framework cation. Furthermore, these observations have been correlated with the different

Enhancement of curcumin water dispersibility and antioxidant activity using core-shell protein-polysaccharide nanoparticles.

Science.gov (United States)

Huang, Xiaoxia; Huang, Xulin; Gong, Yushi; Xiao, Hang; McClements, David Julian; Hu, Kun

2016-09-01

Curcumin has strong antioxidant activity, but poor water-solubility and chemical stability, which limits its utilization as a nutraceutical in many applications. Previously, we developed a core-shell (zein-pectin) nanoparticle delivery system with high curcumin loading efficiency, high particle yield, and good water dispersibility. However, this system was unstable to aggregation around neutral pH and moderate ionic strengths due to weakening of electrostatic repulsion between nanoparticles. In the current study, we used a combination of alginate (high charge density) and pectin (low charge density) to form the shell around zein nanoparticles. Replacement of 30% of pectin with alginate greatly improved aggregation stability at pH 5 to 7 and at high ionic strengths (2000mM NaCl). Curcumin encapsulated within these core-shell nanoparticles exhibited higher antioxidant and radical scavenging activities than curcumin solubilized in ethanol solutions as determined by Fe (III) reducing power, 1, 1-Diphenyl-2-picrylhydrazyl free radical (DPPH·), and 2, 2'-azinobis-(3-ethylbenzothiazoline)-6-sulfonic acid radical cation (ABTS· + ) scavenging analysis. These core-shell nanoparticles may be useful for incorporating chemically unstable hydrophobic nutraceuticals such as curcumin into functional foods, dietary supplements, and pharmaceuticals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture

Science.gov (United States)

Spickermann, C.; Thar, J.; Lehmann, S. B. C.; Zahn, S.; Hunger, J.; Buchner, R.; Hunt, P. A.; Welton, T.; Kirchner, B.

2008-09-01

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C2C1im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C2C1im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H2O )-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C2C1im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

An equations of motion approach for open shell systems

International Nuclear Information System (INIS)

Yeager, D.L.; McKoy, V.

1975-01-01

A straightforward scheme is developed for extending the equations of motion formalism to systems with simple open shell ground states. Equations for open shell random phase approximation (RPA) are given for the cases of one electron outside of a closed shell in a nondegenerate molecular orbital and for the triplet ground state with two electrons outside of a closed shell in degenerate molecular orbitals. Applications to other open shells and extension of the open shell EOM to higher orders are both straightforward. Results for the open shell RPA for lithium atom and oxygen molecule are given

High resolution inner-shell spectroscopies of atoms and molecules in gas phase using the soft x-ray photochemistry beamline at SPring-8

International Nuclear Information System (INIS)

Ueda, Kiyoshi

2003-01-01

This article describes recent activities on inner-shell spectroscopies of atoms and molecules on beamline 27SU, nicknamed soft X-ray photochemistry beamline, at SPring-8, an 8-GeV synchrotron radiation facility in Japan. This beamline provides linearly polarized monochromatic soft X-rays at the resolution higher than 10,000. The end station is designed so that one can perform various kinds of excitation and de-excitation spectroscopies as well as coincidence spectroscopies. Following the description of the beamline and the end station, we present recent results for inner-shell spectroscopies on Ne, CO 2 , BF 3 , and CF 4 . Emphasis is given to illustrate the strategy of the research on this beamline and performance of the beamline and the end station. (author)

Integration or segregation: how do molecules behave at oil/water interfaces?

Science.gov (United States)

Moore, F G; Richmond, G L

2008-06-01

It has been over 250 years since Benjamin Franklin, fascinated with the wave-stilling effect of oil on water, performed his famous oil-drop experiments; nevertheless, the behavior of water molecules adjacent to hydrophobic surfaces continues to fascinate today. In the 18th century, the calming of the seas seemed the most pertinent application of such knowledge; today, we understand that oil-on-water phenomena underlie a range of important chemical, physical, and biological processes, including micelle and membrane formation, protein folding, chemical separation, oil extraction, nanoparticle formation, and interfacial polymerization. Beyond classical experiments of the oil-water interface, recent interest has focused on deriving a molecular-level picture of this interface or, more generally, of water molecules positioned next to any hydrophobic surface. This Account summarizes more than a decade's work from our laboratories aimed at understanding the nature of the hydrogen bonding occurring between water and a series of organic liquids in contact. Although the common perception is that water molecules and oil molecules positioned at the interface between the immiscible liquids want nothing to do with one another, we have found that weak interactions between these hydrophilic and hydrophobic molecules lead to interesting interfacial behavior, including highly oriented water molecules and layering of the organic medium that extends several molecular layers deep into the bulk organic liquid. For some organic liquids, penetration of oriented water into the organic layer is also apparent, facilitated by molecular interactions established at the molecularly thin region of first contact between the two liquids. The studies involve a combined experimental and computational approach. The primary experimental tool that we have used is vibrational sum frequency spectroscopy (VSFS), a powerful surface-specific vibrational spectroscopic method for measuring the molecular

Water-Protein Interactions: The Secret of Protein Dynamics

Directory of Open Access Journals (Sweden)

Silvia Martini

2013-01-01

Full Text Available Water-protein interactions help to maintain flexible conformation conditions which are required for multifunctional protein recognition processes. The intimate relationship between the protein surface and hydration water can be analyzed by studying experimental water properties measured in protein systems in solution. In particular, proteins in solution modify the structure and the dynamics of the bulk water at the solute-solvent interface. The ordering effects of proteins on hydration water are extended for several angstroms. In this paper we propose a method for analyzing the dynamical properties of the water molecules present in the hydration shells of proteins. The approach is based on the analysis of the effects of protein-solvent interactions on water protons NMR relaxation parameters. NMR relaxation parameters, especially the nonselective (R1NS and selective (R1SE spin-lattice relaxation rates of water protons, are useful for investigating the solvent dynamics at the macromolecule-solvent interfaces as well as the perturbation effects caused by the water-macromolecule interactions on the solvent dynamical properties. In this paper we demonstrate that Nuclear Magnetic Resonance Spectroscopy can be used to determine the dynamical contributions of proteins to the water molecules belonging to their hydration shells.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

Science.gov (United States)

Prisk, T. R.; Hoffmann, C.; Kolesnikov, A. I.; Mamontov, E.; Podlesnyak, A. A.; Wang, X.; Kent, P. R. C.; Anovitz, L. M.

2018-05-01

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10-100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

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

Energy Technology Data Exchange (ETDEWEB)

McDowell, R.S.; Kossiakoff, A.A. [Genentech, Inc., South San Francisco, CA (United States)

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.

Compressive strength, flexural strength and water absorption of concrete containing palm oil kernel shell

Science.gov (United States)

Noor, Nurazuwa Md; Xiang-ONG, Jun; Noh, Hamidun Mohd; Hamid, Noor Azlina Abdul; Kuzaiman, Salsabila; Ali, Adiwijaya

2017-11-01

Effect of inclusion of palm oil kernel shell (PKS) and palm oil fibre (POF) in concrete was investigated on the compressive strength and flexural strength. In addition, investigation of palm oil kernel shell on concrete water absorption was also conducted. Total of 48 concrete cubes and 24 concrete prisms with the size of 100mm × 100mm × 100mm and 100mm × 100mm × 500mm were prepared, respectively. Four (4) series of concrete mix consists of coarse aggregate was replaced by 0%, 25%, 50% and 75% palm kernel shell and each series were divided into two (2) main group. The first group is without POF, while the second group was mixed with the 5cm length of 0.25% of the POF volume fraction. All specimen were tested after 7 and 28 days of water curing for a compression test, and flexural test at 28 days of curing period. Water absorption test was conducted on concrete cube age 28 days. The results showed that the replacement of PKS achieves lower compressive and flexural strength in comparison with conventional concrete. However, the 25% replacement of PKS concrete showed acceptable compressive strength which within the range of requirement for structural concrete. Meanwhile, the POF which should act as matrix reinforcement showed no enhancement in flexural strength due to the balling effect in concrete. As expected, water absorption was increasing with the increasing of PKS in the concrete cause by the porous characteristics of PKS

Transport of water molecules through noncylindrical pores in multilayer nanoporous graphene.

Science.gov (United States)

Shahbabaei, Majid; Kim, Daejoong

2017-08-09

In this study, molecular dynamics (MD) simulations are used to examine the water transport properties through asymmetric hourglass-shaped pores in multilayer nanoporous graphene with a constant interlayer separation of 6 Å. The properties of the tested asymmetric hourglass-shaped pores [with the models having long cone (l 1 , -P) and short cone (l 2 , +P) entrances] are compared to a symmetric pore model. The study findings indicate that the water occupancy increases across the asymmetric pore (l 1 , -P) compared to (l 2 , +P), because of the length effect. The asymmetric pore, (l 1 , -P), yields higher flux compared to (l 2 , +P) and even the symmetric model, which can be attributed to the increase in the hydrogen bonds. In addition, the single-file water molecules across the narrowest pore diameter inside the (l 2 , +P) pore exhibit higher viscosity compared to those in the (l 1 , -P) pore because of the increase in the water layering effect. Moreover, it is found that the permeability inside the multilayer hourglass-shaped pore depends on the length of the flow path of the water molecules before approaching the layer with the smallest pore diameter. The probability of dipole orientation exhibits wider distribution inside the (l 1 , -P) system compared to (l 2 , +P), implying an enhanced formation of hydrogen bonding of water molecules. This results in the fast flow of water molecules. The MD trajectory shows that the dipole orientation across the single-layer graphene has frequently flipped compared to the dipole orientation across the pores in multilayer graphene, which is maintained during the whole simulation time (although the dipole orientation has flipped for a few picoseconds at the beginning of the simulation). This can be attributed to the energy barrier induced by the individual layer. The diffusion coefficient of water molecules inside the (l 2 , +P) system increases with pressure difference, however, it decreases inside the (l 1 , -P) system because

Silver atom solvation and desolvation in ice matrices: study of solvation shell geometry by electron spin resonance and electron spin echo methods

Energy Technology Data Exchange (ETDEWEB)

Kevan, L; Narayana, P A

1978-01-01

Results of studies of the solvation shell structure of silver atoms in ice matrix at 4/sup 0/K by electron spin resonance (ESR) and electron spin echo spectrometry are reported. Drastic change in the hyperfine coupling constant of the silver atom was noted when the silver atom initially produced at 4/sup 0/K was warmed to 77/sup 0/K and reexamined by ESR at 4/sup 0/K. This suggested a very drastic rearrangement of the water molecules surrounding the silver atom. The geometric arrangement of water molecules around the silver atom produced at 4/sup 0/K was what would be expected for a solvated silver ion, indicating that no rearrangement had occurred after the silver atom formed. The addition of a little thermal excitation (heating to 77/sup 0/K) results in the geometry changes than can be explained by assuming either that a water molecule rotates around one of its OH bands or by the development of a hydrogen bond between the silver atom and one of the first solvation shell water molecules. Optical excitation in the absorption band of the silver atom in the ice matrix at 400nm resulted in desolvation of the silver ion or a reversion to the structure originally obtained by reaction of solver salts in ic matrix with radiation produced electrons. This was best explained by a charge transfer mechanism. (BLM)

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

International Nuclear Information System (INIS)

Lin, Jau-Wen

2014-01-01

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

Implication of Crystal Water Molecules in Inhibitor Binding at ALR2 Active Site

Directory of Open Access Journals (Sweden)

Hymavati

2012-01-01

Full Text Available 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.

Inner shell excitation in atoms and molecules by high resolution electron impact

International Nuclear Information System (INIS)

King, G.C.

1986-01-01

In this work an inner-shell spin-forbidden transition in N 2 and a parity-forbidden transition in Ar were studied. These transitions were observed by using incident electron energies as low as 1.15 times the excitation energy of the inner-shell states. (Auth.)

Fluorescence lifetime measurements to determine the core-shell nanostructure of FITC-doped silica nanoparticles: An optical approach to evaluate nanoparticle photostability

International Nuclear Information System (INIS)

Santra, Swadeshmukul; Liesenfeld, Bernd; Bertolino, Chiara; Dutta, Debamitra; Cao Zehui; Tan Weihong; Moudgil, Brij M.; Mericle, Robert A.

2006-01-01

In this paper, we described a novel fluorescence lifetime-based approach to determine the core-shell nanostructure of FITC-(fluorescein isothiocyanate, isomer I) doped fluorescent silica nanoparticles (FSNPs). Because of phase homogeneity between the core and the shell, electron microscopic technique could not be used to characterize such core-shell nanostructure. Our optical approach not only revealed the core-shell nanostructure of FSNPs but also evaluated photobleaching of FSNPs both in the solvated and non-solvated (dry) states. The FSNPs were produced via Stoeber's method by hydrolysis and co-condensation reaction of tetraethylorthosilicate (TEOS) and fluorescein linked (3-aminopropyl)triethoxysilane (FITC-APTS conjugate) in the presence of ammonium hydroxide catalyst. To obtain a pure silica surface coating, FSNPs were then post-coated with TEOS. The average particle size was 135 nm as determined by TEM (transmission electron microscope) measurements. Fluorescence excitation and emission spectral data demonstrated successful doping of FITC dye molecules in FSNPs. Fluorescence lifetime data revealed that approximately 62% of dye molecules remained in the solvated silica shell, while 38% of dye molecules remained in the non-solvated (dry) silica core. Photobleaching experiments of FSNPs were conducted both in DI water (solution state) and in air (dry state). Severe photobleaching of FSNPs was observed in air. However, FSNPs were moderately photostable in the solution state. Photostability of FSNPs in both solution and dry states was explained on the basis of fluorescence lifetime data

A numerical investigation of γ-Al2O3-water nanofluids heat transfer and pressure drop in a shell and tube heat exchanger

Directory of Open Access Journals (Sweden)

P. Shahmohammadi

2016-01-01

Full Text Available The effect of γ-Al2O3 nanoparticles on heat transfer rate, baffle spacing and pressure drop in the shell side of small shell and tube heat exchangers was investigated numerically under turbulent regime. γ-Al2O3-water nanofluids and pure water were used in the shell side and the tube side of heat exchangers, respectively. Since the properties of γ-Al2O3-water nanofluids were variable, they were defined using the user define function. The results revealed that heat transfer and pressure drop were increased with mass flow rate as well as baffle numbers. Adding nanoparticles to the based fluid did not have a significant effect on pressure drop in the shell side. The best heat transfer performance of heat exchangers was for γ-Al2O3-water 1 vol.% and higher nanoparticles concentration was not suitable. The suitable baffle spacing was 43.4% of the shell diameter, showing a good agreement with Bell-Delaware method.

Water structure around trehalose

Energy Technology Data Exchange (ETDEWEB)

Pagnotta, S.E. [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, Via della Vasca Navale 84, 00146 Roma (Italy); CNISM-CNR, Unita di Roma Tre, Via della Vasca Navale 84, 00146 Roma (Italy)], E-mail: pagnotta@fis.uniroma3.it; Ricci, M.A.; Bruni, F. [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, Via della Vasca Navale 84, 00146 Roma (Italy); McLain, S. [ISIS Facility, Rutherford Appleton Laboratories, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Magazu, S. [Dipartimento di Fisica, Universita di Messina, C. da Papardo 31, 98166 Messina (Italy)

2008-04-18

A diluted solution of trehalose in water has been investigated by means of neutron diffraction with isotopic H/D substitution of the water hydrogens. Data have been analyzed in terms of site-site radial distribution functions, via the EPSR simulation code. This is the first time that the capabilities of this data refinement method are tested against neutron diffraction data of a complex carbohydrate molecule. A small perturbation of water hydration shell and short hydrogen bonds between trehalose oxygens and water hydrogens has been evidenced.

Insolubilization of Chestnut Shell Pigment for Cu(II Adsorption from Water

Directory of Open Access Journals (Sweden)

Zeng-Yu Yao

2016-03-01

Full Text Available Chestnut shell pigment (CSP is melanin from an agricultural waste. It has potential as an adsorbent for wastewater treatment but cannot be used in its original state because of its solubility in water. We developed a new method to convert CSP to insolubilized chestnut shell pigment (ICSP by heating, and the Cu(II adsorption performance of ICSP was evaluated. The conversion was characterized, and the thermal treatment caused dehydration and loss of carboxyl groups and aliphatic structures in CSP. The kinetic adsorption behavior obeyed the pseudo-second-order rate law, and the equilibrium adsorption data were well described with both the Langmuir and the Freundlich isotherms. ICSP can be used as a renewable, readily-available, easily-producible, environmentally-friendly, inexpensive and effective adsorbent to remove heavy-metal from aquatic environments.

Hydration of ammonia, methylamine, and methanol in amorphous solid water

Science.gov (United States)

Souda, Ryutaro

2016-02-01

Interactions of polar protic molecules with amorphous solid water (ASW) have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. The ammonia and methylamine are incorporated into the interior of porous ASW films. They are caged by water molecules and are released during water crystallization. In contrast, the methanol-water interaction is not influenced by pores of ASW. The methanol additives tend to survive water crystallization and are released during ASW film evaporation. The hydration of n-hexane in ASW is influenced significantly by methanol additives because n-hexane is accommodated in a methanol-induced hydration shell.

Dielectric properties of water in Triton X-100 (nonionic detergent)-water mixtures

International Nuclear Information System (INIS)

Asami, Koji

2007-01-01

Dielectric measurements were carried out for mixtures of Triton X-100 (TX, a nonionic detergent with a poly(ethylene oxide) chain) and water with or without electrolytes over a frequency range of 1 MHz to 10 GHz to study the structure and dynamics of water molecules in the mixtures. Dielectric relaxation was found above 100 MHz, being assigned to the dielectric relaxation of water. The intensity of the dielectric relaxation was proportional to the water content above 0 deg. C. Below the freezing temperature of bulk water, the relaxation intensity decreased at TX concentrations (C TX ) below 50 wt% at -10 deg. Cand below 60 wt% at -20 deg. Cbecause frozen water shifts the dielectric relaxation to a frequency region far below 1 MHz. This indicated that there is no bulk water at C TX above 50 wt% and that at least two water molecules per ethylene oxide (EO) unit are tightly associated with the ethylene oxide chain. The low-frequency conductivity of the mixtures of TX and electrolyte solutions was well represented by Bruggeman's mixture equation at C TX below 40 wt%, if two water molecules per EO unit form an insulating shell surrounding TX micelles

Influence of orientation averaging on the anisotropy of thermal neutrons scattering on water molecules

International Nuclear Information System (INIS)

Markovic, M. I.; Radunovic, J. B.

1976-01-01

Determination of spatial distribution of neutron flux in water, most frequently used moderator in thermal reactors, demands microscopic scattering kernels dependence on cosine of thermal neutrons scattering angle when solving the Boltzmann equation. Since spatial orientation of water molecules influences this dependence it is necessary to perform orientation averaging or rotation-vibrational intermediate scattering function for water molecules. The calculations described in this paper and the obtained results showed that methods of orientation averaging do not influence the anisotropy of thermal neutrons scattering on water molecules, but do influence the inelastic scattering

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin; Liu, Jinyong; Wang, Peng; Werth, Charles; Strathmann, Timothy J.

2014-01-01

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

Palladium nanoparticles encapsulated in core-shell silica: A structured hydrogenation catalyst with enhanced activity for reduction of oxyanion water pollutants

KAUST Repository

Wang, Yin

2014-10-03

Noble metal nanoparticles have been applied to mediate catalytic removal of toxic oxyanions and halogenated hydrocarbons in contaminated water using H2 as a clean and sustainable reductant. However, activity loss by nanoparticle aggregation and difficulty of nanoparticle recovery are two major challenges to widespread technology adoption. Herein, we report the synthesis of a core-shell-structured catalyst with encapsulated Pd nanoparticles and its enhanced catalytic activity in reduction of bromate (BrO3-), a regulated carcinogenic oxyanion produced during drinking water disinfection process, using 1 atm H2 at room temperature. The catalyst material consists of a nonporous silica core decorated with preformed octahedral Pd nanoparticles that were further encapsulated within an ordered mesoporous silica shell (i.e., SiO2@Pd@mSiO2). Well-defined mesopores (2.3 nm) provide a physical barrier to prevent Pd nanoparticle (6 nm) movement, aggregation, and detachment from the support into water. Compared to freely suspended Pd nanoparticles and SiO2@Pd, encapsulation in the mesoporous silica shell significantly enhanced Pd catalytic activity (by a factor of 10) under circumneutral pH conditions that are most relevant to water purification applications. Mechanistic investigation of material surface properties combined with Langmuir-Hinshelwood modeling of kinetic data suggest that mesoporous silica shell enhances activity by promoting BrO3- adsorption near the Pd active sites. The dual function of the mesoporous shell, enhancing Pd catalyst activity and preventing aggregation of active nanoparticles, suggests a promising general strategy of using metal nanoparticle catalysts for water purification and related aqueous-phase applications.

Core-shell nanofibers of curcumin/cyclodextrin inclusion complex and polylactic acid: Enhanced water solubility and slow release of curcumin.

Science.gov (United States)

Aytac, Zeynep; Uyar, Tamer

2017-02-25

Core-shell nanofibers were designed via electrospinning using inclusion complex (IC) of model hydrophobic drug (curcumin, CUR) with cyclodextrin (CD) in the core and polymer (polylactic acid, PLA) in the shell (cCUR/HPβCD-IC-sPLA-NF). CD-IC of CUR and HPβCD was formed at 1:2 molar ratio. The successful formation of core-shell nanofibers was revealed by TEM and CLSM images. cCUR/HPβCD-IC-sPLA-NF released CUR slowly but much more in total than PLA-CUR-NF at pH 1 and pH 7.4 due to the restriction of CUR in the core of nanofibers and solubility improvement shown in phase solubility diagram, respectively. Improved antioxidant activity of cCUR/HPβCD-IC-sPLA-NF in methanol:water (1:1) is related with the solubility enhancement achieved in water based system. The slow reaction of cCUR/HPβCD-IC-sPLA-NF in methanol is associated with the shell inhibiting the quick release of CUR. On the other hand, cCUR/HPβCD-IC-sPLA-NF exhibited slightly higher rate of antioxidant activity than PLA-CUR-NF in methanol:water (1:1) owing to the enhanced solubility. To conclude, slow release of CUR was achieved by core-shell nanofiber structure and inclusion complexation of CUR with HPβCD provides high solubility. Briefly, electrospinning of core-shell nanofibers with CD-IC core could offer slow release of drugs as well as solubility enhancement for hydrophobic drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of the Hydantoin Monomer and its Interaction with Water Molecules

Science.gov (United States)

Gruet, Sébastien; Perez, Cristobal; Schnell, Melanie

2017-06-01

Hydantoin (Imidazolidine-2,4-dione, C_3H_4N_2O_2) is a five-membered heterocyclic compound of astrobiological interest. This molecule has been detected in carbonaceous chondrites [1], and its formation can rise from the presence of glycolic acid and urea, two prebiotic molecules [2]. The hydrolysis of hydantoin under acidic conditions can also produce glycine [3], an amino acid actively searched for in the interstellar medium. Spectroscopic data of hydantoin is very limited and mostly dedicated to the solid phase. The high resolution study in gas phase is restricted to the work recently published by Ozeki et al. reporting the pure rotational spectra of the ground state and two vibrational states of the molecule in the millimeter-wave region (90-370 GHz)[4]. Using chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy, we recorded the jet-cooled rotational spectra of hydantoin with water between 2 to 8 GHz. We observed the ground state of hydantoin monomer and several water complexes with one or two water molecules. All the observed species exhibit a hyperfine structure due to the two nitrogen atoms present in the molecule, which were fully resolved and analyzed. Additional experiments with a ^{18}O enriched water sample were realized to determine the oxygen-atom positions of the water monomers. These experiments yielded accurate structural information on the preferred water binding sites. The observed complexes and the interactions that hold them together, mainly strong directional hydrogen bonds, will be presented and discussed. [1] Shimoyama, A. and Ogasawara, R., Orig. Life Evol. Biosph., 32, 165-179, 2002. DOI:10.1023/A:1016015319112. [2] Menor-Salván, C. and Marín-Yaseli, M.R., Chem. Soc. Rev., 41(16), 5404-5415, 2012. DOI:10.1039/c2cs35060b. [3] De Marcellus P., Bertrand M., Nuevo M., Westall F. and Le Sergeant d'Hendecourt L., Astrobiology. 11(9), 847-854, 2011. DOI:10.1089/ast.2011.0677. [4] Ozeki, H., Miyahara R., Ihara H., Todaka S., Kobayashi

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

Science.gov (United States)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Direct Interferometric Imaging with IOTA Interferometer: Morphology of the Water Shell around U Ori

Science.gov (United States)

Pluzhnik, Eugene; Ragland, S.; Le Coroller, H.; Cotton, W.; Danchi, W.; Traub, W.; Willson, L.

2007-12-01

Optical interferometric observations of Mira stars with adequate resolution using the 3-telescope Infrared Optical Telescope Array (IOTA) interferometer have shown detectable asymmetry in several Mira stars. Several mechanisms have been proposed to explain the observed asymmetry. In this paper, we present subsequent IOTA observations of a Mira star, namely, U Ori taken at 1.51, 1.64 and 1.78 μm in 2005. The reconstructed images based on a model independent algorithm are also presented. These images show asymmetric structures of the water shell that is similar to the structure of 22 GHz masers obtained by Vlemmings et al. in 2003. We explore the possibility of the detection of molecular shell rotation with a period of about 30 years by comparing our results with radio observations and discuss a possible geometric structure of the shell.

Isotope effect in heavy/light water suspensions of optically active gold nanoparticles

Science.gov (United States)

Kutsenko, V. Y.; Artykulnyi, O. P.; Petrenko, V. I.; Avdeev, M. V.; Marchenko, O. A.; Bulavin, L. A.; Snegir, S. V.

2018-04-01

Aqueous suspensions of optically active gold nanoparticles coated with trisodium citrate were synthesized in light (H2O) water and mixture of light and heavy (H2O/D2O) water using the modified Turkevich protocol. The objective of the paper was to verify sensitivity of neutron scattering methods (in particular, neutron reflectometry) to the potential isotope H/D substitution in the stabilizing organic shell around particles in colloidal solutions. First, the isotope effect was studied with respect to the changes in the structural properties of metal particles (size, shape, crystalline morphology) in solutions by electron microscopy including high-resolution transmission electron microscopy from dried systems. The structural factors determining the variation in the adsorption spectra in addition to the change in the optical properties of surrounding medium were discussed. Then, neutron reflectometry was applied to the layered nanoparticles anchored on a silicon wafer via 3-aminopropyltriethoxysilane molecules to reveal the presence of deuterated water molecules in the shell presumably formed by citrate molecules around the metallic core.

Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

NARCIS (Netherlands)

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

2008-01-01

We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at

Rotational and fine structure of open-shell molecules in nearly degenerate electronic states

Science.gov (United States)

Liu, Jinjun

2018-03-01

An effective Hamiltonian without symmetry restriction has been developed to model the rotational and fine structure of two nearly degenerate electronic states of an open-shell molecule. In addition to the rotational Hamiltonian for an asymmetric top, this spectroscopic model includes the energy separation between the two states due to difference potential and zero-point energy difference, as well as the spin-orbit (SO), Coriolis, and electron spin-molecular rotation (SR) interactions. Hamiltonian matrices are computed using orbitally and fully symmetrized case (a) and case (b) basis sets. Intensity formulae and selection rules for rotational transitions between a pair of nearly degenerate states and a nondegenerate state have also been derived using all four basis sets. It is demonstrated using real examples of free radicals that the fine structure of a single electronic state can be simulated with either a SR tensor or a combination of SO and Coriolis constants. The related molecular constants can be determined precisely only when all interacting levels are simulated simultaneously. The present study suggests that analysis of rotational and fine structure can provide quantitative insights into vibronic interactions and related effects.

Shell model in-water frequencies of the core barrel

International Nuclear Information System (INIS)

Takeuchi, K.; De Santo, D.F.

1980-01-01

Natural frequencies of a 1/24th-scale core barrel/vessel model in air and in water are measured by determining frequency responses to applied forces. The measured data are analyzed by the use of the one-dimensional fluid-structure computer code, MULTIFLEX, developed to calculate the hydraulic force. The fluid-structure interaction in the downcomer annulus is computed with a one-dimensional network model formed to be equivalent to two-dimensional fluid-structure interaction. The structural model incorporated in MULTIFLEX is substantially simpler than that necessary for structural analyses. Proposed for computation of structural dynamics is the projector method than can deal with the beam mode by modal analysis and the other shell modes by a direct integration method. Computed in-air and in-water frequencies agree fairly well with the experimental data, verifying the above MULTIFLEX technique

Molecular dynamics study of the solvation of calcium carbonate in water.

Science.gov (United States)

Bruneval, Fabien; Donadio, Davide; Parrinello, Michele

2007-10-25

We performed molecular dynamics simulations of diluted solutions of calcium carbonate in water. To this end, we combined and tested previous polarizable models. The carbonate anion forms long-living hydrogen bonds with water and shows an amphiphilic character, in which the water molecules are expelled in a region close to its C(3) symmetry axis. The calcium cation forms a strongly bound ion pair with the carbonate. The first hydration shell around the CaCO(3) pair is found to be very similar to the location of the water molecules surrounding CaCO(3) in ikaite, the hydrated mineral.

Photoionization of water molecules by high energy photons

Directory of Open Access Journals (Sweden)

Lara Martini

2017-07-01

Full Text Available We theoretically study the photoionization of water molecules by high energy photon impact. We develop a model in which the final state wavefunction is given by a Coulomb continuum wavefunction with effective charges and the water molecule bound states are represented using the Moccia's monocentric wavefunctions. We obtain analytical expressions for the transition matrix element that enable the computation of cross sections by numerical quadratures. We compare our predictions for photon energies between 20 and 300 eV with more elaborated theoretical results and experiments. We obtain a very good agreement with experiments, in particular, at enough high energies where there is a lack of elaborated results due to their high computational cost. Received: 15 March 2017, Accepted: 25 June 2017; Edited by: S. Kais; DOI: http://dx.doi.org/10.4279/PIP.090006 Cite as: L Martini, D I R Boll, O A Fojón, Papers in Physics 9, 090006 (2017

Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

Science.gov (United States)

Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

2018-05-01

We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

Improvement in the reliability of shells for light water reactors by manufacture from hollow ingots

International Nuclear Information System (INIS)

Bocquet, P.; Blondeau, R.; Poitrault, I.; Badeau, J.P.; Dumont, R.

1991-01-01

The problems associated to the segregation located at the inner surface and subsurface of heavy shell forgings used in nuclear light water reactors are presented. The effect of A segregation on cold or reheat cracking HAZ has conducted fabricators to use severe welding procedures with high preheat temperature and refining HAZ grain size sequences. For shells and rings, the hollow ingot as developed by CLI, with a good control of the location of the center line of segregation, is an excellent answer to these problems. The use of core shell forgings issued from this type of hollow ingots, free of segregation at the inner surface and subsurface area, contributes, by reducing the irradiation embrittlement effect, to increase the safety factor relatively to the risk of failure of the reactor. (orig.)

Water Evaporation and Conformational Changes from Partially Solvated Ubiquitin

Directory of Open Access Journals (Sweden)

Saravana Prakash Thirumuruganandham

2010-01-01

Full Text Available Using molecular dynamics simulation, we study the evaporation of water molecules off partially solvated ubiquitin. The evaporation and cooling rates are determined for a molecule at the initial temperature of 300 K. The cooling rate is found to be around 3 K/ns, and decreases with water temperature in the course of the evaporation. The conformation changes are monitored by studying a variety of intermediate partially solvated ubiquitin structures. We find that ubiquitin shrinks with decreasing hydration shell and exposes more of its hydrophilic surface area to the surrounding.

Scattering of thermal neutron by the water molecule

International Nuclear Information System (INIS)

Rosa, L.P.

The calculation of the differenctial cross section for scattering of thermal neutrons by water, taking into account the translational, rotational and vibrational motions of the water molecule, is presented according to Nelkin' model. Some modifications are presented which have been introduced in the original method to improve the results and an application has been made to reactor physics, by calculating the thermal neutron flux in a homogenous medium containing water and absorver. Thirty thermal energy groups have been used to compute the spectra. Within the limits of error, better agreement has been obtained between theory and experiments by using a modified Nelkin kernel consisting of substituting the asymptotic formulae for the rotational and vibrational motions by more exact expressions, similar to the Buttler model for heavy water

On-demand oil-water separation via low-voltage wettability switching of core-shell structures on copper substrates

Science.gov (United States)

Kung, Chun Haow; Zahiri, Beniamin; Sow, Pradeep Kumar; Mérida, Walter

2018-06-01

A copper mesh with dendritic copper-oxide core-shell structure is prepared using an additive-free electrochemical deposition strategy for on-demand oil-water separation. Electrochemical manipulation of the oxidation state of the copper oxide shell phase results in opposite affinities towards water and oil. The copper mesh can be tuned to manifest both superhydrophobic and superoleophilic properties to enable oil-removal. Conversely, switching to superhydrophilic and underwater superoleophobic allows water-removal. These changes correspond to the application of small reduction voltages (air drying. In the oil-removal mode, heavy oil selectively passes through the mesh while water is retained; in water-removal mode, the mesh allows water to permeate but blocks light oil. The smart membrane achieved separation efficiencies higher than 98% for a series of oil-water mixtures. The separation efficiency remains high with less than 5% variation after 30 cycles of oil-water separation in both modes. The switchable wetting mechanism is demonstrated with the aid of microstructural and electrochemical analysis and based on the well-known Cassie-Baxter and Wenzel theories. The selective removal of water or oil from the oil-water mixtures is driven solely by gravity and yields high efficiency and recyclability. The potential applications for the relevant technologies include oil spills cleanup, fuel purification, and wastewater treatment.

Compressibility of the protein-water interface

Science.gov (United States)

Persson, Filip; Halle, Bertil

2018-06-01

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (˜0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ˜45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in

Compressibility of the protein-water interface.

Science.gov (United States)

Persson, Filip; Halle, Bertil

2018-06-07

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (∼0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ∼45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than

Water molecule-enhanced CO2 insertion in lanthanide coordination polymers

International Nuclear Information System (INIS)

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

2009-01-01

Two new lanthanide coordination polymers H 2 N(CH 3 ) 2 .[Eu III 2 (L 1 ) 3 (L 2 )] (1, L 1 =isophthalic acid dianion, L 2 =formic acid anion) and [La III (2,5-PDC)(L 2 )](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L 2 ) is not contained in the stating materials, but arises from the water molecule-enhanced CO 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 2 insertion resulting in the formation of formic anion and dimethylammonium cation were synthesized under solvothermal conditions.

Electric dipole moments of nanosolvated acid molecules in water clusters.

Science.gov (United States)

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

2015-01-30

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.

Aplication of the statistical experimental design to optimize mine-impacted water (MIW) remediation using shrimp-shell.

Science.gov (United States)

Núñez-Gómez, Dámaris; Alves, Alcione Aparecida de Almeida; Lapolli, Flavio Rubens; Lobo-Recio, María A

2017-01-01

Mine-impacted water (MIW) is one of the most serious mining problems and has a high negative impact on water resources and aquatic life. The main characteristics of MIW are a low pH (between 2 and 4) and high concentrations of SO 4 2- and metal ions (Cd, Cu, Ni, Pb, Zn, Fe, Al, Cr, Mn, Mg, etc.), many of which are toxic to ecosystems and human life. Shrimp shell was selected as a MIW treatment agent because it is a low-cost metal-sorbent biopolymer with a high chitin content and contains calcium carbonate, an acid-neutralizing agent. To determine the best metal-removal conditions, a statistical study using statistical planning was carried out. Thus, the objective of this work was to identify the degree of influence and dependence of the shrimp-shell content for the removal of Fe, Al, Mn, Co, and Ni from MIW. In this study, a central composite rotational experimental design (CCRD) with a quadruplicate at the midpoint (2 2 ) was used to evaluate the joint influence of two formulation variables-agitation and the shrimp-shell content. The statistical results showed the significant influence (p < 0.05) of the agitation variable for Fe and Ni removal (linear and quadratic form, respectively) and of the shrimp-shell content variable for Mn (linear form), Al and Co (linear and quadratic form) removal. Analysis of variance (ANOVA) for Al, Co, and Ni removal showed that the model is valid at the 95% confidence interval and that no adjustment needed within the ranges evaluated of agitation (0-251.5 rpm) and shrimp-shell content (1.2-12.8 g L -1 ). The model required adjustments to the 90% and 75% confidence interval for Fe and Mn removal, respectively. In terms of efficiency in removing pollutants, it was possible to determine the best experimental values of the variables considered as 188 rpm and 9.36 g L -1 of shrimp-shells. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pressure Shell Approach to Integrated Environmental Protection

Science.gov (United States)

Kennedy, Kriss J.

2011-01-01

The next generation of exploration mission human systems will require environmental protection such as radiation protection that is effective and efficient. In order to continue human exploration, habitat systems will require special shells to protect astronauts from hostile environments. The Pressure Shell Approach to integrated environmental (radiation) protection is a multi-layer shell that can be used for multifunctional environmental protection. Self-healing, self-repairing nano technologies and sensors are incorporated into the shell. This shell consists of multiple layers that can be tailored for specific environmental protection needs. Mainly, this innovation focuses on protecting crew from exposure to micrometeorites, thermal, solar flares, and galactic cosmic ray (GCR) radiation. The Pressure Shell Approach consists of a micrometeoroid and secondary ejecta protection layer; a thin, composite shell placed in between two layers that is non-structural; an open cavity layer that can be filled with water, regolith, or polyethylene foam; a thicker composite shell that is a structural load bearing that is placed between two layers; and a bladder coating on the interior composite shell. This multi-layer shell creates an effective radiation protection system. Most of its layers can be designed with the materials necessary for specific environments. In situ materials such as water or regolith can be added to the shell design for supplemental radiation protection.

Molecular Design of Branched and Binary Molecules at Ordered Interfaces

Energy Technology Data Exchange (ETDEWEB)

Genson, Kirsten Larson [Iowa State Univ., Ames, IA (United States)

2005-01-01

This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformation which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to exert on the packing structure. The amphiphilic balance of the different molecular series exhibited control on the ordering behavior at the air-water interface and within bulk structures. The shell nature and tail type was determined to dictate the preferential ordering structure and molecular reorganization at interfaces with the core nature effect secondary.

Preparation of keratin-based microcapsules for encapsulation of hydrophilic molecules.

Science.gov (United States)

Rajabinejad, Hossein; Patrucco, Alessia; Caringella, Rosalinda; Montarsolo, Alessio; Zoccola, Marina; Pozzo, Pier Davide

2018-01-01

The interest towards microcapsules based on non-toxic, biodegradable and biocompatible polymers, such as proteins, is increasing considerably. In this work, microcapsules were prepared using water soluble keratin, known as keratoses, with the aim of encapsulating hydrophilic molecules. Keratoses were obtained via oxidizing extraction of pristine wool, previously degreased by Soxhlet. In order to better understand the shell part of microcapsules, pristine wool and obtained keratoses were investigated by FT-IR, gel-electrophoresis and HPLC. Production of the microcapsules was carried out by a sonication method. Thermal properties of microcapsules were investigated by DSC. Microencapsulation and dye encapsulation yields were obtained by UV-spectroscopy. Morphological structure of microcapsules was studied by light microscopy, SEM, and AFM. The molecular weights of proteins analyzed using gel-electrophoresis resulted in the range of 38-62kDa. The results confirmed that the hydrophilic dye (Telon Blue) was introduced inside the keratoses shells by sonication and the final microcapsules diameter ranged from 0.5 to 4µm. Light microscope investigation evidenced the presence of the dye inside the keratoses vesicles, confirming their capability of encapsulating hydrophilic molecules. The microcapsule yield and dye encapsulation yield were found to be 28.87±3% and 83.62±5% respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of the effective mass of water molecule on thermal neutron scattering

International Nuclear Information System (INIS)

Markovic, M.

1981-01-01

The influence of the effective water molecule mass on the thermal neutron scattering on the nucleus of the hydrogen atom has been investigated. Besides the actual water molecule mass (M = 18) the investigations have been carried out with its two effective values (M1 = 16 and M2 = 20). The differential and total cross sections have been calculated for the incident thermal neutron energy E o = 1 eV. Investigation results show different prominence of the quantum effects and for M2 the appearance of peaks in the quasielastic scattering. (author)

A Raman spectroscopy study on the effects of intermolecular hydrogen bonding on water molecules absorbed by borosilicate glass surface

Science.gov (United States)

Li, Fabing; Li, Zhanlong; Wang, Ying; Wang, Shenghan; Wang, Xiaojun; Sun, Chenglin; Men, Zhiwei

2018-05-01

The structural forms of water/deuterated water molecules located on the surface of borosilicate capillaries have been first investigated in this study on the basis of the Raman spectral data obtained at different temperatures and under atmospheric pressure for molecules in bulk and also for molecules absorbed by borosilicate glass surface. The strongest two fundamental bands locating at 3063 cm-1 (2438 cm-1) in the recorded Raman spectra are assigned here to the Osbnd H (Osbnd D) bond stretching vibrations and they are compared with the corresponding bands observed at 3124 cm-1 (2325 cm-1) in the Raman spectrum of ice Ih. Our spectroscopic observations have indicated that the structure of water and deuterated water molecules on borosilicate surface is similar to that of ice Ih (hexagonal phase of ice). These observations have also indicated that water molecules locate on the borosilicate surface so as to construct a bilayer structure and that strong and weak intermolecular hydrogen bonds are formed between water/deuterated molecules and silanol groups on borosilicate surface. In accordance with these findings, water and deuterated water molecules at the interface of capillary have a higher melting temperature.

Transport behavior of water molecules through two-dimensional nanopores

International Nuclear Information System (INIS)

Zhu, Chongqin; Li, Hui; Meng, Sheng

2014-01-01

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

Reactive turbulent flow CFD study in supercritical water oxidation process: application to a stirred double shell reactor

International Nuclear Information System (INIS)

Moussiere, S.

2006-12-01

Supercritical water oxidation is an innovative process to treat organic liquid waste which uses supercritical water properties to mix efficiency the oxidant and the organic compounds. The reactor is a stirred double shell reactor. In the step of adaptation to nuclear constraints, the computational fluid dynamic modeling is a good tool to know required temperature field in the reactor for safety analysis. Firstly, the CFD modeling of tubular reactor confirms the hypothesis of an incompressible fluid and the use of k-w turbulence model to represent the hydrodynamic. Moreover, the EDC model is as efficiency as the kinetic to compute the reaction rate in this reactor. Secondly, the study of turbulent flow in the double shell reactor confirms the use of 2D axisymmetric geometry instead of 3D geometry to compute heat transfer. Moreover, this study reports that water-air mixing is not in single phase. The reactive turbulent flow is well represented by EDC model after adaptation of initial conditions. The reaction rate in supercritical water oxidation reactor is mainly controlled by the mixing. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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.

Cleaning oil refining drainage waters out of emulsified oil products with thermic treated cedar nut shell

Science.gov (United States)

Pyatanova, P. A.; Adeeva, L. N.

2017-08-01

It was elaborated the ability of the sorbent produced by thermic treatment of cedar nut shell to destruct model and real first kind (direct) emulsions in static and dynamic conditions. In static conditions optimal ratio sorbent-emulsion with the original concentration of oil products 800 mg/l was in the range of 2.0 g per 100 ml of emulsion which corresponds to the level of treatment 94.9%. The time of emulsion destruction was 40 minutes. This sorbent is highly active in dynamic processes of oil-contaminated water treatment, the level of treatment 96.0% is being achieved. Full dynamic sorptive capacity of the sorbent is 0.85 g/g. Sorbent based on the thermic treated cedar nut shell can be elaborated as sorptive filter element of local treatment facilities of oil refining and petrochemical processes. After the treatment with this sorbent of drainage waters of oil refinery in dynamic conditions the concentration of oil products became less than mpc on oil products for waste waters coming to biological treatment.

Hydrogen bonding characterization in water and small molecules

Science.gov (United States)

Silvestrelli, Pier Luigi

2017-06-01

The prototypical hydrogen bond in water dimer and hydrogen bonds in the protonated water dimer, in other small molecules, in water cyclic clusters, and in ice, covering a wide range of bond strengths, are theoretically investigated by first-principles calculations based on density functional theory, considering not only a standard generalized gradient approximation functional but also, for the water dimer, hybrid and van der Waals corrected functionals. We compute structural, energetic, and electrostatic (induced molecular dipole moments) properties. In particular, hydrogen bonds are characterized in terms of differential electron density distributions and profiles, and of the shifts of the centres of maximally localized Wannier functions. The information from the latter quantities can be conveyed to a single geometric bonding parameter that appears to be correlated with the Mayer bond order parameter and can be taken as an estimate of the covalent contribution to the hydrogen bond. By considering the water trimer, the cyclic water hexamer, and the hexagonal phase of ice, we also elucidate the importance of cooperative/anticooperative effects in hydrogen-bonding formation.

Isotopic characteristics of shells Mytilus galloprovincialis from eastern coastal area of Adriatic Sea

Directory of Open Access Journals (Sweden)

Tjaša Kanduč

2006-06-01

Full Text Available Samples of Mytilus galloprovincialis were collected from entire Eastern Adriatic coast to determine δ18O and δ13C performed on calcite and aragonite shell layers. The aim of this work was to check whether shells of M. galloprovincialis are good environmental indicators (water temperature, salinity. Based on measured isotopic composition of oxygen in shell layers and assumed isotopic composition in water temperatures of calcite and aragonite of shell layers were calculated. The calculated temperatures for M. galloprovincialis shell growth of calcite and aragonite shell layer are in good agreement with measured temperatures of sea water. According to our results of δ18O and δ13C in shell layers we canseparate the locations of the investigated area into three groups: those with more influence of fresh water, those with less influence of fresh water and those of marine environments.

Synthesis of novel core-shell structured dual-mesoporous silica nanospheres and their application for enhancing the dissolution rate of poorly water-soluble drugs

Energy Technology Data Exchange (ETDEWEB)

Wu, Chao, E-mail: wuchao27@126.com [Department of Pharmaceutics, Liaoning Medical University, 40 Songpo Road, Linghe District, Jinzhou, Liaoning Province 121001 (China); Sun, Xiaohu [Management Center for Experiments, Bohai University, 19 Keji Road, Songshan District, Jinzhou, Liaoning Province 121000 (China); Zhao, Zongzhe; Zhao, Ying; Hao, Yanna; Liu, Ying [Department of Pharmaceutics, Liaoning Medical University, 40 Songpo Road, Linghe District, Jinzhou, Liaoning Province 121001 (China); Gao, Yu, E-mail: gaoyu_1116@163.com [Department of Medical Oncology, First Affiliated Hospital of Liaoning Medical University, 40 Songpo Road, Linghe District, Jinzhou, Liaoning Province 121001 (China)

2014-11-01

Novel core-shell dual-mesoporous silica nanospheres (DMSS) with a tunable pore size were synthesized successfully using a styrene monomer as a channel template for the core and cetyltrimethyl ammonium bromide (CTAB) as a channel template for the shell in order to improve the dissolution rate of poorly water-soluble drugs. Simvastatin was used as a model drug and loaded into DMSS and the mesoporous core without the shell (MSC) by the solvent evaporation method. The drug loading efficiency of DMSS and MSC were determined by thermogravimetric analysis (TGA) and ultraviolet spectroscopy (UV). Characterization, using scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption, powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR) showed that simvastatin adsorbed in DMSS and MSC was in an amorphous state, and in vitro release test results demonstrated that both DMSS and MSC increased the water solubility and dissolution rate of simvastatin. The shell structure of DMSS was able to regulate the release of simvastatin compared with MSC. It is worth noting that DMSS has significant potential as a carrier for improving the dissolution of poorly water-soluble drugs and reducing the rapid release. - Highlights: • A novel core-shell DMSS is prepared for improving the dissolution rate of simvastatin. • The diffusional resistance of the mesoporous shell can delay and regulate drug release. • Simvastatin absorbed in DMSS exists in amorphous form due to spatial confinement.

Synthesis of novel core-shell structured dual-mesoporous silica nanospheres and their application for enhancing the dissolution rate of poorly water-soluble drugs

International Nuclear Information System (INIS)

Wu, Chao; Sun, Xiaohu; Zhao, Zongzhe; Zhao, Ying; Hao, Yanna; Liu, Ying; Gao, Yu

2014-01-01

Novel core-shell dual-mesoporous silica nanospheres (DMSS) with a tunable pore size were synthesized successfully using a styrene monomer as a channel template for the core and cetyltrimethyl ammonium bromide (CTAB) as a channel template for the shell in order to improve the dissolution rate of poorly water-soluble drugs. Simvastatin was used as a model drug and loaded into DMSS and the mesoporous core without the shell (MSC) by the solvent evaporation method. The drug loading efficiency of DMSS and MSC were determined by thermogravimetric analysis (TGA) and ultraviolet spectroscopy (UV). Characterization, using scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption, powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR) showed that simvastatin adsorbed in DMSS and MSC was in an amorphous state, and in vitro release test results demonstrated that both DMSS and MSC increased the water solubility and dissolution rate of simvastatin. The shell structure of DMSS was able to regulate the release of simvastatin compared with MSC. It is worth noting that DMSS has significant potential as a carrier for improving the dissolution of poorly water-soluble drugs and reducing the rapid release. - Highlights: • A novel core-shell DMSS is prepared for improving the dissolution rate of simvastatin. • The diffusional resistance of the mesoporous shell can delay and regulate drug release. • Simvastatin absorbed in DMSS exists in amorphous form due to spatial confinement

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

Science.gov (United States)

Kuffel, Anna; Zielkiewicz, Jan

2016-02-14

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.

Enhanced Performance of Photoelectrochemical Water Splitting with ITO@α-Fe2O3 Core-Shell Nanowire Array as Photoanode.

Science.gov (United States)

Yang, Jie; Bao, Chunxiong; Yu, Tao; Hu, Yingfei; Luo, Wenjun; Zhu, Weidong; Fu, Gao; Li, Zhaosheng; Gao, Hao; Li, Faming; Zou, Zhigang

2015-12-09

Hematite (α-Fe2O3) is one of the most promising candidates for photoelectrodes in photoelectrochemical water splitting system. However, the low visible light absorption coefficient and short hole diffusion length of pure α-Fe2O3 limits the performance of α-Fe2O3 photoelectrodes in water splitting. Herein, to overcome these drawbacks, single-crystalline tin-doped indium oxide (ITO) nanowire core and α-Fe2O3 nanocrystal shell (ITO@α-Fe2O3) electrodes were fabricated by covering the chemical vapor deposited ITO nanowire array with compact thin α-Fe2O3 nanocrystal film using chemical bath deposition (CBD) method. The J-V curves and IPCE of ITO@α-Fe2O3 core-shell nanowire array electrode showed nearly twice as high performance as those of the α-Fe2O3 on planar Pt-coated silicon wafers (Pt/Si) and on planar ITO substrates, which was considered to be attributed to more efficient hole collection and more loading of α-Fe2O3 nanocrystals in the core-shell structure than planar structure. Electrochemical impedance spectra (EIS) characterization demonstrated a low interface resistance between α-Fe2O3 and ITO nanowire arrays, which benefits from the well contact between the core and shell. The stability test indicated that the prepared ITO@α-Fe2O3 core-shell nanowire array electrode was stable under AM1.5 illumination during the test period of 40,000 s.

Core/Shell Microstructure Induced Synergistic Effect for Efficient Water-Droplet Formation and Cloud-Seeding Application.

Science.gov (United States)

Tai, Yanlong; Liang, Haoran; Zaki, Abdelali; El Hadri, Nabil; Abshaev, Ali M; Huchunaev, Buzgigit M; Griffiths, Steve; Jouiad, Mustapha; Zou, Linda

2017-12-26

Cloud-seeding materials as a promising water-augmentation technology have drawn more attention recently. We designed and synthesized a type of core/shell NaCl/TiO 2 (CSNT) particle with controlled particle size, which successfully adsorbed more water vapor (∼295 times at low relative humidity, 20% RH) than that of pure NaCl, deliquesced at a lower environmental RH of 62-66% than the hygroscopic point (h g.p ., 75% RH) of NaCl, and formed larger water droplets ∼6-10 times its original measured size area, whereas the pure NaCl still remained as a crystal at the same conditions. The enhanced performance was attributed to the synergistic effect of the hydrophilic TiO 2 shell and hygroscopic NaCl core microstructure, which attracted a large amount of water vapor and turned it into a liquid faster. Moreover, the critical particle size of the CSNT particles (0.4-10 μm) as cloud-seeding materials was predicted via the classical Kelvin equation based on their surface hydrophilicity. Finally, the benefits of CSNT particles for cloud-seeding applications were determined visually through in situ observation under an environmental scanning electron microscope on the microscale and cloud chamber experiments on the macroscale, respectively. These excellent and consistent performances positively confirmed that CSNT particles could be promising cloud-seeding materials.

The influence of shell thickness of Au@TiO2 core-shell nanoparticles on the plasmonic enhancement effect in dye-sensitized solar cells.

Science.gov (United States)

Liu, Wei-Liang; Lin, Fan-Cheng; Yang, Yu-Chen; Huang, Chen-Hsien; Gwo, Shangjr; Huang, Michael H; Huang, Jer-Shing

2013-09-07

Plasmonic core-shell nanoparticles (PCSNPs) can function as nanoantennas and improve the efficiency of dye-sensitized solar cells (DSSCs). To achieve maximum enhancement, the morphology of PCSNPs needs to be optimized. Here we precisely control the morphology of Au@TiO2 PCSNPs and systematically study its influence on the plasmonic enhancement effect. The enhancement mechanism was found to vary with the thickness of the TiO2 shell. PCSNPs with a thinner shell mainly enhance the current, whereas particles with a thicker shell improve the voltage. While pronounced plasmonic enhancement was found in the near infrared regime, wavelength-independent enhancement in the visible range was observed and attributed to the plasmonic heating effect. Emission lifetime measurement confirms that N719 molecules neighboring nanoparticles with TiO2 shells exhibit a longer lifetime than those in contact with metal cores. Overall, PCSNPs with a 5 nm shell give the highest efficiency enhancement of 23%. Our work provides a new synthesis route for well-controlled Au@TiO2 core-shell nanoparticles and gains insight into the plasmonic enhancement in DSSCs.

Stability of Ag@SiO2 core–shell particles in conditions of photocatalytic overall water-splitting

NARCIS (Netherlands)

Park, Sun Young; Han, Kai; O'Neill, Devin B.; Mul, Guido

2017-01-01

Core–shell nanoparticles containing plasmonic metals (Ag or Au) have been frequently reported to enhance performance of photo-electrochemical (PEC) devices. However, the stability of these particles in water-splitting conditions is usually not addressed. In this study we demonstrate that Ag@SiO2

Hydrogen bond dynamics and water structure in glucose-water solutions by depolarized Rayleigh scattering and low-frequency Raman spectroscopy

Science.gov (United States)

Paolantoni, Marco; Sassi, Paola; Morresi, Assunta; Santini, Sergio

2007-07-01

The effect of glucose on the relaxation process of water at picosecond time scales has been investigated by depolarized Rayleigh scattering (DRS) experiments. The process is assigned to the fast hydrogen bonding dynamics of the water network. In DRS spectra this contribution can be safely separated from the slower relaxation process due to the sugar. The detected relaxation time is studied at different glucose concentrations and modeled considering bulk and hydrating water contributions. As a result, it is found that in diluted conditions the hydrogen bond lifetime of proximal water molecules becomes about three times slower than that of the bulk. The effect of the sugar on the hydrogen bond water structure is investigated by analyzing the low-frequency Raman (LFR) spectrum sensitive to intermolecular modes. The addition of glucose strongly reduces the intensity of the band at 170cm-1 assigned to a collective stretching mode of water molecules arranged in cooperative tetrahedral domains. These findings indicate that proximal water molecules partially lose the tetrahedral ordering typical of the bulk leading to the formation of high density environments around the sugar. Thus the glucose imposes a new local order among water molecules localized in its hydration shell in which the hydrogen bond breaking dynamics is sensitively retarded. This work provides new experimental evidences that support recent molecular dynamics simulation and thermodynamics results.

Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

International Nuclear Information System (INIS)

Bankura, Arindam; Chandra, Amalendu

2015-01-01

The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water

Sub-terahertz spectroscopy reveals that proteins influence the properties of water at greater distances than previously detected

Energy Technology Data Exchange (ETDEWEB)

Sushko, Oleksandr; Dubrovka, Rostyslav; Donnan, Robert S., E-mail: r.donnan@qmul.ac.uk [School of Electronic Engineering and Computer Science, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom)

2015-02-07

The initial purpose of the study is to systematically investigate the solvation properties of different proteins in water solution by terahertz (THz) radiation absorption. Transmission measurements of protein water solutions have been performed using a vector network analyser-driven quasi-optical bench covering the WR-3 waveguide band (0.220–0.325 THz). The following proteins, ranging from low to high molecular weight, were chosen for this study: lysozyme, myoglobin, and bovine serum albumin (BSA). Absorption properties of solutions were studied at different concentrations of proteins ranging from 2 to 100 mg/ml. The concentration-dependent absorption of protein molecules was determined by treating the solution as a two-component model first; then, based on protein absorptivity, the extent of the hydration shell is estimated. Protein molecules are shown to possess a concentration-dependent absorptivity in water solutions. Absorption curves of all three proteins sharply peak towards a dilution-limit that is attributed to the enhanced flexibility of protein and amino acid side chains. An alternative approach to the determination of hydration shell thickness is thereby suggested, based on protein absorptivity. The proposed approach is independent of the absorption of the hydration shell. The derived estimate of hydration shell thickness for each protein supports previous findings that protein-water interaction dynamics extends beyond 2-3 water solvation-layers as predicted by molecular dynamics simulations and other techniques such as NMR, X-ray scattering, and neutron scattering. According to our estimations, the radius of the dynamic hydration shell is 16, 19, and 25 Å, respectively, for lysozyme, myoglobin, and BSA proteins and correlates with the dipole moment of the protein. It is also seen that THz radiation can serve as an initial estimate of the protein hydrophobicity.

Sub-terahertz spectroscopy reveals that proteins influence the properties of water at greater distances than previously detected

International Nuclear Information System (INIS)

Sushko, Oleksandr; Dubrovka, Rostyslav; Donnan, Robert S.

2015-01-01

The initial purpose of the study is to systematically investigate the solvation properties of different proteins in water solution by terahertz (THz) radiation absorption. Transmission measurements of protein water solutions have been performed using a vector network analyser-driven quasi-optical bench covering the WR-3 waveguide band (0.220–0.325 THz). The following proteins, ranging from low to high molecular weight, were chosen for this study: lysozyme, myoglobin, and bovine serum albumin (BSA). Absorption properties of solutions were studied at different concentrations of proteins ranging from 2 to 100 mg/ml. The concentration-dependent absorption of protein molecules was determined by treating the solution as a two-component model first; then, based on protein absorptivity, the extent of the hydration shell is estimated. Protein molecules are shown to possess a concentration-dependent absorptivity in water solutions. Absorption curves of all three proteins sharply peak towards a dilution-limit that is attributed to the enhanced flexibility of protein and amino acid side chains. An alternative approach to the determination of hydration shell thickness is thereby suggested, based on protein absorptivity. The proposed approach is independent of the absorption of the hydration shell. The derived estimate of hydration shell thickness for each protein supports previous findings that protein-water interaction dynamics extends beyond 2-3 water solvation-layers as predicted by molecular dynamics simulations and other techniques such as NMR, X-ray scattering, and neutron scattering. According to our estimations, the radius of the dynamic hydration shell is 16, 19, and 25 Å, respectively, for lysozyme, myoglobin, and BSA proteins and correlates with the dipole moment of the protein. It is also seen that THz radiation can serve as an initial estimate of the protein hydrophobicity

Characterization of Physic nut (Jatropha curcas L.) shells

International Nuclear Information System (INIS)

Wever, Diego-Armando Z.; Heeres, H.J.; Broekhuis, Antonius A.

2012-01-01

The characterization of Physic nut shells was done using the wet chemical analysis of wood components. The obtained fractions were analyzed using IR, NMR, GPC, ICP and MALDI-TOF mass spectroscopy. TGA was used to determine the fixed carbon (+ash) and water content of the shells. The results of wet chemical analysis of wood components offered a clear procedure to isolate the main components in Physic nut shells (a). The fractions obtained were: polar extract (b), non-polar extract (c), Acid Insoluble Lignin (d), Holocellulose (e), α-Cellulose (f). The total Lignin content present in the shells equaled 48.84%. IR and NMR spectroscopy demonstrated that the non-polar extract is Lignin, which corresponds to the extractable Lignin (1.24%) in the Physic nut shells and the Acid Insoluble Lignin was 47.60%. Elemental analysis showed no Sulfur present in the investigated materials. Furthermore both 1 H and 13 C NMR of the non-polar extract showed the presence of aliphatic hydrocarbon chains. The α-Cellulose content (22.29%) and the Hemicelluloses content (23.84%) were in line with that of agricultural residues. The water content and the fixed carbon content (+ash [2.8%]) equal 5–6% and 35.6%, respectively. GPC showed that the polydispersity of the non-polar extract (3.6) lies between Alcell Lignin and Kraft Lignin. The polar extract contains a variety of metals, with especially a high amount of the alkali metals K and Na. The extraction with water is proposed to generate a fertilizer fraction and may be applied to reduce potential sintering issues during eventual combustion or gasification of the shells. -- Highlights: ► Physic nut shell is a potential source of value added chemicals due to its high lignin content (48.8 wt%). ► Lignin extracted from Jatropha curcas L. shells is rich in aliphatic linkages. ► Water extraction of the shells yields a potential fertilizer fraction rich in alkali metals and phosphorous. ► Pre-extraction is recommended to eliminate

Slow neutron scattering by water molecules

Energy Technology Data Exchange (ETDEWEB)

Stancic, V [Boris Kidric Institute of Nuclear Sciences Vinca, Beograd (Yugoslavia)

1970-07-01

In this work some new, preliminary formulae for slow neutron scattering cross section calculation by heavy and light water molecules have been done. The idea was to find, from the sum which exists in well known Nelkin model, other cross sections in a more simple analytical form, so that next approximations may be possible. In order to sum a series it was starting from Euler-Mclaurin formula. Some new summation formulae have been derived there, and defined in two theorems. Extensive calculations, especially during the evaluation of residues, have been made at the CDC 3600 computer. validation of derived formulae was done by comparison with the BNL-325 results. Good agreement is shown. (author)

Slow neutron scattering by water molecules

International Nuclear Information System (INIS)

Stancic, V.

1970-01-01

In this work some new, preliminary formulae for slow neutron scattering cross section calculation by heavy and light water molecules have been done. The idea was to find, from the sum which exists in well known Nelkin model, other cross sections in a more simple analytical form, so that next approximations may be possible. In order to sum a series it was starting from Euler-Mclaurin formula. Some new summation formulae have been derived there, and defined in two theorems. Extensive calculations, especially during the evaluation of residues, have been made at the CDC 3600 computer. validation of derived formulae was done by comparison with the BNL-325 results. Good agreement is shown. (author)

Measurements of water molecule density by tunable diode laser absorption spectroscopy in dielectric barrier discharges with gas-water interface

Science.gov (United States)

Tachibana, Kunihide; Nakamura, Toshihiro; Kawasaki, Mitsuo; Morita, Tatsuo; Umekawa, Toyofumi; Kawasaki, Masahiro

2018-01-01

We measured water molecule (H2O) density by tunable diode-laser absorption spectroscopy (TDLAS) for applications in dielectric barrier discharges (DBDs) with a gas-water interface. First, the effects of water temperature and presence of gas flow were tested using a Petri dish filled with water and a gas injection nozzle. Second, the TDLAS system was applied to the measurements of H2O density in two types of DBDs; one was a normal (non-inverted) type with a dielectric-covered electrode above a water-filled counter electrode and the other was an inverted type with a water-suspending mesh electrode above a dielectric-covered counter electrode. The H2O density in the normal DBD was close to the density estimated from the saturated vapor pressure, whereas the density in the inverted DBD was about half of that in the former type. The difference is attributed to the upward gas flow in the latter type, that pushes the water molecules up towards the gas-water interface.

STICKING OF MOLECULES ON NONPOROUS AMORPHOUS WATER ICE

Energy Technology Data Exchange (ETDEWEB)

He, Jiao; Vidali, Gianfranco [Physics Department, Syracuse University, Syracuse, NY 13244 (United States); Acharyya, Kinsuk, E-mail: gvidali@syr.edu [Department of Chemistry, University of Virginia, Charlottesville, VA 22904 (United States)

2016-05-20

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 H{sub 2}, D{sub 2}, N{sub 2}, O{sub 2}, CO, CH{sub 4}, and CO{sub 2} 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.

Removal of Arsenic with Oyster Shell: Experimental Measurements

Directory of Open Access Journals (Sweden)

Md. Atiqur Rahman, , and

2008-12-01

Full Text Available Oyster shell has tremendous potential as a remediation material for the removal of arsenic from groundwater. A single arsenic removal system was developed with oyster shell for tube well water containing arsenic. The system removes arsenic from water by adsorption through fine oyster shell. Various conditions that affect the adsorption/desorption of arsenic were investigated. Adsorption column methods showed the removal of As(III under the following conditions: initial As concentration, 100 µg /L; oyster shell amount, 6 g; particle size, <355µm ; treatment flow rate, 1.7 mL/min; and pH 6.5. Arsenic concentration of the treated water were below the Bangladesh drinking water standard of 50 µg/L for As. The desorption efficiencies with 2M of KOH after the treatment of groundwater were in the range of 80-83%. A combination of techniques was used to measure the pH, conductivity, cations and anions. The average concentrations of other inorganic constituents of health concern (Na, K, Ca, Mg and Fe in treated water were below their respective WHO guideline for drinking. The present study might provide new avenues to achieve the arsenic concentrations required for drinking water recommended by Bangladesh and the World Health Organization (WHO.

The mechanism of 2-dimensional manipulation of DNA molecules by water and ethanol flows

International Nuclear Information System (INIS)

Shen Zigang; Huang Yibo; Li Bin; Zhang Yi

2007-01-01

Due to its unique physical and chemical properties, DNA has recently become a promising material for building blocks in nanofabrication. Many researches focus on how to use DNA molecules as a template for nanowires. Molecular Combing technique is one of important methods to manipulate DNA molecules by using a water meniscus and form specific DNA nano-structures on surfaces. In this paper, by employing a modified molecular combing technique, special patterns of DNA molecules was formed, and the interaction between liquid flows or meniscus and DNA molecules was analyzed, and the mechanism of manipulating DNA molecules by liquid was studied. (authors)

Coaxial nanofibers containing TiO2 in the shell for water treatment applications

Science.gov (United States)

Kizildag, N.; Geltmeyer, J.; Ucar, N.; De Buysser, K.; De Clerck, K.

2017-10-01

In recent years, the basic electrospinning setup has undergone many modifications carried out to enhance the quality and improve the functionality of the resulting nanofibers. Being one of these modifications, coaxial electrospinning has attracted great attention. It enables to use different materials in nanofiber production and produce multi-layered and functional nanofibers in one step. In this study, TiO2 has been added to the shell layer of coaxial nanofibers to develop functional nanofibers which may be used in water treatment applications. The coaxial nanofibers containing TiO2 in the shell layer are compared to uniaxial nanofibers containing TiO2 in bulk fiber structure, regarding their morphology and photocatalytic activity. Uniform uniaxial and coaxial nanofibers with TiO2 were obtained. The average nanofiber diameter of coaxial nanofibers were higher. Coaxial nanofibers, which contained lower amount of TiO2, displayed similar performance to uniaxial nanofibers with TiO2 in terms of photocatalytic degradation ability against isoproturon.

Mg/Ca of Continental Ostracode Shells

Science.gov (United States)

Ito, E.; Forester, R. M.; Marco-Barba, J.; Mezquita, F.

2007-12-01

Marine ionic chemistry is thought to remain constant. This, together with the belief that marine calcifiers partition Mg/Ca in a systematic manner as functions of temperature (and Mg/Ca) of water forms the basis of the Mg/Ca thermometer. In continental settings both of these assumptions are usually not true. Continental waters contain a wide variety of solutes in absolute and relative ion concentrations. Hence, waters with identical Mg/Ca may have very different concentrations of Mg and Ca and very different anions. Here we use two examples to focus on the effects of ion chemistry on Mg/Ca partitioning in continental ostracode shells and we ignore the complexities of solute evolution, which can change Mg/Ca over timescales of minutes to millennia. Palacios-Fest and Dettman (2001) conducted a monthly study of ,Cypridopsis vidua at El Yeso Lake in Sonora, Mexico. They established a relation between temperature and average shell Mg/Ca using regression analyses on averaged data. When their Mg/Ca-temperature relation is applied to monthly ,C. vidua data from Page Pond near Cleveland, Ohio, water temperatures of -8 to -1°C are obtained. The observed Mg/Ca ranges for El Yeso Lake (0.31 to 0.46) and Page Pond (0.33 to 0.46) are similar, as are their specific conductivities (700 to 850μS for El Yeso Lake; 400 to 600μS for Page Pond). However, [Ca] is 140-260 mg/L for El Yeso, but only 70-90 mg/L for Page Pond. Page Pond data, in fact, shows a good temperature shell Mg/Ca relation for .C. vidua, but the relation is different from that at El Yeso. Hence, shell Mg/Ca is a multi-valued, family of curves function of temperature and Mg/Ca of water that depends on the [Mg] and [Ca] values in water and perhaps other factors. Our second example comes from sites near Valencia, Spain and involves shell data for ,Cyprideis torosa, an estuarine ostracode that is tolerant of a wide range of salinity and can live in continental waters as long as the carbonate alkalinity to Ca ratio is

A new method to make poly acrylate foam shells

International Nuclear Information System (INIS)

Fan Yongheng; Luo Xuan; Fang Yu; Ren Hongbo; Zhang Lin; Cui Yi

2009-01-01

A triple-orifice droplet generator was designed and developed for the size-controllable continuous fabrication of hollow foam micro-shells. Solutions of an internal water phase, an oil phase (trimethylpropane triacrylate monomer, dibutyl phthalate solvent, and benzoin ethyl ether initiator), and an external water phase were used to prepare micro-shells whose diameters are between 1.5 mm and 4.0 mm successfully. Characterization of the foam shells was carried out using a scanning electron microscope and X-ray radiography. The results show that cell diameters of the shells are not above 1 um. The refractive index of the polymer framework is around 1.50. Furthermore, the shells fabricated through the triple-orifice droplet generator have a high survival probability of 93% and exhibit narrow size distribution. (authors)

Polarization and charge transfer in the hydration of chloride ions

International Nuclear Information System (INIS)

Zhao Zhen; Rogers, David M.; Beck, Thomas L.

2010-01-01

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

Identification of Carboxylate, Phosphate, and Phenoxide Functionalities in Deprotonated Molecules Related to Drug Metabolites via Ion-Molecule Reactions with water and Diethylhydroxyborane

Science.gov (United States)

Zhu, Hanyu; Ma, Xin; Kong, John Y.; Zhang, Minli; Kenttämaa, Hilkka I.

2017-10-01

Tandem mass spectrometry based on ion-molecule reactions has emerged as a powerful tool for structural elucidation of ionized analytes. However, most currently used reagents were designed to react with protonated analytes, making them suboptimal for acidic analytes that are preferentially detected in negative ion mode. In this work we demonstrate that the phenoxide, carboxylate, and phosphate functionalities can be identified in deprotonated molecules by use of a combination of two reagents, diethylmethoxyborane (DEMB) and water. A novel reagent introduction setup that allowed DEMB and water to be separately introduced into the ion trap region of the mass spectrometer was developed to facilitate fundamental studies of this reaction. A new reagent, diethylhydroxyborane (DEHB), was generated inside the ion trap by hydrolysis of DEMB on introduction of water. Most carboxylates and phenoxides formed a DEHB adduct, followed by addition of one water molecule and subsequent ethane elimination (DEHB adduct +H2O - CH3CH3) as the major product ion. Phenoxides with a hydroxy group adjacent to the deprotonation site and phosphates formed a DEHB adduct, followed by ethane elimination (DEHB adduct - CH3CH3). Deprotonated molecules with strong intramolecular hydrogen bonds or without the aforementioned functionalities, including sulfates, were unreactive toward DEHB/H2O. Reaction mechanisms were explored via isotope labeling experiments and quantum chemical calculations. The mass spectrometry method allowed the differentiation of phenoxide-, carboxylate-, phosphate-, and sulfate-containing analytes. Finally, it was successfully coupled with high-performance liquid chromatography for the analysis of a mixture containing hymecromone, a biliary spasm drug, and its three possible metabolites. [Figure not available: see fulltext.

The Inferred Distribution of Liquid Water in Europa's Ice Shell: Implications for the Europa Lander Mission

Science.gov (United States)

Noviello, J. L.; Torrano, Z. A.; Rhoden, A.; Manga, M.

2017-12-01

A key objective of the Europa lander mission is to identify liquid water within 30 km of the lander (Europa Lander SDT report, 2017), to provide essential context with which to evaluate samples and enable assessment of Europa's overall habitability. To inform lander mission development, we utilize a model of surface feature formation that invokes liquid water within Europa's ice shell to map out the implied 3D distribution of liquid water and assess the likelihood of a lander to be within 30 km of liquid water given regional variability. Europa's surface displays a variety of microfeatures, also called lenticulae, including pits, domes, spots, and microchaos. A recent model by Manga and Michaut (2017) attributes these features to various stages in the thermal-mechanical evolution of liquid water intrusions (i.e. sills) within the ice shell, from sill emplacement to surface breaching (in the case of microchaos) to freezing of the sill. Pits are of particular interest because they appear only when liquid water is still present. Another key feature of the model is that the size of a microfeature at the surface is controlled by the depth of the sill. Hence, we can apply this model to regions of Europa that contain microfeatures to infer the size, depth, and spatial distribution of liquid water within the ice shell. We are creating a database of microfeatures that includes digitized, collated data from previous mapping efforts along with our own mapping study. We focus on images with 220 m/pixel resolution, which includes the regional mapping data sets. Analysis of a preliminary study area suggests that sills are typically located at depths of 2km or less from the surface. We will present analysis of the full database of microfeatures and the corresponding 3D distribution of sills implied by the model. Our preliminary analysis also shows that pits are clustered in some regions, consistent with previous results, although individual pits are also observed. We apply a

Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

Energy Technology Data Exchange (ETDEWEB)

Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin, E-mail: gaoyq@pku.edu.cn [Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering and Biodynamic Optical Imaging Center, Peking University, Beijing 100871 (China)

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.

Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

International Nuclear Information System (INIS)

Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin

2015-01-01

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

Control of unidirectional transport of single-file water molecules through carbon nanotubes in an electric field.

Science.gov (United States)

Su, Jiaye; Guo, Hongxia

2011-01-25

The transport of water molecules through nanopores is not only crucial to biological activities but also useful for designing novel nanofluidic devices. Despite considerable effort and progress that has been made, a controllable and unidirectional water flow is still difficult to achieve and the underlying mechanism is far from being understood. In this paper, using molecular dynamics simulations, we systematically investigate the effects of an external electric field on the transport of single-file water molecules through a carbon nanotube (CNT). We find that the orientation of water molecules inside the CNT can be well-tuned by the electric field and is strongly coupled to the water flux. This orientation-induced water flux is energetically due to the asymmetrical water-water interaction along the CNT axis. The wavelike water density profiles are disturbed under strong field strengths. The frequency of flipping for the water dipoles will decrease as the field strength is increased, and the flipping events vanish completely for the relatively large field strengths. Most importantly, a critical field strength E(c) related to the water flux is found. The water flux is increased as E is increased for E ≤ E(c), while it is almost unchanged for E > E(c). Thus, the electric field offers a level of governing for unidirectional water flow, which may have some biological applications and provides a route for designing efficient nanopumps.

Adsorption of ethyl xanthate on ZnS(110) surface in the presence of water molecules: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Long, Xianhao [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Chen, Jianhua, E-mail: jhchen@gxu.edu.cn [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Guangxi Colleges and University Key Laboratory of Minerals Engineering, 530004 (China); Chen, Ye, E-mail: fby18@126.com [College of Resources and Metallurgy, Guangxi University, Nanning 530004 (China)

2016-05-01

Graphical abstract: - Highlights: • Adsorption of water molecules decreases the reactivity of surface Zn atom. • Copper impurities decrease the band gap of ZnS surface. • Copper impurities enhance the adsorption of xanthate on the ZnS surface. • Water molecules have little influence on the properties of Cu-substituted ZnS surface. • The xanthate S atom can interact with the surface S atom of Cu-substituted ZnS surface. - Abstracts: The interaction of collector with the mineral surface plays a very important role in the froth flotation of sphalerite. The adsorptions occurred at the interface between the mineral surface and waters; however most of DFT simulations are performed in vacuum, without consideration of water effect. Semiconductor surface has an obvious proximity effect, which will greatly influence the surface reactivity. To understand the mechanism of xanthate interacting with sphalerite surface in the presence of water molecules, the ethyl xanthate molecule adsorption on un-activated and Cu-activated ZnS(110) surface in the absence and presence of water molecules were performed using the density functional theory (DFT) method. The calculated results show that the adsorption of water molecules dramatically changes the properties of ZnS surface, resulting in decreasing the reactivity of surface Zn atoms with xanthate. Copper activation of ZnS surface changes the surface properties, leading to the totally different adsorption behaviors of xanthate. The presence of waters has little influence on the properties of Cu-activated ZnS surface. The xanthate S atom can interact with the surface S atom of Cu-substituted ZnS surface, which would result in the formation of dixanthogen.

Cavity mutants of Savinase. Crystal structures and differential scanning calorimetry experiments give hints of the function of the buried water molecules in subtilisins.

Science.gov (United States)

Pedersen, J T; Olsen, O H; Betzel, C; Eschenburg, S; Branner, S; Hastrup, S

1994-09-23

The subtilisin molecule possesses several internal water molecules, which may be characterised as an integral part of the protein structure. We have introduced specific mutations (T71I, T71S, T71V, T71A and T71G) at position 71 in the subtilisin variant Savinase from Bacillus lentus. This position is involved in a hydrogen bonded network with several internal water molecules, forming a water channel. The water channel and most of the other internal water molecules are positioned in the interface between two half-domains of the subtilisin molecule. The data presented here indicate that the internal water molecules are structural, and may be the result of trapping during the folding process.

Benefits of Silica Core-Shell Structures on the Temperature Sensing Properties of Er,Yb:GdVO4 Up-Conversion Nanoparticles.

Science.gov (United States)

Savchuk, Oleksandr A; Carvajal, Joan J; Cascales, C; Aguiló, M; Díaz, F

2016-03-23

We studied the temperature-dependent luminescence of GdVO4 nanoparticles co-doped with Er(3+) (1 mol %) and Yb(3+) (20 mol %) and determined their thermal sensing properties through the fluorescence intensity ratio (FIR) technique. We also analyzed how a silica coating, in a core-shell structure, affects the temperature sensing properties of this material. Spectra were recorded in the range of biological temperatures (298-343 K). The absolute sensitivity for temperature determination calculated for the core-shell nanoparticles is double the one calculated for bare nanoparticles, achieving a thermal resolution of 0.4 K. Moreover, silica-coated nanoparticles show good dispersibility in different solvents, such as water, DMSO, and methanol. Also, they show good luminescence stability without interactions with solvent molecules. Furthermore, we also observed that the silica coating shell prevents progressive heating of the nanoparticles during prolonged excitation periods with the 980 nm laser, preventing effects on their thermometric applications.

Selective degradation of model pollutants in the presence of core@shell TiO{sub 2}@SiO{sub 2} photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Nadrah, Peter, E-mail: peter.nadrah@zag.si [Slovenian National Building and Civil Engineering Institute, Dimičeva ul. 12, SI-1000 Ljubljana (Slovenia); Gaberšček, Miran [National Institute of Chemistry, Hajdrihova ul. 19, SI-1000 Ljubljana (Slovenia); Sever Škapin, Andrijana [Slovenian National Building and Civil Engineering Institute, Dimičeva ul. 12, SI-1000 Ljubljana (Slovenia)

2017-05-31

Highlights: • TiO{sub 2} encapsulated in mesoporous silica exhibits selective photocatalytic degradation of low-molecular-weight molecules. • Core@shell photocatalyst degrades rhodamine B in presence of fivefold mass concentration of starch, while pure TiO{sub 2} does not. • Potential use for removing water pollutants, while retaining non-harmful and beneficial macromolecules. - Abstract: Photocatalytic TiO{sub 2} degrades organic matter unselectively. However, in certain applications, such as degradation of pollutants, selectivity towards pollutants is beneficial. We synthesized core@shell TiO{sub 2}@SiO{sub 2} nanoparticles with photocatalytic activity featuring a significantly faster preferential degradation of model pollutant (rhodamine B) in presence of abundant concentration of natural organic matter compared to pure TiO{sub 2} (P25). The material’s photocatalytic activity was tested in aqueous medium. The selectivity of prepared effect of core@shell materials is explained based on transmission electron microscopy, nitrogen adsorption, X-ray powder diffraction and zeta potential measurements.

Shell report 2001; Les personnes, la planete, les profits. Shell rapport 2001

Energy Technology Data Exchange (ETDEWEB)

NONE

2002-07-01

In 2001, Shell saw mixed results across the social, environmental and economic spectrum. In order to contribute to the sustainable development, the Group is on track towards meeting its target to reduce greenhouse gas emissions to 10 % below 1990 levels by the end of 2002, although there was a significant increase in spill volumes and greenhouse gas emissions rose. Shell has articulated the business case and defined seven principles of sustainable development for use across the Group in business plans and daily operations: generating robust profitability; delivering value to customers; protecting the environment; managing resources; respecting and safeguarding people; benefiting communities; and working with stakeholders. Key points from the Shell Report include: in the framework of Managing, an independent review of the Shell Nigeria Community Development programme and testing of a human rights assessment tool in Shell South Africa and the implementing of a new Diversity and Inclusiveness Standard; in the framework of the economy the cost improvements of 5,1 billion dollars, ahead of target, the second highest earnings ever in difficult market conditions and the election of Shell top brand for fifth year running by motorists; in the framework of the Social, the safety performance, the avoidance of 100 contracts for incompatibility with Shell Business Principles; in the framework of the Environment, the publication of the Fresh water usage report for the first time, the Greenhouse gas emissions, the increase of spills as a result of a small number of incidents including a pipeline rupture in Nigeria and a well blow out in Oman. The economic, environmental and social data of the Shell Report are externally verified. (A.L.B.)

Modeling of microencapsulated polymer shell solidification

International Nuclear Information System (INIS)

Boone, T.; Cheung, L.; Nelson, D.; Soane, D.; Wilemski, G.; Cook, R.

1995-01-01

A finite element transport model has been developed and implemented to complement experimental efforts to improve the quality of ICF target shells produced via controlled-mass microencapsulation. The model provides an efficient means to explore the effect of processing variables on the dynamics of shell dimensions, concentricity, and phase behavior. Comparisons with experiments showed that the model successfully predicts the evolution of wall thinning and core/wall density differences. The model was used to efficiently explore and identify initial wall compositions and processing temperatures which resulted in concentricity improvements from 65 to 99%. The evolution of trace amounts of water entering into the shell wall was also tracked in the simulations. Comparisons with phase envelope estimations from modified UNIFAP calculations suggest that the water content trajectory approaches the two-phase region where vacuole formation via microphase separation may occur

Influence of Electrostatics on Small Molecule Flux through a Protein Nanoreactor.

Science.gov (United States)

Glasgow, Jeff E; Asensio, Michael A; Jakobson, Christopher M; Francis, Matthew B; Tullman-Ercek, Danielle

2015-09-18

Nature uses protein compartmentalization to great effect for control over enzymatic pathways, and the strategy has great promise for synthetic biology. In particular, encapsulation in nanometer-sized containers to create nanoreactors has the potential to elicit interesting, unexplored effects resulting from deviations from well-understood bulk processes. Self-assembled protein shells for encapsulation are especially desirable for their uniform structures and ease of perturbation through genetic mutation. Here, we use the MS2 capsid, a well-defined porous 27 nm protein shell, as an enzymatic nanoreactor to explore pore-structure effects on substrate and product flux during the catalyzed reaction. Our results suggest that the shell can influence the enzymatic reaction based on charge repulsion between small molecules and point mutations around the pore structure. These findings also lend support to the hypothesis that protein compartments modulate the transport of small molecules and thus influence metabolic reactions and catalysis in vitro.

Removal of mercury from water by carbonaceous sorbents derived from walnut shell

International Nuclear Information System (INIS)

Zabihi, M.; Ahmadpour, A.; Asl, A. Haghighi

2009-01-01

The adsorption ability of a powdered activated carbon (PAC) derived from walnut shell was investigated in an attempt to produce more economic and effective sorbent for the control of Hg(II) ion from industrial liquid streams. Carbonaceous sorbents derived from Iranian walnut shell (WS) were prepared by chemical activation method using ZnCl 2 as an activating reagent. To the best of our knowledge, this adsorbent was not used before for removing mercury from water. Adsorption of Hg(II) from aqueous solutions was carried out under different experimental conditions by varying treatment time, metal ion concentration, adsorbent amount, pH and solution temperature. It was determined that Hg(II) adsorption follows both Langmuir and Freundlich isotherms as well as pseudo-second-order kinetics. It was also shown that Hg(II) uptake decreases with increasing pH of the solution. The proper choice of preparation conditions resulted in a microporous activated carbon with 0.45 g/cm 3 density, 737 mg/g iodine number and 780 m 2 /g BET surface area. The monolayer sorption capacity of this optimum adsorbent was obtained as 151.5 mg/g.

Chemical and thermal stability of core-shelled magnetite nanoparticles and solid silica

Science.gov (United States)

Cendrowski, Krzysztof; Sikora, Pawel; Zielinska, Beata; Horszczaruk, Elzbieta; Mijowska, Ewa

2017-06-01

Pristine nanoparticles of magnetite were coated by solid silica shell forming core/shell structure. 20 nm thick silica coating significantly enhanced the chemical and thermal stability of the iron oxide. Chemical and thermal stability of this structure has been compared to the magnetite coated by mesoporous shell and pristine magnetite nanoparticles. It is assumed that six-membered silica rings in a solid silica shell limit the rate of oxygen diffusion during thermal treatment in air and prevent the access of HCl molecules to the core during chemical etching. Therefore, the core/shell structure with a solid shell requires a longer time to induce the oxidation of iron oxide to a higher oxidation state and, basically, even strong concentrated acid such as HCl is not able to dissolve it totally in one month. This leads to the desired performance of the material in potential applications such as catalysis and environmental protection.

Nanocrystalline p-hydroxyacetanilide (paracetamol) and gold core-shell structure as a model drug deliverable organic-inorganic hybrid nanostructure

Science.gov (United States)

Das, Subhojit; Paul, Anumita; Chattopadhyay, Arun

2013-09-01

We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release. Electronic supplementary information (ESI) available: See DOI: 10.1039/c3nr03566b

Studies of C60 in fossil of dinosaur egg shell

International Nuclear Information System (INIS)

Wang Zhenxia; Li Xuepeng; Wang Wenmin; Xu Xunjiang; Tang Zichao; Huang Rongbin; Zheng Lansun

1998-01-01

The occurrence of C 60 in unearthed fossil of dinosaur egg shell about 70 million years ago was reported. The results are discussed considering possible effects of the conceivable atmosphere pollution on the growth of fullerene molecules

[Interactions of DNA bases with individual water molecules. Molecular mechanics and quantum mechanics computation results vs. experimental data].

Science.gov (United States)

Gonzalez, E; Lino, J; Deriabina, A; Herrera, J N F; Poltev, V I

2013-01-01

To elucidate details of the DNA-water interactions we performed the calculations and systemaitic search for minima of interaction energy of the systems consisting of one of DNA bases and one or two water molecules. The results of calculations using two force fields of molecular mechanics (MM) and correlated ab initio method MP2/6-31G(d, p) of quantum mechanics (QM) have been compared with one another and with experimental data. The calculations demonstrated a qualitative agreement between geometry characteristics of the most of local energy minima obtained via different methods. The deepest minima revealed by MM and QM methods correspond to water molecule position between two neighbor hydrophilic centers of the base and to the formation by water molecule of hydrogen bonds with them. Nevertheless, the relative depth of some minima and peculiarities of mutual water-base positions in' these minima depend on the method used. The analysis revealed insignificance of some differences in the results of calculations performed via different methods and the importance of other ones for the description of DNA hydration. The calculations via MM methods enable us to reproduce quantitatively all the experimental data on the enthalpies of complex formation of single water molecule with the set of mono-, di-, and trimethylated bases, as well as on water molecule locations near base hydrophilic atoms in the crystals of DNA duplex fragments, while some of these data cannot be rationalized by QM calculations.

Continuum simulations of water flow past fullerene molecules

DEFF Research Database (Denmark)

Popadic, A.; Praprotnik, M.; Koumoutsakos, P.

2015-01-01

We present continuum simulations of water flow past fullerene molecules. The governing Navier-Stokes equations are complemented with the Navier slip boundary condition with a slip length that is extracted from related molecular dynamics simulations. We find that several quantities of interest...... as computed by the present model are in good agreement with results from atomistic and atomistic-continuum simulations at a fraction of the cost. We simulate the flow past a single fullerene and an array of fullerenes and demonstrate that such nanoscale flows can be computed efficiently by continuum flow...

Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution

Science.gov (United States)

Salem, Mohamed A.; Bakr, Eman A.; El-Attar, Heba G.

2018-01-01

Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17 nm for Pt@Ag and 8.8 nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH4) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes.

The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation

Energy Technology Data Exchange (ETDEWEB)

Skinner, L. B. [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Mineral Physics Institute, Stony Brook University, Stony Brook, New York, New York 11794-2100 (United States); Galib, M.; Fulton, J. L., E-mail: John.Fulton@pnnl.gov, E-mail: benmore@anl.gov; Mundy, C. J.; Schenter, G. K. [Physical and Computational Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354 (United States); Parise, J. B. [Mineral Physics Institute, Stony Brook University, Stony Brook, New York, New York 11794-2100 (United States); Department of Geosciences, Stony Brook University, Stony Brook, New York, New York 11794-2100 (United States); Photon Sciences Division, Brookhaven National Laboratory, Upton, New York 11973 (United States); Pham, V.-T. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP48, 91192 Gif-sur-Yvette (France); Center for Quantum Electronics, Institute of Physics, Vietnam Academy of Science and Technology, P.O. Box 429, Boho, Hanoi 10000 (Viet Nam); Benmore, C. J., E-mail: John.Fulton@pnnl.gov, E-mail: benmore@anl.gov [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2016-04-07

X-ray diffraction measurements of liquid water are reported at pressures up to 360 MPa corresponding to a density of 0.0373 molecules per Å{sup 3}. The measurements were conducted at a spatial resolution corresponding to Q{sub max} = 16 Å{sup −1}. The method of data analysis and measurement in this study follows the earlier benchmark results reported for water under ambient conditions having a density of 0.0333 molecules per Å{sup 3} and Q{sub max} = 20 Å{sup −1} [J. Chem. Phys. 138, 074506 (2013)] and at 70 °C having a density of 0.0327 molecules per Å{sup 3} and Q{sub max} = 20 Å{sup −1} [J. Chem. Phys. 141, 214507 (2014)]. The structure of water is very different at these three different T and P state points and thus they provide the basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3 and 3 Å are nearly unchanged: the peak position, shape, and coordination number are nearly identical to their values under ambient conditions. However, in the region above 3 Å, large structural changes occur with the collapse of the well-defined 2nd shell and shifting of higher shells to shorter distances. The measured structure is compared to simulated structure using intermolecular potentials described by both first-principles methods (revPBE-D3) and classical potentials (TIP4P/2005, MB-pol, and mW). The DFT-based, revPBE-D3, method and the many-body empirical potential model, MB-pol, provide the best overall representation of the ambient, high-temperature, and high-pressure data. The revPBE-D3, MB-pol, and the TIP4P/2005 models capture the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which partially encroaches the 1st shell at ambient pressure, is pushed further into the local tetrahedral arrangement at higher pressures by the more distant molecules filling the void space in the network between the 1st and 2nd shells.

The spontaneous synchronized dance of pairs of water molecules

Energy Technology Data Exchange (ETDEWEB)

Roncaratti, Luiz F. [Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, 06123 Perugia (Italy); Instituto de Física, Universidade de Brasília, 70910-900 Brasília (Brazil); Cappelletti, David, E-mail: david.cappelletti@unipg.it; Pirani, Fernando [Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, 06123 Perugia (Italy)

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.

The spontaneous synchronized dance of pairs of water molecules

International Nuclear Information System (INIS)

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

2014-01-01

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

Energy transfer in nanowire solar cells with photon-harvesting shells

KAUST Repository

Peters, C. H.; Guichard, A. R.; Hryciw, A. C.; Brongersma, M. L.; McGehee, M. D.

2009-01-01

The concept of a nanowire solar cell with photon-harvesting shells is presented. In this architecture, organic molecules which absorb strongly in the near infrared where silicon absorbs weakly are coupled to silicon nanowires (SiNWs). This enables

Closed-shell variational quantum Monte Carlo simulation for the ...

African Journals Online (AJOL)

Closed-shell variational quantum Monte Carlo simulation for the electric dipole moment calculation of hydrazine molecule using casino-code. ... Nigeria Journal of Pure and Applied Physics ... The variational quantum Monte Carlo (VQMC) technique used in this work employed the restricted Hartree-Fock (RHF) scheme.

Inactivation of Salmonella in Shell Eggs by Hot Water Immersion and Its Effect on Quality.

Science.gov (United States)

Geveke, David J; Gurtler, Joshua B; Jones, Deana R; Bigley, Andrew B W

2016-03-01

Thermal inactivation kinetics of heat resistant strains of Salmonella Enteritidis in shell eggs processed by hot water immersion were determined and the effects of the processing on egg quality were evaluated. Shell eggs were inoculated with a composite of heat resistant Salmonella Enteritidis (SE) strains PT8 C405, 2 (FSIS #OB030832), and 6 (FSIS #OB040159). Eggs were immersed in a circulating hot water bath for various times and temperatures. Come-up time of the coldest location within the egg was 21 min. SE was reduced by 4.5 log at both hot water immersion treatments of 56.7 C for 60 min and 55.6 °C for 100 min. Decimal reduction times (D-values) at 54.4, 55.6, and 56.7 °C were 51.8, 14.6, and 9.33 min, respectively. The z-value was 3.07 °C. Following treatments that resulted in a 4.5 log reduction (56.7 °C/60 min and 55.6 °C/100 min), the surviving population of SE remained static during 4 wk of refrigerated storage. After processing under conditions resulting in 4.5 log reductions, the Haugh unit and albumen height significantly increased (P eggs by 4.5 log, but also significantly affected several egg quality characteristics. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.

Amphiphilic hollow porous shell encapsulated Au@Pd bimetal nanoparticles for aerobic oxidation of alcohols in water

KAUST Repository

Zou, Houbing

2015-01-01

© The Royal Society of Chemistry 2015. This work describes the design, synthesis and analysis of an amphiphilic hollow mesoporous shell encapsulating catalytically active Au@Pd bimetal nanoparticles. The particles exhibited excellent catalytic activity and stability in the aerobic oxidation of primary and secondary alcohols to their corresponding aldehydes or ketones in water when using air as an oxidizing agent under atmospheric pressure.

Sound-structure interaction analysis of an infinite-long cylindrical shell submerged in a quarter water domain and subject to a line-distributed harmonic excitation

Science.gov (United States)

Guo, Wenjie; Li, Tianyun; Zhu, Xiang; Miao, Yuyue

2018-05-01

The sound-structure coupling problem of a cylindrical shell submerged in a quarter water domain is studied. A semi-analytical method based on the double wave reflection method and the Graf's addition theorem is proposed to solve the vibration and acoustic radiation of an infinite cylindrical shell excited by an axially uniform harmonic line force, in which the acoustic boundary conditions consist of a free surface and a vertical rigid surface. The influences of the complex acoustic boundary conditions on the vibration and acoustic radiation of the cylindrical shell are discussed. It is found that the complex acoustic boundary has crucial influence on the vibration of the cylindrical shell when the cylindrical shell approaches the boundary, and the influence tends to vanish when the distances between the cylindrical shell and the boundaries exceed certain values. However, the influence of the complex acoustic boundary on the far-field sound pressure of the cylindrical shell cannot be ignored. The far-field acoustic directivity of the cylindrical shell varies with the distances between the cylindrical shell and the boundaries, besides the driving frequency. The work provides more understanding on the vibration and acoustic radiation behaviors of cylindrical shells with complex acoustic boundary conditions.

Synthesis of soft shell poly(styrene) colloids for filtration experiments

DEFF Research Database (Denmark)

Hinge, Mogens

Separating a solid from a liquid is an important unit operation in many different industries e.g. mining, chemical, pharmaceutical and food industries. Solid liquid separation can roughly be divided into three groups. 1) Separation by gravity forces e.g. sedimentation, centrifugation, 2) Separation...... consisting of a solid poly(styrene) (PS) core with a water swollen shell have been employed in investigating the effect from varying amounts and type of water swollen material on filtration dewatering properties. Three series of model material have been used in this investigation 1) poly......(styrene-co-acrylic acid) core-shell colloids with varying thickness of the poly(acrylic acid) (PAA) shell. 2) poly(styrene-co-acrylic acid) core-shell colloids with varying diameter of the PS core and 3) poly(styrene-co-N-isopropylacrylamide) core-shell colloids with varying thickness of the poly...

On the nature of hydrogen bonding between the phosphatidylcholine head group and water and dimethylsulfoxide

Science.gov (United States)

Dabkowska, Aleksandra P.; Lawrence, M. Jayne; McLain, Sylvia E.; Lorenz, Christian D.

2013-01-01

Molecular dynamics simulations are used to provide a detailed investigation of the hydrogen bond networks around the phosphatidylcholine (PC) head group in 1,2-dipropionyl-sn-glycero-3-phosphocholine in pure water, 10 mol.% and 30 mol.% dimethylsulfoxide (DMSO)-water solutions. Specifically, it is observed that DMSO replaces those water molecules that are within the first solvation shell of the choline, phosphate and ester groups of the PC head group, but are not hydrogen-bonded to the group. The effect of the presence of DMSO on the hydrogen bond network around the PC head groups of the lipid changes with the concentration of DMSO. In comparison to the hydrogen bond network observed in the pure water system, the number of hydrogen-bonded chains of solvent molecules increases slightly for the 10 mol.% DMSO system, while, in the 30 mol.% DMSO system, the number of hydrogen-bonded chains of solvent molecules decreases.

Molecular single photon double K-shell ionization

International Nuclear Information System (INIS)

Penent, F.; Nakano, M.; Tashiro, M.; Grozdanov, T.P.; Žitnik, M.; Carniato, S.; Selles, P.; Andric, L.; Lablanquie, P.; Palaudoux, J.; Shigemasa, E.; Iwayama, H.; Hikosaka, Y.; Soejima, K.; Suzuki, I.H.; Kouchi, N.; Ito, K.

2014-01-01

We have studied single photon double K-shell ionization of small molecules (N 2 , CO, C 2 H 2n (n = 1–3), …) and the Auger decay of the resulting double core hole (DCH) molecular ions thanks to multi-electron coincidence spectroscopy using a magnetic bottle time-of-flight spectrometer. The relative cross-sections for single-site (K −2 ) and two-site (K −1 K −1 ) double K-shell ionization with respect to single K-shell (K −1 ) ionization have been measured that gives important information on the mechanisms of single photon double ionization. The spectroscopy of two-site (K −1 K −1 ) DCH states in the C 2 H 2n (n = 1–3) series shows important chemical shifts due to a strong dependence on the C-C bond length. In addition, the complete cascade Auger decay following single site (K −2 ) ionization has been obtained

Tube in shell heat exchangers

International Nuclear Information System (INIS)

Hayden, O.; Willby, C.R.; Sheward, G.E.; Ormrod, D.T.; Firth, G.F.

1980-01-01

An improved tube-in-shell heat exchanger to be used between liquid metal and water is described for use in the liquid metal coolant system of fast breeder reactors. It is stated that this design is less prone to failures which could result in sodium water reactions than previous exchangers. (UK)

Molecular hydrogen solvated in water – A computational study

International Nuclear Information System (INIS)

Śmiechowski, Maciej

2015-01-01

The aqueous hydrogen molecule is studied with molecular dynamics simulations at ambient temperature and pressure conditions, using a newly developed flexible and polarizable H 2 molecule model. The design and implementation of this model, compatible with an existing flexible and polarizable force field for water, is presented in detail. The structure of the hydration layer suggests that first-shell water molecules accommodate the H 2 molecule without major structural distortions and two-dimensional, radial-angular distribution functions indicate that as opposed to strictly tangential, the orientation of these water molecules is such that the solute is solvated with one of the free electron pairs of H 2 O. The calculated self-diffusion coefficient of H 2 (aq) agrees very well with experimental results and the time dependence of mean square displacement suggests the presence of caging on a time scale corresponding to hydrogen bond network vibrations in liquid water. Orientational correlation function of H 2 experiences an extremely short-scale decay, making the H 2 –H 2 O interaction potential essentially isotropic by virtue of rotational averaging. The inclusion of explicit polarizability in the model allows for the calculation of Raman spectra that agree very well with available experimental data on H 2 (aq) under differing pressure conditions, including accurate reproduction of the experimentally noted trends with solute pressure or concentration

Removal of toxic dichlorophenol from water by sorption with chemically activated carbon of almond shells - a green approach

International Nuclear Information System (INIS)

Jamil, N.; Ahsan, N.; Munwar, M.A.; Anwar, J.; Shafiq, U.

2011-01-01

Chloro phenols (CP) represents a group of organic compounds having substituted chlorines attached to phenol ring. These trace organic pollutants represent a major environmental concern, because of toxicity, non-biodegradability, carcinogenic and stubborn properties. The adsorption of 2, 4-dichlorophenol (DCP) by chemically activated carbon of almond shells (CAC-AS) has been studied in the batch setup. Operational parameters like adsorbent dose, pH, and shaking speed were investigated. Langmuir and Freundlich isotherms were employed to calculate adsorption capacity and other sorption features of CAC-AS. The maximum amount of DCP adsorbed was 24.3 mg per gram of activated carbon derived from almond shells. Optimum conditions for DCP uptake were 2.5 g adsorbent dose, pH 5 and agitation speed of 200 rpm whereas the concentration of DCP solution was 25 mg/L (50 mL). Results corroborated that almond shells pretreated chemically, can be an excellent low cost adsorbents for removal of DCP from contaminated water. (author)

Bandgap Engineering of InP QDs Through Shell Thickness and Composition

Energy Technology Data Exchange (ETDEWEB)

Dennis, Allison M. [Los Alamos National Laboratory; Mangum, Benjamin D. [Los Alamos National Laboratory; Piryatinski, Andrei [Los Alamos National Laboratory; Park, Young-Shin [Los Alamos National Laboratory; Htoon, Han [Los Alamos National Laboratory; Hollingsworth, Jennifer A. [Los Alamos National Laboratory

2012-06-21

Fields as diverse as biological imaging and telecommunications utilize the unique photophysical and electronic properties of nanocrystal quantum dots (NQDs). The development of new NQD compositions promises material properties optimized for specific applications, while addressing material toxicity. Indium phosphide (InP) offers a 'green' alternative to the traditional cadmium-based NQDs, but suffers from extreme susceptibility to oxidation. Coating InP cores with more stable shell materials significantly improves nanocrystal resistance to oxidation and photostability. We have investigated several new InP-based core-shell compositions, correlating our results with theoretical predictions of their optical and electronic properties. Specifically, we can tailor the InP core-shell QDs to a type-I, quasi-type-II, or type-II bandgap structure with emission wavelengths ranging from 500-1300 nm depending on the shell material used (ZnS, ZnSe, CdS, or CdSe) and the thickness of the shell. Single molecule microscopy assessments of photobleaching and blinking are used to correlate NQD properties with shell thickness.

Expansion connection of socket in flow distributed cabin of heavy water research reactor inner shell

International Nuclear Information System (INIS)

Jiang Zhiliang; Li Yanshui

1995-01-01

Expansion connection of aluminium alloy LT21 socket in flow distributed cabin of Heavy Water Research Reactor (HWRR) inner shell is described systematically. The expansion connection technology parameters of products are determined through tests. They are as following: bounce value of inner diameter after expansion, expansion degree, space between socket and plate hole, device for expanding pipes, selection of tools for enlarging or reaming holes, manufacture for socket inner hole and cleaning after expansion

Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

Science.gov (United States)

Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

2017-07-06

The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

Molecular Dynamics Study of Water Molecules in Interlayer of 14 ^|^Aring; Tobermorite

KAUST Repository

Yoon, Seyoon

2013-01-01

The molecular structure and dynamics of interlayer water of 14 Å tobermorite are investigated based on molecular dynamics (MD) simulations. Calculated structural parameters of the interlayer water configuration are in good agreement with current knowledge of the refined structure. The MD simulations provide detailed information on the position and mobility of the hydrogen and oxygen of interlayer water, as well as its self-diffusion coefficient, through the interlayer of 14 Å tobermorite. Comparison of the MD simulation results at 100 and 300 K demonstrates that water molecules in the interlayer maintain their structure but change their mobility. The dominant configuration and self-diffusion coefficient of interlayer water are obtained in this study. Copyright © 2013 Japan Concrete Institute.

Factors affecting the yield of bio-oil from the pyrolysis of coconut shell.

Science.gov (United States)

Gao, Yun; Yang, Yi; Qin, Zhanbin; Sun, Yi

2016-01-01

Coconut is a high-quality agricultural product of the Asia-Pacific region. In this paper, coconut shell which mainly composed of cellulose, hemicellulose, lignin was used as a raw material for coconut shell oil from coconut shell pyrolysis. The influence of the pyrolysis temperature, heating rate and particle size on coconut oil yield was investigated, and the effect of heating rate on coconut oil components was discussed. Experimental results show that the maximum oil yield of 75.74 wt% (including water) were obtained under the conditions that the final pyrolysis temperature 575 °C, heating rate 20 °C/min, coconut shell diameter about 5 mm. Thermal gravimetric analysis was used and it can be seen that coconut shell pyrolysis process can be divided into three stages: water loss, pyrolysis and pyrocondensation. The main components of coconut-shell oil are water (about 50 wt%), aromatic, phenolic, acid, ketone and ether containing compounds.

40 Years of Shell Scenarios

Energy Technology Data Exchange (ETDEWEB)

NONE

2013-02-15

Shell has been using scenario planning for four decades. During that time these scenarios have helped the company and governments across the world to make better strategic choices. Scenarios provide lenses that help see future prospects more clearly, make richer judgments and be more sensitive to uncertainties. Discover how the Shell Scenarios team has helped guide decision makers at major moments in history and get a peek at the team future focus, including the intricate relationship between energy, water and food.

Protection of a PWR nuclear power stations against corrosion using hydrogen molecules to capture oxygen molecules

International Nuclear Information System (INIS)

Nahili, M.

2004-01-01

A protection method for the primary loops metals of nuclear power plants from corrosion was investigated. Hydrogen molecules were added to the primary circuit to eliminate oxygen molecules produced by radiolysis of coolant at the reactor core. The hydrogen molecules were produced by electrolyses of water and then added when the coolant water was passing through the primary coolant circuit. Thermodynamical process and the protection methods from corrosion were discussed, the discussion emphasized on the removal of oxygen molecules as one of the protection methods, and compared with other methods. The amount of hydrogen molecules needed for complete removal of oxygen was estimated in two cases: in the case without passing the water through the oxygen removal system, and in the case of passing water through the system. A pressurized water reactor VVER was chosen to be investigated in this study. The amount of hydrogen molecules was estimated so as to eliminate completely the oxygen molecules from coolant water. The estimated value was found to be less than the permissible range for coolant water for such type of reactors. A simulation study for interaction mechanism between hydrogen and oxygen molecules as water flowing in a tube similar to that of coolant water was performed with different water flow velocities. The interaction between the molecules of hydrogen and oxygen was described. The gas diffusion at the surface of the tube was found to play a major role in the interaction. A mathematical model was found to give full description of the change of oxygen concentration through the tube, as well as, to calculate the length of the tube where the concentration of oxygen reduced to few order of magnitude. (Author)

Embedding of Hollow Polymer Microspheres with Hydrophilic Shell in Nafion Matrix as Proton and Water Micro-Reservoir

Directory of Open Access Journals (Sweden)

Zhaolin Liu

2012-08-01

Full Text Available Assimilating hydrophilic hollow polymer spheres (HPS into Nafion matrix by a loading of 0.5 wt % led to a restructured hydrophilic channel, composed of the pendant sulfonic acid groups (–SO₃H and the imbedded hydrophilic hollow spheres. The tiny hydrophilic hollow chamber was critical to retaining moisture and facilitating proton transfer in the composite membranes. To obtain such a tiny cavity structure, the synthesis included selective generation of a hydrophilic polymer shell on silica microsphere template and the subsequent removal of the template by etching. The hydrophilic HPS (100–200 nm possessed two different spherical shells, the styrenic network with pendant sulfonic acid groups and with methacrylic acid groups, respectively. By behaving as microreservoirs of water, the hydrophilic HPS promoted the Grotthus mechanism and, hence, enhanced proton transport efficiency through the inter-sphere path. In addition, the HPS with the –SO₃H borne shell played a more effective role than those with the –CO₂H borne shell in augmenting proton transport, in particular under low humidity or at medium temperatures. Single H₂-PEMFC test at 70 °C using dry H₂/O₂ further verified the impactful role of hydrophilic HPS in sustaining higher proton flux as compared to pristine Nafion membrane.

How the shape of an H-bonded network controls proton-coupled water activation in HONO formation.

Science.gov (United States)

Relph, Rachael A; Guasco, Timothy L; Elliott, Ben M; Kamrath, Michael Z; McCoy, Anne B; Steele, Ryan P; Schofield, Daniel P; Jordan, Kenneth D; Viggiano, Albert A; Ferguson, Eldon E; Johnson, Mark A

2010-01-15

Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)-bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

Cavity-ligand binding in a simple two-dimensional water model

Directory of Open Access Journals (Sweden)

G. Mazovec

2016-02-01

Full Text Available By means of Monte Carlo computer simulations in the isothermal-isobaric ensemble, we investigated the interaction of a hydrophobic ligand with the hydrophobic surfaces of various curvatures (planar, convex and concave. A simple two-dimensional model of water, hydrophobic ligand and surface was used. Hydration/dehidration phenomena concerning water molecules confined close to the molecular surface were investigated. A notable dewetting of the hydrophobic surfaces was observed together with the reorientation of the water molecules close to the surface. The hydrogen bonding network was formed to accommodate cavities next to the surfaces as well as beyond the first hydration shell. The effects were most strongly pronounced in the case of concave surfaces having large curvature. This simplified model can be further used to evaluate the thermodynamic fingerprint of the docking of hydrophobic ligands.

Carbon isotopes in mollusk shell carbonates

Science.gov (United States)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

Oxidation driven ZnS Core-ZnO shell photocatalysts under controlled oxygen atmosphere for improved photocatalytic solar water splitting

Science.gov (United States)

Bak, Daegil; Kim, Jung Hyeun

2018-06-01

Zinc type photocatalysts attract great attentions in solar hydrogen production due to their easy availability and benign environmental characteristics. Spherical ZnS particles are synthesized with a facile hydrothermal method, and they are further used as core materials to introduce ZnO shell layer surrounding the core part by partial oxidation under controlled oxygen contents. The resulting ZnS core-ZnO shell photocatalysts represent the heterostructural type II band alignment. The existence of oxide layer also influences on proton adsorption power with an aid of strong base cites derived from highly electronegative oxygen atoms in ZnO shell layer. Photocatalytic water splitting reaction is performed to evaluate catalyst efficiency under standard one sun condition, and the highest hydrogen evolution rate (1665 μmolg-1h-1) is achieved from the sample oxidized at 16.2 kPa oxygen pressure. This highest hydrogen production rate is achieved in cooperation with increased light absorption and promoted charge separations. Photoluminescence analysis reveals that the improved visible light response is obtained after thermal oxidation process due to the oxygen vacancy states in the ZnO shell layer. Therefore, overall photocatalytic efficiency in solar hydrogen production is enhanced by improved charge separations, crystallinity, and visible light responses from the ZnS core-ZnO shell structures induced by thermal oxidation.

Characterization of Physic nut (Jatropha curcas L.) shells

NARCIS (Netherlands)

Wever, Diego; Heeres, H. J.; Broekhuis, Antonius A.

The characterization of Physic nut shells was done using the wet chemical analysis of wood components. The obtained fractions were analyzed using IR, NMR, GPC, ICP and MALDI-TOF mass spectroscopy. TGA was used to determine the fixed carbon (+ash) and water content of the shells. The results of wet

Silica diatom shells tailored with Au nanoparticles enable sensitive analysis of molecules for biological, safety and environment applications

KAUST Repository

Onesto, V.; Villani, M.; Coluccio, M. L.; Majewska, R.; Alabastri, A.; Battista, E.; Schirato, A.; Calestani, D.; Coppedé , N.; Cesarelli, M.; Amato, F.; Di Fabrizio, Enzo M.; Gentile, F.

2018-01-01

Diatom shells are a natural, theoretically unlimited material composed of silicon dioxide, with regular patterns of pores penetrating through their surface. For their characteristics, diatom shells show promise to be used as low cost, highly efficient drug carriers, sensor devices or other micro-devices. Here, we demonstrate diatom shells functionalized with gold nanoparticles for the harvesting and detection of biological analytes (bovine serum albumin—BSA) and chemical pollutants (mineral oil) in low abundance ranges, for applications in bioengineering, medicine, safety, and pollution monitoring.

Silica diatom shells tailored with Au nanoparticles enable sensitive analysis of molecules for biological, safety and environment applications

KAUST Repository

Onesto, V.

2018-04-19

Diatom shells are a natural, theoretically unlimited material composed of silicon dioxide, with regular patterns of pores penetrating through their surface. For their characteristics, diatom shells show promise to be used as low cost, highly efficient drug carriers, sensor devices or other micro-devices. Here, we demonstrate diatom shells functionalized with gold nanoparticles for the harvesting and detection of biological analytes (bovine serum albumin—BSA) and chemical pollutants (mineral oil) in low abundance ranges, for applications in bioengineering, medicine, safety, and pollution monitoring.

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

Science.gov (United States)

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 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.

Evaluation of sanitizers for inactivating Salmonella on in-shell pecans and pecan nutmeats.

Science.gov (United States)

Beuchat, Larry R; Mann, David A; Alali, Walid Q

2012-11-01

Chlorine, organic acids, and water extracts of inedible pecan components were tested for effectiveness in killing Salmonella on pecans. In-shell pecans and nutmeats (U.S. Department of Agriculture medium pieces) were immersion inoculated with a mixture of five Salmonella serotypes, dried to 3.7% moisture, and stored at 4°C for 3 to 6 weeks. In-shell nuts were immersed in chlorinated water (200, 400, and 1,000 μg/ml), lactic acid (0.5, 1, and 2%), and levulinic acid (0.5, 1, and 2%) with and without 0.05% sodium dodecyl sulfate (SDS), and a mixed peroxyacid sanitizer (Tsunami 200, 40 μg/ml) for up to 20 min at 21°C. The rate of reduction of free chlorine in conditioning water decreased as the ratio of in-shell nuts/water was increased. The rate of reduction was more rapid when nuts were not precleaned before treatment. The initial population of Salmonella on in-shell nuts (5.9 to 6.3 log CFU/g) was reduced by 2.8 log CFU/g after treating with chlorinated water (1,000 μg/ml). Treatment with 2% lactic acid plus SDS or 2% levulinic acid plus SDS reduced the pathogen by 3.7 and 3.4 log CFU/g, respectively. Lactic and levulinic acids (2%) without SDS were less effective (3.3- and 2.1-log CFU/g reductions, respectively) than acids with SDS. Treatment with Tsunami 200 resulted in a 2.4-log CFU/g reduction. In-shell nuts and nutmeats were immersed in water extracts of ground pecan shucks (hulls), shells, a mixture of shells and pith, and pith. The general order of lethality of extracts to Salmonella was shuck pecans before conditioning in chlorinated water and the need for sanitizers with increased effectiveness in killing Salmonella on pecans.

A theoretical model investigation of peptide bond formation involving two water molecules in ribosome supports the two-step and eight membered ring mechanism

International Nuclear Information System (INIS)

Wang, Qiang; Gao, Jun; Zhang, Dongju; Liu, Chengbu

2015-01-01

Highlights: • We theoretical studied peptide bond formation reaction mechanism with two water molecules. • The first water molecule can decrease the reaction barriers by forming hydrogen bonds. • The water molecule mediated three-proton transfer mechanism is the favorable mechanism. • Our calculation supports the two-step and eight membered ring mechanism. - Abstract: The ribosome is the macromolecular machine that catalyzes protein synthesis. The kinetic isotope effect analysis reported by Strobel group supports the two-step mechanism. However, the destination of the proton originating from the nucleophilic amine is uncertain. A computational simulation of different mechanisms including water molecules is carried out using the same reaction model and theoretical level. Formation the tetrahedral intermediate with proton transfer from nucleophilic nitrogen, is the rate-limiting step when two water molecules participate in peptide bond formation. The first water molecule forming hydrogen bonds with O9′ and H15′ in the A site can decrease the reaction barriers. Combined with results of the solvent isotope effects analysis, we conclude that the three-proton transfer mechanism in which water molecule mediate the proton shuttle between amino and carbon oxygen in rate-limiting step is the favorable mechanism. Our results will shield light on a better understand the reaction mechanism of ribosome

Relationship between diffusivity of water molecules inside hydrating tablets and their drug release behavior elucidated by magnetic resonance imaging.

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Kikuchi, Shingo; Onuki, Yoshinori; Kuribayashi, Hideto; Takayama, Kozo

2012-01-01

We reported previously that sustained release matrix tablets showed zero-order drug release without being affected by pH change. To understand drug release mechanisms more fully, we monitored the swelling and erosion of hydrating tablets using magnetic resonance imaging (MRI). Three different types of tablets comprised of polyion complex-forming materials and a hydroxypropyl methylcellulose (HPMC) were used. Proton density- and diffusion-weighted images of the hydrating tablets were acquired at intervals. Furthermore, apparent self-diffusion coefficient maps were generated from diffusion-weighted imaging to evaluate the state of hydrating tablets. Our findings indicated that water penetration into polyion complex tablets was faster than that into HPMC matrix tablets. In polyion complex tablets, water molecules were dispersed homogeneously and their diffusivity was relatively high, whereas in HPMC matrix tablets, water molecule movement was tightly restricted within the gel. An optimal tablet formulation determined in a previous study had water molecule penetration and diffusivity properties that appeared intermediate to those of polyion complex and HPMC matrix tablets; water molecules were capable of penetrating throughout the tablets and relatively high diffusivity was similar to that in the polyion complex tablet, whereas like the HPMC matrix tablet, it was well swollen. This study succeeded in characterizing the tablet hydration process. MRI provides profound insight into the state of water molecules in hydrating tablets; thus, it is a useful tool for understanding drug release mechanisms at a molecular level.

Pasteurization of shell eggs using radio frequency heating

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The USDA-FSIS estimates that pasteurization of all shell eggs in the U.S. would reduce the annual number of illnesses by more than 110,000, yet less than 1% of shell eggs are commercially pasteurized. One of the main reasons for this is that the current process, hot water immersion, requires approxi...

Shell extracts of the edible mussel and oyster induce an enhancement of the catabolic pathway of human skin fibroblasts, in vitro.

Science.gov (United States)

Latire, Thomas; Legendre, Florence; Bouyoucef, Mouloud; Marin, Frédéric; Carreiras, Franck; Rigot-Jolivet, Muriel; Lebel, Jean-Marc; Galéra, Philippe; Serpentini, Antoine

2017-10-01

Mollusc shells are composed of more than 95% calcium carbonate and less than 5% organic matrix consisting mostly of proteins, glycoproteins and polysaccharides. In this study, we investigated the effects of matrix macromolecular components extracted from the shells of two edible molluscs of economic interest, i.e., the blue mussel Mytilus edulis and the Pacific oyster Crassostrea gigas. The potential biological activities of these organic molecules were analysed on human dermal fibroblasts in primary culture. Our results demonstrate that shell extracts of the two studied molluscs modulate the metabolic activities of the cells. In addition, the extracts caused a decrease of type I collagen and a concomitant increase of active MMP-1, both at the mRNA and the protein levels. Therefore, our results suggest that shell extracts from M. edulis and C. gigas contain molecules that promote the catabolic pathway of human dermal fibroblasts. This work emphasises the potential use of these shell matrices in the context of anti-fibrotic strategies, particularly against scleroderma. More generally, it stresses the usefulness to valorise bivalve shells that are coproducts of shellfish farming activity.

Selective control of photodissociation in deutereted water molecule HOD

International Nuclear Information System (INIS)

Adhikari, S.; Deshpande, Sarin; Sarma, Manabendra; Kurkal, Vandana; Mishra, M.K.

2006-01-01

Bond dissociation in the deutereted water molecule HOD has been investigated to explore the possibility of selective control of dissociation of O-H and O-D bonds using simple field profiles and initial states that do not require high overtone excitations. Preliminary results indicate that considerable selectivity in dissociation of O-H and O-D bonds can be achieved using fundamental and first overtone excitations only and use of field optimized initial state (FOIST) based scheme with appropriate choice of field parameters and initial states may enhance both selectivity and yield

Determination of iodate in iodized salt and water samples by shell-isolated nanoparticle-enhanced Raman spectroscopy

International Nuclear Information System (INIS)

Zhang, Kaige; Liang, Lizhen; Huang, Meiying; Hu, Yuling; Li, Gongke

2014-01-01

We have developed a simple, rapid, and sensitive method for the determination of iodate in iodized salt and water samples. The method is making use of shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and is based on the oxidation of hydroxylammonium chloride by iodate to produce nitrite which then is used to diazotize with p-nitroaniline. The resulting diazonium ion is then coupled to N-(1-naphthyl) ethylenediamine dihydrochloride to form an azo dye whose concentration is determined by SHINERS. The active substrate used in SHINERS is composed of gold nanoparticles coated with an ultrathin silica shell possessing pinholes on their surface. Various factors that influence the chemical reaction and the intensity of SHINERS were investigated. Under the optimal conditions, the Raman intensity is linearly related to the concentration of iodate in the 7.5–130.0 μg L−1 range, with a correlation coefficient of 0.9920. The limit of detection is 2.0 μg L−1, and the relative standard deviation is 7.5 % (for n = 5) at 1,138 cm−1 without additional sample pre-concentration. The method was successfully applied to the determination of iodate in iodized salt and water samples. The accuracy was assessed through recovery tests and independent analysis by a conventional titrimetric method. (author)

Linked-cluster perturbation theory for closed and open-shell systems: derivation of effective π-electron hamiltonians

International Nuclear Information System (INIS)

Brandow, B.H.

1977-01-01

The Brueckner--Goldstone form of linked-cluster perturbation theory is derived, together with its open-shell analog, by an elementary time-independent approach. This serves to focus attention on the physical interpretation of the results. The open-shell expansion is used to provide a straightforward justification for the effective π-electron Hamiltonians of planar organic molecules

NIF Double Shell outer/inner shell collision experiments

Science.gov (United States)

Merritt, E. C.; Loomis, E. N.; Wilson, D. C.; Cardenas, T.; Montgomery, D. S.; Daughton, W. S.; Dodd, E. S.; Desjardins, T.; Renner, D. B.; Palaniyappan, S.; Batha, S. H.; Khan, S. F.; Smalyuk, V.; Ping, Y.; Amendt, P.; Schoff, M.; Hoppe, M.

2017-10-01

Double shell capsules are a potential low convergence path to substantial alpha-heating and ignition on NIF, since they are predicted to ignite and burn at relatively low temperatures via volume ignition. Current LANL NIF double shell designs consist of a low-Z ablator, low-density foam cushion, and high-Z inner shell with liquid DT fill. Central to the Double Shell concept is kinetic energy transfer from the outer to inner shell via collision. The collision determines maximum energy available for compression and implosion shape of the fuel. We present results of a NIF shape-transfer study: two experiments comparing shape and trajectory of the outer and inner shells at post-collision times. An outer-shell-only target shot measured the no-impact shell conditions, while an `imaging' double shell shot measured shell conditions with impact. The `imaging' target uses a low-Z inner shell and is designed to perform in similar collision physics space to a high-Z double shell but can be radiographed at 16keV, near the viable 2DConA BL energy limit. Work conducted under the auspices of the U.S. DOE by LANL under contract DE-AC52-06NA25396.

Chemical Composition of Apricot Pit Shells and Effect of Hot-Water Extraction

Directory of Open Access Journals (Sweden)

Derek B. Corbett

2015-09-01

Full Text Available Agricultural residues, such as corn stover, wheat straw, and nut shells show promise as feedstocks for lignocellulosic biorefinery due to their relatively high polysaccharide content and low or no nutritional value for human consumption. Apricot pit shells (APS were studied in this work to assess their potential for use in a biorefinery. Hot water extraction (HWE; 160 °C, 2 h, proposed to remove easily accessible hemicelluloses, was performed to evaluate the susceptibility of APS to this mild pretreatment process. The chemical composition of APS before and after HWE (EAPS was analyzed by standard methods and 1H-NMR. A low yield of the remaining HW-extracted APS (~59% indicated that APS are highly susceptible to this pretreatment method. 1H-NMR analysis of EAPS revealed that ~77% of xylan present in raw APS was removed along with ~24% of lignin. The energy of combustion of APS was measured before and after HWE showing a slight increase due to HWE (1.61% increase. Near infrared radiation spectroscopy (NIRS, proposed as a quick non-invasive method of biomass analysis, was performed. NIRS corroborated results of traditional analysis and 1H-NMR. Determination of antioxidizing activity (AOA of APS extracts was also undertaken. AOA of organic APS extracts were shown to be more than 20 times higher than that of a synthetic antioxidizing agent.

Synthesis of low density foam shells for inertial confinement fusion experiments

International Nuclear Information System (INIS)

Lattaud, Cecile

2011-01-01

This work deals with the fabrication process of low density foam shells and the sharp control of their shape (diameter, thickness, density, sphericity, non-concentricity). During this PhD we focused on the non-concentricity criterion which has to be lower than 1%. The shells are synthesized using a microencapsulation process leading to a double emulsion and followed by a thermal polymerization at 60 C. According to the literature, three major parameters, the density of the three phases, the deformations of the shells along the process and the kinetics of the polymerization have a direct influence on the shells non-concentricity. The results obtained showed that when the density gap between the internal water phase and the organic phase increases, the TMPTMA shells non-concentricity improves. A density gap of 0.078 g.cm -3 at 60 C, leads to an average non-concentricity of 2.4% with a yield of shells of 58%. It was also shown that the synthesis process can be considered as reproducible. While using the same internal water phase, equivalent non-concentricity results are obtained using either a straight tube, a tube with areas of constriction or a short wound tube. The time required to fix the shell's shape is at least 20 minutes with thermal polymerization. So, it seems that the time spent by the shells inside the rotating flask allows the centering of the internal water phase inside the organic phase, whatever the circulation process used. In order to get higher polymerization rates and to avoid destabilization phenomena, we then focused our study on photo polymerization. When the synthesis is performed using a UV lamp with an efficient light intensity, the shells have a slightly higher thickness than the shells synthesized by thermal polymerization. Moreover, a really higher yield, around 80%, is achieved with UV polymerization. However, the average non-concentricity of the shells synthesized lays around 20%, which is really high compared to the 2.4% average

Energy-switching potential energy surface for the water molecule revisited: A highly accurate singled-sheeted form.

Science.gov (United States)

Galvão, B R L; Rodrigues, S P J; Varandas, A J C

2008-07-28

A global ab initio potential energy surface is proposed for the water molecule by energy-switching/merging a highly accurate isotope-dependent local potential function reported by Polyansky et al. [Science 299, 539 (2003)] with a global form of the many-body expansion type suitably adapted to account explicitly for the dynamical correlation and parametrized from extensive accurate multireference configuration interaction energies extrapolated to the complete basis set limit. The new function mimics also the complicated Sigma/Pi crossing that arises at linear geometries of the water molecule.

Hyperfine structure of 2Σ molecules containing alkaline-earth-metal atoms

Science.gov (United States)

Aldegunde, Jesus; Hutson, Jeremy M.

2018-04-01

Ultracold molecules with both electron spin and an electric dipole moment offer new possibilities in quantum science. We use density-functional theory to calculate hyperfine coupling constants for a selection of molecules important in this area, including RbSr, LiYb, RbYb, CaF, and SrF. We find substantial hyperfine coupling constants for the fermionic isotopes of the alkaline-earth-metal and Yb atoms. We discuss the hyperfine level patterns and Zeeman splittings expected for these molecules. The results will be important both to experiments aimed at forming ultracold open-shell molecules and to their applications.

Direct numerical solution of the Ornstein-Zernike integral equation and spatial distribution of water around hydrophobic molecules

Science.gov (United States)

Ikeguchi, Mitsunori; Doi, Junta

1995-09-01

The Ornstein-Zernike integral equation (OZ equation) has been used to evaluate the distribution function of solvents around solutes, but its numerical solution is difficult for molecules with a complicated shape. This paper proposes a numerical method to directly solve the OZ equation by introducing the 3D lattice. The method employs no approximation the reference interaction site model (RISM) equation employed. The method enables one to obtain the spatial distribution of spherical solvents around solutes with an arbitrary shape. Numerical accuracy is sufficient when the grid-spacing is less than 0.5 Å for solvent water. The spatial water distribution around a propane molecule is demonstrated as an example of a nonspherical hydrophobic molecule using iso-value surfaces. The water model proposed by Pratt and Chandler is used. The distribution agrees with the molecular dynamics simulation. The distribution increases offshore molecular concavities. The spatial distribution of water around 5α-cholest-2-ene (C27H46) is visualized using computer graphics techniques and a similar trend is observed.

Molecular multipole moments of water molecules in ice Ih

International Nuclear Information System (INIS)

Batista, E.R.; Xantheas, S.S.; Jonsson, H.

1998-01-01

We have used an induction model including dipole, dipole endash quadrupole, quadrupole endash quadrupole polarizability and first hyperpolarizability as well as fixed octopole and hexadecapole moments to study the electric field in ice. The self-consistent induction calculations gave an average total dipole moment of 3.09 D, a 67% increase over the dipole moment of an isolated water molecule. A previous, more approximate induction model study by Coulson and Eisenberg [Proc. R. Soc. Lond. A 291, 445 (1966)] suggested a significantly smaller average value of 2.6 D. This value has been used extensively in recent years as a reference point in the development of various polarizable interaction potentials for water as well as for assessment of the convergence of water cluster properties to those of bulk. The reason for this difference is not due to approximations made in the computational scheme of Coulson and Eisenberg but rather due to the use of less accurate values for the molecular multipoles in these earlier calculations. copyright 1998 American Institute of Physics

Insight into the molecular mechanism of water evaporation via the finite temperature string method.

Science.gov (United States)

Musolino, Nicholas; Trout, Bernhardt L

2013-04-07

The process of water's evaporation at its liquid/air interface has proven challenging to study experimentally and, because it constitutes a rare event on molecular time scales, presents a challenge for computer simulations as well. In this work, we simulated water's evaporation using the classical extended simple point charge model water model, and identified a minimum free energy path for this process in terms of 10 descriptive order parameters. The measured free energy change was 7.4 kcal/mol at 298 K, in reasonable agreement with the experimental value of 6.3 kcal/mol, and the mean first-passage time was 1375 ns for a single molecule, corresponding to an evaporation coefficient of 0.25. In the observed minimum free energy process, the water molecule diffuses to the surface, and tends to rotate so that its dipole and one O-H bond are oriented outward as it crosses the Gibbs dividing surface. As the water molecule moves further outward through the interfacial region, its local density is higher than the time-averaged density, indicating a local solvation shell that protrudes from the interface. The water molecule loses donor and acceptor hydrogen bonds, and then, with its dipole nearly normal to the interface, stops donating its remaining hydrogen bond. At that point, when the final, accepted hydrogen bond is broken, the water molecule is free. We also analyzed which order parameters are most important in the process and in reactive trajectories, and found that the relative orientation of water molecules near the evaporating molecule, and the number of accepted hydrogen bonds, were important variables in reactive trajectories and in kinetic descriptions of the process.

Pentachlorophenol removal from aqueous matrices by sorption with almond shell residues

International Nuclear Information System (INIS)

Estevinho, B.N.; Ratola, N.; Alves, A.; Santos, L.

2006-01-01

Sorption with activated carbon has been the technique preferred for pentachlorophenol (PCP) removal from contaminated waters, but regeneration needs and high operation costs are supporting a renewed interest in the search for alternative sorbents. Among them, almond shell, an agricultural by-product, provides interesting economical advantages, once shells account for 50% (in mass) of the whole almond. In this work, the capacity of almond shells to remove PCP from waters without previous activation was studied in batch conditions. While PCP analysis was performed solid-phase microextraction (SPME) followed by gas chromatography with electron capture detection (GC-ECD), mercury porosimetry and Fourier transform infrared spectroscopy (FTIR) provided a preliminary physical and chemical characterization of the sorbent. Almond shells were essentially a macroporous material, with an average surface area of 12.9 ± 2.8 m 2 /g. The efficiency of PCP removal was 93 ± 14%, in 24 h, with an initial concentration of 100 μg/l PCP and 5 μg PCP/g shell. Isotherm data adjusted better to Freundlich equation, where K F and 1/n were 0.075 ± 0.081 mg 1-1/n l 1/n and 1.882 ± 0.289, respectively. Average desorption efficiency was 7%, indicating strong adsorption capacity. Results proved that almond shells may be an excellent low-cost alternative for PCP removal from contaminated waters

Dynamics of ligand exchange mechanism at Cu(II) in water: an ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region.

Science.gov (United States)

Moin, Syed Tarique; Hofer, Thomas S; Weiss, Alexander K H; Rode, Bernd M

2013-07-07

Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment.

Dynamics of ligand exchange mechanism at Cu(II) in water: An ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region

International Nuclear Information System (INIS)

Moin, Syed Tarique; Hofer, Thomas S.; Weiss, Alexander K. H.; Rode, Bernd M.

2013-01-01

Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment

Vibrio cholerae Colonization of Soft-Shelled Turtles.

Science.gov (United States)

Wang, Jiazheng; Yan, Meiying; Gao, He; Lu, Xin; Kan, Biao

2017-07-15

Vibrio cholerae is an important human pathogen and environmental microflora species that can both propagate in the human intestine and proliferate in zooplankton and aquatic organisms. Cholera is transmitted through food and water. In recent years, outbreaks caused by V. cholerae -contaminated soft-shelled turtles, contaminated mainly with toxigenic serogroup O139, have been frequently reported, posing a new foodborne disease public health problem. In this study, the colonization by toxigenic V. cholerae on the body surfaces and intestines of soft-shelled turtles was explored. Preferred colonization sites on the turtle body surfaces, mainly the carapace and calipash of the dorsal side, were observed for the O139 and O1 strains. Intestinal colonization was also found. The colonization factors of V. cholerae played different roles in the colonization of the soft-shelled turtle's body surface and intestine. Mannose-sensitive hemagglutinin (MSHA) of V. cholerae was necessary for body surface colonization, but no roles were found for toxin-coregulated pili (TCP) or N -acetylglucosamine-binding protein A (GBPA). Both TCP and GBPA play important roles for colonization in the intestine, whereas the deletion of MSHA revealed only a minor colonization-promoting role for this factor. Our study demonstrated that V. cholerae can colonize the surfaces and the intestines of soft-shelled turtles and indicated that the soft-shelled turtles played a role in the transmission of cholera. In addition, this study showed that the soft-shelled turtle has potential value as an animal model in studies of the colonization and environmental adaption mechanisms of V. cholerae in aquatic organisms. IMPORTANCE Cholera is transmitted through water and food. Soft-shelled turtles contaminated with Vibrio cholerae (commonly the serogroup O139 strains) have caused many foodborne infections and outbreaks in recent years, and they have become a foodborne disease problem. Except for epidemiological

Solvation of actinide salts in water using a polarizable continuum model.

Science.gov (United States)

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

Structural analysis on mutation residues and interfacial water molecules for human TIM disease understanding

Science.gov (United States)

2013-01-01

Background Human triosephosphate isomerase (HsTIM) deficiency is a genetic disease caused often by the pathogenic mutation E104D. This mutation, located at the side of an abnormally large cluster of water in the inter-subunit interface, reduces the thermostability of the enzyme. Why and how these water molecules are directly related to the excessive thermolability of the mutant have not been investigated in structural biology. Results This work compares the structure of the E104D mutant with its wild type counterparts. It is found that the water topology in the dimer interface of HsTIM is atypical, having a "wet-core-dry-rim" distribution with 16 water molecules tightly packed in a small deep region surrounded by 22 residues including GLU104. These water molecules are co-conserved with their surrounding residues in non-archaeal TIMs (dimers) but not conserved across archaeal TIMs (tetramers), indicating their importance in preserving the overall quaternary structure. As the structural permutation induced by the mutation is not significant, we hypothesize that the excessive thermolability of the E104D mutant is attributed to the easy propagation of atoms' flexibility from the surface into the core via the large cluster of water. It is indeed found that the B factor increment in the wet region is higher than other regions, and, more importantly, the B factor increment in the wet region is maintained in the deeply buried core. Molecular dynamics simulations revealed that for the mutant structure at normal temperature, a clear increase of the root-mean-square deviation is observed for the wet region contacting with the large cluster of interfacial water. Such increase is not observed for other interfacial regions or the whole protein. This clearly suggests that, in the E104D mutant, the large water cluster is responsible for the subunit interface flexibility and overall thermolability, and it ultimately leads to the deficiency of this enzyme. Conclusions Our study

Vibrations of composite circular shell structures due to transient loads

International Nuclear Information System (INIS)

Schrader, K.-H.; Krutzik, N.; Winkel, G.

1975-01-01

Referring to a container consisting of different shell structures - such as spherical, cylindrical and conical shells - the dynamic behavior of coupled spatial shell structures due to transient loads will be investigated. The spatial structure including the filling of water will be idealized as a three-dimensional model consisting of ring elements. The influence of the water filling on the vibrations will be considered by virtual masses added to the shell structures. In circular direction as well as in meridional direction a consistent mass model has been used. By variation of the virtual masses it will be clarified, how these additional masses influence the vibrational behavior of the composed system. Another aspect which will be investigated is the influence of different stiffnesses of substructures or parts of substructures on the natural frequencies, and on their affiliated eigensystems. Furthermore, the maximum and minimum stresses in the structures caused by transient loads acting on the inner surface of the shells will be explored. Here it seems to be possible to locate an area of maximum strain. Rotational loads as well as nonrotational loads will be considered

Finite-bias electronic transport of molecules in a water solution

KAUST Repository

Rungger, Ivan

2010-06-04

The effects of water wetting conditions on the transport properties of molecular nanojunctions are investigated theoretically by using a combination of empirical-potential molecular-dynamics and first-principles electronic-transport calculations. These are at the level of the nonequilibrium Green’s-function method implemented for self-interaction corrected density-functional theory. We find that water effectively produces electrostatic gating to the molecular junction with a gating potential determined by the time-averaged water dipole field. Such a field is large for the polar benzene-dithiol molecule, resulting in a transmission spectrum shifted by about 0.6 eV with respect to that of the dry junction. The situation is drastically different for carbon nanotubes (CNTs). In fact, because of their hydrophobic nature the gating is almost negligible so that the average transmission spectrum of wet Au/CNT/Au junctions is essentially the same as that in dry conditions. This suggests that CNTs can be used as molecular interconnects also in water-wet situations, for instance, as tips for scanning tunnel microscopy in solution or in biological sensors.

Finite-bias electronic transport of molecules in a water solution

KAUST Repository

Rungger, Ivan; Chen, X.; Sanvito, Stefano; Schwingenschlö gl, Udo

2010-01-01

The effects of water wetting conditions on the transport properties of molecular nanojunctions are investigated theoretically by using a combination of empirical-potential molecular-dynamics and first-principles electronic-transport calculations. These are at the level of the nonequilibrium Green’s-function method implemented for self-interaction corrected density-functional theory. We find that water effectively produces electrostatic gating to the molecular junction with a gating potential determined by the time-averaged water dipole field. Such a field is large for the polar benzene-dithiol molecule, resulting in a transmission spectrum shifted by about 0.6 eV with respect to that of the dry junction. The situation is drastically different for carbon nanotubes (CNTs). In fact, because of their hydrophobic nature the gating is almost negligible so that the average transmission spectrum of wet Au/CNT/Au junctions is essentially the same as that in dry conditions. This suggests that CNTs can be used as molecular interconnects also in water-wet situations, for instance, as tips for scanning tunnel microscopy in solution or in biological sensors.

Mixing of alcohol and water molecules studied by neutron probe. Structure and dynamics

International Nuclear Information System (INIS)

Yoshida, Koji

2001-01-01

Structure of water/alcohol mixing solution was studied by three methods such as an isotope-exchanged neutron scattering method, RISM (Reference Interaction Site Model) integral equation and a neutron spin echo method. The principle of methods, experiments and results were reported. The results of experiments of water/tert-butyl alcohol (TBA) solution by the isotope-exchange neutron scattering method showed TBA molecule associated with each other through end methyl group. Especially this effect was the largest at x TBA = 0.06 and decreased with increasing the concentration of TBA. However, hydrogen bonding of TBA was very rare at x TBA = 0.06. By the partial radial distribution function obtained from RISM integral equation, it indicated that the structure of pure TBA became chain structure by hydrogen bond but changed to the structure contacted directly each hydrophobic group with increasing the concentration of water. Water/2-butoxyethanol (BE) mixing solution was measured by a neutron spin echo method. The activation energy of the diffusion coefficients obtained agreed to the energy of hydrogen bonding. The temperature response of diffusion coefficients showed the inverse of the experimental results obtained by the dynamic light scattering method. The difference between two measurement methods was different time scale and space scale. Namely, the object of the neutron scattering method is nano meter and nano second, but one of light scattering method many times over. It was proved from the above results that there was the cluster consisted of the same kind of molecule in the homogeneous two components solution, but the cluster was not stable and constantly exchanged with molecule, where the production and decay of the cluster is repeated at about nano sec. (S.Y.)

Fabrication and evaluation of Au-Pd core-shell nanocomposites for dechlorination of diclofenac in water.

Science.gov (United States)

Wang, Xu; Li, Jian-Rong; Fu, Ming-Lai; Yuan, Baoling; Cui, Hao-Jie; Wang, Ya-Fen

2015-01-01

Nanocomposites with core-shell structure usually exhibit excellent catalytic properties due to unique interfaces and synergistic effect among composites. In this study, Au-Pd bimetallic nanoparticles (NPs) with core-shell structure (Au-Pd cs) by using Au NPs as core and Pd as shell were successfully fabricated and, for the first time, were used to investigate the dechlorination of diclofenac (DCF) at H2 atmosphere in water at room temperature. The degradation products were studied as well by using HPLC/Q-ToF MS/MS. The operational factors such as pH and composition of the Au-Pd cs were also studied. The results showed that nearly 100% of DCF (30 mg L(-1), 50 mL, pH=7) was dechlorinated in 4.5 h by 10 mL of 56 mg L(-1) of Au-Pd cs. Ninety per cent of DCF was degraded in 6.5 h by the mixture of Au and Pd NPs. However, the individual Au NPs had no obvious effect in degrading DCF and the monometallic Pd NPs with comparable concentration only degraded less than 20% of DCF. Furthermore, the reaction mechanism of this catalytic process was studied in detail. It was found that the degradation was a second-order exponential reaction. The two main degradation products were obtained by cleaving the carbon-halogen bond of DCF and this made the degradation products more environmentally friendly.

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

International Nuclear Information System (INIS)

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

2016-01-01

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 10 8 –10 9 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 ⋅ 10 8 V m −1 ) when in the fluid phase with a monovalent counter-ion and ∼1.4 V (∼2.8 ⋅ 10 8 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

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

Energy Technology Data Exchange (ETDEWEB)

Rønnest, A. K.; Peters, G. H.; Hansen, F. Y., E-mail: flemming@kemi.dtu.dk [Department of Chemistry, Technical University of Denmark, IK 207 DTU, DK-2800 Lyngby (Denmark); Taub, H.; Miskowiec, A. [Department of Physics and Astronomy and the University of Missouri Research Reactor,University of Missouri, Columbia, Missouri 65211 (United States)

2016-04-14

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 10{sup 8}–10{sup 9} V m{sup −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 ⋅ 10{sup 8} V m{sup −1}) when in the fluid phase with a monovalent counter-ion and ∼1.4 V (∼2.8 ⋅ 10{sup 8} V m{sup −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

Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

KAUST Repository

Shinagawa, Tatsuya

2015-01-01

Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.

Gastropod shell size and architecture influence the applicability of methods used to estimate internal volume.

Science.gov (United States)

Ragagnin, Marilia Nagata; Gorman, Daniel; McCarthy, Ian Donald; Sant'Anna, Bruno Sampaio; de Castro, Cláudio Campi; Turra, Alexander

2018-01-11

Obtaining accurate and reproducible estimates of internal shell volume is a vital requirement for studies into the ecology of a range of shell-occupying organisms, including hermit crabs. Shell internal volume is usually estimated by filling the shell cavity with water or sand, however, there has been no systematic assessment of the reliability of these methods and moreover no comparison with modern alternatives, e.g., computed tomography (CT). This study undertakes the first assessment of the measurement reproducibility of three contrasting approaches across a spectrum of shell architectures and sizes. While our results suggested a certain level of variability inherent for all methods, we conclude that a single measure using sand/water is likely to be sufficient for the majority of studies. However, care must be taken as precision may decline with increasing shell size and structural complexity. CT provided less variation between repeat measures but volume estimates were consistently lower compared to sand/water and will need methodological improvements before it can be used as an alternative. CT indicated volume may be also underestimated using sand/water due to the presence of air spaces visible in filled shells scanned by CT. Lastly, we encourage authors to clearly describe how volume estimates were obtained.

Core-shell particles as model compound for studying fouling

DEFF Research Database (Denmark)

Christensen, Morten Lykkegaard; Nielsen, Troels Bach; Andersen, Morten Boel Overgaard

2008-01-01

Synthetic colloidal particles with hard cores and soft, water-swollen shells were used to study cake formation during ultrafiltration. The total cake resistance was lowest for particles with thick shells, which indicates that interparticular forces between particles (steric hindrance...... and electrostatic repulsion) influenced cake formation. At low pressure the specific cake resistance could be predicted from the Kozeny-Carman equation. At higher pressures, the resistance increased due to cake compression. Both cake formation and compression were reversible. For particles with thick shells...

Preparation of water-soluble CdTe/CdS core/shell quantum dots with enhanced photostability

International Nuclear Information System (INIS)

Peng Hui; Zhang Lijuan; Soeller, Christian; Travas-Sejdic, Jadranka

2007-01-01

CdTe/CdS core/shell quantum dots (QDs) have been synthesized in an aqueous phase using thioacetamide as a sulfur source. The quantum yield was greatly enhanced by the epitaxial growth of a CdS shell, which was confirmed by X-ray photoelectron spectroscopy (XPS) results. The quantum yield of as-prepared CdTe/CdS core/shell QDs without any post-preparative processing reached 58%. The experimental results illustrate that the QDs with core/shell structure show better photostability than thioglycolic acid (TGA)-capped CdTe QDs. The cyclic voltammograms reveal higher oxidation potentials for CdTe/CdS core/shell QDs than for TGA-capped CdTe QDs, which explains the superior photostability of QDs with a core/shell structure. This enhanced photostability makes these QDs with core/shell structure more suitable for bio-labeling and imaging

High ink absorption performance of inkjet printing based on SiO2@Al13 core-shell composites

Science.gov (United States)

Chen, YiFan; Jiang, Bo; Liu, Li; Du, Yunzhe; Zhang, Tong; Zhao, LiWei; Huang, YuDong

2018-04-01

The increasing growth of the inkjet market makes the inkjet printing more necessary. A composite material based on core-shell structure has been developed and applied to prepare inkjet printing layer. In this contribution, the ink printing record layers based on SiO2@Al13 core-shell composite was elaborated. The prepared core-shell composite materials were characterized by X-ray photoelectron spectroscopy (XPS), zeta potential, X-ray diffraction (XRD), scanning electron microscopy (SEM). The results proved the presence of electrostatic adsorption between SiO2 molecules and Al13 molecules with the formation of the well-dispersed system. In addition, based on the adsorption and the liquid permeability analysis, SiO2@Al13 ink printing record layer achieved a relatively high ink uptake (2.5 gmm-1) and permeability (87%), respectively. The smoothness and glossiness of SiO2@Al13 record layers were higher than SiO2 record layers. The core-shell structure facilitated the dispersion of the silica, thereby improved its ink absorption performance and made the clear printed image. Thus, the proposed procedure based on SiO2@Al13 core-shell structure of dye particles could be applied as a promising strategy for inkjet printing.

Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

KAUST Repository

Shinagawa, Tatsuya; Takanabe, Kazuhiro

2015-01-01

Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed

Novel fluorescent core-shell nanocontainers for cell membrane transport.

Science.gov (United States)

Yin, Meizhen; Kuhlmann, Christoph R W; Sorokina, Ksenia; Li, Chen; Mihov, George; Pietrowski, Eweline; Koynov, Kaloian; Klapper, Markus; Luhmann, Heiko J; Müllen, Klaus; Weil, Tanja

2008-05-01

The synthesis and characterization of novel core-shell macromolecules consisting of a fluorescent perylene-3,4,9,10-tetracarboxdiimide chromophore in the center surrounded by a hydrophobic polyphenylene shell as a first and a flexible hydrophilic polymer shell as a second layer was presented. Following this strategy, several macromolecules bearing varying polymer chain lengths, different polymer shell densities, and increasing numbers of positive and negative charges were achieved. Because all of these macromolecules reveal a good water solubility, their ability to cross cellular membranes was investigated. In this way, a qualitative relationship between the molecular architecture of these macromolecules and the biological response was established.

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

DEFF Research Database (Denmark)

Rønnest, A. K.; Peters, Günther H.J.; Hansen, Flemming Yssing

2016-01-01

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...... 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...

Approximative Krieger-Nelkin orientation averaging and anisotropy of water molecules vibrations; Aproksimativno Krieger-Nelkinovo orijentacijsko usrednjenje i anozotropija vibracija molekula lake vode

Energy Technology Data Exchange (ETDEWEB)

Markovic, M I [Elektrothenicki fakultet, Belgrade (Yugoslavia)

1974-07-01

Quantum-mechanics approach of water molecules dynamics should be taken into account for precise theoretical calculation of differential scattering cross sections of neutrons. Krieger and Nelkin have proposed an approximate method for averaging orientation of molecules regarding directions of incoming and scattered neutron. This paper shows that this approach can be successfully applied for general shape of water molecule vibration anisotropy.

Development of Special Tools for the Straightness Measurement of JRTR Core Inner Shell

International Nuclear Information System (INIS)

Sinjlawi, Abdullah; Cho, Yeong-Garp; Chung, Jong-Ha

2014-01-01

Jordan Research and Training Reactor (JRTR) is an open pool type nuclear research reactor, 5 MW power, JRTR core made from Zircaloy. The JRTR will be used for nuclear applications such as isotopes production, nuclear researches, neutron transmutation doping (NTD), and training. JRTR core structures will be exposed to a large amount of neutron irradiation during the life time of the reactor. The core inner shell also will be exposed to a pressure that comes from heavy water system. JRTR core inner shell will deform due to the neutron irradiation and the mechanical stress. Therefore, the dimensional change of the core inner shell should be periodically (every 10 years) measured as an in-service inspection to confirm the structural integrity. As a result of neutron irradiation, pressure difference of the heavy water vessel, and the mechanical stress, the reactor core will deform as shown in figure 2 to figure 4. The maximum deformation to the normal direction of inner shell wall is 0.75 mm as shown in figure 3. This study discusses development of special tools that will be used for pre-service and in-service inspection of JRTR inner shell. The performance and procedure for the measurements tools will be verified using by the real inner shell of the heavy water vessel at factory before shipping to Jordan.. There will be very delicate working procedure for the measurement in the limited space in JRTR core. Therefore, we will develop the detail procedures to cover the removal of the core components, installation of the measurement tools, measurement, and re-installation of the core components. The measurement of the inner shell at JAEC site during commissioning stage will be the first remote measurement at the same conditions of pool water and heavy water system

Shell Thickness Dependence of Interparticle Energy Transfer in Core-Shell ZnSe/ZnSe Quantum Dots Doping with Europium

Science.gov (United States)

Liu, Ni; Li, Shuxin; Wang, Caifeng; Li, Jie

2018-04-01

Low-toxic core-shell ZnSe:Eu/ZnS quantum dots (QDs) were prepared through two steps in water solution: nucleation doping and epitaxial shell grown. The structural and morphological characteristics of ZnSe/ZnS:Eu QDs with different shell thickness were explored by transmission electron microscopy (TEM) and X-ray diffraction (XRD) results. The characteristic photoluminescence (PL) intensity of Eu ions was enhanced whereas that of band-edge luminescence and defect-related luminescence of ZnSe QDs was decreased with increasing shell thickness. The transformation of PL intensity revealed an efficient energy transfer process between ZnSe and Eu. The PL intensity ratio of Eu ions ( I 613) to ZnSe QDs ( I B ) under different shell thickness was systemically analyzed by PL spectra and time-resolved PL spectra. The obtained results were in agreement with the theory analysis results by the kinetic theory of energy transfer, revealing that energy was transmitted in the form of dipole-electric dipole interaction. This particular method of adjusting luminous via changing the shell thickness can provide valuable insights towards the fundamental understanding and application of QDs in the field of optoelectronics.

Mussel shell evaluation as bioindicator for heavy metals

Energy Technology Data Exchange (ETDEWEB)

Andrello, Avacir Casanova; Lopes, Fabio; Galvao, Tiago D. [Universidade Estadual de Londrina (UEL), PR (Brazil). Dept. de Fisica. Lab. de Fisica Nuclear Aplicada

2009-07-01

Full text: Recently, in Brazil, it has been appearing a new and unusual 'plague' in leisure and commercial fishing, caused by the parasitic larval phase of certain native bivalve mollusks of fresh water known as 'Naiades'. Such situation involves the presence of big bivalve of fresh water, mainly Anodontites trapesialis, in the tanks and dams of the fish creation, such bivalve mollusks belonging to the Ordem Unionoida and the Familia Mycetopodidae. The present work objectified to analyze the shells of such mollusks to verify the possibility of such mollusks as bioindicators of heavy metals in fresh water. The mollusks shells were collected in a commercial fishing at Londrina-PR, and analyzed qualitatively to determine the chemical composition and possible correlation with existent heavy metals in the aquatic environment. Studies of the literature have been showing that those mollusks are susceptible the existent chemical alterations in the aquatic environment due to anthropogenic action. Three different shells were analyzed, with the measures done on the external and internal side, using a portable Energy Dispersive X-Ray Fluorescence system (PXRF-LFNA-02). The measures were realized in the applied nuclear physics laboratory of State University of Londrina, and the PXRF-LFNA-02 is composed by a X-Ray tube (with Ag target and filter) with potency of 4W, and a detector Si-PIN model XR-100CR of Ampetc Inc. with resolution of 221eV for the line of 5.9 keV of the {sup 55}Fe (with a 25{mu}m Be window thickness and Ag collimator), Current 10 mA and High Voltage 28 kV. In the internal part of shells were identified the elements Ca, P, Fe, Mn and Sr and in the external part were identified Ca, P, Fe, Mn, Sr and Cu. The Ca ratio among the external and internal sides of the analyzed shells is around of 1, and it was expected because Ca is the main composed of mollusks shells. The ratio of P, Fe, Mn, and Sr for Ca stayed constant in all analyzed shells

Rare earth elements in the aragonitic shell of freshwater mussel Corbicula fluminea and the bioavailability of anthropogenic lanthanum, samarium and gadolinium in river water

International Nuclear Information System (INIS)

Merschel, Gila; Bau, Michael

2015-01-01

High-technology metals — such as the rare earth elements (REE) — have become emerging contaminants in the hydrosphere, yet little is known about their bioavailability. The Rhine River and the Weser River in Germany are two prime examples of rivers that are subjected to anthropogenic REE input. While both rivers carry significant loads of anthropogenic Gd, originating from contrast agents used for magnetic resonance imaging, the Rhine River also carries large amounts of anthropogenic La and lately Sm which are discharged into the river from an industrial point source. Here, we assess the bioavailability of these anthropogenic microcontaminants in these rivers by analyzing the aragonitic shells of the freshwater bivalve Corbicula fluminea. Concentrations of purely geogenic REE in shells of comparable size cover a wide range of about one order of magnitude between different sampling sites. At a given sampling site, geogenic REE concentrations depend on shell size, i.e. mussel age. Although both rivers show large positive Gd anomalies in their dissolved loads, no anomalous enrichment of Gd relative to the geogenic REE can be observed in any of the analyzed shells. This indicates that the speciations of geogenic and anthropogenic Gd in the river water differ from each other and that the geogenic, but not the anthropogenic Gd is incorporated into the shells. In contrast, all shells sampled at sites downstream of the industrial point source of anthropogenic La and Sm in the Rhine River show positive La and Sm anomalies, revealing that these anthropogenic REE are bioavailable. Only little is known about the effects of long-term exposure to dissolved REE and their general ecotoxicity, but considering that anthropogenic Gd and even La have already been identified in German tap water and that anthropogenic La and Sm are bioavailable, this should be monitored and investigated further. - Highlights: • Corbicula fluminea shells are bioarchives of dissolved geogenic REE in

Rare earth elements in the aragonitic shell of freshwater mussel Corbicula fluminea and the bioavailability of anthropogenic lanthanum, samarium and gadolinium in river water

Energy Technology Data Exchange (ETDEWEB)

Merschel, Gila, E-mail: g.merschel@jacobs-university.de; Bau, Michael

2015-11-15

High-technology metals — such as the rare earth elements (REE) — have become emerging contaminants in the hydrosphere, yet little is known about their bioavailability. The Rhine River and the Weser River in Germany are two prime examples of rivers that are subjected to anthropogenic REE input. While both rivers carry significant loads of anthropogenic Gd, originating from contrast agents used for magnetic resonance imaging, the Rhine River also carries large amounts of anthropogenic La and lately Sm which are discharged into the river from an industrial point source. Here, we assess the bioavailability of these anthropogenic microcontaminants in these rivers by analyzing the aragonitic shells of the freshwater bivalve Corbicula fluminea. Concentrations of purely geogenic REE in shells of comparable size cover a wide range of about one order of magnitude between different sampling sites. At a given sampling site, geogenic REE concentrations depend on shell size, i.e. mussel age. Although both rivers show large positive Gd anomalies in their dissolved loads, no anomalous enrichment of Gd relative to the geogenic REE can be observed in any of the analyzed shells. This indicates that the speciations of geogenic and anthropogenic Gd in the river water differ from each other and that the geogenic, but not the anthropogenic Gd is incorporated into the shells. In contrast, all shells sampled at sites downstream of the industrial point source of anthropogenic La and Sm in the Rhine River show positive La and Sm anomalies, revealing that these anthropogenic REE are bioavailable. Only little is known about the effects of long-term exposure to dissolved REE and their general ecotoxicity, but considering that anthropogenic Gd and even La have already been identified in German tap water and that anthropogenic La and Sm are bioavailable, this should be monitored and investigated further. - Highlights: • Corbicula fluminea shells are bioarchives of dissolved geogenic REE in

Effect of water molecule distribution on the quantitative XRD analysis in the case of Na-montmorillonite exchanged Cu2+

International Nuclear Information System (INIS)

Oueslati, W.; Meftah, M.; Ben Rhaiem, H.; Ben Haj Amara, A.

2010-01-01

Document available in extended abstract form only. Several theoretical models are proposed to describe hydration process for Wyoming-montmorillonite clay exchanged Na + or Cu 2+ . They propose some theoretical distribution and disposition for water molecule in the inter-lamellar space in the case of homogeneous and inter-stratified hydration states. For example, Ben Brahim et al. (1983a) studied the interlayer structure (atomic positions of interlayer cations) and associated H 2 O molecules of Na-saturated montmorillonite and beidellite samples. Moore and Hower (1986) studied ordered structures composed of mono-hydrated and collapsed interlayers in montmorillonite, and Cuadros (1996) estimated the H 2 O content of smectite as a function of the interlayer cation. Using similar approach, Ferrage et al (2005b) proposed a discreet distribution of water molecule layer in the same z coordinate of the exchangeable cation with inhomogeneous distribution. This heterogeneity was attributed to the surface charge. The main objective of this study is to characterize the structural changes in the theoretical XRD profile, induced by different water molecule distribution, used to simulate experimental XRD patterns in the case of Na-montmorillonite exchanged Cu 2+ . This problem was achieved by quantitative XRD analysis using an indirect method based on the comparison of the experimental 001 reflections obtained from oriented films patterns with those calculated from structural models. The starting materials were Ca-montmorillonite originated from bentonites of Wyoming (USA). The XRD patterns were obtained by reflection setting with a D8 ADVANCE Bruker installation using Cu-Kα radiation and equipped with solid state detector. Intensities were measured at an interval of 2Θ 0.04 deg. and 40-50 s counting time per step. The diffracted intensity was calculated according to the matrix formalism detailed by Drits and Tchoubar, (1990). The fitting strategies was detailed by Ferrage et

Larvicidal Activity of A Mixture of Cashew Nut Shell Liquid and Water-Soluble Extract of Soap Nut Fruit (Sapindus rarak DC. Against 3rd Instar Larvae of Aedes aegypti

Directory of Open Access Journals (Sweden)

Glory Resia Raraswati

2015-10-01

Full Text Available Cashew Nut Shell Liquid (CNSL which has been known as a waste of processing cashew fruits which is contain phenolic compounds have activity as larvicides. Cashew nut shell liquid is not soluble in the water where the larvae grow. Cashew nut shell liquid mixed with water-soluble extract of soapnut fruit which serves as a natural surfactant that can emulsify oil in water. The test subjects were larvae of Aedes aegypti third instar. Test subjects were divided into treatment group and control group. In the treatment group, test subjects were  the mixture of CNSL and Ethylacetat Soluble Extract (ESE in tap water. The Larvae mortality observations were done 24 hours after the treatment. LC50 and LC90 as final test data were analyzed using probit analysis. Extract constituents   of CNSL and Water Soluble Extract of SoapNut fruit (WSEoSN were  investigated using Thin Layer Chromatography (TLC method. The effect of CNSL as larvicides against third instar larvae of Ae. aegypti with were LC50 of 14,12 ppm, while the LC90 of 24,85 ppm.

QSPR Study of the Retention/release Property of Odorant Molecules in Water Using Statistical Methods

Directory of Open Access Journals (Sweden)

Assia Belhassan

2017-10-01

Full Text Available An integrated approach physicochemistry and structures property relationships has been carried out to study the odorant molecules retention/release phenomenon in the water. This study aimed to identify the molecular properties (molecular descriptors that govern this phenomenon assuming that modifying the structure leads automatically to a change in the retention/release property of odorant molecules. ACD/ChemSketch, MarvinSketch, and ChemOffice programs were used to calculate several molecular descriptors of 51 odorant molecules (15 alcohols, 11 aldehydes, 9 ketones and 16 esters. A total of 37 molecules (2/3 of the data set were placed in the training set to build the QSPR models, whereas the remaining, 14 molecules (1/3 of the data set constitute the test set. The best descriptors were selected to establish the quantitative structure property relationship (QSPR of the retention/release property of odorant molecules in water using multiple linear regression (MLR, multiple non-linear regression (MNLR and an artificial neural network (ANN methods. We propose a quantitative model according to these analyses. The models were used to predict the retention/release property of the test set compounds, and agreement between the experimental and predicted values was verified. The descriptors showed by QSPR study are used for study and designing of new compounds. The statistical results indicate that the predicted values are in good agreement with the experimental results. To validate the predictive power of the resulting models, external validation multiple correlation coefficient was calculated and has both in addition to a performant prediction power, a favorable estimation of stability. DOI: http://dx.doi.org/10.17807/orbital.v9i4.978 

Peptide Microencapsulation by Core-Shell Printing Technology for Edible Film Application

NARCIS (Netherlands)

Blanco-Pascual, N.; Koldeweij, R.B.J.; Stevens, R.S.A.; Montero, M.P.; Gómez-Guillén, M.C.; Cate, A.T.T.

2014-01-01

This paper presents a new microencapsulation methodology for incorporation of functional ingredients in edible films. Core-shell microcapsules filled with demineralized water (C) or 1 % (w/v) peptide solution (Cp) were prepared using the microencapsulation printer technology. Shell material,

Beneficial effects of water in the colloidal synthesis of InP/ZnS core-shell quantum dots for optoelectronic applications.

Science.gov (United States)

Ramasamy, Parthiban; Kim, Bumjin; Lee, Min-Sang; Lee, Jong-Soo

2016-10-21

We demonstrate that the presence of a small amount of water as an impurity during the hot-injection synthesis can significantly decrease the emission lines full width at half-maximum (FWHM) and improve the quantum yield (QY) of InP/ZnS quantum dots (QDs). By utilizing the water present in the indium precursor and solvent, we obtained InP/ZnS QDs emitting around 530 nm with a FWHM as narrow as 46 nm and a QY up to 45%. Without water, the synthesized QDs have emission around 625 nm with a FWHM of 66 nm and a QY of about 33%. Absorption spectra, XRD and XPS analyses revealed that when water is present, an amorphous phosphate layer is formed over the InP QDs and inhibits the QD growth. This amorphous layer favors the formation of a very thick ZnS shell by decreasing the lattice mismatch between the InP core and the ZnS shell. We further show the possibility to tune the emission wavelengths of InP/ZnS QDs by simply adjusting the amount of water present in the system while keeping all the other reaction parameters (i.e., precursor concentration, reaction temperature and time) constant. As an example of their application in light-emitting diodes (LEDs), the green and red InP/ZnS QDs are combined with a blue LED chip to produce white light.

Shell Venster

International Nuclear Information System (INIS)

De Wit, P.; Looijesteijn, B.; Regeer, B.; Stip, B.

1995-03-01

In the bi-monthly issues of 'Shell Venster' (window on Shell) attention is paid to the activities of the multinational petroleum company Shell Nederland and the Koninklijke/Shell Groep by means of non-specialist articles

Does carbonate ion control planktonic foraminifera shell calcification in upwelling regions?

Digital Repository Service at National Institute of Oceanography (India)

Naik, S.S.; Godad, S.P.; Naidu, P.D.

are still debated and to utilize shell weights of a particular species as a surface water carbonate ion proxy, it is important to understand whether [CO = 3 ] controls shell calcification in that species over a period of time. We therefore utilize...

Fractionation of hydrogen and oxygen isotopes between hydrated and free water molecules in aqueous urea solution

International Nuclear Information System (INIS)

Kakiuchi, M.; Matsuo, S.

1985-01-01

Ratios of D/H and 18 O/ 16 O in the vapor phase in equilibrium with aqueous urea solution with different urea molalities were measured at 15 and 25 0 C. Under the assumption that urea solutions consist of two species, i.e., the urea-water cluster and free water, the results are interpreted to give the average hydration number, i.e., the number of water molecules per urea molecule in the urea-water cluster. Good agreement was obtained for the hydration number estimated independently from hydrogen and oxygen isotopic fractions. On the basis of hydrogen isotopic data at 25 0 C, the average hydration number of urea in the cluster is 6.3 +/- 0.8 at 2.1 m and 2.75 +/- 0.08 at saturation (20.15 m). The corresponding average hydration numbers based on oxygen isotopic data were calculated to be 6.7 +/- 2.4 at 2.1 m and 2.75 +/- 0.25 at urea saturation. HD 16 O is enriched in the urea-water cluster and H 2 18 O is enriched in free water. Isotopic partitioning between the cluster and free water is markedly different from those between hydration spheres and free water in aqueous electrolyte solutions. 29 references, 6 figures, 5 tables

Synthesis of TiC/W core–shell nanoparticles by precipitate-coating process

International Nuclear Information System (INIS)

Xia Min; Yan Qingzhi; Xu Lei; Zhu Lingxu; Guo Hongyan; Ge Changchun

2012-01-01

Graphical abstract: Well-dispersed titanium carbide/tungsten (TiC/W) core-shell nanoparticles with high-purity and uniform diameters were firstly synthesized by precipitate-coating process. Such unique process suggests a new method for preparing X/W (X refers the water-insoluble nanoparticles) core-shell nanoparticles with different cores. Abstract: Well-dispersed titanium carbide/tungsten (TiC/W) core–shell nanoparticles with high-purity and uniform diameters were firstly synthesized by precipitate-coating process. The as-synthesized nanoparticles were characterized by X-ray diffraction (XRD), Filed-emission scanning electron microscope (FESEM), Transmission electron microscopy (TEM), energy dispersive spectrum (EDS). Results revealed that the as-synthesized nanoparticles possess uniform diameters about 100 nm, and high purity. TEM and the corresponding FFT images demonstrate that TiC nanoparticles were well-encapsulated by W shells. Such unique process suggests a new method for preparing X/W (X refers the water-insoluble nanoparticles) core–shell nanoparticles with different cores.

Continuum Navier-Stokes modelling of water ow past fullerene molecules

DEFF Research Database (Denmark)

Walther, J. H.; Popadic, A.; Koumoutsakos, P.

We present continuum simulations of water flow past fullerene molecules. The governing Navier-Stokes equations are complemented with the Navier slip boundary condition with a slip length that is extracted from related molecular dynamics simulations. We find that several quantities of interest...... as computed by the present model are in good agreement with results from atomistic and atomistic-continuum simulations at a fraction of the computational cost. We simulate the flow past a single fullerene and an array of fullerenes and demonstrate that such nanoscale flows can be computed efficiently...

Continuum Navier-Stokes modelling of water flow past fullerene molecules

DEFF Research Database (Denmark)

Walther, J. H.; Popadic, A.; Koumoutsakos, P.

We present continuum simulations of water flow past fullerene molecules. The governing Navier-Stokes equations are complemented with the Navier slip boundary condition with a slip length that is extracted from related molecular dynamics simulations. We find that several quantities of interest...... as computed by the present model are in good agreement with results from atomistic and atomistic-continuum simulations at a fraction of the computational cost. We simulate the flow past a single fullerene and an array of fullerenes and demonstrate that such nanoscale flows can be computed efficiently...

How proteins modify water dynamics

Science.gov (United States)

Persson, Filip; Söderhjelm, Pär; Halle, Bertil

2018-06-01

Much of biology happens at the protein-water interface, so all dynamical processes in this region are of fundamental importance. Local structural fluctuations in the hydration layer can be probed by 17O magnetic relaxation dispersion (MRD), which, at high frequencies, measures the integral of a biaxial rotational time correlation function (TCF)—the integral rotational correlation time. Numerous 17O MRD studies have demonstrated that this correlation time, when averaged over the first hydration shell, is longer than in bulk water by a factor 3-5. This rotational perturbation factor (RPF) has been corroborated by molecular dynamics simulations, which can also reveal the underlying molecular mechanisms. Here, we address several outstanding problems in this area by analyzing an extensive set of molecular dynamics data, including four globular proteins and three water models. The vexed issue of polarity versus topography as the primary determinant of hydration water dynamics is resolved by establishing a protein-invariant exponential dependence of the RPF on a simple confinement index. We conclude that the previously observed correlation of the RPF with surface polarity is a secondary effect of the correlation between polarity and confinement. Water rotation interpolates between a perturbed but bulk-like collective mechanism at low confinement and an exchange-mediated orientational randomization (EMOR) mechanism at high confinement. The EMOR process, which accounts for about half of the RPF, was not recognized in previous simulation studies, where only the early part of the TCF was examined. Based on the analysis of the experimentally relevant TCF over its full time course, we compare simulated and measured RPFs, finding a 30% discrepancy attributable to force field imperfections. We also compute the full 17O MRD profile, including the low-frequency dispersion produced by buried water molecules. Computing a local RPF for each hydration shell, we find that the

DNA nanoparticles with core-shell morphology.

Science.gov (United States)

Chandran, Preethi L; Dimitriadis, Emilios K; Lisziewicz, Julianna; Speransky, Vlad; Horkay, Ferenc

2014-10-14

Mannobiose-modified polyethylenimines (PEI) are used in gene therapy to generate nanoparticles of DNA that can be targeted to the antigen-presenting cells of the immune system. We report that the sugar modification alters the DNA organization within the nanoparticles from homogenous to shell-like packing. The depth-dependent packing of DNA within the nanoparticles was probed using AFM nano-indentation. Unmodified PEI-DNA nanoparticles display linear elastic properties and depth-independent mechanics, characteristic of homogenous materials. Mannobiose-modified nanoparticles, however, showed distinct force regimes that were dependent on indentation depth, with 'buckling'-like response that is reproducible and not due to particle failure. By comparison with theoretical studies of spherical shell mechanics, the structure of mannobiosylated particles was deduced to be a thin shell with wall thickness in the order of few nanometers, and a fluid-filled core. The shell-core structure is also consistent with observations of nanoparticle denting in altered solution conditions, with measurements of nanoparticle water content from AFM images, and with images of DNA distribution in Transmission Electron Microscopy.

Importance-truncated shell model for multi-shell valence spaces

Energy Technology Data Exchange (ETDEWEB)

Stumpf, Christina; Vobig, Klaus; Roth, Robert [Institut fuer Kernphysik, TU Darmstadt (Germany)

2016-07-01

The valence-space shell model is one of the work horses in nuclear structure theory. In traditional applications, shell-model calculations are carried out using effective interactions constructed in a phenomenological framework for rather small valence spaces, typically spanned by one major shell. We improve on this traditional approach addressing two main aspects. First, we use new effective interactions derived in an ab initio approach and, thus, establish a connection to the underlying nuclear interaction providing access to single- and multi-shell valence spaces. Second, we extend the shell model to larger valence spaces by applying an importance-truncation scheme based on a perturbative importance measure. In this way, we reduce the model space to the relevant basis states for the description of a few target eigenstates and solve the eigenvalue problem in this physics-driven truncated model space. In particular multi-shell valence spaces are not tractable otherwise. We combine the importance-truncated shell model with refined extrapolation schemes to approximately recover the exact result. We present first results obtained in the importance-truncated shell model with the newly derived ab initio effective interactions for multi-shell valence spaces, e.g., the sdpf shell.

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

Energy Technology Data Exchange (ETDEWEB)

O, Shepelenko S; S, Salnikov A; V, Rak S; P, Goncharova E; B, Ryzhikov A, E-mail: shep@vector.nsc.r, E-mail: shep@ngs.r [Federal State Research Institution State Research Center of Virology and Biotechnology VECTOR of the Federal Service for Surveillance in Consumer Rights Protection and Human Well-being (FSRI SRC VB VECTOR) Koltsovo, Novosibirsk Region (Russian Federation)

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

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

Science.gov (United States)

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

Studies on Freezing of Shell-Fish-I

Science.gov (United States)

Song, Dae Jin; Konagaya, Shiro; Tanaka, Takeo

Ark shell, Anadara broughtonii(Shrenk), are commonly eaten raw or under-done in Korea, Japan, and East Asian countries. Along with a recent remarkable development of culture fisheries, Ark shell has become one of the commercially important shell-fish species. Transportation and storage of large quantities of shell-fish is becoming increasingly important. This work was begun with this background to make clear the effects of temperature and length of storage time on the quality of frozen stored ark shell. Results are as follows : (1) There was little chang in amounts of free and expressible drip from ark shell flesh frozen stored at -40°CdegC for 6 months. Water holding capacity of the same meat was almost constant over 6 months storage. However, a mounts of both drip increased markedly after 2 months storage at -10°C. (2) Protein extractibility of ark shell flesh tended to decrease gradually from the begining when stored at -10°C, while at -20°C, the protein extractibility was stable for 3 months before decreasing gradually. However at -40°C, the protein extractibility was stable for 6 months. It was found that paramyosin was very stable even when the ark shell was frozen stored at -10°C. (3) It was observed that ark shell flesh became tough when frozen. The toughness of ark shell flesh as measured by an instrument increased with frozen storage time and increased temperature. (4) In the smooth muscle, it was histologically observed that initial small ice crystals formed between muscle bundles grew larger during frozen storage. It was found that the higher the storage temperature, the bigger the ice crystals formed. Aggregation of some muscle fiber and empty spaces between muscle bundles were observd after thawed muscles frozen stored at relatively high temperature such as -10°C.

Enthalpy of solution of potassium iodide in the water-formamide-dimethyl sulfoxide mixtures

International Nuclear Information System (INIS)

Belova, L.N.; Solov'ev, S.N.; Vorob'ev, A.F.

1985-01-01

Solution enthalpies are measured for potassium iodide in the water-formamide-dimethyl sulfoxide mixtures in a sealed oscillating calorimeter with an isothermal shell at a constant water molar fraction equal to 0.3; 0.5 and 0.7 at 298.15 K. A diagram of the dependence of solution enthalpies on the of mixed solvent composition is plotted. Deviations of experimental solution enthalpies from the calculated ones are negative over the entire concentration range studied, which testifies to the preferable solvatation of electrolyte by the formid and dimthyl sulfoxide molecules

Magnetic Fe{sub 3}O{sub 4}-Au core-shell nanostructures for surface enhanced Raman scattering

Energy Technology Data Exchange (ETDEWEB)

Wheeler, D.A.; Adams, S.A.; Zhang, J.Z. [Department of Chemistry and Biochemistry, University of California, Santa Cruz, Santa Cruz, CA 95064 (United States); Lopez-Luke, T. [Department of Chemistry and Biochemistry, University of California, Santa Cruz, Santa Cruz, CA 95064 (United States); Cento de Investigaciones en Optica, A.P. 1-948 Leon, Gto. 37150 (Mexico); Torres-Castro, A. [Universidad Autonoma de Nuevo Leon, A.P. 126-F, Monterrey, NL, 66450 (Mexico)

2012-11-15

The synthesis, structural and optical characterization, and application of superparamagnetic and water-dispersed Fe{sub 3}O{sub 4}-Au core-shell nanoparticles for surface enhanced Raman scattering (SERS) is reported. The structure of the nanoparticles was determined by scanning transmission electron microscopy (STEM) and high-resolution transmission electron microscopy (HRTEM). STEM images of the Fe{sub 3}O{sub 4}-Au core-shell nanoparticles reveal an average diameter of 120 nm and a high degree of surface roughness. The nanoparticles, which display superparamagnetic properties due to the core Fe{sub 3}O{sub 4} material, exhibit a visible surface plasmon resonance (SPR) peaked at 580 nm due to the outer gold shell. The nanoparticles are used as a substrate for surface enhanced Raman scattering (SERS) with rhodamine 6G (R6G) as a Raman reporter molecule. The SERS enhancement factor is estimated to be on the order of 10{sup 6}, which is {proportional_to} 2 times larger than that of conventional gold nanoparticles (AuNPs) under similar conditions. Significantly, magnetically-induced aggregation of the Fe{sub 3}O{sub 4}-Au core-shell nanoparticles substantially enhanced SERS activity compared to non-magnetically-aggregated Fe{sub 3}O{sub 4}-Au nanoparticles. This is attributed to both increased scattering from the aggregates as well as ''hot spots'' due to more junction sites in the magnetically-induced aggregates. The magnetic properties of the Fe{sub 3}O{sub 4} core, coupled with the optical properties of the Au shell, make the Fe{sub 3}O{sub 4}-Au nanoparticles unique for various potential applications including biological sensing and therapy. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Energy Technology Data Exchange (ETDEWEB)

Isailovic, Slavica [Iowa State Univ., Ames, IA (United States)

2005-01-01

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.

MicroShell Minimalist Shell for Xilinx Microprocessors

Science.gov (United States)

Werne, Thomas A.

2011-01-01

MicroShell is a lightweight shell environment for engineers and software developers working with embedded microprocessors in Xilinx FPGAs. (MicroShell has also been successfully ported to run on ARM Cortex-M1 microprocessors in Actel ProASIC3 FPGAs, but without project-integration support.) Micro Shell decreases the time spent performing initial tests of field-programmable gate array (FPGA) designs, simplifies running customizable one-time-only experiments, and provides a familiar-feeling command-line interface. The program comes with a collection of useful functions and enables the designer to add an unlimited number of custom commands, which are callable from the command-line. The commands are parameterizable (using the C-based command-line parameter idiom), so the designer can use one function to exercise hardware with different values. Also, since many hardware peripherals instantiated in FPGAs have reasonably simple register-mapped I/O interfaces, the engineer can edit and view hardware parameter settings at any time without stopping the processor. MicroShell comes with a set of support scripts that interface seamlessly with Xilinx's EDK tool. Adding an instance of MicroShell to a project is as simple as marking a check box in a library configuration dialog box and specifying a software project directory. The support scripts then examine the hardware design, build design-specific functions, conditionally include processor-specific functions, and complete the compilation process. For code-size constrained designs, most of the stock functionality can be excluded from the compiled library. When all of the configurable options are removed from the binary, MicroShell has an unoptimized memory footprint of about 4.8 kB and a size-optimized footprint of about 2.3 kB. Since MicroShell allows unfettered access to all processor-accessible memory locations, it is possible to perform live patching on a running system. This can be useful, for instance, if a bug is

Tetrahedrality and hydrogen bonds in water

Science.gov (United States)

Székely, Eszter; Varga, Imre K.; Baranyai, András

2016-06-01

We carried out extensive calculations of liquid water at different temperatures and pressures using the BK3 model suggested recently [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. In particular, we were interested in undercooled regions to observe the propensity of water to form tetrahedral coordination of closest neighbors around a central molecule. We compared the found tetrahedral order with the number of hydrogen bonds and with the partial pair correlation functions unfolded as distributions of the closest, the second closest, etc. neighbors. We found that contrary to the number of hydrogen bonds, tetrahedrality changes substantially with state variables. Not only the number of tetrahedral arrangements increases with lowering the pressure, the density, and the temperature but the domain size of connecting tetrahedral structures as well. The difference in tetrahedrality is very pronounced between the two sides of the Widom line and even more so between the low density amorphous (LDA) and high density amorphous (HDA) phases. We observed that in liquid water and in HDA, the 5th water molecule, contrary to ice and LDA, is positioned between the first and the second coordination shell. We found no convincing evidence of structural heterogeneity or regions referring to structural transition.

Simultaneous tracking of drug molecules and carriers using aptamer-functionalized fluorescent superstable gold nanorod-carbon nanocapsules during thermo-chemotherapy

Science.gov (United States)

Wang, Xue-Wei; Gao, Wei; Fan, Huanhuan; Ding, Ding; Lai, Xiao-Fang; Zou, Yu-Xiu; Chen, Long; Chen, Zhuo; Tan, Weihong

2016-04-01

Controlling and monitoring the drug delivery process is critical to its intended therapeutic function. Many nanocarrier systems for drug delivery have been successfully developed. However, biocompatibility, stability, and simultaneously tracing drugs and nanocarriers present significant limitations. Herein, we have fabricated a multifunctional nanocomposite by coating the gold nanorod (AuNR) with a biocompatible, superstable and fluorescent carbon layer, obtaining the AuNR@carbon core-shell nanocapsule. In this system, the carbon shell, originally obtained in aqueous glucose solutions and, therefore, biocompatible in physiological environments, could be simply loaded with cell-specific aptamers and therapeutic molecules through π-π interactions, a useful tool for cancer-targeted cellular imaging and therapy. Moreover, such a stable and intrinsic fluorescence effect of the AuNR@carbon enabled simultaneous tracking of released therapeutic molecules and nanocarriers under thermo-chemotherapy. The AuNR@carbons had high surface areas and stable shells, as well as unique optical and photothermal properties, making them promising nanostructures for biomedical applications.Controlling and monitoring the drug delivery process is critical to its intended therapeutic function. Many nanocarrier systems for drug delivery have been successfully developed. However, biocompatibility, stability, and simultaneously tracing drugs and nanocarriers present significant limitations. Herein, we have fabricated a multifunctional nanocomposite by coating the gold nanorod (AuNR) with a biocompatible, superstable and fluorescent carbon layer, obtaining the AuNR@carbon core-shell nanocapsule. In this system, the carbon shell, originally obtained in aqueous glucose solutions and, therefore, biocompatible in physiological environments, could be simply loaded with cell-specific aptamers and therapeutic molecules through π-π interactions, a useful tool for cancer-targeted cellular imaging and

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

Energy Technology Data Exchange (ETDEWEB)

Liu, Zhigang [Wayne State Univ., Detroit, MI (United States); Case Western Reserve Univ., Cleveland, OH (United States); Harbor Hospital Baltimore, MD (United States); Wang, Yong [Wayne State Univ., Detroit, MI (United States); Yedidi, Ravikiran S. [Wayne State Univ., Detroit, MI (United States); National Institutes of Health, Bethesda, MD (United States); Dewdney, Tamaria G. [Wayne State Univ., Detroit, MI (United States); Reiter, Samuel J. [Wayne State Univ., Detroit, MI (United States); Brunzelle, Joseph S. [Northwestern Univ. Feinberg School of Medicine, Chicago, IL (United States); Kovari, Iulia A. [Wayne State Univ., Detroit, MI (United States); Kovari, Ladislau C. [Wayne State Univ., Detroit, MI (United States)

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.

Water Quality of Trickling Biological Periwinkle Shells Filter for ...

African Journals Online (AJOL)

Studies were carried on the design, efficiency and economics of trickling biological periwinkle shells filter in recirculating aquaculture systems for catfish production. The designed biofilter and other system components were constructed, assembled and commissioned for pilot catfish production. The system with the designed ...

Temperature-time distribution and thermal stresses on the RTG fins and shell during water cooling

Science.gov (United States)

Turner, R. H.

1983-01-01

Radioisotope thermoelectric generator (RTG) packages designed for space missions generally do not require active cooling. However, the heat they generate cannot remain inside of the launch vehicle bay and requires active removal. Therefore, before the Shuttle bay door is closed, the RTG coolant tubes attached to the heat rejection fins must be filled with water, which will circulate and remove most of the heat from the cargo bay. There is concern that charging a system at initial temperature around 200 C with water at 24 C can cause unacceptable thermal stresses in the RTG shell and fins. A computer model is developed to estimate the transient temperature distribution resulting from such charging. The thermal stresses resulting from the temperature gradients do not exceed the elastic deformation limit for the material. Since the simplified mathematical model for thermal stresses tends to overestimate stresses, it is concluded that the RTG can be cooled by introducing water at 24 C to the initially hot fin coolant tubes while the RTG is in the Shuttle cargo bay.

Optical properties of core-shell and multi-shell nanorods

Science.gov (United States)

Mokkath, Junais Habeeb; Shehata, Nader

2018-05-01

We report a first-principles time dependent density functional theory study of the optical response modulations in bimetallic core-shell (Na@Al and Al@Na) and multi-shell (Al@Na@Al@Na and Na@Al@Na@Al: concentric shells of Al and Na alternate) nanorods. All of the core-shell and multi-shell configurations display highly enhanced absorption intensity with respect to the pure Al and Na nanorods, showing sensitivity to both composition and chemical ordering. Remarkably large spectral intensity enhancements were found in a couple of core-shell configurations, indicative that optical response averaging based on the individual components can not be considered as true as always in the case of bimetallic core-shell nanorods. We believe that our theoretical results would be useful in promising applications depending on Aluminum-based plasmonic materials such as solar cells and sensors.

Fluorescent nanodiamonds embedded in biocompatible translucent shells.

Science.gov (United States)

Rehor, Ivan; Slegerova, Jitka; Kucka, Jan; Proks, Vladimir; Petrakova, Vladimira; Adam, Marie-Pierre; Treussart, François; Turner, Stuart; Bals, Sara; Sacha, Pavel; Ledvina, Miroslav; Wen, Amy M; Steinmetz, Nicole F; Cigler, Petr

2014-03-26

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio-orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30-nm fluorescent nanodiamonds (FNDs) in 10-20-nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near-spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio-orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin Density Distribution in Open-Shell Transition Metal Systems: A Comparative Post-Hartree-Fock, Density Functional Theory, and Quantum Monte Carlo Study of the CuCl2 Molecule.

Science.gov (United States)

Caffarel, Michel; Giner, Emmanuel; Scemama, Anthony; Ramírez-Solís, Alejandro

2014-12-09

We present a comparative study of the spatial distribution of the spin density of the ground state of CuCl2 using Density Functional Theory (DFT), quantum Monte Carlo (QMC), and post-Hartree-Fock wave function theory (WFT). A number of studies have shown that an accurate description of the electronic structure of the lowest-lying states of this molecule is particularly challenging due to the interplay between the strong dynamical correlation effects in the 3d shell and the delocalization of the 3d hole over the chlorine atoms. More generally, this problem is representative of the difficulties encountered when studying open-shell metal-containing molecular systems. Here, it is shown that qualitatively different results for the spin density distribution are obtained from the various quantum-mechanical approaches. At the DFT level, the spin density distribution is found to be very dependent on the functional employed. At the QMC level, Fixed-Node Diffusion Monte Carlo (FN-DMC) results are strongly dependent on the nodal structure of the trial wave function. Regarding wave function methods, most approaches not including a very high amount of dynamic correlation effects lead to a much too high localization of the spin density on the copper atom, in sharp contrast with DFT. To shed some light on these conflicting results Full CI-type (FCI) calculations using the 6-31G basis set and based on a selection process of the most important determinants, the so-called CIPSI approach (Configuration Interaction with Perturbative Selection done Iteratively) are performed. Quite remarkably, it is found that for this 63-electron molecule and a full CI space including about 10(18) determinants, the FCI limit can almost be reached. Putting all results together, a natural and coherent picture for the spin distribution is proposed.

Prototropic tautomerism of 4-Methyl 1,2,4-Triazole-3-Thione molecule in solvent water medium: DFT and Car–Parrinello molecular dynamics study

International Nuclear Information System (INIS)

Dutta, Bipan; De, Rina; Chowdhury, Joydeep

2015-01-01

Highlights: • The tautomerism of 4-MTTN molecule in solvent water medium has been investigated. • CPMD presage the possibility of PT reactions through the solvent water medium. • Concerted PT processes in 4-MTTN have been estimated from the DFT and NBO analyses. • Percentage evolution and breaking of the concerned bonds are estimated. - Abstract: 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.

Morphology and properties of periwinkle shell asbestos-free brake pad

Directory of Open Access Journals (Sweden)

D.S. Yawas

2016-01-01

Full Text Available The development of asbestos-free automotive brake pad using periwinkle shell particles as frictional filler material is presented. This was with a view to exploiting the characteristics of the periwinkle shell, which is largely deposited as a waste, in replacing asbestos which has been found to be carcinogenic. Five sets of brake pads with different sieve size (710–125 μm of periwinkle shell particles with 35% resin were produced using compressive moulding. The physical, mechanical and tribological properties of the periwinkle shell particle-based brake pads were evaluated and compared with the values for the asbestos-based brake pads. The results obtained showed that compressive strength, hardness and density of the developed brake pad samples increased with decreasing the particle size of periwinkle shell from 710 to 125 μm, while the oil soak, water soak and wear rate decreased with decreasing the particle size of periwinkle shell. The results obtained at 125 μm of periwinkle shell particles compared favourably with that of commercial brake pad. The results of this research indicate that periwinkle shell particles can be effectively used as a replacement for asbestos in brake pad manufacture.

Degree of Acetylization Chitosan Gonggong Snail Shells

Science.gov (United States)

Horiza, H.; Iskandar, I.; Aldo, N.

2018-04-01

Chitosan is a polysaccharide obtained from the deacetylation of chitin, which is generally derived from crustacean animal waste and animal skins other sea. One marine animals that have compounds that can be processed chitin chitosan is derived from the snail Gonggong marine waters of Riau Islands province. The purpose of this study was to determine the degree of chitosan from the shells of snails asetilisasi Gonggong. This research is an experimental research laboratory. The results of this study indicate that the degree of chitosan shell snail deasetilisasi Gonggong is 70.27%.

Structural experiments with ice (composite) shells

NARCIS (Netherlands)

Belis, J.; Martens, K.; Van Lancker, B.; Pronk, A.; Zingoni, Alphose

2016-01-01

ABSTRACT: Ice can be a very suitable building material for temporary structures in a freezing environment. When water, mixed with small fibre reinforcements, is sprayed onto an inflatable membrane structure in suitable cold outdoor conditions, a thin shell is formed which increases thickness layer

Dynamics of valence-shell electrons and nuclei probed by strong-field holography and rescattering

Science.gov (United States)

Walt, Samuel G.; Bhargava Ram, Niraghatam; Atala, Marcos; Shvetsov-Shilovski, Nikolay I; von Conta, Aaron; Baykusheva, Denitsa; Lein, Manfred; Wörner, Hans Jakob

2017-01-01

Strong-field photoelectron holography and laser-induced electron diffraction (LIED) are two powerful emerging methods for probing the ultrafast dynamics of molecules. However, both of them have remained restricted to static systems and to nuclear dynamics induced by strong-field ionization. Here we extend these promising methods to image purely electronic valence-shell dynamics in molecules using photoelectron holography. In the same experiment, we use LIED and photoelectron holography simultaneously, to observe coupled electronic-rotational dynamics taking place on similar timescales. These results offer perspectives for imaging ultrafast dynamics of molecules on femtosecond to attosecond timescales. PMID:28643771

Partial preservation of the Tentaculites Crotalinus shell from Ponta Grossa Formation (Devonian)

International Nuclear Information System (INIS)

Ciguel, J.H.G.; Roesler, O.

1988-01-01

This paper deals with an analysis of a single specimen of Tentaculites crotalinus SALTER emend. CIGUEL et al. (1984) that present a possible partial preservation of the shell. It comes from an outcrop of the Grossa Formation (Devonian) near Jaguariaiva, State of Parana. The skeletal microstructure of the Tentaculitoidea shell rather poorly Known. Thus, the phylogenetic relationships of these invertebrates still uncertain. Tentaculitids are very common fossils in Devonian Ponta Grossa Formation (Parana Basin) but so far Known only from external and internal moulds. The objective of this study is to demonstrate wheter the layer found in between the internal and external mould is or not a case shell preservation. The chemical composition of this layer and of the external mould was analysed by X rays. X rays difratometry was applied only to the matrix (at the external mould). The structure of the supposed shell remain was studied by binocular stereomicroscope and scanning electron microscope. It revealed a foliate structure due to several paralel to subparalel oriented lamelae, with a chemical composition distinct from the matrix, and some elements possibly mantained from the original shell composition. Thus, a partial preservation of the original shell seems to be the better explanation for this case. This shell would be composed by calcium carbonate disposed in laminar layers, the outer ones being impregnated by Fe and Mn molecules during the diagenetic processes. The skeletal composition and microstructure would suggest a molluscan affinity for the tentaculitida Order. (auThor) [pt

Effects of scallop shell extract on scopolamine-induced memory impairment and MK801-induced locomotor activity.

Science.gov (United States)

Hasegawa, Yasushi; Inoue, Tatsuro; Kawaminami, Satoshi; Fujita, Miho

2016-07-01

To evaluate the neuroprotective effects of the organic components of scallop shells (scallop shell extract) on memory impairment and locomotor activity induced by scopolamine or 5-methyl-10,11-dihydro-5H-dibenzo (a,d) cyclohepten-5,10-imine (MK801). Effect of the scallop shell extract on memory impairment and locomotor activity was investigated using the Y-maze test, the Morris water maze test, and the open field test. Scallop shell extract significantly reduced scopolamine-induced short-term memory impairment and partially reduced scopolamine-induced spatial memory impairment in the Morris water maze test. Scallop shell extract suppressed scopolamine-induced elevation of acetylcholine esterase activity in the cerebral cortex. Treatment with scallop shell extract reversed the increase in locomotor activity induced by scopolamine. Scallop shell extract also suppressed the increase in locomotor activity induced by MK801. Our results provide initial evidence that scallop shell extract reduces scopolamine-induced memory impairment and suppresses MK-801-induced hyperlocomotion. Copyright © 2016 Hainan Medical College. Production and hosting by Elsevier B.V. All rights reserved.

Dynamics of water around the complex structures formed between the KH domains of far upstream element binding protein and single-stranded DNA molecules

Energy Technology Data Exchange (ETDEWEB)

Chakraborty, Kaushik; Bandyopadhyay, Sanjoy, E-mail: sanjoy@chem.iitkgp.ernet.in [Molecular Modeling Laboratory, Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India)

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.

Partition Coefficients of Organic Molecules in Squalane and Water/Ethanol Mixtures by Molecular Dynamics Simulations

DEFF Research Database (Denmark)

Lundsgaard, Rasmus; Kontogeorgis, Georgios; Economou, Ioannis G.

2011-01-01

coefficient can be estimated for both a small hydrophilic and a hydrophobic organic molecules between squalane (used here to mimic low density poly ethylene) and water/ethanol solutes using thermodynamic integration to calculate the free energy of solvation. Molecular dynamics simulations are performed, using...... the GROMACS software, by slowly decoupling of firstly the electrostatic and then the Lennard–Jones interactions between molecules in the simulation box. These calculations depend very much on the choice of force field. Two force fields have been tested in this work, the TraPPE-UA (united-atom) and the OPLS...

A Combined SAXS/SANS Study for the in Situ Characterization of Ligand Shells on Small Nanoparticles: The Case of ZnO.

Science.gov (United States)

Schindler, T; Schmiele, M; Schmutzler, T; Kassar, T; Segets, D; Peukert, W; Radulescu, A; Kriele, A; Gilles, R; Unruh, T

2015-09-22

ZnO nanoparticles (NPs) have great potential for their use in, e.g., thin film solar cells due to their electro-optical properties adjustable on the nanoscale. Therefore, the production of well-defined NPs is of major interest. For a targeted production process, the knowledge of the stabilization layer of the NPs during and after their formation is of particular importance. For the study of the stabilizer layer of ZnO NPs prepared in a wet chemical synthesis from zinc acetate, only ex situ studies have been performed so far. An acetate layer bound to the surface of the dried NPs was found; however, an in situ study which addresses the stabilizing layer surrounding the NPs in a native dispersion was missing. By the combination of small angle scattering with neutrons and X-rays (SANS and SAXS) for the same sample, we are now able to observe the acetate shell in situ for the first time. In addition, the changes of this shell could be followed during the ripening process for different temperatures. With increasing size of the ZnO core (d(core)) the surrounding shell (d(shell)) becomes larger, and the acetate concentration within the shell is reduced. For all samples, the shell thickness was found to be larger than the maximum extension of an acetate molecule with acetate concentrations within the shell below 50 vol %. Thus, there is not a monolayer of acetate molecules that covers the NPs but rather a swollen shell of acetate ions. This shell is assumed to hinder the growth of the NPs to larger macrostructures. In addition, we found that the partition coefficient μ between acetate in the shell surrounding the NPs and the total amount of acetate in the solution is about 10% which is in good agreement with ex situ data determined by thermogravimetric analysis.

Atlanta ariejansseni, a new species of shelled heteropod from the Southern Subtropical Convergence Zone (Gastropoda, Pterotracheoidea)

NARCIS (Netherlands)

Wall-Palmer, D.; Burridge, A.K.; Peijnenburg, K.T.C.A.

2016-01-01

The Atlantidae (shelled heteropods) is a family of microscopic aragonite shelled holoplanktonic gastropods with a wide biogeographical distribution in tropical, sub-tropical and temperate waters. The aragonite shell and surface ocean habitat of the atlantids makes them particularly susceptible to

Modeling the Release Kinetics of Poorly Water-Soluble Drug Molecules from Liposomal Nanocarriers

Directory of Open Access Journals (Sweden)

Stephan Loew

2011-01-01

Full Text Available Liposomes are frequently used as pharmaceutical nanocarriers to deliver poorly water-soluble drugs such as temoporfin, cyclosporine A, amphotericin B, and paclitaxel to their target site. Optimal drug delivery depends on understanding the release kinetics of the drug molecules from the host liposomes during the journey to the target site and at the target site. Transfer of drugs in model systems consisting of donor liposomes and acceptor liposomes is known from experimental work to typically exhibit a first-order kinetics with a simple exponential behavior. In some cases, a fast component in the initial transfer is present, in other cases the transfer is sigmoidal. We present and analyze a theoretical model for the transfer that accounts for two physical mechanisms, collisions between liposomes and diffusion of the drug molecules through the aqueous phase. Starting with the detailed distribution of drug molecules among the individual liposomes, we specify the conditions that lead to an apparent first-order kinetic behavior. We also discuss possible implications on the transfer kinetics of (1 high drug loading of donor liposomes, (2 attractive interactions between drug molecules within the liposomes, and (3 slow transfer of drugs between the inner and outer leaflets of the liposomes.

Structural aspects of the solvation shell of lysine and acetylated lysine: A Car-Parrinello and classical molecular dynamics investigation

International Nuclear Information System (INIS)

Carnevale, V.; Raugei, S.

2009-01-01

Lysine acetylation is a post-translational modification, which modulates the affinity of protein-protein and/or protein-DNA complexes. Its crucial role as a switch in signaling pathways highlights the relevance of charged chemical groups in determining the interactions between water and biomolecules. A great effort has been recently devoted to assess the reliability of classical molecular dynamics simulations in describing the solvation properties of charged moieties. In the spirit of these investigations, we performed classical and Car-Parrinello molecular dynamics simulations on lysine and acetylated-lysine in aqueous solution. A comparative analysis between the two computational schemes is presented with a focus on the first solvation shell of the charged groups. An accurate structural analysis unveils subtle, yet statistically significant, differences which are discussed in connection to the significant electronic density charge transfer occurring between the solute and the surrounding water molecules.

Thermodynamic and structural signatures of water-driven methane-methane attraction in coarse-grained mW water.

Science.gov (United States)

Song, Bin; Molinero, Valeria

2013-08-07

Hydrophobic interactions are responsible for water-driven processes such as protein folding and self-assembly of biomolecules. Microscopic theories and molecular simulations have been used to study association of a pair of methanes in water, the paradigmatic example of hydrophobic attraction, and determined that entropy is the driving force for the association of the methane pair, while the enthalpy disfavors it. An open question is to which extent coarse-grained water models can still produce correct thermodynamic and structural signatures of hydrophobic interaction. In this work, we investigate the hydrophobic interaction between a methane pair in water at temperatures from 260 to 340 K through molecular dynamics simulations with the coarse-grained monatomic water model mW. We find that the coarse-grained model correctly represents the free energy of association of the methane pair, the temperature dependence of free energy, and the positive change in entropy and enthalpy upon association. We investigate the relationship between thermodynamic signatures and structural order of water through the analysis of the spatial distribution of the density, energy, and tetrahedral order parameter Qt of water. The simulations reveal an enhancement of tetrahedral order in the region between the first and second hydration shells of the methane molecules. The increase in tetrahedral order, however, is far from what would be expected for a clathrate-like or ice-like shell around the solutes. This work shows that the mW water model reproduces the key signatures of hydrophobic interaction without long ranged electrostatics or the need to be re-parameterized for different thermodynamic states. These characteristics, and its hundred-fold increase in efficiency with respect to atomistic models, make mW a promising water model for studying water-driven hydrophobic processes in more complex systems.

Molecular dynamics study of the coordination sphere of trivalent lanthanum in a highly concentrated LiCl aqueous solution: A combined classical and ab initio approach

International Nuclear Information System (INIS)

Vuilleumier, R.; Petit, L.; Maldivi, P.; Adamo, C.

2008-01-01

The first coordination sphere of trivalent lanthanum in a highly concentrated (14 M) lithium chloride solution is studied with a combination of classical molecular dynamics and density functional theory based first principle molecular dynamics. This method enables us to obtain a solvation shell of La 3+ containing 2 chloride ions and 6 water molecules. After refinement using first principle molecular dynamics, the resulting cation-water and cation-anion distances are in very good agreement with experiment. The 2 Cl - and the 6 water molecules arrange in a square anti-prism around La 3+ . Exchange of water molecules was also observed in the first-principle simulation, with an intermediate structure comprising 7 water molecules stable for 2.5 ps. Finally, evaluation of dipole moments using maximally localized Wannier functions shows a substantial polarization of the chloride anions and the water molecules in the first solvation shell of trivalent lanthanum. (authors)

Water-Soluble CdTe/CdS Core/Shell Semiconductor Nanocrystals: How Their Optical Properties Depend on the Synthesis Methods

Directory of Open Access Journals (Sweden)

Brener R. C. Vale

2016-10-01

Full Text Available We conducted a comparative synthesis of water-soluble CdTe/CdS colloidal nanocrystalline semiconductors of the core/shell type. We prepared the CdS shell using two different methods: a one-pot approach and successive ionic layer adsorption and reaction (SILAR; in both cases, we used 3-mercaptopropionic acid (MPA as the surface ligand. In the one-pot approach, thiourea was added over the freshly formed CdTe dispersion, and served as the sulfur source. We achieved thicker CdS layers by altering the Cd:S stoichiometric ratio (1:1, 1:2, 1:4, and 1:8. The Cd:S ratios 1:1 and 1:2 furnished the best optical properties; these ratios also made the formation of surface defects less likely. For CdTe/CdS obtained using SILAR, we coated the surface of three differently sized CdTe cores (2.17, 3.10, and 3.45 nm with one to five CdS layers using successive injections of the Cd2+ and S2– ions. The results showed that the core size influenced the optical properties of the materials. The deposition of three to five layers over the surface of smaller CdTe colloidal nanocrystals generated strain effects on the core/shell structure.

Acidic electrolyzed water as a novel transmitting medium for high hydrostatic pressure reduction of bacterial loads on shelled fresh shrimp

Directory of Open Access Journals (Sweden)

Suping eDu

2016-03-01

Full Text Available Acidic electrolyzed water (AEW, a novel non-thermal sterilization technology, is widely used in the food industry. In this study, we firstly investigated the effect of AEW as a new pressure transmitting medium for high hydrostatic pressure (AEW-HHP processing on microorganisms inactivation on shelled fresh shrimp. The optimal conditions of AEW-HHP for Vibrio parahaemolyticus inactivation on sterile shelled fresh shrimp were obtained using response surface methodology: NaCl concentration to electrolysis 1.5 g/L, treatment pressure 400 MPa, treatment time 10 min. Under the optimal conditions mentioned above, AEW dramatically enhanced the efficiency of HHP for inactivating V. parahaemolyticus and Listeria monocytogenes on artificially contaminated shelled fresh shrimp, and the log reductions were up to 6.08 and 5.71 log10 CFU/g respectively, while the common HHP could only inactivate the two pathogens up to 4.74 and 4.31 log10 CFU/g respectively. Meanwhile, scanning electron microscopy (SEM showed the same phenomenon. For the naturally contaminated shelled fresh shrimp, AEW-HHP could also significantly reduce the micro flora when examined using plate count and PCR-DGGE. There were also no significant changes, histologically, in the muscle tissues of shrimps undergoing the AEW-HHP treatment. In summary, using AEW as a new transmitting medium for HHP processing is an innovative non thermal technology for improving the food safety of shrimp and other aquatic products.

Acidic Electrolyzed Water as a Novel Transmitting Medium for High Hydrostatic Pressure Reduction of Bacterial Loads on Shelled Fresh Shrimp

Science.gov (United States)

Du, Suping; Zhang, Zhaohuan; Xiao, Lili; Lou, Yang; Pan, Yingjie; Zhao, Yong

2016-01-01

Acidic electrolyzed water (AEW), a novel non-thermal sterilization technology, is widely used in the food industry. In this study, we firstly investigated the effect of AEW as a new pressure transmitting medium for high hydrostatic pressure (AEW-HHP) processing on microorganisms inactivation on shelled fresh shrimp. The optimal conditions of AEW-HHP for Vibrio parahaemolyticus inactivation on sterile shelled fresh shrimp were obtained using response surface methodology: NaCl concentration to electrolysis 1.5 g/L, treatment pressure 400 MPa, treatment time 10 min. Under the optimal conditions mentioned above, AEW dramatically enhanced the efficiency of HHP for inactivating V. parahaemolyticus and Listeria monocytogenes on artificially contaminated shelled fresh shrimp, and the log reductions were up to 6.08 and 5.71 log10 CFU/g respectively, while the common HHP could only inactivate the two pathogens up to 4.74 and 4.31 log10 CFU/g respectively. Meanwhile, scanning electron microscopy (SEM) showed the same phenomenon. For the naturally contaminated shelled fresh shrimp, AEW-HHP could also significantly reduce the micro flora when examined using plate count and PCR-DGGE. There were also no significant changes, histologically, in the muscle tissues of shrimps undergoing the AEW-HHP treatment. In summary, using AEW as a new transmitting medium for HHP processing is an innovative non thermal technology for improving the food safety of shrimp and other aquatic products. PMID:27014228

Development of lipid-shell and polymer core nanoparticles with water-soluble salidroside for anti-cancer therapy.

Science.gov (United States)

Fang, Dai-Long; Chen, Yan; Xu, Bei; Ren, Ke; He, Zhi-Yao; He, Li-Li; Lei, Yi; Fan, Chun-Mei; Song, Xiang-Rong

2014-02-25

Salidroside (Sal) is a potent antitumor drug with high water-solubility. The clinic application of Sal in cancer therapy has been significantly restricted by poor oral absorption and low tumor cell uptake. To solve this problem, lipid-shell and polymer-core nanoparticles (Sal-LPNPs) loaded with Sal were developed by a double emulsification method. The processing parameters including the polymer types, organic phase, PVA types and amount were systemically investigated. The obtained optimal Sal-LPNPs, composed of PLGA-PEG-PLGA triblock copolymers and lipids, had high entrapment efficiency (65%), submicron size (150 nm) and negatively charged surface (-23 mV). DSC analysis demonstrated the successful encapsulation of Sal into LPNPs. The core-shell structure of Sal-LPNPs was verified by TEM. Sal released slowly from the LPNPs without apparent burst release. MTT assay revealed that 4T1 and PANC-1 cancer cell lines were sensitive to Sal treatment. Sal-LPNPs had significantly higher antitumor activities than free Sal in 4T1 and PANC-1 cells. The data indicate that LPNPs are a promising Sal vehicle for anti-cancer therapy and worthy of further investigation.

Development of Lipid-Shell and Polymer Core Nanoparticles with Water-Soluble Salidroside for Anti-Cancer Therapy

Directory of Open Access Journals (Sweden)

Dai-Long Fang

2014-02-01

Full Text Available Salidroside (Sal is a potent antitumor drug with high water-solubility. The clinic application of Sal in cancer therapy has been significantly restricted by poor oral absorption and low tumor cell uptake. To solve this problem, lipid-shell and polymer-core nanoparticles (Sal-LPNPs loaded with Sal were developed by a double emulsification method. The processing parameters including the polymer types, organic phase, PVA types and amount were systemically investigated. The obtained optimal Sal-LPNPs, composed of PLGA-PEG-PLGA triblock copolymers and lipids, had high entrapment efficiency (65%, submicron size (150 nm and negatively charged surface (−23 mV. DSC analysis demonstrated the successful encapsulation of Sal into LPNPs. The core-shell structure of Sal-LPNPs was verified by TEM. Sal released slowly from the LPNPs without apparent burst release. MTT assay revealed that 4T1 and PANC-1 cancer cell lines were sensitive to Sal treatment. Sal-LPNPs had significantly higher antitumor activities than free Sal in 4T1 and PANC-1 cells. The data indicate that LPNPs are a promising Sal vehicle for anti-cancer therapy and worthy of further investigation.

Synergistic Removal of Humic Acid in Water by Coupling Adsorption and Photocatalytic Degradation Using TiO2/Coconut Shell Powder Composite

Directory of Open Access Journals (Sweden)

Jong Kyu Kim

2016-01-01

Full Text Available The feasibility of applying nanoscale TiO2/coconut shell powder (TCNSP composite to remove HA in aqueous solution was evaluated, and the optimization of the photocatalytic systems using newly developed TCNSP composite was performed. The developed TCNSP composite has high specific surface area (i.e., 454 m2/g and great porosity (i.e., 66.9% with pore size of less than 5 μm. High removal efficiencies (≥95% of HA were observed due to the significant synergistic effects by coupling adsorption and photocatalytic reaction of TCNSP composite. As the initial concentration of HA increased, the degradation rate (Kapp decreased due to HA sorption saturation to the surface of TCNSP composite and the photon interception by HA molecules in aqueous solution. Since the increased loading amount of TCNSP composite enhanced the number of active sites, Kapp values increased until the optimum loading amount of TCNSP composite. As pH values increased, HA removal efficiency decreased due to increasing electrostatic repulsion between HA and TCNSP composite. Based on the response surface methodology, higher HA removal efficiencies were obtained with acidic condition, longer reaction time, and appropriated loading amount of TCNSP. Further pilot-scale study is in progress using TCNSP composite combined with UVC to remove HA from large amounts of surface water (i.e., 200 m3/d.

Multipole moments of water molecules in clusters and ice Ih from first principles calculations

International Nuclear Information System (INIS)

Batista, E.R.; Xantheas, S.S.; Jonsson, H.

1999-01-01

We have calculated molecular multipole moments for water molecules in clusters and in ice Ih by partitioning the charge density obtained from first principles calculations. Various schemes for dividing the electronic charge density among the water molecules were used. They include Bader close-quote s zero flux surfaces and Voronoi partitioning schemes. A comparison was also made with an induction model including dipole, dipole-quadrupole, quadrupole-quadrupole polarizability and first hyperpolarizability as well as fixed octopole and hexadecapole moments. We have found that the different density partitioning schemes lead to widely different values for the molecular multipoles, illustrating how poorly defined molecular multipoles are in clusters and condensed environments. For instance, the magnitude of the molecular dipole moment in ice Ih ranges between 2.3 D and 3.1 D depending on the partitioning scheme used. Within each scheme, though, the value for the molecular dipole moment in ice is larger than in the hexamer. The magnitude of the molecular dipole moment in the clusters shows a monotonic increase from the gas phase value to the one in ice Ih, with the molecular dipole moment in the water ring hexamer being smaller than the one in ice Ih for all the partitioning schemes used. copyright 1999 American Institute of Physics

Plasmon enhanced water splitting mediated by hybrid bimetallic Au-Ag core-shell nanostructures.

Science.gov (United States)

Erwin, William R; Coppola, Andrew; Zarick, Holly F; Arora, Poorva; Miller, Kevin J; Bardhan, Rizia

2014-11-07

In this work, we employed wet chemically synthesized bimetallic Au-Ag core-shell nanostructures (Au-AgNSs) to enhance the photocurrent density of mesoporous TiO2 for water splitting and we compared the results with monometallic Au nanoparticles (AuNPs). While Au-AgNSs incorporated photoanodes give rise to 14× enhancement in incident photon to charge carrier efficiency, AuNPs embedded photoanodes result in 6× enhancement. By varying nanoparticle concentration in the photoanodes, we observed ∼245× less Au-AgNSs are required relative to AuNPs to generate similar photocurrent enhancement for solar fuel conversion. Power-dependent measurements of Au-AgNSs and AuNPs showed a first order dependence to incident light intensity, relative to half-order dependence for TiO2 only photoanodes. This indicated that plasmonic nanostructures enhance charge carriers formed on the surface of the TiO2 which effectively participate in photochemical reactions. Our experiments and simulations suggest the enhanced near-field, far-field, and multipolar resonances of Au-AgNSs facilitating broadband absorption of solar radiation collectively gives rise to their superior performance in water splitting.

Synthesis, characterization and evaluation of uniformly sized core-shell imprinted microspheres for the separation trans-resveratrol from giant knotweed

International Nuclear Information System (INIS)

Zhang Zhaohui; Liu Li; Li Hui; Yao Shouzhuo

2009-01-01

A novel core-shell molecularly imprinting microspheres (MIMs) with trans-resveratrol as the template molecule; acrylamide (AA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker, was prepared based on SiO 2 microspheres with surface imprinting technique. These core-shell trans-resveratrol imprinted microspheres were characterized by infrared spectra (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and high performance liquid chromatography (HPLC). The results showed that these core-shell imprinted microspheres, which take on perfect spherical shape with average shell thickness of 150 nm, exhibit especially selective recognition for trans-resveratrol. These imprinted microspheres were applied as solid-phase extraction materials for selective extraction of trans-resveratrol from giant knotweed extracting solution successfully.

Synthesis, characterization and evaluation of uniformly sized core-shell imprinted microspheres for the separation trans-resveratrol from giant knotweed

Energy Technology Data Exchange (ETDEWEB)

Zhang Zhaohui, E-mail: zhaohuizhang77@hotmail.com [College of Chemistry and Chemical Engineering, Jishou University, Jishou, 416000 (China); State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha, 410082 (China); Liu Li; Li Hui [College of Chemistry and Chemical Engineering, Jishou University, Jishou, 416000 (China); Yao Shouzhuo [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha, 410082 (China)

2009-09-15

A novel core-shell molecularly imprinting microspheres (MIMs) with trans-resveratrol as the template molecule; acrylamide (AA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker, was prepared based on SiO{sub 2} microspheres with surface imprinting technique. These core-shell trans-resveratrol imprinted microspheres were characterized by infrared spectra (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and high performance liquid chromatography (HPLC). The results showed that these core-shell imprinted microspheres, which take on perfect spherical shape with average shell thickness of 150 nm, exhibit especially selective recognition for trans-resveratrol. These imprinted microspheres were applied as solid-phase extraction materials for selective extraction of trans-resveratrol from giant knotweed extracting solution successfully.

Single-crystal apatite nanowires sheathed in graphitic shells: synthesis, characterization, and application.

Science.gov (United States)

Jeong, Namjo; Cha, Misun; Park, Yun Chang; Lee, Kyung Mee; Lee, Jae Hyup; Park, Byong Chon; Lee, Junghoon

2013-07-23

Vertically aligned one-dimensional hybrid structures, which are composed of apatite and graphitic structures, can be beneficial for orthopedic applications. However, they are difficult to generate using the current method. Here, we report the first synthesis of a single-crystal apatite nanowire encapsulated in graphitic shells by a one-step chemical vapor deposition. Incipient nucleation of apatite and its subsequent transformation to an oriented crystal are directed by derived gaseous phosphorine. Longitudinal growth of the oriented apatite crystal is achieved by a vapor-solid growth mechanism, whereas lateral growth is suppressed by the graphitic layers formed through arrangement of the derived aromatic hydrocarbon molecules. We show that this unusual combination of the apatite crystal and the graphitic shells can lead to an excellent osteogenic differentiation and bony fusion through a programmed smart behavior. For instance, the graphitic shells are degraded after the initial cell growth promoted by the graphitic nanostructures, and the cells continue proliferation on the bare apatite nanowires. Furthermore, a bending experiment indicates that such core-shell nanowires exhibited a superior bending stiffness compared to single-crystal apatite nanowires without graphitic shells. The results suggest a new strategy and direction for bone grafting materials with a highly controllable morphology and material conditions that can best stimulate bone cell differentiation and growth.

Solvation study of the non-specific lipid transfer protein from wheat by intermolecular NOEs with water and small organic molecules

International Nuclear Information System (INIS)

Liepinsh, Edvards; Sodano, Patrick; Tassin, Severine; Marion, Didier; Vovelle, Francoise; Otting, Gottfried

1999-01-01

Intermolecular nuclear Overhauser effects (NOEs) were measured between the protons of various small solvent or gas molecules and the non-specific lipid transfer protein (ns-LTP) from wheat. Intermolecular NOEs were observed with the hydrophobic pocket in the interior of wheat ns-LTP, which grew in intensity in the order cyclopropane (saturated solution) < methane (140 bar) < ethane (40 bar) < acetonitrile (5% in water) < cyclohexane (saturated solution) < benzene (saturated solution). No intermolecular NOEs were observed with dioxane (5% in water). The intermolecular NOEs were negative for all of the organic molecules tested. Intermolecular NOEs between wheat ns-LTP and water were weak or could not be distinguished from exchange-relayed NOEs. As illustrated by the NOEs with cyclohexane versus dioxane, the hydrophobic pocket in wheat ns-LTP preferably binds non-polar molecules. Yet, polar molecules like acetonitrile can also be accommodated. The pressure dependence of the NOEs between methane and wheat ns-LTP indicated incomplete occupancy, even at 190 bar methane pressure. In general, NOE intensities increased with the size of the ligand molecule and its vapor pressure. NMR of the vapor phase showed excellent resolution between the signals from the gas phase and those from the liquid phase. The vapor concentration of cyclohexane was fivefold higher than that of the dioxane solution, supporting the binding of cyclohexane versus uptake of dioxane

Core-shell-corona micelles by PS-b-P2VP-b-PEO copolymers: focus on the water-induced micellization process.

Science.gov (United States)

Willet, Nicolas; Gohy, Jean-François; Auvray, Loïc; Varshney, Sunil; Jérôme, Robert; Leyh, Bernard

2008-04-01

It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process.

Shell Properties, Water Vapor Loss, and Hatching Success of Eggs from a Rain Forest Population of the Pearly-eyed Thrasher (Margarops fuscatus)

Science.gov (United States)

WAYNE J. ARENDT

2005-01-01

I calculated various shell properties, water vapor loss, and hatching success of eggs of the Pearly-eyed Thrasher (Margarops fuscatus) using measurements obtained during a long-term study in the Luquillo Mountains, Puerto Rico. Empirical results were comparable to standard reference formulae, demonstrating that published formulae can be used with confidence by field...

Micellizationa and Gelation of Water Soluable Thermo-and Light-sensitive Block Copolymer Investigated by SANS

Science.gov (United States)

He, Lilin; Hu, Bin; Zhao, Bin

2015-03-01

Here we present an extensive small-angle neutron scattering (SANS) characterization of micellization and gelation of PEO-b-P(TEGEA-co-NBA) in deuterated water in a wide range of temperatures and concentrations before and after the removal of o-nitrobenzyl group by UV irradiation. Scattering data analysis indicated that unimers predominated in the solutions at low temperatures and concentrations. The polymer self-assembled into micelles with the P(TEGEA-co-NBA) block packed into the core and PEO forming the corona layer. A core-shell model was used to fit SANS data and obtain sizes and scattering length densities. Structural parameters such as the aggregation numbers, the radius of gyration of the chains in the shell region, the number of water molecules in the both regions were determined. The structural information combined with the rheological data were used to describe the phase behaviors of the diblock copolymer in aqueous solution.

Water and oxygen induced degradation of small molecule organic solar cells

DEFF Research Database (Denmark)

Hermenau, Martin; Riede, Moritz; Leo, Karl

2011-01-01

Small molecule organic solar cells were studied with respect to water and oxygen induced degradation by mapping the spatial distribution of reaction products in order to elucidate the degradation patterns and failure mechanisms. The active layers consist of a 30 nm bulk heterojunction formed......,4′-diamine p-doped with C60F36 (MeO-TPD:C60F36), which acted as hole transporting layer. Indium-tin-oxide (ITO) and aluminum served as hole and electron collecting electrode, respectively. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) in conjunction...... of aluminum oxide at the BPhen/Al interface, and diffusion of water into the ZnPc:C60 layer where ZnPc becomes oxidized. Finally, diffusion from the electrodes was found to have no or a negligible effect on the device lifetime....

Combined quantum mechanics/molecular mechanics (QM/MM) simulations for protein-ligand complexes: free energies of binding of water molecules in influenza neuraminidase.

Science.gov (United States)

Woods, Christopher J; Shaw, Katherine E; Mulholland, Adrian J

2015-01-22

The applicability of combined quantum mechanics/molecular mechanics (QM/MM) methods for the calculation of absolute binding free energies of conserved water molecules in protein/ligand complexes is demonstrated. Here, we apply QM/MM Monte Carlo simulations to investigate binding of water molecules to influenza neuraminidase. We investigate five different complexes, including those with the drugs oseltamivir and peramivir. We investigate water molecules in two different environments, one more hydrophobic and one hydrophilic. We calculate the free-energy change for perturbation of a QM to MM representation of the bound water molecule. The calculations are performed at the BLYP/aVDZ (QM) and TIP4P (MM) levels of theory, which we have previously demonstrated to be consistent with one another for QM/MM modeling. The results show that the QM to MM perturbation is significant in both environments (greater than 1 kcal mol(-1)) and larger in the more hydrophilic site. Comparison with the same perturbation in bulk water shows that this makes a contribution to binding. The results quantify how electronic polarization differences in different environments affect binding affinity and also demonstrate that extensive, converged QM/MM free-energy simulations, with good levels of QM theory, are now practical for protein/ligand complexes.

Surface characterization of hydrophobic core-shell QDs using NMR techniques

Science.gov (United States)

Zhang, Chengqi; Zeng, Birong; Palui, Goutam; Mattoussi, Hedi

2018-02-01

Using a few solution phase NMR spectroscopy techniques, including 1H NMR and 31P NMR, we have characterized the organic shell on CdSe-ZnS core-shell quantum dots and tracked changes in its composition when the QD dispersions are subjected to varying degrees of purification. Combining solution phase NMR with diffusion ordered spectroscopy (DOSY), we were able to distinguish between freely diffusing ligands in the sample from those bound on the surfaces. Additionally, matrix assisted laser desorption ionization (MALDI) and FTIR measurements were used to provide complementary and supporting information on the organic ligand coating for these nanocrystals. We found that the organic shell is dominated by monomeric or oligomeric n-hexylphosphonic acid (HPA), along with small portion of 1-hexadecyl amine (HDA). The presence of TOP/TOPO (tri-n-octylphosphine / tri-noctylphosphine oxide) molecules is much smaller, even though large excess of TOP/TOPO were used during the QD growth. These results indicate that HPA (alkyl phosphonate) exhibits the strongest coordination affinity to ZnS-rich QD surfaces grown using the high temperature injection route.

Hi shells, supershells, shell-like objects, and ''worms''

International Nuclear Information System (INIS)

Heiles, C.

1984-01-01

We present photographic representations of the combination of two Hi surveys, so as to eliminate the survey boundaries at Vertical BarbVertical Bar = 10 0 . We also present high-contrast photographs for particular velocities to exhibit weak Hi features. All of these photographs were used to prepare a new list of Hi shells, supershells, and shell-like objects. We discuss the structure of three shell-like objects that are associated with high-velocity gas, and with gas at all velocities that is associated with radio continuum loops I, II, and III. We use spatial filtering to find wiggly gas filaments: ''worms'': crawling away from the galactic plane in the inner Galaxy. The ''worms'' are probably parts of shells that are open at the top; such shells should be good sources of hot gas for the galactic halo

Fabrication of PLA/CaCO3 hybrid micro-particles as carriers for water-soluble bioactive molecules.

Science.gov (United States)

Kudryavtseva, Valeriya L; Zhao, Li; Tverdokhlebov, Sergei I; Sukhorukov, Gleb B

2017-09-01

We propose the use of polylactic acid/calcium carbonate (PLA/CaCO 3 ) hybrid micro-particles for achieving improved encapsulation of water-soluble substances. Biodegradable porous CaCO 3 microparticles can be loaded with wide range of bioactive substance. Thus, the formation of hydrophobic polymeric shell on surface of these loaded microparticles results on encapsulation and, hence, sealing internal cargo and preventing their release in aqueous media. In this study, to encapsulate proteins, we explore the solid-in-oil-in-water emulsion method for fabricating core/shell PLA/CaCO 3 systems. We used CaCO 3 particles as a protective core for encapsulated bovine serum albumin, which served as a model protein system. We prepared a PLA coating using dichloromethane as an organic solvent and polyvinyl alcohol as a surfactant for emulsification; in addition, we varied experimental parameters such as surfactant concentration and polymer-to-CaCO 3 ratio to determine their effect on particle-size distribution, encapsulation efficiency and capsule permeability. The results show that the particle size decreased and the size distribution narrowed as the surfactant concentration increased in the external aqueous phase. In addition, when the CaCO 3 /PLA mass ratio dropped below 0.8, the hybrid micro-particles were more likely to resist treatment by ethylenediaminetetraacetic acid and thus retained their bioactive cargos within the polymer-coated micro-particles. Copyright © 2017 Elsevier B.V. All rights reserved.

The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

Science.gov (United States)

Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

2017-10-13

Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

Docking ligands into flexible and solvated macromolecules. 7. Impact of protein flexibility and water molecules on docking-based virtual screening accuracy.

Science.gov (United States)

Therrien, Eric; Weill, Nathanael; Tomberg, Anna; Corbeil, Christopher R; Lee, Devin; Moitessier, Nicolas

2014-11-24

The use of predictive computational methods in the drug discovery process is in a state of continual growth. Over the last two decades, an increasingly large number of docking tools have been developed to identify hits or optimize lead molecules through in-silico screening of chemical libraries to proteins. In recent years, the focus has been on implementing protein flexibility and water molecules. Our efforts led to the development of Fitted first reported in 2007 and further developed since then. In this study, we wished to evaluate the impact of protein flexibility and occurrence of water molecules on the accuracy of the Fitted docking program to discriminate active compounds from inactive compounds in virtual screening (VS) campaigns. For this purpose, a total of 171 proteins cocrystallized with small molecules representing 40 unique enzymes and receptors as well as sets of known ligands and decoys were selected from the Protein Data Bank (PDB) and the Directory of Useful Decoys (DUD), respectively. This study revealed that implementing displaceable crystallographic or computationally placed particle water molecules and protein flexibility can improve the enrichment in active compounds. In addition, an informed decision based on library diversity or research objectives (hit discovery vs lead optimization) on which implementation to use may lead to significant improvements.

Red-Light-Driven Water Splitting by Au(Core)-CdS(Shell) Half-Cut Nanoegg with Heteroepitaxial Junction.

Science.gov (United States)

Naya, Shin-Ichi; Kume, Takahiro; Akashi, Ryo; Fujishima, Musashi; Tada, Hiroaki

2018-01-31

A key material for artificial photosynthesis including water splitting is heteronanostructured (HNS) photocatalysts. The photocatalytic activity depends on the geometry and dimension, and the quality of junctions between the components. Here we present a half-cut Au(core)-CdS(shell) (HC-Au@CdS) nanoegg as a new HNS plasmonic photocatalyst for water splitting. UV-light irradiation of Au nanoparticle (NP)-loaded ZnO (Au/ZnO) at 50 °C induces the selective deposition of hexagonal CdS on the Au surface of Au/ZnO with an epitaxial (EPI) relation of CdS{0001}/Au{111}. The subsequent selective dissolution of the ZnO support at room temperature yields HC-Au@CdS with the Au NP size and EPI junction (#) retained. Red-light irradiation (λ ex = 640 nm) of HC-Au@#CdS gives rise to continuous stoichiometric water splitting with an unprecedentedly high external quantum yield of 0.24%.

(e,3e) and (e,3-1e) differential cross sections for the double ionization of water molecule

International Nuclear Information System (INIS)

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

2009-01-01

We report new results for differential cross sections for the double ionization of water molecule by 1 keV electron impact. The present calculation is based on the first Born approximation. We describe the water molecule by a single centre wave function of Moccia. For the final state, an approximation of the well-known 3C wave function is used. An extensive study has been made by varying the angles of detection and the energies of each ejected electron. We have investigated the double ionization of each molecular state (1b 1 , 3a 1 , 1b 2 and 2a 1 ) and identified the mechanisms of this process.

Gene expression correlated with delay in shell formation in larval Pacific oysters (Crassostrea gigas) exposed to experimental ocean acidification provides insights into shell formation mechanisms.

Science.gov (United States)

De Wit, Pierre; Durland, Evan; Ventura, Alexander; Langdon, Chris J

2018-02-22

Despite recent work to characterize gene expression changes associated with larval development in oysters, the mechanism by which the larval shell is first formed is still largely unknown. In Crassostrea gigas, this shell forms within the first 24 h post fertilization, and it has been demonstrated that changes in water chemistry can cause delays in shell formation, shell deformations and higher mortality rates. In this study, we use the delay in shell formation associated with exposure to CO 2 -acidified seawater to identify genes correlated with initial shell deposition. By fitting linear models to gene expression data in ambient and low aragonite saturation treatments, we are able to isolate 37 annotated genes correlated with initial larval shell formation, which can be categorized into 1) ion transporters, 2) shell matrix proteins and 3) protease inhibitors. Clustering of the gene expression data into co-expression networks further supports the result of the linear models, and also implies an important role of dynein motor proteins as transporters of cellular components during the initial shell formation process. Using an RNA-Seq approach with high temporal resolution allows us to identify a conceptual model for how oyster larval calcification is initiated. This work provides a foundation for further studies on how genetic variation in these identified genes could affect fitness of oyster populations subjected to future environmental changes, such as ocean acidification.

A generalized operational formula based on total electronic densities to obtain 3D pictures of the dual descriptor to reveal nucleophilic and electrophilic sites accurately on closed-shell molecules.

Science.gov (United States)

Martínez-Araya, Jorge I

2016-09-30

By means of the conceptual density functional theory, the so-called dual descriptor (DD) has been adapted to be used in any closed-shell molecule that presents degeneracy in its frontier molecular orbitals. The latter is of paramount importance because a correct description of local reactivity will allow to predict the most favorable sites on a molecule to undergo nucleophilic or electrophilic attacks; on the contrary, an incomplete description of local reactivity might have serio us consequences, particularly for those experimental chemists that have the need of getting an insight about reactivity of chemical reagents before using them in synthesis to obtain a new compound. In the present work, the old approach based only on electronic densities of frontier molecular orbitals is replaced by the most accurate procedure that implies the use of total electronic densities thus keeping consistency with the essential principle of the DFT in which the electronic density is the fundamental variable and not the molecular orbitals. As a result of the present work, the DD will be able to properly describe local reactivities only in terms of total electronic densities. To test the proposed operational formula, 12 very common molecules were selected as the original definition of the DD was not able to describe their local reactivities properly. The ethylene molecule was additionally used to test the capability of the proposed operational formula to reveal a correct local reactivity even in absence of degeneracy in frontier molecular orbitals. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Effect of an improved molecular potential on strong-field tunneling ionization of molecules

International Nuclear Information System (INIS)

Zhao Songfeng; Jin Cheng; Le, Anh-Thu; Lin, C. D.

2010-01-01

We study the effect of one-electron model potentials on the tunneling ionization rates of molecules in strong fields. By including electron correlation using the modified Leeuwen-Baerends (LB α) model, the binding energies of outer shells of molecules are significantly improved. However, we show that the tunneling ionization rates from the LB α do not differ much from the earlier calculations [Phys. Rev. A 81, 033423 (2010)], in which the local correlation potential was neglected.

STABILIZATION OF THE NEUTRAL PROTEASE OF BACILLUS-STEAROTHERMOPHILUS BY REMOVAL OF A BURIED WATER MOLECULE

NARCIS (Netherlands)

VRIEND, G; BERENDSEN, HJC; VANDERZEE, [No Value; VANDENBURG, B; VENEMA, G; EIJSINK, VGH

1991-01-01

Using site-directed mutagenesis, Ala166 in the neutral protease of Bacillus stearothermophilus was changed into Ser. Model building and molecular dynamics simulations of the mutant enzyme indicated that the Ser hydroxyl group fits well in a cavity which contains a water molecule in the wild-type

Change in organic molecule adhesion on α-alumina (Sapphire) with change in NaCl and CaCl₂ solution salinity

DEFF Research Database (Denmark)

Juhl, Klaus; Bovet, Nicolas Emile; Hassenkam, Tue

2014-01-01

We investigated the adhesion of two functional groups to α-alumina as a model for the adsorption of organic molecules on clay minerals. Interactions between organic compounds and clay minerals play an important role in processes such as drinking water treatment, remediation of contaminated soil...... the growth of bones, teeth, and shells. Adhesion of carboxylic acid, -COO(H), and pyridine, -C5H5N(H+), on the {0001} plane of α-alumina wafers has been investigated with atomic force microscopy (AFM) in chemical force mapping (CFM) mode. Both functional groups adhered to α-alumina in deionized water at p...... in surface properties, controlling surface tension (i.e., contact angle) and adsorption affinity on α-alumina and, by analogy, on clay minerals....

Initiation and elimination of vacuoles in microencapsulated shells

International Nuclear Information System (INIS)

Du Kai; You Dan

2000-01-01

Two mechanisms of vacuole formation in microencapsulated micro-shells wall are introduced. It is verified that phase separation of trace amount of water in the organic solvent is the most possible course of vacuole formation

Molecular effects in carbon K-shell Auger-electron production by 0.6-2.0 MeV protons and extraction of an atomic cross section

International Nuclear Information System (INIS)

McDaniel, F.D.; Lapicki, G.

1987-01-01

Carbon K-shell Auger-electron production cross sections are reported for 0.6-2.0 MeV protons incident on CH 4 (methane), C 2 H 2 (acetylene), C 2 H 4 (ethylene), C 2 H 6 (ethane), n-C 4 H 10 (normal butane), i-C 4 H 10 (isobutane), C 6 H 6 (benzene), CO (carbon monoxide), and CO 2 (carbon dioxide). A constant-energy mode 45 0 parallel-plate electrostatic analyzer was used for detection of Auger electrons. The carbon KLL Auger-electron cross sections for all molecules were found to be lower than that found for CH 4 by 9-23%. All carbon KLL Auger-electron data could be brought into agreement when corrected for the chemical shift of the carbon K-shell binding energy in molecules and for intramolecular scattering. KLL Auger-electron production cross sections are compared to first Born and ECPSSR theories and show good agreement with both after the chemical shift of the carbon K-shell binding energy in molecules and the effects of intramolecular scattering are considered. (orig.)

Solvation of positive ions in water: the dominant role of water-water interaction

International Nuclear Information System (INIS)

Krekeler, Christian; Site, Luigi Delle

2007-01-01

Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car-Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water-water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion. (fast track communication)

A 100 au Wide Bipolar Rotating Shell Emanating from the HH 212 Protostellar Disk: A Disk Wind?

Science.gov (United States)

Lee, Chin-Fei; Li, Zhi-Yun; Codella, Claudio; Ho, Paul T. P.; Podio, Linda; Hirano, Naomi; Shang, Hsien; Turner, Neal J.; Zhang, Qizhou

2018-03-01

HH 212 is a Class 0 protostellar system found to host a “hamburger”-shaped dusty disk with a rotating disk atmosphere and a collimated SiO jet at a distance of ∼400 pc. Recently, a compact rotating outflow has been detected in SO and SO2 toward the center along the jet axis at ∼52 au (0.″13) resolution. Here we resolve the compact outflow into a small-scale wide-opening rotating outflow shell and a collimated jet, with the observations in the same S-bearing molecules at ∼16 au (0.″04) resolution. The collimated jet is aligned with the SiO jet, tracing the shock interactions in the jet. The wide-opening outflow shell is seen extending out from the inner disk around the SiO jet and has a width of ∼100 au. It is not only expanding away from the center, but also rotating around the jet axis. The specific angular momentum of the outflow shell is ∼40 au km s‑1. Simple modeling of the observed kinematics suggests that the rotating outflow shell can trace either a disk wind or disk material pushed away by an unseen wind from the inner disk or protostar. We also resolve the disk atmosphere in the same S-bearing molecules, confirming the Keplerian rotation there.

Brine Pockets in the Icy Shell on Europa: Distribution, Chemistry, and Habitability

Science.gov (United States)

Zolotov, M. Yu; Shock, E. L.; Barr, A. C.; Pappalardo, R. T.

2004-01-01

On Earth, sea ice is rich in brine, salt, and gas inclusions that form through capturing of seawater during ice formation. Cooling of the ice over time leads to sequential freezing of captured sea-water, precipitation of salts, exsolution of gases, and formation of brine channels and pockets. Distribution and composition of brines in sea ice depend on the rate of ice formation, vertical temperature gradient, and the age of the ice. With aging, the abundance of brine pockets decreases through downward migration. De- spite low temperatures and elevated salinities, brines in sea ice provide a habitat for photosynthetic and chemosynthetic organisms. On Europa, brine pockets and channels could exist in the icy shell that may be from a few km to a few tens of km thick and is probably underlain by a water ocean. If the icy shell is relatively thick, convection could develop, affecting the temperature pattern in the ice. To predict the distribution and chemistry of brine pockets in the icy shell we have combined numerical models of the temperature distribution within a convecting shell, a model for oceanic chemistry, and a model for freezing of Europan oceanic water. Possible effects of brine and gas inclusions on ice rheology and tectonics are discussed.

Controlled-release and preserved bioactivity of proteins from (self-assembled core-shell double-walled microspheres

Directory of Open Access Journals (Sweden)

Yuan W

2012-01-01

Full Text Available Weien Yuan1,2, Zhenguo Liu11Department of Neurology, Xinhua Hospital, affiliated to Shanghai Jiao Tong University School of Medicine, Shanghai, 2School of Pharmacy, Shanghai Jiao Tong University, Shanghai, People’s Republic of ChinaAbstract: In order to address preserved protein bioactivities and protein sustained-release problems, a method for preparing double-walled microspheres with a core (protein-loaded nanoparticles with a polymer-suspended granule system-formed core and a second shell (a polymer-formed shell for controlled drug release and preserved protein bioactivities has been developed using (solid-in-oil phase-in-hydrophilic oil-in-water (S/O/Oh/W phases. The method, based on our previous microsphere preparation method (solid-in-oil phase-in-hydrophilic oil-in-water (S/O/Oh/W, employs different concentric poly(D,L-lactide-co-glycolide, poly(D,L-lactide, and protein-loaded nanoparticles to produce a suspended liquid which then self-assembles to form shell-core microspheres in the hydrophilic oil phase, which are then solidified in the water phase. Variations in the preparation parameters allowed complete encapsulation by the shell phase, including the efficient formation of a poly(D,L-lactide shell encapsulating a protein-loaded nanoparticle-based poly(D,L-lactide-co-glycolide core. This method produces core-shell double-walled microspheres that show controlled protein release and preserved protein bioactivities for 60 days. Based upon these results, we concluded that the core-shell double-walled microspheres might be applied for tissue engineering and therapy for chronic diseases, etc.Keywords: protein delivery, protein stability, core-shell microspheres, dextran nanoparticles

Primary processes of the electron-protic species coupling in pure aqueous phases: - femtosecond laser spectroscopy study; - quantum approach of the electron-water interaction

International Nuclear Information System (INIS)

Pommeret, Stanislas

1991-01-01

This thesis work deals with the coupling mechanisms between an electron, water molecules or protic species (hydronium ion, hydroxyl radical). Two complementary studies have been carry out in pure aqueous phases. The first one is concerned with the structural aspect of the hydrated electron which is studied via a semi-quantum approach Splitting Operator Method. The results indicates the importance of the second hydration shell in the localisation of an electron at 77 and 300 Kelvin. The second part of this work relates to the dynamic of the primary processes in light or heavy water at room temperature: the ion-molecule reaction, radical pair formation, geminate recombination of the hydrated electron with the hydronium ion and the hydroxyl radical. The dynamic of these reactions is studied by time resolved absorption spectroscopy from the near infrared to the near ultraviolet with a few tens femto-seconds temporal precision. The analysis of the primary processes takes into account the protic properties of water molecules. (author) [fr

The effect of water on the microstructure of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/benzene ionic liquid microemulsions.

Science.gov (United States)

Gao, Yan'an; Li, Na; Zheng, Liqiang; Zhao, Xueyan; Zhang, Jin; Cao, Quan; Zhao, Mingwei; Li, Zhen; Zhang, Gaoyong

2007-01-01

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) forms nonaqueous microemulsions with benzene with the aid of nonionic surfactant TX-100. The phase diagram of the ternary system was prepared, and the microstructures of the microemulsion were recognized. On the basis of the phase diagram, a series of ionic liquid-in-oil (IL/O) microemulsions were chosen and characterized by dynamic light scattering (DLS), which shows a similar swelling behavior to typical water-in-oil (W/O) microemulsions. The existence of IL pools in the IL/O microemulsion was confirmed by UV/Vis spectroscopic analysis with CoCl2 and methylene blue (MB) as the absorption probes. A constant polarity of the IL pool is observed, even if small amounts of water are added to the microemulsion, thus suggesting that the water molecules are solubilized in the polar outer shell of the microemulsion, as confirmed by FTIR spectra. 1H NMR spectroscopic analysis shows that these water molecules interact with the electronegative oxygen atoms of the oxyethylene (OE) units of TX-100 through hydrogen-bonding interactions, and the electronegative oxygen atoms of the water molecules attract the electropositive imidazolium rings of [bmim][BF4]. Hence, the water molecules are like a glue that stick the IL and OE units more tightly together and thus make the microemulsion system more stable. Considering the unique solubilization behavior of added water molecules, the IL/O microemulsion system may be used as a medium to prepare porous or hollow nanomaterials by hydrolysis reactions.

Buckling shells are also swimmers

Science.gov (United States)

Quilliet, Catherine; Dyfcom Bubbleboost Team

We present an experimental and numerical study on the displacement of shells undergoing deformations in a fluid. When submitted to cycles of pressure difference between outside and inside, a shell buckles and debuckles, showing a succession of shapes and a dynamics that are different during the two phases. Hence such objects are likely to swim, including at low Reynolds (microscopic scale). We studied the swimming of buckling/debuckling shells at macroscopic scale using different approaches (force quantization, shape recording, displacement along a frictionless rail, study of external flow using PIV), and showed that inertia plays a role in propulsion, even in situations where dimensionless numbers correspond also to microswimmers in water. Different fluid viscosities were explored, showing an optimum for the displacement. Interestingly, the most favorable cases lead to displacements in the same direction and sense during both motor stroke (buckling phase) and recovery stroke (de-buckling phase). This work opens the route for the synthesis with high throughput of abusively simple synthetic swimmers, possibly gathered into nanorobots, actuated by a scalar field such as the pressure in echographic devices. Universite Grenoble Alpes, CNRS, European Research Council.

Thick or Thin Ice Shell on Europa?

Science.gov (United States)

2007-01-01

Scientists are all but certain that Europa has an ocean underneath its icy surface, but they do not know how thick this ice might be. This artist concept illustrates two possible cut-away views through Europa's ice shell. In both, heat escapes, possibly volcanically, from Europa's rocky mantle and is carried upward by buoyant oceanic currents. If the heat from below is intense and the ice shell is thin enough (left), the ice shell can directly melt, causing what are called 'chaos' on Europa, regions of what appear to be broken, rotated and tilted ice blocks. On the other hand, if the ice shell is sufficiently thick (right), the less intense interior heat will be transferred to the warmer ice at the bottom of the shell, and additional heat is generated by tidal squeezing of the warmer ice. This warmer ice will slowly rise, flowing as glaciers do on Earth, and the slow but steady motion may also disrupt the extremely cold, brittle ice at the surface. Europa is no larger than Earth's moon, and its internal heating stems from its eccentric orbit about Jupiter, seen in the distance. As tides raised by Jupiter in Europa's ocean rise and fall, they may cause cracking, additional heating and even venting of water vapor into the airless sky above Europa's icy surface. (Artwork by Michael Carroll.)

Aqueous solvation of polyalanine α-helices with specific water molecules and with the CPCM and SM5.2 aqueous continuum models using density functional theory.

Science.gov (United States)

Marianski, Mateusz; Dannenberg, J J

2012-02-02

We present density functional theory (DFT) calculations at the X3LYP/D95(d,p) level on the solvation of polyalanine α-helices in water. The study includes the effects of discrete water molecules and the CPCM and AMSOL SM5.2 solvent continuum model both separately and in combination. We find that individual water molecules cooperatively hydrogen-bond to both the C- and N-termini of the helix, which results in increases in the dipole moment of the helix/water complex to more than the vector sum of their individual dipole moments. These waters are found to be more stable than in bulk solvent. On the other hand, individual water molecules that interact with the backbone lower the dipole moment of the helix/water complex to below that of the helix itself. Small clusters of waters at the termini increase the dipole moments of the helix/water aggregates, but the effect diminishes as more waters are added. We discuss the somewhat complex behavior of the helix with the discrete waters in the continuum models.

Pasteurization of shell eggs using radio frequency heating

International Nuclear Information System (INIS)

Geveke, David J.; Bigley, Andrew B. W.; Brunkhorst, Christopher D.

2016-01-01

The USDA-FSIS estimates that pasteurization of all shell eggs in the U.S. would reduce the annual number of illnesses by more than 110,000. However, less than 3% of shell eggs are commercially pasteurized. One of the main reasons for this is that the commercial hot water process requires as much as 60 min to complete. In the present study, a radio frequency (RF) apparatus was constructed, and a two-step process was developed that uses RF energy and hot water, to pasteurize eggs in less than half the time. In order to select an appropriate RF generator, the impedance of shell eggs was measured in the frequency range of 10–70 MHz. The power density within the egg was modeled to prevent potential hotspots. Escherichia coli (ATCC 35218) was inoculated in the yolk to approximately 7.5 log CFU/ml. The combination process first heated the egg in 35.0 °C water for 3.5 min using 60 MHz RF energy. This resulted in the yolk being preferentially heated to 61 °C. Then, the egg was heated for an additional 20 min with 56.7 °C water. This two-step process reduced the population of E. coli by 6.5 log. The total time for the process was 23.5 min. By contrast, processing for 60 min was required to reduce the E. coli by 6.6 log using just hot water. The novel RF pasteurization process presented in this study was considerably faster than the existing commercial process. As a result, this should lead to an increase in the percentage of eggs being pasteurized, as well as a reduction of foodborne illnesses.

Dynamics of Inhomogeneous Shell Systems Under Non-Stationary Loading (Survey)

Science.gov (United States)

Lugovoi, P. Z.; Meish, V. F.

2017-09-01

Experimental works on the determination of dynamics of smooth and stiffened cylindrical shells contacting with a soil medium under various non-stationary loading are reviewed. The results of studying three-layer shells of revolution whose motion equations are obtained within the framework of the hypotheses of the Timoshenko geometrically nonlinear theory are stated. The numerical results for shells with a piecewise or discrete filler enable the analysis of estimation of the influence of geometrical and physical-mechanical parameters of structures on their dynamics and reveal new mechanical effects. Basing on the classical theory of shells and rods, the effect of the discrete arrangement of ribs and coefficients of the Winkler or Pasternak elastic foundation on the normal frequencies and modes of rectangular planar cylindrical and spherical shells is studied. The number and shape of dispersion curves for longitudinal harmonic waves in a stiffened cylindrical shell are determined. The equations of vibrations of ribbed shells of revolution on Winkler or Pasternak elastic foundation are obtained using the geometrically nonlinear theory and the Timoshenko hypotheses. On applying the integral-interpolational method, numerical algorithms are developed and the corresponding non-stationary problems are solved. The special attention is paid to the statement and solution of coupled problems on the dynamical interaction of cylindrical or spherical shells with the soil water-saturated medium of different structure.

Gibbs Free Energy of Hydrolytic Water Molecule in Acyl-Enzyme Intermediates of a Serine Protease: A Potential Application for Computer-Aided Discovery of Mechanism-Based Reversible Covalent Inhibitors.

Science.gov (United States)

Masuda, Yosuke; Yamaotsu, Noriyuki; Hirono, Shuichi

2017-01-01

In order to predict the potencies of mechanism-based reversible covalent inhibitors, the relationships between calculated Gibbs free energy of hydrolytic water molecule in acyl-trypsin intermediates and experimentally measured catalytic rate constants (k cat ) were investigated. After obtaining representative solution structures by molecular dynamics (MD) simulations, hydration thermodynamics analyses using WaterMap™ were conducted. Consequently, we found for the first time that when Gibbs free energy of the hydrolytic water molecule was lower, logarithms of k cat were also lower. The hydrolytic water molecule with favorable Gibbs free energy may hydrolyze acylated serine slowly. Gibbs free energy of hydrolytic water molecule might be a useful descriptor for computer-aided discovery of mechanism-based reversible covalent inhibitors of hydrolytic enzymes.

Hydrophobic fluorine mediated switching of the hydrogen bonding site as well as orientation of water molecules in the aqueous mixture of monofluoroethanol: IR, molecular dynamics and quantum chemical studies.

Science.gov (United States)

Mondal, Saptarsi; Biswas, Biswajit; Nandy, Tonima; Singh, Prashant Chandra

2017-09-20

The local structures between water-water, alcohol-water and alcohol-alcohol have been investigated for aqueous mixtures of ethanol (ETH) and monofluoroethanol (MFE) by the deconvolution of IR bands in the OH stretching region, molecular dynamics simulation and quantum chemical calculations. It has been found that the addition of a small amount of ETH into the aqueous medium increases the strength of the hydrogen bonds between water molecules. In an aqueous mixture of MFE, the substitution of a single fluorine induces a change in the orientation as well as the hydrogen bonding site of water molecules from the oxygen to the fluorine terminal of MFE. The switching of the hydrogen bonding site of water in the aqueous mixture of MFE results in comparatively strong hydrogen bonds between MFE and water molecules as well as less clustering of water molecules, unlike the case of the aqueous mixture of ETH. These findings about the modification of a hydrogen bond network by the hydrophobic fluorine group probably make fluorinated molecules useful for pharmaceutical as well as biological applications.

Discovery of Molecular Gas Shells around the Unusual Galaxy Centaurus A

Science.gov (United States)

2000-03-01

Recent observations by an international team of astronomers [1] with the 15-metre Swedish-ESO Submillimetre Telescope at the La Silla observatory (Chile) have shown that the unusual, nearby galaxy Centaurus A is surrounded by shells in which carbon monoxide molecules are present. These new exciting results are the first of their kind. In addition to the intrinsic scientific value of this discovery, it also provides an instructive example of what will become possible for more distant galaxies with the projected Atacama Large Millimeter Array (ALMA) , now in the planning phase. Ellipticals and spirals Galaxies come in different shapes. Some of these take the form of more or less perfect spirals, some have the form of ellipsoids and still others have an irregular appearance. One of the major differences between elliptical and spiral galaxies is that the former do not possess extensive gaseous discs in which young stars can be formed. This is despite the fact that most elliptical galaxies are probably formed by the merger of two or more spiral galaxies. However, during such a process most of the gas in the spirals is either quickly turned into stars by massive bursts of star formation or is completely lost into the surrounding space. Shells around elliptical galaxies Most galaxies are members of groups. Once they have been formed, massive elliptical galaxies in these often behave like "cannibals" by swallowing one or more smaller companion galaxies. Some vestiges of such an event may remain visible for a certain time after the merger, normally in the form of weak structures in the otherwise smooth light distribution over the elliptical galaxy. These structures resemble the ripples or waves that develop on the water surface when you throw a small stone into a calm pond. While long-exposure photos show them as faint "rings" around the galaxy, they are in fact the projected images of three-dimensional structures and are often referred to as shells . By means of

Expressional Changes of Water Transport-related Molecules in the Efferent Ductules and Initial Segment of Mouse Treated with Bisphenol A-Containing Drinking Water for Two Generations.

Science.gov (United States)

Han, Su-Yong; Lee, Ki-Ho

2013-09-01

Bisphenol A (BPA) is an estrogenic endocrine disrupter. However, depending on a way of treatment, the harmful effects of BPA have not been confirmed. Also, trans-generational effects of BPA on male reproduction are still controversial. Because the reabsorption of testicular fluid in the efferent ductules (ED) and initial segment (IS) is important for sperm maturation, the present study was designed to determine trans-generational effect of BPA administrated orally on expression of water transport-related molecules in the mouse ED and IS. Ethanol-dissolved BPA was diluted in water to be 100 ng (low), 10 μg (medium), and 1 mg/Ml water (high). BPA-containing water was provided for two generations. Expression of ion transporters and water channels in the ED and IS were measured by relative real-time PCR analysis. In the ED, BPA treatment caused expressional increases of carbonic anhydrase II, cystic fibrosis transmembrane regulator, Na(+)/K(+) ATPase α1 subunit, and aquaporin (AQP) 1. No change of Na(+)/H(+) exchange (NHE) 3 expression was detected. BPA treatment at medium dose resulted in an increase of AQP9 expression. In the IS, the highest expressional levels of all molecules tested were observed in medium-dose BPA treatment. Generally, high-dose BPA treatment resulted in a decrease or no change of gene expression. Fluctuation of NHE3 gene expression by BPA treatment at different concentrations was detected. These findings suggest that trans-generational exposure to BPA, even at low dose, could affect gene expression of water-transport related molecules. However, such effects of BPA would be differentially occurred in the ED and IS.

Silver-gold core-shell nanoparticles containing methylene blue as SERS labels for probing and imaging of live cells

International Nuclear Information System (INIS)

Guo, X.; Guo, Z.; Jin, Y.; Liu, Z.; Zhang, W.; Huang, D.

2012-01-01

We report on silver-gold core-shell nanostructures that contain Methylene Blue (MB) at the gold/x96silver interface. They can be used as reporter molecules in surface-enhanced Raman scattering (SERS) labels. The labels are stable and have strong SERS activity. TEM imaging revealed that these nanoparticles display bright and dark stripe structures. In addition, these labels can act as probes that can be detected and imaged through the specific Raman signatures of the reporters. We show that such SERS probes can identify cellular structures due to enhanced Raman spectra of intrinsic cellular molecules measured in the local optical fields of the core-shell nanostructures. They also provide structural information on the cellular environment as demonstrated for these nanoparticles as new SERS-active and biocompatible substrates for imaging of live cells. (author)

Free vibration analysis of delaminated composite shells using different shell theories

International Nuclear Information System (INIS)

Nanda, Namita; Sahu, S.K.

2012-01-01

Free vibration response of laminated composite shells with delamination is presented using the finite element method based on first order shear deformation theory. The shell theory used is the extension of dynamic, shear deformable theory according to the Sanders' first approximation for doubly curved shells, which can be reduced to Love's and Donnell's theories by means of tracers. An eight-noded C 0 continuity, isoparametric quadrilateral element with five degrees of freedom per node is used in the formulation. For modeling the delamination, multipoint constraint algorithm is incorporated in the finite element code. The natural frequencies of the delaminated cylindrical (CYL), spherical (SPH) and hyperbolic paraboloid (HYP) shells are determined by using the above mentioned shell theories, namely Sanders', Love's, and Donnell's. The validity of the present approach is established by comparing the authors' results with those available in the literature. Additional studies on free vibration response of CYL, SPH and HYP shells are conducted to assess the effects of delamination size and number of layers considering all three shell theories. It is shown that shell theories according to Sanders and Love always predict practically identical frequencies. Donnell's theory gives reliable results only for shallow shells. Moreover, the natural frequency is found to be very sensitive to delamination size and number of layers in the shell.

Using Pteropod Shells to Trace Aragonite Dissolution: Toward a Multi-Basin Calibration

Science.gov (United States)

Mekik, F. A.

2013-12-01

We developed a new proxy for tracing aragonite dissolution in marine sediments. The core tops we used are from the tropical and subtropical latitudes of two ocean basins: Atlantic and Pacific. This allows for a multi-basin calibration for our proxy which is based on the fragmentation trend of pteropod shells. The ratio of fragmented pteropod shells to whole plus fragmented pteropod shells within our core tops has an excellent relationship with the aragonite saturation of bottom waters. Combining our pteropod-based aragonite dissolution proxy with the Globorotalia menradii Fragmentation Index, which is a calcite dissolution proxy, allows tracing carbonate chemistry of bottom waters for the entire ocean depth profile including regions well above the calcite saturation horizon. We also present new data on size normalized weights of pteropod shells which supports the aragonite dissolution trend seen in the pteropod fragmentation data. Unlike previous findings with other proxies, both aragonite and calcite dissolution data from a high resolution core in the western equatorial Pacific reveal no evidence of a degacial carbonate preservation maximum.

Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

Energy Technology Data Exchange (ETDEWEB)

Du Yang; Lian Fei [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhu Lingyan, E-mail: zhuly@nankai.edu.cn [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

2011-07-15

The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb{sup 2+}, Cd{sup 2+} and Zn{sup 2+} from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbent's dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent. - Highlights: > Mollusk shells display high removal efficiency to heavy metals in contaminated water. > Surface precipitation leading to crystal growth takes place during the sorption. > Crystal structure similarity between precipitates and substrates affects the sorption. > pH, sorbent dosage and grain size of adsorbent affects the removal efficiency. > Organic matter in mollusk shells affects the removal efficiency to a less extent. - Mollusk shells display high sorption ability to heavy metals and crystal structure similarity between precipitates and substrates affects the sorption.

Photo-physical properties enhancement of bare and core-shell quantum dots

Energy Technology Data Exchange (ETDEWEB)

Mumin, Md Abdul, E-mail: pcharpentier@eng.uwo.ca; Akhter, Kazi Farida, E-mail: pcharpentier@eng.uwo.ca; Charpentier, Paul A., E-mail: pcharpentier@eng.uwo.ca [Chemical and Biochemical Engineering, Western University, London Ontario (Canada)

2014-03-31

Semiconductor nanocrystals (NCs) (also known as quantum dots, QDs) have attracted immense attention for their size-tunable optical properties that makes them impressive candidates for solar cells, light emitting devices, lasers, as well as biomedical imaging. However monodispersity, high and consistent photoluminescence, photostability, and biocompatibility are still major challenges. This work focuses on optimizing the photophysical properties and biocompatibility of QDs by forming core-shell nanostructures and their encapsulation by a carrier. Highly luminescent CdS and CdS-ZnS core-shell QDs with 5 nm sizes were synthesized using a facile approach based on pyrolysis of the single molecule precursors. After capping the CdS QDs with a thin layer of ZnS to reduce toxicity, the photoluminescence and photostability of the core-shell QDs was significantly enhanced. To make both the bare and core/shell structure QDs more resistant against photochemical reactions, a mesoporous silica layer was grown on the QDs through a reverse microemulsion technique based on hydrophobic interaction. This encapsulation enhanced the quantum yield and photostability compared to the bare QDs by providing much stronger resistance to oxidation and Oswald ripening of QDs. Encapsulation also improved biocompatibility of QDs that was evaluated with human umbilical vein endothelial cell lines (HUVEC)

Characterization of the core-shell interaction of differently stabilized transition-metal nanoparticles by means of X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Bucher, S.

2002-05-01

Transition metal nanoparticles with different surfactants were investigated using X-ray absorption spectroscopy (XAS) to obtain information about the interaction between metal core and protecting shell. For tetraalkylammoniumchloride stabilized Pd- and Co-colloids, a detailed model of the interaction between the metal core and the stabilizing shell could be established, in which chlorine is the connecting element between the metal core and the organic protection cover. Different lengths of the alkyl-chains can cause different equilibrium positions for the chlorine atoms. At aluminum-organic stabilized Pt-colloids, Al K-XANES and Pt L III -XAS were carried out. In this case, it turned out that aluminum is the connecting element between metal core and protection shell. After modification of the shell by connecting different molecules to the outside of the shell, rearrangements of the shell could be observed. In contrast to the surfactant stabilized systems discussed above, metallic covers, especially gold coatings, of Co-particles did not lead to a complete protection shell. In all cases, the cobalt in the nanoparticles was oxidized. A core shell structure could not be verified for any of the metallic stabilized colloids. (orig.)

Ancient limpet shells as paleo-environmental and ethno-archaeological archives: the case of Beniguet Island's shell middens (Iroise Sea)

Science.gov (United States)

Cudennec, Jean-François; Stephan, Pierre; Dupont, Catherine; Pailler, Yvan; Thébault, Julien; Schöne, Bernd; Paulet, Yves-Marie

2017-04-01

During the winter 2013-2014, severe storm events caused a coastal erosion in the southern part of the Beniguet Island (Brittany, France). The associated shoreline retreat had uncovered three layers of shell middens interbedded into an aeolian sand dune deposit. From several radiocarbon dating crossed with the study of ceramic and lithic contents, the shell middens were dated to the Final Neolithic (2400 BC), the Early Bronze Age (2000 BC) and the Early Middle Age (800 AD) respectively. This site offers a unique opportunity to collect two types of information: palaeo-environmental (palaeo-temperature of sea water) and archaeological (determination of harvest season). In this study, we focus on gastropod of the genus Patella which represent 90% of the remains found in this midden. This organism is potentially a highly valuable archive for these environments because they are intertidal and relatively sedentary. We studied the growth rings in the outer calcitic layer of individual limpet shells from the Neolithic, Early Bronze Age and Present Day populations. We report here the results of δ18O analyses. We found a similarity between the reconstructed palaeo-temperature in the Neolithic and the Present periods (between 13 and 14°C in summer and about 8 - 9°C in winter). However, palaeo-temperatures of the Early Bronze Age shells are significantly lower in winter (5 - 6 °C). Moreover, the initial results of the δ18O analyses at the margin of these shells showed that they were harvested during a specific season (end of spring or early summer). Additional work will be done to address questions about shell growth dynamics of these species. These results confirm the interest of using ancient limpet shells as palaeo-environmental and archaeological archives.

Stable isotope ratios in freshwater mussel shells as high resolution recorders of riverine environmental variation

Science.gov (United States)

Kukolich, S.; Kendall, C.; Dettman, D. L.

2017-12-01

The geochemical record stored in growth increments of freshwater mussel shells reveals annual to sub-annual changes in environmental conditions during the lifetime of the organism. The carbon, nitrogen, and oxygen stable isotope composition of aragonite shells responds to changes in water chemistry, temperature, streamflow, turbidity, growth rate, size, age, and reproduction. The goals of this study are to determine how stable isotopes can be used to reconstruct the conditions in which the mussels lived and to illuminate any vital effects that might obscure the isotopic record of those conditions. Previous research has suggested that annual δ13C values decrease in older freshwater mussel shells due to lower growth rates and greater incorporation of dietary carbon into the shell with increasing age. However, a high-resolution, seasonal investigation of δ13C, δ15N, and δ18O as they relate to organism age has not yet been attempted in freshwater mussels. A total of 28 Unionid mussels of three different species were collected live in 2011 in the Tennessee River near Paducah, Kentucky, USA. In this study, we analyzed the shell nacre and external organic layers for stable carbon, nitrogen, and oxygen isotope ratios, focusing on growth bands formed between 2006 and 2011. We present a time series of shell δ13C, δ18O, and δ15N values with monthly resolution. We also compare the shell-derived geochemical time series to a time series of the δ13C and δ15N of particulate organic matter, δ13C of DIC, δ18OWater, and water temperature in which the mussels lived. Results show that environmental factors such as water temperature and primary productivity dominate shell chemistry while animal age has little or no effect.

Composted oyster shell as lime fertilizer is more effective than fresh oyster shell.

Science.gov (United States)

Lee, Young Han; Islam, Shah Md Asraful; Hong, Sun Joo; Cho, Kye Man; Math, Renukaradhya K; Heo, Jae Young; Kim, Hoon; Yun, Han Dae

2010-01-01

Physio-chemical changes in oyster shell were examined, and fresh and composted oyster shell meals were compared as lime fertilizers in soybean cultivation. Structural changes in oyster shell were observed by AFM and FE-SEM. We found that grains of the oyster shell surface became smoother and smaller over time. FT-IR analysis indicated the degradation of a chitin-like compound of oyster shell. In chemical analysis, pH (12.3+/-0.24), electrical conductivity (4.1+/-0.24 dS m(-1)), and alkaline powder (53.3+/-1.12%) were highest in commercial lime. Besides, pH was higher in composted oyster shell meal (9.9+/-0.53) than in fresh oyster shell meal (8.4+/-0.32). The highest organic matter (1.1+/-0.08%), NaCl (0.54+/-0.03%), and moisture (15.1+/-1.95%) contents were found in fresh oyster shell meal. A significant higher yield of soybean (1.33 t ha(-1)) was obtained by applying composted oyster shell meal (a 21% higher yield than with fresh oyster shell meal). Thus composting of oyster shell increases the utility of oyster shell as a liming material for crop cultivation.

Degradation of Bacterial Quorum Sensing Signaling Molecules by the Microscopic Yeast Trichosporon loubieri Isolated from Tropical Wetland Waters

Directory of Open Access Journals (Sweden)

Cheng-Siang Wong

2013-09-01

Full Text Available Proteobacteria produce N-acylhomoserine lactones as signaling molecules, which will bind to their cognate receptor and activate quorum sensing-mediated phenotypes in a population-dependent manner. Although quorum sensing signaling molecules can be degraded by bacteria or fungi, there is no reported work on the degradation of such molecules by basidiomycetous yeast. By using a minimal growth medium containing N-3-oxohexanoylhomoserine lactone as the sole source of carbon, a wetland water sample from Malaysia was enriched for microbial strains that can degrade N-acylhomoserine lactones, and consequently, a basidiomycetous yeast strain WW1C was isolated. Morphological phenotype and molecular analyses confirmed that WW1C was a strain of Trichosporon loubieri. We showed that WW1C degraded AHLs with N-acyl side chains ranging from 4 to 10 carbons in length, with or without oxo group substitutions at the C3 position. Re-lactonisation bioassays revealed that WW1C degraded AHLs via a lactonase activity. To the best of our knowledge, this is the first report of degradation of N-acyl-homoserine lactones and utilization of N-3-oxohexanoylhomoserine as carbon and nitrogen source for growth by basidiomycetous yeast from tropical wetland water; and the degradation of bacterial quorum sensing molecules by an eukaryotic yeast.

On the core-mass-shell-luminosity relation for shell-burning stars

International Nuclear Information System (INIS)

Jeffery, C.S.; Saint Andrews Univ.

1988-01-01

Core-mass-shell-luminosity relations for several types of shell-burning star have been calculated using simultaneous differential equations derived from simple homology approximations. The principal objective of obtaining a mass-luminosity relation for helium giants was achieved. This relation gives substantially higher luminosities than the equivalent relation for H-shell stars with core masses greater than 1 solar mass. The algorithm for calculating mass-luminosity relations in this fashion was investigated in detail. Most of the assumptions regarding the physics in the shell do not play a critical role in determining the core-mass-shell-luminosity relation. The behaviour of the core-mass-core-radius relation for a growing degenerate core as a single unique function of mass and growth rate needs to be defined before a single core-mass-shell-luminosity relation for all H-shell stars can be obtained directly from the homology approximations. (author)

Calibration of hydroclimate proxies in freshwater bivalve shells from Central and West Africa

Science.gov (United States)

Kelemen, Zita; Gillikin, David P.; Graniero, Lauren E.; Havel, Holly; Darchambeau, François; Borges, Alberto V.; Yambélé, Athanase; Bassirou, Alhou; Bouillon, Steven

2017-07-01

Freshwater bivalve shell oxygen and carbon stable isotope ratios (δ18O, δ13C) may act as recorders of hydroclimate (e.g., precipitation-evaporation balance, discharge) and aquatic biogeochemistry. We investigate the potential of these hydroclimate proxies measured along the growth axis of shells collected from the Oubangui River (Bangui, Central African Republic) and the Niger River (Niamey, Niger). Biweekly water samples and in situ measurements collected over several years, along with daily discharge data from both sites allowed a direct comparison with proxies recorded in the shells. Data from a total of 14 unionid shells, including three species (Chambardia wissmanni, Aspatharia dahomeyensis, and Aspatharia chaiziana), confirmed that shells precipitate carbonate in oxygen isotope equilibrium with ambient water. Because water temperature variations were small, shell δ18O values (δ18Oshell) also accurately record the seasonality and the range observed in water δ18O (δ18Ow) values when calculated using an average temperature. Calculated δ18Ow values were in good agreement over the entire record of measured δ18Ow values, thus δ18Oshell records can be reliably used to reconstruct past δ18Ow values. Discharge and δ18Ow values from both rivers fit a logarithmic relationship, which was used to attempt reconstruction of past hydrological conditions, after calculating δ18Ow values from δ18Oshell values. A comparison with measured discharge data suggests that for the two rivers considered, δ18Oshell data are good proxies for recording discharge conditions during low(er) discharge levels, but that high discharge values cannot be accurately reconstructed due to the large scatter in the discharge-δ18Ow relationship. Moreover, periods of bivalve shell growth cessation due to high turbidity or air exposure should be taken into account. While δ13C values of dissolved inorganic carbon in both rivers showed clear seasonality and correlated well with discharge

Variation in Orthologous Shell-Forming Proteins Contribute to Molluscan Shell Diversity.

Science.gov (United States)

Jackson, Daniel J; Reim, Laurin; Randow, Clemens; Cerveau, Nicolas; Degnan, Bernard M; Fleck, Claudia

2017-11-01

Despite the evolutionary success and ancient heritage of the molluscan shell, little is known about the molecular details of its formation, evolutionary origins, or the interactions between the material properties of the shell and its organic constituents. In contrast to this dearth of information, a growing collection of molluscan shell-forming proteomes and transcriptomes suggest they are comprised of both deeply conserved, and lineage specific elements. Analyses of these sequence data sets have suggested that mechanisms such as exon shuffling, gene co-option, and gene family expansion facilitated the rapid evolution of shell-forming proteomes and supported the diversification of this phylum specific structure. In order to further investigate and test these ideas we have examined the molecular features and spatial expression patterns of two shell-forming genes (Lustrin and ML1A2) and coupled these observations with materials properties measurements of shells from a group of closely related gastropods (abalone). We find that the prominent "GS" domain of Lustrin, a domain believed to confer elastomeric properties to the shell, varies significantly in length between the species we investigated. Furthermore, the spatial expression patterns of Lustrin and ML1A2 also vary significantly between species, suggesting that both protein architecture, and the regulation of spatial gene expression patterns, are important drivers of molluscan shell evolution. Variation in these molecular features might relate to certain materials properties of the shells of these species. These insights reveal an important and underappreciated source of variation within shell-forming proteomes that must contribute to the diversity of molluscan shell phenotypes. © The Author 2017. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Optical absorption of carbon-gold core-shell nanoparticles

Science.gov (United States)

Wang, Zhaolong; Quan, Xiaojun; Zhang, Zhuomin; Cheng, Ping

2018-01-01

In order to enhance the solar thermal energy conversion efficiency, we propose to use carbon-gold core-shell nanoparticles dispersed in liquid water. This work demonstrates theoretically that an absorbing carbon (C) core enclosed in a plasmonic gold (Au) nanoshell can enhance the absorption peak while broadening the absorption band; giving rise to a much higher solar absorption than most previously studied core-shell combinations. The exact Mie solution is used to evaluate the absorption efficiency factor of spherical nanoparticles in the wavelength region from 300 nm to 1100 nm as well as the electric field and power dissipation profiles inside the nanoparticles at specified wavelengths (mostly at the localized surface plasmon resonance wavelength). The field enhancement by the localized plasmons at the gold surfaces boosts the absorption of the carbon particle, resulting in a redshift of the absorption peak with increased peak height and bandwidth. In addition to spherical nanoparticles, we use the finite-difference time-domain method to calculate the absorption of cubic core-shell nanoparticles. Even stronger enhancement can be achieved with cubic C-Au core-shell structures due to the localized plasmonic resonances at the sharp edges of the Au shell. The solar absorption efficiency factor can exceed 1.5 in the spherical case and reach 2.3 in the cubic case with a shell thickness of 10 nm. Such broadband absorption enhancement is in great demand for solar thermal applications including steam generation.

Off-shell CHY amplitudes

Energy Technology Data Exchange (ETDEWEB)

Lam, C.S., E-mail: Lam@physics.mcgill.ca [Department of Physics, McGill University, Montreal, Q.C., H3A 2T8 (Canada); Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Yao, York-Peng, E-mail: yyao@umich.edu [Department of Physics, The University of Michigan Ann Arbor, MI 48109 (United States)

2016-06-15

The Cachazo–He–Yuan (CHY) formula for on-shell scattering amplitudes is extended off-shell. The off-shell amplitudes (amputated Green's functions) are Möbius invariant, and have the same momentum poles as the on-shell amplitudes. The working principles which drive the modifications to the scattering equations are mainly Möbius covariance and energy momentum conservation in off-shell kinematics. The same technique is also used to obtain off-shell massive scalars. A simple off-shell extension of the CHY gauge formula which is Möbius invariant is proposed, but its true nature awaits further study.

Shell condition and survival of Puget Sound pteropods are impaired by ocean acidification conditions.

Directory of Open Access Journals (Sweden)

D Shallin Busch

Full Text Available We tested whether the thecosome pteropod Limacina helicina from Puget Sound, an urbanized estuary in the northwest continental US, experiences shell dissolution and altered mortality rates when exposed to the high CO2, low aragonite saturation state (Ωa conditions that occur in Puget Sound and the northeast Pacific Ocean. Five, week-long experiments were conducted in which we incubated pteropods collected from Puget Sound in four carbon chemistry conditions: current summer surface (∼460-500 µatm CO2, Ωa≈1.59, current deep water or surface conditions during upwelling (∼760 and ∼1600-1700 µatm CO2, Ωa≈1.17 and 0.56, and future deep water or surface conditions during upwelling (∼2800-3400 µatm CO2, Ωa≈0.28. We measured shell condition using a scoring regime of five shell characteristics that capture different aspects of shell dissolution. We characterized carbon chemistry conditions in statistical analyses with Ωa, and conducted analyses considering Ωa both as a continuous dataset and as discrete treatments. Shell dissolution increased linearly as aragonite saturation state decreased. Discrete treatment comparisons indicate that shell dissolution was greater in undersaturated treatments compared to oversaturated treatments. Survival increased linearly with aragonite saturation state, though discrete treatment comparisons indicated that survival was similar in all but the lowest saturation state treatment. These results indicate that, under starvation conditions, pteropod survival may not be greatly affected by current and expected near-future aragonite saturation state in the NE Pacific, but shell dissolution may. Given that subsurface waters in Puget Sound's main basin are undersaturated with respect to aragonite in the winter and can be undersaturated in the summer, the condition and persistence of the species in this estuary warrants further study.

Shell condition and survival of Puget Sound pteropods are impaired by ocean acidification conditions.

Science.gov (United States)

Busch, D Shallin; Maher, Michael; Thibodeau, Patricia; McElhany, Paul

2014-01-01

We tested whether the thecosome pteropod Limacina helicina from Puget Sound, an urbanized estuary in the northwest continental US, experiences shell dissolution and altered mortality rates when exposed to the high CO2, low aragonite saturation state (Ωa) conditions that occur in Puget Sound and the northeast Pacific Ocean. Five, week-long experiments were conducted in which we incubated pteropods collected from Puget Sound in four carbon chemistry conditions: current summer surface (∼460-500 µatm CO2, Ωa≈1.59), current deep water or surface conditions during upwelling (∼760 and ∼1600-1700 µatm CO2, Ωa≈1.17 and 0.56), and future deep water or surface conditions during upwelling (∼2800-3400 µatm CO2, Ωa≈0.28). We measured shell condition using a scoring regime of five shell characteristics that capture different aspects of shell dissolution. We characterized carbon chemistry conditions in statistical analyses with Ωa, and conducted analyses considering Ωa both as a continuous dataset and as discrete treatments. Shell dissolution increased linearly as aragonite saturation state decreased. Discrete treatment comparisons indicate that shell dissolution was greater in undersaturated treatments compared to oversaturated treatments. Survival increased linearly with aragonite saturation state, though discrete treatment comparisons indicated that survival was similar in all but the lowest saturation state treatment. These results indicate that, under starvation conditions, pteropod survival may not be greatly affected by current and expected near-future aragonite saturation state in the NE Pacific, but shell dissolution may. Given that subsurface waters in Puget Sound's main basin are undersaturated with respect to aragonite in the winter and can be undersaturated in the summer, the condition and persistence of the species in this estuary warrants further study.

Effects of the microbubble shell physicochemical properties on ultrasound-mediated drug delivery to the brain.

Science.gov (United States)

Wu, Shih-Ying; Chen, Cherry C; Tung, Yao-Sheng; Olumolade, Oluyemi O; Konofagou, Elisa E

2015-08-28

Lipid-shelled microbubbles have been used in ultrasound-mediated drug delivery. The physicochemical properties of the microbubble shell could affect the delivery efficiency since they determine the microbubble mechanical properties, circulation persistence, and dissolution behavior during cavitation. Therefore, the aim of this study was to investigate the shell effects on drug delivery efficiency in the brain via blood-brain barrier (BBB) opening in vivo using monodisperse microbubbles with different phospholipid shell components. The physicochemical properties of the monolayer were varied by using phospholipids with different hydrophobic chain lengths (C16, C18, and C24). The dependence on the molecular size and acoustic energy (both pressure and pulse length) were investigated. Our results showed that a relatively small increase in the microbubble shell rigidity resulted in a significant increase in the delivery of 40-kDa dextran, especially at higher pressures. Smaller (3kDa) dextran did not show significant difference in the delivery amount, suggesting that the observed shell effect was molecular size-dependent. In studying the impact of acoustic energy on the shell effects, it was found that they occurred most significantly at pressures causing microbubble destruction (450kPa and 600kPa); by increasing the pulse length to deliver the 40-kDa dextran, the difference between C16 and C18 disappeared while C24 still achieved the highest delivery efficiency. These indicated that the acoustic energy could be used to modulate the shell effects. The acoustic cavitation emission revealed the physical mechanisms associated with different shells. Overall, lipid-shelled microbubbles with long hydrophobic chain length could achieve high delivery efficiency for larger molecules especially with high acoustic energy. Our study, for the first time, offered evidence directly linking the microbubble monolayer shell with their efficacy for drug delivery in vivo. Copyright © 2015

Smaller calcite lattice deformation caused by occluded organic material in coccoliths than in mollusk shell

DEFF Research Database (Denmark)

Frølich, Simon; Sørensen, Henning Osholm; Hakim, Sepideh Sadat

2015-01-01

The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil....... Two heating cycles allow us to differentiate the effects of thermal agitation and organic molecules. Single peak analysis and Rietveld refinement were combined to show significant differences resulting from the occluded biomolecules on the mineral phase in biogenic calcite in the mollusk shell...

Room-temperature fabrication of core-shell nano-ZnO/pollen grain biocomposite for adsorptive removal of organic dye from water

International Nuclear Information System (INIS)

Tzvetkov, George; Kaneva, Nina; Spassov, Tony

2017-01-01

Highlights: • Meso-/macro-porous nano-ZnO covered pollen grains are prepared at room temperature. • A possible formation mechanism of the core-shell microparticles was proposed. • Adsorptive removal of Malachite Green from water by the biocomposite is studied. - Abstract: A new core-shell nano-ZnO/pollen grain (n-ZnO/PG) biocomposite has been successfully synthesized via simple and low-temperature two-step liquid precipitation method. The synthetic strategy consists of grafting the surface of pine pollen grains (PG) with Zn"2"+-organic complexes followed by a treatment in Zn(CH_3COO)_2/NaOH solution, thus producing a closed n-ZnO shell around the organic core, with a thickness of ∼450 nm. Scanning electron microscopy, X-ray diffraction, FTIR, XPS and UV–vis spectroscopy measurements along with N_2 adsorption/desorption were used to characterize the resulting n-ZnO/PG biocomposite. The as-prepared core-shell microparticles are meso-/macro-porous with BET surface area of 25 m"2 g"−"1 and total pore volume of 0.26 cm"3 g"−"1. The adsorption properties of n-ZnO/PG were evaluated through adsorption of Malachite Green (MG) from aqueous medium at room temperature (25 °C). For the sake of comparison, the physico-chemical and adsorptive properties of the raw PG and pure n-ZnO were also examined. Results indicate that n-ZnO/PG is the most favorable for the adsorption of MG under the conditions used in this study. The adsorption kinetic data for PG, n-ZnO and n-ZnO/PG follow the pseudo-second order equation and the maximum adsorption capacity follows an order of n-ZnO/PG > n-ZnO > PG. For n-ZnO/PG an adsorption uptake up to 145.9 mg g"−"1 is observed. The as-prepared core-shell biocomposite material is a promising cost-effective and environmentally friendly adsorbent due to its textural properties, surface chemistry, adsorption capacity and recyclability.

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

Energy Technology Data Exchange (ETDEWEB)

Al-Hamdani, Yasmine S. [Thomas Young Centre and London Centre for Nanotechnology, 17–19 Gordon Street, London WC1H 0AH (United Kingdom); Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Alfè, Dario [Thomas Young Centre and London Centre for Nanotechnology, 17–19 Gordon Street, London WC1H 0AH (United Kingdom); Department of Earth Sciences, University College London, Gower Street, London WC1E 6BT (United Kingdom); Lilienfeld, O. Anatole von [Institute of Physical Chemistry and National Center for Computational Design and Discovery of Novel Materials (MARVEL), Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel (Switzerland); Michaelides, Angelos, E-mail: angelos.michaelides@ucl.ac.uk [Thomas Young Centre and London Centre for Nanotechnology, 17–19 Gordon Street, London WC1H 0AH (United Kingdom); Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom)

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 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.

Adaptive resolution simulation of a biomolecule and its hydration shell: Structural and dynamical properties

International Nuclear Information System (INIS)

Fogarty, Aoife C.; Potestio, Raffaello; Kremer, Kurt

2015-01-01

A fully atomistic modelling of many biophysical and biochemical processes at biologically relevant length- and time scales is beyond our reach with current computational resources, and one approach to overcome this difficulty is the use of multiscale simulation techniques. In such simulations, when system properties necessitate a boundary between resolutions that falls within the solvent region, one can use an approach such as the Adaptive Resolution Scheme (AdResS), in which solvent particles change their resolution on the fly during the simulation. Here, we apply the existing AdResS methodology to biomolecular systems, simulating a fully atomistic protein with an atomistic hydration shell, solvated in a coarse-grained particle reservoir and heat bath. Using as a test case an aqueous solution of the regulatory protein ubiquitin, we first confirm the validity of the AdResS approach for such systems, via an examination of protein and solvent structural and dynamical properties. We then demonstrate how, in addition to providing a computational speedup, such a multiscale AdResS approach can yield otherwise inaccessible physical insights into biomolecular function. We use our methodology to show that protein structure and dynamics can still be correctly modelled using only a few shells of atomistic water molecules. We also discuss aspects of the AdResS methodology peculiar to biomolecular simulations

Adaptive resolution simulation of a biomolecule and its hydration shell: Structural and dynamical properties

Energy Technology Data Exchange (ETDEWEB)

Fogarty, Aoife C., E-mail: fogarty@mpip-mainz.mpg.de; Potestio, Raffaello, E-mail: potestio@mpip-mainz.mpg.de; Kremer, Kurt, E-mail: kremer@mpip-mainz.mpg.de [Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany)

2015-05-21

A fully atomistic modelling of many biophysical and biochemical processes at biologically relevant length- and time scales is beyond our reach with current computational resources, and one approach to overcome this difficulty is the use of multiscale simulation techniques. In such simulations, when system properties necessitate a boundary between resolutions that falls within the solvent region, one can use an approach such as the Adaptive Resolution Scheme (AdResS), in which solvent particles change their resolution on the fly during the simulation. Here, we apply the existing AdResS methodology to biomolecular systems, simulating a fully atomistic protein with an atomistic hydration shell, solvated in a coarse-grained particle reservoir and heat bath. Using as a test case an aqueous solution of the regulatory protein ubiquitin, we first confirm the validity of the AdResS approach for such systems, via an examination of protein and solvent structural and dynamical properties. We then demonstrate how, in addition to providing a computational speedup, such a multiscale AdResS approach can yield otherwise inaccessible physical insights into biomolecular function. We use our methodology to show that protein structure and dynamics can still be correctly modelled using only a few shells of atomistic water molecules. We also discuss aspects of the AdResS methodology peculiar to biomolecular simulations.

Effects of scallop shell extract on scopolamine-induced memory impairment and MK801-induced locomotor activity

OpenAIRE

HASEGAWA, Yasushi; INOUE, Tatsuro; KAWAMINAMI, Satoshi; FUJITA, Miho

2016-01-01

ObjectiveTo evaluate the neuroprotective effects of the organic components of scallop shells (scallop shell extract) on memory impairment and locomotor activity induced by scopolamine or 5-methyl-10,11-dihydro-5H-dibenzo (a,d) cyclohepten-5,10-imine (MK801).MethodsEffect of the scallop shell extract on memory impairment and locomotor activity was investigated using the Y-maze test, the Morris water maze test, and the open field test.ResultsScallop shell extract significantly reduced scopolami...

Comparing the effects of oil palm kernel shell and cockle shell on properties of pervious concrete pavement

Directory of Open Access Journals (Sweden)

Elnaz Khankhaje

2017-09-01

Full Text Available Nowadays, pervious concrete pavement is one of the best materials used in construction industry as a top layer of permeable pavement system to control the storm water at source. In addition, increasing production of waste materials, increased the interest in utilising the waste materials for environmental and technical benefits. Therefore, this paper compared the effect of using two different sizes of oil palm kernel shell (OPKS and cockleshell (CS as partial replacement of natural coarse aggregate on properties of pervious concrete pavement. Thirteen mixtures were made, in which 6.30-mm natural gravel was replaced with 0, 25, 50 and 75% of 6.30-mm and 4.75-mm of both shells. The relationships between the properties of pervious concrete mixtures was also determined. The replacement of OPKS and CS as the natural aggregate decreased the compressive strength, while the angular shape of both shells caused higher void content and permeability as compared to those of control pervious concrete. On the other hand, pervious concrete containing CS showed better properties than those of incorporating OPKS. Apart from that, strong relationships between density, void content, permeability, compressive strength values indicated that they can be used as a pervious concrete quality control tests for prediction of properties of pervious concrete pavement before placement in the field. Keywords: Pervious concrete pavement, Void content, Permeability, Cockleshell, Palm oil kernel shell

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

Energy Technology Data Exchange (ETDEWEB)

Shishodia, Manmohan Singh, E-mail: manmohan@gbu.ac.in; Juneja, Soniya [Department of Applied Physics, School of Vocational Studies and Applied Sciences, Gautam Buddha University, Greater Noida 201308 (India)

2016-05-28

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. The theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.

Preparation of hollow shell ICF targets using a depolymerizing model

International Nuclear Information System (INIS)

Letts, S.A.; Fearon, E.M.; Buckley, S.R.

1994-11-01

A new technique for producing hollow shell laser fusion capsules was developed that starts with a depolymerizable mandrel. In this technique we use poly(alpha-methylstyrene) (PAMS) beads or shells as mandrels which are overcoated with plasma polymer. The PAMS mandrel is thermally depolymerized to gas phase monomer, which diffuses through the permeable and thermally more stable plasma polymer coating, leaving a hollow shell. We have developed methods for controlling the size of the PAMS mandrel by either grinding to make smaller sizes or melt sintering to form larger mandrels. Sphericity and surface finish are improved by heating the PAMS mandrels in hot water using a surfactant to prevent aggregation. Using this technique we have made shells from 200 μm to 5 mm diameter with 15 to 100 μm wall thickness having sphericity better than 2 μm and surface finish better than 10 nm RMS

Synthesis and characterization of carbon nanotube from coconut shells activated carbon

Science.gov (United States)

Melati, A.; Hidayati, E.

2016-03-01

Carbon nanotubes (CNTs) have been explored in almost every single cancer treatment modality, including drug delivery, lymphatic targeted chemotherapy, photodynamic therapy, and gene therapy. They are considered as one of the most promising nanomaterial with the capability of both detecting the cancerous cells and delivering drugs or small therapeutic molecules to the cells. CNTs have unique physical and chemical properties such as high aspect ratio, ultralight weight, high mechanical strength, high electrical conductivity, and high thermal conductivity. Coconut Shell was researched as active carbon source on 500 - 600°C. These activated carbon was synthesized becomes carbon nanotube and have been proposed as a promising tool for detecting the expression of indicative biological molecules at early stage of cancer. Clinically, biomarkers cancer can be detected by CNT Biosensor. We are using pyrolysis methods combined with CVD process or Wet Chemical Process on 600°C. Our team has successfully obtained high purity, and aligned MWCNT (Multi Wall Nanotube) bundles on synthesis CNT based on coconut shells raw materials. CNTs can be used to cross the mammalian cell membrane by endocytosis or other mechanisms. SEM characterization of these materials have 179 nm bundles on phase 83° and their materials compound known by using FTIR characterization.

Biodiesel production from waste cooking oil using calcined scallop shell as catalyst

International Nuclear Information System (INIS)

Sirisomboonchai, Suchada; Abuduwayiti, Maidinamu; Guan, Guoqing; Samart, Chanatip; Abliz, Shawket; Hao, Xiaogang; Kusakabe, Katsuki; Abudula, Abuliti

2015-01-01

Highlights: • Calcined scallop shell was used as low-cost and effective catalyst for biodiesel production. • BDF yield from waste cooking oil reached 86% at 65 °C with a catalyst loading amount of 5 wt%. • Calcined scallop shell showed good reusability. • Calcium glyceroxide played an important role on the reusability of calcined scallop shell. • Water in the waste cooking oil had negative effect on the catalytic activity of calcined scallop shell. - Abstract: Transesterification of waste cooking oil (WCO) and methanol by using calcined scallop shell (CSS) as catalyst was carried out in a closed system for biodiesel fuel (BDF) production. It is found that the optimum calcination temperature for the preparation of CSS was 1000 °C. The effects of transesterification temperature, reaction time, methanol/oil molar ratio and catalyst loading amount on the BDF yield were investigated. Compared with the commercial CaO, CSS showed higher catalytic activity and the BDF yield reached 86% at 65 °C with a catalyst loading amount of 5 wt% (WCO basis) and a reaction time of 2 h. The catalyst was reused for 5 cycles whilst the BDF yield decreased 23%. It is found that CaO in CSS was transferred to calcium glyceroxide after the transesterification reaction, and calcium glyceroxide also showed good catalytic activity and reusability. Furthermore, Water content in WCO had negative effect on BDF yield. It is found that BDF yield reduced 15% due to the occurring of saponification when the water content was increased from 0.64% to 2.48%. It is expected that CCS can be used as an alternative and cheap catalyst for the biodiesel production

Ab Initio Density Functional Theory Investigation of the Interaction between Carbon Nanotubes and Water Molecules during Water Desalination Process

Directory of Open Access Journals (Sweden)

Loay A. Elalfy

2013-01-01

Full Text Available Density functional theory calculations using B3LYP/3-21G level of theory have been implemented on 6 carbon nanotubes (CNTs structures (3 zigzag and 3 armchair CNTs to study the energetics of the reverse osmosis during water desalination process. Calculations of the band gap, interaction energy, highest occupied molecular orbital, lowest unoccupied molecular orbital, electronegativity, hardness, and pressure of the system are discussed. The calculations showed that the water molecule that exists inside the CNT is about 2-3 Å away from its wall. The calculations have proven that the zigzag CNTs are more efficient for reverse osmosis water desalination process than armchair CNTs as the reverse osmosis process requires pressure of approximately 200 MPa for armchair CNTs, which is consistent with the values used in molecular dynamics simulations, while that needed when using zigzag CNTs was in the order of 60 MPa.

Influence of the effective mass of water molecule on thermal neutron scattering; Uticaj efektivne mase molekula vode na rasejanje termalnih neutrona

Energy Technology Data Exchange (ETDEWEB)

Markovic, M [Belgrade Univ. (Yugoslavia). Elektrotehnicki Fakultet

1981-07-01

The influence of the effective water molecule mass on the thermal neutron scattering on the nucleus of the hydrogen atom has been investigated. Besides the actual water molecule mass (M = 18) the investigations have been carried out with its two effective values (M1 = 16 and M2 = 20). The differential and total cross sections have been calculated for the incident thermal neutron energy E{sub o} = 1 eV. Investigation results show different prominence of the quantum effects and for M2 the appearance of peaks in the quasielastic scattering. (author)

One-pot synthesis of stable water soluble Mn:ZnSe/ZnS core/shell quantum dots

Energy Technology Data Exchange (ETDEWEB)

Zhang Hao; Gao Xue; Liu Siyu; Su Xingguang, E-mail: suxg@jlu.edu.cn [College of Chemistry, Jilin University, Department of Analytical Chemistry (China)

2013-06-15

In this paper, Mn:ZnSe/ZnS core/shell-doped quantum dots (d-dots) with 3-mercaptopropionic acid as the stabilizer are successfully synthesized through a simple one-pot synthesis procedure in aqueous solution. The average diameter of Mn:ZnSe/ZnS core/shell d-dots is about 2.9 nm, which is lager than that of Mn:ZnSe cores (about 1.9 nm). The optical features and structure of the obtained Mn:ZnSe/ZnS core/shell quantum dots have been characterized by UV-Vis and fluorescence spectroscopy, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The photostability against UV irradiation and chemical stability against H{sub 2}O{sub 2} etching have been studied, and the results showed that the prepared Mn:ZnSe/ZnS core/shell d-dots are more stable than CdTe quantum dots prepared in aqueous solution. Finally, the resulting core/shell quantum dots are used as fluorescent label in human osteoblast-like HepG2 cell imaging.

In Situ Generation of Two-Dimensional Au–Pt Core–Shell Nanoparticle Assemblies

Directory of Open Access Journals (Sweden)

Khalid Madiha

2009-01-01

Full Text Available Abstract Two-dimensional assemblies of Au–Pt bimetallic nanoparticles are generated in situ on polyethyleneimmine (PEI silane functionalized silicon and indium tin oxide (ITO coated glass surfaces. Atomic force microscopy (AFM, UV–Visible spectroscopy, and electrochemical measurements reveal the formation of core–shell structure with Au as core and Pt as shell. The core–shell structure is further supported by comparing with the corresponding data of Au nanoparticle assemblies. Static contact angle measurements with water show an increase in hydrophilic character due to bimetallic nanoparticle generation on different surfaces. It is further observed that these Au–Pt core–shell bimetallic nanoparticle assemblies are catalytically active towards methanol electro-oxidation, which is the key reaction for direct methanol fuel cells (DMFCs.

EVOLUTION OF THE WATER MASER EXPANDING SHELL IN W75N VLA 2

Energy Technology Data Exchange (ETDEWEB)

Kim, Jeong-Sook; Kim, Sang Joon [School of Space Science, Kyunghee University, Seocheon-dong, Giheung-si, Gyeonggi-do, 446-701 (Korea, Republic of); Kim, Soon-Wook [Korea Astronomy and Space Science Institute, 776 Daedeokdaero, Yuseong, Daejeon 305-348 (Korea, Republic of); Kurayama, Tomoharu [Graduate School of Science and Engineering, Kagoshima University, 1-21-35 Korimoto, Kagoshima, Kagoshima 890-0065 (Japan); Honma, Mareki [National Astronomical Observatory of Japan, 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Sasao, Tesuo [Yaeyama Star Club, Ookawa, Ishigaki, Okinawa 904-0022 (Japan); Surcis, Gabriele [Joint Institute for VLBI in Europe, Postbus 2, 7990 AA Dwingeloo (Netherlands); Canto, Jorge [Instituto de Astronomia (UNAM), Apartado 70-264, 04510 Mexico D. F. (Mexico); Torrelles, Jose M., E-mail: evony@kasi.re.kr, E-mail: skim@kasi.re.kr [Instituto de Ciencias del Espacio (CSIC)-UB/IEEC, Universitat de Barcelona, Marti i Franques 1, E-08028 Barcelona (Spain)

2013-04-10

We present Very Long Baseline Interferometry (VLBI) observations of 22 GHz H{sub 2}O masers in the high-mass star-forming region of W75N, carried out with VLBI Exploration of Radio Astrometry (VERA) for three epochs in 2007 with an angular resolution of {approx}1 mas. We detected H{sub 2}O maser emission toward the radio jet in VLA 1 and the expanding shell-like structure in VLA 2. The spatial distribution of the H{sub 2}O masers detected with VERA and measured proper motions around VLA 1 and VLA 2 are similar to those found with previous VLBI observations in epochs 1999 and 2005, with the masers in VLA 1 mainly distributed along a linear structure parallel to the radio jet and, on the other hand, forming a shell-like structure around VLA 2. We have made elliptical fits to the VLA 2 H{sub 2}O maser shell-like structure observed in the different epochs (1999, 2005, and 2007), and found that the shell is still expanding eight years after its discovery. From the difference in the size of the semi-major axes of the fitted ellipses in epochs 1999 ({approx_equal}71 {+-} 1 mas), 2005 ({approx_equal}97 {+-} 3 mas), and 2007 ({approx_equal}111 {+-} 1 mas), we estimate an average expanding velocity of {approx}5 mas yr{sup -1}, similar to the proper motions measured in the individual H{sub 2}O maser features. A kinematic age of {approx}20 yr is derived for this structure. In addition, our VERA observations indicate an increase in the ellipticity of the expanding shell around VLA 2 from epochs 1999 to 2007. In fact, the elliptical fit of the VERA data shows a ratio of the minor and major axes of {approx}0.6, in contrast with an almost circular shape for the shell detected in 1999 and 2005 (b/a {approx} 0.9). This suggests that we are probably observing the formation of a jet-driven H{sub 2}O maser structure in VLA2, evolving from a non-collimated pulsed-outflow event during the first stages of evolution of a massive young stellar object (YSO). This may support predictions made

The environmental effect on the radial breathing mode of carbon nanotubes. II. Shell model approximation for internally and externally adsorbed fluids

Science.gov (United States)

Longhurst, M. J.; Quirke, N.

2006-11-01

We have previously shown that the upshift in the radial breathing mode (RBM) of closed (or infinite) carbon nanotubes in solution is almost entirely due to coupling of the RBM with an adsorbed layer of fluid on the nanotube surface. The upshift can be modeled analytically by considering the adsorbed fluid as an infinitesimally thin shell, which interacts with the nanotube via a continuum Lennard-Jones potential. Here we extend the model to include internally as well as externally adsorbed waterlike molecules, and find that filling the nanotubes leads to an additional upshift of two to six wave numbers. We show that using molecular dynamics, the RBM can be accurately reproduced by replacing the fluid molecules with a mean field harmonic shell potential, greatly reducing simulation times.

Dossier Shell Eco-Marathon; Dossier Shell Eco-Marathon

Energy Technology Data Exchange (ETDEWEB)

Matla, P.

2012-05-15

Three articles address subjects concerning the annual race with highly energy efficient cars: the Shell Eco-Marathon. [Dutch] In 3 artikelen wordt aandacht besteed aan de ontwerpen voor de jaarlijkse race met superzuinige auto's, de Shell Eco-Marathon.

Dynamic reponse of a cylindrical shell immersed in a potential fluid

International Nuclear Information System (INIS)

Cummings, G.E.

1978-01-01

A numerical solution technique is presented for determining the dynamic response of a thin, elastic, circular, cylindrical shell of constant wall thickness and density, immersed in a potential fluid. The shell may be excited by an arbitrary radial forcing function with a specified time history and spatial distribution. In addition, a pressure history may be specified over a segment of the fluid outer boundary. Any of the natural shell end conditions may be prescribed. A numerical instability prevented direct solutions where the ratio of the hydrodynamic forces to shell inertial forces is greater than two. This instability is believed to be the result of the weak coupling between the equations describing the fluid to those describing the shell. To circumvent this instability, an effective mass was calculated and added to the shell. Comparison of numerical to experimental results are made using a 1 / 12 scale model of a nuclear reactor core support barrel. Natural frequencies and modes are determined for this model in air, water, and oil. The computed frequencies compare to experimental results to within 15%. The use of this numerical technique is illustrated by comparing it to an analytical solution for shell beam modes and an uncertainty in the analytical technique concerning the proper effective mass to use, is resolved

Dynamic reponse of a cylindrical shell immersed in a potential fluid

Energy Technology Data Exchange (ETDEWEB)

Cummings, G.E.

1978-04-18

A numerical solution technique is presented for determining the dynamic response of a thin, elastic, circular, cylindrical shell of constant wall thickness and density, immersed in a potential fluid. The shell may be excited by an arbitrary radial forcing function with a specified time history and spatial distribution. In addition, a pressure history may be specified over a segment of the fluid outer boundary. Any of the natural shell end conditions may be prescribed. A numerical instability prevented direct solutions where the ratio of the hydrodynamic forces to shell inertial forces is greater than two. This instability is believed to be the result of the weak coupling between the equations describing the fluid to those describing the shell. To circumvent this instability, an effective mass was calculated and added to the shell. Comparison of numerical to experimental results are made using a /sup 1///sub 12/ scale model of a nuclear reactor core support barrel. Natural frequencies and modes are determined for this model in air, water, and oil. The computed frequencies compare to experimental results to within 15%. The use of this numerical technique is illustrated by comparing it to an analytical solution for shell beam modes and an uncertainty in the analytical technique concerning the proper effective mass to use, is resolved.

Energy transfer in nanowire solar cells with photon-harvesting shells

KAUST Repository

Peters, C. H.

2009-01-01

The concept of a nanowire solar cell with photon-harvesting shells is presented. In this architecture, organic molecules which absorb strongly in the near infrared where silicon absorbs weakly are coupled to silicon nanowires (SiNWs). This enables an array of 7-μm -long nanowires with a diameter of 50 nm to absorb over 85% of the photons above the bandgap of silicon. The organic molecules are bonded to the surface of the SiNWs forming a thin shell. They absorb the low-energy photons and subsequently transfer the energy to the SiNWs via Förster resonant energy transfer, creating free electrons and holes within the SiNWs. The carriers are then separated at a radial p-n junction in a nanowire and extracted at the respective electrodes. The shortness of the nanowires is expected to lower the dark current due to the decrease in p-n junction surface area, which scales linearly with wire length. The theoretical power conversion efficiency is 15%. To demonstrate this concept, we measure a 60% increase in photocurrent from a planar silicon-on-insulator diode when a 5 nm layer of poly[2-methoxy-5-(2′ -ethyl-hexyloxy)-1,4-phenylene vinylene is applied to the surface of the silicon. This increase is in excellent agreement with theoretical predictions. © 2009 American Institute of Physics.

Folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell composite particles: synthesis and application in drug release.

Science.gov (United States)

Yang, Dandan; Wei, Kaiwei; Liu, Qi; Yang, Yong; Guo, Xue; Rong, Hongren; Cheng, Mei-Ling; Wang, Guoxiu

2013-07-01

A drug delivery system was designed by deliberately combining the useful functions into one entity, which was composed of magnetic ZnFe2O4 hollow microsphere as the core, and mesoporous silica with folic acid molecules as the outer shell. Amine groups coated magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NH2) composite particles were first synthesized by a one-pot direct co-condensation method. Subsequently a novel kind of folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NHFA) composite particles were synthesized by conjugating folic acid as targeted molecule to MZHM-MSS-NH2. Ibuprofen, a well-known antiphlogistic drug, was used as a model drug to assess the loading and releasing behavior of the composite microspheres. The results show that the MZHM-MSS-NHFA system has the higher capacity of drug storage and good sustained drug-release property. Copyright © 2013 Elsevier B.V. All rights reserved.

Dominant thermogravimetric signatures of lignin in cashew shell as compared to cashew shell cake.

Science.gov (United States)

Gangil, Sandip

2014-03-01

Dominant thermogravimetric signatures related to lignin were observed in cashew shell as compared to these signatures in cashew shell cake. The phenomenon of weakening of lignin from cashew shell to cashew shell cake was explained on the basis of changes in the activation energies. The pertinent temperature regimes responsible for the release of different constituents of both the bio-materials were identified and compared. The activation energies of cashew shell and cashew shell cake were compared using Kissinger-Akahira-Sunose method. Thermogravimetric profiling of cashew shell and cashew shell cake indicated that these were different kinds of bio-materials. Copyright © 2013 Elsevier Ltd. All rights reserved.

Enhanced adsorption of trivalent arsenic from water by functionalized diatom silica shells.

Directory of Open Access Journals (Sweden)

Jianying Zhang

Full Text Available The potential of porous diatom silica shells as a naturally abundant low-cost sorbent for the removal of arsenic in aqueous solutions was investigated in a batch study. The objective of this work was to chemically modify the silica shells of a diatom Melosira sp. with bifunctional (thiol and amino groups to effectively remove arsenic in its toxic As(III form (arsenite predominant in the aquatic environment. Sorption experiments with this novel sorbent were conducted under varying conditions of pH, time, dosage, and As(III concentration. A maximum adsorption capacity of 10.99 mg g-1 was achieved within 26 h for a solution containing 12 mg L-1 As(III at pH 4 and sorbent dosage of 2 g L-1. The functionalized diatom silica shells had a surface morphological change which was accompanied by increased pore size at the expense of reduced specific surface area and total pore volume. As(III adsorption was best fitted with the Langmuir-Freundlich model, and the adsorption kinetic data using pore surface diffusion model showed that both the external (film and internal (intraparticle diffusion can be rate-determining for As(III adsorption. Fourier transform infrared spectroscopy (FTIR indicated that the thiol and amino groups potentially responsible for As(III adsorption were grafted on the surface of diatom silica shells. X-ray photoelectron spectroscopy (XPS further verified that this unique sorbent proceeded via a chemisorption mechanism through the exchange between oxygen-containing groups of neutral As(III and thiol groups, and through the surface complexation between As(III and protonated nitrogen and hydroxyl groups. Results indicate that this functionalized bioadsorbent with a high As(III adsorption capacity holds promise for the treatment of As(III containing wastewater.

Improvement in the reliability of shells for light water reactors by manufacturing from hollow ingots

International Nuclear Information System (INIS)

Bocquet, P.; Blondeau, R.; Poitrault, I.; Badeau, J.P.; Dumont, R.

1989-01-01

The example of forging shells for PWR type reactors is proposed to show how the choice of the manufacturing process may be of prime importance for the component integrity by the reduction of the detrimental effects of segregations. The forging shells (20MnMoNi55) manufactured from hollow ingot are free of any segregation in the critical area located just at the internal surface and sub-surface. Manufacturing problems associated to these segregations in shells issued from conventional ingots, in particular welding difficulties for cladding, have been reduced or eleminated. The reliability of these components present an improved resistance to irradiation embrittlement. (DG)

Preparation of hydrosol suspensions of elemental and core–shell nanoparticles by co-deposition with water vapour from the gas-phase in ultra-high vacuum conditions

International Nuclear Information System (INIS)

Binns, Chris; Prieto, Pilar; Baker, Stephen; Howes, Paul; Dondi, Ruggero; Burley, Glenn; Lari, Leonardo; Kröger, Roland; Pratt, Andrew; Aktas, Sitki; Mellon, John K.

2012-01-01

We report a new method to produce liquid suspensions of nanoparticles by co-deposition with water vapour from the gas-phase in ultra-high vacuum (UHV) conditions. The water is injected from outside the vacuum as a molecular beam onto a substrate maintained at 77 K and forms an ice layer with a UHV vapour pressure. Molecular dynamics simulations confirm that the nanoparticles are soft-landed close to the surface of the growing ice layer. We show that the un-agglomerated size distribution within the liquid is similar to the gas-phase size distribution and demonstrate that the inclusion of surfactants in the injected water prevents agglomeration. The method allows the flexibility and tight size control available with gas-phase production methods to be applied to making nanoparticle suspensions with any desired properties. This is important for practical applications, especially in medicine. We have extended the method to include core–shell nanoparticles, in which there is flexible control over the core size and shell thickness and free choice of the material in either. Here, we report the production of suspensions of Cu, Ag and Au elemental nanoparticles and Fe-Au and Fe-Fe-oxide core–shell nanoparticles with diameters in the range 5–15 nm. We demonstrate the power of the method in practical applications in the case of Fe-Fe-oxide nanoparticles, which have a specific absorption rate of an applied oscillating magnetic field that is significantly higher than available Fe-oxide nanoparticle suspensions and the highest yet reported. These will thus have a very high-performance in the treatment of tumours by magnetic nanoparticle hyperthermia.

From harmful Microcystis blooms to multi-functional core-double-shell microsphere bio-hydrochar materials.

Science.gov (United States)

Bi, Lei; Pan, Gang

2017-11-13

Harmful algal blooms (HABs) induced by eutrophication is becoming a serious global environmental problem affecting public health and aquatic ecological sustainability. A novel strategy for the utilization of biomass from HABs was developed by converting the algae cells into hollow mesoporous bio-hydrochar microspheres via hydrothermal carbonization method. The hollow microspheres were used as microreactors and carriers for constructing CaO 2 core-mesoporous shell-CaO 2 shell microspheres (OCRMs). The CaO 2 shells could quickly increase dissolved oxygen to extremely anaerobic water in the initial 40 min until the CaO 2 shells were consumed. The mesoporous shells continued to act as regulators restricting the release of oxygen from CaO 2 cores. The oxygen-release time using OCRMs was 7 times longer than when directly using CaO 2 . More interestingly, OCRMs presented a high phosphate removal efficiency (95.6%) and prevented the pH of the solution from rising to high levels in comparison with directly adding CaO 2 due to the OH - controlled-release effect of OCRMs. The distinct core-double-shell micro/nanostructure endowed the OCRMs with triple functions for oxygen controlled-release, phosphorus removal and less impact on water pH. The study is to explore the possibility to prepare smarter bio-hydrochar materials by utilizing algal blooms.

Hydrothermal synthesis of core–shell TiO_2 to enhance the photocatalytic hydrogen evolution

International Nuclear Information System (INIS)

Jiang, Jinghui; Zhou, Han; Zhang, Fan; Fan, Tongxiang; Zhang, Di

2016-01-01

Graphical abstract: Core–shell TiO_2 with interior cavity was synthesized by a hydrothermal approach to enhance the photocatalytic performance. - Highlights: • Core–shell TiO_2 with interior cavity can be synthesized by hydrothermal approach. • Multiple reflection of incident light in cavity can increase the absorption. • Rutile can optimize the bandgap and delay the charge recombination. - Abstract: A hydrothermal approach was designed to synthesize core–shell TiO_2 with interior cavity by making sodium dodecyl sulfonate (SDS) as the surfactant and the mixture of water and ethanol as the solvent. The control experiment of solvent reveals ethanol and water are responsible for the formation of sphere and interior cavity, respectively. Besides, SDS can assist the growth of core–shell structure, and the sizes of sphere and interior cavity can be tuned by regulating the reaction time or temperature. UV–vis absorption proves core–shell structure with interior cavity can increase the absorption of incident light to enhance the optical activity of final product. The calculated bandgap and photoluminescence (PL) analyses reveal the coexistence of rutile in final product can optimize the bandgap to 3.03 eV and delay the charge recombination. As a result, an effective photocatalytic hydrogen evolution under full spectrum irradiation can be harvested by the as-synthesized core–shell spheres to reach a quantum yield, approximately 9.57% at 340 nm wavelength.

Aqueous Solvation of Polyalanine α-Helices with Specific Water Molecules and with the CPCM and SM5.2 Aqueous Continuum Models using Density Functional Theory

OpenAIRE

Marianski, Mateusz; Dannenberg, J. J.

2012-01-01

We present density functional theory (DFT) calculations at the X3LYP/D95(d,p) level on the solvation of polyalanine α-helices in water. The study includes the effects of discrete water molecules and the CPCM and AMSOL SM5.2 solvent continuum model both separately and in combination. We find that individual water molecules cooperatively hydrogen-bond to both the C- and N-termini of the helix, which results in increases in the dipole moment of the helix/water complex to more than the vector sum...

Explosion-Induced Implosions of Cylindrical Shell Structures

Science.gov (United States)

Ikeda, C. M.; Duncan, J. H.

2010-11-01

An experimental study of the explosion-induced implosion of cylindrical shell structures in a high-pressure water environment was performed. The shell structures are filled with air at atmospheric pressure and are placed in a large water-filled pressure vessel. The vessel is then pressurized to various levels P∞=αPc, where Pc is the natural implosion pressure of the model and α is a factor that ranges from 0.1 to 0.9. An explosive is then set off at various standoff distances, d, from the model center line, where d varies from R to 10R and R is the maximum radius of the explosion bubble. High-speed photography (27,000 fps) was used to observe the explosion and resulting shell structure implosion. High-frequency underwater blast sensors recorded dynamic pressure waves at 6 positions. The cylindrical models were made from aluminum (diameter D = 39.1 mm, wall thickness t = 0.89 mm, length L = 240 mm) and brass (D = 16.7 mm, t = 0.36 mm, L=152 mm) tubes. The pressure records are interpreted in light of the high-speed movies. It is found that the implosion is induced by two mechanisms: the shockwave generated by the explosion and the jet formed during the explosion-bubble collapse. Whether an implosion is caused by the shockwave or the jet depends on the maximum bubble diameter and the standoff distance.

Spectral luminescence studies of eosin solvation in water-alcohol mixtures

Energy Technology Data Exchange (ETDEWEB)

Ketsle, G.A.; Levshin, L.V.; Mel' nikov, G.V.; Saletskii, A.M.

1987-11-01

The authors investigate the effects of solvation of eosin molecules in binary water-propanol mixtures with the goal of assessing eosin as a candidate dye laser material. The fluorescence was measured with a Hitachi spectrofluorimeter and the absorption spectra were taken on a Specord spectrophotometer. Absorption and fluorescence were measured for different amounts of propanol in the solvent. Data are also given on excitation and de-excitation kinetics between ground and excited states. Values for quantum yields of fluorescence and phosphorescence, average excited state lifetime, and molecular volume of the dye with the solvated shell are tabulated.

Shell-like structures

CERN Document Server

Altenbach, Holm

2011-01-01

In this volume, scientists and researchers from industry discuss the new trends in simulation and computing shell-like structures. The focus is put on the following problems: new theories (based on two-dimensional field equations but describing non-classical effects), new constitutive equations (for materials like sandwiches, foams, etc. and which can be combined with the two-dimensional shell equations), complex structures (folded, branching and/or self intersecting shell structures, etc.) and shell-like structures on different scales (for example: nano-tubes) or very thin structures (similar

Preparation, process optimization and characterization of core-shell polyurethane/chitosan nanofibers as a potential platform for bioactive scaffolds.

Science.gov (United States)

Maleknia, Laleh; Dilamian, Mandana; Pilehrood, Mohammad Kazemi; Sadeghi-Aliabadi, Hojjat; Hekmati, Amir Houshang

2018-06-01

In this paper, polyurethane (PU), chitosan (Cs)/polyethylene oxide (PEO), and core-shell PU/Cs nanofibers were produced at the optimal processing conditions using electrospinning technique. Several methods including SEM, TEM, FTIR, XRD, DSC, TGA and image analysis were utilized to characterize these nanofibrous structures. SEM images exhibited that the core-shell PU/Cs nanofibers were spun without any structural imperfections at the optimized processing conditions. TEM image confirmed the PU/Cs core-shell nanofibers were formed apparently. It that seems the inclusion of Cs/PEO to the shell, did not induce the significant variations in the crystallinity in the core-shell nanofibers. DSC analysis showed that the inclusion of Cs/PEO led to the glass temperature of the composition increased significantly compared to those of neat PU nanofibers. The thermal degradation of core-shell PU/Cs was similar to PU nanofibers degradation due to the higher PU concentration compared to other components. It was hypothesized that the core-shell PU/Cs nanofibers can be used as a potential platform for the bioactive scaffolds in tissue engineering. Further biological tests should be conducted to evaluate this platform as a three dimensional scaffold with the capabilities of releasing the bioactive molecules in a sustained manner.

One-by-one imprinting in two eccentric layers of hollow core-shells: Sequential electroanalysis of anti-HIV drugs.

Science.gov (United States)

Singh, Kislay; Jaiswal, Swadha; Singh, Richa; Fatma, Sana; Prasad, Bhim Bali

2018-07-15

Double layered one-by-one imprinted hollow core-shells@ pencil graphite electrode was fabricated for sequential sensing of anti-HIV drugs. For this, two eccentric layers were developed on the surface of vinylated silica nanospheres to obtain double layered one-by-one imprinted solid core-shells. This yielded hollow core-shells on treatment with hydrofluoric acid. The modified hollow core-shells (single layered dual imprinted) evolved competitive diffusion of probe/analyte molecules. However, the corresponding double layered one-by-one imprinted hollow core-shells (outer layer imprinted with Zidovudine, and inner layer with Lamivudine) were found relatively better owing to their bilateral diffusions into molecular cavities, without any competition. The entire work is based on differential pulse anodic stripping voltammetry at double layered one-by-one imprinted hollow core-shells. This resulted in indirect detection of electro inactive targets with limits of detection as low as 0.91 and 0.12 (aqueous sample), 0.94 and 0.13 (blood serum), and 0.99 and 0.20 ng mL -1 (pharmaceutics) for lamivudine and zidovudine, respectively in anti-HIV drug combination. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparation of paclitaxel/chitosan co-assembled core-shell nanofibers for drug-eluting stent

Energy Technology Data Exchange (ETDEWEB)

Tang, Jing; Liu, Yongjia [Instrumental Analysis Center, Shanghai Jiao Tong University, 200240 Shanghai (China); State Key Laboratory of Metal Matrix Composites, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 200240 Shanghai (China); Zhu, Bangshang, E-mail: bshzhu@sjtu.edu.cn [Instrumental Analysis Center, Shanghai Jiao Tong University, 200240 Shanghai (China); State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 201620 Shanghai (China); Su, Yue; Zhu, Xinyuan [State Key Laboratory of Metal Matrix Composites, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 200240 Shanghai (China)

2017-01-30

Highlights: • The core-shell nanofibers (NFs) were made by the co-assembly of paclitaxel (PTX) and chitosan(CS). • The PTX/CS NFs have high PTX loading content, slow drug release and low adherence of platelets. • The PTX/CS NFs have low cytotoxicity and good haemocompatibility. • The PTX/CS NFs which could be easily coated on stents could have potential application for drug eluting stents. - Abstract: The paclitaxel/chitosan (PTX/CS) core-shell nanofibers (NFs) are easily prepared by co-assembly of PTX and CS and used in drug-eluting stent. The mixture solution of PTX (dissolved in ethanol) and CS (dissolved in 1% acetic acid water solution) under sonication will make the formation of NFs, in which small molecule PTX co-assembles with biomacromolecular CS through non-covalent interactions. The obtained NFs are tens to hundreds nanometers in diameter and millimeter level in length. Furthermore, the structure of PTX/CS NFs was characterized by confocal laser scanning microscopy (CLSM), zeta potential, X-ray photoelectron spectroscopy (XPS) and nanoscale infra-red (nanoIR), which provided evidences demonstrated that PTX/CS NFs are core-shell structures. The ‘shell’ of CS wrapped outside of the NFs, while PTX is located in the core. Thus it resulted in high drug loading content (>40 wt.%). The well-controlled drug release, low cytotoxicity and good haemocompatibility were also found in drug carrier system of PTX/CS NFs. In addition, the hydrophilic and flexible properties of NFs make them easily coating and filming on stent to prepare drug-eluting stent (DES). Therefore, this study provides a convenient method to prepare high PTX loaded NFs, which is a promising nano-drug carrier used for DES and other biomedical applications. The possible molecular mechanism of PTX and CS co-assembly and core-shell nanofiber formation is also explored. Statement of significance: We develop a convenient and efficient approach to fabricate core-shell nanofibers (NFs) through

Swimming of a Sea Butterfly with an Elongated Shell

Science.gov (United States)

Karakas, Ferhat; Maas, Amy E.; Murphy, David W.

2017-11-01

Sea butterflies (pteropods) are small, zooplanktonic marine snails which swim by flapping highly flexible parapodia. Previous studies show that the swimming hydrodynamics of Limacina helicina, a polar pteropod with a spiraled shell, is similar to tiny insect flight aerodynamics and that forward-backward pitching is key for lift generation. However, swimming by diverse pteropod species with different shell shapes has not been examined. We present measurements of the swimming of Cuvierina columnella, a warm water species with an elongated non-spiraled shell collected off the coast of Bermuda. With a body length of 9 mm, wing beat frequency of 4-6 Hz and swimming speed of 35 mm/s, these organisms swim at a Reynolds number of approximately 300, larger than that of L. helicina. High speed 3D kinematics acquired via two orthogonal cameras reveals that the elongated shell correlates with reduced body pitching and that the wings bend approximately 180 degrees in each direction, overlapping at the end of each half-stroke. Time resolved 2D flow measurements collected with a micro-PIV system reveal leading edge vortices present in both power and recovery strokes. Interactions between the overlapping wings and the shell also likely play a role in lift generation.

Study Added of Waste Chicken Egg Shell in Soils

Directory of Open Access Journals (Sweden)

Keng Wong Irwan Lie

2016-01-01

Full Text Available Soil is the foundation of structure or construction that will receive the load transfer through to foundation. If the soil has a carrying capacity of small and cannot withstand the load transfer can result in the failure of construction. If the soil has a carrying capacity of small ground it is necessary to stabilize or improve the soil so that an increase in the carrying capacity of the land so that it can be used for construction. One material is commonly used for soil stabilization with the addition of lime. Waste chicken egg shell is waste that is still rarely used, the results of research [1], states that composition egg shell broadly consists of water (1,6% and dry material (98,4%. The total dry ingredients are there, in shell eggs contained mineral elements (95,1% and protein (3,3%. Based on the existing mineral composition, then the egg shells are composed of crystalline CaCO3 (98,43%, MgCO3 (0,84% and Ca3(PO42 (0,75%. This research was done by adding powdered chicken egg shell waste in clay with a composition of 5%, 7,5%, 10% and 14% with physical properties test and soil compaction test.

On the spectral properties of Dirac operators with electrostatic delta-shell interactions

Czech Academy of Sciences Publication Activity Database

Behrndt, J.; Exner, Pavel; Holzmann, M.; Lotoreichik, Vladimir

2018-01-01

Roč. 111, č. 3 (2018), s. 47-78 ISSN 0021-7824 R&D Projects: GA ČR(CZ) GA14-06818S Institutional support: RVO:61389005 Keywords : Dirac operator * self-adjoint extension * shell interaction * spectral properties Subject RIV: BE - Theoretical Physics OBOR OECD: Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect) Impact factor: 1.802, year: 2016

Calculation of the dose distribution in water from {sup 71}Ge K-shell x-rays

Energy Technology Data Exchange (ETDEWEB)

Cho, Sang H.; Reece, Warren D.; Poston, John W. Sr. [Department of Nuclear Engineering, Texas A and M University, College Station, TX (United States)

1997-06-01

The dose distribution in water from {sup 71}Ge K-shell x-rays (E{sub ave}=9.44 eV) was calculated for various source configurations using both analytic and GS4 Monte Carlo calculations. The point source kernel and the buildup factor are presented. The buildup factor for a point source in water has been found to increase up to about 1.1 as radial distance approaches 1 cm. Comparison between {sup 71}Ge and {sup 90}Sr/Y shows a similarity between their relative dose distribution in water. The dose distribution from a disc source was calculated using the EGS4 code and compared with the results from analytic calculation. Excellent agreement was observed, confirming the validity of analytic calculations. The dose rate at 0.01 cm from a {sup 71}Ge disc source was calculated to be about 1.3x10{sup -5} Gy MBq{sup -1}s{sup -1}. Based on the results from his study, {sup 71}Ge activity of the order of 3.7x10{sup 10} Bq({approx}1 Ci) might be necessary to obtain dose rates typical of {sup 90}Sr/Y ophthalmic applicators. The possibility of using {sup 71}Ge as a source of radioactive stents was also investigated. A {sup 71}Ge stent was modelled as a cylindrical shell source and the dose rates were determined by Monte Carlo calculations. Some calculated results are compared with published values for a {sup 32}P-coated stent. The dose rate at 0.01 cm from a {sup 71}Ge stent has been calculated to be about .5x10{sup -3} Gy MBq{sup -1}h{sup -1}, which is much lower than the reported dose rate at the same distance from a {sup 32}P-coated stent. However, an initial source activity of the order of 3.7x10{sup 7} Bq ({approx}1 mCi) would easily result in a typical target dose ({approx}24 Gy) needed for intravascular stent applications. In conclusion, {sup 71}Ge sources could be used as alternatives to beta sources and, unlike high-energy ({approx}MeV) beta sources, may provide easily predictable dose distributions in heterogeneous media and low dose rates, which might be beneficial for

Heat exchanger, head and shell acceptance criteria

International Nuclear Information System (INIS)

Lam, P.S.; Sindelar, R.L.

1992-09-01

Instability of postulated flaws in the head component of the heat exchanger could not produce a large break, equivalent to a DEGB in the PWS piping, due to the configuration of the head and restraint provided by the staybolts. Rather, leakage from throughwall flaws in the head would increase with flaw length with finite leakage areas that are bounded by a post-instability flaw configuration. Postulated flaws at instability in the shell of the heat exchanger or in the cooling water nozzles could produce a large break in the Cooling Water System (CWS) pressure boundary. An initial analysis of flaw stability for postulated flaws in the heat exchanger head was performed in January 1992. This present report updates that analysis and, additionally, provides acceptable flaw configurations to maintain defined structural or safety margins against flaw instability of the external pressure boundary components of the heat exchanger, namely the head, shell, and cooling water nozzles. Structural and flaw stability analyses of the heat exchanger tubes, the internal pressure boundary of the heat exchangers or interface boundary between the PWS and CWS, were previously completed in February 1992 as part of the heat exchanger restart evaluation and are not covered in this report