Science.gov

Sample records for clathrate compound induced

  1. Clathrate compounds and method of manufacturing

    DOEpatents

    Nolas, George S.; Witanachchi, Sarath; Mukherjee, Pritish

    2009-05-19

    The present invention comprises new materials, material structures, and processes of fabrication of such that may be used in technologies involving the conversion of light to electricity and/or heat to electricity, and in optoelectronics technologies. The present invention provide for the fabrication of a clathrate compound comprising a type II clathrate lattice with atoms of silicon and germanium as a main framework forming lattice spacings within the framework, wherein the clathrate lattice follows the general formula Si.sub.136-yGe.sub.y, where y indicates the number of Ge atoms present in the main framework and 136-y indicates the number of Si atoms present in the main framework, and wherein y>0.

  2. Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

    SciTech Connect

    Krishna, Lakshmi; Koh, Carolyn A.

    2015-01-01

    ABSTRACT

    This review article evaluates the structure–property relations of inorganic clathrates and clathrate hydrates and their potential role in energy harvesting. There is potential cross-fertilization between the two research areas.

    Guest–host clathrate compounds exhibit unique structural and physical properties, which lead to their versatile roles in energy applications. Prominent classes of clathrate compounds are gas hydrates and inorganic clathrates. That said, there is limited cross-fertilization between the clathrate hydrate and inorganic clathrate communities, with researchers in the respective fields being less informed on the other field. Yet the structures and unique guest–host interactions in both these compounds are common important features of these clathrates. Common features and procedures can inspire and inform development between the compound classes, which may be important to the technological advancements for the different clathrate materials, e.g., structure characterization techniques and guest–host dynamics in which the “guest” tends to be imprisoned in the host structure, until external forces are applied. Conversely, the diversity in chemical compositions of these two classes of materials leads to the different applications from methane capture and storage to converting waste heat to electricity (thermoelectrics). This article highlights the structural and physical similarities and differences of inorganic and methane clathrates. The most promising state-of-the-art applications of the clathrates are highlighted for harvesting energy from methane (clathrate) hydrate deposits under the ocean and for inorganic clathrates as promising thermoelectric materials.

  3. NMR and transport measurements of copper chalcogenide and clathrate compounds

    NASA Astrophysics Data System (ADS)

    Sirusi Arvij, Ali

    Due to limited sources of fossil fuels worldwide and a large percentage wasted as heat energy, searching for efficient thermoelectric materials to convert heat to electricity has gained a great deal of attention. Most of the attempts are focused on materials with substantially lower lattice thermal conductivity and narrow band gaps. Among them, inorganic clathrates and copper-based chalcogenides possess intrinsic low thermal conductivity which makes them promising thermoelectrics. In this work, nuclear magnetic resonance (NMR), transport, and magnetic measurements were performed on clathrates and copper-based chalcogenides to investigate their vibrational and electronic charge carrier properties, as well as the unknown structures of Cu2Se and Cu 2Te at low temperatures, and the effect of rattling of guest atoms in the clathrates. The NMR results in Ba8Ga16Ge30 indicate a pseudogap in the Ga electronic density of states, superposed upon a surprisingly large Ba contribution to the conduction band. Meanwhile, the phonon contributions to the Ga relaxation rates are large and increase more rapidly with temperature than typical semiconductors due to enhanced anharmonicity of the propagative phonon modes over a wide range. Moreover, the observed NMR shifts in the Ba8Cu5Si xGe41-x clathrates change in a nonlinear way with increasing Si substitution: from x = 0 to about 20 the shifts are essentially constant, while approaching x = 41 they increase rapidly, demonstrating a significant change in hybridizations vs Si substitution. NMR studies of Cu2Se show an initial appearance of ionic hopping in a narrow temperature range above 100 K, coinciding with the recently observed low-temperature phase transition. At room temperature and above, this goes over to rapid Cu-ion hopping and a single motionally narrowed line both above and below the alpha-beta structural transition. Furthermore, the NMR results on Cu2Te and Cu 1.98Ag0.2Te demonstrate unusually large negative chemical

  4. Pressure-induced homothetic volume collapse in silicon clathrates

    NASA Astrophysics Data System (ADS)

    San Miguel, A.; Merlen, A.; Toulemonde, P.; Kume, T.; LeFloch, S.; Aouizerat, A.; Pascarelli, S.; Aquilanti, G.; Mathon, O.; LeBihan, T.; Itié, J.-P.; Yamanaka, S.

    2005-02-01

    The high-pressure properties of the Ba-doped silicon clathrate Ba8Si46 have been investigated combining X-ray diffraction and X-ray absorption spectroscopy. A pressure-induced isostructural phase transition associated with an important volume collapse takes place at 11.5 14 GPa. This transformation is characterized by the homothetic contraction of the silicon cages containing the Ba atoms. This transition is preceded by a change in the electronic structure at 5 GPa in good agreement with Raman spectroscopy observations (T. Kume et al., Phys. Rev. Lett., 90 (2003) 155503) that it is also of isostructural nature. The cage structure is preserved through the phase transitions allowing to obtain tetrahedral silicon with record interatomic distances as low as 2.13 Å. At the highest studied pressure of 49 GPa, the structure becomes irreversibly amorphous. The physical origin of the homothetic isostructural transitions is discussed.

  5. Monoclinic 122-Type BaIr₂Ge₂ with a Channel Framework: A Structural Connection between Clathrate and Layered Compounds.

    PubMed

    Gui, Xin; Chang, Tay-Rong; Kong, Tai; Pan, Max T; Cava, Robert J; Xie, Weiwei

    2017-07-18

    A new 122-type phase, monoclinic BaIr₂Ge₂ is successfully synthesized by arc melting; X-ray diffraction and scanning electron microscopy are used to purify the phase and determine its crystal structure. BaIr₂Ge₂ adopts a clathrate-like channel framework structure of the monoclinic BaRh₂Si₂-type, with space group P2₁/c. Structural comparisons of clathrate, ThCr₂Si₂, CaBe₂Ge₂, and BaRh₂Si2 structure types indicate that BaIr₂Ge₂ can be considered as an intermediate between clathrate and layered compounds. Magnetic measurements show it to be diamagnetic and non-superconducting down to 1.8 K. Different from many layered or clathrate compounds, monoclinic BaIr₂Ge₂ displays a metallic resistivity. Electronic structure calculations performed for BaIr₂Ge₂ support its observed structural stability and physical properties.

  6. Simulations of guest transport in clathrates of Dianin's compound and hydroquinone.

    PubMed

    Nemkevich, Alexandra; Spackman, Mark A; Corry, Ben

    2013-02-18

    Clathrates have been proposed for use in a variety of applications including gas storage, mixture separation and catalysis due to the potential for controlled guest diffusion through their porous lattices. Here molecular dynamics simulations are employed to study guest transport in clathrates of hydroquinone (HQ) and Dianin's compound (DC). Systems investigated were HQ with methanol and acetonitrile, and DC with methanol and ethanol. Simulations were set up with one guest in the pore, two guests in the pore and one vacancy in the pore and a filled pore, and free-energy barriers for movement between cavities of the pore were estimated for all cases. Comparison between these simulations indicates that guest transport most likely proceeds by molecules moving from full to empty cavities consecutively, one by one, rather than in a concerted manner. Thus, the presence of empty cavities is very important for guest transport, which becomes more energetically demanding in fully loaded systems. Flexibility of the host can assist guest transport. In the studied DC clathrates transport occurs via an intermediate conformation in which the hydroxyl group of the alcohol guest molecule participates in the hydrogen-bonded ring of the host. We also address the issue of the number of methanol guest molecules that DC accommodates, for which conflicting information exists. We found that this is likely to be temperature dependent and suggest that under some conditions the system is most likely non-stoichiometric.

  7. Pressure-induced collapse of ice clathrate and hexagonal ice mixtures formed by freezing.

    PubMed

    Andersson, Ove; Johari, G P

    2009-09-21

    We report thermal conductivity kappa measurements of the pressure-induced collapse of two mixtures of ice and tetrahydrofuran (THF) clathrate hydrate formed by freezing aqueous solutions, THF23 H(2)O and THF20 H(2)O, one containing twice as much excess water than the other. On pressurizing, kappa of the solid mixture first decreases at the onset pressure of approximately 0.8 GPa, as occurs for collapse of pure ice, reaches a local minimum at a pressure of approximately 1.0 GPa, and then increases as occurs for the collapse of the pure clathrate THF17 H(2)O. This shows that in the apparently homogeneous mixture, the ice and the clathrate collapse as if the two were in a mechanically mixed state. The manner in which the clathrate aggregate can arrange in the solid indicates that ice occupies the interstitial space in the tightly packed aggregates and H(2)O molecules belonging to the lattice of one form hydrogen bond with that of the other, a feature that is preserved in their collapsed states. On decompression, the original clathrate is partially recovered in the THF20 H(2)O mixture, but the collapsed ice does not transform to the low density amorph. We surmise that on irreversible transformation to the original clathrate, the aggregates expand. Any pressure thus exerted on the small domains of the collapsed ice with a hydrogen bonded interface with the clathrate aggregates could prevent it from transforming to the low density amorph. Measurements of kappa are useful in investigating structural collapse of crystals when dilatometry is unable to do so, as kappa seems to be more sensitive to pressure-induced changes than the volume.

  8. Molten gallium flux synthesis of known thermoelectric and novel magnetic inorganic clathrate compounds: Improving thermoelectric performance

    NASA Astrophysics Data System (ADS)

    Bryan, John Daniel

    Molten gallium metal has been used as a solvent to grow large single crystals of known inorganic thermoelectric clathrates Sr8Ga 16Ge30, Ba8Ga16Ge30, and Ba8Ga16Si30. X-ray diffraction, thermal analysis, electron microprobe, Glow Discharge Mass Spectrometry, temperature dependent electrical conductivity and Seebeck coefficient measurements characterized the single crystals. The Thermoelectric performance was shown to be heavily dependent on the synthetic conditions including container choice, thermal history and impurity concentration. Inorganic Clathrates have attracted intense interest in last several years as potential new materials for thermoelectric devices. If a small to moderate increase in thermoelectric performance over the currently used materials is realized, substantial environmental and technological gains could be achieved. Since thermoelectric refrigeration modules require no moving parts or heat exchange gas (freon) they offer significant advantages over conventional refrigeration technology that tends to fail due to the finite lifetime of the pumping equipment. High temperature devices are also extremely useful for power generation in harsh unforgiving environments where excess heat is available. The thermoelectric performance, primarily at room temperature, of these compounds was found to be heavily dependent on the synthetic procedures used to obtain them. A flux growth procedure was developed to overcome the problems of the traditional melt-quench-anneal solid-state chemical approach. This procedure yielded large single crystals of the Sr8Ga16Ge 30, Ba8Ga16Ge30 and Ba8Ga 16Si30 compounds which ready facilitated their chemical and electronic study. Finally, an outlook on the application of these compounds as thermoelectric devices is given. Application of the flux method to other systems was also successful in the discovery of two new inorganic clathrate compounds: type IV Eu4Ga 8Ge16 and type V Yb8Ga16Ge14. The Eu4Ga8Ge16 compound was found to

  9. An attempt to prepare carbon clathrate compounds using high-pressure and high-temperature conditions

    NASA Astrophysics Data System (ADS)

    Yamanaka, Shoji; Kubo, Akira; Kini, N. S.; Inumaru, Kei

    2006-08-01

    In an attempt to prepare a crystalline carbon compound having a three-dimensional (3D) network similar to silicon clathrate superconductors, fullerene C 60 molecules were three-dimensionally polymerized using high-pressure and high-temperature conditions. A single crystal of 3D polymer was obtained from a two-dimensional C 60 polymer with a body-centered orthorhombic symmetry. The X-ray structural analysis of the 3D polymer revealed that the spherical C 60 monomer molecules were substantially deformed to cuboidal shapes, each unit being bonded to eight neighboring units to form a body-centered orthorhombic lattice. The new 3D polymer was electrically conductive and showed high micro-Vickers hardness comparable to that of cubic BN.

  10. 73Ge-NMR study and ab initio calculations on clathrate compound Ba24Ge100

    NASA Astrophysics Data System (ADS)

    Kanetake, F.; Harada, A.; Rachi, T.; Nagara, H.; Mukuda, H.; Kusakabe, K.; Kitaoka, Y.; Suzuki, N.; Tanigaki, K.; Itoh, K.; Haller, E. E.

    2008-07-01

    Through 73Ge-NMR measurements and ab initio calculations, we have studied electronic properties of a type-III clathrate compound Ba24Ge100. At ambient pressure, the nuclear spin-lattice relaxation rate 1/T1T has a peak around 200K followed by an activation type decrease with decreasing temperature and it becomes constant at very low temperatures. Near the peak temperature, the successive structural transformations have been observed at TS1 = 215K and TS2 = 180K. The constant value of 1/T1T at low temperatures is considerably smaller than the value at temperatures higher than TS1, which implies that the density of states at the Fermi level D(EF) significantly decreases from the high temperature value at ambient pressure. From ab initio calculations on Ba24Ge100 as well as Ba24Si100, we speculate the phase changes of Ba24Ge100 in the relevant region of the T-P plane. Our results of NMR measurements and D(EF) calculations for the P4132 and an R3 structures imply that, at high pressures ~ 2.8 GPa, there should be increase of D(EF) from the value at ambient pressure and low temperatures. We conclude that this result is predominantly related with the large enhancement of the superconducting transition temperature Tc from 0.24 K (at P = 0) to 3.8 K (at P = 2.7 GPa) observed in Ba24Ge100

  11. Laser Raman and infrared spectroscopic studies of molecular systems: Structural analysis of some clathrate compounds

    NASA Astrophysics Data System (ADS)

    Akyuz, S.

    1990-09-01

    The structural analyses of some molecular systems, namely clathrates, depending on the laser Raman and infrared spectroscopic studies are reported. The following subject areas are covered: Raman effect; Raman spectroscopy; IR spectroscopy; mutual exclusion principle; vibrational spectra of the polymeric layers; and fundamental vibrations of pyrazine molecules.

  12. Liquidus projection of the Ag-Ba-Ge system and melting points of clathrate type-I compounds

    NASA Astrophysics Data System (ADS)

    Zeiringer, I.; Grytsiv, A.; Brož, P.; Rogl, P.

    2012-12-01

    The liquidus and solidus projection has been constructed for the Ag-Ba-Ge system up to 33.3 at% Ba, using electron micro probe analysis (EPMA), X-ray powder diffraction (XRD) and differential thermal analysis (DSC/DTA). Eight different primary crystallization regions were found: (Ge), Ba8AgxGe46-x-y□y (κI) (□ is a vacancy), Ba6AgxGe25-x (κIx), BaGe2, Ba(Ag1-xGex)2 (τ1), BaAg2-xGe2+x (τ2) BaAg5 and (Ag). The ternary invariant reactions have been determined for the region investigated and are the basis for a Schulz-Scheil diagram. The second part of this work provides a comprehensive compilation of melting points of ternary A8TxM46-x and quaternary (A=Sr, Ba, Eu; T=Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga; M=Si, Ge, Sn) clathrate type-I compounds and decomposition temperatures of inverse clathrate type-I Ge38{P,As,Sb}8{Cl,Br,I}8, Si46-xPxTey and tin based compounds.

  13. Transient oxygen clathrate-like hydrate and water networks induced by magnetic fields.

    PubMed

    Ozeki, Sumio; Otsuka, Ichiro

    2006-10-19

    Recently, careful experiments of oxygen-dissolved pure water treated by high magnetic fields showed indirectly the existence of magnetic field-affecting water (MFA water), which brought about a decrease in the contact angle of water on metals, an increase in the electrolytic potential of water, inhibition of metal corrosion, and changes in the crystal structure of calcium carbonate due to magnetic treatment. Here we report the infrared and Raman spectroscopic evidence indicating quasi-stable structures in the MFA water; oxygen clathrate-like hydrate and developed water networks, which were induced by magnetic interactions while a vacuum-distilled water, followed by oxygen exposure, crossed a steady magnetic field. The mechanism of MFA water formation and survival under thermal fluctuation is a challenging problem for the science community.

  14. Vibrational modes in silicon clathrate compounds: A key to understanding superconductivity

    NASA Astrophysics Data System (ADS)

    Reny, E.; San-Miguel, A.; Guyot, Y.; Masenelli, B.; Mélinon, P.; Saviot, L.; Yamanaka, S.; Champagnon, B.; Cros, C.; Pouchard, M.; Borowski, M.; Dianoux, A. J.

    2002-07-01

    Several doped type-I silicon clathrates (Na8@Si46, K8@Si46, Ba8@Si46 and I8@Si46) have been investigated both experimentally by inelastic neutron scattering and x-ray-absorption spectroscopy and theoretically by ab initio calculations. We find that Ba atoms have a stronger coupling with the host lattice than Na or K ones. We show that in the superconductor Ba8@Si46 the coupling is effectively done by host acoustic phonons exciting guest acoustic modes. These features suggest that the host-guest vibrational coupling is a crucial parameter to explain the appearance of superconductivity in addition to the density of states near the Fermi level.

  15. Liquidus projection of the Ag-Ba-Ge system and melting points of clathrate type-I compounds

    SciTech Connect

    Zeiringer, I.; Grytsiv, A.; Broz, P.

    2012-12-15

    The liquidus and solidus projection has been constructed for the Ag-Ba-Ge system up to 33.3 at% Ba, using electron micro probe analysis (EPMA), X-ray powder diffraction (XRD) and differential thermal analysis (DSC/DTA). Eight different primary crystallization regions were found: (Ge), Ba{sub 8}Ag{sub x}Ge{sub 46-x-y}{open_square}{sub y} ({kappa}{sub I}) ({open_square} is a vacancy), Ba{sub 6}Ag{sub x}Ge{sub 25-x} ({kappa}{sub Ix}), BaGe{sub 2}, Ba(Ag{sub 1-x}Ge{sub x}){sub 2} ({tau}{sub 1}), BaAg{sub 2-x}Ge{sub 2+x} ({tau}{sub 2}) BaAg{sub 5} and (Ag). The ternary invariant reactions have been determined for the region investigated and are the basis for a Schulz-Scheil diagram. The second part of this work provides a comprehensive compilation of melting points of ternary A{sub 8}T{sub x}M{sub 46-x} and quaternary (A=Sr, Ba, Eu; T=Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga; M=Si, Ge, Sn) clathrate type-I compounds and decomposition temperatures of inverse clathrate type-I Ge{sub 38}{l_brace}P,As,Sb{r_brace}{sub 8}{l_brace}Cl,Br,I{r_brace}{sub 8}, Si{sub 46-x}P{sub x}Te{sub y} and tin based compounds. - Graphical Abstract: Partial liquidus projection of the Ag-Ba-Ge system. Highlights: Black-Right-Pointing-Pointer The liquidus and solidus projection has been constructed for the Ag-Ba-Ge system up to 33.33 at% Ba. Black-Right-Pointing-Pointer Eight different primary crystallization fields have been found. Black-Right-Pointing-Pointer All the ternary compounds form congruently from the melt. Black-Right-Pointing-Pointer The ternary invariant reactions have been determined and are the basis for a Schulz-Scheil diagram.

  16. Methane clathrates in the solar system.

    PubMed

    Mousis, Olivier; Chassefière, Eric; Holm, Nils G; Bouquet, Alexis; Waite, Jack Hunter; Geppert, Wolf Dietrich; Picaud, Sylvain; Aikawa, Yuri; Ali-Dib, Mohamad; Charlou, Jean-Luc; Rousselot, Philippe

    2015-04-01

    We review the reservoirs of methane clathrates that may exist in the different bodies of the Solar System. Methane was formed in the interstellar medium prior to having been embedded in the protosolar nebula gas phase. This molecule was subsequently trapped in clathrates that formed from crystalline water ice during the cooling of the disk and incorporated in this form into the building blocks of comets, icy bodies, and giant planets. Methane clathrates may play an important role in the evolution of planetary atmospheres. On Earth, the production of methane in clathrates is essentially biological, and these compounds are mostly found in permafrost regions or in the sediments of continental shelves. On Mars, methane would more likely derive from hydrothermal reactions with olivine-rich material. If they do exist, martian methane clathrates would be stable only at depth in the cryosphere and sporadically release some methane into the atmosphere via mechanisms that remain to be determined. In the case of Titan, most of its methane probably originates from the protosolar nebula, where it would have been trapped in the clathrates agglomerated by the satellite's building blocks. Methane clathrates are still believed to play an important role in the present state of Titan. Their presence is invoked in the satellite's subsurface as a means of replenishing its atmosphere with methane via outgassing episodes. The internal oceans of Enceladus and Europa also provide appropriate thermodynamic conditions that allow formation of methane clathrates. In turn, these clathrates might influence the composition of these liquid reservoirs. Finally, comets and Kuiper Belt Objects might have formed from the agglomeration of clathrates and pure ices in the nebula. The methane observed in comets would then result from the destabilization of clathrate layers in the nuclei concurrent with their approach to perihelion. Thermodynamic equilibrium calculations show that methane-rich clathrate

  17. Stability of clathrate hydrates in Martian crust

    NASA Astrophysics Data System (ADS)

    Gloesener, Elodie; Karatekin, Özgür; Dehant, Véronique

    2014-05-01

    Clathrate hydrates are crystalline compounds constituted by cages formed by hydrogen-bonded water molecules inside of which guest gas molecules are trapped. These materials are typically stable at high pressure and low temperature and are present on Earth mainly in marine sediments and in permafrost. Moreover, clathrate hydrates are expected to exist on celestial bodies like the icy moons Titan, Europa or Enceladus. Current conditions in the Martian crust are favourable to the presence of clathrate hydrates. In this study, we focused on the stability of methane and carbon dioxide clathrates in the Martian crust. We coupled the stability conditions of clathrates with a 1D thermal model in order to obtain the variations of the clathrate stability zone in the crust of Mars with time and for different crust compositions. Indeed, the type of soil directly controls the geothermal conditions and therefore the depth of clathrates formation. Unconsolidated soil acts as a thermal insulator and prevents the clathrates formation in the crust except on a small part of a few tens of meters thick. In contrast, sandstone or ice-cemented soil allows the clathrates formation with a stability zone of several kilometers. This is explained by the fact that they evacuate heat more efficiently and thus maintain lower temperatures. We also studied the stability zone of clathrates formed from a mixture of methane and hydrogen sulphide as well as from a mixture of methane and nitrogen. Contrary to the addition of N2, the addition of H2S to CH4 clathrates extends the stability zone and thus brings it closer to the surface. Therefore, mixed clathrates CH4-H2S will be more easily destabilized by changes in surface temperature than CH4 clathrates.

  18. Structural, elastic, and electronic properties of sodium atoms encapsulated type-I silicon-clathrate compound under high pressure

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Chen, Qing-Yun; Zeng, Zhao-Yi; Cai, Ling-Cang

    2015-10-01

    We calculated the structural, elastic, and electronic properties of alkali metal Na atoms doped type-I silicon-clathrate compound (Na8Si46) under pressure using first-principles methods. The obtained dependencies of bond lengths and bond angles on pressure show heterogeneous behaviors which may bring out a structural transition. By using the elastic stability criteria from the calculated elastic constants, we confirm that the Na8Si46 is elastically unstable under high pressure. Some of the mechanical and thermal quantities include bulk modulus, shear modulus, Young’s modulus, Debye temperature, sound velocity, melting point, and hardness, which are also derived from the elastic constants. The calculated total and partial electron densities of states of Na8Si46 indicate a weak interaction between the encapsulated Na atoms and the silicon framework. Moreover, the effect of pressure on its electronic structure is also investigated, which suggests that pressure is not a good choice to enhance the thermoelectricity performance of Na8Si46. Project supported by National Natural Science Foundation of China (Grant Nos. 11347134 and 11304254) and the Doctor Foundation of Southwest University of Science and Technology, China (Grant No. 13zx7125).

  19. Methane clathrate hydrate infrared spectrum. II. Near-infrared overtones, combination modes and cages assignments

    NASA Astrophysics Data System (ADS)

    Dartois, E.; Deboffle, D.; Bouzit, M.

    2010-05-01

    Context. Recently, we recorded the infrared spectrum of the methane clathrate hydrate stretching mode at low temperature, a caged compound of possible interest for solar system studies as well as interstellar ice mantles. Aims: We provide a practical infrared spectroscopic identification for methane clathrate hydrate to examine its astrophysical presence or absence. We investigate the crystal field induced shifts, and assign the different transitions to the different encaged molecules environments in this clathrate hydrate. Methods: A methane clathrate crystal is produced in an infrared transmitting moderate-pressure closed cell. Using Fourier transform infrared (FTIR) spectroscopy, the overtones (3ν4, 2ν3) and combination modes (ν2+2ν4, ν1+ν4, ν3+ν4, ν2+ν3, ν3+2ν4, 2ν2+2ν4, ν2+ν3+ν4) falling in the 6000-3000 cm-1 (~1.65-3.4 μm) and their temperature behaviour are investigated. In addition, non-astrophysical CH4/CF4 gas mixtures are used to build clathrates with different methane large and small cage occupancies to help in assignments. Results: Combination modes show the two distinct cages and the quasi-free rotor low temperature ro-vibrational structure expected for methane clathrate hydrates. A comparison with the pure phase I is performed. Implications for methane clathrate hydrate detection are clearly identified. Conclusions: Solid methane actual remote observations of solar system objects surfaces do not display the clathrate hydrates' specific shift and occupancy signatures. Observationnally, a search for their infrared spectroscopic specific signatures should be performed, focusing on thermodynamically favourable objects like trans- neptunian objects (TNOs) or recently exposed (e.g. fresh impact) planet (or their satellites) surfaces. On the modeling side, efforts must be undertaken to progressively implement clathrate formation kinetics.

  20. -Based Clathrate

    NASA Astrophysics Data System (ADS)

    Anno, Hiroaki; Shirataki, Ritsuko

    2014-06-01

    A polycrystalline silicon-based clathrate of nominal composition Ba8Al15Si31 was prepared by a combination of arc melting and spark plasma sintering. Its thermal stability in air and the effect on the surface of heat treatment in air, which are of practical importance for use of the material at elevated temperatures, were examined for different temperatures (873 K, 973 K, and 1073 K) and heating times (0-480 h). Thermogravimetry and differential thermal analysis in air in the range 300-1523 K indicated that Ba8Al15Si31 in the bulk form had relatively good thermal stability in air at high temperatures. X-ray diffraction measurements, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy revealed that a thin layer of oxide (probably a barium aluminate, BaAl2O4) was formed on the surface by heat treatment in air. The thickness of the oxide layer increased with increasing temperature and heating time. Growth of the oxide layer can be explained well in terms of a diffusion mechanism. The activation energy for oxidation was estimated to be approximately 201 kJ/mol, which is comparable with that for thermal oxidation of silicon. The chemical composition of the interior of the Ba8Al15Si31 was found to be stable to heat treatment in air.

  1. Evaluation of the possible presence of clathrate hydrates in Europa's icy shell or seafloor

    NASA Astrophysics Data System (ADS)

    Prieto-Ballesteros, Olga; Kargel, Jeffrey S.; Fernández-Sampedro, Maite; Selsis, Franck; Martínez, Eduardo Sebastián; Hogenboom, David L.

    2005-10-01

    lower salinity would allow all these clathrates to sink, except that CH 4 clathrate would still float. Many geological processes may be driven or affected by the formation, presence, and destruction of clathrates in Europa such as explosive cryomagmatic activity [Stevenson, D.J., 1982. Volcanism and igneous processes in small icy satellites. Nature 298, 142-144], partial differentiation of the crust driven by its clathration, or the local retention of heat within or beneath clathrate-rich layers because of the low thermal conductivity of clathrate hydrates [Ross, R.G., Kargel, J.S., 1998. Thermal conductivity of Solar System ices, with special reference to martian polar caps. In: Schmitt, B., De Berg, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Dordrecht, pp. 33-62]. On the surface, destabilization of these minerals and compounds, triggered by fracture decompression or heating could result in formation of chaotic terrain morphologies, a mechanism that also has been proposed for some martian chaotic terrains [Tanaka, K.L., Kargel, J.S., MacKinnon, D.J., Hare, T.M., Hoffman, N., 2002. Catastrophic erosion of Hellas basin rim on Mars induced by magmatic intrusion into volatile-rich rocks. Geophys. Res. Lett. 29 (8); Kargel, J.S., Prieto-Ballesteros, O., Tanaka K.L., 2003. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton? Geophys. Res. 5. Abstract 14252]. Models of the evolution of the ice shell of Europa might take into account the presence of clathrate hydrates because if gases are vented from the silicate interior to the water ocean, they first would dissolve in the ocean and then, if the gas concentrations are sufficient, may crystallize. If any methane releases occur in Europa by hydrothermal or biological activity, they also might form clathrates. Then, from both geological and astrobiological perspectives, future missions to Europa should carry instrumentation capable of clathrate hydrate detection.

  2. New silica clathrate minerals that are isostructural with natural gas hydrates.

    PubMed

    Momma, Koichi; Ikeda, Takuji; Nishikubo, Katsumi; Takahashi, Naoki; Honma, Chibune; Takada, Masayuki; Furukawa, Yoshihiro; Nagase, Toshiro; Kudoh, Yasuhiro

    2011-02-15

    Silica clathrate compounds (clathrasils) and clathrate hydrates are structurally analogous because both materials have framework structures with cage-like voids occupied by guest species. The following three structural types of clathrate hydrates are recognized in nature: cubic structure I (sI); cubic structure II (sII); and hexagonal structure H (sH). In contrast, only one naturally occurring silica clathrate mineral, melanophlogite (sI-type framework), has been found to date. Here, we report the discovery of two new silica clathrate minerals that are isostructural with sII and sH hydrates and contain hydrocarbon gases. Geological and mineralogical observations show that these silica clathrate minerals are traces of low-temperature hydrothermal systems at convergent plate margins, which are the sources of thermogenic natural gas hydrates. Given the widespread occurrence of submarine hydrocarbon seeps, silica clathrate minerals are likely to be found in a wide range of marine sediments.

  3. Experimental and Computational Insight into the Chemical Bonding and Electronic Structure of Clathrate Compounds in the Sn-In-As-I System.

    PubMed

    Yashina, Lada V; Volykhov, Andrey A; Neudachina, Vera S; Aleksandrova, Nadezhda V; Reshetova, Liudmila N; Tamm, Marina E; Pérez-Dieste, Virginia; Escudero, Carlos; Vyalikh, Denis V; Shevelkov, Andrei V

    2015-12-07

    Inorganic clathrate materials are of great fundamental interest and potential practical use for application as thermoelectric materials in freon-free refrigerators, waste-heat converters, direct solar thermal energy converters, and many others. Experimental studies of their electronic structure and bonding have been, however, strongly restricted by (i) the crystal size and (ii) essential difficulties linked with the clean surface preparation. Overcoming these handicaps, we present for the first time a comprehensive picture of the electronic band structure and the chemical bonding for the Sn(24-x-δ)InxAs(22-y)I8 clathrates obtained by means of photoelectron spectroscopy and complementary quantum modeling.

  4. Clathrates (gas hydrates) in deep-sea as a next global hydrocarbon province

    SciTech Connect

    Lowrie, A.; Michael, M. )

    1991-03-01

    Preliminary reconnaissance of ocean basins indicates that more hydrocarbons may be located in clathrates (gas hydrates) and trapped gases than hitherto found on all continents, including coal. Clathrates are medium- to high-pressure stabilized, icelike compounds. Natural gas clathrates are stabilized by higher than sea level, ambient pressure, and are stable in the cold, deep-ocean environment. Location of clathrates on a regional scale would include using seismic reflection data. Bottom simulating reflections (BSR) are the most common indicators. The BSR reflections do indeed generally mimic the water bottom at a relatively uniform depth of some tenths of a second. Apparently, the strong acoustic impedance marking the lower clathrate/upper trapped gas reservoir contact creates the BSR. Sea floor bathymetry determines the configuration of the clathrate. Clathrate serves as a trapping mechanism; clathrate and methane gas accumulated beneath it, depending on geometry, are the reservoir; the entire sediment section is the source. Clathrates are commonly near or at the sea bottom, below 200-400 m water depth, under at least 20 to 50 atmospheres of pressure. Clathrates in the Arctic basin have been found to be up to 1700 m thick, and along continental shelves and slope of the Atlantic basin, up to 1100 m thick. Exploration may proceed either by drilling vertically into the clathrate or drilling laterally along the flanks of the clathrate. Drilling into the clathrate involves the problem of rupturing the 'seal' and permitting gas to escape. Indirect drilling under the flanks could permit 'draining' the accumulated gases and then removing the gas within the clathrate.

  5. Vibrational Dynamics and Guest-Host Coupling in Clathrate Hydrates

    NASA Astrophysics Data System (ADS)

    Koza, Michael M.; Schober, Helmut

    Clathrate hydrates may turn out either a blessing or a curse for mankind. On one hand, they constitute a huge reservoir of fossil fuel. On the other hand, their decomposition may liberate large amounts of green house gas and have disastrous consequences on sea floor stability. It is thus of paramount importance to understand the formation and stability of these guest-host compounds. Neutron diffraction has successfully occupied a prominent place on the stage of these scientific investigations. Complete understanding, however, is not achieved without an explanation for the thermal properties of clathrates. In particular, the thermal conductivity has a large influence on clathrate formation and conservation. Neutron spectroscopy allows probing the microscopic dynamics of clathrate hydrates. We will show how comparative studies of vibrations in clathrate hydrates give insight into the coupling of the guest to the host lattice. This coupling together with the anharmonicity of the vibrational modes is shown to lay the foundations for the peculiar thermodynamic properties of clathrate hydrates. The results obtained reach far beyond the specific clathrate system. Similar mechanisms are expected to be at work in any guest-host complex.

  6. Fully quantal calculation of H{sub 2} translation-rotation states in the (p-H{sub 2}){sub 2}@5{sup 12}6{sup 4} clathrate hydrate inclusion compound

    SciTech Connect

    Felker, Peter M.

    2014-11-14

    The quantal translation-rotation (TR) states of the (p-H{sub 2}){sub 2}@5{sup 12}6{sup 4} clathrate hydrate inclusion compound have been computed. The ten-dimensional problem (in the rigid-cage and rigid-H{sub 2} approximation) is solved by first approximating the H{sub 2} moieties as spherically symmetric and solving for their 6D translational eigenstates. These are then combined with H{sub 2} free rotational states in a product basis that is used to diagonalize the full TR hamiltonian. The computed low-energy eigenstates have translational components that are essentially identical to the 6D translational eigenstates and rotational components that are 99.9% composed of rotationally unexcited H{sub 2} moieties. In other words, TR coupling is minimal for the low-energy states of the species. The low-energy level structure is found to be substantially more congested than that of the more tightly packed (p-H{sub 2}){sub 4}@5{sup 12}6{sup 4} clathrate species. The level structure is also shown to be understandable in terms of a model of (H{sub 2}){sub 2} as a semirigid diatomic species consisting of two spherically symmetric H{sub 2} pseudo-atoms.

  7. Clathrate colloidal crystals

    NASA Astrophysics Data System (ADS)

    Lin, Haixin; Lee, Sangmin; Sun, Lin; Spellings, Matthew; Engel, Michael; Glotzer, Sharon C.; Mirkin, Chad A.

    2017-03-01

    DNA-programmable assembly has been used to deliberately synthesize hundreds of different colloidal crystals spanning dozens of symmetries, but the complexity of the achieved structures has so far been limited to small unit cells. We assembled DNA-modified triangular bipyramids (~250-nanometer long edge, 177-nanometer short edge) into clathrate architectures. Electron microscopy images revealed that at least three different structures form as large single-domain architectures or as multidomain materials. Ordered assemblies, isostructural to clathrates, were identified with the help of molecular simulations and geometric analysis. These structures are the most sophisticated architectures made via programmable assembly, and their formation can be understood based on the shape of the nanoparticle building blocks and mode of DNA functionalization.

  8. Silicon clathrates and carbon analogs: high pressure synthesis, structure, and superconductivity.

    PubMed

    Yamanaka, Shoji

    2010-02-28

    Compounds with cage-like structures of elemental silicon and carbon are comparatively reviewed. Barium containing silicon clathrate compounds isomorphous with type I gas hydrates were prepared using high pressure and high temperature (HPHT) conditions, and found to become superconductors. The application of HPHT conditions to Zintl binary silicides have produced a number of silicon-rich cage-like structures including new clathrate structures; most of them are superconductors. Carbon analogs of silicon clathrates can be prepared by 3D polymerization of C(60) under HPHT conditions, which are new allotropes of carbon with expanded framework structures. The crystal chemistry and characteristic properties of some related compounds are also reviewed.

  9. First principles calculations of thermodynamical properties of cage-like silicon clathrate materials

    NASA Astrophysics Data System (ADS)

    Jack, Deslippe; Dong, Jianjun

    2003-03-01

    Si, Ge, and Sn based clathrate materials are potential high ZT thermoelectric materials due to their electron-crystal-phon-glass properties. Recently, the synthesis of guest-free type-II Si clathrate (Si136) was reported. The pristine (guest-free) Si and Ge clathrate can be viewed as "negative-pressure" phases, which might exist metastably at ambient conditions. In this talk, we will report our recent calculations of the thermodynamic properties of silicon type-I and -II Clathrate phases, as well as the ground state Si diamond phase. Statistical quasi-harmonic theory is used in conjunction with first-principles static bonding energy and dynamic phonon spectrum calculations to obtain free energies of the lattices. At zero temperature, the transition pressures of diamond-to-clathrate-I and diamond-to-clathrates-II transitions are predicted to be -46.9 kbar and -38.9 kbar respectively, while the Clapeyron slopes (dP/dT) of the two transitions at 300K are 8.64 bar/K and 7.38 bar/K respectively. Thermal properties of the Si materials, such as (linear) thermal expansion coefficients, Gruneisen parameters, heat capacities, and thermal bulk moduli etc. are also calculated. We find good agreement with experiment in the Si diamond phase. The results of the Si clathrates are discussed in comparison to those of the Si diamond, as well as available data of metal-encapsulated Si-based clathrate compounds (such as Na8Si46).

  10. Experimental study on the effect of ammonia on the phase behavior of tetrahydrofuran clathrates.

    PubMed

    Vu, Tuan Hoang; Gloesener, Elodie; Choukroun, Mathieu; Ibourichene, Anaïs; Hodyss, Robert

    2014-11-26

    Clathrate hydrates, ice-like crystalline compounds in which small guest molecules are enclosed inside cages formed by tetrahedrally hydrogen-bonded water molecules, are naturally abundant on Earth and are generally expected to exist on icy celestial bodies. A prototypical example is Saturn's moon Titan, where dissociation of methane clathrates, a major crustal component, could contribute significantly to the replenishment of atmospheric methane. Ammonia is an important clathrate inhibiting agent that may be present (potentially at high concentrations) in Titan's interior. In this study, low-temperature Raman experiments are conducted to examine the dissociation point of tetrahydrofuran clathrates, an ambient-pressure analogue of methane clathrates, over a wide range of ammonia concentrations from 0 to 25 wt %. A phase diagram for the H2O-THF-NH3 system is generated, showing two main results: (i) ammonia lowers the dissociation point of clathrate hydrates to a similar extent compared to the melting of water ice and (ii) THF clathrate exhibits a "liquidus-like" behavior in the presence of ammonia, with a eutectic temperature of about 203.6 K. As temperatures higher than this estimated eutectic are anticipated within Titan's icy crust, these results imply that partial dissociation of clathrates can occur readily and may contribute to outgassing from the interior.

  11. Glass-like thermal transport in symmetry-broken clathrates.

    SciTech Connect

    Kanashita, E.; Nakayama, T.; Toyota Phys. Chem. Res. Inst.

    2009-01-01

    We present the quantitative interpretation for the glass-like behavior of thermal conductivities {kappa}(T) for type-I clathrate compounds involving off-centered guest ions. It is shown that the dipole-dipole interaction generated in cage/guest-ion systems is crucial to reproduce the characteristics of thermal conductivities for these symmetry-broken clathrates. The above scenario also explains well the difference of {kappa}(T) between the p-type and the n-type {beta}-BGS found recently by K. Suekuni et al.

  12. Complex admixtures of clathrate hydrates in a water desalination method

    DOEpatents

    Simmons, Blake A.; Bradshaw, Robert W.; Dedrick, Daniel E.; Anderson, David W.

    2009-07-14

    Disclosed is a method that achieves water desalination by utilizing and optimizing clathrate hydrate phenomena. Clathrate hydrates are crystalline compounds of gas and water that desalinate water by excluding salt molecules during crystallization. Contacting a hydrate forming gaseous species with water will spontaneously form hydrates at specific temperatures and pressures through the extraction of water molecules from the bulk phase followed by crystallite nucleation. Subsequent dissociation of pure hydrates yields fresh water and, if operated correctly, allows the hydrate-forming gas to be efficiently recycled into the process stream.

  13. Clathrate hydrates in cometary nuclei and porosity

    NASA Technical Reports Server (NTRS)

    Smoluchowski, R.

    1988-01-01

    Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

  14. Liquid clathrate formation in ionic liquid-aromatic mixtures.

    PubMed

    Holbrey, John D; Reichert, W Matthew; Nieuwenhuyzen, Mark; Sheppard, Oonagh; Hardacre, Christopher; Rogers, Robin D

    2003-02-21

    1-Alkyl-3-methylimidazolium containing ionic liquids with hexafluorophosphate, bis(trifyl)imide, tetrafluoroborate, and chloride anions form liquid clathrates when mixed with aromatic hydrocarbons; in the system 1,3-dimethylimidazolium hexafluorophosphate-benzene, the aromatic solute could be trapped in the solid state forming a crystalline 2:1 inclusion compound.

  15. Clathrate hydrates in nature.

    PubMed

    Hester, Keith C; Brewer, Peter G

    2009-01-01

    Scientific knowledge of natural clathrate hydrates has grown enormously over the past decade, with spectacular new findings of large exposures of complex hydrates on the sea floor, the development of new tools for examining the solid phase in situ, significant progress in modeling natural hydrate systems, and the discovery of exotic hydrates associated with sea floor venting of liquid CO2. Major unresolved questions remain about the role of hydrates in response to climate change today, and correlations between the hydrate reservoir of Earth and the stable isotopic evidence of massive hydrate dissociation in the geologic past. The examination of hydrates as a possible energy resource is proceeding apace for the subpermafrost accumulations in the Arctic, but serious questions remain about the viability of marine hydrates as an economic resource. New and energetic explorations by nations such as India and China are quickly uncovering large hydrate findings on their continental shelves.

  16. Clathrate hydrates of oxidants in the ice shell of Europa.

    PubMed

    Hand, Kevin P; Chyba, Christopher F; Carlson, Robert W; Cooper, John F

    2006-06-01

    Europa's icy surface is radiolytically modified by high-energy electrons and ions, and photolytically modified by solar ultraviolet photons. Observations from the Galileo Near Infrared Mapping Spectrometer, ground-based telescopes, the International Ultraviolet Explorer, and the Hubble Space Telescope, along with laboratory experiment results, indicate that the production of oxidants, such as H2O2, O2, CO2, and SO2, is a consequence of the surface radiolytic chemistry. Once created, some of the products may be entrained deeper into the ice shell through impact gardening or other resurfacing processes. The temperature and pressure environments of regions within the europan hydrosphere are expected to permit the formation of mixed clathrate compounds. The formation of carbon dioxide and sulfur dioxide clathrates has been examined in some detail. Here we add to this analysis by considering oxidants produced radiolytically on the surface of Europa. Our results indicate that the bulk ice shell could have a approximately 1.7-7.6% by number contamination of oxidants resulting from radiolysis at the surface. Oxidant-hosting clathrates would consequently make up approximately 12-53% of the ice shell by number relative to ice, if oxidants were entrained throughout. We examine, in brief, the consequences of such contamination on bulk ice shell thickness and find that clathrate formation could lead to substantially thinner ice shells on Europa than otherwise expected. Finally, we propose that double occupancy of clathrate cages by O2 molecules could serve as an explanation for the observation of condensed-phase O2 on Europa. Clathrate-sealed, gas-filled bubbles in the near surface ice could also provide an effective trapping mechanism, though they cannot explain the 5771 A (O2)2 absorption.

  17. High-pressure synthesis and structural characterization of the type II clathrate compound Na(30.5)Si(136) encapsulating two sodium atoms in the same silicon polyhedral cages.

    PubMed

    Yamanaka, Shoji; Komatsu, Masaya; Tanaka, Masashi; Sawa, Hiroshi; Inumaru, Kei

    2014-05-28

    Single crystals of sodium containing silicon clathrate compounds Na8Si46 (type I) and NaxSi136 (type II) were prepared from the mixtures of NaSi and Si under high-pressure and high-temperature conditions of 5 GPa at 600-1000 °C. The type II crystals were obtained at relatively low-temperature conditions of 700-800 °C, which were found to have a Na excess composition Na30.5Si136 in comparison with the compounds NaxSi136 (x ≤ 24) obtained by a thermal decomposition of NaSi under vacuum. The single crystal study revealed that the Na excess type II compound crystallizes in space group Fd3̅m with a lattice parameter of a = 14.796(1) Å, slightly larger than that of the ambient phase (Na24Si136), and the large silicon hexakaidecahedral cages (@Si28) are occupied by two sodium atoms disordered in the two 32e sites around the center of the @Si28 cages. At temperatures <90 K, the crystal symmetry of the compound changes from the face-centered to the primitive cell with space group P213, and the Na atoms in the @Si28 cages are aligned as Na2 pairs. The temperature dependence of the magnetic susceptibility of Na30.5Si136 suggests that the two Na ions (2 Na(+)) in the cage are changed to a Na2 molecule. The Na atoms of Na30.5Si136 can be deintercalated from the cages topochemically by evacuation at elevated temperatures. The single crystal study of the deintercalated phases NaxSi136 (x = 25.5 and 5.5) revealed that only excess Na atoms have disordered arrangements.

  18. Thermodynamic stability of hydrogen clathrates

    PubMed Central

    Patchkovskii, Serguei; Tse, John S.

    2003-01-01

    The stability of the recently characterized type II hydrogen clathrate [Mao, W. L., Mao, H.-K., Goncharov, A. F., Struzhkin, V. V., Guo, Q., et al. (2002) Science 297, 2247–2249] with respect to hydrogen occupancy is examined with a statistical mechanical model in conjunction with first-principles quantum chemistry calculations. It is found that the stability of the clathrate is mainly caused by dispersive interactions between H2 molecules and the water forming the cage walls. Theoretical analysis shows that both individual hydrogen molecules and nH2 guest clusters undergo essentially free rotations inside the clathrate cages. Calculations at the experimental conditions – 2,000 bar (1 bar = 100 kPa) and 250 K confirm multiple occupancy of the clathrate cages with average occupations of 2.00 and 3.96 H2 molecules per D-512 (small) and H-51264 (large) cage, respectively. The H2–H2O interactions also are responsible for the experimentally observed softening of the H—H stretching modes. The clathrate is found to be thermodynamically stable at 25 bar and 150 K. PMID:14657391

  19. Micro-Tomographic Investigation of Ice and Clathrate Formation and Decomposition under Thermodynamic Monitoring

    PubMed Central

    Arzbacher, Stefan; Petrasch, Jörg; Ostermann, Alexander; Loerting, Thomas

    2016-01-01

    Clathrate hydrates are inclusion compounds in which guest molecules are trapped in a host lattice formed by water molecules. They are considered an interesting option for future energy supply and storage technologies. In the current paper, time lapse 3D micro computed tomographic (µCT) imaging with ice and tetrahydrofuran (THF) clathrate hydrate particles is carried out in conjunction with an accurate temperature control and pressure monitoring. µCT imaging reveals similar behavior of the ice and the THF clathrate hydrate at low temperatures while at higher temperatures (3 K below the melting point), significant differences can be observed. Strong indications for micropores are found in the ice as well as the THF clathrate hydrate. They are stable in the ice while unstable in the clathrate hydrate at temperatures slightly below the melting point. Significant transformations in surface and bulk structure can be observed within the full temperature range investigated in both the ice and the THF clathrate hydrate. Additionally, our results point towards an uptake of molecular nitrogen in the THF clathrate hydrate at ambient pressures and temperatures from 230 K to 271 K. PMID:28773789

  20. Structure of the Ice-Clathrate Interface

    NASA Astrophysics Data System (ADS)

    Nguyen, Andrew; Koc, Matthew; Shepherd, Tricia; Molinero, Valeria

    2015-03-01

    In the laboratory, clathrates are customarily synthesized from ice and gas guest. It is not clear how and whether ice assists in the nucleation of clathrate hydrates. The structure of the ice-clathrate interface can help assess the role of ice in clathrate nucleation. However, only few studies have addressed the structure of the ice-clathrate interface. Here, we use molecular dynamic simulations to study the structure of the ice-clathrate interface. There is no lattice matching between any plane of ice and clathrate hydrates, therefore an interfacial transition layer has to form to connect the two crystals. We investigate the structure of the ice-clathrate interface produced by alignment and equilibration of the crystals, competitive growth of the two crystals from a common solution, and nucleation of hydrate in the presence of a growing ice front. We find that the interfacial transition layer between ice and clathrate has a width of two to three water layers and it is disordered in all cases. Water in the interfacial transition layer has tetrahedral order lower than either ice or clathrate and higher than liquid water under the same thermodynamic conditions. The work is supported by NSF Grant Number CHE-1012651.

  1. Synthesis and electrochemical characterization of Silicon clathrates as anode materials for Lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Raghavan, Rahul

    Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown

  2. Marine clathrate mining and sediment separation

    DOEpatents

    Borns, David J.; Hinkebein, Thomas E.; Lynch, Richard W.; Northrop, David A.

    2001-01-01

    A method and apparatus for mining of hydrocarbons from a hydrocarbon-containing clathrate such as is found on the ocean floor. The hydrocarbon containing clathrate is disaggregated from sediment by first disrupting clathrate-containing strata using continuous mining means such as a rotary tilling drum, a fluid injector, or a drill. The clathrate-rich portion of sediment thus disrupted from the sea floor strata are carried through the apparatus to regions of relative lower pressure and/or relative higher temperature where the clathrate further dissociates into component hydrocarbons and water. The hydrocarbon is recovered with the assistance of a gas that is injected and buoys the hydrocarbon containing clathrate helping it to rise to regions of lower pressure and temperature where hydrocarbon is released. The sediment separated from the hydrocarbon returns to the ocean floor.

  3. Controlling superstructural ordering in the clathrate-I Ba 8 M 16 P 30 (M = Cu, Zn) through the formation of metal–metal bonds

    SciTech Connect

    Dolyniuk, J.; Whitfield, P. S.; Lee, K.; Lebedev, O. I.; Kovnir, K.

    2017-01-01

    Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in the additional substitution of Zn for P in Ba8M16+yP30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm[3 with combining macron]n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.

  4. Methane clathrate stability zone variations and gas transport in the Martian subsurface

    NASA Astrophysics Data System (ADS)

    Karatekin, O.; Gloesener, E.; Dehant, V. M. A.; Temel, O.

    2016-12-01

    During the last years, several detections of methane in the atmosphere of Mars were reported from Earth-based and Mars orbit instruments with abundances ranging to tens of parts-per-billion by volume (ppbv). Recently, the Curiosity rover detected methane with background levels of 0.7 ppbv and episodic releases of 7 ppbv. Although the methane sources are still unknown, this gas may have been stored in reservoirs of clathrate hydrate in the Martian subsurface where thermodynamics conditions are favourable to their presence. Clathrate hydrates are crystalline compounds constituted by cages formed by hydrogen-bonded water molecules inside of which guest gas molecules are trapped. In this study, methane clathrate stability in the Martian subsurface are investigated and their temporal and spatial variations are studied. Present-day maps of methane clathrate stability zone are produced by coupling the stability conditions of methane clathrate with a subsurface model using the available observations such as the the thermal inertia derived from TES MGS data. Then, a gas transport model has been used to study the methane flux at the surface due to the diffusion of different plausible methane volumes released by clathrate hydrates at variable depths under the Martian surface.

  5. The Antimony-Based Type I Clathrate compounds Cs8Cd18Sb28 and Cs8Zn18Sb28**

    SciTech Connect

    Liu, Yi; Wu, Li-Ming; Li, Long-Hua; Du, Shao-Wu; Corbett, John D.; Chen, Ling

    2009-06-17

    The title compounds lie in a new region of phase space for such a structure, and have stoichiometries in accord with a classical Zintl phase formulation. The small semiconductor gaps indicated by DFT calculations are also supported by their diamagnetic susceptibilities.

  6. Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8 M24 P28+δ (M=Cu/Zn).

    PubMed

    Dolyniuk, Juli-Anna; Zaikina, Julia V; Kaseman, Derrick C; Sen, Sabyasachi; Kovnir, Kirill

    2017-02-20

    A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba8 M24 P28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba8 M24 P28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined by a combination of X-ray and neutron diffraction and was confirmed with solid-state (31) P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. CO2 capture using semi-clathrates of quaternary ammonium salt: structure change induced by CO2 and N2 enclathration.

    PubMed

    Chazallon, Bertrand; Ziskind, Michael; Carpentier, Yvain; Focsa, Cristian

    2014-11-26

    Semi-clathrates of tetrabutylammonium bromide (TBAB) are investigated for their potential application in the CO2 capture context based on hydrate technology. The three-phase lines of semi-clathrates of CO2-TBAB-H2O and N2-TBAB-H2O are established simultaneously with their structure using in situ Raman scattering performed at high pressure. The preferred crystal phase obtained at ambient pressure from solutions of 5 and 40 wt % TBAB initial concentrations is shown to change upon enclathration of CO2 or N2, or by applying a higher pressure on the system. Deep in the stability field, metastable hydrate phases are occurring at the onset of the formation and correspond to the ones expected under ambient pressure conditions. Depending on the pressure, they progressively transformed into the most stable ones when approaching equilibrium and dissociation points. Besides, it is shown that a 5 wt % TBAB original solution forms preferentially a mixed structure of both type B and type A at low gas pressure with CO2 as the guest gas. A new structure is spectroscopically characterized at pressures higher than ∼2 MPa CO2. Type A is demonstrated to be stable at 5 wt % initial TBAB concentration with N2 as the guest molecule and pressure between 8 and 12 MPa. These structural data address new insights on the relationship between the hydrophilic-anion and hydrophobic-cation intercalation with a guest gas producing hydrophobic interaction in a distorted water lattice.

  8. Alloys of clathrate allotropes for rechargeable batteries

    DOEpatents

    Chan, Candace K; Miller, Michael A; Chan, Kwai S

    2014-12-09

    The present disclosure is directed at an electrode for a battery wherein the electrode comprises clathrate alloys of silicon, germanium or tin. In method form, the present disclosure is directed at methods of forming clathrate alloys of silicon, germanium or tin which methods lead to the formation of empty cage structures suitable for use as electrodes in rechargeable type batteries.

  9. Application of nuclear quadrupole resonance to the study of clathrates. sup 35 Cl NQR and crystallography of clathrated CCl sub 4

    SciTech Connect

    Pang, Li; Lucken, E.A.C.; Bernardinelli, G. )

    1990-11-21

    The {sup 35}Cl nuclear quadrupole resonance (NQR) spectra of CCl{sub 4} in more than 20 clathrates have been measured in the range 4-200 K. The crystal structures of CCl{sub 4}/Dianin's compound (1), CCl{sub 4}/Fe(AcAc){sub 3} (3), CCl{sub 4}/Ni(SCN){sub 2}(3-MePy){sub 4} (4), and CCl{sub 4}/Ni(exan){sub 2}(4,4{prime}-dm-2,2{prime}-bpy) (19) clathrates are also reported. Site symmetry and site multiplicity of the guest molecule in clathrates were determined by NQR spectroscopy and by x-ray crystallography. The degree of host-guest interaction was estimated from the NQR frequency shifts. The libration frequencies of the guest molecules in trigonal cavities were determined from NQR frequencies by Bayer-Kushida theory analysis.

  10. Kinetics of Ethane Clathrate Hydrate Formation under Titan-Like Conditions

    NASA Astrophysics Data System (ADS)

    Vu, T. H.; Munoz Iglesias, V.; Choukroun, M.; Maynard-Casely, H. E.

    2016-12-01

    Clathrate hydrates are inclusion compounds where small guest molecules are trapped inside highly symmetric water cages. These ice-like crystalline solids are an abundant source of hydrocarbons on Earth that primarily exist in the permafrost and marine sediments. Icy celestial bodies whose pressure and temperature conditions are favorable to the formation of gas hydrates are also expected to contain substantial amounts of these materials. One such example is Saturn's moon Titan, where clathrates are conjectured to be a major crustal component. In fact, clathrate dissociation has been suggested to play a significant role in the replenishment of atmospheric methane on this satellite. In addition to having a substantial atmosphere dominated by nitrogen, Titan is the only body in the Solar System aside from Earth that has standing bodies of liquid on its surface. Liquid methane and ethane have been identified as principal components of the hundreds of lakes that have been observed by the Cassini spacecraft on Titan's surface. As lake fluids come into contact with the pre-existing icy crust, stable layers of ethane clathrate hydrates are expected to form. In this work, we provide experimental evidence for the rapid formation of ethane clathrate from direct contact of liquid ethane with water ice at 1 bar using micro-Raman spectroscopy. Conversion of ice into clathrates is confirmed by the emergence of the characteristic peak at 999 cm-1, which represents the C-C stretch of enclathrated ethane. Kinetics experiments in the temperature range 140-173 K yields an activation energy of 6.75 ± 0.88 kJ/mol for the formation of ethane clathrate. Subsequent thermal analysis indicates a clathrate dissociation temperature of 240 K, consistent with extrapolated literature data. Preliminary synchrotron powder X-ray diffraction experiments have also been carried out to examine the formation kinetics of ethane clathrate from ice/gas mixture at 1 bar. The relatively fast timescale and

  11. Silicon clathrates for lithium ion batteries: A perspective

    NASA Astrophysics Data System (ADS)

    Warrier, Pramod; Koh, Carolyn A.

    2016-12-01

    Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15-20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

  12. Silicon clathrates for lithium ion batteries: A perspective

    SciTech Connect

    Warrier, Pramod Koh, Carolyn A.

    2016-12-15

    Development of novel energy storage techniques is essential for the development of sustainable energy resources. Li-ion batteries have the highest rated energy density among rechargeable batteries and have attracted a lot of attention for energy storage in the last 15–20 years. However, significant advancements are required in anode materials before Li-ion batteries become viable for a wide variety of applications, including in renewable energy storage, grid storage, and electric vehicles. While graphite is the current standard anode material in commercial Li-ion batteries, it is Si that exhibits the highest specific energy density among all materials considered for this purpose. Si, however, suffers from significant volume expansion/contraction and the formation of a thick solid-electrolyte interface layer. To resolve these issues, Si clathrates are being considered for anode materials. Clathrates are inclusion compounds and contain cages in which Li could be captured. While Si clathrates offer promising advantages due to their caged structure which enables negligible volume change upon Li insertion, there remains scientific challenges and knowledge gaps to be overcome before these materials can be utilized for Li-ion battery applications, i.e., understanding lithiation/de-lithiation mechanisms, optimizing guest concentrations, as well as safe and economic synthesis routes.

  13. Linking microscopic guest properties to macroscopic observables in clathrate hydrates: Guest-host hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Susilo, Robin; Ripmeester, John A.

    2009-05-01

    Molecular dynamics simulations are used to compare microscopic structures and guest dynamics to macroscopic properties in structure II clathrate hydrates with cyclopentane, tetrahydrofuran (THF), 1,3-dioxolane, tetrahydropyran (THP), and p-dioxane as guests. Significant differences are observed between structural parameters and rotational dynamics for the different guests. The simulations show the formation of guest-host hydrogen bonds between the ether oxygen atoms of THF and THP and the cage water hydrogen atoms of the clathrate but the absence of similar hydrogen bonds in the clathrate hydrates of the other guests on the time scale of the calculations. This guest-host hydrogen bonding leads to the formation of Bjerrum L-defects in the clathrate water lattice where two adjacent water molecules have no covalently bonded hydrogen atom between them. Unlike Bjerrum defects of ice lattices, these guest-induced L-defects are not accompanied by the formation of a D-defect at an adjacent site in the water lattice. At the simulation temperature of 200 K, the guest-water hydrogen bonds in the THF clathrate are short lived (lifetime less than 1 ps) but in the THP they are longer lived (a minimum of 100 ps). A van't Hoff plot for the probability of defect formation in THF as a function of temperature gives an activation barrier of ˜8.3 kJ/mol for guest-host defect formation in the THF clathrate. The consequences of the defect formation on the thermal expansivity, isothermal compressibility, dipole-dipole correlation function, and mechanical stability of the clathrate are discussed.

  14. Laboratory study of CH4-N2 clathrate hydrates applied to Titan's surface conditions

    NASA Astrophysics Data System (ADS)

    Nna Mvondo, D.; Tobie, G.; Le Menn, E.; Bollengier, O.; Grasset, O.

    2013-12-01

    It is proposed that clathrate hydrates may be present at the surface of Titan (Choukroun et al., 2013, 2010). At Titan's surface pressure, pure methane and ethane hydrate (as well as other guests) could exist in the sI structure and nitrogen hydrate as sII structure. The large reservoir of several guest compounds in Titan's atmosphere is expected to result in the formation of multicomponent (compound) clathrate hydrates, as sII or sH structures, stable relative to water ice on the surface of Titan, and with faster expected growth kinetics relative to pure hydrate (Osegovic et al., 2005). Compound hydrate could be a likely sink for many chemicals occurring on Titan's surface. We note that experimental studies on the formation and thermodynamics of the methane-water system, at low and high pressures applied to Titan have been carried out (Lunine and Stevenson; 1985; Choukroun et al., 2013, 2010 and references therein). However, laboratory work on mixing of methane with other compounds in the clathrate phase (ethane, N2, CO2, etc...) applied to Titan conditions (and other icy moons) has still to be addressed. In this context, we have studied the formation and spectral signatures of CH4-N2 clathrate hydrates at temperature and pressure conditions relevant for Titan's surface. Clathrate hydrates samples have been synthesized in an autoclave combined with a cooling system and a multi-gas mixer. Few ml of deionized water was introduced in the autoclave and pressurized with the N2 and CH4 gaseous species for a couple of days, at controlled low temperature and low pressure of the formation and stability of clathrate hydrates. Their formation has been monitored by gas chromatography. Their spectral characterization at low temperature was performed by infrared (FTIR) reflectance spectroscopy. Raman spectroscopy was also used to give constraints on the composition, structure and cage occupancy of the formed clathrates. Here we present the results obtained for different mixing

  15. Carbon dioxide-water clathrate as a reservoir of CO2 on Mars

    NASA Technical Reports Server (NTRS)

    Dobrovolskis, A.; Ingersell, A. P.

    1975-01-01

    It has been suggested that the residual polar caps of Mars contain a resorvoir of permanently frozen carbon dioxide which is controlling the atmospheric pressure. However, observational data and models of the polar heat balance suggest that the temperatures of the Martian poles are too high for solid CO2 to survive permanently. On the other hand, the icelike compound carbon dioxide-water clathrate could function as a CO2 reservoir instead of solid CO2, because it is stable at higher temperatures. This paper shows that the permanent polar caps may contain several millibars of CO2 in the form of clathrate, and discusses the implications of this permanent clathrate reservoir for the present and past atmospheric pressure on Mars.

  16. Carbon dioxide-water clathrate as a reservoir of CO2 on Mars

    NASA Technical Reports Server (NTRS)

    Dobrovolskis, A.; Ingersell, A. P.

    1975-01-01

    It has been suggested that the residual polar caps of Mars contain a resorvoir of permanently frozen carbon dioxide which is controlling the atmospheric pressure. However, observational data and models of the polar heat balance suggest that the temperatures of the Martian poles are too high for solid CO2 to survive permanently. On the other hand, the icelike compound carbon dioxide-water clathrate could function as a CO2 reservoir instead of solid CO2, because it is stable at higher temperatures. This paper shows that the permanent polar caps may contain several millibars of CO2 in the form of clathrate, and discusses the implications of this permanent clathrate reservoir for the present and past atmospheric pressure on Mars.

  17. Iodine-starch clathrate complexes in low-field acoustic fields

    NASA Astrophysics Data System (ADS)

    Fadeev, G. N.; Boldyrev, V. S.; Ermolaeva, V. I.; Eliseeva, N. M.

    2013-01-01

    Experimental data on the kinetics of formation and decomposition of iodine-starch clathrate complexes (amyloiodine and amylopectoiodine) in low-frequency (5-45 Hz) acoustic fields are reported. The biological activity of these compounds suggests their use as a model of biocatalysts, in which iodine represents the coenzyme active group and starch homopolysaccharides (amylopectin and amylose) represents the apoenzyme.

  18. Inorganic Clathrates: A Polyhedron with 22 Vertices and up to Ninefold Coordinated Phosphorus Atoms.

    PubMed

    Baumer, Franziska; Nilges, Tom

    2017-02-09

    Attractive phosphorus: Phosphorus atoms coordinated to up to nine neighbors can be found in the host structure of the clathrate Ba8 M24 P28+δ , which results in a new 22-vertex polyhedron (yellow). The physical properties can be tuned by adjusting the amount of phosphorus incorporated in the host framework of this new cage compound.

  19. Clathrate hydrate formation in amorphous cometary ice analogs in vacuo

    NASA Technical Reports Server (NTRS)

    Blake, David; Allamandola, Louis; Sandford, Scott; Hudgins, Doug; Freund, Friedemann

    1991-01-01

    Experiments conducted in clathrate hydrates with a modified electron microscope have demonstrated the possibility of such compounds' formation during the warming of vapor-deposited amorphous ices in vacuo, through rearrangements in the solid state. Subsolidus crystallization of compositionally complex amorphous ices may therefore be a general and ubiquitous process. Phase separations and microporous textures thus formed may be able to account for such anomalous cometary phenomena as the release of gas at large radial distances from the sun and the retention of volatiles to elevated temperatures.

  20. Clathrate hydrate formation in amorphous cometary ice analogs in vacuo

    NASA Technical Reports Server (NTRS)

    Blake, David; Allamandola, Louis; Sandford, Scott; Hudgins, Doug; Freund, Friedemann

    1991-01-01

    Experiments conducted in clathrate hydrates with a modified electron microscope have demonstrated the possibility of such compounds' formation during the warming of vapor-deposited amorphous ices in vacuo, through rearrangements in the solid state. Subsolidus crystallization of compositionally complex amorphous ices may therefore be a general and ubiquitous process. Phase separations and microporous textures thus formed may be able to account for such anomalous cometary phenomena as the release of gas at large radial distances from the sun and the retention of volatiles to elevated temperatures.

  1. Method of forming clathrate ice

    DOEpatents

    Hino, Toshiyuki; Gorski, Anthony J.

    1987-01-01

    A method of forming clathrate ice in a supercooled water-based liquid contained in a vessel is disclosed. Initially, an oscillator device is located in the liquid in the vessel. The oscillator device is then oscillated ultrasonically so that small crystals are formed in the liquid. These small crystals serve as seed crystals for ice formation in the liquid and thereby prevent supercooling of the liquid. Preferably, the oscillating device is controlled by a thermostat which initiates operation of the oscillator device when the temperature of the liquid is lowered to the freezing point. Thereafter, the operation of the oscillator device is terminated when ice is sensed in the liquid by an ice sensor.

  2. Clathrate hydrates in the solar system

    NASA Technical Reports Server (NTRS)

    Miller, S. L.

    1985-01-01

    Clathrate hydrates are crystalline compounds in which an expanded ice lattice forms cages that contain gas molecules. There are two principal hydrate structures. Structure I, with a 12 A cubic unit cell, contains 46 water molecules and 8 cages of two types, giving an ideal formula (for CH4) of CH4.5.75H2O. The actual formula contains somewhat more water as the cages are not completely filled. Other examples that form Structure I hydrates are C2H6, C2H4, C2H2, CO2, SO2, OCS, Xe, H2S. Structure II, with a 17 A cubic unit cell, contains 136 water molecules, and 8 large and 16 small cages. The ideal formula for CHCl3 is CHCL3.17H2O. Other examples of Structure II hydrates include C3H8, C2H5Cl, acetone, and tetrahydrofuran. Small molecules such as Ar, Kr and probably N2 and O2 also form a Structure II hydrate. The small molecules occupy both the large and small cages, giving an ideal formula of Ar.5.67H2O. The conditions of pressure and temperature for hydrate formation are discussed.

  3. Clathrate hydrates in the solar system

    NASA Technical Reports Server (NTRS)

    Miller, S. L.

    1985-01-01

    Clathrate hydrates are crystalline compounds in which an expanded ice lattice forms cages that contain gas molecules. There are two principal hydrate structures. Structure I, with a 12 A cubic unit cell, contains 46 water molecules and 8 cages of two types, giving an ideal formula (for CH4) of CH4.5.75H2O. The actual formula contains somewhat more water as the cages are not completely filled. Other examples that form Structure I hydrates are C2H6, C2H4, C2H2, CO2, SO2, OCS, Xe, H2S. Structure II, with a 17 A cubic unit cell, contains 136 water molecules, and 8 large and 16 small cages. The ideal formula for CHCl3 is CHCL3.17H2O. Other examples of Structure II hydrates include C3H8, C2H5Cl, acetone, and tetrahydrofuran. Small molecules such as Ar, Kr and probably N2 and O2 also form a Structure II hydrate. The small molecules occupy both the large and small cages, giving an ideal formula of Ar.5.67H2O. The conditions of pressure and temperature for hydrate formation are discussed.

  4. Intermediate bands in type-II silicon clathrate with Cu and Ag guest atoms

    NASA Astrophysics Data System (ADS)

    Huang, Zhaohui; Li, Huashan; Lusk, Mark T.; Wu, Zhigang

    2017-05-01

    The unique host-guest structure of the type-II silicon (Si) clathrate offers tunable electronic structures by doping guest atoms or molecules to the Si28 cages. Here we investigate the possibility of inducing intermediate bands (IBs) by Cu and Ag atoms employing first-principles calculations based on the density functional theory. Our analyses reveal that one or two isolated Cu/Ag atoms around the cage center are required to obtain IBs useful for photovoltaics; however, further clustering is likely to occur, which removes IBs and converts these Si clathrates into metal. Specifically, the formation of Cu and Ag clusters is mainly determined by local thermodynamics and local kinetics, respectively. All the Cu-clathrate structures presenting IBs are not energetically favorable, making Cu inappropriate for IB solar cells, whereas clathrates with one or two Ag atoms inside the cage that have IBs are thermodynamically stable, but the subsequent aggregation to form 3Ag or 4Ag clusters will destroy IBs. Thus, preventing clustering is crucial to realize IBs in Si clathrates by doping noble-metal atoms.

  5. Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form.

    PubMed

    Takeya, Satoshi; Fujihisa, Hiroshi; Yamawaki, Hiroshi; Gotoh, Yoshito; Ohmura, Ryo; Alavi, Saman; Ripmeester, John A

    2016-08-01

    The crystal structure and phase transition of cubic structure II (sII) binary clathrate hydrates of methane (CH4 ) and propanol are reported from powder X-ray diffraction measurements. The deformation of host water cages at the cubic-tetragonal phase transition of 2-propanol+CH4 hydrate, but not 1-propanol+CH4 hydrate, was observed below about 110 K. It is shown that the deformation of the host water cages of 2-propanol+CH4 hydrate can be explained by the restriction of the motion of 2-propanol within the 5(12) 6(4) host water cages. This result provides a low-temperature structure due to a temperature-induced symmetry-lowering transition of clathrate hydrate. This is the first example of a cubic structure of the common clathrate hydrate families at a fixed composition.

  6. Clathrate hydrate stability models for Titan: implications for a global subsurface ocean

    NASA Astrophysics Data System (ADS)

    Basu Sarkar, D.; Elwood Madden, M.

    2013-12-01

    Titan is the only planetary body in the solar system, apart from the Earth, with liquid at its surface. Titan's changing rotational period suggests that a global subsurface ocean decouples the icy crust from the interior. Several studies predict the existence of such an internal ocean below an Ice I layer, ranging in depth between a few tens of kilometers to a few hundreds of kilometers, depending on the composition of the icy crust and liquid-ocean. While the overall density of Titan is well constrained, the degree of differentiation within the interior is unclear. These uncertainties lead to poor understanding of the volatile content of the moon. However, unlike other similar large icy moons like Ganymede and Callisto, Titan has a thick nitrogen atmosphere, with methane as the second most abundant constituent - 5% near the surface. Titan's atmosphere, surface, and interior are likely home to various compounds such as C2H6, CO2, Ar, N2 and CH4, capable of forming clathrate hydrates. In addition, the moon has low temperature and low-to-high pressure conditions required for clathrate formation. Therefore the occurrence of extensive multicomponent hydrates may effect the composition of near-surface materials, the subsurface ocean, as well as the atmosphere. This work uses models of hydrate stability for a number of plausible hydrate formers including CH4, C2H6, CH4 + C2H6 and CH4 + NH3, and equilibrium geothermal gradients for probable near-surface materials to delineate the lateral and vertical extent of clathrate hydrate stability zones for Titan. By comparing geothermal gradients with clathrate stability fields for these systems we investigate possible compositions of Titan's global subsurface ocean. Preliminary model results indicate that ethane hydrates or compound hydrates of ethane and methane could be destabilized within the proposed depth range of the internal ocean, while methane/ammonia or pure methane hydrates may not be affected. Therefore, ethane or

  7. Radiation-induced amorphization of intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Lam, N. Q.; Sabochick, M. J.; Okamoto, P. R.

    1994-06-01

    In the present paper, important results of our recent computer simulation of radiation-induced amorphization in the ordered compounds CuTi and Cu4Ti3 are summarized. The energetic, structural, thermodynamic and mechanical responses of these intermetallics during chemical disordering, point-defect production and heating were simulated, using molecular dynamics and embedded-atom potentials. From the atomistic details obtained, the critical role of radiation-induced structural disorder in driving the crystalline-to-amorphous phase transformation is discussed.

  8. Superconductivity in Al-substituted Ba8Si46 clathrates

    NASA Astrophysics Data System (ADS)

    Li, Yang; Garcia, Jose; Chen, Ning; Liu, Lihua; Li, Feng; Wei, Yuping; Bi, Shanli; Cao, Guohui; Feng, Z. S.

    2013-05-01

    There is a great deal of interest vested in the superconductivity of Si clathrate compounds with sp3 network, in which the structure is dominated by strong covalent bonds among silicon atoms, rather than the metallic bonding that is more typical of traditional superconductors. A joint experimental and theoretical investigation of superconductivity in Al-substituted type-I silicon clathrates is reported. Samples of the general formula Ba8Si46-xAlx, with different values of x were prepared. With an increase in the Al composition, the superconducting transition temperature TC was observed to decrease systematically. The resistivity measurement revealed that Ba8Si42Al4 is superconductive with transition temperature at TC = 5.5 K. The magnetic measurements showed that the bulk superconducting Ba8Si42Al4 is a type II superconductor. For x = 6 sample Ba8Si40Al6, the superconducting transition was observed down to TC = 4.7 K which pointed to a strong suppression of superconductivity with increasing Al content as compared with TC = 8 K for Ba8Si46. Suppression of superconductivity can be attributed primarily to a decrease in the density of states at the Fermi level, caused by reduced integrity of the sp3 hybridized networks as well as the lowering of carrier concentration. These results corroborated by first-principles calculations showed that Al substitution results in a large decrease of the electronic density of states at the Fermi level, which also explains the decreased superconducting critical temperature within the BCS framework. The work provided a comprehensive understanding of the doping effect on superconductivity of clathrates.

  9. Overview: Nucleation of clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

    2016-12-01

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  10. Overview: Nucleation of clathrate hydrates.

    PubMed

    Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

    2016-12-07

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  11. Clathrate type 2 hydrate formation in vacuo under astrophysical conditions

    NASA Technical Reports Server (NTRS)

    Blake, D. F.; Allamandola, L. J.; Sandford, S. A.; Freund, F.

    1991-01-01

    The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K.

  12. In situ synthesis studies of silicon clathrates

    NASA Astrophysics Data System (ADS)

    Hutchins, Peter Thomas

    Solid state clathrates have shown considerable potential as a new class of materials over the past 30 years. Experimental and theoretical studies have shown that precise tuning and synthetic control of these materials, may lead to desirable properties. Very little is known about the mechanism of formation of the clathrates and so the desire to have accurate synthetic control was, until now, unrealistic. This thesis address the problem using in situ synchrotron x-ray techniques. In this study, experiments were designed to utilise time-resolved in situ diffraction techniques and high temperature 23Na NMR, in efforts to understand the mechanism of formation for this class of expanded framework materials. A complex high vacuum capillary synthesis cell was designed for loading under inert conditions and operation under high vacuum at station 6.2 of the SRS Daresbury. The cell was designed to operate in conjunction with a custom made furnace capable of temperatures in excess of 1000 C, as well as a vacuum system capable of 10"5 bar. The clathrate system was studied in situ, using rapid data collection to elucidate the mechanism of formation. The data were analysed using Rietveld methods and showed a structural link between the monoclinic, C2/c, Zintl precursors and the cubic, Pm3n, clathrate I phase. The phases were found to be linked by relation of the sodium planes in the silicide and the sodium atoms resident at cages centres in the clathrate system. This evidence suggests the guest species is instrumental in formation of the clathrate structure by templating the formation of the cages in the structure. Solid state 23Na NMR was utilised to complete specially design experiments, similar to those complete in situ using synchrotron x-ray techniques. The experiments showed increased spherical symmetry of the alkali metal sites and suggested increased mobility of the guest atoms during heating. In addition, cyclic heating experiments using in situ diffraction showed

  13. Reaction coordinate of incipient methane clathrate hydrate nucleation.

    PubMed

    Barnes, Brian C; Knott, Brandon C; Beckham, Gregg T; Wu, David T; Sum, Amadeu K

    2014-11-20

    Nucleation from solution is a ubiquitous phenomenon with relevance to myriad scientific disciplines, including pharmaceuticals, biomineralization, and disease. One prominent example is the nucleation of clathrate hydrates, multicomponent crystalline inclusion compounds relevant to the energy industry where they block pipelines and also constitute a potential vast energy resource. Despite their importance, the molecular mechanism of incipient hydrate formation remains unknown. Herein, we employ advanced molecular simulation tools (pB histogram, equilibrium path sampling) to provide a statistical-mechanical basis for extracting physical insight into the molecular steps by which clathrates form. Through testing the Mutually Coordinated Guest (MCG) order parameter, we demonstrate that both guest (methane) and host (water) structuring are crucial to accurately describe the nucleation of hydrates and determine a critical nucleus size of MCG-1 = 16 at 255 K and 500 bar. Equipped with a validated (and novel) reaction coordinate, subsequent equilibrium path sampling simulations yield the free energy barrier and nucleation rate. The resulting quantitative nucleation process is described by the MCG clustering mechanism. This constitutes a significant advance in the field of hydrates research, as the fitness of a molecular descriptor has never been statistically verified. More broadly, this work has significance to a wide range of multicomponent nucleation contexts wherein the formation mechanism depends on contributions from both solute and solvent.

  14. Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization

    PubMed Central

    Veremchuk, Igor; Beekman, Matt; Antonyshyn, Iryna; Schnelle, Walter; Baitinger, Michael; Nolas, George S.; Grin, Yuri

    2016-01-01

    The binary intermetallic clathrates K8-xSi46 (x = 0.4; 1.2), Rb6.2Si46, Rb11.5Si136 and Cs7.8Si136 were prepared from M4Si4 (M = K, Rb, Cs) precursors by spark-plasma route (SPS) and structurally characterized by Rietveld refinement of PXRD data. The clathrate-II phase Rb11.5Si136 was synthesized for the first time. Partial crystallographic site occupancy of the alkali metals, particularly for the smaller Si20 dodecahedra, was found in all compounds. SPS preparation of Na24Si136 with different SPS current polarities and tooling were performed in order to investigate the role of the electric field on clathrate formation. The electrical and thermal transport properties of K7.6Si46 and K6.8Si46 in the temperature range 4–700 K were investigated. Our findings demonstrate that SPS is a novel tool for the synthesis of intermetallic clathrate phases that are not easily accessible by conventional synthesis techniques. PMID:28773710

  15. Clathrate hydrates as possible source of episodic methane releases on Mars

    NASA Astrophysics Data System (ADS)

    Karatekin, Özgür; Gloesener, Elodie; Temel, Orkun

    2017-04-01

    Methane has been shown to vary with location and time in the Martian atmosphere, with abundances of up to tens of parts-per-billion by volume (ppbv). Since methane is short-lived on geological time scales, its presence implies the existence of an active, current source of methane that is yet to be understood. In this study we investigate the destabilization of subsurface reservoirs of clathrate hydrates as a possible geological source of methane. Clathrate hydrates are crystalline compounds constituted by cages of hydrogen-bonded water molecules, inside of which guest gas molecules are trapped. We show the present-day maps of methane clathrate stability zones, in particular in the vicinity of Gale Crater where the Sample Analysis at Mars (SAM) suite on the Curiosity rover has made in situ measurements of atmospheric methane, during more than 3 years. Curiosity has observed spikes of elevated methane levels of 7 ppbv on four sequential observations over a 2-month period. The possibility of episodic releases consistent with curiosity observations from a subsurface clathrate source, is investigated using a gas transport through porous Martian regolith considering different depths of reservoirs. Transport of the released methane spike into the atmosphere is simulated using the PlanetWRF model.

  16. Stability of clathrate hydrates and gas transport in the Martian subsurface

    NASA Astrophysics Data System (ADS)

    Gloesener, Elodie; Karatekin, Özgür; Dehant, Véronique

    2015-04-01

    Current conditions in the Martian crust are favourable to the presence of clathrate hydrates, crystalline compounds constituted by cages formed by hydrogen-bonded water molecules inside of which guest gas molecules are trapped. In this study, we focused on the stability of methane and carbon dioxide clathrates in the Martian subsurface. We coupled the stability conditions of clathrates with a 1D thermal model in order to obtain the variations of the hydrate stability zone within the Martian crust as a function of time. Our 1D thermal model includes the diffusion of water vapor through porous regolith. The mass conservation equation takes into account the different phases of water: vapor, ice or adsorbed H2O. The flow is calculated by combining the advective flow, due to pressure gradients and given by Darcy's law, and the Fickian diffusion due to density gradients of water vapor. Finally, we considered the diffusion of methane through the crust from the place where clathrates are dissociated into the atmosphere.

  17. Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate

    NASA Astrophysics Data System (ADS)

    Falenty, Andrzej; Hansen, Thomas C.; Kuhs, Werner F.

    2014-12-01

    Gas hydrates are ice-like solids, in which guest molecules or atoms are trapped inside cages formed within a crystalline host framework (clathrate) of hydrogen-bonded water molecules. They are naturally present in large quantities on the deep ocean floor and as permafrost, can form in and block gas pipelines, and are thought to occur widely on Earth and beyond. A natural point of reference for this large and ubiquitous family of inclusion compounds is the empty hydrate lattice, which is usually regarded as experimentally inaccessible because the guest species stabilize the host framework. However, it has been suggested that sufficiently small guests may be removed to leave behind metastable empty clathrates, and guest-free Si- and Ge-clathrates have indeed been obtained. Here we show that this strategy can also be applied to water-based clathrates: five days of continuous vacuum pumping on small particles of neon hydrate (of structure sII) removes all guests, allowing us to determine the crystal structure, thermal expansivity and limit of metastability of the empty hydrate. It is the seventeenth experimentally established crystalline ice phase, ice XVI according to the current ice nomenclature, has a density of 0.81 grams per cubic centimetre (making it the least dense of all known crystalline water phases) and is expected to be the stable low-temperature phase of water at negative pressures (that is, under tension). We find that the empty hydrate structure exhibits negative thermal expansion below about 55 kelvin, and that it is mechanically more stable and has at low temperatures larger lattice constants than the filled hydrate. These observations attest to the importance of kinetic effects and host-guest interactions in clathrate hydrates, with further characterization of the empty hydrate expected to improve our understanding of the structure, properties and behaviour of these unique materials.

  18. Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate.

    PubMed

    Falenty, Andrzej; Hansen, Thomas C; Kuhs, Werner F

    2014-12-11

    Gas hydrates are ice-like solids, in which guest molecules or atoms are trapped inside cages formed within a crystalline host framework (clathrate) of hydrogen-bonded water molecules. They are naturally present in large quantities on the deep ocean floor and as permafrost, can form in and block gas pipelines, and are thought to occur widely on Earth and beyond. A natural point of reference for this large and ubiquitous family of inclusion compounds is the empty hydrate lattice, which is usually regarded as experimentally inaccessible because the guest species stabilize the host framework. However, it has been suggested that sufficiently small guests may be removed to leave behind metastable empty clathrates, and guest-free Si- and Ge-clathrates have indeed been obtained. Here we show that this strategy can also be applied to water-based clathrates: five days of continuous vacuum pumping on small particles of neon hydrate (of structure sII) removes all guests, allowing us to determine the crystal structure, thermal expansivity and limit of metastability of the empty hydrate. It is the seventeenth experimentally established crystalline ice phase, ice XVI according to the current ice nomenclature, has a density of 0.81 grams per cubic centimetre (making it the least dense of all known crystalline water phases) and is expected to be the stable low-temperature phase of water at negative pressures (that is, under tension). We find that the empty hydrate structure exhibits negative thermal expansion below about 55 kelvin, and that it is mechanically more stable and has at low temperatures larger lattice constants than the filled hydrate. These observations attest to the importance of kinetic effects and host-guest interactions in clathrate hydrates, with further characterization of the empty hydrate expected to improve our understanding of the structure, properties and behaviour of these unique materials.

  19. Controlling superstructural ordering in the clathrate-I Ba8M16P30 (M = Cu, Zn) through the formation of metal–metal bonds† †Electronic supplementary information (ESI) available: Experimental details, tables of crystal structure refinements and structural parameters and associated CIFs, synchrotron X-ray and neutron powder diffraction Rietveld refinement plots, additional TEM and elemental analysis figures, LMTO DOS and band structure diagrams. See DOI: 10.1039/c7sc00354d Click here for additional data file.

    PubMed Central

    Dolyniuk, J.; Whitfield, P. S.; Lee, K.; Lebedev, O. I.

    2017-01-01

    Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16–xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in the additional substitution of Zn for P in Ba8M16+yP30–y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm3n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30. PMID:28580103

  20. Roles of Clathrate Hydrates in Crustal Heating and Volatile Storage/Release on Earth, Mars, and Beyond

    NASA Astrophysics Data System (ADS)

    Kargel, J. S.; Beget, J.; Furfaro, R.; Prieto-Ballesteros, O.; Palmero-Rodriguez, J. A.

    2007-12-01

    Clathrate hydrates are stable through much of the Solar System. These materials and hydrate-like amorphous associations of water with N2, CO, CH4, CO2, O2 and other molecules could, in fact, constitute the bulk of the non-rock components of some icy satellites, comets, and Kuiper Belt Objects. CO2 clathrate is thermodynamically stable at the Martian South Pole surface and could form a significant fraction of both Martian polar caps and icy permafrost distributed across one-third of the Martian surface. CH4 clathrate is the largest clathrate material in Earth's permafrost and cold seafloor regions, and it may be a major volatile reservoir on Mars, too. CO2 clathrate is less abundant on Earth but it might store most of Mars' CO2 inventory and thus may be one of the critical components in the climate system of that planet, just as CH4 clathrate is for Earth. These ice-like phases not only store biologically, geologically, and climatologically important gases, but they also are natural thermal insulators. Thus, they retard the conductive flow of geothermal heat, and thick accumulations of them can modify geotherms, cause brines to exist where otherwise they would not, and induce low-grade metamorphism of upper crustal rocks underlying the insulating bodies. This mechanism of crustal heating may be especially important in assisting hydrogeologic activity on Mars, gas-rich carbonaceous asteroids, icy satellites, and Kuiper Belt Objects. These worlds, compared to Earth, are comparatively energy starved and frozen but may partly make up for their deficit of joules by having large accumulations of joule-conserving hydrates. Thick, continuous layers of clathrate may seal in gases and produce high gas fugacities in aquifers underlying the clathrates, thus producing gas-rich reservoirs capable of erupting violently. This may have happened repeatedly in Earth history, with global climatic consequences for abrupt climate change. We have hypothesized that such eruptions may have

  1. Dynamics of Kr in dense clathrate hydrates.

    SciTech Connect

    Klug, D. D.; Tse, J. S.; Zhao, J. Y.; Sturhahn, W.; Alp, E. E.; Tulk, C. A.

    2011-01-01

    The dynamics of Kr atoms as guests in dense clathrate hydrate structures are investigated using site specific {sup 83}Kr nuclear resonant inelastic x-ray scattering (NRIXS) spectroscopy in combination with molecular dynamics simulations. The dense structure H hydrate and filled-ice structures are studied at high pressures in a diamond anvil high-pressure cell. The dynamics of Kr in the structure H clathrate hydrate quench recovered at 77 K is also investigated. The Kr phonon density of states obtained from the experimental NRIXS data are compared with molecular dynamics simulations. The temperature and pressure dependence of the phonon spectra provide details of the Kr dynamics in the clathrate hydrate cages. Comparison with the dynamics of Kr atoms in the low-pressure structure II obtained previously was made. The Lamb-Mossbauer factor obtained from NRIXS experiments and molecular dynamics calculations are in excellent agreement and are shown to yield unique information on the strength and temperature dependence of guest-host interactions.

  2. A new phase diagram of water under negative pressure: The rise of the lowest-density clathrate s-III.

    PubMed

    Huang, Yingying; Zhu, Chongqin; Wang, Lu; Cao, Xiaoxiao; Su, Yan; Jiang, Xue; Meng, Sheng; Zhao, Jijun; Zeng, Xiao Cheng

    2016-02-01

    Ice and ice clathrate are not only omnipresent across polar regions of Earth or under terrestrial oceans but also ubiquitous in the solar system such as on comets, asteroids, or icy moons of the giant planets. Depending on the surrounding environment (temperature and pressure), ice alone exhibits an exceptionally rich and complicated phase diagram with 17 known crystalline polymorphs. Water molecules also form clathrate compounds with inclusion of guest molecules, such as cubic structure I (s-I), cubic structure II (s-II), hexagonal structure H (s-H), tetragonal structure T (s-T), and tetragonal structure K (s-K). Recently, guest-free clathrate structure II (s-II), also known as ice XVI located in the negative-pressure region of the phase diagram of water, is synthesized in the laboratory and motivates scientists to reexamine other ice clathrates with low density. Using extensive Monte Carlo packing algorithm and dispersion-corrected density functional theory optimization, we predict a crystalline clathrate of cubic structure III (s-III) composed of two large icosihexahedral cavities (8(6)6(8)4(12)) and six small decahedral cavities (8(2)4(8)) per unit cell, which is dynamically stable by itself and can be fully stabilized by encapsulating an appropriate guest molecule in the large cavity. A new phase diagram of water ice with TIP4P/2005 (four-point transferable intermolecular potential/2005) model potential is constructed by considering a variety of candidate phases. The guest-free s-III clathrate with ultralow density overtakes s-II and s-H phases and emerges as the most stable ice polymorph in the pressure region below -5834 bar at 0 K and below -3411 bar at 300 K.

  3. A new phase diagram of water under negative pressure: The rise of the lowest-density clathrate s-III

    PubMed Central

    Huang, Yingying; Zhu, Chongqin; Wang, Lu; Cao, Xiaoxiao; Su, Yan; Jiang, Xue; Meng, Sheng; Zhao, Jijun; Zeng, Xiao Cheng

    2016-01-01

    Ice and ice clathrate are not only omnipresent across polar regions of Earth or under terrestrial oceans but also ubiquitous in the solar system such as on comets, asteroids, or icy moons of the giant planets. Depending on the surrounding environment (temperature and pressure), ice alone exhibits an exceptionally rich and complicated phase diagram with 17 known crystalline polymorphs. Water molecules also form clathrate compounds with inclusion of guest molecules, such as cubic structure I (s-I), cubic structure II (s-II), hexagonal structure H (s-H), tetragonal structure T (s-T), and tetragonal structure K (s-K). Recently, guest-free clathrate structure II (s-II), also known as ice XVI located in the negative-pressure region of the phase diagram of water, is synthesized in the laboratory and motivates scientists to reexamine other ice clathrates with low density. Using extensive Monte Carlo packing algorithm and dispersion-corrected density functional theory optimization, we predict a crystalline clathrate of cubic structure III (s-III) composed of two large icosihexahedral cavities (8668412) and six small decahedral cavities (8248) per unit cell, which is dynamically stable by itself and can be fully stabilized by encapsulating an appropriate guest molecule in the large cavity. A new phase diagram of water ice with TIP4P/2005 (four-point transferable intermolecular potential/2005) model potential is constructed by considering a variety of candidate phases. The guest-free s-III clathrate with ultralow density overtakes s-II and s-H phases and emerges as the most stable ice polymorph in the pressure region below −5834 bar at 0 K and below −3411 bar at 300 K. PMID:26933681

  4. Triple Guest Occupancy and Negative Compressibility in Hydrogen-Loaded β-Hydroquinone Clathrate.

    PubMed

    Rozsa, Viktor F; Strobel, Timothy A

    2014-06-05

    The molecular interactions and structural behavior of a previously unexplored clathrate system, hydrogen-loaded β-hydroquinone (β-HQ+H2), were investigated under high pressure with synchrotron X-ray diffraction and Raman/infrared spectroscopies. The β-HQ+H2 system exhibits coupling of two independently rare phenomena: multiple occupancy and negative compressibility. The number of H2 molecules per cavity increases from one to three, causing unit cell volume increase by way of unique crystallographic interstitial guest positioning. We anticipate these occupancy-derived trends may be general to a range of inclusion compounds and may aid the chemical and crystallographic design of both high-occupancy hydrogen storage clathrates and novel, variable-composition materials with tunable mechanical properties.

  5. Clathrate hydrate tuning for technological purposes

    NASA Astrophysics Data System (ADS)

    di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco

    2010-05-01

    Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006

  6. Ice method for production of hydrogen clathrate hydrates

    DOEpatents

    Lokshin, Konstantin; Zhao, Yusheng

    2008-05-13

    The present invention includes a method for hydrogen clathrate hydrate synthesis. First, ice and hydrogen gas are supplied to a containment volume at a first temperature and a first pressure. Next, the containment volume is pressurized with hydrogen gas to a second higher pressure, where hydrogen clathrate hydrates are formed in the process.

  7. K and Ba distribution in the structures of the clathrate compounds K(x)Ba(16-x)(Ga,Sn)136 (x = 0.8, 4.4, and 12.9) and K(x)Ba(8-x)(Ga,Sn)46 (x = 0.3).

    PubMed

    Schäfer, Marion C; Bobev, Svilen

    2013-04-01

    Studies of the K-Ba-Ga-Sn system produced the clathrate compounds K(0.8(2))Ba(15.2(2))Ga(31.0(5))Sn(105.0(5)) [a = 17.0178 (4) Å], K(4.3(3))Ba(11.7(3))Ga(27.4(4))Sn(108.6(4)) [a = 17.0709 (6) Å] and K(12.9(2))Ba(3.1(2))Ga(19.5(4))Sn(116.5(4)) [a = 17.1946 (8) Å], with the type-II structure (cubic, space group Fd3m), and K(7.7(1))Ba(0.3(1))Ga(8.3(4))Sn(37.7(4)) [a = 11.9447 (4) Å], with the type-I structure (cubic, space group Pm3n). For the type-II structures, only the smaller (Ga,Sn)24 pentagonal dodecahedral cages are filled, while the (Ga,Sn)28 hexakaidecahedral cages remain empty. The unit-cell volume is directly correlated with the K:Ba ratio, since an increasing amount of monovalent K occupying the cages causes a decreasing substitution of the smaller Ga in the framework. All three formulae have an electron count that is in good agreement with the Zintl-Klemm rules. For the type-I compound, all framework sites are occupied by a mixture of Ga and Sn atoms, with Ga showing a preference for Wyckoff site 6c. The (Ga,Sn)20 pentagonal dodecahedral cages are occupied by statistically disordered K and Ba atoms, while the (Ga,Sn)24 tetrakaidecahedral cages encapsulate only K atoms. Large anisotropic displacement parameters for K in the latter cages suggest an off-centering of the guest atoms.

  8. First-principles calculations of carbon clathrates: Comparison to silicon and germanium clathrates

    NASA Astrophysics Data System (ADS)

    Connétable, Damien

    2010-08-01

    We employ state-of-the-art first-principles calculations based on density-functional theory and density-functional perturbation theory to investigate relevant physical properties and phase diagram of the free guest type-I (X-46) and type-II (X-34) carbon clathrates. Their properties and those of silicon and germanium diamonds, and clathrates have been computed and compared within the same approach. We briefly present and discuss their structural, cohesive, and electronic properties. In particular, we present different results about electronic properties of carbon clathrates. From the symmetry analysis of electronic states around the band gap, we deduce their optical properties, and we forecast the effects of hypothetical-doped elements on their electronic band gap. We then report first-principles calculations of vibrational, thermodynamical, and elastic properties. Whereas vibrational properties of Si and Ge systems can be linked through their atomic weight ratio, we show that the vibrational properties of carbon structures differ strongly. Raman and infrared spectra of all clathrates are also calculated and compared. The effects of pressure and temperature on thermodynamical properties (heat capacity, entropy, thermal expansion, etc.) within static and quasiharmonic approximations are investigated. It is shown that thermodynamical properties of carbon clathrates and diamond present a similar evolution up to high pressures (100 GPa) and over a large range of temperatures ([0, 1500] K). Then we deduce the equilibrium phase diagram (P,T) of C-2/C-34/C-46. We conclude the paper with a presentation of elastic properties computed from acoustic slopes.

  9. Evaluation method of the performance of kinetic inhibitor for clathrate hydrate

    NASA Astrophysics Data System (ADS)

    Muraoka, M.; Susuki, N.; Yamamoto, Y.

    2016-12-01

    As a part of a Japanese National hydrate research program (MH21, funded by METI), we study the formation of tetrahydrofuran (THF) clathrate hydrate from polyvinylpyrrolidone (PVP) aqueous solution as a function of growth rate V and adsorbed PVP concentration c using the unidirectional growth technique. This study aims to propose a simple method for evaluating the performance of kinetic hydrate inhibitors (KHIs) for the clathrate hydrate-aqueous solution system. The degree of super cooling ∆T calculated from the growth-induced interface shift under steady-state conditions was used for evaluating the KHIs performance. Using this method, a single experimental run can be completed within 3.5 h of the compulsory nucleation by setting V = 5 μm s-1. We believe this method is useful for screening various KHIs and clarifying the inhibition mechanism of KHIs.

  10. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    SciTech Connect

    Koh, Carolyn Ann

    2014-11-18

    Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathrate hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate

  11. Stability and metastability of bromine clathrate polymorphs.

    PubMed

    Nguyen, Andrew H; Molinero, Valeria

    2013-05-23

    Clathrate hydrates are crystals in which water forms a network of fully hydrogen-bonded polyhedral cages that contain small guests. Clathrate hydrates occur mostly in two cubic crystal polymorphs, sI and sII. Bromine is one of two guests that yield a hydrate with the tetragonal structure (TS), the topological dual of the Frank-Kasper σ phase. There has been a long-standing disagreement on whether bromine hydrate also forms metastable sI and sII crystals. To date there are no data on the thermodynamic range of stability (e.g., the melting temperatures) of the metastable polymorphs. Here we use molecular dynamics simulations with the coarse-grained model of water mW to (i) investigate the thermodynamic stability of the empty and guest-filled the sI, sII, TS, and HS-I hydrate polymorphs, (ii) develop a coarse-grained model of bromine compatible with mW water, and (iii) evaluate the stability of the bromine hydrate polymorphs. The mW model predicts the same relative energy of the empty clathrate polymorphs and the same phase diagram as a function of water-guest interaction than the fully atomistic TIP4P water model. There is a narrow region in water-guest parameter space for which TS is marginally more stable than sI or sII. We parametrize a coarse-grained model of bromine compatible with mW water and use it to determine the order of stability of the bromine hydrate polymorphs. The melting temperatures of the bromine hydrate polymorphs predicted by the coarse-grained model are 281 ± 1 K for TS, 279 ± 1 K for sII, and 276 ± 1 K for sI. The closeness of the melting temperatures supports the plausibility of formation of metastable sII and sI bromine hydrates.

  12. Understanding decomposition and encapsulation energies of structure I and II clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ohmura, Ryo

    2016-10-01

    When compressed with water or ice under high pressure and low temperature conditions, some gases form solid gas hydrate inclusion compounds which have higher melting points than ice under those pressures. In this work, we study the balance of the guest-water and water-water interaction energies that lead to the formation of the clathrate hydrate phases. In particular, molecular dynamics simulations with accurate water potentials are used to study the energetics of the formation of structure I (sI) and II (sII) clathrate hydrates of methane, ethane, and propane. The dissociation enthalpy of the clathrate hydrate phases, the encapsulation enthalpy of methane, ethane, and propane guests in the corresponding phases, and the average bonding enthalpy of water molecules are calculated and compared with accurate calorimetric measurements and previous classical and quantum mechanical calculations, when available. The encapsulation energies of methane, ethane, and propane guests stabilize the small and large sI and sII hydrate cages, with the larger molecules giving larger encapsulation energies. The average water-water interactions are weakened in the sI and sII phases compared to ice. The relative magnitudes of the van der Waals potential energy in ice and the hydrate phases are similar, but in the ice phase, the electrostatic interactions are stronger. The stabilizing guest-water "hydrophobic" interactions compensate for the weaker water-water interactions and stabilize the hydrate phases. A number of common assumptions regarding the guest-cage water interactions are used in the van der Waals-Platteeuw statistical mechanical theory to predict the clathrate hydrate phase stability under different pressure-temperature conditions. The present calculations show that some of these assumptions may not accurately reflect the physical nature of the interactions between guest molecules and the lattice waters.

  13. Hopping processes explain linear rise in temperature of thermal conductivity in thermoelectric clathrates with off-center guest atoms

    NASA Astrophysics Data System (ADS)

    Xi, Qing; Zhang, Zhongwei; Chen, Jie; Zhou, Jun; Nakayama, Tsuneyoshi; Li, Baowen

    2017-08-01

    Type-I clathrate compounds with off-center guest ions can be used to realize the concept of phonon-glass electron-crystal because they exhibit lattice thermal conductivities κL that are almost identical to those observed in network-forming glasses. This is in contrast with type-I clathrates with on-center guest ions, which show κL of conventional crystalline structures. Glasslike κL stems from the peculiar THz frequency dynamics in off-center type-I clathrates, in which there appear three kinds of modes classified as extended, weakly localized (WL) and strongly localized (SL) modes, as demonstrated by Liu et al. [Phys. Rev. B 93, 214305 (2016), 10.1103/PhysRevB.93.214305]. Our calculated results based on the hopping mechanism of SL modes via anharmonic interactions show fairly good agreement with the observed T -linear rise of κL above the plateau at a few tens Kelvin. We emphasize that both the magnitude and the temperature dependence are in accord with the experimental data of off-center type-I clathrates.

  14. Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition.

    PubMed

    Alavi, Saman; Ripmeester, J A

    2010-04-14

    Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

  15. CLATHRATE HYDRATES FORMATION IN SHORT-PERIOD COMETS

    SciTech Connect

    Marboeuf, Ulysse; Mousis, Olivier; Petit, Jean-Marc; Schmitt, Bernard

    2010-01-01

    The initial composition of current models of cometary nuclei is only based on two forms of ice: crystalline ice for long-period comets and amorphous ice for short-period comets. A third form of ice, i.e., clathrate hydrate, could exist within the short-period cometary nuclei, but the area of formation of this crystalline structure in these objects has never been studied. Here, we show that the thermodynamic conditions in the interior of short-period comets allow the existence of clathrate hydrates in Halley-type comets. We show that their existence is viable in the Jupiter family comets only when the equilibrium pressure of CO clathrate hydrate is at least 1 order of magnitude lower than the usually assumed theoretical value. We calculate that the amount of volatiles that could be trapped in the clathrate hydrate layer may be orders of magnitude greater than the daily amount of gas released at the surface of the nucleus at perihelion. The formation and the destruction of the clathrate hydrate cages could then explain the diversity of composition of volatiles observed in comets, as well as some pre-perihelion outbursts. We finally show that the potential clathrate hydrate layer in comet 67P/Churyumov-Gerasimenko would, unfortunately, be deep inside the nucleus, out of reach of the Rosetta lander. However, such a clathrate hydrate layer would show up by the gas composition of the coma.

  16. Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ripmeester, J. A.

    2010-04-01

    Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

  17. The Impact of Methane Clathrate Emissions on the Earth System

    NASA Astrophysics Data System (ADS)

    Cameron-Smith, P. J.; Bhattacharyya, S.; Bergmann, D. J.; Reagan, M. T.; Elliott, S.; Moridis, G. J.

    2013-12-01

    Methane is locked in ice-like deposits called clathrates in ocean sediments and underneath permafrost regions. Clathrates are stable under high pressures and low temperatures, so in a warming climate, increases in ocean temperatures could lead to dissociation of the clathrates and release methane into the ocean and subsequently the atmosphere, where methane is both an important greenhouse gas and a key species in atmospheric chemistry. Clathrates in the shallower parts of the Arctic Ocean (around 300m depth) are predicted to be particularly important since clathrates at that depth are expected to start outgassing abruptly in the next few decades. We will present the atmospheric impact of such methane emissions using multi-century steady-state simulations with a version of the Community Earth System Model (CESM) that includes atmospheric chemistry. Our simulations include a plausible release from clathrates in the Arctic that increases global methane emissions above present-day conditions by 22%, as well as a scenario with 10 times those clathrate emissions. The CESM model includes a fully interactive physical ocean, to which we added a fast atmospheric chemistry mechanism that represents methane as a fully interactive tracer (with emissions rather than concentration boundary conditions). The results indicate that such Arctic clathrate emissions (1) increase global methane concentrations by an average of 38%, non-uniformly; (2) increase surface ozone concentrations by around 10% globally, and even more in polluted regions; (3) increase methane lifetime by 13%; (4) increase the interannual variability in surface methane, surface ozone, and methane lifetime, and (5) show modest differences in surface temperature and methane lifetime compared to simulations in which the clathrate emissions are distributed uniformly. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  18. Far-infrared spectra of CO2 clathrate hydrate frosts

    NASA Technical Reports Server (NTRS)

    Landry, J. C.; England, A. W.

    1993-01-01

    As a product of our interest in remote sensing of planetary ices, frost samples of CO2 clathrate hydrate were grown by depositing water vapor on a cooled surface and pressurizing the resulting water frost with CO2 gas. At pressures above the dissociation pressure of the clathrate, the samples exhibit an absorption peak at 75 cm (sup -1). At pressures below the dissociation pressure, the peak disappears. Since the free CO2 molecule does not have rotational or vibrational absorption in this region, the absorption is attributed to a CO2 rattling mode within a clathrate cage.

  19. Practical reactor production of 41Ar from argon clathrate.

    PubMed

    Mercer, J R; Duke, M J; McQuarrie, S A

    2000-06-01

    The radionuclide 41Ar has many ideal properties as a gas flow tracer. However, the modest cross-section of 40Ar for thermal neutron activation makes preparation of suitable activities of 41Ar technically difficult particularly for low flux reactors. Argon can however be trapped in a molecular complex called a clathrate that can then be irradiated. We prepared argon clathrate and explored its irradiation and stability characteristics. Argon clathrate can be used to provide gigabecquerel quantities of 41Ar even with low power reactors.

  20. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle D.

    1995-01-01

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member and/or six member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone.

  1. Pressure-amorphized cubic structure II clathrate hydrate: crystallization in slow motion.

    PubMed

    Bauer, Marion; Többens, Daniel M; Mayer, Erwin; Loerting, Thomas

    2011-02-14

    A range of techniques has so far been employed for producing amorphous aqueous solutions. In case of aqueous tetrahydrofuran (THF) this comprises hyperquenching of liquid droplets, vapour co-deposition and pressure-induced amorphization of the crystalline cubic structure II clathrate. All of these samples are thermally labile and crystallize at temperatures above 110 K. We here outline a variant of the pressure-amorphization protocol developed by Suzuki [Phys. Rev. B, 2004, 70, 172108], which results in a highly crystallization resistant amorphous THF hydrate. The hydrate produced according to our protocol (annealing to 180 K at 1.8 GPa rather than to 150 K at 1.5 GPa) does not transform to the cubic structure II THF clathrate even at 150 K. We track the reason for this higher stability to the presence of crystalline remnants when following the Suzuki protocol, which are removed when using our protocol involving higher pressures and an annealing step. These crystalline remnants later serve as crystallization seeds lowering the thermal stability of the amorphous sample. Our protocol thus makes a purely amorphous THF hydrate available to the research community. We use powder X-ray diffraction to study the process of nucleation and slow crystal growth in the temperature range 160-200 K and find that the local cage structure and periodicity of the fully crystalline hydrate develops even at the earliest stages of crystallization, when the "clathrate crystal" has a size of about two unit cells.

  2. Chiral organic compounds in induced cholesteric mesophases

    NASA Astrophysics Data System (ADS)

    Kutulya, Lidiya A.

    1998-09-01

    The results of original investigations being in touch with regularities of the chiral components molecular structure effect on the properties of induced cholesteric mesophases were generalized. It was shown that presence of an elongate (pi) -electron fragment in the chiral dopants molecules is general requirement of high helical twisting power ((beta) ). (beta) values and the character of temperature dependences of induced helical pitch are significantly effected by molecular shape of chiral dopants. Variation of the extent of (pi) -electron fragment anisometry, and also incorporation and variation of terminal alkyl or alkoxyl groups at chiral dopants molecules are useful approach to a regulation of temperature dependences of induced cholesteric helix pitch. Influence on thermal stability of mesophases of different types of chiral dopants was analyzed.

  3. [Study on the technological process of extraction and clathration for Rhizoma Atractylodis Macrocephalae oil with beta-cyclodextrin].

    PubMed

    Huang, Jiang-Hong

    2007-05-01

    To study the optimal extraction and clathration technology of Rhizoma Atractylodis Macrocephalae oil in Heweilichang Pill. Orthogonal test was employed for selecting the optimum of extraction technology of Rhizoma Atractylodis Macrocephalae oil and the oil extraction rate were used as a index. The optimum including technology was chosen by determining the oil-bearing rate and extract ratio of inclusion compound. The inclusion compound were identified with thin chromatogram. The extraction technology was 10 volumes of water, extracted 6h with thick granula of Rhizoma Atractylodis Macrocephalae. The optimum preparation conditions for clathrate were established as beta-CD: oil was 6: 1, 3. 5 times of water, triturated for 75 minutes. The process is feasible and the method can be used for production.

  4. “Glass-like” thermal conductivity gradually induced in thermoelectric Sr{sub 8}Ga{sub 16}Ge{sub 30} clathrate by off-centered guest atoms

    SciTech Connect

    Christensen, Sebastian; Schmøkel, Mette Stokkebro; Borup, Kasper Andersen; Christensen, Mogens E-mail: bo@chem.au.dk; Iversen, Bo Brummerstedt E-mail: bo@chem.au.dk; Madsen, Georg K. H.; McIntyre, Garry J.; Capelli, Silvia C.

    2016-05-14

    The origin of the “glass-like” plateau in thermal conductivity of inorganic type I clathrates has been debated for more than a decade. Here, it is demonstrated that the low temperature thermal conductivity of Sr{sub 8}Ga{sub 16}Ge{sub 30} can be controlled by the synthesis method: A flux-grown sample has a “glass-like” plateau in thermal conductivity at low temperature, while a zone-melted sample instead has a crystalline peak. A combination of flux-growth and zone-melting produces an intermediate thermal conductivity. In a comprehensive study of three single crystal samples, it is shown by neutron diffraction that the transition from crystalline peak to “glass-like” plateau is related to an increase in Sr guest atom off-centering distance from 0.24 Å to 0.43 Å. By modifying ab initio calculated force constants for the guest atom to an isotropic model, we reproduce both measured heat capacity and inelastic neutron scattering data. The transition from peak to plateau in the thermal conductivity can be modeled by a combined increase of Rayleigh and disorder scattering. Measurement of heat capacity refutes simple models for tunneling of Sr between off-center sites. Furthermore, the electronic properties of the same samples are characterized by Hall carrier density, Seebeck coefficient, and resistivity. The present comprehensive analysis excludes tunneling and charge carrier scattering as dominant contributors to the “glass-like” plateau. The increased guest atom off-centering distance controlled by synthesis provides a possible microscopic mechanism for reducing the low temperature thermal conductivity of clathrates.

  5. Anharmonic motions of Kr in the clathrate hydrate.

    PubMed

    Tse, J S; Klug, D D; Zhao, J Y; Sturhahn, W; Alp, E E; Baumert, J; Gutt, C; Johnson, M R; Press, W

    2005-12-01

    The anomalous glass-like thermal conductivity of crystalline clathrates has been suggested to be the result of the scattering of thermal phonons of the framework by 'rattling' motions of the guests in the clathrate cages. Using the site-specific (83)Kr nuclear resonant inelastic scattering spectroscopy in combination with conventional incoherent inelastic neutron scattering and molecular-dynamics simulations, we provide unambiguous evidence and characterization of the effects on these guest-host interactions in a structure-II Kr clathrate hydrate. The resonant scattering of phonons led to unprecedented large anharmonic motions of the guest atoms. The anharmonic interaction underlies the anomalous thermal transport in this system. Clathrates are prototypical models for a class of crystalline framework materials with glass-like thermal conductivity. The explanation of the unusual molecular dynamics has a wide implication for the understanding of the thermal properties of disordered solids and structural glasses.

  6. Novel synthetic organosulfur compounds induce apoptosis of human leukemic cells.

    PubMed

    Wong, W W; Macdonald, S; Langler, R F; Penn, L Z

    2000-01-01

    It has been well documented that natural organosulfur compounds (OSCs) derived from plants such as garlic, onions and mahogany trees possess antiproliferative properties; however, the essential chemical features of the active OSC compounds remain unclear. To investigate the association between OSC structure and growth inhibitory activity, we synthesized novel relatives of dysoxysulfone, a natural OSC derived from the Fijian medicinal plant, Dysoxylum richii. In this study, we have examined the antiproliferative effects of these novel OSCs on a model human leukemic cell system and show that the compounds segregate into three groups. Group I, consisting of compounds A, B, G and J, did not affect either cell proliferation or the cell cycle profile of the leukemic cell lines. Group II, consisting of compounds F and H, induced the cells to undergo apoptosis from the G2/M phase of the cell cycle. Group III, consisting of compounds C, D, E and I, decreased cell proliferation and induced apoptosis throughout the cell cycle. The apoptotic agonists of Group II and III shared a common disulfide moiety, essential for leukemic cell cytotoxicity. Interestingly, Group II compounds did not affect cell viability of normal human diploid cells, suggesting the regions flanking the disulfide group contributes to the specificity of cell killing. Thus, we provide evidence that structure-activity analysis of natural products can identify novel compounds for the development of new therapeutics that can trigger apoptosis in a tumor-specific manner.

  7. Open-framework clathrates of group IV elements: Synthesis, structure, and characterization

    NASA Astrophysics Data System (ADS)

    Ramachandran, Ganesh K.

    This study addresses the synthesis, the characterization by x-ray diffraction and nuclear magnetic resonance (NMR) spectroscopy, and the measurement of the electrical properties of members of a class of compounds known as silicon and germanium clathrates. A quantitative 29Si NMR study of Na8Si 46 along with Rietveld refinement of site occupancies demonstrates that the compound is the stoichiometric clathrate Na8Si46, rather than an intermetallic Zintl compound containing silicon vacancies. In line with the observations on Na8Si46, the homologous K8Si46 and Rb6Si46 alkali-silicon clathrates are also observed to be fully stoichiometric at the framework sites, i.e., devoid of framework vacancies. In contrast two vacancies are formed predominantly at one-third of the crystallographic 6c tetrahedral sites in the homologous alkali-germanium and alkali-tin systems. This result is understood generally in terms of weaker Tt-Tt (Tt = Si, Ge, Sn) bonding as one descends the periodic table. The synthesis and characterization of the Structure II silicon clathrate NaxSi136 (x = 4--23) by powder x-ray diffraction combined with Rietveld profile analysis is also reported. In NaxSi 136, systematic changes in x-ray diffraction intensities enable the Na content and site occupancy to be characterized. In the same structure, we observe a 0.5% increase in the unit cell edge upon progressing from Na 4Si136 to Na23Si136. A statistical mechanical model combined with experimental data for this phase reveals a preference for the removal of sodium from the smaller of the two available cages by 0.190 +/- 0.050 eV. The Structure II clathrate Na16Cs8Si136 was synthesized employing the silicides of sodium and cesium as intermediates. In the same compound, large 23Na and 29Si Knight shifts are observed in 29Si magic angle spinning (MAS) NMR experiments. Electrical conductivity measurements on cold pressed samples of the material also indicate metallic behavior, with a room temperature value of rho

  8. Density driven structural transformations in amorphous semiconductor clathrates

    DOE PAGES

    Tulk, Christopher A.; dos Santos, Antonio M.; Neuefeind, Joerg C.; ...

    2015-01-16

    The pressure induced crystalline collapse at 14.7 GPa and polyamorphic structures of the semiconductor clathrate Sr8Ga16Ge30 are reported up to 35 GPa. In-situ total scattering measurements under pressure allow the direct microscopic inspection of the mechanisms associated with pressure induced amorphization in these systems, as well as the structure of the recovered phase. It is observed that, between 14.7 and 35 GPa the second peak in the structure factor function gradually disappears. Analysis of the radial distribution function extracted from those data indicate that this feature is associated with gradual cage collapse and breakdown of the tetrahedral structure with themore » consequent systematic lengthening of the nearest-neighbor framework bonds. This suggests an overall local coordination change to an even higher density amorphous form. Upon recovery from high pressure, the sample remains amorphous, and while there is some indication of the guest-host cage reforming, it doesn't seem that the tetrahedral coordination is recovered. As such, the compresion-decompression process in this systems gives rise to three distict amorphous forms.« less

  9. Density driven structural transformations in amorphous semiconductor clathrates

    SciTech Connect

    Tulk, Christopher A.; dos Santos, Antonio M.; Neuefeind, Joerg C.; Molaison, Jamie J.; Sales, Brian C.; Honkimaeki, Veijo

    2015-01-16

    The pressure induced crystalline collapse at 14.7 GPa and polyamorphic structures of the semiconductor clathrate Sr8Ga16Ge30 are reported up to 35 GPa. In-situ total scattering measurements under pressure allow the direct microscopic inspection of the mechanisms associated with pressure induced amorphization in these systems, as well as the structure of the recovered phase. It is observed that, between 14.7 and 35 GPa the second peak in the structure factor function gradually disappears. Analysis of the radial distribution function extracted from those data indicate that this feature is associated with gradual cage collapse and breakdown of the tetrahedral structure with the consequent systematic lengthening of the nearest-neighbor framework bonds. This suggests an overall local coordination change to an even higher density amorphous form. Upon recovery from high pressure, the sample remains amorphous, and while there is some indication of the guest-host cage reforming, it doesn't seem that the tetrahedral coordination is recovered. As such, the compresion-decompression process in this systems gives rise to three distict amorphous forms.

  10. Heat capacity of tetrahydrofuran clathrate hydrate and of its components, and the clathrate formation from supercooled melt.

    PubMed

    Tombari, E; Presto, S; Salvetti, G; Johari, G P

    2006-04-21

    We report a thermodynamic study of the formation of tetrahydrofuran clathrate hydrate by explosive crystallization of water-deficient, near stoichiometric, and water-rich solutions, as well as of the heat capacity, C(p), of (i) supercooled tetrahydrofuran-H2O solutions and of the clathrate hydrate, (ii) tetrathydrofuran (THF) liquid, and (iii) supercooled water and the ice formed on its explosive crystallization. In explosive freezing of supercooled solutions at a temperature below 257 K, THF clathrate hydrate formed first. The nucleation temperature depends on the cooling rate, and excess water freezes on further cooling. The clathrate hydrate melts reversibly at 277 K and C(p) increases by 770 J/mol K on melting. The enthalpy of melting is 99.5 kJ/mol and entropy is 358 J/mol K. Molar C(p) of the empty host lattice is less than that of the ice, which is inconsistent with the known lower phonon frequency of H2O in the clathrate lattice. Analysis shows that C(p) of THF and ice are not additive in the clathrate. C(p) of the supercooled THF-H2O solutions is the same as that of water at 247 K, but less at lower temperatures and more at higher temperatures. The difference tends to become constant at 283 K. The results are discussed in terms of the hydrogen-bonding changes between THF and H2O.

  11. Valproic Acid Induces Antimicrobial Compound Production in Doratomyces microspores

    PubMed Central

    Zutz, Christoph; Bacher, Markus; Parich, Alexandra; Kluger, Bernhard; Gacek-Matthews, Agnieszka; Schuhmacher, Rainer; Wagner, Martin; Rychli, Kathrin; Strauss, Joseph

    2016-01-01

    One of the biggest challenges in public health is the rising number of antibiotic resistant pathogens and the lack of novel antibiotics. In recent years there is a rising focus on fungi as sources of antimicrobial compounds due to their ability to produce a large variety of bioactive compounds and the observation that virtually every fungus may still contain yet unknown so called “cryptic,” often silenced, compounds. These putative metabolites could include novel bioactive compounds. Considerable effort is spent on methods to induce production of these “cryptic” metabolites. One approach is the use of small molecule effectors, potentially influencing chromatin landscape in fungi. We observed that the supernatant of the fungus Doratomyces (D.) microsporus treated with valproic acid (VPA) displayed antimicrobial activity against Staphylococcus (S.) aureus and two methicillin resistant clinical S. aureus isolates. VPA treatment resulted in enhanced production of seven antimicrobial compounds: cyclo-(L-proline-L-methionine) (cPM), p-hydroxybenzaldehyde, cyclo-(phenylalanine-proline) (cFP), indole-3-carboxylic acid, phenylacetic acid (PAA) and indole-3-acetic acid. The production of the antimicrobial compound phenyllactic acid was exclusively detectable after VPA treatment. Furthermore three compounds, cPM, cFP, and PAA, were able to boost the antimicrobial activity of other antimicrobial compounds. cPM, for the first time isolated from fungi, and to a lesser extent PAA, are even able to decrease the minimal inhibitory concentration of ampicillin in MRSA strains. In conclusion we could show in this study that VPA treatment is a potent tool for induction of “cryptic” antimicrobial compound production in fungi, and that the induced compounds are not exclusively linked to the secondary metabolism. Furthermore this is the first discovery of the rare diketopiperazine cPM in fungi. Additionally we could demonstrate that cPM and PAA boost antibiotic activity

  12. Regimes of Decomposition of Clathrate in Natural Strata Purged by Methane

    NASA Astrophysics Data System (ADS)

    Khasanov, M.; Shagapov, V.

    2016-06-01

    The process of decomposition of a methane clathrate in a finite-length stratum initially saturated with methane clathrate and methane, which is purged by warm methane, is studied. The influence of the initial parameters of the stratum and purging conditions on the evolution of methane clathrate temperature and saturation is examined. The existence of solutions is demonstrated, which predict methane clathrate decomposition both on the frontal surface and in the volume zone.

  13. Dynamics of radiation-induced amorphization in intermetallic compounds

    SciTech Connect

    Lam, N.Q.; Okamoto, P.R. ); Devanathan, R. Northwestern Univ., Evanston, IL . Dept. of Materials Science and Engineering); Meshii, M. . Dept. of Materials Science and Engineering)

    1992-06-01

    Recent progress in molecular-dynamics simulations of radiation-induced crystalline-to-amorphous transition in intermetallic compounds and the relationship between amorphization and melting are discussed. By focusing on the mean-square static displacement, which provides a generic measure of energy stored in the lattice in the forms of chemical and topological disorder, a unified description of solid-state amorphization as a disorder-induced, isothermal melting process can be developed within the framework of a generalized Lindemann criterion.

  14. [Application of small molecule compounds inducing differentiation of stem cells].

    PubMed

    Li, Xia; Shan, Lei; Li, Wen-lin; Zhang, Shou-de; Zhang, Wei-dong

    2011-02-01

    With the development of stem cells and regenerative medicine (treatment of various diseases using stem cells) research, the induction of differentiation of human stem cell technology has also made significant progress. The development of chemical biology offers a variety of small biological molecules for stem cell biology. This review focuses on how small molecule compounds (natural and synthetic) induce differentiation of stem cells.

  15. Kinetics of Methane Clathrate Formation in the Presolar Nebula

    NASA Astrophysics Data System (ADS)

    Vu, Tuan; Choukroun, Mathieu

    2016-10-01

    Clathrate hydrates are a distinct form of water ice wherein the crystal lattice of the host water molecules forms symmetric, polyhedral cages that trap volatile guest species under appropriate pressures and temperatures. These materials are an abundant source of hydrocarbons on Earth, and have been expected to be present on a number of icy celestial bodies, including Mars, Europa, Titan, and Enceladus. Clathrates are also thought to be one of the most likely traps for volatiles during the condensation of the protostellar nebulae. Prior to the Voyager mission, the prevailing expectation was that the elemental composition of the giant planets would reflect the composition of the solar nebula and therefore be similar to solar abundances. However, spacecraft observations by Voyager, Galileo, and Cassini-Huygens, as well as ground-based observations, have revealed unexpected elemental enrichment, relative to solar abundances, of C, N, S, As, P, and noble gases in the giant planets and in comets. One of the contending explanations is the retention of these volatiles as clathrate hydrates, which may have enabled their capture early in the history of the Solar System.While the formation and stability of clathrates have been addressed theoretically and, to some extent, experimentally at relatively high pressures (10-7-10-3 bar), there is a scarcity of experimental undertaking on the kinetics of clathrate formation and their stability at the low pressures relevant to the early outer solar nebula (~10-11 bar). This study seeks to elucidate the clathrate formation kinetics under nebula-relevant conditions via a series of optical Raman experiments on ice/gas mixtures over a range of pressures and temperatures. Our work on the methane gas/ice system shows that clathrate formation occurs on a rather fast timescale (typically within minutes at 223-253 K and 30-50 bar CH4). In addition, the rate of enclathration increases with pressures and temperatures, and the activation energy

  16. Melting Process of Clathrate in a Rectangular Cell

    NASA Astrophysics Data System (ADS)

    Chiba, Takashi; Okada, Masashi; Matsumoto, Koji

    In order to clarify the mechanism of heat transfer during melting of a clathrate in rectangular cells, two melting processes, namely, two-dimensional melting process with natural convection from a vertical wall and one-dimensional melting process by heat conduction from an upper horizontal wall, are studied experimentally. The R-141b was used for generating clathrate. One experiment was carried out by melting the clathrate filled into a 150mm high and 100mm wide rectangular cell from a vertical wall. And in the other experiment, the clathrate was melted from the upper horizontal wall of a rectangular cell with 88mm height and 180mm width. The temperature distributions in cells were measured. The melting front was measured by pictures taken on fixed times. The concentration of freon in the melt was measured by gas-chromatography. The following results are obtained. (1) In the melting process, the clathrate decomposes into an emulsion region which is a water-freon mixture and a liquid freon region under the emulsion. (2) Concentration gradient of freon in the emulsion plyas an important role in the natural convection in the melt. The Nusselt number on the heated vertical wall is depressed by the concentration gradients.

  17. Phase diagrams for clathrate hydrates of methane, ethane, and propane from first-principles thermodynamics.

    PubMed

    Cao, Xiaoxiao; Huang, Yingying; Li, Wenbo; Zheng, Zhaoyang; Jiang, Xue; Su, Yan; Zhao, Jijun; Liu, Changling

    2016-01-28

    Natural gas hydrates are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, and C3H8) and a water clathrate framework. Understanding the phase stability and formation conditions of natural gas hydrates is crucial for their future exploitation and applications and requires an accurate description of intermolecular interactions. Previous ab initio calculations on gas hydrates were mainly limited by the cluster models, whereas the phase diagram and equilibrium conditions of hydrate formation were usually investigated using the thermodynamic models or empirical molecular simulations. For the first time, we construct the chemical potential phase diagrams of type II clathrate hydrates encapsulated with methane/ethane/propane guest molecules using first-principles thermodynamics. We find that the partially occupied structures (136H2O·1CH4, 136H2O·16CH4, 136H2O·20CH4, 136H2O·1C2H6, and 136H2O·1C3H8) and fully occupied structures (136H2O·24CH4, 136H2O·8C2H6, and 136H2O·8C3H8) are thermodynamically favorable under given pressure-temperature (p-T) conditions. The theoretically predicted equilibrium pressures for pure CH4, C2H6 and C3H8 hydrates at the phase transition point are consistent with the experimental data. These results provide valuable guidance for establishing the relationship between the accurate description of intermolecular noncovalent interactions and the p-T equilibrium conditions of clathrate hydrates and other molecular crystals.

  18. Unusually high chemical compressibility of normally rigid type-I clathrate framework: synthesis and structural study of Sn(24)P(19.3)Br(x)I(8)(-)(x) solid solution, the prospective thermoelectric material.

    PubMed

    Kovnir, Kirill A; Zaikina, Julia V; Reshetova, Lyudmila N; Olenev, Andrei V; Dikarev, Evgeny V; Shevelkov, Andrei V

    2004-05-17

    A novel tin phosphide bromide, Sn(24)P(19.3(2))Br(8), and Sn(24)P(19.3(2))Br(x)()I(8)(-)(x) (x = 0-8) solid solution have been prepared and structurally characterized. All compounds crystallize with the type-I clathrate structure in the cubic space group Pmn (No. 223). The clathrate framework of the title solid solution shows a remarkable chemical compressibility: the unit cell parameter drops from 10.954(1) to 10.820(1) A on going from x = 0 to x = 8, a feature that has never been observed for normally rigid clathrate frameworks. The chemical compressibility as well as non-Vegard dependence of the unit cell parameter upon the bromine content is attributed to the nonuniform distribution of the guest halogen atoms in the polyhedral cavities of the clathrate framework. The temperature-dependent structural study performed on Sn(24)P(19.3(2))Br(8) has shown that, in contrast to the chemical compressibility, the thermal compressibility (linear contraction) of the phase is similar to that observed for the Group 14 anionic clathrates. The tin phosphide bromide does not undergo phase transition down to 90 K, and the atomic displacement parameters for all atoms decrease linearly upon lowering the temperature. These linear dependencies have been used to assess such physical constants as Debye temperature, 220 K, and the lattice part of thermal conductivity, 0.7 W/(m K). Principal differences between the title compounds and the group 14 anionic clathrates are highlighted, and the prospects of creating new thermoelectric materials based on cationic clathrates are briefly discussed.

  19. Far-infrared investigations of a methanol clathrate hydrate - Implications for astronomical observations

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Moore, Marla H.

    1993-01-01

    Observations of nonterrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over 40 years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. We have prepared a methanol (CH3OH) clathrate hydrate, using a recently published procedure, and have investigated its far-infrared spectrum. The spectrum is quite different from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

  20. Far-infrared investigations of a methanol clathrate hydrate - Implications for astronomical observations

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Moore, Marla H.

    1993-01-01

    Observations of nonterrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over 40 years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. We have prepared a methanol (CH3OH) clathrate hydrate, using a recently published procedure, and have investigated its far-infrared spectrum. The spectrum is quite different from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

  1. Measurement of clathrate hydrates via Raman spectroscopy

    USGS Publications Warehouse

    Sum, A.K.; Burruss, R.C.; Sloan, E.D.

    1997-01-01

    Raman spectra of clathrate hydrate guest molecules are presented for three known structures (I (sI), II (sII), and H (sH)) in the following systems: CH4 (sI), CO2 (sI), C3H8 (sII), CH4 + CO2 (sI), CD4 + C3H8 (sII), CH4 + N2 (sI), CH4 + THF-d8 (sII), and CH4 + C7D14 (sH). Relative occupancy of CH4 in the large and small cavities of sI were determined by deconvoluting the ??1 symmetric bands, resulting in hydration numbers of 6.04 ?? 0.03. The frequency of the ??1 bands for CH4 in structures I, II, and H differ statistically, so that Raman spectroscopy is a potential tool to identify hydrate crystal structure. Hydrate guest compositions were also measured for two vapor compositions of the CH4 + CO2 system, and they compared favorably with predictions. The large cavities were measured to be almost fully occupied by CH4 and CO2, whereas only a small fraction of the small cavities are occupied by CH4. No CO2 was found in the small cavities. Hydration numbers from 7.27 to 7.45 were calculated for the mixed hydrate.

  2. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, E.D. Jr.

    1995-07-11

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone. Additives can also contain multiple cyclic chemical groupings having different size rings. One such additive is sold under the name Gaffix VC-713.

  3. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle D.

    1995-01-01

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone. Additives can also contain multiple cyclic chemical groupings having different size rings. One such additive is sold under the name Gaffix VC-713.

  4. Rearrangement dynamics of the hydrogen-bonded network of clathrate hydrates encaging polar guest

    NASA Astrophysics Data System (ADS)

    Koga, Kenichiro; Tanaka, Hideki

    1996-01-01

    Mechanisms of rearrangement process in a defect-bearing solid hydrogen-bonded network system —a clathrate hydrate encaging polar guest—are examined in terms of the waiting time distribution functions for connectivity changes of water molecules. As previously found for the lifetime distributions of hydrogen bonds in supercooled water by Sciortino et al., a power-law-like behavior is observed for the waiting time distribution in short-time region in the clathrate hydrates; in long time region the distribution is close to an exponential form. It is revealed that the behavior is accounted for by assuming two kinds of processes of the connectivity changes: one is caused by thermal excitation in a perfect network region, which can be regarded as a Poisson process and another is induced by defects in the environmental network, which is responsible for the power-law-like behavior. Also the waiting time for the defect-induced connectivity changes of a molecule is related to how many other molecules are involved in local network rearrangement processes. By a simple model of single-axis rotator for reorientational jumps of a water molecule, we show that a power-law-like behavior appears in the dipole autocorrelation function when the waiting time for jump events is a strong power-law type distribution as observed in the defect-induced connectivity changes.

  5. Cardiac mitochondrial membrane stability after deep hypothermia using a xenon clathrate cryostasis protocol - an electron microscopy study.

    PubMed

    Sheleg, Sergey; Hixon, Hugh; Cohen, Bruce; Lowry, David; Nedzved, Mikhail

    2008-01-01

    We investigated a new cryopreservation method using xenon, a clathrate-forming gas, under medium pressure (100psi). The objective of the study was to determine whether this cryostasis protocol could protect cardiac mitochondria at cryogenic temperatures (below 100 degrees Celsius).We analyzed transmission electron microscopy images to obtain information about changes in mitochondrial morphology induced by cryopreservation of the hearts. Our data showed absence of mitochondrial swelling, rupture of inner and outer membranes, and leakage of mitochondrial matrix into the cytoplasm after applying this cryostasis protocol. The electron microscopy results provided the first evidence that a cryostasis protocol using xenon as a clathrate-forming gas under pressure may have protective effects on intracellular membranes. This cryostasis technology may find applications in developing new approaches for long-term cryopreservation protocols.

  6. Cardiac Mitochondria l Membrane Stability after Deep Hypothermia using a Xenon Clathrate Cryostasis Protocol – an Electron Microscopy Study

    PubMed Central

    Sheleg, Sergey; Hixon, Hugh; Cohen, Bruce; Lowry, David; Nedzved, Mikhail

    2008-01-01

    We investigated a new cryopreservation method using xenon, a clathrate-forming gas, under medium pressure (100psi). The objective of the study was to determine whether this cryostasis protocol could protect cardiac mitochondria at cryogenic temperatures (below 100 degrees Celsius).We analyzed transmission electron microscopy images to obtain information about changes in mitochondrial morphology induced by cryopreservation of the hearts. Our data showed absence of mitochondrial swelling, rupture of inner and outer membranes, and leakage of mitochondrial matrix into the cytoplasm after applying this cryostasis protocol. The electron microscopy results provided the first evidence that a cryostasis protocol using xenon as a clathrate-forming gas under pressure may have protective effects on intracellular membranes. This cryostasis technology may find applications in developing new approaches for long-term cryopreservation protocols. PMID:18787624

  7. Analysis of Subsurface Clathrates in the Upper Crust of Titan

    NASA Technical Reports Server (NTRS)

    Elliott, John

    2011-01-01

    Titan has an atmosphere rich in methane, which should have long since been depleted unless a mechanism exists for storing this molecule below the surface. One hypothesis is that methane could be stored in the form of a clathrate hydrate, which is a structure with an ice lattice forming molecular cages in which gases are trapped. It is stable at low temperatures and over a wide range of pressures, suggesting that a clathrate hydrate may have stored methane on Titan from the beginning of its history.

  8. Analysis of Subsurface Clathrates in the Upper Crust of Titan

    NASA Technical Reports Server (NTRS)

    Elliott, John

    2011-01-01

    Titan has an atmosphere rich in methane, which should have long since been depleted unless a mechanism exists for storing this molecule below the surface. One hypothesis is that methane could be stored in the form of a clathrate hydrate, which is a structure with an ice lattice forming molecular cages in which gases are trapped. It is stable at low temperatures and over a wide range of pressures, suggesting that a clathrate hydrate may have stored methane on Titan from the beginning of its history.

  9. A clathrate reservoir hypothesis for Enceladus' south polar plume.

    PubMed

    Kieffer, Susan W; Lu, Xinli; Bethke, Craig M; Spencer, John R; Marshak, Stephen; Navrotsky, Alexandra

    2006-12-15

    We hypothesize that active tectonic processes in the south polar terrain of Enceladus, the 500-kilometer-diameter moon of Saturn, are creating fractures that cause degassing of a clathrate reservoir to produce the plume documented by the instruments on the Cassini spacecraft. Advection of gas and ice transports energy, supplied at depth as latent heat of clathrate decomposition, to shallower levels, where it reappears as latent heat of condensation of ice. The plume itself, which has a discharge rate comparable to Old Faithful Geyser in Yellowstone National Park, probably represents small leaks from this massive advective system.

  10. The effect of Al-substitution on superconducting type-I clathrate Ba8Si46

    NASA Astrophysics Data System (ADS)

    Liu, Lihua; Bi, Shanli; Chen, Ning; Li, Feng; Liu, Yang; Cao, Guohui; Li, Yang

    2014-11-01

    A series of samples with the chemical formula Ba8Si46-xAlx (x = 2, 3, 5, 6, 7 and 8) were prepared by arc melting, ball milling and washing with diluted HCl. The lattice parameter of Ba8Si46-xAlx increases linearly with the increase of nominal Al content x. The composition analysis by energy-dispersive X-ray spectroscopy (EDS) shown that the actual Al contents in clathrates are lager than the nominal compositions because the dilute Al-contained impurity phases were washed out. The experimental results show that the minimum incorporation of Al into clathrate structure is expected to be about 3 at ambient pressure, which is in agreement with a first-principle simulation. The Al substitution for Si results in the decrease of superconducting transition temperature TC, which can be explained on the BCS theoretical frame. The electron density of state at Fermi level N(EF) decreases with the increment of x except for an abnormal increase for the sample x = 6. Such sample has a higher spatial symmetry of the structure in which all the six Si atoms at 6c sites were substituted by Al atoms. Its higher N(EF) causes to a higher TC. In addition, we calculated the phonon-dispersion relations and vibrational density of states for Al-doped silicon clathrates. The high frequency acoustic branch has a red shift from 430 cm-1 to 420 cm-1 with the doping of Al. The decreased frequency of bond-stretching vibration modes is another reason for the suppression of TC induced by Al substitution.

  11. Volatile inventories in clathrate hydrates formed in the primordial nebula.

    PubMed

    Mousis, Olivier; Lunine, Jonathan I; Picaud, Sylvain; Cordier, Daniel

    2010-01-01

    The examination of ambient thermodynamic conditions suggests that clathrate hydrates could exist in the Martian permafrost, on the surface and in the interior of Titan, as well as in other icy satellites. Clathrate hydrates are probably formed in a significant fraction of planetesimals in the solar system. Thus, these crystalline solids may have been accreted in comets, in the forming giant planets and in their surrounding satellite systems. In this work, we use a statistical thermodynamic model to investigate the composition of clathrate hydrates that may have formed in the primordial nebula. In our approach, we consider the formation sequence of the different ices occurring during the cooling of the nebula, a reasonable idealization of the process by which volatiles are trapped in planetesimals. We then determine the fractional occupancies of guests in each clathrate hydrate formed at a given temperature. The major ingredient of our model is the description of the guest-clathrate hydrate interaction by a spherically averaged Kihara potential with a nominal set of parameters, most of which are fitted to experimental equilibrium data. Our model allows us to find that Kr, Ar and N2 can be efficiently encaged in clathrate hydrates formed at temperatures higher than approximately 48.5 K in the primitive nebula, instead of forming pure condensates below 30 K. However, we find at the same time that the determination of the relative abundances of guest species incorporated in these clathrate hydrates strongly depends on the choice of the parameters of the Kihara potential and also on the adopted size of cages. Indeed, by testing different potential parameters, we have noted that even minor dispersions between the different existing sets can lead to non-negligible variations in the determination of the volatiles trapped in clathrate hydrates formed in the primordial nebula. However, these variations are not found to be strong enough to reverse the relative abundances

  12. Compound K suppresses ultraviolet radiation-induced apoptosis by inducing DNA repair in human keratinocytes.

    PubMed

    Cai, Bao-Xiang; Luo, Dan; Lin, Xiang-Fei; Gao, Jie

    2008-11-01

    Ultraviolet (UV)-induced DNA damage is a crucial molecular trigger for sunburn cell formation and skin cancer. Nucleotide excision repair (NER) is the main mechanism in repairing UVB-induced DNA damage of mammalian cells. The purpose of this study is to investigate the functional role of ginsenoside compound K on HaCaT cells (a keratinocyte-derived permanent cell line) irradiated by UV. Hoechst 33258 staining were performed in analyzing UV-induced apoptosis on keratinocytes which were treated with compound K. ImmunoDotBlot assay was used in detecting cyclobutane pyrimidine dimers, the main DNA damage. Western blot analysis was applied for analyzing XPC and ERCC1, two of the NER proteins. Compound K inhibited UV-induced apoptosis of keratinocytes and caused a notable reduction in UV-specific DNA lesions which was due to induction of DNA repair. In agreement with this, compound K induced the expression of particular components of the NER complex, such as XPC and ERCC1. Our results demonstrate that compound K can protect cells from apoptosis induced by UV radiation by inducing DNA repair.

  13. Thermoelectric properties of low-dimensional clathrates from first principles

    NASA Astrophysics Data System (ADS)

    Kasinathan, Deepa; Rosner, Helge

    2011-03-01

    Type-I inorganic clathrates are host-guest structures with the guest atoms trapped in the framework of the host structure. From a thermoelectric point of view, they are interesting because they are semiconductors with adjustable bandgaps. Investigations in the past decade have shown that type-I clathrates X8 Ga 16 Ge 30 (X = Ba, Sr, Eu) may have the unusual property of ``phonon glass-electron crystal'' for good thermoelectric materials. Among the known clathrates, Ba 8 Ga 16 Ge 30 has the highest figure of merit (ZT~1). To enable a more widespread usage of thermoelectric technology power generation and heating/cooling applications, ZT of at least 2-3 is required. Two different research approaches have been proposed for developing next generation thermoelectric materials: one investigating new families of advanced bulk materials, and the other studying low-dimensional materials. In our work, we concentrate on understanding the thermoelectric properties of the nanostructured Ba-based clathrates. We use semi-classical Boltzmann transport equations to calculate the various thermoelectric properties as a function of reduced dimensions. We observe that there exists a delicate balance between the electrical conductivity and the electronic part of the thermal conductivity in reduced dimensions. Insights from these results can directly be used to control particle size in nanostructuring experiments.

  14. Clathrate formation in the systems Sr–Cu–Ge and (Ba,Sr)–Cu–Ge

    SciTech Connect

    Zeiringer, I.; Moser, R.; Kneidinger, F.; Podloucky, R.; Royanian, E.; Grytsiv, A.; Bauer, E.; Giester, G.; Falmbigl, M.; Rogl, P.

    2014-09-15

    In the ternary system Sr–Cu–Ge, a novel clathrate type-I phase was detected, Sr{sub 8}Cu{sub x}Ge{sub 46−x} (5.2≤x<5.4), which exists close to the Zintl limit in a small temperature interval. Sr{sub 8}Cu{sub 5.3}Ge{sub 40.7} decomposes eutectoidally on cooling at 730±3 °C into (Ge), SrGe{sub 2} and τ{sub 1}-SrCu{sub 2−x}Ge{sub 2+x}. Phase equilibria at 700 °C have been established for the Ge rich part and are characterized by the appearance of only one ternary compound, τ{sub 1}-SrCu{sub 2−x}Ge{sub 2+x}, which crystallizes with the ThCr{sub 2}Si{sub 2} structure type and forms a homogeneity range up to x=0.4 (a=0.42850(4), c=1.0370(1) nm). Additionally, the extent of the clathrate type-I solid solution Ba{sub 8−y}Sr{sub y}Cu{sub x}Ge{sub 46−x} (0≤y≤∼5.6; 5.2≤x≤5.4, from as cast alloys) has been studied at various temperatures. The clathrate type-I crystal structure (space group Pm3{sup ¯}n) has been proven by X-ray single crystal diffraction on two single crystals with the composition (from refinement): Sr{sub 8}Cu{sub 5.36}Ge{sub 40.64} (a=1.06368(2) nm at 300 K) and Ba{sub 4.86}Sr{sub 3.14}Cu{sub 5.36}Ge{sub 40.64} (a=1.06748(2) nm at 300 K) measured at 300, 200 and 100 K. From the temperature dependence of the lattice parameters and the atomic displacement parameters, thermal expansion coefficients, Debye- and Einstein-temperatures and the speed of sound have been determined. From heat capacity measurements of Sr{sub 8}Cu{sub 5.3}Ge{sub 40.7} at low temperatures the Sommerfeld coefficient (γ=24 mJ/mol K{sup 2}) and the Debye temperature (Θ{sub D}{sup LT}=273 K) have been extracted. From a detailed analysis of these data at higher temperatures, Einstein branches of the phonon dispersion relation have been derived and compared to those obtained from the atomic displacement parameters. Electrical resistivity measurements of Sr{sub 8}Cu{sub 5.3}Ge{sub 40.7} reveal a rather metallic behavior in the low temperature range (<300 K

  15. Phonon dynamics in type-VIII silicon clathrates: Beyond the rattler concept

    NASA Astrophysics Data System (ADS)

    Norouzzadeh, Payam; Myles, Charles W.; Vashaee, Daryoosh

    2017-05-01

    Clathrates can form a type of guest-host solid structures that, unlike most crystalline solids, have very low thermal conductivity. It is generally thought that the guest atoms caged inside the host framework act as "rattlers" and induce lattice dynamics disorders responsible for the small thermal conductivity. We performed a systematic study of the lattice dynamical properties of type-VIII clathrates with alkali and alkaline-earth guests, i.e., X8S i46 (X =Na , K, Rb, Cs, Ca, Sr, and Ba). The energy dependent participation ratio (PR) and the atomic participation ratio of phonon modes extracted from density functional theory calculations revealed that the rattler concept is not adequate to describe the effect of fillers as they manifest strong hybridization with the framework. For the case of heavy fillers, such as Rb, Sr, Cs, and Ba, a phonon band gap was formed between the acoustic and optical branches. The calculated PR indicated that the fillers suppress the acoustic phonon modes and change the energy transport mechanism from propagative to diffusive or localized resulting in "phonon-glass" characteristics. This effect is stronger for the heavy fillers. Furthermore, in all cases, the guest insertion depressed the phonon bandwidth, reduced the Debye temperature, and reduced the phonon group velocity, all of which should lead to reduction of the thermal conductivity.

  16. Impact of the Condensed-Phase Environment on the Translation-Rotation Eigenstates and Spectra of a Hydrogen Molecule in Clathrate Hydrates.

    PubMed

    Powers, Anna; Marsalek, Ondrej; Xu, Minzhong; Ulivi, Lorenzo; Colognesi, Daniele; Tuckerman, Mark E; Bačić, Zlatko

    2016-01-21

    We systematically investigate the manifestations of the condensed-phase environment of the structure II clathrate hydrate in the translation-rotation (TR) dynamics and the inelastic neutron scattering (INS) spectra of an H2 molecule confined in the small dodecahedral cage of the hydrate. The aim is to elucidate the extent to which these properties are affected by the clathrate water molecules beyond the confining cage and the proton disorder of the water framework. For this purpose, quantum calculations of the TR eigenstates and INS spectra are performed for H2 inside spherical clathrate domains of gradually increasing radius and the number of water molecules ranging from 20 for the isolated small cage to more than 1800. For each domain size, several hundred distinct hydrogen-bonding topologies are constructed in order to simulate the effects of the proton disorder. Our study reveals that the clathrate-induced splittings of the j = 1 rotational level and the translational fundamental of the guest H2 are influenced by the condensed-phase environment to a dramatically different degree, the former very strongly and the latter only weakly.

  17. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  18. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton?

    NASA Astrophysics Data System (ADS)

    Kargel, J. S.; Prieto-Ballesteros, O.; Tanaka, K. L.

    2003-04-01

    Clathrate hydrates are potentially the most abundant class of solids in the outer Solar System. The mass of clathrates in the icy satellites may exceed that of all silicates, metals, sulfides, salts, water ice, and other non-clathrate volatiles combined. Clathrates may store most of the Solar System's (Earth's included) inventories of nonpolar condensed carbonaceous molecular gases (CO, CO_2, CH_4, and others), if the gas giants are excluded. Yet, clathrates are not inert repositories of these gases. Rather, fluctuations in temperature, pressure, and fluid composition cause the formation and destruction of clathrates. Thus, in large, geologically active worlds the nonpolar gases cycle through the solid clathrates and various fluid phases. The molar volume changes associated with clathrate formation and dissociation are substantial. The hissing and popping of terrestrial natural gas hydrate, when extracted in drill cores or dredged from the seafloor and depressurized to ambient surface conditions, is well documented and has natural analogs on larger scales. Catastrophic destabilization of clathrate due to either temperature increase or pressure decrease has been documented on Earth. For example, latest-Paleocene global warming and associated biologic extinctions are interpreted to have resulted from massive destabilization of seafloor clathrates and emission of CH_4 (G.R. Dickens et al., 1997, Geology, 25, 259-262). This event may be linked to clathrate-associated fault, slump, and landslide features widely observed on submarine ridges and edges of shelves (e.g., Dillon et al., 1998, in: J.P. Henriet and J. Mienert (Eds.), Geol. Soc. Lond. Spec. Pub. 137, 293-302) Such terrains may be good analogs of Martian chaotic terrain. Today, dynamic clathrate formation and dissociation occurs on a smaller scale, with consequent seafloor mud volcanism, mud diapirism, and seafloor sediment brecciation widely reported. Catastrophic clathrate dissociation and related events may

  19. Pressure induced phase transitions in ceramic compounds containing tetragonal zirconia

    SciTech Connect

    Sparks, R.G.; Pfeiffer, G.; Paesler, M.A.

    1988-12-01

    Stabilized tetragonal zirconia compounds exhibit a transformation toughening process in which stress applied to the material induces a crystallographic phase transition. The phase transition is accompanied by a volume expansion in the stressed region thereby dissipating stress and increasing the fracture strength of the material. The hydrostatic component of the stress required to induce the phase transition can be investigated by the use of a high pressure technique in combination with Micro-Raman spectroscopy. The intensity of Raman lines characteristic for the crystallographic phases can be used to calculate the amount of material that has undergone the transition as a function of pressure. It was found that pressures on the order of 2-5 kBar were sufficient to produce an almost complete transition from the original tetragonal to the less dense monoclinic phase; while a further increase in pressure caused a gradual reversal of the transition back to the original tetragonal structure.

  20. Prediction of Giant Thermoelectric Power Factor in Type-VIII Clathrate Si46

    PubMed Central

    Norouzzadeh, Payam; Myles, Charles W.; Vashaee, Daryoosh

    2014-01-01

    Clathrate materials have been the subject of intense interest and research for thermoelectric application. Nevertheless, from the very large number of conceivable clathrate structures, only a small fraction of them have been examined. Since the thermal conductivity of clathrates is inherently small due to their large unit cell size and open-framework structure, the current research on clathrates is focused on finding the ones with large thermoelectric power factor. Here we predict an extraordinarily large power factor for type-VIII clathrate Si46. We show the existence of a large density of closely packed elongated ellipsoidal carrier pockets near the band edges of this so far hypothetical material structure, which is higher than that of the best thermoelectric materials known today. The high crystallographic symmetry near the energy band edges for Si46-VIII clathrates is responsible for the formation of such a large number of carrier pockets. PMID:25391971

  1. Identification of benzazole compounds that induce HIV-1 transcription

    PubMed Central

    Michaels, Daniel; Chen, Guangming; Schiralli Lester, Gillian M.; Nodder, Sarah; Weetall, Marla; Karp, Gary M.; Gu, Zhengxian; Colacino, Joseph M.; Henderson, Andrew J.

    2017-01-01

    Despite advances in antiretroviral therapy, HIV-1 infection remains incurable in patients and continues to present a significant public health burden worldwide. While a number of factors contribute to persistent HIV-1 infection in patients, the presence of a stable, long-lived reservoir of latent provirus represents a significant hurdle in realizing an effective cure. One potential strategy to eliminate HIV-1 reservoirs in patients is reactivation of latent provirus with latency reversing agents in combination with antiretroviral therapy, a strategy termed “shock and kill”. This strategy has shown limited clinical effectiveness thus far, potentially due to limitations of the few therapeutics currently available. We have identified a novel class of benzazole compounds effective at inducing HIV-1 expression in several cellular models. These compounds do not act via histone deacetylase inhibition or T cell activation, and show specificity in activating HIV-1 in vitro. Initial exploration of structure-activity relationships and pharmaceutical properties indicates that these compounds represent a potential scaffold for development of more potent HIV-1 latency reversing agents. PMID:28658263

  2. Compound ICA-105574 prevents arrhythmias induced by cardiac delayed repolarization.

    PubMed

    Meng, Jing; Shi, Chenxia; Li, Lin; Du, Yumin; Xu, Yanfang

    2013-10-15

    Impaired ventricular repolarization can lead to long QT syndrome (LQT), a proarrhythmic disease with high risk of developing lethal ventricular tachyarrhythmias. The compound ICA-105574 is a recently developed hERG activator and it enhances IKr current with very high potency by removing the channel inactivation. The present study was designed to investigate antiarrhythmic properties of ICA-105574. For comparison, the effects of another compound NS1643 was in-parallel assessed, which also acts primarily to attenuate channel inactivation with moderate potency. We found that both ICA-105574 and NS1643 concentration-dependently shortened action potential duration (APD) in ventricular myocytes, and QT/QTc intervals in isolated guinea-pig hearts. ICA-105574, but not NS1643, completely prevented ventricular arrhythmias in intact guinea-pig hearts caused by IKr and IKs inhibitors, although both ICA-105574 and NS1643 could reverse the drug-induced prolongation of APD in ventricular myocytes. Reversing prolongation of QT/QTc intervals and antagonizing the increases in transmural dispersion of repolarization and instability of the QT interval induced by IKr and IKs inhibitors contributed to antiarrhythmic effect of ICA-105574. Meanwhile, ICA-105574 at higher concentrations showed a potential proarrhythmic risk in normal hearts. Our results suggest that ICA-105574 has more efficient antiarrhythmic activity than NS1643. However, its potential proarrhythmic risk implies that benefits and risks should be seriously taken into consideration for further developing this type of hERG activators.

  3. Clathrate Ba8Au16P30: the "gold standard" for lattice thermal conductivity.

    PubMed

    Fulmer, James; Lebedev, Oleg I; Roddatis, Vladimir V; Kaseman, Derrick C; Sen, Sabyasachi; Dolyniuk, Juli-Anna; Lee, Kathleen; Olenev, Andrei V; Kovnir, Kirill

    2013-08-21

    A novel clathrate phase, Ba8Au16P30, was synthesized from its elements. High-resolution powder X-ray diffraction and transmission electron microscopy were used to establish the crystal structure of the new compound. Ba8Au16P30 crystallizes in an orthorhombic superstructure of clathrate-I featuring a complete separation of gold and phosphorus atoms over different crystallographic positions, similar to the Cu-containing analogue, Ba8Cu16P30. Barium cations are trapped inside the large polyhedral cages of the gold-phosphorus tetrahedral framework. X-ray diffraction indicated that one out of 15 crystallographically independent phosphorus atoms appears to be three-coordinate. Probing the local structure and chemical bonding of phosphorus atoms with (31)P solid-state NMR spectroscopy confirmed the three-coordinate nature of one of the phosphorus atomic positions. High-resolution high-angle annular dark-field scanning transmission electron microscopy indicated that the clathrate Ba8Au16P30 is well-ordered on the atomic scale, although numerous twinning and intergrowth defects as well as antiphase boundaries were detected. The presence of such defects results in the pseudo-body-centered-cubic diffraction patterns observed in single-crystal X-ray diffraction experiments. NMR and resistivity characterization of Ba8Au16P30 indicated paramagnetic metallic properties with a room-temperature resistivity of 1.7 mΩ cm. Ba8Au16P30 exhibits a low total thermal conductivity (0.62 W m(-1) K(-1)) and an unprecedentedly low lattice thermal conductivity (0.18 W m(-1) K(-1)) at room temperature. The values of the thermal conductivity for Ba8Au16P30 are significantly lower than the typical values reported for solid crystalline compounds. We attribute such low thermal conductivity values to the presence of a large number of heavy atoms (Au) in the framework and the formation of multiple twinning interfaces and antiphase defects, which are effective scatterers of heat-carrying phonons.

  4. Semiconductiong Properties of Clathrates Ba8@Ge43: ab initio Study

    NASA Astrophysics Data System (ADS)

    Eguchi, Haruki; Tsumuraya, Kazuo; Takenaka, Hiroyuki; Suzuki, Akihiko; Tanigaki, Katsumi

    2003-03-01

    The Si-clathrates have been usually synthesized when alkaline or alkaline-earth atoms are coexisted with the host Si atoms, which is also the case for the Ge-clathrates. The I-encapsulating Si-clathrates have been also synthesized recently. In the case of the hydrate clathrates, the formation has been controlled by both the sizes of the endohedral molecules and the hydrophobic interactions of the molecules in the water.[1] We study the mechanism of the clathrate formation through the binding nature of the Si-X and Ge-X dimers, where X is selected elements in the periodic table. We calculate the charge transfers (population analysis), the binding energies, and the bonding distances using the ab-initio molecular dynamics method with planewaves and pseudo-potentials. We discuss the mechanism of the formation of the Si-clathrates comparing with that of the hydrate clathrates and evaluate the stability of clathrates predicted by the present study. [1]E.Dendy Sloan,Jr, Clathrate Hydrates of Natural Gasses, Marcel Dekker, 1998.

  5. Formation and spectra of clathrate hydrates of methanol and methanol-ether mixtures

    NASA Astrophysics Data System (ADS)

    Williams, Kenneth Dixon; Devlin, J. Paul

    1997-10-01

    Infrared spectra of mixed clathrate hydrates, with either ethylene oxide (EO) or tetrahydrofuran (THF) and methanol molecules as the guest species, have been obtained from thin films prepared by vapor deposition of D 2O mixtures in the 115-130 K range. Although methanol acts as a suppressant to the direct vapor deposition of a type I clathrate with EO, nearly complete conversion of 115 K amorphous codeposits, to the crystalline mixed clathrate, occurs upon warming near 150 K. By contrast, the type II clathrate of THF shows an increased crystalline quality when methanol is included in the vapor deposits of the mixed clathrate hydrate at 130 K. The observation of the OD stretch-mode band of weakly bonded CD 3OD near 2575 cm -1 is part of the evidence that the methanol molecules are encaged. However, as shown theoretically by Tanaka, the clathrate hydrates of methanol, even when mixed with an ether help gas, are not stable structures but form at low temperatures because of kinetic factors, only to decompose in the 140-160 K range. Attempts to prepare a simple type I or type II clathrate hydrate of methanol have produced mixed results. Limited amounts of clathrate hydrate form during deposition but annealing does not result in complete conversion to crystalline clathrates, particularly for host : guest ratios of 17 : 1.

  6. Ft-Ir Spectroscopic Study Of Co(1-Propanethiol)2Ni(Cn)4·Benzene Clathrate

    NASA Astrophysics Data System (ADS)

    Türköz, D.; Kartal, Z.; Bahçeli, S.

    2004-08-01

    By vibrational spectroscopy of the new Hofmann-propanethiol-type clathrate Co(1-propanethiol) 2Ni(CN)4·Benzene it is shown that its structure is similar structure to those of other Hofmanntype clathrates.

  7. Gas storage in "dry water" and "dry gel" clathrates.

    PubMed

    Carter, Benjamin O; Wang, Weixing; Adams, Dave J; Cooper, Andrew I

    2010-03-02

    "Dry water" (DW) is a free-flowing powder prepared by mixing water, hydrophobic silica particles, and air at high speeds. We demonstrated recently that DW can be used to dramatically enhance methane uptake rates in methane gas hydrate (MGH). Here, we expand on our initial work, demonstrating that DW can be used to increase the kinetics of formation of gas clathrates for gases other than methane, such as CO(2) and Kr. We also show that the stability of the system toward coalescence can be increased via the inclusion of a gelling agent to form a "dry gel", thus dramatically improving the recyclability of the material. For example, the addition of gellan gum allows effective reuse over at least eight clathration cycles without the need for reblending. DW and its "dry gel" modification may represent a potential platform for recyclable gas storage or gas separation on a practicable time scale in a static, unmixed system.

  8. Potential infrared relaxation channels calculated for CO2 clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Lakhlifi, Azzedine; Dahoo, Pierre Richard; Chassefière, Eric

    2017-01-01

    The infrared bar-spectrum of a single carbon dioxide molecule encapsulated in nano-cage clathrate hydrate is determined using the LD (Lakhlifi-Dahoo) extended site inclusion model successfully applied to analyze the spectra of CO2 isotopologues isolated in rare gas matrices. Trapping is energetically more favorable in clathrate structure of type sI than sII. CO2 exhibits hindered orientational motions (librational motions) around its equilibrium configurations in the small and large nano-cages. The orientation transitions are weak, and the spectra are purely vibrational. In the static field inside the cage, the doubly degenerate bending mode ν2 is blue shifted and split. From the scheme of the calculated energy levels for the different degrees of freedom, which is comparable to that of CO2 in rare gas matrices, it is conjectured that infrared excited CO2 will rather relax radiatively. Non-radiative channels can be analyzed by binary collision model.

  9. On the possibilty of clathrate hydrates on the Moon

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Nealson, K.; Romanovsky, V.

    2000-01-01

    One of the most important inferences of the Lunar Prospector mission data was the existence of subsurface water ice in the permanently shadowed craters near both lunar poles [Feldman et al., 1998]. We propose and substantiate an alternative explanation that hydrogen can exist in the shallow lunar subsurface in the form of clathrate hydrates: CH4 . 6H(2)o and/or CO2 . 6H(2)o.

  10. CO2-SO2 clathrate hydrate formation on early Mars

    NASA Astrophysics Data System (ADS)

    Chassefiere, E.; Dartois, E.; Herri, J.; Tian, F.; Schmidt, F.; Mousis, O.; Lakhlifi, A.

    2013-12-01

    It is generally agreed that a dense CO2-dominant atmosphere was necessary in order to keep early Mars warm and wet. However, current models have not been able to produce surface temperature higher than the freezing point of water. Most sulfate minerals discovered on Mars are dated no earlier than the Hesperian, despite likely much stronger volcanic activities and more substantial release of sulfur-bearing gases into Martian atmosphere during the Noachian. Here we show, using a 1-D radiative-convective-photochemical model, that clathrate formation during the Noachian would have buffered the atmospheric CO2 pressure of early Mars at ~2 bar and maintained a global average surface temperature ~230 K. Because clathrates trap SO2 more favorably than CO2, all volcanically outgassed sulfur would have been trapped in Noachian Mars cryosphere, preventing a significant formation of sulfate minerals during the Noachian and inhibiting carbonates from forming at the surface in acidic water resulting from the local melting of the SO2-rich cryosphere. The massive formation of sulfate minerals at the surface of Mars during the Hesperian could be the consequence of a drop of the CO2 pressure below a 2-bar threshold value at the late Noachian-Hesperian transition, which would have released sulfur gases into the atmosphere from both the Noachian sulfur-rich cryosphere and still active Tharsis volcanism. A lower value of the pressure threshold, down to ~0.5 bar, could have been sufficient to maintain middle and high latitude regions below the clathrate formation temperature during the Noachian and to make the trapping of SO2 in clathrates efficient. Our hypothesis could allow to explain the formation of chaotic terrains and outflow channels, and the occurrence of episodic warm episodes facilitated by the release of SO2 to the atmosphere. These episodes could explain the formation of valley networks and the degradation of impact craters, but remain to be confirmed by further modeling.

  11. CO2-SO2 clathrate hydrate formation on early Mars

    NASA Astrophysics Data System (ADS)

    Chassefière, Eric; Dartois, Emmanuel; Herri, Jean-Michel; Tian, Feng; Schmidt, Frédéric; Mousis, Olivier; Lakhlifi, Azzedine

    2013-04-01

    It is generally agreed that a dense CO2-dominant atmosphere was necessary in order to keep early Mars warm and wet. However, current models have not been able to produce surface temperature higher than the freezing point of water. Most sulfate minerals discovered on Mars are dated no earlier than the Hesperian, despite likely much stronger volcanic activities and more substantial release of sulfur-bearing gases into martian atmosphere during the Noachian. Here we show, using a 1-D radiative-convective-photochemical model, that clathrate formation during the Noachian would have buffered the atmospheric CO2 pressure of early Mars at ˜2 bar and maintained a global average surface temperature ˜230 K. Because clathrates trap SO2 more favorably than CO2, all volcanically outgassed sulfur would have been trapped in Noachian Mars cryosphere, preventing a significant formation of sulfate minerals during the Noachian and inhibiting carbonates from forming at the surface in acidic water resulting from the local melting of the SO2-rich cryosphere. The massive formation of sulfate minerals at the surface of Mars during the Hesperian could be the consequence of a drop of the CO2 pressure below a 2-bar threshold value at the late Noachian-Hesperian transition, which would have released sulfur gases into the atmosphere from both the Noachian sulfur-rich cryosphere and still active Tharsis volcanism. A lower value of the pressure threshold, down to ˜0.5 bar, could have been sufficient to maintain middle and high latitude regions below the clathrate formation temperature during the Noachian and to make the trapping of SO2 in clathrates efficient. Our hypothesis could allow to explain the formation of chaotic terrains and outflow channels, and the occurrence of episodic warm episodes facilitated by the release of SO2 to the atmosphere. These episodes could explain the formation of valley networks and the degradation of impact craters, but remain to be confirmed by further modeling.

  12. On the possibilty of clathrate hydrates on the Moon

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Nealson, K.; Romanovsky, V.

    2000-01-01

    One of the most important inferences of the Lunar Prospector mission data was the existence of subsurface water ice in the permanently shadowed craters near both lunar poles [Feldman et al., 1998]. We propose and substantiate an alternative explanation that hydrogen can exist in the shallow lunar subsurface in the form of clathrate hydrates: CH4 . 6H(2)o and/or CO2 . 6H(2)o.

  13. Noble gas encapsulation: clathrate hydrates and their HF doped analogues.

    PubMed

    Mondal, Sukanta; Chattaraj, Pratim Kumar

    2014-09-07

    The significance of clathrate hydrates lies in their ability to encapsulate a vast range of inert gases. Although the natural abundance of a few noble gases (Kr and Xe) is poor their hydrates are generally abundant. It has already been reported that HF doping enhances the stability of hydrogen hydrates and methane hydrates, which prompted us to perform a model study on helium, neon and argon hydrates with their HF doped analogues. For this purpose 5(12), 5(12)6(8) and their HF doped analogues are taken as the model clathrate hydrates, which are among the building blocks of sI, sII and sH types of clathrate hydrate crystals. We use the dispersion corrected and gradient corrected hybrid density functional theory for the calculation of thermodynamic parameters as well as conceptual density functional theory based reactivity descriptors. The method of the ab initio molecular dynamics (AIMD) simulation is used through atom centered density matrix propagation (ADMP) techniques to envisage the structural behaviour of different noble gas hydrates on a 500 fs timescale. Electron density analysis is carried out to understand the nature of Ng-OH2, Ng-FH and Ng-Ng interactions. The current results noticeably demonstrate that the noble gas (He, Ne, and Ar) encapsulation ability of 5(12), 5(12)6(8) and their HF doped analogues is thermodynamically favourable.

  14. Alteration of volatile inventories by polar clathrate formation on Mars.

    PubMed

    Musselwhite, D; Lunine, J I

    1995-11-25

    Recent models of chaotic variation in the Martian obliquity suggest that CO2 could be released during times of high obliquity and then recaptured in the polar caps as ice or clathrate during times of lower obliquity (Jakosky, et al., 1995). A natural implication of clathrate trapping is that other species in the Martian atmosphere, including noble gases, must incorporate in the water ice structure as well, in varying amounts according to the size and polarizability of the molecules as well as their atmospheric abundances. For nominal estimates of cap volume and amount of incorporated CO2 , we find that the current atmospheric inventory of noble gases is not representative of the bulk inventory in the Martian surface-atmosphere system. In particular, xenon and krypton are underrepresented in the present atmosphere. Models of source regions for Martian volatiles, which are constrained by noble gas abundances, must be modified to take these fractionation effects into account if indeed evidence for large amounts of polar clathrates is found.

  15. A theoretical examination of known and hypothetical clathrate hydrate materials

    NASA Astrophysics Data System (ADS)

    Tribello, Gareth A.; Slater, Ben

    2009-07-01

    The recent synthesis of a new hydrogen binary hydrate with the sH structure has highlighted the potential storage capabilities of water clathrates [T. A. Strobel, C. A. Koh, and E. D. Sloan, J. Phys. Chem. B 112, 1885 (2008) and A. R. C. Duarte, A. Shariati, L. J. Rovetto, and C. J. Peters, J. Phys. Chem. B 112, 1888 (2008)]. In this work, the absorption of hydrogen and the promoters used in the experimental work are considered using a simplified model for the host-guest interaction, which allows one to understand the stabilizing effects of multiple help molecules. Two further hypothetical clathrates, which are isostructural with known zeolite structures, are also investigated. It is shown that the energy gained by absorbing adamantane into these two frameworks is far greater than that gained upon absorption of adamantane into the sH structure. Hence, a clathrate with the same topology as the DDR (Sigma 1) zeolite may be synthesizable with adamantane and hydrogen as guest molecules as, in the conditions explored here, this phase appears to be more stable than the sH structure.

  16. Encapsulation kinetics and dynamics of carbon monoxide in clathrate hydrate

    PubMed Central

    Zhu, Jinlong; Du, Shiyu; Yu, Xiaohui; Zhang, Jianzhong; Xu, Hongwu; Vogel, Sven C.; Germann, Timothy C.; Francisco, Joseph S.; Izumi, Fujio; Momma, Koichi; Kawamura, Yukihiko; Jin, Changqing; Zhao, Yusheng

    2014-01-01

    Carbon monoxide clathrate hydrate is a potentially important constituent in the solar system. In contrast to the well-established relation between the size of gaseous molecule and hydrate structure, previous work showed that carbon monoxide molecules preferentially form structure-I rather than structure-II gas hydrate. Resolving this discrepancy is fundamentally important to understanding clathrate formation, structure stabilization and the role the dipole moment/molecular polarizability plays in these processes. Here we report the synthesis of structure-II carbon monoxide hydrate under moderate high-pressure/low-temperature conditions. We demonstrate that the relative stability between structure-I and structure-II hydrates is primarily determined by kinetically controlled cage filling and associated binding energies. Within hexakaidecahedral cage, molecular dynamic simulations of density distributions reveal eight low-energy wells forming a cubic geometry in favour of the occupancy of carbon monoxide molecules, suggesting that the carbon monoxide–water and carbon monoxide–carbon monoxide interactions with adjacent cages provide a significant source of stability for the structure-II clathrate framework. PMID:24936712

  17. Physical modeling of the formation of clathrate hydrates of methane

    NASA Astrophysics Data System (ADS)

    Drobyshev, A.; Aldiyarov, A.; Kurnosov, V.; Katpaeva, K.; Korshikov, E.; Sokolov, D.; Shinbayeva, A.; Timchenko, A.

    2015-06-01

    Nowadays natural gas hydrates attract special attention as a possible source of fossil fuel. According to various estimates, the reserves of hydrocarbons in hydrates exceed considerably explored reserves of natural gas. Due to the clathrate structure the unit volume of the gas hydrate can contain up to 160-180 volumes of pure gas. In recent years interest to a problem of gas hydrates has considerably increased. Such changes are connected with the progress in searches of the alternative sources of hydrocarbonic raw materials in countries that do not possess the resources of energy carriers. Thus gas hydrates are nonconventional sources of the hydrocarbonic raw materials which can be developed in the near future. At the same time, mechanisms of methane clathrate hydrates formations have not reached an advanced level, their thermophysical and mechanical properties have not been investigated profoundly. Thereby our experimental modeling of the processes of formation of methane clathrate hydrates in water cryomatrix prepared by co-condensation from the gas phase onto a cooled substrate was carried out over the range of condensation temperatures 12-60 K and pressures 10-4-10-6 Torr. In our experiments the concentration of methane in water varied in the range of 5%-90%. The thickness deposited films was 30-60 μm. The vibrational spectra of two-component thin films of CH4 + H2O condensates were measured and analyzed.

  18. Blue-colored tert-butylamine clathrate hydrate.

    PubMed

    Tani, Atsushi; Koyama, Satoshi; Urabe, Yusuke; Takato, Kenji; Sugahara, Takeshi; Ohgaki, Kazunari

    2014-11-26

    Clathrate hydrates preserve active species more stably than the other icy materials and investigation of the behavior of the active species elucidates the physicochemical properties of clathrate hydrates like guest-guest interaction. Color of the tert-butylamine clathrate hydrate changes to blue after gamma irradiation and is bleachable with visible light. The electron spin resonance (ESR) spectrum at 120 K mainly consists of a triplet signal of the C-centered radical NH2C(CH3)2CH2• together with a single signal at g = 2.0008. The latter signal disappears after light exposure. These results indicate that both the blue color and the single ESR signal are derived from trapped electrons in the hydrate. They thermally decay around 140-160 K by the first-order reaction, and the activation energy is 27 kJ/mol. Since tert-butylamine molecules can capture protons due to the high proton affinity, electrons may remain in the hydrate without reacting with protons, making the hydrate blue after gamma irradiation. The long-lived trapped electrons in the tert-butylamine hydrate have an advantage to investigate those in icy materials because tert-butylamine hydrate is nonionic and has a tetra-coordinated host water network like crystalline ice without any substitution for water molecules.

  19. Atomistic Simulation of Radiation-Induced Amorphization of Intermetallic Compounds.

    NASA Astrophysics Data System (ADS)

    Devanathan, Ramaswami

    Electron irradiation-induced amorphization of the intermetallic compounds NiZr, NiZr_2, FeTi and CuTi was examined using molecular dynamics simulations. Embedded-atom potentials, fitted to the properties of the pure metals and compounds, were used to model the interactions between the atoms. Electron irradiation was simulated by two different processes: randomly chosen atoms of different species were exchanged to create chemical disorder, and Frenkel pairs were introduced into the simulation cell at random. The resulting configurations corresponding to various damage doses were relaxed and the thermodynamic, structural, and mechanical properties were evaluated as functions of dose. The evolution of the system structure during the simulation was monitored using a new approach that combines molecular dynamics with the multislice method. Electron diffraction patterns were calculated from simulated configurations in an effort to maintain consistency with experiments, and improve the sensitivity to structural changes. The results of the simulation indicate that the mechanism of amorphization can vary from compound to compound. Chemical disorder was sufficient to cause amorphization in NiZr and NiZr_2, while Frenkel pairs were required in addition to chemical disorder in CuTi, and FeTi. During the process of amorphization, the energy and volume increased with dose and saturated at the corresponding levels of a quenched liquid. The variation of the volume with dose was remarkably similar to that of the energy. The pair-correlation functions, diffraction patterns, and projection of atom positions indicated the occurence of amorphization. In addition, the elastic constants C_{44 } and C^' became equal. Prior to the attainment of elastic isotropy, the average shear elastic constant decreased by about 50% of its value in the perfect crystal. In an effort to understand the elastic softening prior to amorphization and explore similarities between melting and amorphization, the

  20. Synthesis and structural characterization of the new clathrates K8Cd4Ge42, Rb8Cd4Ge42, and Cs8Cd4Ge42

    DOE PAGES

    Schafer, Marion; Bobev, Svilen

    2016-03-25

    This paper presents results from our exploratory work in the systems K-Cd-Ge, Rb-Cd-Ge, and Cs-Cd-Ge, which yielded the novel type-I clathrates with refined compositions K8Cd3.77(7)Ge42.23, Rb8Cd3.65(7)Ge42.35, and Cs7.80(1)Cd3.65(6)Ge42.35. The three compounds represent rare examples of clathrates of germanium with the alkali metals, where a d10 element substitutes a group 14 element. The three structures, established by single-crystal X-ray diffraction, indicate that the framework-building Ge atoms are randomly substituted by Cd atoms on only one of the three possible crystallographic sites. Furthermore, this and several other details of the crystal chemistry are elaborated.

  1. Gas Clathrate Hydrates Experiment for High School Projects and Undergraduate Laboratories

    ERIC Educational Resources Information Center

    Prado, Melissa P.; Pham, Annie; Ferazzi, Robert E.; Edwards, Kimberly; Janda, Kenneth C.

    2007-01-01

    We present a laboratory procedure, suitable for high school and undergraduate students, for preparing and studying propane clathrate hydrate. Because of their gas storage potential and large natural deposits, gas clathrate hydrates may have economic importance both as an energy source and a transportation medium. Similar to pure ice, the gas…

  2. Yb-substituted clathrates Ba8-xYbxGa16Ge30

    NASA Astrophysics Data System (ADS)

    Liu, L. H.; Wei, Y. P.; Yang, S. W.; Zhu, J.; Li, Y.

    2014-06-01

    Exploration of new rare-earth captured clathrates is an important field of clathrate application. Study on the second phases produced in the synthesis process is crucial for confirming the incorporation of rare earth atoms into the clathrate lattice. In the current study, the Yb-doped clathrate samples with nominal composition of Ba6Yb2Ga16Ge30 were prepared by combining arc melting (ARC), melt spinning (MS) and spark plasma sintering (SPS) techniques. By using the TEM with EDS analysis and X-ray diffraction refinement, phase analysis was systemically performed in different steps of the preparation process. Although the clathrate was the main phase in obtained samples, the Yb content in the clathrate phase was found to be much lower than the nominal composition as the Yb atoms strongly tend to create other byproduct phases including Yb2O3 — which is the main obstacle in the synthesis of Yb-substituted clathrates. For the dilute Yb-doped germanium clathrate sample a decrease in the thermal conductivity and electrical conductivity was simultaneously observed, therefore, no expected improvement of ZT occurred.

  3. Gas Clathrate Hydrates Experiment for High School Projects and Undergraduate Laboratories

    ERIC Educational Resources Information Center

    Prado, Melissa P.; Pham, Annie; Ferazzi, Robert E.; Edwards, Kimberly; Janda, Kenneth C.

    2007-01-01

    We present a laboratory procedure, suitable for high school and undergraduate students, for preparing and studying propane clathrate hydrate. Because of their gas storage potential and large natural deposits, gas clathrate hydrates may have economic importance both as an energy source and a transportation medium. Similar to pure ice, the gas…

  4. p53 modulates the AMPK inhibitor compound C induced apoptosis in human skin cancer cells

    SciTech Connect

    Huang, Shi-Wei; Wu, Chun-Ying; Wang, Yen-Ting; Kao, Jun-Kai; Lin, Chi-Chen; Chang, Chia-Che; Mu, Szu-Wei; Chen, Yu-Yu; Chiu, Husan-Wen; Chang, Chuan-Hsun; Liang, Shu-Mei; Chen, Yi-Ju; Huang, Jau-Ling; Shieh, Jeng-Jer

    2013-02-15

    Compound C, a well-known inhibitor of the intracellular energy sensor AMP-activated protein kinase (AMPK), has been reported to cause apoptotic cell death in myeloma, breast cancer cells and glioma cells. In this study, we have demonstrated that compound C not only induced autophagy in all tested skin cancer cell lines but also caused more apoptosis in p53 wildtype skin cancer cells than in p53-mutant skin cancer cells. Compound C can induce upregulation, phosphorylation and nuclear translocalization of the p53 protein and upregulate expression of p53 target genes in wildtype p53-expressing skin basal cell carcinoma (BCC) cells. The changes of p53 status were dependent on DNA damage which was caused by compound C induced reactive oxygen species (ROS) generation and associated with activated ataxia-telangiectasia mutated (ATM) protein. Using the wildtype p53-expressing BCC cells versus stable p53-knockdown BCC sublines, we present evidence that p53-knockdown cancer cells were much less sensitive to compound C treatment with significant G2/M cell cycle arrest and attenuated the compound C-induced apoptosis but not autophagy. The compound C induced G2/M arrest in p53-knockdown BCC cells was associated with the sustained inactive Tyr15 phosphor-Cdc2 expression. Overall, our results established that compound C-induced apoptosis in skin cancer cells was dependent on the cell's p53 status. - Highlights: ► Compound C caused more apoptosis in p53 wildtype than p53-mutant skin cancer cells. ► Compound C can upregulate p53 expression and induce p53 activation. ► Compound C induced p53 effects were dependent on ROS induced DNA damage pathway. ► p53-knockdown attenuated compound C-induced apoptosis but not autophagy. ► Compound C-induced apoptosis in skin cancer cells was dependent on p53 status.

  5. Clathrate formation and phase equilibria in the thiourea-bromoform system

    NASA Astrophysics Data System (ADS)

    Chekhova, G. N.; Shubin, Yu. V.; Pinakov, D. V.; Alferova, N. I.

    2008-07-01

    Phase equilibria in the thiourea (host)-bromoform (guest) binary system were studied by physicochemical analysis methods over the temperature range 270 455 K. The stoichiometry and stability region were determined for the channel-type compound CHBr3 · 2.40(2)(NH2)2CS; the compound was observed for the first time. When heated, the clathrate incongruently decomposed at 424.0 ± 0.8 K to rhombic thiourea and the guest component. The solubility isotherm of the thiourea-bromoform-acetic acid system was studied to find that the compound was thermodynamically stable at 293 K over the range of guest component concentrations 100 35 wt %. A decrease in its content in an equilibrium mother liquor resulted in the appearance of X-ray diffraction reflections of the initial host α polymorph. Rhombohedral cell parameters were determined (space group R-3 c, a = 15.89(1) Å, c = 12.40(1) Å, V = 2711(6) Å3, d calcd = 2.000 g/cm3, and d expt = 1.98(2) g/cm3). The mode of packing of bromoform molecules was compared with the organization of the guest subsystem in inclusion compounds formed by the substances studied.

  6. Oxime-induced reactivation of carboxylesterase inhibited by organophosphorus compounds

    SciTech Connect

    Maxwell, D.M.; Lieske, C.N.; Brecht, K.M.

    1994-06-01

    A structure-activity analysis of the ability of oximes to reactivate rat plasma carboxylesterase (CaE) that was inhibited by organophosphorus (OP) compounds revealed that uncharged oximes, such as 2,3-butanedione monoxime (diacetylmonoxime) or monoisonitrosoacetone, were better reactivators than cationic oximes. Cationic oximes that are excellent reactivators of OP-inhibited acetylcholinesterase, such as pyridine-2-aldoxime or the bis-pyridine aldoximes, HI-6 and TMB. 4, produced poor reactivation of OP-inhibited CaE. The best uncharged reactivator was 2,3. butanedione monoxime, which produced complete reactivation at 0.3 mM in 2 h of CaE that was inhibited by phosphinates, alkoxy-containing phosphates, and alkoxy-containing phosphonates. Complete reactivation of CaE could be achieved even after inhibition by phosphonates with highly branched alkoxy groups, such as sarin and soman, that undergo rapid aging with acetylcholinesterase. CaE that was inhibited by phosphonates or phosphates that contained aryloxy groups were reactivated to a lesser extent. The cause of this decreased reactivation appears to be an oxime-induced aging reaction that competes with the reactivation reaction. This oxime-induced aging reaction is accelerated by electron-withdrawing substituents on the aryloxy groups of phosphonates and by the presence of multiple aryloxy groups on phosphates. Thus, reactivation and aging of OP-inhibited CaE differ from the same processes for OP- inhibited acetylcholinesterase in both their oxime specificity and inhibitor specificity and, presumably, in their underlying mechanisms.

  7. Dissociation of Methane Clathrate Hydrates and Cryovolcanism on Titan: Experimental Constraints.

    NASA Astrophysics Data System (ADS)

    Choukroun, M.; Le Menn, E.; Tobie, G.; Grasset, O.; Sotin, C.

    2007-12-01

    In absence of any replenishment mechanism, the present-day atmospheric methane on Titan should be removed in a few tens of millions of years owing to UV-driven active photochemistry. Remote sensing observations by Cassini (Sotin et al. 2005, Lopes et al. 2007) and numerical models (Tobie et al. 2006) suggest that methane may be released during cryovolcanic events, from the dissociation of a subsurface clathrate reservoir. However, processes leading to clathrate dissociation at depth remain poorly understood, mainly because methane clathrates are very stable structures within the icy crust of Titan. High pressure - low temperature experiments have been conducted in order to investigate the variability of methane clathrate stability in Titan's conditions, using a sapphire-anvil cell cooled within a nitrogen cryostat. Three main factors may influence the stability of clathrates at depth: 1) the presence of ammonia in the icy crust and in the putative liquid layer; 2) the low amount of methane within the ice - possibly lower than the stochiometric value of the filled-cages clathrates structure; and 3) the antagonism between N2 and CH4 in the clathrate cages. In this work, a synthesis of the last three years of experimental and theoretical investigations of the ammonia effect on methane clathrates" stability will be proposed. In addition, it will be shown that experimental results concerning the effect of nitrogen and of the methane concentration relative to water are in good agreement with thermodynamic models. A low methane concentration decreases the dissociation temperature of structure I clathrates by more than 20-30 degrees, while the methane - nitrogen competition yields a shift that could reach 15 degrees. A combination of these two factors and the ammonia inhibition of methane clathrates is taken into account for providing new constraints on cryovolcanic processes within Titan.

  8. Rheology and Thermal State of Titan's Crust: Potential Role of Methane Clathrates

    NASA Astrophysics Data System (ADS)

    Basu Sarkar, D.; Elwood Madden, M.

    2014-12-01

    Gravity and topography data including new results obtained from recent Cassini RADAR and Visible and Infrared Mapping Spectrometer (VIMS) observations suggest that Titan has a rigid and conductive crust, greater than 40 km in thickness (Beghin et al., 2012; Hemingway et al., 2013; Lopes et al., 2013; Mitri et al., 2014; Lefevre et al., 2014; Baland et al., 2014). In this work we employed rheological models based on clathrate hydrate stability fields and modeled geothermal gradients to investigate how clathrate hydrates may influence the rheology of Titan's crust. Our findings suggest that a thick, rigid, and conductive crust composed of pure water ice is unlikely. Instead, a mixed phase crust comprised of water ice and clathrate hydrates, with up to 40 to 50% methane clathrates, results in thermal conductivity, viscosity, and density values consistent with Cassini observations. We modeled variations in Rayleigh number with crustal thickness for different crustal compositions assuming constant viscosity. Addition of methane clathrates makes the mixed ice-clathrate crust more viscous resulting in smaller Rayleigh numbers with depth compared to ice-only models. This slower rate of increase in Rayleigh number is also associated with increasing critical Rayleigh numbers, and hence, the potential thickness of a rigid, conductive crust. Modeling basal viscosity for different crustal compositions, following McKinnon (2006), we also determined that a methane clathrate-rich conductive crust would likely be much thicker (~60 km) than a non-convecting pure water-ice crust (~12 km). Titan's carbon content constrained by different formation models (Tobie et al., 2012) shows that even a pure methane clathrate crust is possible. However, a pure methane clathrate crust is unlikely because it would be relatively thin, less than 20 km due to clathrate's low thermal conductivity. Therefore, a mixed phase crust may explain both the geophysical observations and significant methane

  9. Non Equilibrium Transformations of Molecular Compounds Induced Mechanically

    SciTech Connect

    Descamps, M.; Willart, J. F.; Dudognon, E.

    2006-05-05

    Results clarifying the effects of mechanical milling on molecular solids are shortly reviewed. Special attention has been paid to the temperature of milling with regard to the glass transition temperature of the compounds. It is shown that decreasing the grinding temperature has for incidence to increase the amorphization tendency whereas milling above Tg produces a crystal-to-crystal transformation between polymorphic varieties. These observations contradict the usual proposition that grinding transforms the physical state only by a heating effect which induces a local melting. Equilibrium thermodynamics does not seem to be appropriate for describing the process. The driven alloys concept offers a more rational framework to interpret the effect of the milling temperature. Other results are presented which demonstrate the possibility for grinding to realize low temperature solid state alloying which offers new promising ways to stabilize amorphous molecular solids. In a second part the effect of dehydration of a molecular hydrate is described. It is shown that the rate of the dehydration process is a driving force for this other type of mechanical non equilibrium transformation.

  10. New Compounds Induce Brassinosteroid Deficient-like Phenotypes in Rice.

    PubMed

    Matsumoto, Tadashi; Yamada, Kazuhiro; Iwasaki, Ikuko; Yoshizawa, Yuko; Oh, Keimei

    2013-08-13

    Brassinosteroids (BRs) are steroidal plant hormones with potent plant growth promoting activity. Because BR-deficient mutants of rice exhibit altered plant architecture and important agronomic traits, we conducted a systemic search for specific inhibitors of BR biosynthesis to manipulate the BR levels in plant tissues. Although previous studies have been conducted with BR biosynthesis inhibitors in dicots, little is known regarding the effects of BR biosynthesis inhibition in monocot plants. In this work, we used potent inhibitors of BR biosynthesis in Arabidopsis, and we performed a hydroponic culture of rice seedlings to evaluate the effects of BR biosynthesis inhibition. Among the test compounds, we found that 1-[[2-(4-Chlorophenyl)-4-(phenoxymethyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (1) is a potent inhibitor that could induce phenotypes in rice seedlings that were similar to those observed in brassinosteroid deficient plants. The IC50 value for the retardation of plant growth in rice seedlings was approximately 1.27 ± 0.43 μM. The IC50 value for reducing the bending angle of the lamina joint was approximately 0.55 ± 0.15 μM.

  11. Ion beam induced luminescence of doped yttrium compounds

    NASA Astrophysics Data System (ADS)

    Rossi, P.; Brice, D. K.; Seager, C. H.; McDaniel, F. D.; Vizkelethy, G.; Doyle, B. L.

    2004-06-01

    Rare earth doped yttrium oxide (yttria) and silicate, Y 2O 3:Eu and Y 2SiO 5:Tb, are the most promising phosphors for advanced devices such as flat panel field-emission-displays. However, their light yield for electron excitation has proven to be lower than that predicted by early models. New experimental data are needed to improve the theoretical understanding of the cathodoluminescence (CL) that will, in turn, lead to materials that are significantly brighter. Beside the existing CL and photo luminescence (PL) measurements, one can provide new information by studying ion-induced luminescence (IL). Ions penetrate substantially deeper than electrons and their light yield should therefore not depend on surface effects. Moreover, the energy density released by ions can be much higher than that of electrons and photons, which results in possible saturation effects, further testing the adequacy of models. We exposed the above yttrium compounds to three ion beams, H (3 MeV), C (20 MeV), Cu (50 MeV), which have substantially different electronic stopping powers. H was selected to provide an excitation close to CL, but without surface effects. The C and Cu allowed an evaluation of saturation effects because of their higher stopping powers. The IL experiments involved measuring the transient light intensity signal radiating from thin phosphor layers following their exposure to ˜200 ns ion beam pulses. We present the transient yield curves for the two materials and discuss a general model for this behavior.

  12. Bulk and surface structure and high-temperature thermoelectric properties of inverse clathrate-III in the Si-P-Te system.

    PubMed

    Zaikina, Julia V; Mori, Takao; Kovnir, Kirill; Teschner, Detre; Senyshyn, Anatoliy; Schwarz, Ulrich; Grin, Yuri; Shevelkov, Andrei V

    2010-11-08

    The creation of thermoelectric materials for waste heat recovery and direct solar energy conversion is a challenge that forces the development of compounds that combine appreciable thermoelectric figure-of-merit with high thermal and chemical stability. Here we propose a new candidate for high-temperature thermoelectric materials, the type-III Si(172-x)P(x)Te(y) cationic clathrate, in which the framework is composed of partially ordered silicon and phosphorus atoms, whereas tellurium atoms occupy guest positions. We show that the utmost stability of this clathrate (up to 1500 K) in air is ensured by the formation of a nanosized layer of phosphorus-doped silica on the surface, which prevents further oxidation and degradation. As-cast (non-optimized) Si-P-Te clathrates display rather high values of the thermoelectric figure-of-merit (ZT=0.24-0.36) in the temperature range of 700-1100 K. These ZT values are comparable to the best values achieved for the properly doped transition-metal-oxide materials. The methods of the thermoelectric efficiency optimization are discussed.

  13. Thermoelectric Properties of Au- Containing Type-I Clathrates Ba8AuxGa16-3xGe30+2x

    SciTech Connect

    Ye, Zuxin; Cho, Jung Young; Tessema, Misle M.; Salvador, James R.; Waldo, Richard A.; Yang, Jihui; Wang, Hsin; Cai, Wei; Kirkham, Melanie J; Yang, Jiong; Zhang, Wenqing

    2014-01-01

    Type I clathrates, with compositions based on Ba8Ga16Ge30, are a class of promising thermoelectric materials due to their intrinsically low thermal conductivity. It has been demonstrated previously that the thermoelectric performance can be improved by transition metal substitution of the framework atoms. In this study, the effects of Au substitution for Ga/Ge on thermal and electrical transport properties of type I clathrate compounds have been investigated. Polycrystalline samples with a large range of Au content have been synthesized using conventional solid state techniques with the actual compositions of resulting materials approximately following Zintl-Klemm rules. The charge carrier type changes from electrons (n) to holes (p) as the Au content increases. The Seebeck coefficient (S) and power factor (S2/ where is the electrical resistivity) were improved by Au substitution and the resulting overall thermoelectric properties were enhanced by Au substitution with a thermoelectric figure of merit ZT ~ 0.63 at temperature T = 740 K for the composition Ba8Au5.47Ge39.96. The results presented herein show that Au-containing type I clathrates are promising p-type thermoelectric materials for high temperature applications.

  14. Migration of hydrogen radicals through clathrate hydrate cages

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ripmeester, John A.

    2009-09-01

    Electronic structure calculations are used to determine energy barriers to hydrogen radical migration in structure II clathrate small and large cages. Migration of H-radicals through pentagonal and hexagonal faces of small and large cages are considered and energies barriers calculated at the MP2 level with the 6-311++G( d, p) basis set are 61 and 17 kJ mol -1, respectively. Energy barriers (with tunneling corrections) are used to estimate escape rates from the cages and to explain results of recent experiments on the transformation of n-propyl radical in the propane hydrate and the behavior of hydrogen radicals in tetrahydrofuran/H 2 hydrates.

  15. Heat-pump cool storage in a clathrate of freon

    NASA Astrophysics Data System (ADS)

    Tomlinson, J. J.

    Presented are the analytical description and assessment of a unique heat pump/storage system in which the conventional evaporator of the vapor compression cycle is replaced by a highly efficient direct contract crystallizer. The thermal storage technique requires the formation of a refrigerant gas hydrate (a clathrate) and exploits an enthalpy of reaction comparable to the heat of fusion of ice. Additional system operational benefits include cool storage at the favorable temperatures of 4 to 7 C (40 to 45 F), and highly efficient heat transfer ates afforded by he direct contact mechanism. In addition, the experimental approach underway at ORNL to study such a system is discussed.

  16. HPHT synthesis, structure and electrical properties of type-I clathrates Ba8AlxSi46-x

    NASA Astrophysics Data System (ADS)

    Liu, Binwu; Jia, Xiaopeng; Sun, Hairui; Sun, Bing; Zhang, Yuewen; Liu, Haiqiang; Kong, Lingjiao; Huo, Dexuan; Ma, Hongan

    2016-01-01

    Clathrate compounds Ba8AlxSi46-x were successfully synthesized using the method of high-pressure and high-temperature (HPHT). In this process, we used BaSi2 as one of the starting materials in place of Ba metals, which reduces the complexity of the program caused by the extremely high chemical reactivity. By using this method, the processing time was reduced from few days to an hour. X-ray diffraction and structural refinement indicated this composition crystallized in type-I clathrate phase. Bond length analysis showed the Ba atoms in small dodecahedron had spherical thermal ellipsoids while those in large tetrakaidecahedron displayed anisotropic thermal ellipsoids. The negative Seebeck coefficient indicated transport processes were dominated by electrons as carriers, and increased with the increasing temperature. The electrical properties, including Seebeck coefficient and Power factor, were greatly enhanced by Al substitution. Middle: X-ray Rietveld refinement profile for Ba8Si46 and element mapping for Ba8Al16Si30. Right: Temperature dependence of Seebeck coefficient for Ba8AlxSi46-x prepared by HPHT.

  17. Stability and Vibrations of Guest Molecules in the Type II Clathrate Hydrate: A First-Principles Study of Solid Phase.

    PubMed

    Cao, Xiaoxiao; Su, Yan; Zhao, Jijun

    2015-07-09

    Natural gas mixtures are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, C3H6, and C3H8). Previous ab initio calculations were mainly limited by the cluster models. For the first time, we report first-principles calculations on the stability and vibrational properties of the gas molecules inside the crystalline lattice of type II clathrate. In accordance with our calculations, the larger the size of guest molecule, the more stable the clathrate hydrate for small-sized alkane guest molecules (CnHm, n ≤ 3, m ≤ 8). The interaction energy per guest molecule gradually increases as the number of guest molecules increase for both sII pure and sII mixed hydrates. In addition, the vibrational frequencies of guest molecules trapped in sII hydrate are also simulated. The C-C stretching frequency shows a blue shift as the amount of guest molecules increase. Our theoretical results prove to be valuable insight for identifying the types of guest molecules from experimental spectroscopic data.

  18. Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system

    NASA Technical Reports Server (NTRS)

    Lunine, J. I.; Stevenson, D. J.

    1985-01-01

    The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

  19. High pressure-temperature Raman spectroscopy of H2-H2O clathrate.

    NASA Astrophysics Data System (ADS)

    Somayazulu, Maddury; Levedahl, Alexander; Goncharov, Alexander; Mao, Ho-Kwang; Hemley, Russell

    2007-03-01

    The melting curve of the C2 clathrate H2-H2O has been determined by in-situ Raman spectroscopy measurements in an externally heated diamond anvil cell. We have determined the melting curve to a maximum pressure of 27 GPa. These are the first measurements on the melting line in this clathrate. Depending on the stoichiometry of the starting mixture of H2 and H2O, we are able to study either a mixture of C2 and H2O or C2 and H2. In either case, we were able to pinpoint the melting of the clathrate from the measurements of the molecular stretching mode (vibron) in the clathrate. In the case of C2 + Ice VII, we observe the vibron in the clathrate at a frequency higher than in pure H2 at the same pressure. We have cross-calibrated the melting temperatures using the Stokes-anti Stokes ratio of the diamond first order and Raman active TO phonon of cubic Boron Nitride. We find that the clathrate melts well above the H2 melting at all pressures studied indicating that the stabilization of this clathrate at high pressures is indeed due to interactions between the host and guest molecules.

  20. Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system

    NASA Technical Reports Server (NTRS)

    Lunine, J. I.; Stevenson, D. J.

    1985-01-01

    The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

  1. Anisotropy in growth kinetics of tetrahydrofuran clathrate hydrate: a molecular dynamics study.

    PubMed

    Nada, Hiroki

    2009-04-09

    The growth kinetics of a tetrahydrofuran (THF) clathrate hydrate at the interface between the clathrate and an aqueous THF solution were investigated by means of a molecular dynamic simulation. The simulation was carried out for the interface of both the {100} and {111} planes of the THF clathrate. The simulation indicated the same anisotropic growth as that observed in real systems: the growth of the THF clathrate was much slower at the {111} interface than at the {100} interface. When the THF clathrate grew, THF molecules that were dissolved in the solution first were arranged at both large and small cage sites on the interface. Subsequently, the formation of cages by H(2)O molecules occurred in regions surrounded or sandwiched by those arranged THF molecules. As the formation of cages progressed, the THF molecules that had once been arranged at small cage sites gradually moved away from the sites, and finally the structure of the clathrate was completely formed. Simulation results strongly suggested that the rate-determining process for clathrate growth was the rearrangement of THF molecules at the interface from a disordered state to a state in which THF molecules were ideally arranged at large cage sites only. This rearrangement occurred much more slowly at the {111} interface than at the {100} interface, owing to the formation of a modified structure in which large and small cages were formed at opposite positions of the {111} interface. The anisotropic growth kinetics of the THF clathrate, which were obtained in this study, are consistent with the fact that growth shapes of THF clathrates in real systems are octahedral with flat {111} planes.

  2. Prediction of clathrate structure type and guest position by molecular mechanics.

    PubMed

    Fleischer, Everly B; Janda, Kenneth C

    2013-05-16

    The clathrate hydrates occur in various types in which the number, size, and shape of the various cages differ. Usually the clathrate type of a specific guest is predicted by the size and shape of the molecular guest. We have developed a methodology to determine the clathrate type employing molecular mechanics with the MMFF force field employing a strategy to calculate the energy of formation of the clathrate from the sum of the guest/cage energies. The clathrate type with the most negative (most stable) energy of formation would be the type predicted (we mainly focused on type I, type II, or bromine type). This strategy allows for a calculation to predict the clathrate type for any cage guest in a few minutes on a laptop computer. It proved successful in predicting the clathrate structure for 46 out of 47 guest molecules. The molecular mechanics calculations also provide a prediction of the guest position within the cage and clathrate structure. These predictions are generally consistent with the X-ray and neutron diffraction studies. By supplementing the diffraction study with molecular mechanics, we gain a more detailed insight regarding the details of the structure. We have also compared MM calculations to studies of the multiple occupancy of the cages. Finally, we present a density functional calculation that demonstrates that the inside of the clathrates cages have a relatively uniform and low electrostatic potential in comparison with the outside oxygen and hydrogen atoms. This implies that van der Waals forces will usually be dominant in the guest-cage interactions.

  3. Coincident sediment slump/clathrate complexes on the U.S. Atlantic continental slope

    USGS Publications Warehouse

    Carpenter, G.

    1981-01-01

    High-resolution seismic reflection data recorded on the continental slope off the east coast of the United States have revealed instances of sediment mass movement (slumps) which appear to occur above clathrate accumulations. The slumping is believed to be related to the liberation of free gas by clathrate decomposition and consequent weakening of unconsolidated sediments above the clathrate. Pleistocene sea-level lowering and/or post-Pleistocene bottom water temperature increases may have had a significant role in this process. ?? 1981 A.M. Dowden, Inc.

  4. Multiple H2 occupancy of cages of clathrate hydrate under mild conditions.

    PubMed

    Lu, Hailong; Wang, Jianwei; Liu, Changling; Ratcliffe, Christopher I; Becker, Udo; Kumar, Rajnish; Ripmeester, John

    2012-06-06

    Experiments were carried out by reacting H(2) gas with N(2) hydrate at a temperature of 243 K and a pressure of 15 MPa. The characterizations of the reaction products indicated that multiple H(2) molecules can be loaded into both large and small cages of structure II clathrate hydrates. The realization of multiple H(2) occupancy of hydrate cages under moderate conditions not only brings new insights into hydrogen clathrates but also refreshes the perspective of clathrate hydrates as hydrogen storage media.

  5. Mechanism of Rare Earth Incorporation and Crystal Growth of Rare Earth Containing Type-I Clathrates.

    PubMed

    Prokofiev, Andrey; Svagera, Robert; Waas, Monika; Weil, Matthias; Bernardi, Johannes; Paschen, Silke

    2016-01-06

    Type-I clathrates possess extremely low thermal conductivities, a property that makes them promising materials for thermoelectric applications. The incorporation of cerium into one such clathrate has recently been shown to lead to a drastic enhancement of the thermopower, another property determining the thermoelectric efficiency. Here we explore the mechanism of the incorporation of rare earth elements into type-I clathrates. Our investigation of the crystal growth and the composition of the phase Ba8-x RE x TM y Si46-y (RE = rare earth element; TM = Au, Pd, Pt) reveals that the RE content x is mainly governed by two factors, the free cage space and the electron balance.

  6. Ginsenoside compound K induces apoptosis in nasopharyngeal carcinoma cells via activation of apoptosis-inducing factor

    PubMed Central

    2014-01-01

    Background Nasopharyngeal carcinoma (NPC) has a high incidence rate in Southern China. Although there are conventional therapies, the side effects and toxicities are not always tolerable for patients. Recently, the tumoricidal effect of ginsenosides on different cancer cells has been studied. This study aims to investigate the anti-cancer effect of ginsenosides on NPC cells and their underlying mechanism. Methods The cytotoxicity of ginsenosides on NPC cell line HK-1 was measured by MTT assay. Apoptosis was detected by propidium iodide staining followed by flow cytometry. A xenograft tumor model was established by injecting nude mice with HK-1 cells. The activation of caspases and apoptosis-inducing factor (AIF) were evaluated by Western blot analysis. Nuclear translocation of AIF was also studied by immunofluorescence staining. Mitochondrial membrane potential was measured by JC-1 dye using flow cytometry. Results Four ginsenosides, 20 (S)-Rh2, compound K (CK), panaxadiol (PD) and protopanaxadiol (PPD), induced apoptotic cell death in HK-1 cells in a concentration-dependent manner. CK inhibited HK-1 xenograft tumor growth most extensively and depleted mitochondrial membrane potential depolarization and induced translocation of AIF from cytoplasm to nucleus in HK-1 cells. In addition, depletion of AIF by siRNA abolished CK-induced HK-1 cell death. Conclusion Ginsenoside CK-induced apoptosis of HK-1 cells was mediated by the mitochondrial pathway and could significantly inhibit tumor growth in vivo. PMID:24690317

  7. Geochemistry of clathrate-derived methane in Arctic ocean waters

    NASA Astrophysics Data System (ADS)

    Elliott, Scott; Reagan, Matthew; Moridis, George; Smith, Philip Cameron

    2010-06-01

    Alterations to the composition of seawater are estimated for microbial oxidation of methane from large polar clathrate destabilizations, which may arise in the coming century. Gas fluxes are taken from porous flow models of warming Arctic sediment. Plume spread parameters are then used to bracket the volume of dilution. Consumption stoichiometries for the marine methanotrophs are based on growth efficiency and elemental/enzyme composition data. The nutritional demand implied by extra CH4 removal is compared with supply in various high latitude water masses. For emissions sized to fit the shelf break, reaction potential begins at one hundred micromolar and falls to order ten a thousand kilometers downstream. Oxygen loss and carbon dioxide production are sufficient respectively to hypoxify and acidify poorly ventilated basins. Nitrogen and the monooxygenase transition metals may be depleted in some locations as well. Deprivation is implied relative to existing ecosystems, along with dispersal of the excess dissolved gas. Physical uncertainties are inherent in the clathrate abundance, patch size, outflow buoyancy and mixing rate. Microbial ecology is even less defined but may involve nutrient recycling and anaerobic oxidizers.

  8. Geochemistry of clathrate-derived methane in Arctic Ocean waters

    SciTech Connect

    Elliott, S.M.; Reagan, M.T.; Moridis, G.J.; Cameron-Smith, P.J.

    2010-03-15

    Alterations to the composition of seawater are estimated for microbial oxidation of methane from large polar clathrate destabilizations, which may arise in the coming century. Gas fluxes are taken from porous flow models of warming Arctic sediment. Plume spread parameters are then used to bracket the volume of dilution. Consumption stoichiometries for the marine methanotrophs are based on growth efficiency and elemental/enzyme composition data. The nutritional demand implied by extra CH{sub 4} removal is compared with supply in various high latitude water masses. For emissions sized to fit the shelf break, reaction potential begins at one hundred micromolar and falls to order ten a thousand kilometers downstream. Oxygen loss and carbon dioxide production are sufficient respectively to hypoxify and acidify poorly ventilated basins. Nitrogen and the monooxygenase transition metals may be depleted in some locations as well. Deprivation is implied relative to existing ecosystems, along with dispersal of the excess dissolved gas. Physical uncertainties are inherent in the clathrate abundance, patch size, outflow buoyancy and mixing rate. Microbial ecology is even less defined but may involve nutrient recycling and anaerobic oxidizers.

  9. Additives and method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle Dendy; Christiansen, Richard Lee; Lederhos, Joseph P.; Long, Jin Ping; Panchalingam, Vaithilingam; Du, Yahe; Sum, Amadeu Kun Wan

    1997-01-01

    Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hinderance and/or charge repulsion. Also, polymers having an amide on which a C.sub.1 -C.sub.4 group is attached to the nitrogen and/or the carbonyl carbon of the amide may be used alone, or in combination with ring-containing polymers for enhanced effectiveness. Polymers having at least some repeating units representative of polymerizing at least one of an oxazoline, an N-substituted acrylamide and an N-vinyl alkyl amide are preferred.

  10. Additives and method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, E.D. Jr.; Christiansen, R.L.; Lederhos, J.P.; Long, J.P.; Panchalingam, V.; Du, Y.; Sum, A.K.W.

    1997-06-17

    Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hindrance and/or charge repulsion. Also, polymers having an amide on which a C{sub 1}-C{sub 4} group is attached to the nitrogen and/or the carbonyl carbon of the amide may be used alone, or in combination with ring-containing polymers for enhanced effectiveness. Polymers having at least some repeating units representative of polymerizing at least one of an oxazoline, an N-substituted acrylamide and an N-vinyl alkyl amide are preferred.

  11. Light scattering studies of clathrate hydrate forming systems

    NASA Astrophysics Data System (ADS)

    Zachary, Ralph Karl

    The current importance of clathrate hydrates lies primarily in the problems they pose for the oil and gas industry; in the future they may represent an important source of energy. These studies were persued in an effort to determine the utility of light scattering for elucidating changes in the dynamical structure of aqueous solutions that occur prior to hydrate formation. Such an understanding has direct relevance to the kinetics of clathrate hydrate formation, and may contribute to our knowledge of the many other systems in which water plays an important role. Aqueous solutions of tetrahydrofuran were at the center of this research which included experimental spectroscopic studies of such solutions as a function of temperature and system composition. Light scattering spectra were found to contain important information concerning the extent and nature of hydrogen bonding, and the structural changes that precede hydrate nucleation. Specifically, the OH stretching band due to water and the COC stretch band due to tetrahydrofuran were seen to vary in a predictable manner with changes in the composition, temperature, and thermal history of the system. Computer simulation studies were performed and used to aid in the interpretation of experimental spectra. Low wavenumber polarizability fluctuations were calculated and found to give reorientation times in good agreement with those found using other methods.

  12. Polarization response of clathrate hydrates capsulated with guest molecules.

    PubMed

    Zeng, Qun; Li, Jinshan; Huang, Hui; Wang, Xinqin; Yang, Mingli

    2016-05-28

    Clathrate hydrates are characterized by their water cages encapsulating various guest atoms or molecules. The polarization effect of these guest-cage complexes was studied with combined density functional theory and finite-field calculations. An addition rule was noted for these systems whose total polarizability is approximately equal to the polarizability sum of the guest and the cage. However, their distributional polarizability computed with Hirshfeld partitioning scheme indicates that the guest-cage interaction has considerable influence on their polarization response. The polarization of encapsulated guest is reduced while the polarization of water cage is enhanced. The counteraction of these two opposite effects leads to the almost unchanged total polarizability. Further analysis reveals that the reduced polarizability of encapsulated guest results from the shielding effect of water cage against the external field and the enhanced polarizability of water cage from the enhanced bonding of hydrogen bonds among water molecules. Although the charge transfer through the hydrogen bonds is rather small in the water cage, the polarization response of clathrate hydrates is sensitive to the changes of hydrogen bonding strength. The guest encapsulation strengthens the hydrogen bonding network and leads to enhanced polarizability.

  13. Dense Semi-Clathrates at High Pressure: A Study of the Water-tert-Butylamine System.

    PubMed

    Granero-García, Rubén; Falenty, Andrzej; Fabbiani, Francesca P A

    2017-03-13

    In situ high-pressure crystallization and diffraction techniques have been applied to obtain two very structurally distinct semi-clathrates of the tert-butylamine-water system with hydration numbers 5.65 and 5.8, respectively, thereby considerably reducing a notable hydration gap between the monohydrate and the 71/4 -hydrate that results when crystallization space is explored by temperature alone. Both structures can be considered as an intriguing solid-state example of hydrophobic hydration, in which the water network creates wide tert-butylamine-filled channels stabilized by cross-linking hydrogen bonds. The existence of interconnected channels might also add low hydration structures to a list of potential targets for hydrogen storage. A detailed analysis of the topology of host water and host-guest interactions is reported and extended to those of other hydrates of the compound. This analysis offers new insight into properties of the tert-butylamine-water system and provides some clues as to the occurrence of the sizable number of hydrates of this compound.

  14. Rhenium(IV) compounds inducing apoptosis in cancer cells.

    PubMed

    Martínez-Lillo, José; Mastropietro, Teresa F; Lappano, Rosamaria; Madeo, Antonio; Alberto, Marta E; Russo, Nino; Maggiolini, Marcello; De Munno, Giovanni

    2011-05-14

    The anticancer properties of a series of mononuclear Re(IV) compounds of formula ReCl(4)L (where L is bpy = 2,2'-bipyridine; bpym = 2,2'-bipyrimidine; dmbpy = 4,4'-dimethyl-2,2'-bipyridine; phen = 1,10-phenanthroline) were investigated for the first time. All compounds displayed potent in vitro antiproliferative activity against selected cancer cells. © The Royal Society of Chemistry 2011

  15. On the possibility for Rb- and Eu-cation ordering in type-I clathrates: synthesis and homogeneity range of the novel compounds Rb(8-x)Eu(x)(In,Ge)46 (0.6 ≤ x ≤ 1.8).

    PubMed

    Schäfer, Marion C; Bobev, Svilen

    2013-12-15

    Studies in the Rb-Eu-In-Ge system confirm the existence of the phase Rb(8-x)Eu(x)(In,Ge)46 (0.6 ≤ x ≤ 1.8), crystallizing with the cubic clathrate type-I structure. The In and Ge content can be varied, concomitant with changes in the Rb-Eu ratio. Two of the three framework sites are occupied by statistical mixtures of Ge and In atoms, while the site with the lowest multiplicity is taken by the In atoms only. Based on the three refined formulae [heptarubidium europium nonaindium heptatriacontagermanide, Rb7.39(3)Eu0.61(3)In8.88(5)Ge37.12(5), and two forms of hexarubidium dieuropium decaindium hexatriacontagermanide, Rb6.30(3)Eu1.70(3)In9.76(4)Ge36.24(4) and Rb6.24(2)Eu1.76(2)In10.16(5)Ge35.84(5)] and the explored different synthetic routes, it can be suggested that the known ternary phase Rb8In8Ge38 and the hypothetical quaternary phase Rb6Eu2In10Ge36 represent the boundaries of the homogeneity range. In the former limiting composition, both the (Ge,In)20 and the (Ge,In)24 cages are fully occupied by Rb atoms only, whereas Rb6Eu2In10Ge36 has Rb atoms encapsulated in the larger tetrakaidecahedra, with Eu atoms filling the smaller pentagonal dodecahedra. For the solid solutions Rb(8-x)Eu(x)(In,Ge)46, Rb and Eu are statistically disordered in the dodecahedral cage, and the tetrakaidecahedral cage is only occupied by Rb atoms.

  16. Two host-inducible genes of Rhizobium fredii and characterization of the inducing compound.

    PubMed Central

    Sadowsky, M J; Olson, E R; Foster, V E; Kosslak, R M; Verma, D P

    1988-01-01

    Random transcription fusions with Mu d1(Kan lac) generated three mutants in Rhizobium fredii (strain USDA 201) which showed induction of beta-galactosidase when grown in root exudate of the host plants Glycine max, Phaseolus vulgaris, and Vigna ungliculata. Two genes were isolated from a library of total plasmid DNA of one of the mutants, 3F1. These genes, present in tandem on a 4.2-kilobase HindIII fragment, appear in one copy each on the symbiotic plasmid and do not hybridize to the Rhizobium meliloti common nodulation region. They comprise two separate transcriptional units coding for about 450 and 950 nucleotides, both of which are transcribed in the same direction. The two open reading frames are separated by 586 base pairs, and the 5H regions of the two genes show a common sequence. No similarity was found with the promoter areas of Rhizobium trifolii, R. meliloti, or Bradyrhizobium japonicum nif genes and with any known nodulation genes. Regions homologous to both sequences were detected in EcoRI digests of genomic DNAs from B. japonicum USDA 110, USDA 122, and 61A76, but not in genomic DNA from R. trifolii, Rhizobium leguminosarum, or Rhizobium phaseoli. Mass spectrometry and nuclear magnetic resonance analysis indicated that the inducing compound has properties of 4',7-dihydroxyisoflavone, daidzein. These results suggest that, in addition to common nodulation genes, several other genes appear to be specifically induced by compounds in the root exudate of the host plants. Images PMID:2447061

  17. Benzene solubility in ionic liquids: working toward an understanding of liquid clathrate formation.

    PubMed

    Pereira, Jorge F B; Flores, Luis A; Wang, Hui; Rogers, Robin D

    2014-11-17

    The solubility of benzene in 15 imidazolium, pyrrolidinium, pyridinium, and piperidinium ionic liquids has been determined; the resulting, benzene-saturated ionic liquid solutions, also known as liquid clathrates, were examined with (1) H and (19) F nuclear magnetic resonance spectroscopy to try and understand the molecular interactions that control liquid clathrate formation. The results suggest that benzene interacts primarily with the cation of the ionic liquid, and that liquid clathrate formation (and benzene solubility) is controlled by the strength of the cation-anion interactions, that is, the stronger the cation-anion interaction, the lower the benzene solubility. Other factors that were determined to be important in the final amount of benzene in any given liquid clathrate phase included attractive interactions between the anion and benzene (when significant), and larger steric or free volume demands of the ions, both of which lead to greater benzene solubility.

  18. Physicochemical Nature of Perfluoroalkyl Compounds Induced by Fluorine.

    PubMed

    Hasegawa, Takeshi

    2017-05-09

    Perfluoroalkyl (Rf ) compounds have unique characters represented by a significantly high hydrophobic property, which often makes us consider that Rf groups should be interacted with each other via the 'hydrophobic interaction' as found for a normal hydrocarbon. Due to a similar intuitive and simplistic speculation, the Rf -specific material properties have long been enveloped in darkness for comprehensive understanding, which should lucidly be discussed within a framework of physical chemistry. Here, we show studies on the stratified dipole arrays (SDA) theory, which readily explains the Rf -specific material characters in a comprehensive manner based on only a few fundamental physical parameters of fluorine. The SDA theory encompasses some conventional theories that account for only a part of material properties. In addition, we show that the concept of vibrational spectroscopy of Rf compounds should also be revised, since the mass of fluorine is larger than that of carbon, which is opposite to the hydrocarbon case. In this manner, chemistry of Rf compounds needs another fully revised concept, which cannot be replaced by an extended concept of normal hydrocarbon compounds. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions

    NASA Astrophysics Data System (ADS)

    Nagashima, Hironori D.; Takeya, Satoshi; Uchida, Tsutomu; Ohmura, Ryo

    2016-01-01

    To investigate the preservation of CO2 clathrate hydrate in the presence of sugar for the novel frozen dessert, mass fractions of CO2 clathrate hydrate in CO2 clathrate hydrate samples coexisting with trehalose were intermittently measured. The samples were prepared from trehalose aqueous solution with trehalose mass fractions of 0.05 and 0.10 at 3.0 MPa and 276.2 K. The samples having particle sizes of 1.0 mm and 5.6–8.0 mm were stored at 243.2 K and 253.2 K for three weeks under atmospheric pressure. The mass fractions of CO2 clathrate hydrate in the samples were 0.87–0.97 before the preservation, and CO2 clathrate hydrate still remained 0.56–0.76 in the mass fractions for 5.6–8.0 mm samples and 0.37–0.55 for 1.0 mm samples after the preservation. The preservation in the trehalose system was better than in the sucrose system and comparable to that in the pure CO2 clathrate hydrate system. This comparison indicates that trehalose is a more suitable sugar for the novel frozen carbonated dessert using CO2 clathrate hydrate than sucrose in terms of CO2 concentration in the dessert. It is inferred that existence of aqueous solution in the samples is a significant factor of the preservation of CO2 clathrate hydrate in the presence of sugar.

  20. Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions

    PubMed Central

    Nagashima, Hironori D.; Takeya, Satoshi; Uchida, Tsutomu; Ohmura, Ryo

    2016-01-01

    To investigate the preservation of CO2 clathrate hydrate in the presence of sugar for the novel frozen dessert, mass fractions of CO2 clathrate hydrate in CO2 clathrate hydrate samples coexisting with trehalose were intermittently measured. The samples were prepared from trehalose aqueous solution with trehalose mass fractions of 0.05 and 0.10 at 3.0 MPa and 276.2 K. The samples having particle sizes of 1.0 mm and 5.6–8.0 mm were stored at 243.2 K and 253.2 K for three weeks under atmospheric pressure. The mass fractions of CO2 clathrate hydrate in the samples were 0.87–0.97 before the preservation, and CO2 clathrate hydrate still remained 0.56–0.76 in the mass fractions for 5.6–8.0 mm samples and 0.37–0.55 for 1.0 mm samples after the preservation. The preservation in the trehalose system was better than in the sucrose system and comparable to that in the pure CO2 clathrate hydrate system. This comparison indicates that trehalose is a more suitable sugar for the novel frozen carbonated dessert using CO2 clathrate hydrate than sucrose in terms of CO2 concentration in the dessert. It is inferred that existence of aqueous solution in the samples is a significant factor of the preservation of CO2 clathrate hydrate in the presence of sugar. PMID:26780867

  1. Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions.

    PubMed

    Nagashima, Hironori D; Takeya, Satoshi; Uchida, Tsutomu; Ohmura, Ryo

    2016-01-19

    To investigate the preservation of CO2 clathrate hydrate in the presence of sugar for the novel frozen dessert, mass fractions of CO2 clathrate hydrate in CO2 clathrate hydrate samples coexisting with trehalose were intermittently measured. The samples were prepared from trehalose aqueous solution with trehalose mass fractions of 0.05 and 0.10 at 3.0 MPa and 276.2 K. The samples having particle sizes of 1.0 mm and 5.6-8.0 mm were stored at 243.2 K and 253.2 K for three weeks under atmospheric pressure. The mass fractions of CO2 clathrate hydrate in the samples were 0.87-0.97 before the preservation, and CO2 clathrate hydrate still remained 0.56-0.76 in the mass fractions for 5.6-8.0 mm samples and 0.37-0.55 for 1.0 mm samples after the preservation. The preservation in the trehalose system was better than in the sucrose system and comparable to that in the pure CO2 clathrate hydrate system. This comparison indicates that trehalose is a more suitable sugar for the novel frozen carbonated dessert using CO2 clathrate hydrate than sucrose in terms of CO2 concentration in the dessert. It is inferred that existence of aqueous solution in the samples is a significant factor of the preservation of CO2 clathrate hydrate in the presence of sugar.

  2. Snowball Earth termination by destabilization of equatorial permafrost methane clathrate.

    PubMed

    Kennedy, Martin; Mrofka, David; von der Borch, Chris

    2008-05-29

    The start of the Ediacaran period is defined by one of the most severe climate change events recorded in Earth history--the recovery from the Marinoan 'snowball' ice age, approximately 635 Myr ago (ref. 1). Marinoan glacial-marine deposits occur at equatorial palaeolatitudes, and are sharply overlain by a thin interval of carbonate that preserves marine carbon and sulphur isotopic excursions of about -5 and +15 parts per thousand, respectively; these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise. This abrupt transition records a climate system in profound disequilibrium and contrasts sharply with the cyclical stratigraphic signal imparted by the balanced feedbacks modulating Phanerozoic deglaciation. Hypotheses accounting for the abruptness of deglaciation include ice albedo feedback, deep-ocean out-gassing during post-glacial oceanic overturn or methane hydrate destabilization. Here we report the broadest range of oxygen isotope values yet measured in marine sediments (-25 per thousand to +12 per thousand) in methane seeps in Marinoan deglacial sediments underlying the cap carbonate. This range of values is likely to be the result of mixing between ice-sheet-derived meteoric waters and clathrate-derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater. The equatorial palaeolatitude implies a highly volatile shelf permafrost pool that is an order of magnitude larger than that of the present day. A pool of this size could have provided a massive biogeochemical feedback capable of triggering deglaciation and accounting for the global postglacial marine carbon and sulphur isotopic excursions, abrupt unidirectional warming, cap carbonate deposition, and a marine oxygen crisis. Our findings suggest that methane released from low-latitude permafrost clathrates therefore acted as a trigger and/or strong positive feedback for deglaciation and warming. Methane hydrate

  3. Models of a partially hydrated Titan interior with clathrate crust

    NASA Astrophysics Data System (ADS)

    Lunine, J. I.; Castillo-Rogez, J.

    2012-04-01

    We present an updated model of the interior evolution of Titan over time, assuming the silicate core was hydrated early in Titan's history and is dehydrating over time. The original model presented in Castillo-Rogez and Lunine (2010) was motivated by a Cassini-derived moment of inertia (Iess et al., 2010) for Titan too large to be accommodated by classical fully differentiated models in which an anhydrous silicate core was overlain by a water ice (with possible perched ocean) mantle. Our model consisted of a silicate core still in the process of dehydrating today, a situation made possible by the leaching of radiogenic potassium from the silicates into the liquid water ocean. The crust of Titan was assumed to be pure water ice I. The model was consistent with the moment of inertia of Titan, but neglected the presence of large amounts of methane in the upper crust invoked to explain methane's persistence at present and through geologic time (Tobie et al. 2006). We have updated our model with such a feature. We have also improved our modeling with a better physical model for the dehydration of antigorite and other hydrated minerals. In particular our modeling now simulates heat advection resulting from water circulation (e.g., Seipold and Schilling 2003), rather than the purely conductive heat transfer regime assumed in the first version of our model. The modeling proceeds as in Castillo-Rogez and Lunine (2010), with the thermal conductivity of the methane clathrate crust rather than that of ice I. The former is several times lower than that of the latter, and the two have rather different temperature dependences (English and Tse, 2009). The crust turns out to have essentially no bearing on the temperature of the silicate core and hence the timing of dehydration, but it profoundly affects the thickness of the high-pressure ice layer beneath the ocean. Indeed, with the insulating methane clathrate crust, there must be a liquid water ocean beneath the methane clathrate

  4. Vacancy and copper-doping effect on superconductivity for clathrate materials

    NASA Astrophysics Data System (ADS)

    Li, Yang; Liu, Yang; Chen, Ning; Cao, Guohui; Feng, Zhaosheng; Ross, Joseph H.

    2005-10-01

    We present a joint experimental and theoretical study of the superconductivity and electronic structures in type-I Cu-doped silicon clathrates and germanium clathrates. The superconducting critical temperature in Ba8Si46 xCux is shown to decrease strongly with copper content increasing. These results are corroborated by CASTEP approach, first-principles simulations calculated from the density-functional theory with plane waves and pseudopotentials. The simulations show that Cu-doping results in a large decrease of electronic density of states in Fermi level, which can explain the superconducting critical temperature decrease with Cu-doping in the BCS theoretical frame. Further, comparison of Ba8Ge46 and Ba8Si46 within the CASTEP approach shows that the superconductivity is an intrinsic property of the sp silicon and germanium clathrates without vacancy in the cage framework. By analysis of the density of states (DOS) and reported experimental results of the Zintl-like Ba8Ge43, a new mechanism of vacancy defect is suggested to explain the absence of superconductivity in Ge clathrates, which is of benefit to eliminating the divarication between theoretical prediction and the experimental observation for superconductivity in Ge clathrates. Keeping an entire Si and Ge cage structure without vacancy is the prerequisite for occurrence of superconductivity in clathrates.

  5. Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs

    NASA Technical Reports Server (NTRS)

    Blake, D. F.; Allamandola, L. J.; Sandford, S.; Hudgins, D.; Freund, F.

    1991-01-01

    In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.

  6. Radiation induced chemical changes of phenolic compounds in strawberries

    NASA Astrophysics Data System (ADS)

    Breitfellner, F.; Solar, S.; Sontag, G.

    2003-06-01

    In unirradiated strawberries four phenolic acids (gallic acid, p-coumaric acid, caffeic acid and 4-hydroxybenzoic acid), the flavonoids (+)-catechin, (-)-epicatechin and glycosides from kaempferol and quercetin were determined by reversed phase chromatography with diode array detection. Characteristic linear dose/concentration relationships were found for 4-hydroxybenzoic acid and two unidentified compounds. One of them may be usable as marker to prove an irradiation treatment.

  7. Residual entropy of ices and clathrates from Monte Carlo simulation

    SciTech Connect

    Kolafa, Jiří

    2014-05-28

    We calculated the residual entropy of ices (Ih, Ic, III, V, VI) and clathrates (I, II, H), assuming the same energy of all configurations satisfying the Bernal–Fowler ice rules. The Metropolis Monte Carlo simulations in the range of temperatures from infinity to a size-dependent threshold were followed by the thermodynamic integration. Convergence of the simulation and the finite-size effects were analyzed using the quasichemical approximation and the Debye–Hückel theory applied to the Bjerrum defects. The leading finite-size error terms, ln N/N, 1/N, and for the two-dimensional square ice model also 1/N{sup 3/2}, were used for an extrapolation to the thermodynamic limit. Finally, we discuss the influence of unequal energies of proton configurations.

  8. High-Pressure Torsion to Improve Thermoelectric Efficiency of Clathrates?

    NASA Astrophysics Data System (ADS)

    Yan, X.; Falmbigl, M.; Rogl, G.; Grytsiv, A.; Prokofiev, A.; Bauer, E.; Rogl, P.; Zehetbauer, M.; Paschen, S.

    2013-07-01

    High-pressure torsion (HPT), as a technique to produce severe plastic deformation, has been proven effective to improve the thermoelectric performance of skutterudites. In this report, we present microstructural and thermoelectric properties of the clathrate Ba8Cu3.5Ge41In1.5 processed by HPT. The sample was synthesized from high-purity elements, subsequently annealed, ball milled, and hot pressed, and finally subject to HPT. Compared with the ball-milled and hot-pressed sample, the HPT-processed sample has higher electrical resistivity and Seebeck coefficient, and lower thermal conductivity, electron concentration, and mobility, which is attributed to the reduced grain size and increased density of dislocations, point defects, and cracks. No essential improvement of the dimensionless thermoelectric figure of merit is observed in the investigated temperature range, questioning the universal versatility of this technique for improvement of thermoelectric materials.

  9. CO2 and clathrate as past erosive agents on Mars

    NASA Technical Reports Server (NTRS)

    Lambert, R. ST.J.; Chamberlain, V. E.

    1992-01-01

    The debate on the history of the Martian atmosphere continues without resolution. Much hinges on a satisfactory solution to the problem of what liquid was responsible for the extensive development of canyons, channels, fretted terrain, and similar features. The 1960s and 1970s saw much debate about the roles of various fluids, namely water or brine, liquid CO2, or H2O sources in CO2 clathrate (CC), or magma. The last was discounted long ago, CC is largely ignored, and the most recent look at CO2 was by ourselves, utilizing the phase diagrams for the CO2-H2O system. In this article, we will further investigate this dilemma.

  10. Novel Glycopyrrolidine Compounds Inhibit Human Cancer Cell Proliferation and Induce Apoptotic Mode of Cell Death.

    PubMed

    Bhoopalan, Hemadev; Tentu, Shilpa; R, Prasana; S, Purushothaman; Venu, Akkanapally; Raghunathan, Ragavachary; Pakala, Suresh Babu; Rayala, Suresh Kumar; Venkatraman, Ganesh

    2017-04-21

    Spirocyclic compounds, present in a number of bioactive natural alkaloids, are cyclic systems containing one carbon atom common to two rings. A highly regioselective glycopyrrolidine compound library was synthesized using 1,3-dipolar cycloaddition method, and its efficacy was tested on cell lines representing most commonly occurring cancers and the molecular mechanism of cell death deciphered. Results showed that among the 16 compounds screened, RPRR210 showed the most potent anticancer activity and induced cell cycle arrest, inhibited migration, caused cell death by inducing apoptosis through the intrinsic pathway, and were nontoxic to normal cells.

  11. Compound

    NASA Astrophysics Data System (ADS)

    Suzumura, Akitoshi; Watanabe, Masaki; Nagasako, Naoyuki; Asahi, Ryoji

    2014-06-01

    Recently, Cu-based chalcogenides such as Cu3SbSe4, Cu2Se, and Cu2SnSe3 have attracted much attention because of their high thermoelectric performance and their common feature of very low thermal conductivity. However, for practical use, materials without toxic elements such as selenium are preferable. In this paper, we report Se-free Cu3SbS4 thermoelectric material and improvement of its figure of merit ( ZT) by chemical substitutions. Substitutions of 3 at.% Ag for Cu and 2 at.% Ge for Sb lead to significant reductions in the thermal conductivity by 37% and 22%, respectively. These substitutions do not sacrifice the power factor, thus resulting in enhancement of the ZT value. The sensitivity of the thermal conductivity to chemical substitutions in these compounds is discussed in terms of the calculated phonon dispersion and previously proposed models for Cu-based chalcogenides. To improve the power factor, we optimize the hole carrier concentration by substitution of Ge for Sb, achieving a power factor of 16 μW/cm K2 at 573 K, which is better than the best reported for Se-based Cu3SbSe4 compounds.

  12. Hydroxyl radical-induced formation of highly oxidized organic compounds.

    PubMed

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V; Kjaergaard, Henrik G; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-12-02

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere.

  13. Hydroxyl radical-induced formation of highly oxidized organic compounds

    PubMed Central

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-01-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere. PMID:27910849

  14. Hydroxyl radical-induced formation of highly oxidized organic compounds

    NASA Astrophysics Data System (ADS)

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-12-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere.

  15. (N2)6Ne7: A High Pressure van der Waals Insertion Compound

    NASA Astrophysics Data System (ADS)

    Plisson, Thomas; Weck, Gunnar; Loubeyre, Paul

    2014-07-01

    The binary phase diagram of N2-Ne mixtures has been measured at 296 K by visual observation and Raman spectroscopy. The topology of the phase diagram points to the existence of the stoichiometric compound (N2)6Ne7. Its structure has been solved by single-crystal synchrotron x-ray diffraction. The N2 molecules form a guest lattice that hosts the Ne atoms. This insertion compound can be viewed as a clathrate with the centers of the N2 molecules forming distorted dodecahedron cages, each enclosing 14 Ne atoms. Remarkably, the (N2)6Ne7 compound is somehow the first clathrate organized by the quadrupolar interaction.

  16. (N(2))(6)Ne(7): A high pressure van der Waals insertion compound.

    PubMed

    Plisson, Thomas; Weck, Gunnar; Loubeyre, Paul

    2014-07-11

    The binary phase diagram of N(2)-Ne mixtures has been measured at 296 K by visual observation and Raman spectroscopy. The topology of the phase diagram points to the existence of the stoichiometric compound N(2))(6)Ne(7). Its structure has been solved by single-crystal synchrotron x-ray diffraction. The N(2) molecules form a guest lattice that hosts the Ne atoms. This insertion compound can be viewed as a clathrate with the centers of the N(2) molecules forming distorted dodecahedron cages, each enclosing 14 Ne atoms. Remarkably, the N(2))(6)Ne(7) compound is somehow the first clathrate organized by the quadrupolar interaction.

  17. Direct measurements of the interactions between clathrate hydrate particles and water droplets.

    PubMed

    Liu, Chenwei; Li, Mingzhong; Zhang, Guodong; Koh, Carolyn A

    2015-08-14

    Clathrate hydrate particle agglomeration is often considered to be one of the key limiting factors in plug formation. The hydrate particle-water interaction can play a critical role in describing hydrate agglomeration, yet is severely underexplored. Therefore, this work investigates the interactions between water droplets and cyclopentane hydrate particles using a micromechanical force (MMF) apparatus. Specifically, the effect of contact time, temperature/subcooling, contact area, and the addition of Sorbitane monooleate (Span 80) surfactant on the water droplet-hydrate particle interaction behavior are studied. The measurements indicate that hydrate formation during the measurement would increase the water-hydrate interaction force significantly. The results also indicate that the contact time, subcooling and concentration of cyclopentane, which determine the hydrate formation rate and hydrate amount, will affect the hydrate-water interaction force. In addition, the interaction forces also increase with the water-hydrate contact area. The addition of Span 80 surfactant induces a change in the hydrate morphology and renders the interfaces stable versus unstable (leading to coalescence), and the contact force can affect the hydrate-water interaction behavior significantly. Compared with the hydrate-hydrate cohesion force (measured in cyclopentane), the hydrate-water adhesion force is an order of magnitude larger. These new measurements can help to provide new and critical insights into the hydrate agglomeration process and potential strategies to control this process.

  18. Radioactive-induced tumors by phosphorus-32 as colloidal compound

    SciTech Connect

    Ubios, A.M.; Silberman, F.S.; Cabrini, R.L.

    1983-05-01

    Chromic colloidal phosphate labeled with 32P, which has been proposed for the treatment of several articular diseases, was injected intra-articularly in the knee joint of adult Wistar rats. After a 270 days minimum latent period, tumors began to appear in the injected zone, to a 70% frequency. Ten lung metastases were detected. In five cases, squamous cell carcinomas were induced in the injected area. The relevance of a sound evaluation of the risk involved in treatments with radioactive isotopes, is discussed.

  19. Competition between the compound and the pre-compound emission processes in α-induced reactions at near astrophysical energy to well above it

    NASA Astrophysics Data System (ADS)

    Sharma, Manoj Kumar; Sharma, Vijay Raj; Yadav, Abhiskek; Singh, Pushpendra P.; Singh, B. P.; Prasad, R.

    2016-04-01

    The study of pre-compound emission in α-induced reactions, particularly at the low incident energies, is of considerable interest as the pre-compound emission is more likely to occur at higher energies. With a view to study the competition between the compound and the pre-compound emission processes in α-induced reactions at different energies and with different targets, a systematics for neutron emission channels in targets 51V, 55Mn, 93Nb, 121, 123Sb and 141Pr at energy ranging from astrophysical interest to well above it, has been developed. The off-line γ-ray-spectrometry based activation technique has been adopted to measure the excitation functions. The experimental excitation functions have been analysed within the framework of the compound nucleus mechanism based on the Weisskopf-Ewing model and the pre-compound emission calculations based on the geometry dependent hybrid model. The analysis of the data shows that experimental excitation functions could be reproduced only when the pre-compound emission, simulated theoretically, is taken into account. The strength of pre-compound emission process for each system has been obtained by deducing the pre-compound fraction. Analysis of data indicates that in α-induced reactions, the pre-compound emission process plays an important role, particularly at the low incident energies, where the pure compound nucleus process is likely to dominate.

  20. The effect of classical and quantum dynamics on vibrational frequency shifts of H2 in clathrate hydrates.

    PubMed

    Plattner, Nuria; Meuwly, Markus

    2014-01-14

    Vibrational frequency shifts of H2 in clathrate hydrates are important to understand the properties and elucidate details of the clathrate structure. Experimental spectra of H2 in clathrate hydrates have been measured for different clathrate compositions, temperatures, and pressures. In order to establish reliable relationships between the clathrate structure, dynamics, and observed frequencies, calculations of vibrational frequency shifts in different clathrate environments are required. In this study, a combination of classical molecular dynamics simulations, electronic structure calculations, and quantum dynamical simulation is used to calculate relative vibrational frequencies of H2 in clathrate hydrates. This approach allows us to assess dynamical effects and simulate the change of vibrational frequencies with temperature and pressure. The frequency distributions of the H2 vibrations in the different clathrate cage types agree favorably with experiment. Also, the simulations demonstrate that H2 in the 5(12) cage is more sensitive to the details of the environment and to quantum dynamical effects, in particular when the cage is doubly occupied. We show that for the 5(12) cage quantum effects lead to frequency increases and double occupation is unlikely. This is different for the 5(12)6(4) cages for which higher occupation numbers than one H2 per cage are likely.

  1. Mechanism of Clathrate Formation through Binding Nature of Si-X and Ge-X dimers: ab initio Study

    NASA Astrophysics Data System (ADS)

    Tsumuraya, Kazuo; Eguchi, Haruki; Takenaka, Hiroyuki; Suzuki, Akihiko

    2003-03-01

    The Si-clathrates have been synthesized when alkaline or alkaline-earth atoms are coexisted with the host Si atoms, which is also the case for the Ge-clathrates. The I-encapsulating Si-clathrates have been also synthesized recently. In the case of the hydrate clathrates, the formation has been controlled by both the sizes and the hydrophobic interactions of the endohedral molecules.[1] We study the mechanism of the clathrate formation through the binding nature of the Si-X and Ge-X dimmers, where X is selected elements in the periodic table. We calculate the charge transfers (population analysis), the binding energies, and the bonding distances using the ab-initio molecular dynamics method with planewaves and pseudo-potentials. We discuss the mechanism of the formation comparing with that of hydrate clathrates and evaluate the stability of clathrates predicted by the present study. [1]E.Dendy Sloan,Jr, Clathrate Hydrates of Natural Gasses, Marcel Dekker, 1998.

  2. The effect of classical and quantum dynamics on vibrational frequency shifts of H{sub 2} in clathrate hydrates

    SciTech Connect

    Plattner, Nuria; Meuwly, Markus

    2014-01-14

    Vibrational frequency shifts of H{sub 2} in clathrate hydrates are important to understand the properties and elucidate details of the clathrate structure. Experimental spectra of H{sub 2} in clathrate hydrates have been measured for different clathrate compositions, temperatures, and pressures. In order to establish reliable relationships between the clathrate structure, dynamics, and observed frequencies, calculations of vibrational frequency shifts in different clathrate environments are required. In this study, a combination of classical molecular dynamics simulations, electronic structure calculations, and quantum dynamical simulation is used to calculate relative vibrational frequencies of H{sub 2} in clathrate hydrates. This approach allows us to assess dynamical effects and simulate the change of vibrational frequencies with temperature and pressure. The frequency distributions of the H{sub 2} vibrations in the different clathrate cage types agree favorably with experiment. Also, the simulations demonstrate that H{sub 2} in the 5{sup 12} cage is more sensitive to the details of the environment and to quantum dynamical effects, in particular when the cage is doubly occupied. We show that for the 5{sup 12} cage quantum effects lead to frequency increases and double occupation is unlikely. This is different for the 5{sup 12}6{sup 4} cages for which higher occupation numbers than one H{sub 2} per cage are likely.

  3. The mechanism of alcoholic beverage induced superconductivity in Fe-chalcogenide compounds

    NASA Astrophysics Data System (ADS)

    Deguchi, Keita; Demura, Satoshi; Okazaki, Hiroyuki; Denholme, Saleem; Fujioka, Masaya; Ozaki, Toshinori; Yamaguchi, Takahide; Takeya, Hiroyuki; Takano, Yoshihiko

    2013-03-01

    We have clarified the mechanism of alcoholic beverage induced superconductivity in Fe-chalcogenide compounds. Previously we reported that the bulk superconductivity in Fe-based compounds Fe(Te, Se) and Fe(Te, S) is achieved by heating in alcoholic beverages. However, the exact mechanism of how they act to enhance the superconductivity in the compounds remains unsolved. To understand the effect of alcoholic beverage treatment, we investigated the mechanism using a technology of metabolomic analysis. We found that weak acid in alcoholic beverages has the ability to deintercalate the excess Fe, which is not in favor of superconductivity. In this presentation, we will discuss the systematic mechanism to induce superconductivity in Fe-chalcogenide compounds.

  4. Anti-inflammatory and Quinone Reductase Inducing Compounds from Fermented Noni (Morinda citrifolia) Juice Exudates.

    PubMed

    Youn, Ui Joung; Park, Eun-Jung; Kondratyuk, Tamara P; Sang-Ngern, Mayuramas; Wall, Marisa M; Wei, Yanzhang; Pezzuto, John M; Chang, Leng Chee

    2016-06-24

    A new fatty acid ester disaccharide, 2-O-(β-d-glucopyranosyl)-1-O-(2E,4Z,7Z)-deca-2,4,7-trienoyl-β-d-glucopyranose (1), a new ascorbic acid derivative, 2-caffeoyl-3-ketohexulofuranosonic acid γ-lactone (2), and a new iridoid glycoside, 10-dimethoxyfermiloside (3), were isolated along with 13 known compounds (4-16) from fermented noni fruit juice (Morinda citrifolia). The structures of the new compounds, together with 4 and 5, were determined by 1D and 2D NMR experiments, as well as comparison with published values. Compounds 2 and 7 showed moderate inhibitory activities in a TNF-α-induced NF-κB assay, and compounds 4 and 6 exhibited considerable quinone reductase-1 (QR1) inducing effects.

  5. Type I clathrates as novel silicon anodes: An electrochemical and structural investigation

    SciTech Connect

    Li, Ying; Raghavan, Rahul; Wagner, Nicholas A.; Davidowski, Stephen K.; Baggetto, Loic; Zhao, Ran; Cheng, Qian; Yarger, Jeffery L.; Veith, Gabriel M.; Ellis-Terrell, Carol; Miller, Michael A.; Chan, Kwai S.; Chan, Candace K.

    2015-05-05

    In this study, silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. Here we present an electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46-y for the anode material in lithium-ion batteries. Post-cycling characterization with NMR and XRD show no discernible structural or volume changes even after electrochemical insertion of 44 Li into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from larger volume changes. The lithiation/delithiation processes are proposed to occur in single phase reactions at approximately 0.2 and 0.4 V vs. Li/Li+, respectively, distinct from other diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g-1 at a 5 mA g-1 rate were observed for silicon clathrate with composition Ba8Al8.54Si37.46, corresponding to Li:Si of 1.18:1. The results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

  6. Type I clathrates as novel silicon anodes: An electrochemical and structural investigation

    DOE PAGES

    Li, Ying; Raghavan, Rahul; Wagner, Nicholas A.; ...

    2015-05-05

    In this study, silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. Here we present an electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46-y for the anode material in lithium-ion batteries. Post-cycling characterization with NMR and XRD show no discernible structural or volume changes even after electrochemical insertion of 44 Li into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from larger volume changes. The lithiation/delithiation processes are proposed to occur in single phase reactions at approximately 0.2 and 0.4 Vmore » vs. Li/Li+, respectively, distinct from other diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g-1 at a 5 mA g-1 rate were observed for silicon clathrate with composition Ba8Al8.54Si37.46, corresponding to Li:Si of 1.18:1. The results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.« less

  7. A model for the formation and stabilization of charged water clathrates

    NASA Technical Reports Server (NTRS)

    Holland, P. M.; Castleman, A. W., Jr.

    1980-01-01

    A model for the formation and stabilization of charged water clathrates is presented which accounts for observed anomalies in H(+)(H2O)n ion distributions. These anomalies are observed in both ion cluster and neutral expansions and are consistent with the sizes expected for clathrate ions. That the same sizes are observed in both ion cluster and neutral expansions strongly suggests that a rapid ionic process is responsible for their formation. The proposed model is based on the high mobility and bonding effects of the excess proton in water. Computer simulations suggest that excess proton movement in a water clathrate would be suitable for stabilizing the clathrate structure as well as giving it access to a large number of nearly degenerate proton configurations. The formation of clathrates in charged water clusters of proper size can be ascribed to the following: rapid excess proton movement, a strong preference of the H3O(+) for a three-coordinate bonding structure (which is compatible with hydrogen bonding), and finally, relatively slow processes leading to thermal disorder.

  8. The inhibition of tetrahydrofuran clathrate-hydrate formation with antifreeze protein

    NASA Astrophysics Data System (ADS)

    Zeng, H.; Wilson, L. D.; Walker, V. K.; Ripmeester, J. A.

    2003-01-01

    The effect of Type I fish antifreeze protein (AFP) from the winter flounder, Pleuronectes americanus (Walbaum), (WfAFP) on the formation of tetrahydrofuran (THF) clathrate hydrate was studied by observing changes in THF crystal morphology and determining the induction time for nucleation. AFP retarded THF clathrate-hydrate growth at the tested temperatures and modified the THF clathrate-hydrate crystal morphology from octahedral to plate-like. AFP appears to be even more effective than the kinetic inhibitor, polyvinylpyrrolidone (PVP). Recombinant AFP from an insect, a spruce budworm, Choristoneura fumiferana (Clem.), moth, (Cf) was also tested for inhibition activity by observation of the THF-hydrate-crystal-growth habit. Like WfAFP, CfAFP appeared to show adsorption on multiple THF-hydrate-crystal faces. A protein with no antifreeze activity, cytochrome C, was used as a control and it neither changed the morphology of the THF clathrate-hydrate crystals, nor retarded the formation of the hydrate. Preliminary experiments on the inhibition activity of WfAFP on a natural gas hydrate assessed induction time and the amount of propane gas consumed. Similar to the observations for THF, the data indicated that WfAFP inhibited propane-hydrate growth. Taken together, these results support our hypothesis that AFPs can inhibit clathrate-hydrate growth and as well, offer promise for the understanding of the inhibition mechanism.

  9. Gas-Phase Synthesis and Characterization of CH4-Loaded Hydroquinone Clathrates

    SciTech Connect

    Lee, J.; Lee, Y; Takeya, S; Kawamura, T; Yamamoto, Y; Lee, Y; Yoon, J

    2010-01-01

    A CH{sub 4}-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the {alpha}-form of crystalline HQ and CH{sub 4} gas at 12 MPa and room temperature. Solid-state {sup 13}C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH{sub 4} molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH{sub 4} molecules, that is, 0.69 CH{sub 4} per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH{sub 4}-loaded HQ clathrate adopts the {beta}-form of HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 {angstrom} and c = 5.5038 {angstrom}. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH{sub 4}-loaded HQ clathrate is stable up to 368 K and gradually transforms to the {alpha}-form by releasing the confined CH{sub 4} gases between 368-378 K. Using solid-state {sup 13}C CP/MAS NMR, the reaction kinetics between the {alpha}-form HQ and CH{sub 4} gas is qualitatively described in terms of the particle size of the crystalline HQ.

  10. Gas-phase synthesis and characterization of CH4-loaded hydroquinone clathrates.

    PubMed

    Lee, Jong-Won; Lee, Yongjae; Takeya, Satoshi; Kawamura, Taro; Yamamoto, Yoshitaka; Lee, Yun-Je; Yoon, Ji-Ho

    2010-03-11

    A CH(4)-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the alpha-form of crystalline HQ and CH(4) gas at 12 MPa and room temperature. Solid-state (13)C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH(4) molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH(4) molecules, that is, 0.69 CH(4) per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH(4)-loaded HQ clathrate adopts the beta-form of HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 A and c = 5.5038 A. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH(4)-loaded HQ clathrate is stable up to 368 K and gradually transforms to the alpha-form by releasing the confined CH(4) gases between 368-378 K. Using solid-state (13)C CP/MAS NMR, the reaction kinetics between the alpha-form HQ and CH(4) gas is qualitatively described in terms of the particle size of the crystalline HQ.

  11. A model for the formation and stabilization of charged water clathrates

    NASA Technical Reports Server (NTRS)

    Holland, P. M.; Castleman, A. W., Jr.

    1980-01-01

    A model for the formation and stabilization of charged water clathrates is presented which accounts for observed anomalies in H(+)(H2O)n ion distributions. These anomalies are observed in both ion cluster and neutral expansions and are consistent with the sizes expected for clathrate ions. That the same sizes are observed in both ion cluster and neutral expansions strongly suggests that a rapid ionic process is responsible for their formation. The proposed model is based on the high mobility and bonding effects of the excess proton in water. Computer simulations suggest that excess proton movement in a water clathrate would be suitable for stabilizing the clathrate structure as well as giving it access to a large number of nearly degenerate proton configurations. The formation of clathrates in charged water clusters of proper size can be ascribed to the following: rapid excess proton movement, a strong preference of the H3O(+) for a three-coordinate bonding structure (which is compatible with hydrogen bonding), and finally, relatively slow processes leading to thermal disorder.

  12. Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization

    NASA Astrophysics Data System (ADS)

    Prokofiev, A.; Yan, X.; Ikeda, M.; Löffler, S.; Paschen, S.

    2014-09-01

    We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46-x and Ba8Cu4.8GaxGe41.2-x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41 and Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.

  13. Influence of gravitational potential on the thermodynamic stability of pure and mixed clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Lasich, Matthew; Ramjugernath, Deresh

    2017-05-01

    Clathrate hydrates are an ice-like material consisting of gas molecules confined within cavities in a crystalline water lattice. Phase equilibria of clathrate hydrates systems was described using the statistical mechanical theory of van der Waals and Platteeuw. This theory makes use of the fractional occupancy of cavities within the clathrate hydrate lattice in the determination of chemical equilibria. Classical density functional theory with intermolecular interactions restricted to the first hydration shell was employed to determine the fractional occupancy. In addition to the external field describing the gas-water interactions, the effect of a gravitational field was introduced. The results of the calculations show that although the gravitational potential term may be orders of magnitude smaller than the thermal kinetic energy of the gas species or the hydrogen-bond energy holding the clathrate lattice together, it can nevertheless influence the phase equilibrium of the clathrate hydrate system to some degree. The effect of the magnitudes of both the gravitational potential and the local gravitational field are considered too.

  14. Computational study on the antifreeze glycoproteins as inhibitors of clathrate-hydrate formation.

    PubMed

    Cruz-Torres, Armando; Romero-Martínez, Ascención; Galano, Annia

    2008-08-04

    The ability of antifreeze glycoproteins to inhibit clathrate-hydrate formation is studied using DFT. A 5(12) cavity, dodecahedral (H(2)O)(20), and the AATA peptide are used to model the inhibitor-clathrate interaction. The presence of AATA in the vicinity of the water cavities not only leads to the formation of complexes, with different peptide/cavity ratios, but also to the deformation of the cavity and to the elongation of several of the hydrogen bonds responsible for keeping the dodecahedral (H(2)O)(20) together. The complexes are formed through hydrogen bonding between the peptides and the water cavities. The glycoproteins are expected to anchor onto the clathrate surface, blocking the access of new water molecules and preventing the incipient crystals from growing. They are also expected to weaken the clathrate structure. Amide IR bands are associated with the complexes' formation. They are significantly red-shifted in the hydrogen-bonded systems compared to isolated AATA. The amide A band is the most sensitive to hydrogen bonding. In addition a distinctive band around 3100 cm(-1) is proposed for the identification of clathrate-peptide hydrogen-bonded complexes.

  15. Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation.

    PubMed

    Li, Ying; Raghavan, Rahul; Wagner, Nicholas A; Davidowski, Stephen K; Baggetto, Loïc; Zhao, Ran; Cheng, Qian; Yarger, Jeffery L; Veith, Gabriel M; Ellis-Terrell, Carol; Miller, Michael A; Chan, Kwai S; Chan, Candace K

    2015-06-01

    Silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8Al y Si46-y as the anode material for lithium-ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X-ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li(+) during lithiation and delithiation, respectively, distinct from diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g-(1) at a 5 mA g(-1) rate were observed for silicon clathrate with composition Ba8Al8.54Si37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

  16. High temperature thermoelectric transport properties of p-type Ba8Ga16AlxGe30-x type-I clathrates with high performance

    NASA Astrophysics Data System (ADS)

    Deng, Shukang; Tang, Xinfeng; Li, Peng; Zhang, Qingjie

    2008-04-01

    Using group-III atom Al as doping element, Ba8Ga16AlxGe30-x (x =1.0, 2.0, 3.0, 4.0, and 5.0) type-I clathrates with different Al content were synthesized by combining melting reaction with spark plasma sintering method. The effects of Al content on thermoelectric properties are investigated. X-ray diffraction patterns and Rietveld analysis reveal that the compounds prepared by this method are type-I clathrates and Al atom preference for the 6c site. The Al substitutions do not affect the atomic displacement parameters (ADPs) of framework atoms (Ge/Ga) and filled atoms (Ba) compared to that of Ba8Ga16Ge30, and the ADPs of Al are nearly equivalent to that of other framework Ge /Ga atoms. All specimens exhibit the behavior of the p-type conduction. The carrier concentration and electrical conductivity increase while Seebeck coefficient decreases with the increasing Al content for the specimens with ⩽4.0. Ba8Ga16Al3.0Ge27.0 compound possesses the relatively lower lattice thermal conductivity κL due to the mass fluctuation between Al atoms and other atoms in the framework; it is as low as 0.96W/mK at 300K. The maximum ZT value of 0.61 is obtained at 760K for Ba8Ga16Al3.0Ge27.0.

  17. HPHT synthesis, structure and electrical properties of type-I clathrates Ba{sub 8}Al{sub x}Si{sub 46−x}

    SciTech Connect

    Liu, Binwu; Jia, Xiaopeng; Sun, Hairui; Sun, Bing; Zhang, Yuewen; Liu, Haiqiang; Kong, Lingjiao; Huo, Dexuan; Ma, Hongan

    2016-01-15

    Clathrate compounds Ba{sub 8}Al{sub x}Si{sub 46−x} were successfully synthesized using the method of high-pressure and high-temperature (HPHT). In this process, we used BaSi{sub 2} as one of the starting materials in place of Ba metals, which reduces the complexity of the program caused by the extremely high chemical reactivity. By using this method, the processing time was reduced from few days to an hour. X-ray diffraction and structural refinement indicated this composition crystallized in type-I clathrate phase. Bond length analysis showed the Ba atoms in small dodecahedron had spherical thermal ellipsoids while those in large tetrakaidecahedron displayed anisotropic thermal ellipsoids. The negative Seebeck coefficient indicated transport processes were dominated by electrons as carriers, and increased with the increasing temperature. The electrical properties, including Seebeck coefficient and Power factor, were greatly enhanced by Al substitution. - Graphical abstract: Left: The cavity structure diagram of a China-type large volume cubic high-pressure apparatus, and the Type-I clathrate structure of sample synthesized using HPHT. Middle: X-ray Rietveld refinement profile for Ba{sub 8}Si{sub 46} and element mapping for Ba{sub 8}Al{sub 16}Si{sub 30}. Right: Temperature dependence of Seebeck coefficient for Ba{sub 8}Al{sub x}Si{sub 46−x} prepared by HPHT. - Highlights: • HPHT is a simple and rapid synthetic approach. • We use BaSi{sub 2} as one of the starting materials replacing Ba metals. • The processing time reduces from few days to an hour. • Structure determination is refined by Rietveld analysis of XRD data. • Variable temperature electrical properties are characterized.

  18. Monte Carlo calculations of the free energy of binary sII hydrogen clathrate hydrates for identifying efficient promoter molecules.

    PubMed

    Atamas, Alexander A; Cuppen, Herma M; Koudriachova, Marina V; de Leeuw, Simon W

    2013-01-31

    The thermodynamics of binary sII hydrogen clathrates with secondary guest molecules is studied with Monte Carlo simulations. The small cages of the sII unit cell are occupied by one H(2) guest molecule. Different promoter molecules entrapped in the large cages are considered. Simulations are conducted at a pressure of 1000 atm in a temperature range of 233-293 K. To determine the stabilizing effect of different promoter molecules on the clathrate, the Gibbs free energy of fully and partially occupied sII hydrogen clathrates are calculated. Our aim is to predict what would be an efficient promoter molecule using properties such as size, dipole moment, and hydrogen bonding capability. The gas clathrate configurational and free energies are compared. The entropy makes a considerable contribution to the free energy and should be taken into account in determining stability conditions of binary sII hydrogen clathrates.

  19. Ultrafast laser induced local magnetization dynamics in Heusler compounds

    NASA Astrophysics Data System (ADS)

    Elliott, P.; Müller, T.; Dewhurst, J. K.; Sharma, S.; Gross, E. K. U.

    2016-12-01

    The overarching goal of the field of femtomagnetism is to control, via laser light, the magnetic structure of matter on a femtosecond time scale. The temporal limits to the light-magnetism interaction are governed by the fact that the electron spin interacts indirectly with light, with current studies showing a laser induced global loss in the magnetic moment on a time scale of the order of a few 100 s of femtoseconds. In this work, by means of ab-initio calculations, we show that more complex magnetic materials - we use the example of the Heusler and half-Heusler alloys - allow for purely optical excitations to cause a significant change in the local moments on the order of 5 fs. This, being purely optical in nature, represents the ultimate mechanism for the short time scale manipulation of spins. Furthermore, we demonstrate that qualitative behaviour of this rich magnetic response to laser light can be deduced from the ground-state spectrum, thus providing a route to tailoring the response of some complex magnetic materials, like the Heuslers, to laser light by the well established methods for material design from ground-state calculations.

  20. Ultrafast laser induced local magnetization dynamics in Heusler compounds

    PubMed Central

    Elliott, P.; Müller, T.; Dewhurst, J. K.; Sharma, S.; Gross, E. K. U.

    2016-01-01

    The overarching goal of the field of femtomagnetism is to control, via laser light, the magnetic structure of matter on a femtosecond time scale. The temporal limits to the light-magnetism interaction are governed by the fact that the electron spin interacts indirectly with light, with current studies showing a laser induced global loss in the magnetic moment on a time scale of the order of a few 100 s of femtoseconds. In this work, by means of ab-initio calculations, we show that more complex magnetic materials - we use the example of the Heusler and half-Heusler alloys - allow for purely optical excitations to cause a significant change in the local moments on the order of 5 fs. This, being purely optical in nature, represents the ultimate mechanism for the short time scale manipulation of spins. Furthermore, we demonstrate that qualitative behaviour of this rich magnetic response to laser light can be deduced from the ground-state spectrum, thus providing a route to tailoring the response of some complex magnetic materials, like the Heuslers, to laser light by the well established methods for material design from ground-state calculations. PMID:27966585

  1. Calculation of radiation damage induced by neutrons in compound materials

    NASA Astrophysics Data System (ADS)

    Lunéville, L.; Simeone, D.; Jouanne, C.

    2006-07-01

    Many years have been devoted to study the behaviour of solids submitted to impinging particles like ions or neutrons. The nuclear evaluations describe more and more accurately the various neutron-atom interactions. Anisotropic neutron-atom cross-sections are now available for many elements. Moreover, clear mathematical formalism now allows to calculate the number of displacements per atom in polyatomic targets in a realistic way using the binary collision approximation (BCA) framework. Even if these calculations do not take into account relaxation processes at the end of the displacement spike, they can be used to compare damages induced by different facilities like pressurized water reactors (PWR), fast breeder reactors (FBR), high temperature reactors (HTR) and fusion facilities like the European Spallation Source (ESS) and the International Fusion Material Irradiation Facility (IFMIF) on a defined material. In this paper, a formalism is presented to describe the neutron-atom cross-section and primary recoil spectra taking into account the anisotropy of nuclear reactions extracted from nuclear evaluations. Such a formalism permitted to compute displacement per atom production rate, primary and weighted recoil spectra within the BCA. The multigroup approximation has been used to calculate displacement per atom production rate and recoil spectra for a define nuclear reactor. All these informations are useful to compare recoil spectra and displacement per atom production rate produced by particle accelerator and nuclear reactor.

  2. Ultrafast laser induced local magnetization dynamics in Heusler compounds.

    PubMed

    Elliott, P; Müller, T; Dewhurst, J K; Sharma, S; Gross, E K U

    2016-12-14

    The overarching goal of the field of femtomagnetism is to control, via laser light, the magnetic structure of matter on a femtosecond time scale. The temporal limits to the light-magnetism interaction are governed by the fact that the electron spin interacts indirectly with light, with current studies showing a laser induced global loss in the magnetic moment on a time scale of the order of a few 100 s of femtoseconds. In this work, by means of ab-initio calculations, we show that more complex magnetic materials - we use the example of the Heusler and half-Heusler alloys - allow for purely optical excitations to cause a significant change in the local moments on the order of 5 fs. This, being purely optical in nature, represents the ultimate mechanism for the short time scale manipulation of spins. Furthermore, we demonstrate that qualitative behaviour of this rich magnetic response to laser light can be deduced from the ground-state spectrum, thus providing a route to tailoring the response of some complex magnetic materials, like the Heuslers, to laser light by the well established methods for material design from ground-state calculations.

  3. Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

    DOEpatents

    Marling, John B.

    1981-01-01

    A method for producing a deuterium enriched material by photoinduced dissociation which uses as the working material a gas phase photolytically dissociable organic carbonyl compound containing at least one hydrogen atom bonded to an atom which is adjacent to a carbonyl group and consisting of molecules wherein said hydrogen atom is present as deuterium and molecules wherein said hydrogen atom is present as another isotope of hydrogen. The organic carbonyl compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of the deuterium containing species to yield a deuterium enriched stable molecular product. Undissociated carbonyl compound, depleted in deuterium, is preferably redeuterated for reuse.

  4. Phenolic compounds from Pueraria lobata protect PC12 cells against Aβ-induced toxicity.

    PubMed

    Choi, Yun-hyeok; Hong, Seong Su; Shin, Yu Su; Hwang, Bang Yeon; Park, So-Young; Lee, Dongho

    2010-10-01

    Bioassay-guided fractionation of the EtOAc-soluble extract of Pueraria lobata based on the inhibition of Aβ-induced toxicity in PC12 cells resulted in the isolation of four known active compounds, genistein (8), biochanin A (9), sissotrin (10), and puerol B (11). Of these, genistein (8) and biochanin A (9) exhibited potent neuroprotective effects with ED(50) values of 33.7 and 27.8 μM, respectively. In addition, a new coumestan, 2-(α,α-dimethylallyl)coumestrol (1) was isolated and characterized, but proved to be inactive, as were additional seven known compounds. The structure of new compound 1 was determined using spectroscopic techniques.

  5. Study of irradiation-induced amorphization in intermetallic compounds

    SciTech Connect

    Koike, J.

    1989-01-01

    Irradiation-induced amorphization was studied in situ in the high voltage electron microscope interfaced to a tandem accelerator. Variation of elastic properties during irradiation was studied with Brillouin scattering spectroscopy, and its relation to amorphization were explored. Four important topics were investigated. (1) The temperature dependence of the critical dose for amorphization and its correlation with chemical disordering were studied in CuTi and Zr{sub 3}Al with 1-MeV electron irradiation from 10 to 295 K. Similar temperature dependence was observed in CuTi between the critical dose for amorphization and the chemical disordering rate. Chemical disordering is a major driving force for amorphization. The critical dose for amorphization of Zr{sub 3}Al was twenty times larger than that of CuTi and attributed to the differences in point defect mobility and ordering energy. (2) Projectile mass dependence of amorphization behavior was studied in CuTi irradiated with Ne{sup +},Kr{sup +},Xe{sup +}ions. The dose dependence of the amorphous volume fraction indicated that with increasing mass from Ne{sup +} to Kr{sup +} amorphization kinetics changes from the cascade overlap to the direct-impact amorphization. In relation to the kinetics variation, the critical temperature increased with increasing projectile mass and explained in terms of the thermal stability of the primary damage. (3) Effects of simultaneous and sequential irradiation with Kr+ and electrons were studied in CuTi and Zr{sub 3}Al. Both additive and retardation effects were observed depending on temperature and the electron-to-Kri dose rate ratio and explained as the interaction between point defects and cascade damages. (4) Study of elastic properties during Kr{sup +} irradiation revealed that in FeTi, a large dilation and shear modulus softening accompanied with chemical disordering preceded amorphization, but not observed in NiAl.

  6. Thermodynamic stability and growth of guest-free clathrate hydrates: a low-density crystal phase of water.

    PubMed

    Jacobson, Liam C; Hujo, Waldemar; Molinero, Valeria

    2009-07-30

    We use molecular dynamics simulations with the monatomic water (mW) model to investigate the phase diagram, metastability, and growth of guest-free water clathrates of structure sI and sII. At 1 atm pressure, the simulated guest-free water clathrates are metastable with respect to ice and stable with respect to the liquid up to their melting temperatures, 245+/-2 and 252+/-2 K for sI and sII, respectively. We characterize the growth of the sI and sII water crystals from supercooled water and find that the clathrates are unable to nucleate ice, the stable crystal. We computed the phase relations of ice, guest-free sII clathrate, and liquid water from -1500 to 500 atm. The resulting phase diagram indicates that empty sII may be the stable phase of water at pressures lower than approximately -1300 atm and temperatures lower than 275 K. The simulations show that, even in the region of stability of the empty clathrates, supercooled liquid water crystallizes to ice. This suggests that the barrier for nucleation of ice is lower than that for clathrates. We find no evidence for the existence of the characteristic polyhedral clathrate cages in supercooled extended water. Our results show that clathrates do not need the presence of a guest molecule to grow, but they need the guest to nucleate from liquid water. We conclude that nucleation of empty clathrates from supercooled liquid water would be extremely challenging if not impossible to attain in experiments. We propose two strategies to produce empty water clathrates in laboratory experiments at low positive pressures.

  7. Anchored clathrate waters bind antifreeze proteins to ice.

    PubMed

    Garnham, Christopher P; Campbell, Robert L; Davies, Peter L

    2011-05-03

    The mechanism by which antifreeze proteins (AFPs) irreversibly bind to ice has not yet been resolved. The ice-binding site of an AFP is relatively hydrophobic, but also contains many potential hydrogen bond donors/acceptors. The extent to which hydrogen bonding and the hydrophobic effect contribute to ice binding has been debated for over 30 years. Here we have elucidated the ice-binding mechanism through solving the first crystal structure of an Antarctic bacterial AFP. This 34-kDa domain, the largest AFP structure determined to date, folds as a Ca(2+)-bound parallel beta-helix with an extensive array of ice-like surface waters that are anchored via hydrogen bonds directly to the polypeptide backbone and adjacent side chains. These bound waters make an excellent three-dimensional match to both the primary prism and basal planes of ice and in effect provide an extensive X-ray crystallographic picture of the AFPice interaction. This unobstructed view, free from crystal-packing artefacts, shows the contributions of both the hydrophobic effect and hydrogen bonding during AFP adsorption to ice. We term this mode of binding the "anchored clathrate" mechanism of AFP action.

  8. Anchored Clathrate Waters Bind Antifreeze Proteins to Ice

    SciTech Connect

    C Garnham; R Campbell; P Davies

    2011-12-31

    The mechanism by which antifreeze proteins (AFPs) irreversibly bind to ice has not yet been resolved. The ice-binding site of an AFP is relatively hydrophobic, but also contains many potential hydrogen bond donors/acceptors. The extent to which hydrogen bonding and the hydrophobic effect contribute to ice binding has been debated for over 30 years. Here we have elucidated the ice-binding mechanism through solving the first crystal structure of an Antarctic bacterial AFP. This 34-kDa domain, the largest AFP structure determined to date, folds as a Ca{sup 2+}-bound parallel beta-helix with an extensive array of ice-like surface waters that are anchored via hydrogen bonds directly to the polypeptide backbone and adjacent side chains. These bound waters make an excellent three-dimensional match to both the primary prism and basal planes of ice and in effect provide an extensive X-ray crystallographic picture of the AFP{vert_ellipsis}ice interaction. This unobstructed view, free from crystal-packing artefacts, shows the contributions of both the hydrophobic effect and hydrogen bonding during AFP adsorption to ice. We term this mode of binding the 'anchored clathrate' mechanism of AFP action.

  9. Clathrate Structure Determination by Combining Crystal Structure Prediction with Computational and Experimental (129) Xe NMR Spectroscopy.

    PubMed

    Selent, Marcin; Nyman, Jonas; Roukala, Juho; Ilczyszyn, Marek; Oilunkaniemi, Raija; Bygrave, Peter J; Laitinen, Risto; Jokisaari, Jukka; Day, Graeme M; Lantto, Perttu

    2017-01-23

    An approach is presented for the structure determination of clathrates using NMR spectroscopy of enclathrated xenon to select from a set of predicted crystal structures. Crystal structure prediction methods have been used to generate an ensemble of putative structures of o- and m-fluorophenol, whose previously unknown clathrate structures have been studied by (129) Xe NMR spectroscopy. The high sensitivity of the (129) Xe chemical shift tensor to the chemical environment and shape of the crystalline cavity makes it ideal as a probe for porous materials. The experimental powder NMR spectra can be used to directly confirm or reject hypothetical crystal structures generated by computational prediction, whose chemical shift tensors have been simulated using density functional theory. For each fluorophenol isomer one predicted crystal structure was found, whose measured and computed chemical shift tensors agree within experimental and computational error margins and these are thus proposed as the true fluorophenol xenon clathrate structures.

  10. Mechanism of Rare Earth Incorporation and Crystal Growth of Rare Earth Containing Type-I Clathrates

    PubMed Central

    2015-01-01

    Type-I clathrates possess extremely low thermal conductivities, a property that makes them promising materials for thermoelectric applications. The incorporation of cerium into one such clathrate has recently been shown to lead to a drastic enhancement of the thermopower, another property determining the thermoelectric efficiency. Here we explore the mechanism of the incorporation of rare earth elements into type-I clathrates. Our investigation of the crystal growth and the composition of the phase Ba8–xRExTMySi46–y (RE = rare earth element; TM = Au, Pd, Pt) reveals that the RE content x is mainly governed by two factors, the free cage space and the electron balance. PMID:26823658

  11. Do clathrate hydrates have any influence on the atmosphere of Mars?

    NASA Astrophysics Data System (ADS)

    Thomas, C.; Mousis, O.; Picaud, S.; Ballenegger, V.; Schmitt, B.

    2008-09-01

    Introduction Recent observations have evidenced traces of methane (CH4) heterogeneously distributed in the Martian atmosphere [1]. However, because the lifetime of CH4 in the atmosphere of Mars is estimated to be around 250-430 years on the basis of gas-phase chemistry [1], its actual sources on Mars remain controversial. Among other assumptions, it has been proposed [2] that clathrate hydrates located in the subsurface of Mars could be at the origin of the small quantities of CH4 detected. In the present work, we have calculated the relative abundance of CH4 in clathrate hydrates on Mars, using a statistical model based on the theory of van der Waals and Platteeuw [3]. Thermodynamic approach To calculate the relative abundance of CH4 incorporated in clathrates formed from the martian atmosphere, we use the same approach as in our previous studies devoted to the trapping of gases by clathrates on Titan [4][5]. This approach is based on the statistical model proposed by van der Waals and Platteuw [3] and it is only briefly summarized here. In this formalism, the relative abundance fG of a guest species G in a clathrate (of structure I or II) is defined as the ratio of the average number of guest molecules of species G in the clathrate over the average total number of enclathrated molecules, as : fG = bLyG;L + bSyG;S bL P J yJ;L + bS P J yJ;S ; (1) where the sums in the denominator run over all species present in the system, and bS and bL are the number of small and large cages per unit cell, respectively. The occupancy fractions yG of the guest species G for a given type of cage and for a given type of clathrate are determined from the Langmuir constants which are related to the strength of the interaction between each guest species and each type of cage. Thus, this statistical approach relies on the accurate determination of the interactions between the guest species G and the water molecules forming the surrounding cage. In a first approximation, this cage is

  12. Stable low-pressure hydrogen clusters stored in a binary clathrate hydrate.

    PubMed

    Florusse, Louw J; Peters, Cor J; Schoonman, Joop; Hester, Keith C; Koh, Carolyn A; Dec, Steven F; Marsh, Kenneth N; Sloan, E Dendy

    2004-10-15

    Thermodynamic, x-ray diffraction, and Raman and nuclear magnetic resonance spectroscopy measurements show that clusters of H2 can be stabilized and stored at low pressures in a sII binary clathrate hydrate. Clusters of H2 molecules occupy small water cages, whereas large water cages are singly occupied by tetrahydrofuran. The presence of this second guest component stabilizes the clathrate at pressures of 5 megapascals at 279.6 kelvin, versus 300 megapascals at 280 kelvin for pure H2 hydrate.

  13. Water cavities of sH clathrate hydrate stabilized by molecular hydrogen: phase equilibrium measurements.

    PubMed

    Duarte, Ana Rita C; Shariati, Alireza; Rovetto, Laura J; Peters, Cor J

    2008-02-21

    In this experimental phase equilibrium study, we show for the first time that it is possible to stabilize structure sH of hydrogen clathrate hydrate with the help of some selected promoters. It was established that the formation pressures of these systems are significantly higher than that of structure sII of hydrogen clathrate hydrate when tetrahydrofuran (THF) is used as a promoter. Although no experimental evidence is available yet, it is estimated that the hydrogen storage capacity of structure sH can be as high as 1.4 wt % of H2, which is about 40% higher compared to the hydrogen storage capacity in structure sII.

  14. Measurement of Clathrate Hydrate Thermodynamic Stability in the Presence of Ammonia

    NASA Technical Reports Server (NTRS)

    Dunham, Marc

    2012-01-01

    There is a lack of data available for the stability of clathrate hydrates in the presence of ammonia for low-to-moderate pressures in the 0-10 MPa range. Providing such data will allow for a better understanding of natural mass transfer processes on celestial bodies like Titan and Enceladus, on which destabilization of clathrates may be responsible for replenishment of gases in the atmosphere. The experimental process utilizes a custom-built gas handling system (GHS) and a cryogenic calorimeter to allow for the efficient testing of samples under varying pressures and gas species.

  15. Measurement of Clathrate Hydrate Thermodynamic Stability in the Presence of Ammonia

    NASA Technical Reports Server (NTRS)

    Dunham, Marc

    2012-01-01

    There is a lack of data available for the stability of clathrate hydrates in the presence of ammonia for low-to-moderate pressures in the 0-10 MPa range. Providing such data will allow for a better understanding of natural mass transfer processes on celestial bodies like Titan and Enceladus, on which destabilization of clathrates may be responsible for replenishment of gases in the atmosphere. The experimental process utilizes a custom-built gas handling system (GHS) and a cryogenic calorimeter to allow for the efficient testing of samples under varying pressures and gas species.

  16. Cationic clathrate I Si(46-x)P(x)Te(y) (6.6(1) < or = y < or = 7.5(1), x < or = 2y): crystal structure, homogeneity range, and physical properties.

    PubMed

    Zaikina, J V; Kovnir, K A; Burkhardt, U; Schnelle, W; Haarmann, F; Schwarz, U; Grin, Yu; Shevelkov, A V

    2009-04-20

    A new cationic clathrate I Si(46-x)P(x)Te(y) (6.6(1) < or = y < or = 7.5(1), x < or = 2y at 1375 K) was synthesized from the elements and characterized by X-ray powder diffraction, thermal analysis, scanning electron microscopy, wavelength dispersive X-ray spectroscopy (WDXS), neutron powder diffraction, and (31)P NMR spectroscopy. The thermal behaviors of the magnetic susceptibility and resistivity were investigated as well. Si(46-x)P(x)Te(y) reveals a wide homogeneity range due to the presence of vacancies in the tellurium guest positions inside the smaller cage of the clathrate I structure. The vacancy ordering in the structure of Si(46-x)P(x)Te(y) causes the change of space group from Pm3n (ideal clathrate I) to Pm3 accompanied by the redistribution of P and Si atoms over different framework positions. Neutron powder diffraction confirmed that P atoms preferably form a cage around the vacancy-containing tellurium guest position. Additionally, (31)P NMR spin-spin relaxation experiments revealed the presence of sites with different coordination of phosphorus atoms. Precise determination of the composition of Si(46-x)P(x)Te(y) by WDXS showed slight but noticeable deviation (x < or = 2y) of phosphorus content from the Zintl counting scheme (x = 2y). The compound is diamagnetic while resistivity measurements show activated behavior or that of heavily doped semiconductors. Thermal analysis revealed high stability of the investigated clathrate: Si(46-x)P(x)Te(y) melts incongruently at approximately 1460 K in vacuum and is stable in air against oxidation up to 1295 K.

  17. Tunable ultraviolet laser-induced fluorescence detection of trace plastics and dissolved organic compounds in water.

    PubMed

    Sivaprakasam, Vasanthi; Killinger, Dennis K

    2003-11-20

    We developed a tunable (220-285-nm) UV and fixed 266-nm laser-induced fluorescence (LIF) system using a spectrometer and a cooled CCD imaging detector to measure the excitation-emission matrix spectra of various compounds in water, including quinine sulfate and plastic compound bisphenol-A. The LIF instrument was used for the fast, nonspecific determination of trace amounts of dissolved organic compounds present in natural water supplies and various brand name bottled distilled water and bottled drinking water. Plastic-related compounds that leached out of plastic utensils and containers were also detected with this instrument. The sensitivity of the system was approximately 1-2 orders of magnitude better than that for a commercial system.

  18. Tunable ultraviolet laser-induced fluorescence detection of trace plastics and dissolved organic compounds in water

    NASA Astrophysics Data System (ADS)

    Sivaprakasam, Vasanthi; Killinger, Dennis K.

    2003-11-01

    We developed a tunable (220-285-nm) UV and fixed 266-nm laser-induced fluorescence (LIF) system using a spectrometer and a cooled CCD imaging detector to measure the excitation-emission matrix spectra of various compounds in water, including quinine sulfate and plastic compound bisphenol-A. The LIF instrument was used for the fast, nonspecific determination of trace amounts of dissolved organic compounds present in natural water supplies and various brand name bottled distilled water and bottled drinking water. Plastic-related compounds that leached out of plastic utensils and containers were also detected with this instrument. The sensitivity of the system was approximately 1-2 orders of magnitude better than that for a commercial system.

  19. Identification of Biologically Relevant Compounds in Aboveground and Belowground Induced Volatile Blends

    PubMed Central

    Qiu, Bao-Li; Hordijk, Cornelis A.; Vet, Louise E. M.; Jansen, Jeroen J.

    2010-01-01

    Plants under attack by aboveground herbivores emit complex blends of volatile organic compounds (VOCs). Specific compounds in these blends are used by parasitic wasps to find their hosts. Belowground induction causes shifts in the composition of aboveground induced VOC blends, which affect the preference of parasitic wasps. To identify which of the many volatiles in the complex VOC blends may explain parasitoid preference poses a challenge to ecologists. Here, we present a case study in which we use a novel bioinformatics approach to identify biologically relevant differences between VOC blends of feral cabbage (Brassica oleracea L.). The plants were induced aboveground or belowground with jasmonic acid (JA) and shoot feeding caterpillars (Pieris brassicae or P. rapae). We used Partial Least Squares—Discriminant Analysis (PLSDA) to integrate and visualize the relation between plant-emitted VOCs and the preference of female Cotesia glomerata. Overall, female wasps preferred JA-induced plants over controls, but they strongly preferred aboveground JA-induced plants over belowground JA-induced plants. PLSDA revealed that the emission of several monoterpenes was enhanced similarly in all JA-treated plants, whereas homoterpenes and sesquiterpenes increased exclusively in aboveground JA-induced plants. Wasps may use the ratio between these two classes of terpenes to discriminate between aboveground and belowground induced plants. Additionally, it shows that aboveground applied JA induces different VOC biosynthetic pathways than JA applied to the root. Our bioinformatic approach, thus, successfully identified which VOCs matched the preferences of the wasps in the various choice tests. Additionally, the analysis generated novel hypotheses about the role of JA as a signaling compound in aboveground and belowground induced responses in plants. PMID:20737198

  20. The strength and rheology of methane clathrate hydrate

    USGS Publications Warehouse

    Durham, W.B.; Kirby, S.H.; Stern, L.A.; Zhang, W.

    2003-01-01

    Methane clathrate hydrate (structure I) is found to be very strong, based on laboratory triaxial deformation experiments we have carried out on samples of synthetic, high-purity, polycrystalline material. Samples were deformed in compressional creep tests (i.e., constant applied stress, ??), at conditions of confining pressure P = 50 and 100 MPa, strain rate 4.5 ?? 10-8 ??? ?? ??? 4.3 ?? 10-4 s-1, temperature 260 ??? T ??? 287 K, and internal methane pressure 10 ??? PCH4 ??? 15 MPa. At steady state, typically reached in a few percent strain, methane hydrate exhibited strength that was far higher than expected on the basis of published work. In terms of the standard high-temperature creep law, ?? = A??ne-(E*+PV*)/RT the rheology is described by the constants A = 108.55 MPa-n s-1, n = 2.2, E* = 90,000 J mol-1, and V* = 19 cm3 mol-1. For comparison at temperatures just below the ice point, methane hydrate at a given strain rate is over 20 times stronger than ice, and the contrast increases at lower temperatures. The possible occurrence of syntectonic dissociation of methane hydrate to methane plus free water in these experiments suggests that the high strength measured here may be only a lower bound. On Earth, high strength in hydrate-bearing formations implies higher energy release upon decomposition and subsequent failure. In the outer solar system, if Titan has a 100-km-thick near-surface layer of high-strength, low-thermal conductivity methane hydrate as has been suggested, its interior is likely to be considerably warmer than previously expected.

  1. Measurements of clathrate-hydrate film thickness using laser interferometry

    NASA Astrophysics Data System (ADS)

    Ohmura, Ryo; Kashiwazaki, Shigetoyo; Mori, Yasuhiko H.

    2000-09-01

    Using a laser interferometer having a resolution of ˜1 μm, we directly measured the thicknesses of clathrate-hydrate films at the planar interface between a liquid hydrofluorocarbon, R-134a (CH 2FCF 3), and liquid water. The interferometer was mounted on a specially designed, pressure- and temperature-controlled cell filled with both liquids. After a hydrate film was formed with either pure water having no prior contact with R-134a or water presaturated with R-134a, we made a series of intermittent measurements until the film was aged up to 150 h. For hydrate films formed with pure water held at a large subcooling (˜7 K) below the triple (liquid-R-134a/hydrate/liquid-water) equilibrium temperature, the initial thickness was ˜10 μm. This thickness was maintained for a few tens of hours; then it gradually increased, reaching ˜30 μm 100 h after the film formed. With pure water at a smaller subcooling (≲2 K), the thickness of hydrate films was initially as large as ˜80 μm; it rapidly decreased to 15-20 μm and then increased to 30-40 μm 150 h after the film formed. With presaturated water at small subcoolings (≲2 K), each hydrate film was a mosaic of polygonal hydrate crystal plates. Each plate was several millimeters wide and 20-170 μm thick. No measurement could be made with presaturated water at a large subcooling (≳6 K) because of sword-like hydrate crystals that have grown in crowds into the water phase from the hydrate film surface.

  2. Cryolava flow destabilization of crustal methane clathrate hydrate on Titan

    NASA Astrophysics Data System (ADS)

    Davies, Ashley Gerard; Sotin, Christophe; Choukroun, Mathieu; Matson, Dennis L.; Johnson, Torrence V.

    2016-08-01

    To date, there has been no conclusive observation of ongoing endogenous volcanic activity on Saturn's moon Titan. However, with time, Titan's atmospheric methane is lost and must be replenished. We have modeled one possible mechanism for the replenishment of Titan's methane loss. Cryolavas can supply enough heat to release large amounts of methane from methane clathrate hydrates (MCH). The volume of methane released is controlled by the flow thickness and its areal extent. The depth of the destabilisation layer is typically ≈30% of the thickness of the lava flow (≈3 m for a 10-m thick flow). For this flow example, a maximum of 372 kg of methane is released per m2 of flow area. Such an event would release methane for nearly a year. One or two events per year covering ∼20 km2 would be sufficient to resupply atmospheric methane. A much larger effusive event covering an area of ≈9000 km2 with flows 200 m thick would release enough methane to sustain current methane concentrations for 10,000 years. The minimum size of "cryo-flows" sufficient to maintain the current atmospheric methane is small enough that their detection with current instruments (e.g., Cassini) could be challenging. We do not suggest that Titan's original atmosphere was generated by this mechanism. It is unlikely that small-scale surface MCH destabilisation is solely responsible for long-term (> a few Myr) sustenance of Titan's atmospheric methane, but rather we present it as a possible contributor to Titan's past and current atmospheric methane.

  3. The Phenomenology of Ion Implantation-Induced Blistering and Thin-Layer Splitting in Compound Semiconductors

    NASA Astrophysics Data System (ADS)

    Singh, R.; Christiansen, S. H.; Moutanabbir, O.; Gösele, U.

    2010-10-01

    Hydrogen and/or helium implantation-induced surface blistering and layer splitting in compound semiconductors such as InP, GaAs, GaN, AlN, and ZnO are discussed. The blistering phenomenon depends on many parameters such as the semiconductor material, ion fluence, ion energy, and implantation temperature. The optimum values of these parameters for compound semiconductors are presented. The blistering and splitting processes in silicon have been studied in detail, motivated by the fabrication of the widely used silicon-on-insulator wafers. Hence, a comparison of the blistering process in Si and compound semiconductors is also presented. This comparative study is technologically relevant since ion implantation-induced layer splitting combined with direct wafer bonding in principle allows the transfer of any type of semiconductor layer onto any foreign substrate of choice—the technique is known as the ion-cut or Smart-Cut™ method. For the aforementioned compound semiconductors, investigations regarding layer transfer using the ion-cut method are still in their infancy. We report feasibility studies of layer transfer by the ion-cut method for some of the most important and widely used compound semiconductors. The importance of characteristic values for successful wafer bonding such as wafer bow and surface flatness as well as roughness are discussed, and difficulties in achieving some of these values are pointed out.

  4. Potential for ion-induced nucleation of volatile organic compounds by radon decay in indoor environments

    SciTech Connect

    Daisey, J.M.

    1991-11-01

    There is considerable interest in the unattached'' fraction of radon progeny in indoor air because of its significance to the estimation of the risks of radon exposure. Because of its high mobility in air, the unattached fraction is more efficiently deposited in the respiratory tract. Variation in the diameter of the unattached'' fraction and in its diffusion coefficient can be due to clustering of other atmospheric species around the {sup 218}PoO{sub 2}{sup +} ion. The purpose of this study was to investigate the potential for the formation of clusters of vapor phase organic compounds, found in indoor air, around the {sup 218}PoO{sub 2}{sup +} ion and to determine which were most likely to form clusters. A secondary purpose was to provide a compilation of measurements of indoor organic compounds for future experiments and theoretical calculations by the radon research community. The classical charged liquid droplet theory (Thomson equation) was used to estimate the Gibbs free energy of ion-induced nucleation and to provide an indication of the indoor organic compounds most likely to undergo ion-induced nucleation. Forty-four volatile and semi-volatile organic compounds out of the more than 300 which have been reported in indoor air were investigated. Water vapor was included for comparison. The results indicate that there is a potential for the formation of clusters of organic compounds around the {sup 218}PoO{sub 2}{sup +} ion. The compounds with the greatest potential for cluster formation are the volatile oxidized hydrocarbons (e.g., n-butanol, phenol, hexanal, nonanal, benzaldehyde, the ketones and the acetates) and the semi-volatile organic compounds (pentachlorophenol, nicotine, chlordane, chlorpyrifos).

  5. Potential for ion-induced nucleation of volatile organic compounds by radon decay in indoor environments

    SciTech Connect

    Daisey, J.M.

    1991-11-01

    There is considerable interest in the ``unattached`` fraction of radon progeny in indoor air because of its significance to the estimation of the risks of radon exposure. Because of its high mobility in air, the unattached fraction is more efficiently deposited in the respiratory tract. Variation in the diameter of the ``unattached`` fraction and in its diffusion coefficient can be due to clustering of other atmospheric species around the {sup 218}PoO{sub 2}{sup +} ion. The purpose of this study was to investigate the potential for the formation of clusters of vapor phase organic compounds, found in indoor air, around the {sup 218}PoO{sub 2}{sup +} ion and to determine which were most likely to form clusters. A secondary purpose was to provide a compilation of measurements of indoor organic compounds for future experiments and theoretical calculations by the radon research community. The classical charged liquid droplet theory (Thomson equation) was used to estimate the Gibbs free energy of ion-induced nucleation and to provide an indication of the indoor organic compounds most likely to undergo ion-induced nucleation. Forty-four volatile and semi-volatile organic compounds out of the more than 300 which have been reported in indoor air were investigated. Water vapor was included for comparison. The results indicate that there is a potential for the formation of clusters of organic compounds around the {sup 218}PoO{sub 2}{sup +} ion. The compounds with the greatest potential for cluster formation are the volatile oxidized hydrocarbons (e.g., n-butanol, phenol, hexanal, nonanal, benzaldehyde, the ketones and the acetates) and the semi-volatile organic compounds (pentachlorophenol, nicotine, chlordane, chlorpyrifos).

  6. Peculiarities of methane clathrate hydrate formation and solid-state deformation, including possible superheating of water ice

    USGS Publications Warehouse

    Stern, L.A.; Kirby, S.H.; Durham, W.B.

    1996-01-01

    Slow, constant-volume heating of water ice plus methane gas mixtures forms methane clathrate hydrate by a progressive reaction that occurs at the nascent ice/liquid water interface. As this reaction proceeds, the rate of melting of metastable water ice may be suppressed to allow short-lived superheating of ice to at least 276 kelvin. Plastic flow properties measured on clathrate test specimens are significantly different from those of water ice; under nonhydrostatic stress, methane clathrate undergoes extensive strain hardening and a process of solid-state disproportionation or exsolution at conditions well within its conventional hydrostatic stability field.

  7. Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems.

    PubMed

    Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A; Alavi, Saman; Ripmeester, John A

    2012-09-11

    There is interest in the role of ammonia on Saturn's moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons' atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods.

  8. Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems

    PubMed Central

    Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A.; Alavi, Saman; Ripmeester, John A.

    2012-01-01

    There is interest in the role of ammonia on Saturn’s moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons’ atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods. PMID:22908239

  9. Selective occupancy of methane by cage symmetry in TBAB ionic clathrate hydrate.

    PubMed

    Muromachi, Sanehiro; Udachin, Konstantin A; Alavi, Saman; Ohmura, Ryo; Ripmeester, John A

    2016-04-25

    Methane trapped in the two distinct dodecahedral cages of the ionic clathrate hydrate of TBAB was studied by single crystal XRD and MD simulation. The relative CH4 occupancies over the cage types were opposite to those of CO2, which illustrates the interplay between the cage symmetry and guest shape and dynamics, and thus the gas selectivity.

  10. REMOVAL OF TITAN'S ATMOSPHERIC NOBLE GASES BY THEIR SEQUESTRATION IN SURFACE CLATHRATES

    SciTech Connect

    Mousis, Olivier; Picaud, Sylvain; Cordier, Daniel; Mandt, Kathleen E.; Hunter Waite, J. Jr.

    2011-10-10

    A striking feature of the atmosphere of Titan is that no heavy noble gases other than argon were detected by the Gas Chromatograph Mass Spectrometer aboard the Huygens probe during its descent to Titan's surface in 2005 January. Here we provide an explanation of the mysterious absence or rarity of these noble gases in Titan's atmosphere: the thermodynamic conditions prevailing at the surface-atmosphere interface of the satellite allow the formation of multiple guest clathrates that preferentially store some species, including all heavy noble gases, over others. The clean water ice needed for the formation of these clathrates could be delivered by successive episodes of cryovolcanic lavas that have been hypothesized to regularly cover the surface of Titan. The formation of clathrates in the porous lavas and their propensity for trapping Ar, Kr, and Xe would progressively remove these species from the atmosphere of Titan over the course of its history. In some circumstances, a global clathrate crust with an average thickness not exceeding a few meters could be sufficient on Titan for a complete removal of the heavy noble gases from the atmosphere.

  11. A simplified Van der Waals-Platteeuw model of clathrate hydrates with multiple occupancy of cavities.

    PubMed

    Martín, Angel

    2010-07-29

    In clathrate hydrates formed by small guest molecules such as H(2) or He, hydrate cavities may be occupied by clusters of several guest molecules. Multiple occupancy of cavities is important for applications of clathrate hydrates as gas storage and transportation media due to the increase of storage capacity of the material associated with multiple occupancy. Computational approaches for clathrate hydrates with multiple occupancy such as Grand Canonical Monte Carlo (GCMC) simulations or van der Waals-Platteeuw (vdW-P) models with rigorous calculations of Langmuir adsorption constants are complex and require considerable computational effort. In this work, a simplified vdW-P model for clathrate hydrates with multiple occupancy is presented. In this model, it is assumed that guest molecules inside cavities form clusters in which molecules occupy fixed positions with respect to each other. For validation of this supposition, results obtained with this model have been compared with GCMC simulations of sII He and H(2) hydrates with multiple occupancy. Results of the simplified procedure presented in this work regarding the fractional occupancy of cavities by molecular clusters agree well with GCMC simulations. The simplified vdW-P model presented in this work requires a small computational effort, equivalent to calculations with the standard vdW-P model for hydrates with single occupancy.

  12. Dynamical interrogation of the hydration cage of bromine in single crystal clathrate hydrates versus water.

    PubMed

    Goldschleger, I U; Kerenskaya, G; Senekerimyan, V; Janda, K C; Apkarian, V A

    2008-12-28

    We report transient grating measurements carried out on single crystals of bromine clathrate hydrates and on bromine dissolved in water. In all cases, excitation into the B-state of Br2 leads to prompt predissociation, followed by cage-induced recombination on the A/A' electronic surfaces. In liquid water, the vibrationally incoherent recombinant population peaks at t=1 ps and decays with a time constant of 1.8 ps. In the hydrate crystals, the recombination is sufficiently impulsive to manifest coherent oscillations of the reformed bond. In tetragonal TS-I crystals, with the smaller cages, the recombination is fast, t=360 fs, and the bond oscillation period is 240 fs. In cubic CS-II crystals, the recombination is slower, t=490 fs, and the visibility of the vibrational coherence, which shows a period of 290 fs, is significantly reduced due to the larger cages and the looser fit around bromine. The mechanical cage effect is quantified in terms of the recombination time-distribution, the first three moments of which are associated with size, structural rigidity, and anelasticity of the cage. In the crystalline cages, the distribution is symmetric about the mean: mean time tm=300 fs, 400 fs and standard deviation sigma=70 fs, 100 fs, in TS-I and CS-II, respectively. The finding is consistent with the assignment of occupied cages: principally 5(12)6(2) polyhedra in TS-I and 5(12)6(4) polyhedra in CS-II. In liquid water, with diffuse cages, the distribution characterized by tm=555 fs and sigma=400 fs, is strongly skewed (gamma1=1.88) toward delayed recombination-the effective liquid phase hydration shell is larger than that in a hydrate phase, structurally disordered, and anelastic. Information about dipolar disorder, comparable in all three media, is extracted from electronic predissociation rates of the B-state, which is sensitive to the symmetry in the guest-host interaction.

  13. Phase behaviour of methane clathrate under conditions relevant to Titan's interior

    NASA Astrophysics Data System (ADS)

    Sclater, G.; Wood, I. G.; Tucker, M. G.; Crawford, I. A.; Fortes, A. D.

    2013-09-01

    Microporous gas hydrates - known as clathrates - are common on the Earth and are also thought to be abundant in the outer Solar System [1]. The conditions for the existence of clathrates prevail throughout the Solar System and they are considered to be abundant from the Martian permafrost to the surfaces and interiors of many icy satellites [7]. These materials have been extensively studied in the range 0 - 5 GPa at ambient temperatures [2-5]; however, their behaviour in the range close to the dissociation (or melting) point is not well known at all, with some suggesting the occurrence of a facecentred cubic (sII) phase, and others that the clathrate becomes unstable with respect to mixtures of solid methane and ice. The high-pressure behaviour underpins planetary modelling; for example, the behaviour of methane hydrate in the ranges 0-6 GPa and 100-400 K is crucial to accurate modelling of Saturn's largest moon, Titan where clathrates are hypothesised to be the source of CH4 in Titan's atmosphere [6]. In order to address these problems we are carrying out a program of investigation using neutron diffraction to investigate the phase behaviour of methane clathrate close to its dissociation temperature in the 0.6-2.5 GPa region. Our goals were to obtain data to provide the first in-situ diffraction-based evidence for the phase behaviour of methane clathrate near to its high-pressure dissociation temperature (along with a control measurement at room temperature for comparison with other workers), to obtain P-V curves along two isotherms for each of the phases observed, and to complete structure refinements of all three clathrate polymorphs, thereby allowing us to carry out a full audit of the methane concentration in each phase as a function of pressure (including cage occupancies). Thus far we have successfully completed our RT measurements and will make the higher temperature observations in July 2013; we anticipate being able to report our findings from this second

  14. Preliminary Comparison of the Attenuation Properties of Polycrystalline Water Ice and CO2 Clathrate Hydrates

    NASA Astrophysics Data System (ADS)

    Choukroun, Mathieu; Castillo-Rogez, J.; Mielke, R. E.; Young, J. B.; Engelhardt, H.; Sotin, C.

    2009-09-01

    We will present measurements of the attenuation properties of CO2 clathrate hydrates and polycrystalline water ice. These laboratory data are necessary to support models of tidal heating within the icy shells of Europa and Enceladus. Particularly, the attenuation properties of clathrates, likely involved in Enceladus’ outgassing, remain unconstrained. Samples are synthesized from ice seeds with a grain size of 150 - 425 microns. Seeds of carbon dioxide clathrate hydrates are synthesized within a high pressure - low temperature vessel, by reaction of CO2 at 30-40 bars with the ice seeds at -10 to -1 °C. Solid samples are produced from the compaction of the seeds at -80 °C, under vacuum and at a 100-MPa pressure applied over several hours. The microstructure of the samples before and after testing is characterized by optical cryo-microscopy and by Cryo - Scanning Electron Microprobe (CryoSEM). The CryoSEM is equipped with an Energy Dispersive Spectrometer, which provides elemental composition of the samples. Microstructural evolution and potential changes in composition resulting from clathrate dissociation can be assessed with these techniques. Cyclic loading measurements are being conducted with the Planetary Tides Simulation Facility at JPL, a cryogenic uniaxial compression system, within the frequency range 3x10-6 - 10-3 Hz, which encompasses the orbital frequencies of Enceladus and Europa. We will compare and contrast the attenuation observed for clathrate hydrates and polycrystalline ice in order to characterize the microstructural mechanisms driving dissipation in these samples. We will address the implications of these new observations in the context of icy satellites. Acknowledgements: MC is supported by a NASA Postdoctoral Program Fellowship, administered by Oak Ridge Associated Universities. This work has been conducted at the Jet Propulsion Laboratory, California Institute of Technology, under contract with NASA. Copyright 2009, California Institute

  15. A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates.

    PubMed

    Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K; Alavi, Saman; Yasuoka, Kenji

    2015-05-21

    Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C5H11OH can be enclosed into the 5(12)6(4) cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates. The simulations clearly showed the formation of guest-host hydrogen bonds and the incorporation of the O-H group of 3-methyl-1-butanol guest molecules into the framework of the sII 5(12)6(4) cages, with the remaining hydrophobic part of the amyl-alcohol molecule well accommodated into the cages. The calculated vibrational spectra of alcohol O-H bonds showed large frequency shifts due to the strong guest-host hydrogen bonding. The 2-methyl-2-butanol guests form strong hydrogen bonds with the cage water molecules in the sH clathrate, but are not incorporated into the water framework. By comparing the structures of the alcohols in the hydrate phases, the effect of the location of O-H groups in the butyl chain of the guest molecules on the crystalline structure of the clathrate hydrates is indicated.

  16. Phenolic compounds isolated from Dioscorea zingiberensis protect against pancreatic acinar cells necrosis induced by sodium taurocholate.

    PubMed

    Du, Dan; Jin, Tao; Zhang, Rui; Hu, Liqiang; Xing, Zhihua; Shi, Na; Shen, Yan; Gong, Meng

    2017-03-15

    One new bibenzyl (1) and one new phenanthrene (2), together with two known bibenzyls (3-4) and four known diarylheptanoids (5-8) were isolated from the rhizomes of Dioscorea zingiberensis. The structures of 1-2 were elucidated by spectroscopic methods including 1D and 2D NMR. Phenols 1-8 were evaluated for their anti-pancreatitic activities on sodium taurocholate (NaT)-induced pancreatic acinars necrosis. Notably, 0.5mM of compound 6 exhibited comparable inhibitory effect with 5mM of caffeine. Furthermore, compound 6 prevented the ATP depletion and excessive ROS production which could be also involved in mitochondria-mediated injuries in acute pancreatitis. As a result, compound 6 has been demonstrated to be a potential candidate for mediating mitochondrial dysfunction to prevent pancreatic necrosis. This study is also the first report on the isolation of bibenzyls and diarylheptanoids from this plant. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Volatile compounds induced by herbivory act as aggregation kairomones for the Japanese beetle (Popillia japonica Newman).

    PubMed

    Loughrin, J H; Potter, D A; Hamilton-Kemp, T R

    1995-10-01

    The Japanese beetle is a polyphagous insect that typically aggregates on preferred host plants in the field. We studied the response of Japanese beetles to artificial damage, fresh feeding damage, and overnight feeding damage to test the hypothesis that beetles are attracted to feeding-induced volatiles. Crabapple leaves that had been damaged overnight by Japanese beetles or fall webworms attracted significantly more Japanese beetles than did undamaged leaves. Artificially damaged leaves or leaves freshly damaged by Japanese beetles, however, were not significantly more attractive than undamaged leaves. Leaves that had been damaged overnight by Japanese beetles or fall webworms produced a complex mixture of aliphatic compounds, phenylpropanoid-derived compounds, and terpenoids. In comparison, artificially damaged leaves or leaves with fresh Japanese beetle feeding damage generated a less complex blend of volatiles, mainly consisting of green-leaf odors. Feeding-induced odors may facilitate host location and/or mate finding by the Japanese beetle.

  18. Pressure-induced anomalous valence crossover in cubic YbCu5-based compounds.

    PubMed

    Yamaoka, Hitoshi; Tsujii, Naohito; Suzuki, Michi-To; Yamamoto, Yoshiya; Jarrige, Ignace; Sato, Hitoshi; Lin, Jung-Fu; Mito, Takeshi; Mizuki, Jun'ichiro; Sakurai, Hiroya; Sakai, Osamu; Hiraoka, Nozomu; Ishii, Hirofumi; Tsuei, Ku-Ding; Giovannini, Mauro; Bauer, Ernst

    2017-07-19

    A pressure-induced anomalous valence crossover without structural phase transition is observed in archetypal cubic YbCu5 based heavy Fermion systems. The Yb valence is found to decrease with increasing pressure, indicating a pressure-induced crossover from a localized 4f (13) state to the valence fluctuation regime, which is not expected for Yb systems with conventional c-f hybridization. This result further highlights the remarkable singularity of the valence behavior in compressed YbCu5-based compounds. The intermetallics Yb2Pd2Sn, which shows two quantum critical points (QCP) under pressure and has been proposed as a potential candidate for a reentrant Yb(2+) state at high pressure, was also studied for comparison. In this compound, the Yb valence monotonically increases with pressure, disproving a scenario of a reentrant non-magnetic Yb(2+) state at the second QCP.

  19. Molecular and crystal structures of noble gas compounds

    NASA Astrophysics Data System (ADS)

    Nabiev, Sh Sh; Sokolov (deceased, V. B.; Chaivanov, B. B.

    2014-12-01

    Data on the structures of xenon and krypton compounds in various physical states are analyzed and generalized. The structures of simple, coordination, polymeric and clathrate-like compounds of these elements with various types of bonds are considered. Characteristic features of their vibrational spectra are discussed in relation to structural transformations caused by cation-anion interactions, structurally non-rigid intramolecular rearrangements and other factors. The bibliography includes 332 references.

  20. Lattice Dynamics Study of Phonon Instability and Thermal Properties of Type-I Clathrate K8Si46 under High Pressure

    PubMed Central

    Zhang, Wei; Zeng, Zhao Yi; Ge, Ni Na; Li, Zhi Guo

    2016-01-01

    For a further understanding of the phase transitions mechanism in type-I silicon clathrates K8Si46, ab initio self-consistent electronic calculations combined with linear-response method have been performed to investigate the vibrational properties of alkali metal K atoms encapsulated type-I silicon-clathrate under pressure within the framework of density functional perturbation theory. Our lattice dynamics simulation results showed that the pressure induced phase transition of K8Si46 was believed to be driven by the phonon instability of the calthrate lattice. Analysis of the evolution of the partial phonon density of state with pressure, a legible dynamic picture for both guest K atoms and host lattice, was given. In addition, based on phonon calculations and combined with quasi-harmonic approximation, the specific heat of K8Si46 was derived, which agreed very well with experimental results. Also, other important thermal properties including the thermal expansion coefficients and Grüneisen parameters of K8Si46 under different temperature and pressure were also predicted. PMID:28773736

  1. Resveratrol may reduce oxidative stress induced by platinum compounds in human plasma, blood platelets and lymphocytes.

    PubMed

    Olas, Beata; Wachowicz, Barbara; Majsterek, Ireneusz; Blasiak, Janusz

    2005-07-01

    Resveratrol (trans-3,4',5-trihydroxystilbene), a polyphenolic compound found in grapes and wine, has been shown to have anti-inflammatory, anti-oxidant, anti-tumor and anti-platelet activities. Using different methods, we show that resveratrol reduces oxidative stress induced by cisplatin (cis-diamminedichloroplatinum II) and selenium-cisplatin conjugate ([NH(3)](2)Pt(SeO(3)), Se-Pt) in human blood platelets, lymphocytes and plasma. Resveratrol decreased the production of 8-epi-prostaglandin F(2) (a biomarker of lipid peroxidation) in control blood platelets and platelets treated with platinum compounds (10 microg/ml), and markedly reduced activities of different anti-oxidative enzymes (glutathione peroxidase, superoxide dismutase and catalase) in these cells. A combined action of resveratrol and Se-Pt evoked a significant decrease of DNA damage (measured by comet assay) in lymphocytes compared with cells treated with Se-Pt only. Resveratrol also caused a distinct reduction of total anti-oxidant level in plasma after incubation with platinum compounds. Therefore, anti-oxidative activity of resveratrol may diminish oxidative stress and damage to cellular biomolecules (lipids, proteins and DNA) induced by platinum compounds.

  2. Isolation of furocoumarins from bergamot fruits as HL-60 differentiation-inducing compounds.

    PubMed

    Kawaii, S; Tomono, Y; Katase, E; Ogawa, K; Yano, M

    1999-10-01

    The HL-60 differentiation-inducing compounds in bergamot fruits were isolated with column chromatography and identified as bergamottin, bergapten, and citropten by (1)H and (13)C NMR. Their HL-60 differentiation-inducing activity was measured by examining nitro blue tetrazolium (NBT) reducing, nonspecific acid esterase (NSE), specific esterase (SE), and phagocytic activities, and bergamottin showed the strongest activity among the coumarins isolated from bergamot fruits. The structure-activity relationship obtained from HL-60 differentiation assay suggests that hydrophobicity of furocoumarins is correlated with their activity.

  3. SIRT1 activating compounds reduce oxidative stress mediated neuronal loss in viral induced CNS demyelinating disease.

    PubMed

    Khan, Reas S; Dine, Kimberly; Das Sarma, Jayasri; Shindler, Kenneth S

    2014-01-02

    Multiple sclerosis (MS) is characterized by central nervous system inflammation and demyelination, and increasing evidence demonstrates significant neuronal damage also occurs and is associated with permanent functional impairment. Current MS therapies have limited ability to prevent neuronal damage, suggesting additional neuroprotective therapies are needed. Compounds that activate the NAD+-dependent SIRT1 deacetylase prevent neuronal loss in an autoimmune-mediated MS model, but the mechanism of this effect is unknown, and it is unclear whether SIRT1 activating compounds exert similar effects in demyelinating disease induced by other etiologies. We measured neuronal loss in C57BL/6 mice inoculated with a neurotropic strain of mouse hepatitis virus, MHV-A59, that induces an MS-like disease. Oral treatment with the SIRT1 activating compound SRTAW04 significantly increased SIRT1 activity within optic nerves and prevented neuronal loss during optic neuritis, an inflammatory demyelinating optic nerve lesion that occurs in MS and its animal models. MHV-A59 induced neuronal loss was associated with reactive oxygen species (ROS) accumulation, and SRTAW04 treatment significantly reduced ROS levels while promoting increased expression of enzymes involved in mitochondrial function and reduction of ROS. SRTAW04 exerted similar protective effects in EAE spinal cords, with decreased demyelination. Results demonstrate that SIRT1 activating compounds prevent neuronal loss in viral-induced demyelinating disease similar to their effects in autoimmune-mediated disease. One mechanism of this neuroprotective effect involves increasing mitochondrial biogenesis with reduction of oxidative stress. SIRT1 activators represent a potential neuroprotective therapy for MS. Understanding common mechanisms of these effects in distinct disease models will help identify targets for more specific therapies.

  4. Vitexins, nature-derived lignan compounds, induce apoptosis and suppress tumor growth.

    PubMed

    Zhou, YingJun; Liu, Yiliang Ellie; Cao, JianGuo; Zeng, GuangYao; Shen, Cui; Li, YanLan; Zhou, MeiChen; Chen, Yiding; Pu, Weiping; Potters, Louis; Shi, Y Eric

    2009-08-15

    Lignans such as secoisolariciresinol diglucoside in flaxseed, are metabolizes to bioactive mammalian lignans of END and ENL. Because mammalian lignans have chemical structural similarity to the natural estrogen, they are thought to behave like selective estrogen receptor modulators and therefore have anticancer effect against hormone-related cancers. We isolated a series of lignan compounds, named as Vitexins, from the seed of Chinese herb Vitex Negundo. We purified several Vitexin lignan compounds. Cytotoxic and antitumor effects were analyzed in cancer cells and in tumor xenograft models. In vivo metabolism of Vitexins was determined in rat. Contrasts to the classic lignans, Vitexins were not metabolized to END and ENL. A mixture of Vitexins EVn-50 and purified Vitexin compound 6-hydroxy-4-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-7-methoxy-3, 4-dihydro-2-naphthaldehyde have cytotoxic effect on breast, prostate, and ovarian cancer cells and induces apoptosis with cleavage in poly ADP ribose polymerase protein, up-regulation of Bax, and down-regulation of Bcl-2. This induction of apoptosis seems to be mediated by activation of caspases because inhibition of caspases activity significantly reduced induced apoptosis. We showed a broad antitumor activity of EVn-50 on seven tumor xenograft models including breast, prostate, liver, and cervical cancers. Consistent with in vitro data, EVn-50 treatment induced apoptosis, down-regulated of Bcl-2, and up-regulated Bax in tumor xenografts. Vitexin is a class of nature lignan compounds, whose action and anticancer effect is mediated by the mechanisms different from the classic lignans. Vitexin-induced antitumor effect and cytotoxic activity is exerted through proapoptotic process, which is mediated by a decreased Bcl-2/Bax ratio and activation of caspases.

  5. Compound K induces apoptosis via CAMK-IV/AMPK pathways in HT-29 colon cancer cells.

    PubMed

    Kim, Do Yeon; Park, Min Woo; Yuan, Hai Dan; Lee, Hyo Jung; Kim, Sung Hoon; Chung, Sung Hyun

    2009-11-25

    Although compound K (CK), an intestinal metabolite of ginseng protopanaxadiol saponins, has been known to induce apoptosis in various cancer cells, association of AMP-activated protein kinase (AMPK) with apoptosis in HT-29 colon cancer cells remains unclear. We hypothesized that CK may exert an anticancer activity through modulating the AMPK pathway in HT-29 cells. CK-induced apoptosis was associated with the disruption of the mitochondrial membrane potential, release of apoptogenic factors (cytochrome c and apoptosis-inducing factor) from mitochondria, and cleavage of caspase-9, caspase-3, caspase-8, Bid, and PARP proteins. This apoptotic effect of CK on colon cancer cells was found to be initiated by AMPK activation, and AMPK was activated through phosphorylation by Ca2+/calmodulin-activated protein kinase-IV (CAMK-IV). Treatment of HT-29 cells with compound C (AMPK inhibitor) or siRNA for AMPK completely abolished the CK-induced apoptosis. STO-609, CAMKs inhibitor, also attenuated CK-induced AMPK activation and apoptosis. In conclusion, the present study demonstrates that CK-mediated cell death of HT-29 colon cancer cells is regulated by CAMK-IV/AMPK pathways, and these findings provide a molecular basis for the anticancer effect of CK.

  6. Instant detection and identification of concealed explosive-related compounds: Induced Stokes Raman versus infrared.

    PubMed

    Elbasuney, Sherif; El-Sherif, Ashraf F

    2017-01-01

    The instant detection of explosives and explosive-related compounds has become an urgent priority in recent years for homeland security and counter-terrorism applications. Modern techniques should offer enhancement in selectivity, sensitivity, and standoff distances. Miniaturisation, portability, and field-ruggedisation are crucial requirements. This study reports on instant and standoff identification of concealed explosive-related compounds using customized Raman technique. Stokes Raman spectra of common explosive-related compounds were generated and spectrally resolved to create characteristic finger print spectra. The scattered Raman emissions over the band 400:2000cm(-1) were compared to infrared absorption using FTIR. It has been demonstrated that the two vibrational spectroscopic techniques were opposite and completing each other. Molecular vibrations with strong absorption in infrared (those involve strong change in dipole moments) induced weak signals in Raman and vice versa. The tailored Raman offered instant detection, high sensitivity, and standoff detection capabilities. Raman demonstrated characteristic fingerprint spectra with stable baseline and sharp intense peaks. Complete correlations of absorption/scattered signals to certain molecular vibrations were conducted to generate an entire spectroscopic profile of explosive-related compounds. This manuscript shades the light on Raman as one of the prevailing technologies for instantaneous detection of explosive-related compounds. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  7. Lipoic acid suppresses compound 48/80-induced anaphylaxis-like reaction

    PubMed Central

    Choi, Yun Ho; Chai, Ok Hee; Han, Eui-Hyeog; Choi, Su-Young; Kim, Hyoung Tae

    2010-01-01

    Alpha-lipoic acid (LA), a naturally occurring dithiol compound, is an essential cofactor in metabolic reactions involved in energy utilization. LA improves glycemic control, reduces diabetic polyneuropathies, atherosclerosis, and allergic inflammation. The effects of LA on mast cell-mediated anaphylactic reactions, however, are unknown. LA dose-dependently inhibited systemic and passive cutaneous anaphylaxis-like reactions in mice induced by compound 48/80, a condensation product of N-methyl-p-methoxyphenethylamine and formaldehyde. Pretreatment with LA, prior to induction of the systemic anaphylaxis-like reaction with compound 48/80, reduced plasma histamine levels in a dose-dependent manner. In our in vitro study, LA decreased histamine release from rat peritoneal mast cells (RPMCs) triggered by compound 48/80. Moreover, an increase in calcium uptake activated by compound 48/80 was inhibited by LA. LA also significantly elevated intracellular cyclic adenosine-3',5' monophosphate (cAMP) levels in RPMCs. This inhibition of mediator release from RPMCs may be due to inhibition of calcium uptake and augmentation of intracellular cAMP levels. Based on these results, we suggest that LA may be a potential remedy for allergy-related diseases. PMID:21267406

  8. Spontaneous nitric oxide in hepatocyte monolayers and inhibition of compound-induced apoptosis.

    PubMed

    Dilworth, C; Bigot-Lasserre, D; Bars, R

    2001-12-01

    Primary cultures of hepatocytes are a widely used in vitro model for biochemical research. Following isolation, hepatocytes produce large amounts of nitric oxide (NO), which is known to have both pro- and anti-apoptotic effects in hepatocytes in vivo and in vitro. Previous work has not determined the effect of these increased levels of NO on the response of hepatocytes to apoptotic stimuli. Here we report that levels of nitrites are elevated in hepatocyte monolayers from 24 h onwards. Addition of the inducible nitric oxide synthase (iNOS) inhibitor, Nomega-nitro-L-arginine methyl ester (L-NAME), to the medium inhibited this increase in nitrites. These results indicate that the increase in nitrite is most likely due to the formation of NO. Elevated nitrite levels had no effect either on basal levels of apoptosis or on ATP and GSH. Apoptosis was induced by transforming growth factor beta-1 (TGFbeta-1) or glycochenodeoxycholate (GCDC). Both compounds caused moderate hepatocyte apoptosis; however, addition of L-NAME prior to exposure significantly increased the level of apoptosis observed with the two compounds. Both TGFbeta-1 and GCDC had no effect on hepatocyte ATP or GSH levels; however, as a consequence of secondary necrosis, TGFbeta-1 exposure significantly increased levels of lactate dehydrogenase (LDH) leakage. These findings indicate that the increased levels of NO associated with the culture of hepatocytes have an inhibitory effect on compound-induced apoptosis in the cells.

  9. The HD molecule in small and medium cages of clathrate hydrates: Quantum dynamics studied by neutron scattering measurements and computation

    NASA Astrophysics Data System (ADS)

    Colognesi, Daniele; Powers, Anna; Celli, Milva; Xu, Minzhong; Bačić, Zlatko; Ulivi, Lorenzo

    2014-10-01

    We report inelastic neutron scattering (INS) measurements on molecular hydrogen deuteride (HD) trapped in binary cubic (sII) and hexagonal (sH) clathrate hydrates, performed at low temperature using two different neutron spectrometers in order to probe both energy and momentum transfer. The INS spectra of binary clathrate samples exhibit a rich structure containing sharp bands arising from both the rotational transitions and the rattling modes of the guest molecule. For the clathrates with sII structure, there is a very good agreement with the rigorous fully quantum simulations which account for the subtle effects of the anisotropy, angular and radial, of the host cage on the HD microscopic dynamics. The sH clathrate sample presents a much greater challenge, due to the uncertainties regarding the crystal structure, which is known only for similar crystals with different promoter, but nor for HD (or H2) plus methyl tert-butyl ether (MTBE-d12).

  10. The HD molecule in small and medium cages of clathrate hydrates: Quantum dynamics studied by neutron scattering measurements and computation

    SciTech Connect

    Colognesi, Daniele; Celli, Milva; Ulivi, Lorenzo; Powers, Anna; Xu, Minzhong; Bačić, Zlatko

    2014-10-07

    We report inelastic neutron scattering (INS) measurements on molecular hydrogen deuteride (HD) trapped in binary cubic (sII) and hexagonal (sH) clathrate hydrates, performed at low temperature using two different neutron spectrometers in order to probe both energy and momentum transfer. The INS spectra of binary clathrate samples exhibit a rich structure containing sharp bands arising from both the rotational transitions and the rattling modes of the guest molecule. For the clathrates with sII structure, there is a very good agreement with the rigorous fully quantum simulations which account for the subtle effects of the anisotropy, angular and radial, of the host cage on the HD microscopic dynamics. The sH clathrate sample presents a much greater challenge, due to the uncertainties regarding the crystal structure, which is known only for similar crystals with different promoter, but nor for HD (or H{sub 2}) plus methyl tert-butyl ether (MTBE-d12)

  11. Preliminary Measurements on the Mechanical Properties of Clathrate Hydrates with Implications for the Internal Dynamics of Icy Satellites

    NASA Astrophysics Data System (ADS)

    Choukroun, M.; Barmatz, M. B.; Castillo, J. C.; Sotin, C.

    2008-12-01

    Surface features potentially associated with cryovolcanism have been identified on Titan, and the processes taking place beneath the surface are likely associated with the dissociation of clathrate hydrates and the release of methane. On Enceladus, the South Pole plume discovered by the Cassini-Huygens mission contains a large proportion of volatiles, in amounts consistent with models of clathrate hydrates dissociation at depth (Kieffer et al., Science 314, 1764-1766, 2006). The stability of clathrate hydrates is relatively well constrained in pure and mixed gas systems (e.g., Sloan, Clathrate hydrates of natural gases, Marcel Dekker, New York, 1998). Recent measurements of clathrate destabilization in presence of ammonia, a likely component of Titan's interior, led to the development of a new model of cryovolcanism (Choukroun et al., Lunar Planet. Sci. Conf., #1837, Houston, 2008). Internal dynamics relies on ice convection at depth on Titan and Enceladus (e.g., Tobie et al., Icarus 175, 496-502, 2005), and on relatively large tidal stresses on Enceladus. Clathrates are expected to destabilize when subject to stress (Durham et al., J. Geophys. Res. 108 (B4), 2182, 2003). Therefore, addressing the mechanical properties of clathrate hydrates in these environments is a necessary step toward better understanding cryovolcanic processes. We have developed a new apparatus for growing clathrate hydrates samples with controlled geometry, composition, and grain size. This system consists of a high-pressure autoclave and a cooling system and supports gas pressures up to 500 bars, and temperatures within the range -50 - 150 °C. We have started the production of clathrate hydrates of CH4, CO2, and N2 with this system, with the purpose to test their mechanical properties using an Instron compression system (Castillo-Rogez et al., submitted to J. Geophys. Res.; Castillo-Rogez et al., this meeting). We will present initial measurements on the creep response and on the

  12. Thioredoxin 1 modulates apoptosis induced by bioactive compounds in prostate cancer cells.

    PubMed

    Rodriguez-Garcia, Aida; Hevia, David; Mayo, Juan C; Gonzalez-Menendez, Pedro; Coppo, Lucia; Lu, Jun; Holmgren, Arne; Sainz, Rosa M

    2017-08-01

    Accumulating evidence suggests that natural bioactive compounds, alone or in combination with traditional chemotherapeutic agents, could be used as potential therapies to fight cancer. In this study, we employed four natural bioactive compounds (curcumin, resveratrol, melatonin, and silibinin) and studied their role in redox control and ability to promote apoptosis in androgen sensitive and insensitive prostate cancer cells. Here is shown that curcumin and resveratrol promote ROS production and induce apoptosis in LNCaP and PC-3. An increase in reactive species is a trigger event in curcumin-induced apoptosis and a consequence of resveratrol effects on other pathways within these cells. Moreover, here we demonstrated that these four compounds affect differently one of the main intracellular redox regulator, the thioredoxin system. Exposure to curcumin and resveratrol promoted TRX1 oxidation and altered its subcellular location. Furthermore, resveratrol diminished TRX1 levels in PC-3 cells and increased the expression of its inhibitor TXNIP. Conversly, melatonin and silibinin only worked as cytostatic agents, reducing ROS levels and showing preventive effects against TRX oxidation. All together, this work explores the effect of compounds currently tested as chemo-preventive agents in prostate cancer therapy, on the TRX1 redox state and function. Our work shows the importance that the TRX system might have within the differences found in their mechanisms of action. These bioactive compounds trigger different responses and affect ROS production and redox systems in prostate cancer cells, suggesting the key role that redox-related pathways might play in processes like differentiation or survival in prostate cancer. Copyright © 2017. Published by Elsevier B.V.

  13. Photo-induced spin transition of Iron(III) compounds with pi-pi intermolecular interactions.

    PubMed

    Hayami, Shinya; Hiki, Kenji; Kawahara, Takayoshi; Maeda, Yonezo; Urakami, Daisuke; Inoue, Katsuya; Ohama, Mitsuo; Kawata, Satoshi; Sato, Osamu

    2009-01-01

    Iron(III) spin-crossover compounds [Fe(pap)(2)]ClO(4) (1), [Fe(pap)(2)]BF(4) (2), [Fe(pap)(2)]PF(6) (3), [Fe(qsal)(2)]NCS (4), and [Fe(qsal)(2)]NCSe (5) (Hpap=2-(2-pyridylmethyleneamino)phenol and Hqsal=2-[(8-quinolinylimino)methyl]phenol) were prepared and their spin-transition properties investigated by magnetic susceptibility and Mössbauer spectroscopy measurements. The iron(III) compounds exhibited spin transition with thermal hysteresis. Single crystals of the iron(III) compounds were obtained as suitable solvent adducts for X-ray analysis, and structures in high-spin (HS) and low-spin (LS) states were revealed. Light-induced excited-spin-state trapping (LIESST) effects of the iron(III) compounds were induced by light irradiation at 532 nm for 1-3 and at 800 nm for 4 and 5. The activation energy E(a) and the low-temperature tunneling rate k(HL)(T-->0) of iron(III) LIESST compound 1 were estimated to be 1079 cm(-1) and 2.4x10(-8) s(-1), respectively, by HS-->LS relaxation experiments. The Huang-Rhys factor S of 1 was also estimated to be 50, which was similar to that expected for iron(II) complexes. It is thought that the slow relaxation in iron(III) systems is achieved by the large structural distortion between HS and LS states. Introduction of strong intermolecular interactions, such as pi-pi stacking, can also play an important role in the relaxation behavior, because it can enhance the structural distortion of the LIESST complex.

  14. Modulation of 17{beta}-estradiol-induced responses in fish by cytochrome P4501A1 inducing compounds

    SciTech Connect

    Anderson, M.J.; Hinton, D.E.

    1995-12-31

    Some compounds which induce cytochrome P4501A1 (CYP1A1) are antiestrogenic in mammalian bioassay, and this effect is linked to aryl hydrocarbon (Ah) receptor. Liver of fish synthesizes estrogen-inducible egg yolk precursor protein vitellogenin (Vg) which is critical for oocyte maturation and ovarian development. To determine if Ah receptor-linked endocrine modulation could occur in fish liver, primary cultures of juvenile rainbow trout (Oncorhynchus mykiss) liver cells were co-administered 17{beta}-estradiol and CYP1A1 inducing compounds. Vitellogenin and albumin, estimated by ELISA measurement of concentration in the media 48 hrs after treatment, formed the basis for the test. Cellular CYP1A1 protein content and catalytic activity was estimated by ELISA and ethoxyresorufin-O-deethylase (EROD) activity assays respectively. Equivalent viability (mitochondrial dehydrogenase activity) and secretary functional capacity (albumin synthesis) were estimated and correlated with other results. In descending order, 2,3,4,7,8 pentachlorodibenzofuran (10{sup {minus}12} to 10{sup {minus}8} M) > 2,3,7,8 tetrachlorodibenzo-p-dioxin {approx_equal} 2,3,7,8 tetrachlorodibenzofuran (10{sup {minus}11} to 10{sup {minus}8} M) > {beta}-naphthoflavone (10{sup {minus}7} to 10{sup {minus}6} M) inhibited Vg synthesis in 17{beta}-estradiol treated liver cells. Potency of inhibition directly related to strength as an inducer of CYP1A1 protein. At 10-8 M, PCB congeners 77, 126, and 156 did not inhibit Vg synthesis and induced no or only moderate CYP1A1 protein. At 10-8 M, PCB congener 114, a weak CYP1A1 inducer, potentiated Vg synthesis relative to cells treated with 17{beta}-estradiol alone. This study increases their understanding of the consequences of hepatic CYP1A1 induction, forewarns of reproductive impairment of sexually maturing fishes exposed to CYP1A1 inducing compounds and argues for further, more detailed in vivo investigation.

  15. Bioactive compounds from liverworts: Inhibition of lipopolysaccharide-induced inducible NOS mRNA in RAW 264.7 cells by herbertenoids and cuparenoids.

    PubMed

    Harinantenaina, Liva; Quang, Dang Ngoc; Nishizawa, Takashi; Hashimoto, Toshihiro; Kohchi, Chie; Soma, Gen-Ichiro; Asakawa, Yoshinori

    2007-08-01

    The inhibition of lipopolysaccharide (LPS)-induced inducible nitric oxide synthase (iNOS) by herbertenoids and cuparenoids isolated from liverworts in RAW 264.7 macrophages was evaluated. Among compounds tested, herbertenediol, cuparenediol, 1,2-diacetoxyherbertene and 2-hydroxy-4-methoxycuparene exhibited significant activity. For 2-hydroxy-4-methoxycuparene, chosen as representative compound, the strong inhibitory activity was related to the inhibition on LPS-induced iNOS mRNA. The structure-activity relationship will be discussed.

  16. Marine Benthic Diatoms Contain Compounds Able to Induce Leukemia Cell Death and Modulate Blood Platelet Activity

    PubMed Central

    Prestegard, Siv Kristin; Oftedal, Linn; Coyne, Rosie Theresa; Nygaard, Gyrid; Skjærven, Kaja Helvik; Knutsen, Gjert; Døskeland, Stein Ove; Herfindal, Lars

    2009-01-01

    In spite of the high abundance and species diversity of diatoms, only a few bioactive compounds from them have been described. The present study reveals a high number of mammalian cell death inducing substances in biofilm-associated diatoms sampled from the intertidal zone. Extracts from the genera Melosira, Amphora, Phaeodactylum and Nitzschia were all found to induce leukemia cell death, with either classical apoptotic or autophagic features. Several extracts also contained inhibitors of thrombin-induced blood platelet activation. Some of this activity was caused by a high content of adenosine in the diatoms, ranging from 0.07 to 0.31 μg/mg dry weight. However, most of the bioactivity was adenosine deaminase-resistant. An adenosine deaminase-resistant active fraction from one of the extracts was partially purified and shown to induce apoptosis with a distinct phenotype. The results show that benthic diatoms typically found in the intertidal zone may represent a richer source of interesting bioactive compounds than hitherto recognized. PMID:20098602

  17. Prevention of acrylonitrile-induced gastrointestinal bleeding by sulfhydryl compounds, atropine and cimetidine

    SciTech Connect

    Ghanayem, B.I.; Ahmed, A.E.

    1986-07-01

    We have recently demonstrated that acrylonitrile (VCN) causes acute gastric hemorrhage and mucosal erosions. The current studies were undertaken to investigate the effects of the sulfhydryl-containing compounds, cysteine and cysteamine, the cholinergic blocking agent atropine and the histamine H2 receptor antagonist, cimetidine on the VCN-induced gastrointestinal (GI) bleeding in rats. Our data shows that pretreatment with L-cysteine, cysteamine, atropine or cimetidine has significantly protected rats against the VCN-induced GI bleeding. A possible mechanism of the VCN-induced GI bleeding may involve the interaction of VCN with critical sulfhydryl groups that, in turn, causes alteration of acetylcholine muscarinic receptors to lead to gastric hemorrhagic lesions and bleeding.

  18. Compound mechanism hypothesis on +Gz induced brain injury and dysfunction of learning and memory

    NASA Astrophysics Data System (ADS)

    Sun, Xi-Qing; Li, Jin-Sheng; Cao, Xin-Sheng; Wu, Xing-Yu

    2005-08-01

    We systematically studied the effect of high- sustained +Gz on the brain and its mechanism in past ten years by animal centrifuge experiments. On the basis of the facts we observed and the more recent advances in acceleration physiology, we put forward a compound mechanism hypothesis to offer a possible explanation for +Gz-induced brain injury and dysfunction of learning and memory. It states that, ischemia during high G exposure might be the main factor accounting for +Gz-induced brain injury and dysfunction of learning and memory, including transient depression of brain energy metabolism, disturbance of ion homeostasis, increased blood-brain barrier permeability, increased brain nitric oxide synthase expression, and the protective effect of heat shock protein 70. In addition, the large rapid change of intracranial pressure and increased stress during +Gz exposure, and the hemorrheologic change after +Gz exposure might be one of the important factors accounting for +Gz-induced brain injury and dysfunction of learning and memory.

  19. Growth mechanism of a gas clathrate hydrate from a dilute aqueous gas solution: a molecular dynamics simulation of a three-phase system.

    PubMed

    Nada, Hiroki

    2006-08-24

    A molecular dynamics simulation of a three-phase system including a gas clathrate, liquid water, and a gas was carried out at 298 K and high pressure in order to investigate the growth mechanism of the clathrate from a dilute aqueous gas solution. The simulation indicated that the clathrate grew on interfaces between the clathrate and the liquid water, after transfer of the gas molecules from the gas phase to the interfaces. The results suggest a two-step process for growth: first, gas molecules are arranged at cage sites, and second, H(2)O molecules are ordered near the gas molecules. The results also suggest that only the H(2)O molecules, which are surrounded or sandwiched by the gas molecules, form the stable polygons that constitute the cages of the clathrate. In addition, the growth of the clathrate from a concentrated aqueous gas solution was also simulated, and the results suggested a growth mechanism in which many H(2)O and gas molecules correctively form the structure of the clathrate. The clathrate grown from the concentrated solution contained some empty cages, whereas the formation of empty cages was not observed during the growth from the dilute solution. The results obtained by both simulations are compared with the results of an experimental study, and the growth mechanism of the clathrate in a real system is discussed.

  20. Chemiluminescence response induced by mesenteric ischaemia/reperfusion: effect of antioxidative compounds ex vivo

    PubMed Central

    Nosál'ová, Viera; Sotníková, Ružena; Drábiková, Katarína; Fialová, Silvia; Košťálová, Daniela; Banášová, Silvia; Navarová, Jana

    2010-01-01

    Ischaemia and reperfusion (I/R) play an important role in human pathophysiology as they occur in many clinical conditions and are associated with high morbidity and mortality. Interruption of blood supply rapidly damages metabolically active tissues. Restoration of blood flow after a period of ischaemia may further worsen cell injury due to an increased formation of free radicals. The aim of our work was to assess macroscopically the extent of intestinal pathological changes caused by mesenteric I/R, and to study free radical production by luminol enhanced chemiluminescence (CL) of ileal samples. In further experiments, the antioxidative activity of the drugs tested was evaluated spectrophotometrically by the use of the DPPH radical. We studied the potential protective ex vivo effect of the plant origin compound arbutin as well as of the pyridoindole stobadine and its derivative SMe1EC2. I/R induced pronounced haemorrhagic intestinal injury accompanied by increase of myeloperoxidase (MPO) and N-acetyl-β-D-glucosaminidase (NAGA) activity. Compared to sham operated (control) rats, there was only a slight increase of CL response after I/R, probably in association with neutrophil increase, indicated by enhanced MPO activity. All compounds significantly reduced the peak values of CL responses of the ileal samples ex vivo, thus reducing the I/R induced increase of free radical production. The antioxidants studied showed a similar inhibitory effect on the CL response influenced by mesenteric I/R. If proved in vivo, these compounds would represent potentially useful therapeutic antioxidants. PMID:21217883

  1. 73Ge- and 135/137Ba-NMR Studies of Clathrate Superconductor Ba24Ge100

    NASA Astrophysics Data System (ADS)

    Kanetake, Fumiya; Harada, Atsushi; Mukuda, Hidekazu; Kitaoka, Yoshio; Rachi, Takeshi; Tanigaki, Katsumi; Itoh, Kohei M.; Haller, Eugene E.

    2009-10-01

    We report on the normal-state properties of a superconducting type-III clathrate compound Ba24Ge100 investigated by 73Ge-NMR at cage sites and by 135/137Ba-NMR at guest sites at ambient pressure (P=0) and 2.7 GPa. The measurements of the nuclear spin-lattice relaxation rate 1/T1 have revealed a significant increase in 1/T1T of approximately 200 K at P=0, which may be relevant to the rattling motion of Ba atoms in Ge cages. This increase in 1/T1T at high temperatures is markedly suppressed at P=2.7 GPa. As a result of the suppression of the successive structural transformations, the 1/T1T=const. in a low-temperature regime is increased, proving the increase in the density of states at the Fermi level, N(EF), at P. It is this increase in N(EF) that increases the superconducting transition temperature Tc from 0.24 K at P=0 to 3.8 K at P˜ 2.7 GPa.

  2. Single laser pulse induces spin state transition within the hysteresis loop of an Iron compound

    NASA Astrophysics Data System (ADS)

    Freysz, E.; Montant, S.; Létard, S.; Létard, J.-F.

    2004-08-01

    Within the thermal hysteresis loop of the [Fe(PM-BiA) 2(NCS) 2] compound, a single laser pulse of 14 mJ cm -2 induces a photo-conversion from the low spin (LS, S = 0) to the high spin (HS, S = 2) state of the Fe 2+ metallic center. The temporal dynamic of this phenomena indicates that the system is firstly photo-excited into the HS state and then slowly relaxes to a mixture of HS/LS state. Subsequent laser pulses do not affect the HS/LS ratio. The system can be brought back to its initial LS state by adjusting the temperature of the compound. A simple model accounts qualitatively for the observed phenomenon.

  3. The natural compounds piperovatine and piperlonguminine induce autophagic cell death on Trypanosoma cruzi.

    PubMed

    Veiga-Santos, Phercyles; Desoti, Vânia Cristina; Miranda, Nathielle; Ueda-Nakamura, Tânia; Dias-Filho, Benedito Prado; Silva, Sueli Oliveira; Cortez, Diogenes Aparício Garcia; de Mello, João Carlos Palazzo; Nakamura, Celso Vataru

    2013-03-01

    The currently available treatments for Chagas disease show limited therapeutic potential and are associated with serious side effects. Our group has been attempting to find alternative drugs isolated from natural products as a potential source of pharmacological agents against Trypanosoma cruzi. Here, we demonstrate the antitrypanosomal activity of the amides piperovatine and piperlonguminine isolated from Piper ovatum against epimastigotes and intracellular amastigotes. We also investigated the mechanisms of action of these compounds on extracellular amastigote and epimastigote forms of T. cruzi. These amides showed low toxicity to LLCMK(2) mammalian cells. By using transmission and scanning electron microscopy, we observed that the compounds caused severe alterations in T. cruzi. These alterations were mainly located in plasma membrane and mitochondria. Furthermore, the study of treated parasites labeled with Rh123, PI and MDC corroborate with our TEM data. These mitochondrial dysfunctions induced by the amides might trigger biochemical alterations that lead to cell death. Altogether, our data evidence a possible autophagic process.

  4. Plant compounds that induce polychlorinated biphenyl biodegradation by Arthrobacter sp. strain B1B.

    PubMed Central

    Gilbert, E S; Crowley, D E

    1997-01-01

    Plant compounds that induced Arthrobacter sp. strain B1B to cometabolize polychlorinated biphenyls (PCBs) were identified by a screening assay based on the formation of a 4,4'-dichlorobiphenyl ring fission product. A chemical component of spearmint (Mentha spicata), l-carvone, induced Arthrobacter sp. strain B1B to cometabolize Aroclor 1242, resulting in significant degradation of 26 peaks in the mixture, including selected tetra- and pentachlorobiphenyls. Evidence for PCB biodegradation included peak disappearance, formation of a phenylhexdienoate ring fission product, and chlorobenzoate accumulation in the culture supernatant. Carvone was not utilized as a growth substrate and was toxic at concentrations of greater than 500 mg liter-1. Several compounds structurally related to l-carvone, including limonene, p-cymene, and isoprene, also induced cometabolism of PCBs by Arthrobacter sp. strain B1B. A structure-activity analysis showed that chemicals with an unsaturated p-menthane structural motif promoted the strongest cometabolism activity. These data suggest that certain plant-derived terpenoids may be useful for promoting enhanced rates of PCB biodegradation by soil bacteria. PMID:9143124

  5. Protective effect of an aminothiazole compound against γ-radiation induced oxidative damage.

    PubMed

    De, Strayo; Devasagayam, Thomas P A

    2011-11-01

    Ionizing radiation causes its biological effects mainly through oxidative damage induced by reactive oxygen species. During radiotherapy of cancer, one of the undesirable side-effects is toxicity to normal cells. Compounds with antioxidant activities are being tried as 'prophylactic radioprotectants' to overcome this problem. We evaluated the protective effect of an aminothiazole compound, in the form of dendrodoine analogue (DA) originally derived from a marine tunicate, against γ-radiation-induced damage to lipid, protein, and DNA besides its cytotoxicity. Oxidative damage was examined by different biochemcial assays. Our studies reveal that DA gave significant protection, in fairly low concentrations, against damage induced by γ-radiation to rat liver mitochondria, plasmid pBR322 DNA, and mouse splenic lymphocytes in vitro. It also protected against oxidative damage in whole-body irradiated mice exposed to therapeutic dose of radiation (2 Gy) in vivo. Spleen, a major target organ for radiation damage, of the irradiated mice showed significant protection when treated with DA, as examined by histopathology. In conclusion, due to the possible protective effects against normal cells/tissues both in vitro and in vivo, DA shows potential to be a radioprotector for possible use during radiotherapy.

  6. Allergy-Inducing Chromium Compounds Trigger Potent Innate Immune Stimulation Via ROS-Dependent Inflammasome Activation.

    PubMed

    Adam, Christian; Wohlfarth, Jonas; Haußmann, Maike; Sennefelder, Helga; Rodin, Annette; Maler, Mareike; Martin, Stefan F; Goebeler, Matthias; Schmidt, Marc

    2017-02-01

    Chromium allergy is a common occupational skin disease mediated by chromium (VI)-specific T cells that induce delayed-type hypersensitivity in sensitized individuals. Additionally, chromium (VI) can act as an irritant. Both responses critically require innate immune activation, but if and how chromium (VI) elicits this signal is currently unclear. Using human monocytes, primary human keratinocytes, and murine dendritic cells we show that chromium (VI) compounds fail to trigger direct proinflammatory activation but potently induce processing and secretion of IL-1β. IL-1β release required priming by phorbol-ester or toll-like receptor stimulation and was prevented by inhibition of K(+) efflux, NLRP3 depletion or caspase-1 inhibition, identifying chromium (VI) as a hapten activator of the NLRP3 inflammasome. Inflammasome activation was initiated by mitochondrial reactive oxygen species production triggered by chromium (VI), as indicated by sensitivity to treatment with the ROS scavenger N-acetyl cysteine and a coinciding failure of K(+) efflux, caspase-1, or NLRP3 inhibition to prevent mitochondrial reactive oxygen species accumulation. IL-1β release further correlated with cytotoxicity that was secondary to reactive oxygen species, K(+) efflux, and NLRP3 activation. Trivalent chromium was unable to induce mitochondrial reactive oxygen species production, inflammasome activation, and cytotoxicity, suggesting that oxidation state-specific differences in mitochondrial reactivity may determine inflammasome activation and allergic/irritant capacity of different chromium compounds.

  7. Novel hydrogen sulfide-releasing compound, S-propargyl-cysteine, prevents STZ-induced diabetic nephropathy

    SciTech Connect

    Qian, Xin; Li, Xinghui; Ma, Fenfen; Luo, Shanshan; Ge, Ruowen; Zhu, Yizhun

    2016-05-13

    In this work, we demonstrated for the first time that S-propargyl-cysteine (SPRC, also named as ZYZ-802), a novel hydrogen sulfide (H{sub 2}S)-releasing compound, had renoprotective effects on streptozotocin (STZ)-induced diabetic kidney injury. SPRC treatment significantly reduced the level of creatinine, kidney to body weight ratio and in particular, markedly decreased 24-h urine microalbuminuria excretion. SPRC suppressed the mRNA expression of fibronectin and type IV collagen. In vitro, SPRC inhibited mesangial cells over-proliferation and hypertrophy induced by high glucose. Additionally, SPRC attenuated inflammation in diabetic kidneys. SPRC also reduced transforming growth factor β1 (TGF-β1) signaling and expression of phosphorylated Smad3 (p-Smad3) pathway. Moreover, SPRC inhibited phosphorylation of ERK, p38 protein. Taken together, SPRC was demonstrated to be a potential therapeutic candidate to suppress diabetic nephropathy. - Highlights: • We synthesized a novel hydrogen sulfide-releasing compound, S-propargyl-cysteine (SPRC). • SPRC was preliminarily demonstrated to prevent STZ-induced diabetic nephropathy (DN). • SPRC may exert potential therapeutic candidate to suppress DN.

  8. Novel synthetic protective compound, KR-22335, against cisplatin-induced auditory cell death.

    PubMed

    Shin, Yoo Seob; Song, Suk Jin; Kang, Sungun; Hwang, Hye Sook; Jung, Young-Sik; Kim, Chul-Ho

    2014-02-01

    Cisplatin [cis-diammine-dichloroplatinum (II)] is a widely used chemotherapeutic agent, and one of its most severe side effects is ototoxicity. In the course of developing a new protective agent against cisplatin-induced ototoxicity, we have been interested in a novel synthetic compound, 3-Amino-3-(4-fluoro-phenyl)-1H-quinoline-2,4-dione (KR-22335). We evaluated the effectiveness of KR-22335 as an otoprotective agent against cisplatin-induced toxicity. The otoprotective effect of KR-22335 against cisplatin was tested in vitro in cochlear organs of Corti-derived cell lines, HEI-OC1, and in vivo in a zebrafish (Danio rerio) model. Cisplatin-induced apoptosis, cell cycle arrest and an increase in intracellular reactive oxygen species (ROS) generation were demonstrated in HEI-OC1 cells. KR-22335 inhibited cisplatin-induced apoptosis and mitochondrial injury in HEI-OC1 cells. KR-22335 inhibited cisplatin-induced activation of JNK, p-38, caspase-3 and PARP in HEI-OC1 cells. Scanning and transmission electron micrographs showed that KR-22335 prevented cisplatin-induced destruction of kinocilium and stereocilia in zebrafish neuromasts. Tissue TUNEL of neuromasts in zebrafish demonstrated that KR-22335 blocked cisplatin-induced TUNEL positive hair cells in neuromasts. The results of this study suggest that KR-22335 may prevent ototoxicity caused by the administration of cisplatin through the inhibition of mitochondrial dysfunction and suppression of ROS generation. KR-22335 may be considered as a potential candidate for protective agents against cisplatin-induced ototoxicity. Copyright © 2013 John Wiley & Sons, Ltd.

  9. Structure-activity relationship of 9-methylstreptimidone, a compound that induces apoptosis selectively in adult T-cell leukemia cells.

    PubMed

    Takeiri, Masatoshi; Ota, Eisuke; Nishiyama, Shigeru; Kiyota, Hiromasa; Umezawa, Kazuo

    2012-01-01

    We previously reported that 9-methylstreptimidone, a piperidine compound isolated from a culture filtrate of Streptomyces, induces apoptosis selectively in adult T-cell leukemia cells. It was screened for a compound that inhibits LPS-induced NF-kappaB and NO production in mouse macrophages. However, 9-methystreptimidone is poorly obtained from the producing microorganism and difficult to synthesize. Therefore, in the present research, we studied the structure-activity relationship to look for new selective inhibitors. We found that the structure of the unsaturated hydrophobic portion of 9-methylstreptimidone was essential for the inhibition of LPS-induced NO production. Among the 9-methylstreptimidone-related compounds tested, (+/-)-4,alpha-diepi-streptovitacin A inhibited NO production in macrophage-like cells as potently as 9-methylstreptimidone and without cellular toxicity. Moreover, this compound selectively induced apoptosis in adult T-cell leukemia MT-1 cells.

  10. Fluid clathrate system for continuous removal of heavy noble gases from mixtures of lighter gases

    DOEpatents

    Gross, K.C.; Markun, F.; Zawadzki, M.T.

    1998-04-28

    An apparatus and method are disclosed for separation of heavy noble gas in a gas volume. An apparatus and method have been devised which includes a reservoir containing an oil exhibiting a clathrate effect for heavy noble gases with a reservoir input port and the reservoir is designed to enable the input gas volume to bubble through the oil with the heavy noble gas being absorbed by the oil exhibiting a clathrate effect. The gas having reduced amounts of heavy noble gas is output from the oil reservoir, and the oil having absorbed heavy noble gas can be treated by mechanical agitation and/or heating to desorb the heavy noble gas for analysis and/or containment and allow recycling of the oil to the reservoir. 6 figs.

  11. Fluid clathrate system for continuous removal of heavy noble gases from mixtures of lighter gases

    DOEpatents

    Gross, Kenneth C.; Markun, Francis; Zawadzki, Mary T.

    1998-01-01

    An apparatus and method for separation of heavy noble gas in a gas volume. An apparatus and method have been devised which includes a reservoir containing an oil exhibiting a clathrate effect for heavy noble gases with a reservoir input port and the reservoir is designed to enable the input gas volume to bubble through the oil with the heavy noble gas being absorbed by the oil exhibiting a clathrate effect. The gas having reduced amounts of heavy noble gas is output from the oil reservoir, and the oil having absorbed heavy noble gas can be treated by mechanical agitation and/or heating to desorb the heavy noble gas for analysis and/or containment and allow recycling of the oil to the reservoir.

  12. High pressure optical cell for synthesis and in situ Raman spectroscopy of hydrogen clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Celli, Milva; Zoppi, Marco; Zaghloul, Mohamed A. S.; Ulivi, Lorenzo

    2012-11-01

    We report the design, realization, and test of a high-pressure optical cell that we have used to measure the Raman spectra of hydrogen clathrate hydrates, synthesized in situ by the application of 200-300 MPa of gas pressure on solid water. The optical apparatus is mounted on a cryogenic system so to allow measurements and sample treatment at any temperature between 300 and 20 K. A capillary pipe is connected to the inside of the cell to allow the gas flow into and out of the cell, and to regulate the internal pressure at any value from 0 to 300 MPa. In the experimental test described in this paper, the cell has been partly filled, at room temperature, with a small amount of water, then frozen at 263 K before injecting hydrogen gas, at pressure of 150 MPa, into the cell. This procedure has permitted to study hydrogen clathrate formation, by measuring Raman spectra as a function of time.

  13. A study of a host-guest interaction in Hofmann-type clathrates

    NASA Astrophysics Data System (ADS)

    Minceva-Sukarova, B.; Andreeva, L.; Ivanovski, G.

    1990-03-01

    A host-guest interaction in a series of Hofmann-type clathrates : M (NH 3) 2Ni (CH) 4·2C 6H 6 where M = Ni, Fe, Co, Zn, Mn and Cd has been studied using IR spectroscopy. The influence of the guest molecules (enclathrate benzene molecules) has been studied through the changes of the shape of the bands due to CH out-of-plane deformations. In some of the clathrates, a considerable splitting of these bands has been observed at low temperature. This is especially true for the band near 980 cm -1. The splitting of this band increases as the volume of the unit cell decreases in the order : Cd, Mn, Zn, Co, Fe, Ni. An attempt has been made to interpret this in terms of tunneling effect, using a simple model based on a double-minimum potential function.

  14. An Antifreeze Protein Folds with an Interior Network of More Than 400 Semi-Clathrate Waters

    SciTech Connect

    Sun, T.; Lin, F. -H.; Campbell, R. L.; Allingham, J. S.; Davies, P. L.

    2014-02-13

    When polypeptide chains fold into a protein, hydrophobic groups are compacted in the center with exclusion of water. We report the crystal structure of an alanine-rich antifreeze protein that retains ~400 waters in its core. The putative ice-binding residues of this dimeric, four-helix bundle protein point inwards and coordinate the interior waters into two intersecting polypentagonal networks. The bundle makes minimal protein contacts between helices, but is stabilized by anchoring to the semi-clathrate water monolayers through backbone carbonyl groups in the protein interior. The ordered waters extend outwards to the protein surface and likely are involved in ice binding. This protein fold supports both the anchored-clathrate water mechanism of antifreeze protein adsorption to ice and the water-expulsion mechanism of protein folding.

  15. Organic free radicals in clathrate hydrates investigated by muon spin spectroscopy.

    PubMed

    Percival, Paul W; Mozafari, Mina; Brodovitch, Jean-Claude; Chandrasena, Lalangi

    2014-02-20

    Very little is known about the behavior of free H atoms and small organic radicals inside clathrate hydrate structures despite the relevance of such species to combustion of hydrocarbon hydrates. Muonium is an H atom analog, essentially a light isotope of hydrogen, and can be used to probe the chemistry of H atoms and transient free radicals. We demonstrate the first application of muon spin spectroscopy to characterize radicals in clathrate hydrates. Atomic muonium was detected in hydrates of cyclopentane and tetrahydrofuran, and muoniated free radicals were detected in the hydrates of cyclopentene and 2,5-dihydrofuran, indicating rapid addition of muonium to the organic guest. Muon avoided level-crossing spectra of the radicals in hydrates are markedly different to those of the same radicals in pure organic liquids at the same temperature, and this can be explained by limited mobility of the enclathrated radicals, leading to anisotropy in the hyperfine interactions.

  16. Generalized Electron Counting in Determination of Metal-Induced Reconstruction of Compound Semiconductor Surfaces

    SciTech Connect

    Zhang, Lixin; Wang, E. G.; Xue, Qi-Kun; Zhang, S. B.; Zhang, Zhenyu

    2006-01-01

    Based on theoretical analysis, first-principles calculations, and experimental observations, we establish a generic guiding principle, embodied in generalized electron counting (GEC), that governs the surface reconstruction of compound semiconductors induced by different metal adsorbates. Within the GEC model, the adsorbates serve as an electron bath, donating or accepting the right number of electrons as the host surface chooses a specific reconstruction that obeys the classic electron-counting model. The predictive power of the GEC model is illustrated for a wide range of metal adsorbates.

  17. Laser-induced forward transfer of a bis-pyrene compound for OTFTs

    NASA Astrophysics Data System (ADS)

    Constantinescu, Catalin; Diallo, Abdou Karim; D'Aleo, Anthony; Fages, Frédéric; Videlot-Ackermann, Christine; Delaporte, Philippe; Alloncle, Anne-Patricia

    2015-05-01

    We present results on a newly synthesized bis-pyrene compound that, besides the typical fluorescence, also exhibits semiconducting properties. Thin films have been grown by vacuum thermal evaporation on oxidized silicon and on transparent quartz substrates. Micrometric-sized pixels have subsequently been printed by laser-induced forward transfer (LIFT), in air and at low pressure (90 mbar), by using a Nd:YAG laser source (355 nm, 50 ps pulse duration) to produce functional organic thin film transistors (o-TFTs). Top-contact (TC) configurations are emphasized, and the influence of the pressure and laser fluence during the LIFT procedure is discussed.

  18. Effect of dietary phenolic compounds on apoptosis of human cultured endothelial cells induced by oxidized LDL

    PubMed Central

    Vieira, Otilia; Escargueil-Blanc, Isabelle; Meilhac, Olivier; Basile, Jean-Pierre; Laranjinha, Joao; Almeida, Leonor; Salvayre, Robert; Nègre-Salvayre, Anne

    1998-01-01

    Oxidized low density lipoproteins (LDL) are toxic to cultured endothelial cells. Mildly oxidized LDL, characterized by relatively low levels of TBARS and only minor modifications of apoB, were obtained by using 2 experimental model systems of oxidation, namely oxidation by u.v. radiation or ferrylmyoglobin (a two electron oxidation product from the reaction of metmyoglobin with H2O2). Toxic concentrations of mildly oxidized LDL induce apoptosis (programmed cell death) of cultured endothelial cells, as shown by typical morphological features, by the in situ TUNEL procedure and by DNA fragmentation revealed on gel electrophoresis. This apoptosis is calcium-dependent and subsequent to the intense and sustained cytosolic [Ca2+]i peak elicited by oxidized LDL. Five naturally occurring phenolic compounds present in food and beverages were able to prevent, in a concentration-dependent manner, the apoptosis of endothelial cells induced by oxidized LDL. Among the compounds tested, caffeic acid was the most effective. Under the conditions used, the protective effect of caffeic acid (IC50 8.3±2.1 μmol  l−1) in the prevention of apoptosis induced by oxidized LDL was significantly higher than that of the other compounds tested (IC50s were 12.4±3.2, 14.1±4.1, 20.4±4.4 and 72.6±9.2 μmol  l−1 for ferulic, protocatechuic, ellagic and p-coumaric acids, respectively). The anti-apoptotic effect of caffeic acid results from the addition of two effects, (i) the antioxidant effect which prevents LDL oxidation and subsequent toxicity (‘indirect' protective effect); (ii) a ‘direct' cytoprotective effect, acting at the cellular level. Effective concentrations of caffeic acid acted at the cellular level by blocking the intense and sustained cytosolic [Ca2+]i rise elicited by oxidized LDL. In conclusion, phenolic acids (caffeic and ferulic acids being the most potent of the compounds tested under the conditions used) exhibit a potent cytoprotective effect of

  19. Global inventory of methane clathrate: sensitivity to changes in the deep ocean

    NASA Astrophysics Data System (ADS)

    Buffett, Bruce; Archer, David

    2004-11-01

    We present a mechanistic model for the distribution of methane clathrate in marine sediments, and use it to predict the sensitivity of the steady-state methane inventory to changes in the deep ocean. The methane inventory is determined by binning the seafloor area according to water depth, temperature, and O 2 concentration. Organic carbon rain to the seafloor is treated as a simple function of water depth, and carbon burial for each bin is estimated using a sediment diagenesis model called Muds [Glob. Biogeochem. Cycles 16 (2002)]. The predicted concentration of organic carbon is fed into a clathrate model [J. Geophys. Res. 108 (2003)] to calculate steady-state profiles of dissolved, frozen, and gaseous methane. We estimate the amount of methane in ocean sediments by multiplying the sediment column inventories by the corresponding binned seafloor areas. Our estimate of the methane inventory is sensitive to the efficiency of methane production from organic matter and to the rate of fluid flow within the sediment column. Preferred values for these parameters are taken from previous studies of both passive and active margins, yielding a global estimate of 3×10 18 g of carbon (3000 Gton C) in clathrate and 2×10 18 g (2000 Gton C) in methane bubbles. The predicted methane inventory decreases by 85% in response to 3 °C of warming. Conversely, the methane inventory increases by a factor of 2 if the O 2 concentration of the deep ocean decreases by 40 μM or carbon rain increases by 50% (due to an increase in primary production). Changes in sea level have a small effect. We use these sensitivities to assess the past and future state of the methane clathrate reservoir.

  20. Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2004-01-01

    Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

  1. A simple van't Hoff law for calculating Langmuir constants in clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Lakhlifi, Azzedine; Dahoo, Pierre Richard; Picaud, Sylvain; Mousis, Olivier

    2015-02-01

    This work gives a van't Hoff law expression of Langmuir constants of different species for determining their occupancy in clathrate hydrates. First, a pairwise site-site interaction potential energy model is used to calculate the Langmuir constants in an otherwise anisotropic potential environment, as a function of temperature. The results are then fitted to a van't Hoff law expression to give a set of parameters that can be used for calculating clathrates compositions. The van't Hoff law's parameters are given for eighteen gas species trapped in the small and large cavities of structure types I and II. The accuracy of this approach is based on a detailed comparison with available experimental and/or previously calculated data for ethane, cyclo-propane, methane and carbon dioxide clathrate hydrates. A comparison with the analytical cell method is also carried out to better understand the importance of asymmetry and possible limitations of the van't Hoff temperature dependence.

  2. Vibrational modes of methane in the structure H clathrate hydrate from ab initio molecular dynamics simulation.

    PubMed

    Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K; Yasuoka, Kenji

    2012-10-14

    Vibrational spectra of guest molecules in clathrate hydrates are frequently measured to determine the characteristic signatures of the molecular environment and dynamical properties of guest-host interactions. Here, we present results of our study on the vibrational frequencies of methane molecules in structure H clathrate hydrates, namely, in the 5(12) and 4(3)5(6)6(3) cages, as the frequencies of stretching vibrational modes in these environments are still unclear. The vibrational spectra of methane molecules in structure H clathrate hydrate were obtained from ab initio molecular dynamics simulation and computed from Fourier transform of autocorrelation functions for each distinct vibrational mode. The calculated symmetric and asymmetric stretching vibrational frequencies of methane molecules were found to be lower in the 4(3)5(6)6(3) cages than in the 5(12) cages (3.8 cm(-1) for symmetric stretching and 6.0 cm(-1) for asymmetric stretching). The C-H bond length and average distance between methane molecules and host-water molecules in 4(3)5(6)6(3) cages were slightly longer than those in the 5(12) cages.

  3. Homogeneous two-dimensional nucleation of guest-free silicon clathrates

    NASA Astrophysics Data System (ADS)

    Lü, Yong jun

    2015-01-01

    The difficulty in synthesizing guest-free semiconductor clathrates complicates the process of determining how these cage-like structures form. This work studies the microscopic mechanism of the nucleation of guest-free Si136 clathrate using molecular dynamics simulations with the Stillinger-Weber potential. The homogeneous nucleation of Si136, which is realized in a narrow negative pressure range before liquid cavitation, exhibits the characteristic feature of the two-dimensional (2D) mode. The critical nucleus is composed of one to two five-membered rings, and the nucleation barrier is close to 1 kBT. According to a thermodynamic model based on atomistic nucleation theory, the effective binding energy associated with the formation of 2D critical nuclei is significantly low, which is responsible for the low nucleation barrier of Si136 clathrate. In the post-nucleation period, the critical nucleus preferentially grows into a dodecahedron, and the latter continuously grows with sharing face along <1 1 0>.

  4. Effects of the CO2 Guest Molecule on the sI Clathrate Hydrate Structure

    PubMed Central

    Izquierdo-Ruiz, Fernando; Otero-de-la-Roza, Alberto; Contreras-García, Julia; Prieto-Ballesteros, Olga; Recio, Jose Manuel

    2016-01-01

    This paper analyzes the structural, energetic and mechanical properties of carbon dioxide hydrate clathrates calculated using finite cluster and periodic ab initio density-functional theory methodologies. Intermolecular interactions are described by the exchange-hole dipole moment method. The stability, gas saturation energetics, guest–host interactions, cage deformations, vibrational frequencies, and equation of state parameters for the low-pressure sI cubic phase of the CO2@H2O clathrate hydrate are presented. Our results reveal that: (i) the gas saturation process energetically favors complete filling; (ii) carbon dioxide molecules prefer to occupy the larger of the two cages in the sI structure; (iii) blue shifts occur in both the symmetric and antisymmetric stretching frequencies of CO2 upon encapsulation; and (iv) free rotation of guest molecules is restricted to a plane parallel to the hexagonal faces of the large cages. In addition, we calculate the librational frequency of the hindered rotation of the guest molecule in the plane perpendicular to the hexagonal faces. Our calculated spectroscopic data can be used as signatures for the detection of clathrate hydrates in planetary environments. PMID:28773898

  5. High Pressure Properties of a Ba-Cu-Zn-P Clathrate-I

    SciTech Connect

    Dolyniuk, Juli -Anna; Kovnir, Kirill

    2016-08-12

    Here, the high pressure properties of the novel tetrel-free clathrate, Ba8Cu13.1Zn3.3P29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba8Cu13.1Zn3.3P29.6 using a third-order Birch-Murnaghan equation of state is 65(6) GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A8Ga16Ge30 (A = Sr, Ba) and Sn19.3Cu4.7P22I8, but lower than those for the transition metal-containing silicon-based clathrates, Ba8TxSi46–x, T = Ni, Cu; 3 ≤ x ≤ 5.

  6. Nonequilibrium air clathrate hydrates in Antarctic ice: a paleopiezomdter for polar ice caps.

    PubMed

    Craig, H; Shoji, H; Langway, C C

    1993-12-01

    "Craigite," the mixed-air clathrate hydrate found in polar ice caps below the depth of air-bubble stability, is a clathrate mixed crystal of approximate composition (N2O2).6H2O. Recent observations on the Byrd Station Antarctic core show that the air hydrate is present at a depth of 727 m, well above the predicted depth for the onset of hydrate stability. We propose that the air hydrate occurs some 100 m above the equilibrium phase boundary at Byrd Station because of "piezometry"--i.e., that the anomalous depth of hydrate occurrence is a relic of a previous greater equilibrium depth along the flow trajectory, followed by vertical advection of ice through the local phase-boundary depth. Flowline trajectories in the ice based on numerical models show that the required vertical displacement does indeed occur just upstream of Byrd Station. Air-hydrate piezometry can thus be used as a general parameter to study the details of ice flow in polar ice caps and the metastable persistence of the clathrate phase in regions of upwelling blue ice.

  7. Nonequilibrium air clathrate hydrates in Antarctic ice: a paleopiezomdter for polar ice caps.

    PubMed Central

    Craig, H; Shoji, H; Langway, C C

    1993-01-01

    "Craigite," the mixed-air clathrate hydrate found in polar ice caps below the depth of air-bubble stability, is a clathrate mixed crystal of approximate composition (N2O2).6H2O. Recent observations on the Byrd Station Antarctic core show that the air hydrate is present at a depth of 727 m, well above the predicted depth for the onset of hydrate stability. We propose that the air hydrate occurs some 100 m above the equilibrium phase boundary at Byrd Station because of "piezometry"--i.e., that the anomalous depth of hydrate occurrence is a relic of a previous greater equilibrium depth along the flow trajectory, followed by vertical advection of ice through the local phase-boundary depth. Flowline trajectories in the ice based on numerical models show that the required vertical displacement does indeed occur just upstream of Byrd Station. Air-hydrate piezometry can thus be used as a general parameter to study the details of ice flow in polar ice caps and the metastable persistence of the clathrate phase in regions of upwelling blue ice. Images Fig. 2 PMID:11607442

  8. High Pressure Properties of a Ba-Cu-Zn-P Clathrate-I

    DOE PAGES

    Dolyniuk, Juli -Anna; Kovnir, Kirill

    2016-08-12

    Here, the high pressure properties of the novel tetrel-free clathrate, Ba8Cu13.1Zn3.3P29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba8Cu13.1Zn3.3P29.6 using a third-order Birch-Murnaghan equation of state is 65(6) GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A8Ga16Ge30 (A = Sr, Ba) and Sn19.3Cu4.7P22I8, but lower than those for the transition metal-containing silicon-based clathrates, Ba8TxSi46–x, T = Ni, Cu; 3 ≤more » x ≤ 5.« less

  9. NMR Evidence of Cage-to-Cage Diffusion of H2 in H2-Clathrates

    NASA Astrophysics Data System (ADS)

    Senadheera, Lasitha; Conradi, Mark

    2008-03-01

    H2 and heavy-ice at P>1 kbar and T ˜250 K form H2-D2O clathrate; four and one H2 may occupy each large (L) and small (S) cage, respectively. In H2-THF-H2O clathrate, H2 occupies singly and only S cages. Previous electronic-structure calculations estimate the barriers for H2 passage though hexagonal and pentagonal faces of cages as ˜6 and ˜25 kcal/mol, respectively. Our H2 NMR linewidth data reflect random crystal fields from frozen cage-wall D2O orientations. We find dramatic reductions in linewidth starting at 120 K (175 K) for H2-D2O (H2-TDF-D2O) indicating time-averaging of the crystal fields. Assuming Arrhenius behavior, our data imply energies for escape from L (S) cages of about ˜4 (˜6) kcal/mol. For L cages, the agreement with the calculated (cages were treated as rigid) barrier is reasonable. For H2 in S cages, in H2-TDF-D2O, the extreme disagreement with theory points to another mechanism of time-averaging, reorientations of the cage-wall D2O molecules, as suggested by previous work in TDH-H2O clathrate. Our limited NMR spectra at high T ˜145 K in H2-D2O show evidence of distinct resonances from diffusionally mobile and immobile H2 molecules, as expected.

  10. On the Design of High Efficiency Thermoelectric Type I Clathrates through Transition Metal Doping

    SciTech Connect

    Shi, Xun; Yang, Jiong; Yang, Jihui; Salvador, James R.; Bai, Shengqiang; Zhang, Weiqing; Chen, Lidong; Wong-Ng, W.; Wang, Hsin

    2010-01-01

    The lack of high efficiency thermoelectric materials hinders their deployment into wide ranging applications such as power generation from waste heat and solid state heating and cooling, which could lead to significant energy savings. Type I clathrates have recently been identified as prospective thermoelectric materials for power generation purposes due to their very low lattice thermal conductivity values. The maximum thermoelectric figure of merit of almost all type I clathrates is, however, less than 1; and occurs at, or above, 1000 K making them unfavorable especially for intermediate temperature applications. In this report, we demonstrate that transition metal doping introduces charge distortion and lattice defects into these materials which increases the ionized impurity scattering of carriers and point defect scattering of lattice phonons, respectively; leading to an enhanced power factor, reduced lattice thermal conductivity, and therefore improved thermoelectric figure of merit. Most importantly, the band gap of these materials can be tuned between 0.1 eV and 0.5 eV by adjusting the transition metal content, making it possible to design type I clathrates with excellent thermoelectric properties between 500 K and 1000 K.

  11. [Nervous system disorders induced by occupational exposure to arsenic and its inorganic compounds: a literature review].

    PubMed

    Sińczuk-Walczak, Halina

    2009-01-01

    This paper presents a review of the effect of arsenic (As) and its inorganic compounds on the nervous system. In humans, inhalation exposure mostly occurs in occupational conditions. In the occupational environment, the most extensive exposure to this element is observed in the copper industry. Chronic As poisoning is manifested by skin and mucous membrane lesions, impairment of the nervous system in the form of disorders of psychic functions and polyneuropathies, retrobulbar neuritis, disorders of peripheral circulation and the risk for Raynaud's syndrome. Arsenic-induced polyneuropathy is usually a very serious and chronic disease. A complete recovery is observed in only 15-20% of patients. As-induced encephalopathy is an irreversible process.

  12. Pressure-induced superconductivity in topological parent compound Bi2Te3

    PubMed Central

    Zhang, J. L.; Zhang, S. J.; Weng, H. M.; Zhang, W.; Yang, L. X.; Liu, Q. Q.; Feng, S. M.; Wang, X. C.; Yu, R. C.; Cao, L. Z.; Wang, L.; Yang, W. G.; Liu, H. Z.; Zhao, W. Y.; Zhang, S. C.; Dai, X.; Fang, Z.; Jin, C. Q.

    2011-01-01

    We report a successful observation of pressure-induced superconductivity in a topological compound Bi2Te3 with Tc of ∼3 K between 3 to 6 GPa. The combined high-pressure structure investigations with synchrotron radiation indicated that the superconductivity occurred at the ambient phase without crystal structure phase transition. The Hall effects measurements indicated the hole-type carrier in the pressure-induced superconducting Bi2Te3 single crystal. Consequently, the first-principles calculations based on the structural data obtained by the Rietveld refinement of X-ray diffraction patterns at high pressure showed that the electronic structure under pressure remained topologically nontrivial. The results suggested that topological superconductivity can be realized in Bi2Te3 due to the proximity effect between superconducting bulk states and Dirac-type surface states. We also discuss the possibility that the bulk state could be a topological superconductor. PMID:21173267

  13. Cytoprotective Effects of Organosulfur Compounds against Methimazole Induced Toxicity in Isolated Rat Hepatocytes

    PubMed Central

    Heidari, Reza; Babaei, Hossein; Eghbal, Mohammad Ali

    2013-01-01

    Purpose: Methimazole is a drug widely used in hyperthyroidism. However, life threatening hepatotoxicity has been associated with its clinical use. No protective agent has been found to be effective against methimazole induced hepatotoxicity yet. Hence, the capacity of organosulfur compounds to protect rat hepatocytes against cytotoxic effects of methimazole and its proposed toxic metabolite, N-methylthiourea was evaluated. Methods: Hepatocytes were prepared by the method of collagenase enzyme perfusion via portal vein. Cells were treated with different concentrations of methimazole, N methylthiourea, and organosulfur chemicals. Cell death, protein carbonylation, reactive oxygen species formation, lipid peroxidation, and mitochondrial depolarization were assessed as toxicity markers and the role of organosulfurs administration on them was investigated. Results: Methimazole caused a decrease in cellular glutathione content, mitochondrial membrane potential (ΔΨm) collapse, and protein carbonylation. In addition, an increase in reactive oxygen species (ROS) formation and lipid peroxidation was observed. Treating hepatocytes with N methylthiourea caused a reduction in hepatocytes glutathione reservoirs and an elevation in carbonylated proteins, but no significant ROS formation, lipid peroxidation, or mitochondrial depolarization was observed. N-acetyl cysteine, allylmercaptan, and diallyldisulfide attenuated cell death and prevented ROS formation and lipid peroxidation caused by methimazole. Furthermore, organosulfur compounds diminished methimazole induced mitochondrial damage and reduced the carbonylated proteins. In addition, these chemicals showed protective effects against cell death and protein carbonylation induced by methimazole metabolite. Conclusion: Organosulfur chemicals extend their protective effects against methimazole-induced toxicity by attenuating oxidative stress caused by this drug and preventing the adverse effects of methimazole and/or its

  14. The Sophora Flavescens flavonoid compound trifolirhizin inhibits acetylcholine induced airway smooth muscle contraction

    PubMed Central

    Zeng, Jia; Zhan, Jixun; Brown, LaVerne; Sampson, Hugh; Goldfarb, Joseph; Emala, Charles; Li, Xiu-Min

    2014-01-01

    Asthma is a serious health problem worldwide, particularly in industrialized countries. Despite a better understanding of the pathophysiology of asthma, there are still considerable gaps in knowledge as well as a need for new classes of drugs. ASHMI™ (Anti-asthma Herbal Medicine Intervention) is an aqueous extract of Ganoderma lucidum (Fr.) P. Karst (Ling Zhi), Sophora flavescens Aiton (Ku Shen) and Glycyrrhiza uralensis Fisch. ex DC (Gan Cao). It prevents allergic asthma airway hyper-reactivity in mice and inhibits acetylcholine (ACh) induced airway smooth muscle (ASM) contraction in tracheal rings from allergic asthmatic mice. The purpose of this research was to identify individual herb(s) and their active compound(s) that inhibit ASM contraction. It was found that Sophora flavescens (S. flavescens), but not Ganoderma lucidum (G. lucidum) or Glycyrrhiza uralensis (G. uralensis) aqueous extracts, inhibited ASM contraction in tracheal rings from asthmatic mice. Bioassay-guided isolation and identification of flavonoid fractions/compound(s) via methylene chloride extraction, preparative HPLC fractionation, and LC-MS and NMR spectroscopic analyses showed that trifolirhizin is an active constituent that inhibits acetylcholine mediated ASM contraction or directly relaxes pre-contracted ASM independent of β2-adrenoceptors. PMID:23993294

  15. The Sophora flavescens flavonoid compound trifolirhizin inhibits acetylcholine induced airway smooth muscle contraction.

    PubMed

    Yang, Nan; Liang, Banghao; Srivastava, Kamal; Zeng, Jia; Zhan, Jixun; Brown, LaVerne; Sampson, Hugh; Goldfarb, Joseph; Emala, Charles; Li, Xiu-Min

    2013-11-01

    Asthma is a serious health problem worldwide, particularly in industrialized countries. Despite a better understanding of the pathophysiology of asthma, there are still considerable gaps in knowledge as well as a need for classes of drugs. ASHMI™ (Anti-asthma Herbal Medicine Intervention) is an aqueous extract of Ganoderma lucidum (Fr.) P. Karst (Ling Zhi), Sophora flavescens Aiton (Ku Shen) and Glycyrrhiza uralensis Fisch. ex DC (Gan Cao). It prevents allergic asthma airway hyper-reactivity in mice and inhibits acetylcholine (ACh) induced airway smooth muscle (ASM) contraction in tracheal rings from allergic asthmatic mice. The purpose of this research was to identify individual herb(s) and their active compound(s) that inhibit ASM contraction. It was found that S. flavescens, but not G. lucidum or G. uralensis aqueous extracts, inhibited ASM contraction in tracheal rings from asthmatic mice. Bioassay-guided isolation and identification of flavonoid fractions/compound(s) via methylene chloride extraction, preparative HPLC fractionation, and LC-MS and NMR spectroscopic analyses showed that trifolirhizin is an active constituent that inhibits acetylcholine mediated ASM contraction or directly relaxes pre-contracted ASM independent of β2-adrenoceptors. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Ambient ionization and direct identification of volatile organic compounds with microwave-induced plasma mass spectrometry.

    PubMed

    Li, Dandan; Tian, Yong-Hui; Zhao, Zhongjun; Li, Wenwen; Duan, Yixiang

    2015-02-01

    An innovative method of volatile organic compounds analysis by using microwave-induced plasma ionization (MIPI) source in combination with an ambient ion trap mass spectrometer is presented here. Using MIPI for direct sample vapor, analysis was achieved without any sample preparation or subsequent heating. The relative abundance of the target compounds can be obtained almost instantly within a few seconds. The ionization processes of different volatile compounds was optimized, and the limits of detection were identified in the range of 0.15-4.5 pptv or 0.73-8.80 pg ml(-1). The relative standard deviation (RSD) is in the range of 4-14%, while correlation coefficients of the working curves (R(2)) are better than 0.98. The new method possesses advantages of ease operation, time-saving, high sensitivity and inexpensive setup. In addition, the ionization processes of short n-alkane chains were investigated with the MIPI technique, and a unique [M + 13](+) was detected, which has not been reported in detail by any other related ionization techniques. An ionization mechanism was proposed on the basis of the experimental results obtained in this work and available information in literatures, in which the n-alkanes in the plasma environment possibly generate protonated cyclopentadiene [M - 5](+) or alkyl-substituted analogues as well as hydrous ions [M + 13](+) and [M + 13 + 18](+), as shown in Scheme 1 in the main text.

  17. Induced root-secreted phenolic compounds as a belowground plant defense

    PubMed Central

    Burlat, Vincent; Schurr, Ulrich; Röse, Ursula SR

    2010-01-01

    Rhizosphere is the complex place of numerous interactions between plant roots, microbes and soil fauna. Whereas plant interactions with aboveground organisms are largely described, unravelling plant belowground interactions remains challenging. Plant root chemical communication can lead to positive interactions with nodulating bacteria, mycorriza or biocontrol agents or to negative interactions with pathogens or root herbivores. A recent study1 suggested that root exudates contribute to plant pathogen resistance via secretion of antimicrobial compounds. These findings point to the importance of plant root exudates as belowground signalling molecules, particularly in defense responses. In our report,2 we showed that under Fusarium attack the barley root system launched secretion of phenolic compounds with antimicrobial activity. The secretion of de novo biosynthesized t-cinnamic acid induced within 2 days illustrates the dynamic of plant defense mechanisms at the root level. We discuss the costs and benefits of induced defense responses in the rhizosphere. We suggest that plant defense through root exudation may be cultivar dependent and higher in wild or less domesticated varieties. PMID:20699651

  18. Large reversible magnetocaloric effect induced by metamagnetic transition in antiferromagnetic HoNiGa compound

    NASA Astrophysics Data System (ADS)

    Wang, Yi-Xu; Zhang, Hu; Wu, Mei-Ling; Tao, Kun; Li, Ya-Wei; Yan, Tim; Long, Ke-Wen; Long, Teng; Pang, Zheng; Long, Yi

    2016-12-01

    The magnetic properties and magnetocaloric effects (MCE) of HoNiGa compound are investigated systematically. The HoNiGa exhibits a weak antiferromagnetic (AFM) ground state below the Ńeel temperature TN of 10 K, and the AFM ordering could be converted into ferromagnetic (FM) ordering by external magnetic field. Moreover, the field-induced FM phase exhibits a high saturation magnetic moment and a large change of magnetization around the transition temperature, which then result in a large MCE. A large -ΔSM of 22.0 J/kg K and a high RC value of 279 J/kg without magnetic hysteresis are obtained for a magnetic field change of 5 T, which are comparable to or even larger than those of some other magnetic refrigerant materials in the same temperature range. Besides, the μ0H2/3 dependence of well follows the linear fitting according to the mean-field approximation, suggesting the nature of second-order FM-PM magnetic transition under high magnetic fields. The large reversible MCE induced by metamagnetic transition suggests that HoNiGa compound could be a promising material for magnetic refrigeration in low temperature range. Project supported by the National Natural Science Foundation of China (Grant Nos. 51671022 and 51427806), the Beijing Natural Science Foundation, China (Grant No. 2162022), and the Fundamental Research Funds for the Central Universities, China (Grant No. FRF-TP-15-002A3).

  19. Novel application of brain-targeting polyphenol compounds in sleep deprivation-induced cognitive dysfunction

    PubMed Central

    Zhao, Wei; Wang, Jun; Bi, Weina; Ferruzzi, Mario; Yemul, Shrishailam; Freire, Daniel; Mazzola, Paolo; Ho, Lap; Dubner, Lauren; Pasinetti, Giulio Maria

    2016-01-01

    Sleep deprivation produces deficits in hippocampal synaptic plasticity and hippocampal-dependent memory storage. Recent evidence suggests that sleep deprivation disrupts memory consolidation through multiple mechanisms, including the down-regulation of the cAMP-response element-binding protein (CREB) and of mammalian target of rapamycin (mTOR) signaling. In this study, we tested the effects of a Bioactive Dietary Polyphenol Preparation (BDPP), comprised of grape seed polyphenol extract, Concord grape juice, and resveratrol, on the attenuation of sleep deprivation-induced cognitive impairment. We found that BDPP significantly improves sleep deprivation-induced contextual memory deficits, possibly through the activation of CREB and mTOR signaling pathways. We also identified brain-available polyphenol metabolites from BDPP, among which quercetin-3-O-glucuronide activates CREB signaling and malvidin-3-O-glucoside activates mTOR signaling. In combination, quercetin and malvidin-glucoside significantly attenuated sleep deprivation-induced cognitive impairment in -a mouse model of acute sleep deprivation. Our data suggests the feasibility of using select brain-targeting polyphenol compounds derived from BDPP as potential therapeutic agents in promoting resilience against sleep deprivation-induced cognitive dysfunction. PMID:26235983

  20. Novel application of brain-targeting polyphenol compounds in sleep deprivation-induced cognitive dysfunction.

    PubMed

    Zhao, Wei; Wang, Jun; Bi, Weina; Ferruzzi, Mario; Yemul, Shrishailam; Freire, Daniel; Mazzola, Paolo; Ho, Lap; Dubner, Lauren; Pasinetti, Giulio Maria

    2015-10-01

    Sleep deprivation produces deficits in hippocampal synaptic plasticity and hippocampal-dependent memory storage. Recent evidence suggests that sleep deprivation disrupts memory consolidation through multiple mechanisms, including the down-regulation of the cAMP-response element-binding protein (CREB) and of mammalian target of rapamycin (mTOR) signaling. In this study, we tested the effects of a Bioactive Dietary Polyphenol Preparation (BDPP), comprised of grape seed polyphenol extract, Concord grape juice, and resveratrol, on the attenuation of sleep deprivation-induced cognitive impairment. We found that BDPP significantly improves sleep deprivation-induced contextual memory deficits, possibly through the activation of CREB and mTOR signaling pathways. We also identified brain-available polyphenol metabolites from BDPP, among which quercetin-3-O-glucuronide activates CREB signaling and malvidin-3-O-glucoside activates mTOR signaling. In combination, quercetin and malvidin-glucoside significantly attenuated sleep deprivation-induced cognitive impairment in -a mouse model of acute sleep deprivation. Our data suggests the feasibility of using select brain-targeting polyphenol compounds derived from BDPP as potential therapeutic agents in promoting resilience against sleep deprivation-induced cognitive dysfunction.

  1. Copper compound induces autophagy and apoptosis of glioma cells by reactive oxygen species and jnk activation

    PubMed Central

    2012-01-01

    Background Glioblastoma multiforme (GBM) is the most aggressive of the primary brain tumors, with a grim prognosis despite intensive treatment. In the past decades, progress in research has not significantly increased overall survival rate. Methods The in vitro antineoplastic effect and mechanism of action of Casiopeina III-ia (Cas III-ia), a copper compound, on rat malignant glioma C6 cells was investigated. Results Cas III-ia significantly inhibited cell proliferation, inducing autophagy and apoptosis, which correlated with the formation of autophagic vacuoles, overexpression of LC3, Beclin 1, Atg 7, Bax and Bid proteins. A decrease was detected in the mitochondrial membrane potential and in the activity of caspase 3 and 8, together with the generation of intracellular reactive oxygen species (ROS) and increased activity of c-jun NH2-terminal kinase (JNK). The presence of 3-methyladenine (as selective autophagy inhibitor) increased the antineoplastic effect of Cas III-ia, while Z-VAD-FMK only showed partial protection from the antineoplastic effect induced by Cas III-ia, and ROS antioxidants (N-acetylcysteine) decreased apoptosis, autophagy and JNK activity. Moreover, the JNK –specific inhibitor SP600125 prevented Cas III-ia-induced cell death. Conclusions Our data suggest that Cas III-ia induces cell death by autophagy and apoptosis, in part due to the activation of ROS –dependent JNK signaling. These findings support further studies of Cas III-ia as candidate for treatment of human malignant glioma. PMID:22540380

  2. Effect of histamine antagonists on myocardial carcinine metabolism during compound 48/80-induced shock.

    PubMed

    Fitzpatrick, J C; Fisher, H; Flancbaum, L

    1990-10-01

    Carcinine (beta-alanylhistamine) is an imidazole dipeptide that exists in mammalian hearts, increases cardiac contractility, and is metabolically linked to carnosine (beta-alanylhistidine), a non-mast cell histidine and histamine precursor during stress. We have previously shown that tissue carnosine levels are regulated by H1 and H2 receptors. This study evaluated the effects of H1, H2, and mast cell degranulation blockers on metabolism of carcinine and related imidazoles during shock induced by compound 48/80, a mast cell degranulator. Fifty 125-g male Sprague-Dawley rats were divided into nine ip treatment groups: saline, 48/80, lodoxamide (LOD, mast cell degranulation inhibitor), diphenhydramine (DPH, H1 antagonist), cimetidine (CIM, H2 antagonist), LOD + 48/80, CIM + 48/80, DPH + 48/80, or DPH + CIM + 48/80. Heart tissue was analyzed at 30 min by HPLC. 48/80 caused decreases in myocardial carnosine (P less than 0.01) and histidine (P less than 0.0001) levels and concomitant increases in carcinine (P less than 0.01), histamine (P less than 0.01), and 3-methylhistamine (P less than 0.05) compared to those of controls. These changes were inhibited by LOD or DPH. Treatment with CIM significantly increased myocardial carcinine levels compared to 48/80 alone (P less than 0.001) without an additional effect on the other compounds. These data indicate that carcinine is involved in the cardiac response to stress via the carnosine-histidine-histamine pathway. Compound 48/80-induced shock increases histamine metabolism via this pathway resulting in mobilization of myocardial carnosine and histidine to carcinine and histamine; this effect is increased by H2 receptor blockade.

  3. Synthesis of a fluorescently labeled compound for the detection of arsenic-induced apoptotic HL60 cells.

    PubMed

    Femia, A Lis; Temprana, C Facundo; Amor, M Silvia; Grasselli, Mariano; Alonso, Silvia Del V

    2012-03-01

    Arsenic compounds have shown medical usefulness since they proved to be effective in causing complete remission of acute promyelocytic leukemia. In this work we obtained a fluorescently labeled arsenic compound that can be used with current fluorescence techniques for basic and applied research, focused on arsenic-induced apoptosis studies. This compound is an arsanilic acid bearing a covalently linked FITC that was chemically synthesized and characterized by fluorescence, UV-Vis, mass and FTIR spectrometry. In addition, we assessed its apoptotic activity as well as its fluorescent labeling properties in HL60 cell line as a leukemia cell model through flow cytometry. We obtained a compound with a 1:1 FITC:arsenic ratio and a 595 m/z, confirming its structure by FTIR. This compound proved to be useful at inducing apoptosis in the leukemia cell model and labeling this apoptotic cell population, in such a way that the highest FITC fluorescence correlated with the highest arsenic amount.

  4. Compound Danshen injection improves endotoxin-induced microcirculatory disturbance in rat mesentery

    PubMed Central

    Han, Jing-Yan; Horie, Yoshinori; Miura, Soichiro; Akiba, Yasutada; Guo, Jun; Li, Dan; Fan, Jing-Yu; Liu, Yu-Ying; Hu, Bai-He; An, Li-Hua; Chang, Xin; Xu, Man; Guo, De-An; Sun, Kai; Yang, Ji-Ying; Fang, Shu-Ping; Xian, Ming-Ji; Kizaki, Masahiro; Nagata, Hiroshi; Hibi, Toshifumi

    2007-01-01

    AIM: To investigate the effect of compound Danshen injection on lipopolysaccharide (LPS)-induced rat mesenteric microcirculatory dysfunctions and the underlying possible mechanism by an inverted intravital microscope and high-speed video camera system. METHODS: LPS was continuously infused through the jugular artery of male Wistar rats at the dose of 2 mg/kg per hour. Changes in mesenteric microcirculation, such as diameters of arterioles and venules, velocity of RBCs in venules, leukocyte rolling, adhesion and emigration, free radicals released from post-capillary venules, FITC-albumin leakage and mast cell degranulation, were observed through an inverted intravital microscope assisted with CCD camera and SIT camera. Meanwhile, the expression of adhesion molecules CD11b/CD18 and the production of free radical in neutrophils, and the expression of intercellular adhesion molecule 1 (ICAM-1) in human umbilical vein endothelial cells (HUVECs) were quantified by flow cytometry (FACS) in vitro. RESULTS: The continuous infusion with LPS resulted in a number of responses in microcirculation, including a significant increase in the positive region of venule stained with Monastral blue B, rolling and adhesion of leukocytes, production of oxygen radical in venular wall, albumin efflux and enhanced mast cell degranulation in vivo, all of which, except for the leukocyte rolling, were attenuated by the treatment with compound Danshen injection. Experiments performed in vitro further revealed that the expression of CD11b/CD18 and the production of oxygen free radical in neutrophils, and the expression of ICAM-1 in HUVECs were increased by exposure to LPS, and they were attenuated by compound Danshen injection. CONCLUSION: These results suggest that compound Danshen injection is an efficient drug with multi-targeting potential for improving the microcirculatory disturbance. PMID:17659708

  5. Attenuation of 2-methoxyethanol-induced testicular toxicity in the rat by simple physiological compounds.

    PubMed

    Mebus, C A; Welsch, F; Working, P K

    1989-06-01

    2-Methoxyethanol (2-ME) is an industrial solvent which is toxic to both male and female reproductive systems of laboratory animals. Earlier data have demonstrated that the developmental toxicity of 2-ME can be attenuated by simple physiological compounds such as serine, acetate, sarcosine, glycine, and D-glucose. The present experiments were designed to evaluate the same compounds for their ability to ameliorate the testicular toxicity that occurs in rats after 2-ME exposure. The extent of testicular damage was assessed by quantitating daily sperm production (DSP) on Day 24 following a single dose of 2-ME (6.6 mmol/kg, 500 mg/kg). Serine completely eliminated 2-ME-induced decreases in DSP, while glucose was without effect. Acetate, sarcosine, and glycine were of similar efficacy resulting in DSP that was significantly greater than that observed in rats which received 2-ME alone. Histopathological studies revealed that 2-ME treatment resulted in stage-specific degeneration of late stage pachytene spermatocytes 24 hr after treatment. No apparent degenerative changes occurred after concurrent treatment with serine. Similarly, serine also prevented the decreased number of spermatids in the lumina of the seminiferous tubules on Day 24 after 2-ME exposure alone. All of the compounds utilized in this study are linked to oxidation pathways involving tetrahydrofolic acid as a catalyst for one-carbon moiety transfer into purine and pyrimidine bases which are necessary precursors for DNA and RNA synthesis. The ability of these compounds to attenuate the testicular toxicity of 2-ME may result from their ability to donate one-carbon units which can be used in purine base biosynthesis. Reduced availability of bases would be expected to affect late stage pachytene spermatocytes which are known to be undergoing rapid RNA synthesis.

  6. Volcanic Destabilisation of Methane Clathrate Hydrate on Titan: the Mechanism for Resupplying Atmospheric CH4?

    NASA Astrophysics Data System (ADS)

    Davies, Ashley; Sotin, C.; Choukroun, M.; Matson, D. L.; Johnson, T. V.

    2013-10-01

    Titan may have an upper crust rich in methane clathrates which would have formed early in Titan’s history [1-3]. The abundance of atmospheric methane, which has a limited lifetime, and the presence of 40Ar require replenishment over time. Volcanic processes may release these gases from Titan’s interior, although, so far, no conclusive evidence of an ongoing volcanic event has been observed: no “smoking gun” has been seen. Still, some process has recently supplied a considerable amount of methane to Titan’s atmosphere. We have investigated the emplacement of “cryolavas” of varying composition to quantify thermal exchange and lava solidification processes to model thermal wave penetration into a methane-rich substrate (see [4]), and to determine event detectability. Clathrate destabilisation releases methane and other trapped gases, such as argon. A 10-m-thick cryolava covering 100 km2 raises 3 x 108 m3 of substrate methane clathrates to destabilization temperature in ~108 s. With a density of 920 kg/m3, and ≈13% of the mass being methane, 4 x 1010 kg of methane is released. This is an impressive amount, but it would take 5 million similar events to yield the current mass of atmospheric methane. However, meeting Titan’s current global methane replenishment rate is feasible through the thermal interaction between cryolavas and methane clathrate deposits, but only (1) after the flow has solidified; (2) if cracks form, connecting surface to substrate; and (3) the cracks form while the temperature of the clathrates is greater than the destabilisation temperature. The relatively small scale of this activity may be hard to detect. This work was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Choukroun, M. and Sotin, C. (2012) GRL, 39, L04201. [2] Tobie, G. et al. (2006) Nature, 440, 61-64. [3] Lunine, J. et al. (2009) Origin and Evolution of Titan, in Titan From Cassini-Huygens, ed. R. Brown et al

  7. Tyrphostin AG-related compounds attenuate H2O2-induced TRPM2-dependent and -independent cellular responses.

    PubMed

    Yamamoto, Shinichiro; Toda, Takahiro; Yonezawa, Ryo; Negoro, Takaharu; Shimizu, Shunichi

    2017-05-01

    TRPM2 is a Ca(2+)-permeable channel that is activated by H2O2. TRPM2-mediated Ca(2+) signaling has been implicated in the aggravation of inflammatory diseases. Therefore, the development of TRPM2 inhibitors to prevent the aggravation of these diseases is expected. We recently reported that some Tyrphostin AG-related compounds inhibited the H2O2-induced activation of TRPM2 by scavenging the intracellular hydroxyl radical. In the present study, we examined the effects of AG-related compounds on H2O2-induced cellular responses in human monocytic U937 cells, which functionally express TRPM2. The effects of AG-related compounds on H2O2-induced changes in intracellular Ca(2+) concentrations, extracellular signal-regulated kinase (ERK) activation, and CXCL8 secretion were assessed using U937 cells. Ca(2+) influxes via TRPM2 in response to H2O2 were blocked by AG-related compounds. AG-related compounds also inhibited the H2O2-induced activation of ERK, and subsequent secretion of CXCL8 mediated by TRPM2-dependent and -independent mechanisms. Our results show that AG-related compounds inhibit H2O2-induced CXCL8 secretion following ERK activation, which is mediated by TRPM2-dependent and -independent mechanisms in U937 cells. We previously reported that AG-related compounds blocked H2O2-induced TRPM2 activation by scavenging the hydroxyl radical. The inhibitory effects of AG-related compounds on TRPM2-independent responses may be due to scavenging of the hydroxyl radical. Copyright © 2017 The Authors. Production and hosting by Elsevier B.V. All rights reserved.

  8. A spectroscopic study of the structure and occupancies of clathrate hydrates incorporating hydrogen

    NASA Astrophysics Data System (ADS)

    Grim, R. Gary

    With the ability to store and concentrate gases inside a clean and abundant water framework, clathrate hydrates are considered to be a promising material for many applications related to gas storage, separation, and sequestration. Hydrates of hydrogen are particularly interesting, for in addition to these potential applications, the small molecular size provides an opportunity for use as a model guest in many fundamental studies such as guest diffusion, multiple guest occupancy, and quantum mechanical effects upon confinement. In attempt to study these effects and the viability of H 2 hydrates as an energy storage material, a combined experimental and theoretical approach incorporating Raman spectroscopy, X-ray and neutron diffraction, nuclear magnetic resonance, ab-initio calculations, and molecular dynamic simulations was performed. One of the most significant challenges in the application of H2 clathrate hydrates is the demanding thermodynamic requirements needed for stability. In recent years, a mechanism known as the `tuning' effect had reportedly solved this issue where thermodynamic requirements could be reduced while simultaneously maintaining high storage capacities. In this work, the viability and validity of this technique is explored and alternative explanations in the form of epitaxial hydrate growth under high driving force conditions are discussed. A second, and equally important challenge facing clathrate hydrates as a future storage material is the overall storage capacity of H2. In previous work, H2 has only been experimentally verified to occupy the small 512 and 43566 3 cages and also in the large 51264 cages of the type II clathrate, often with an energy deficient promoter. In order to achieve more robust energy densities, other hydrate cages must be accessible. Herein a new method for increasing overall hydrate energy densities is presented involving the incorporation of H2 in the large cages of the type I clathrate with CH4 as a co

  9. UV radiation-induced accumulation of photoprotective compounds in the green alga Tetraspora sp. CU2551.

    PubMed

    Rastogi, Rajesh P; Incharoensakdi, Aran

    2013-09-01

    The effect of UV radiation on the accumulation of novel mycosporine-like amino acids (MAAs) along with their photoprotective function was investigated in the green alga Tetraspora sp. CU2551. No UV-absorbing compound was detected in this organism growing under normal light condition while two MAAs with absorption maxima at 324 nm and 322 nm were found to be accumulated after UV irradiation. The effects of UV exposure time with different cut-off filter foils namely 295 (PAR + UV-A + UV-B), 320 (PAR + UV-A) and 395 nm (PAR only) were studied on induction of the synthesis of these MAAs. Concentration of MAAs was found to increase with increase in exposure time under UV radiation. Furthermore, the antioxidant and photoprotective action of these MAAs was also investigated. The role of MAAs in diminishing the UV-induced production of ROS in vivo was also demonstrated using the oxidant-sensing probe 2',7'-dichlorodihydrofluorescein diacetate (DCFH-DA) and results obtained supported the results of DPPH free radical scavenging assay. The MAAs also exhibited efficient photoprotective ability on Escherichia coli cells against UV-B stress. Thus, the MAAs in Tetraspora sp. CU2551 may act as efficient antioxidants as well as UV-sunscreen. This is the first report for the UV-induced synthesis and co-accumulation of these MAAs and their photoprotective actions in Tetraspora sp. which is a member of the class Chlorophyceae. Moreover, UV-induced accumulation as well as photoprotective function of these compounds may facilitate this chlorophyte to perform important ecological functions in harsh environmental conditions with high UV-B fluxes in their brightly lit habitats.

  10. Compound 48/80-induced serotonin release from brain mast cells

    SciTech Connect

    Lambracht-Hall, M.; Marathias, K.P.; Theoharides, T.C.

    1986-03-01

    Mast cells secrete a variety of potent mediators and are mostly known to participate in allergic reactions. Here the authors report that perfused brain mast cells can take up and release serotonin (5-HT) in response to compound 48/80. Thalamic or hypothalamic slices were loaded with /sup 3/H-5-HT (5 x 10/sup -7/M, for 12 min at 37/sup 0/C), washed and placed in individual 2 ml-perfusion wells. A Krebs-Ringer bicarbonate buffer with 1 x 10/sup -6/M imipramine (KRB + IMI) saturated with 5% CO/sub 2//95% O/sub 2/ at 37/sup 0/C and pH 7.4, was used throughout at a perfusion rate of 1 ml/min. After a 60 min wash in KRB + IMI, with or without Ca/sup +2/ + 0.1 M EDTA, the slices were perfused for 45 min with 100 ..mu..g/ml compound 48/80 with or without Ca/sup +2/. The tissue was washed for 30 min as before and then perfused with high K/sup +/ KRB (40mM KCl) for 45 min to induce neuronal depolarization. Finally, calcium was restored to Ca/sup +2/-depleted tissues and all samples were again perfused for 45 min with high K/sup +/ KRB. The first 5-HT peak due to 48/80-induced mast cell release was independent of extracellular Ca/sup +2/, while the second 5-HT peak due to high K/sup +/ was not. These studies indicate that the 48/80-induced 5-HT release was not of neuronal origin and that brain mast cells can utilize intracellular Ca/sup +2/, much like their peritoneal counterparts. The authors are now studying brain mast cells secretion in response to neuropeptides.

  11. Toxic but Drank: Gustatory Aversive Compounds Induce Post-ingestional Malaise in Harnessed Honeybees

    PubMed Central

    Ayestaran, Ainara

    2010-01-01

    Background Deterrent substances produced by plants are relevant due to their potential toxicity. The fact that most of these substances have an unpalatable taste for humans and other mammals contrasts with the fact that honeybees do not reject them in the range of concentrations in which these compounds are present in flower nectars. Here we asked whether honeybees detect and ingest deterrent substances and whether these substances are really toxic to them. Results We show that pairing aversive substances with an odor retards learning of this odor when it is subsequently paired with sucrose. Harnessed honeybees in the laboratory ingest without reluctance a considerable volume (20 µl) of various aversive substances, even if some of them induce significant post-ingestional mortality. These substances do not seem, therefore, to be unpalatable to harnessed bees but induce a malaise-like state that in some cases results in death. Consistently with this finding, bees learning that one odor is associated with sugar, and experiencing in a subsequent phase that the sugar was paired with 20 µl of an aversive substance (devaluation phase), respond less than control bees to the odor and the sugar. Such stimulus devaluation can be accounted for by the malaise-like state induced by the aversive substances. Conclusion Our results indicate that substances that taste bitter to humans as well as concentrated saline solutions base their aversive effect on the physiological consequences that their ingestion generates in harnessed bees rather than on an unpalatable taste. This conclusion is only valid for harnessed bees in the laboratory as freely-moving bees might react differently to aversive compounds could actively reject aversive substances. Our results open a new possibility to study conditioned taste aversion based on post-ingestional malaise and thus broaden the spectrum of aversive learning protocols available in honeybees. PMID:21060877

  12. Fractographic finger printing of proton-irradiation-induced disordering and amorphization of intermetallic compounds

    SciTech Connect

    Cheng, J.; Yuan, M.; Wagner, C. N. J.; Ardell, A. J.

    1989-05-01

    The intermetallic compounds NiTi, NiTi/sub 2/, CuZr, CuTi/sub 2/, and Zr/sub 3/Al were irradiated by 2 MeV protons at various temperatures between --175 /degree/C and --44 /degree/C to a fluence of 1.9/times/10/sup 22/ H/sup +//m/sup 2/. Transmission electron microscopy, electron diffraction, and x-ray diffraction were used to evaluate the extents of disordering and amorphization induced by irradiation in the samples. Both phenomena progressed to varying extents in the five compounds, depending on the irradiation temperature and dose. It was observed that the C-A transition began before the degree of long-range order was reduced significantly, and that the amorphous phase nucleated homogeneously throughout the crystalline matrix. A major finding of the current investigation is that the technique of scanning electron fractography provides a useful correlation between the features of the fractured surfaces and the microstructural alterations induced by the proton irradiations. When amorphization is complete the fracture surfaces are either featureless (e.g., NiTi/sub 2/) or contain branching features resembling river patterns. In some cases (especially in CuZr) these are similar to the markings seen on the surface of fractured amorphous ribbons produced by melt-spinning. In general, however, there is not a particularly good correlation between the features on the fracture surfaces of the irradiated and melt-spun ribbons. When the microstructure consists of amorphous regions embedded in a partially disordered crystalline matrix, there is consierable evidence for irradiation-induced ductility. In such cases, exemplified by the results on NiTi and Zr/sub 3/Al, the fracture surfaces contain dimples, characteristic of ductile fracture, suggesting that disordering promotes ductility.

  13. A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ohmura, Ryo; Ripmeester, John A.

    2011-02-01

    Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO2 molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

  14. A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2.

    PubMed

    Alavi, Saman; Ohmura, Ryo; Ripmeester, John A

    2011-02-07

    Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO(2) molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

  15. Phyllostachys edulis Compounds Inhibit Palmitic Acid-Induced Monocyte Chemoattractant Protein 1 (MCP-1) Production

    PubMed Central

    Higa, Jason K.; Liang, Zhibin; Williams, Philip G.; Panee, Jun

    2012-01-01

    Background Phyllostachys edulis Carriere (Poaceae) is a bamboo species that is part of the traditional Chinese medicine pharmacopoeia. Compounds and extracts from this species have shown potential applications towards several diseases. One of many complications found in obesity and diabetes is the link between elevated circulatory free fatty acids (FFAs) and chronic inflammation. This study aims to present a possible application of P. edulis extract in relieving inflammation caused by FFAs. Monocyte chemoattractant protein 1 (MCP-1/CCL2) is a pro-inflammatory cytokine implicated in chronic inflammation. Nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) and activator protein 1 (AP-1) are transcription factors activated in response to inflammatory stimuli, and upregulate pro-inflammatory cytokines such as MCP-1. This study examines the effect of P. edulis extract on cellular production of MCP-1 and on the NF-κB and AP-1 pathways in response to treatment with palmitic acid (PA), a FFA. Methodology/Principal Findings MCP-1 protein was measured by cytometric bead assay. NF-κB and AP-1 nuclear localization was detected by colorimetric DNA-binding ELISA. Relative MCP-1 mRNA was measured by real-time quantitative PCR. Murine cells were treated with PA to induce inflammation. PA increased expression of MCP-1 mRNA and protein, and increased nuclear localization of NF-κB and AP-1. Adding bamboo extract (BEX) inhibited the effects of PA, reduced MCP-1 production, and inhibited nuclear translocation of NF-κB and AP-1 subunits. Compounds isolated from BEX inhibited MCP-1 secretion with different potencies. Conclusions/Significance PA induced MCP-1 production in murine adipose, muscle, and liver cells. BEX ameliorated PA-induced production of MCP-1 by inhibiting nuclear translocation of NF-κB and AP-1. Two O-methylated flavones were isolated from BEX with functional effects on MCP-1 production. These results may represent a possible therapeutic

  16. Auranofin, as an anti-rheumatic gold compound, suppresses LPS-induced homodimerization of TLR4.

    PubMed

    Youn, Hyung S; Lee, Joo Y; Saitoh, Shin I; Miyake, Kensuke; Hwang, Daniel H

    2006-12-01

    Toll-like receptors (TLRs), which are activated by invading microorganisms or endogenous molecules, evoke immune and inflammatory responses. TLR activation is closely linked to the development of many chronic inflammatory diseases including rheumatoid arthritis. Auranofin, an Au(I) compound, is a well-known and long-used anti-rheumatic drug. However, the mechanism as to how auranofin relieves the symptom of rheumatoid arthritis has not been fully clarified. Our results demonstrated that auranofin suppressed TLR4-mediated activation of transcription factors, NF-kappaB and IRF3, and expression of COX-2, a pro-inflammatory enzyme. This suppression was well correlated with the inhibitory effect of auranofin on the homodimerization of TLR4 induced by an agonist. Furthermore, auranofin inhibited NF-kappaB activation induced by MyD88-dependent downstream signaling components of TLR4, MyD88, IKKbeta, and p65. IRF3 activation induced by MyD88-independent signaling components, TRIF and TBK1, was also downregulated by auranofin. Our results first demonstrate that auranofin suppresses the multiple steps in TLR4 signaling, especially the homodimerization of TLR4. The results suggest that the suppression of TLR4 activity by auranofin may be the molecular mechanism through which auranofin exerts anti-rheumatic activity.

  17. Inhibition of sodium current by taurine magnesium coordination compound prevents cesium chloride-induced arrhythmias.

    PubMed

    Yin, Yongqiang; Wen, Ke; Wu, Yanna; Kang, Yi; Lou, Jianshi

    2012-05-01

    The mechanism(s) by which taurine magnesium coordination compound (TMCC) inhibits experimental arrhythmias remains poorly understood. The purpose of this study was to observe the effects of TMCC against cesium chloride-induced arrhythmia in the rabbit heart and find whether the antiarrhythmic activity is related to inhibition of sodium current. Early afterdepolarization was induced by 1.5 mM cesium chloride (1 ml kg(-1)) through intravenous injection. The monophasic action potentials (MAP) and electrocardiograms were simultaneously recorded. The effect of TMCC on functional refractory periods (FRPs) in the left atrium was also observed in vitro. Arrhythmias onset was significantly retarded by TMCC. The number of ventricular premature contractions and incidence of monophasic ventricular tachycardia and polyphasic ventricular tachycardia in 10 min were decreased by TMCC. These effects can be abolished by veratridine (10 μg kg(-1)). MAP duration at 90% repolarization was significantly prolonged by TMCC, which can be prolonged even longer by veratridine (10 μg kg(-1)). In vitro experiments showed that FRPs was prolonged by TMCC which can be cancelled by veratridine (10 μg kg(-1)). TMCC prevents cesium chloride-induced arrhythmias, and inhibition of sodium current, in part, contributes to the antiarrhythmic effect of TMCC.

  18. Transition metal-induced degradation of a pharmaceutical compound in reversed-phase liquid chromatographic analysis.

    PubMed

    Wang, Qinggang; He, Brian Lingfeng; Zhang, Jin; Huang, Yande; Kleintop, Brent; Raglione, Thomas

    2015-01-01

    Drug degradation that occurs in HPLC analysis, during either sample preparation or chromatographic separation, can greatly impact method robustness and result accuracy. In this work, we report a case study of drug dimerization in HPLC analysis where proximate causes were attributed to either the LC columns or the HPLC instrument. Solution stress studies indicated that the same pseudo-dimeric degradants could also be formed rapidly when the compound was exposed to certain oxidative transition metal ions, such as Cu(II) and Fe(III). Two pseudo-dimeric degradants were isolated from transition metal stressed samples and their structures were elucidated. A degradation pathway was proposed, whereby the degradation was initiated through transition metal-induced single electron transfer oxidation. Further studies confirmed that the dimerization was induced by trace transition metals in the HPLC flow path, which could arise from either the stainless steel frits in the LC column or stainless steel tubing in the HPLC instrument. Various procedures to prevent transition metal-induced drug degradation were explored, and a general strategy to mitigate such risks is briefly discussed.

  19. Natural compound Alternol induces oxidative stress-dependent apoptotic cell death preferentially in prostate cancer cells.

    PubMed

    Tang, Yuzhe; Chen, Ruibao; Huang, Yan; Li, Guodong; Huang, Yiling; Chen, Jiepeng; Duan, Lili; Zhu, Bao-Ting; Thrasher, J Brantley; Zhang, Xu; Li, Benyi

    2014-06-01

    Prostate cancers at the late stage of castration resistance are not responding well to most of current therapies available in clinic, reflecting a desperate need of novel treatment for this life-threatening disease. In this study, we evaluated the anticancer effect of a recently isolated natural compound, Alternol, in multiple prostate cancer cell lines with the properties of advanced prostate cancers in comparison to prostate-derived nonmalignant cells. As assessed by trypan blue exclusion assay, significant cell death was observed in all prostate cancer cell lines except DU145 but not in nonmalignant (RWPE-1 and BPH1) cells. Further analyses revealed that Alternol-induced cell death was an apoptotic response in a dose- and time-dependent manner, as evidenced by the appearance of apoptosis hallmarks such as caspase-3 processing and PARP cleavage. Interestingly, Alternol-induced cell death was completely abolished by reactive oxygen species scavengers N-acetylcysteine and dihydrolipoic acid. We also demonstrated that the proapoptotic Bax protein was activated after Alternol treatment and was critical for Alternol-induced apoptosis. Animal xenograft experiments in nude mice showed that Alternol treatment largely suppressed tumor growth of PC-3 xenografts but not Bax-null DU-145 xenografts in vivo. These data suggest that Alternol might serve as a novel anticancer agent for patients with late-stage prostate cancer. ©2014 American Association for Cancer Research.

  20. Metabolical shifts towards alternative BTEX biodegradation intermediates induced by perfluorinated compounds in firefighting foams.

    PubMed

    Montagnolli, Renato Nallin; Lopes, Paulo Renato Matos; Cruz, Jaqueline Matos; Claro, Marina Turini; Quiterio, Gabriela Mercuri; Bidoia, Ederio Dino

    2017-04-01

    The type and concentration of perfluorinated compounds (PFCs) can induce different types of enzymes and promote alternate patterns of BTEX transformation. However, it is not known how the presence of active fluorocarbon-degrading microbial populations affects the transformation of BTEX. In addition to chemical analysis at the molecular level, our research approached the aqueous film forming fire-fighting foams (AFFF) and BTEX co-contamination at a large-scale with respirometers to quantify the total microbial metabolism of soil via CO2 output levels. The intended outcome of this research was to obtain and characterize shifts in BTEX degradation at a set realistic environmental condition while measuring byproducts and CO2 production. Both methodologies complimentarily provided an in-depth knowledge of the environmental behavior of fire-fighting foams. The biodegradation was monitored using headspace sampling and two types of gas chromatography: thermal conductivity detector and flame ionization detector. Headspace samples were periodically withdrawn for BTEX biodegradation and CO2 production analysis. Our research suggests the discovery of an altered metabolic pathway in aromatic hydrocarbons biodegradation that is directly affected by fluorinated substances. The fluorinated compounds affected the BTEX biodegradation kinetics, as PFCs may contribute to a shift in styrene and catechol concentrations in co-contamination scenarios. A faster production of styrene and catechol was detected. Catechol is also rapidly consumed, thus undergoing further metabolic stages earlier under the presence of PFCs. The release of AFFF compounds not only changes byproducts output but also drastically disturbs the soil microbiota according to the highly variable CO2 yields. Therefore, we observed a high sensitivity of microbial consortia due to PFCs in the AFFF formulation, therefore shifting their BTEX degradation routes in terms of intermediate products concentration. Copyright © 2016

  1. Irradiation-induced disordering and amorphization of Al3Ti-based intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Park, Jeong-Yong; Kim, Il-Hyun; Motta, Arthur T.; Ulmer, Christopher J.; Kirk, Marquis A.; Ryan, Edward A.; Baldo, Peter M.

    2015-12-01

    An in situ ion-irradiation study, simultaneously examined using transmission electron microscopy, was performed to investigate irradiation-induced disordering and amorphization of Al3Ti-based intermetallic compounds. Thin foil samples of two crystalline structures: D022-structured Al3Ti and L12-structured (Al,Cr)3Ti were irradiated using 1.0 MeV Kr ions at a temperature range from 40 K to 573 K to doses up to 4.06 × 1015 ions/cm2. The results showed that both the compounds underwent an order-disorder transformation under irradiation, where both Al3Ti and (Al,Cr)3Ti ordered structures were fully transformed to the disordered face-centered cubic (FCC) structure except at the highest irradiation temperature of 573 K. A slightly higher irradiation dose was required for order-disorder transformation in case of Al3Ti as compared to (Al,Cr)3Ti at a given temperature. However, their amorphization resistances were different: while the disordered FCC (Al,Cr)3Ti amorphized at the irradiation dose of 6.25 × 1014 ions/cm2 (0.92 dpa) at 40 K and 100 K, the Al3Ti compound with the same disordered FCC structure maintained crystallinity up to 4.06 × 1015 ions/cm2 (5.62 dpa) at 40 K. The critical temperature for amorphization of (Al,Cr)3Ti under Kr ion irradiation is likely between 100 K and room temperature and the critical temperature for disordering between room temperature and 573 K.

  2. A Novel Gallium Compound Synergistically Enhances Bortezomib-induced Apoptosis in Mantle Cell Lymphoma Cells

    PubMed Central

    Chitambar, Christopher R.; Purpi, David P.

    2010-01-01

    Combination chemotherapy forms the backbone of cancer treatment. There is a need for new drug combinations for the treatment of mantle cell lymphoma (MCL). Herein, we show that gallium maltolate, a novel gallium compound, synergizes with bortezomib, a proteasome inhibitor, to induce cell death in MCL Granta cells. Cells exposed to either agent displayed caspase-3 activation, a loss of mitochondrial membrane potential, and a decrease in chymotrypsin-like activity. These effects were increased with both agents in combination. Our results show for the first time that the proteasome may be a target for gallium maltolate and suggest that the therapeutic potential of combination bortezomib and gallium maltolate warrants further investigation. PMID:20334913

  3. Two new compounds from Semen celosiae and their protective effects against CCl₄-induced hepatotoxicity.

    PubMed

    Xue, Qian; Sun, Zhen-Liang; Guo, Mei-Li; Wang, Ying; Zhang, Ge; Wang, Xiao-Kang

    2011-04-01

    Two new oleanolic acid saponins, namely celosin A (1) and celosin B (2), together with six known compounds, stigmasterol, β-sitosterol, β-daucosterol, hexacosoic acid, palmitic acid and stearic acid, were isolated from the ethanolic extract of Semen celosiae. The structures of celosin A (1) and celosin B (2) were determined by spectral analysis (including 1D- and 2D-NMR). The hepatoprotective activity of 1 and 2 with oral doses 1.0, 2.0 and 4.0 mg kg⁻¹ were investigated by carbon tetrachloride CCl₄-induced hepatotoxicity in mice. The results indicate that they have significant hepatoprotective effects, and that these hepatoprotective effects may be due to the antioxidant capability.

  4. Hydration structures of lactic acid: characterization of the ionic clathrate hydrate formed with a biological organic acid anion.

    PubMed

    Muromachi, Sanehiro; Abe, Toru; Yamamoto, Yoshitaka; Takeya, Satoshi

    2014-10-21

    Ionic clathrate hydrates are water-based materials that have unique properties, such as a wide range of melting temperatures and high gas capacities. In their structure, water molecules coordinate around ionic substances, which is regarded as the actual hydration structure and also linking of the hydrate clusters, giving insight into the dynamics of the water molecules and ions. This paper reports the synthesis and characterization of the ionic clathrate hydrate of tetra-n-butylammonium lactate (TBAL), the anion of which is a biological organic material. Phase equilibrium measurements and optical observations of the crystal morphology and crystal structure analysis were performed. The TBAL hydrate has a melting temperature of 284.8 K suitable for cool energy storage applications. The actual hydration patterns around a lactate anion are shown in the form of ionic clathrate hydrate structure.

  5. Pressure induced structural phase transition in IB transition metal nitrides compounds

    SciTech Connect

    Soni, Shubhangi; Kaurav, Netram Jain, A.; Shah, S.; Choudhary, K. K.

    2015-06-24

    Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.

  6. Effect of phenolic compounds against Aβ aggregation and Aβ-induced toxicity in transgenic C. elegans.

    PubMed

    Jagota, Seema; Rajadas, Jayakumar

    2012-01-01

    Substantial evidence suggests that the aggregation of amyloid-β (Aβ) peptide into fibrillar structures that is rich in β-sheets is implicated as the cause of Alzheimer's disease. Therefore, an attractive therapeutic strategy is to prevent or alter Aβ aggregation. Phenolic compounds are natural substances that are composed of one or more aromatic phenolic rings and present in wine, tea, fruits, vegetables and a wide variety of plants. In this work, we investigated the effects of ferulic acid, morin, quercetin and gossypol against Aβ aggregation. From the ThT and turbidity assays, it is observed that in addition to the fibril aggregate, another type of aggregate is formed in the presence of morin, quercetin, and gossypol. On the other hand, ferulic acid did not prevent fibril formation, but it did appear to reduce the average length of fibrils compared to Aβ alone. To study the protective effects of phenolic compounds on Aβ-induced toxicity, we utilized the nematode Caenorhabditis elegans (C. elegans) as an in vivo model organism, human Aβ is expressed intracellularly in the body wall muscle. We found that exposure of Caenorhabditis elegans to ferulic acid give more protection against Aβ toxicity than morin, quercetin and gossypol.

  7. Pressure induced structural phase transition in IB transition metal nitrides compounds

    NASA Astrophysics Data System (ADS)

    Soni, Shubhangi; Kaurav, Netram; Jain, A.; Shah, S.; Choudhary, K. K.

    2015-06-01

    Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.

  8. Procaspase-activating compound 1 induces a caspase-3-dependent cell death in cerebellar granule neurons

    SciTech Connect

    Aziz, Gulzeb; Akselsen, Oyvind W.; Hansen, Trond V.; Paulsen, Ragnhild E.

    2010-09-15

    Procaspase-activating compound 1, PAC-1, has been introduced as a direct activator of procaspase-3 and has been suggested as a therapeutic agent against cancer. Its activation of procaspase-3 is dependent on the chelation of zinc. We have tested PAC-1 and an analogue of PAC-1 as zinc chelators in vitro as well as their ability to activate caspase-3 and induce cell death in chicken cerebellar granule neuron cultures. These neurons are non-dividing, primary cells with normal caspase-3. The results reported herein show that PAC-1 chelates zinc, activates procaspase-3, and leads to caspase-3-dependent cell death in neurons, as the specific caspase-3-inhibitor Ac-DEVD-cmk inhibited both the caspase-3 activity and cell death. Thus, chicken cerebellar granule neurons is a suitable model to study mechanisms of interference with apoptosis of PAC-1 and similar compounds. Furthermore, the present study also raises concern about potential neurotoxicity of PAC-1 if used in cancer therapy.

  9. Nickel compounds induce histone ubiquitination by inhibiting histone deubiquitinating enzyme activity

    SciTech Connect

    Ke Qingdong; Ellen, Thomas P.; Costa, Max

    2008-04-15

    Nickel (Ni) compounds are known carcinogens but underlying mechanisms are not clear. Epigenetic changes are likely to play an important role in nickel ion carcinogenesis. Previous studies have shown epigenetic effects of nickel ions, including the loss of histone acetylation and a pronounced increase in dimethylated H3K9 in nickel-exposed cells. In this study, we demonstrated that both water-soluble and insoluble nickel compounds induce histone ubiquitination (uH2A and uH2B) in a variety of cell lines. Investigations of the mechanism by which nickel increases histone ubiquitination in cells reveal that nickel does not affect cellular levels of the substrates of this modification, i.e., ubiquitin, histones, and other non-histone ubiquitinated proteins. In vitro ubiquitination and deubiquitination assays have been developed to further investigate possible effects of nickel on enzymes responsible for histone ubiquitination. Results from the in vitro assays demonstrate that the presence of nickel did not affect the levels of ubiquitinated histones in the ubiquitinating assay. Instead, the addition of nickel significantly prevents loss of uH2A and uH2B in the deubiquitinating assay, suggesting that nickel-induced histone ubiquitination is the result of inhibition of (a) putative deubiquitinating enzyme(s). Additional supporting evidence comes from the comparison of the response to nickel ions with a known deubiquitinating enzyme inhibitor, iodoacetamide (IAA). This study is the first to demonstrate such effects of nickel ions on histone ubiquitination. It also sheds light on the possible mechanisms involved in altering the steady state of this modification. The study provides further evidence that supports the notion that nickel ions alter epigenetic homeostasis in cells, which may lead to altered programs of gene expression and carcinogenesis.

  10. Purified vitexin compound 1 induces apoptosis through activation of FOXO3a in hepatocellular carcinoma.

    PubMed

    Wang, Jian-Gang; Zheng, Xing-Xing; Zeng, Guang-Yao; Zhou, Ying-Jun; Yuan, Hong

    2014-01-01

    We previously reported that purified vitexin compound 1 (VB1, a neolignan from the seed of Chinese herb Vitex negundo) exhibited antitumor activity in cancer cell lines and xenograft models. In the present study, we examined the molecular mechanisms by which activation of the FOXO3a transcription factor mediated VB1-induced apoptosis in hepatocellular carcinoma (HCC) cells. The effects of VB1 on the proliferation of HCC cell lines HepG2, Hep3B, Huh-7 and human embryo liver L-02 cells were investigated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Apoptotic death in HepG2 cells was examined using an enzyme-linked immunosorbent assay (ELISA) detection kit, flow cytometry after propidium iodide (PI) staining, and by DNA agarose gel electrophoresis. Caspase activity was measured using ELISA. The AKT/FOXO3a and ERK/FOXO3a pathways were analyzed using western blotting. VB1 inhibited human HCC cell proliferation in a concentration-dependent manner and increased the percentage of sub-G1 population HepG2 cells. Histone/DNA fragmentation and active caspase-3, -8 and -9 levels increased in a concentration-dependent manner and a DNA ladder was formed. The phosphorylation of AKT and ERK1/2 were inhibited and FOXO3a transcription factor was activated, resulting in apoptotic death. Knockdown of AKT1 by small interfering RNA (siRNA) and the MEK1/2 inhibitor, PD98059, enhanced VB1-induced apoptosis and FOXO3a transcriptional activity. Suppression of FOXO3a expression by siRNA inhibited VB1-induced apoptosis. VB1 induced expression of Bim, TRAIL, DR4 and DR5. Activation of the FOXO3a transcription factor appears to mediate pro-apoptotic effects of VB1 by inhibiting the AKT and ERK pathways.

  11. Morphine-induced Straub tail reaction in mice treated with serotonergic compounds.

    PubMed

    Belozertseva, Irina V; Dravolina, Olga A; Tur, Margarita A; Semina, Marina G; Zvartau, Edwin E; Bespalov, Anton Yu

    2016-11-15

    Constitutively active 5-HT2 receptors have been suggested to contribute to motoneuronal excitability, muscle spasms and spasticity. Accordingly, 5-HT2C receptor inverse agonists have been demonstrated in pilot experiments to reduce spasticity in animal model of spasticity and patients with spinal cord injuries. Thus, 5-HT2C receptor inverse agonists may represent a novel class of anti-spasticity agents justifying a search for compounds with robust 5-HT2C receptor inverse agonist activity either among the existing medications or via a dedicated drug discovery program. Morphine-induced Straub tail response in mice is regarded as a model of transient spasticity that may be suitable for supporting such drug discovery efforts. Subcutaneous injection of morphine (10-60mg/kg) induced a dose-dependent Straub tail reaction in male Swiss mice with maximum response obtained 15-30min after the morphine administration. When given prior to morphine, 5-HT2B/2C receptor inverse agonists cyproheptadine (1-10mg/kg, i.p.) and SB206553 (0.3-3mg/kg, i.p.) diminished Straub tail reaction dose-dependently without affecting spontaneous locomotor activity. In contrast, 5-HT2B/2C receptor antagonist methysergide (1-5.6mg/kg, i.p.) and 5-HT2C receptor antagonist SB242084 (1-5.6mg/kg, i.p.) as well as 5-HT2A receptor inverse agonist pimavanserin (1-10mg/kg, i.p.) had no appreciable effects on Straub tail response. Taken together, the findings indicate that constitutive activity of 5-HT2B/2C receptor may be involved in the mechanisms of morphine-induced spasticity. Thus, morphine-induced Straub tail response may be evaluated further as a candidate higher throughput test to identify 5-HT2C receptor inverse agonists with anti-spasticity effects in vivo.

  12. Enzyme entrapped nanoporous scaffolds formed through flow induced gelation in microfluidic filter device for sensitive biosensing of organophosphorus compounds

    SciTech Connect

    Lu, Donglai; Shao, Guocheng; Du, Dan; Wang, Jun; Wang, Limin; Wang, Wanjun; Lin, Yuehe

    2011-02-01

    A novel and versatile processing method was developed for the formation of gel scaffolds with in-situ AChE-AuNPs immobilization for biosensing of organophosphorus compounds. The biosensor designed by our new approach shows high sensitivity, selectivity and reactivation efficiency. This flow induced immobilziation technique opens up new pathways for designing simple, fast, biocompatible, and cost-effective process for enhanced sensor performance and on-site testing of a variety of toxic organophosphorus compounds.

  13. Synthesis of new heterocyclic compounds based on pyrazolopyridine scaffold and evaluation of their neuroprotective potential in MPP(+)-induced neurodegeneration.

    PubMed

    Jouha, Jabrane; Loubidi, Mohammed; Bouali, Jamila; Hamri, Salha; Hafid, Abderrafia; Suzenet, Franck; Guillaumet, Gérald; Dagcı, Taner; Khouili, Mostafa; Aydın, Fadime; Saso, Luciano; Armagan, Güliz

    2017-03-31

    Neurodegenerative disorders including Alzheimer's disease, Parkinson's disease, and Huntington's disease affect millions of people in the world. Thus several new approaches to treat brain disorders are under development. The aim of the present study is to synthesize potential neuroprotective heterocyclic compounds based on pyrazolopyridine derivatives and then to evaluate their effects in MPP(+)-induced neurodegeneration in human neuroblastoma cell line (SH-SY5Y cells). The effects of the compounds on cell viability were measured by MTT assay and the changes in apoptosis-related proteins including bax, Bcl-2, Bcl-xl and caspase-3 were investigated by western blot technique. Based on the cell viability results obtained by MTT assay, the percentage of neuroprotection-induced by compounds against MPP(+)-induced neurotoxicity in SH-SY5Y cells was between 20% and 30% at 5 μM concentrations of all synthesized compounds. Moreover, the downregulation in pro-apoptotic proteins including bax and caspase-3 were found following the novel synthesized compounds treatments and these effects were observed in a dose-dependent manner. Our results provide an evidence that these heterocyclic compounds based on pyrazolopyridine derivatives may have a role on dopaminergic neuroprotection via antiapoptotic pathways.

  14. Organopalladium compound 7b targets mitochondrial thiols and induces caspase-dependent apoptosis in human myeloid leukemia cells.

    PubMed

    Moraes, V W R; Caires, A C F; Paredes-Gamero, E J; Rodrigues, T

    2013-06-06

    The advances in the treatment of chronic myeloid leukemia (CML) during the last years were also accompanied by the development of evading strategies by tumor cells, resulting in chemotherapy resistance in some patients. Patented organopalladium compounds derived from the reaction of N,N-dimethyl-1-phenethylamine (dmpa) with [1,2-ethanebis(diphenylphosphine)] (dppe) exhibited a potent antitumor activity in vivo and in vitro in melanoma cells. We showed here that the cyclopalladated derivative [Pd2(R(+))C(2), N-dmpa)2(μ-dppe)Cl2], named compound 7b, was highly effective to promote cell death in the K562 human leukemia cells and its mechanisms of action were investigated. It was shown that compound 7b was able to promote exclusively apoptotic cell death in K562 cells associated to cytochrome c release and caspase 3 activation. This cytotoxic effect was not observed in normal peripheral mononuclear blood cells. The compound 7b-induced intrinsic apoptotic pathway was triggered by the protein thiol oxidation that resulted in the dissipation of the mitochondrial transmembrane potential. The preventive effect of the dithiothreitol on the compound 7b-induced cell death and all downstream events associated to apoptosis confirmed that death signal was elicited by the thiol oxidation. These findings contribute to the elucidation of the palladacycle 7b-induced cell death mechanism and present this compound as a promising drug in the CML antitumor chemotherapy.

  15. Organopalladium compound 7b targets mitochondrial thiols and induces caspase-dependent apoptosis in human myeloid leukemia cells

    PubMed Central

    Moraes, V W R; Caires, A C F; Paredes-Gamero, E J; Rodrigues, T

    2013-01-01

    The advances in the treatment of chronic myeloid leukemia (CML) during the last years were also accompanied by the development of evading strategies by tumor cells, resulting in chemotherapy resistance in some patients. Patented organopalladium compounds derived from the reaction of N,N-dimethyl-1-phenethylamine (dmpa) with [1,2-ethanebis(diphenylphosphine)] (dppe) exhibited a potent antitumor activity in vivo and in vitro in melanoma cells. We showed here that the cyclopalladated derivative [Pd2(R(+))C2, N-dmpa)2(μ-dppe)Cl2], named compound 7b, was highly effective to promote cell death in the K562 human leukemia cells and its mechanisms of action were investigated. It was shown that compound 7b was able to promote exclusively apoptotic cell death in K562 cells associated to cytochrome c release and caspase 3 activation. This cytotoxic effect was not observed in normal peripheral mononuclear blood cells. The compound 7b-induced intrinsic apoptotic pathway was triggered by the protein thiol oxidation that resulted in the dissipation of the mitochondrial transmembrane potential. The preventive effect of the dithiothreitol on the compound 7b-induced cell death and all downstream events associated to apoptosis confirmed that death signal was elicited by the thiol oxidation. These findings contribute to the elucidation of the palladacycle 7b-induced cell death mechanism and present this compound as a promising drug in the CML antitumor chemotherapy. PMID:23744358

  16. Cytotoxicity of the compounds isolated from Pulsatilla chinensis saponins and apoptosis induced by 23-hydroxybetulinic acid.

    PubMed

    Liu, Ming; Zhao, Xingzeng; Xiao, Lin; Liu, Ge; Liu, Haizhou; Wang, Xiangyun; Feng, Xu; Lin, Xiukun

    2015-01-01

    The rizoma of Pulsatilla chinensis (Bunge) Regel has been used as a traditional Chinese medicinal herb for thousands of years. Total saponins from P. chinensis can induce the apoptosis of solid cancer cells; however, their activity on chronic myeloid leukemia and the mechanisms remains unknown. To study the activity of total saponins and the main active fractions from P. chinensis saponins on chronic myeloid leukemia, and to illustrate the mechanisms underlying the anticancer activities. The cytotoxic activity were assayed by MTT; cell cycle arrest and apoptosis were tested by flow cytometry system; changes in the mitochondrial membrane potential were determined using JC-1; and the apoptosis signaling pathway was determined by western blotting. We demonstrated that total P. chinensis saponin displayed cytotoxic activity against K562 cell line. In addition, we identified 23-hydroxybetulinic acid (HBA), pulchinenoside A (PA), and anemoside B4 (AB4) from the total saponins, with the most cytotoxic compound HBA. Glycosylation at C3 and C28 of HBA significantly reduces its cytotoxicity. HBA could promote cell cycle arrest at S phase and induce apoptosis via intrinsic pathway. HBA disrupts mitochondrial membrane potential significantly (p < 0.01) and selectively downregulates the levels of Bcl-2, survivin and upregulates Bax, cytochrome C, cleaved caspase-9 and -3. Total saponins from P. chinensis may be effective natural products against human chronic myelogenous leukemia; HBA is one of the bioactive components responsible for its anticancer activity, and could be further investigated as an alternative therapeutic drug for leukemia.

  17. Protective effect of captopril, olmesartan, melatonin and compound 21 on doxorubicin-induced nephrotoxicity in rats.

    PubMed

    Hrenák, J; Arendášová, K; Rajkovičová, R; Aziriová, S; Repová, K; Krajčírovičová, K; Celec, P; Kamodyová, N; Bárta, A; Adamcová, M; Paulis, L; Simko, F

    2013-01-01

    Chronic kidney disease (CKD) represents a serious public health problem with increasing prevalence and novel approaches to renal protection are continuously under investigation. The aim of this study was to compare the effect of melatonin and angiotensin II type 2 receptor agonist compound 21 (C21) to angiotensin converting enzyme inhibitor captopril and angiotensin II type 1 receptor blocker olmesartan on animal model of doxorubicin nephrotoxicity. Six groups of 3-month-old male Wistar rats (12 per group) were treated for four weeks. The first group served as a control. The remaining groups were injected with a single dose of doxorubicin (5 mg/kg i.v.) at the same day as administration of either vehicle or captopril (100 mg/kg/day) or olmesartan (10 mg/kg/day) or melatonin (10 mg/kg/day) or C21 (0.3 mg/kg/day) was initiated. After four week treatment, the blood pressure and the level of oxidative stress were enhanced along with reduced glomerular density and increased glomerular size. Captopril, olmesartan and melatonin prevented the doxorubicin-induced increase in systolic blood pressure. All four substances significantly diminished the level of oxidative burden and prevented the reduction of glomerular density and modestly prevented the increase of glomerular size. We conclude that captopril, olmesartan, melatonin and C21 exerted a similar level of renoprotective effects in doxorubicin-induced nephrotoxicity.

  18. Olive oil phenolic compounds inhibit homocysteine-induced endothelial cell adhesion regardless of their different antioxidant activity.

    PubMed

    Manna, Caterina; Napoli, Daniela; Cacciapuoti, Giovanna; Porcelli, Marina; Zappia, Vincenzo

    2009-05-13

    In this study, we examine the effect of extra virgin olive oil phenolic compounds on homocysteine-induced endothelial dysfunction and whether the protective effects are related to their different scavenging activities. Structurally related compounds have been assayed for their ability to reduce homocysteine-induced monocyte adhesion as well as the cell surface expression of intercellular adhesion molecule-1 (ICAM-1) in EA.hy.926 cells. As well-known, among the selected phenolic compounds, hydroxytyrosol, homovanillyl alcohol, and the hydroxycinnamic acid derivatives caffeic and ferulic acid display high scavenging activities, while tyrosol and p-coumaric acid are poorly active. All of the tested compounds, approaching potential in vivo concentrations, significantly reduce homocysteine-induced cell adhesion and ICAM-1 expression. Interestingly, we report the first evidence that monophenols tyrosol and p-coumaric acid are selectively protective only in homocysteine-activated cells, while they are ineffective in reducing ICAM-1 expression induced by TNFalpha. Finally, we report the synergistic effect of o-diphenolic and monophenolic compounds.

  19. Quinuclidine compounds differently act as agonists of Kenyon cell nicotinic acetylcholine receptors and induced distinct effect on insect ganglionic depolarizations.

    PubMed

    Mathé-Allainmat, Monique; Swale, Daniel; Leray, Xavier; Benzidane, Yassine; Lebreton, Jacques; Bloomquist, Jeffrey R; Thany, Steeve H

    2013-12-01

    We have recently demonstrated that a new quinuclidine benzamide compound named LMA10203 acted as an agonist of insect nicotinic acetylcholine receptors. Its specific pharmacological profile on cockroach dorsal unpaired median neurons (DUM) helped to identify alpha-bungarotoxin-insensitive nAChR2 receptors. In the present study, we tested its effect on cockroach Kenyon cells. We found that it induced an inward current demonstrating that it bounds to nicotinic acetylcholine receptors expressed on Kenyon cells. Interestingly, LMA10203-induced currents were completely blocked by the nicotinic antagonist α-bungarotoxin. We suggested that LMA10203 effect occurred through the activation of α-bungarotoxin-sensitive receptors and did not involve α-bungarotoxin-insensitive nAChR2, previously identified in DUM neurons. In addition, we have synthesized two new compounds, LMA10210 and LMA10211, and compared their effects on Kenyon cells. These compounds were members of the 3-quinuclidinyl benzamide or benzoate families. Interestingly, 1 mM LMA10210 was not able to induce an inward current on Kenyon cells compared to LMA10211. Similarly, we did not find any significant effect of LMA10210 on cockroach ganglionic depolarization, whereas these three compounds were able to induce an effect on the central nervous system of the third instar M. domestica larvae. Our data suggested that these three compounds could bind to distinct cockroach nicotinic acetylcholine receptors.

  20. Global-density fluctuations in methane clathrate hydrates in externally applied electromagnetic fields

    NASA Astrophysics Data System (ADS)

    Waldron, Conor J.; English, Niall J.

    2017-07-01

    Non-equilibrium molecular-dynamics simulations of bulk methane clathrate hydrates have been conducted in a range of externally applied electromagnetic (e/m) fields. Studies into frequencies of system(or "global")-mass-density fluctuations showed that these clathrates have three major modes: the dominant one is attributable to water molecules' librations and occurs at 720 cm-1, regardless of any applied e/m fields. One of the more minor system-density fluctuations arises at 10-12 cm-1 and is caused by the propagation of local-density fluctuations; again, this is independent of e/m fields. The final density fluctuation is caused by e/m fields, and it only becomes apparent for field strengths of 1.2 V/nm or higher. The frequency of this mode is always twice the frequency of the applied e/m field. It was shown that the main qualitative features of the translational and librational densities of states (DOSs) were unaffected by the application of e/m fields; however, a slight coupling effect was observed, producing a peak in all DOSs at the frequency of the applied field. This study showed that e/m fields below a certain intensity threshold do not lead to any marked structural distortion or dissociation effect on pre-existing bulk clathrates, in which the hydrogen-bonding structure of the lattice remains intact. This is verified by system-density and configurational-energy values as well as radial distribution functions.

  1. A new family of multifunctional silicon clathrates: Optoelectronic and thermoelectric applications

    NASA Astrophysics Data System (ADS)

    Liu, Yinqiao; Jiang, Xue; Huang, Yingying; Zhou, Si; Zhao, Jijun

    2017-02-01

    To develop Si structures for multifunctional applications, here we proposed four new low-density silicon clathrates (Si-CL-A, Si-CL-B, Si-CL-C, and Si-CL-D) based on the same bonding topologies of clathrate hydrates. The electronic and thermal properties have been revealed by first-principles calculations. By computing their equation of states, phonon dispersion, and elastic constants, the thermodynamic, dynamic, and mechanical stabilities of Si-CL-A, Si-CL-B, Si-CL-C, and Si-CL-D allotropes are confirmed. In the low-density region of the phase diagram, Si-CL-B, Si-CL-D, and Si-CL-C would overtake diamond silicon and type II clathrate (Si-CL-II) and emerge as the most stable Si allotropes successively. Among them, the two direct semiconductors with bandgaps of 1.147 eV (Si-CL-A) and 1.086 eV (Si-CL-D) are found. The suitable bandgaps close to the optimal Shockley-Queisser limit result in better absorption efficiency in solar spectrum than conventional diamond silicon. Owing to the unique cage-based framework, the thermal conductivity of these Si allotropes at room temperature are very low (2.7-5.7 Wm-1 K-1), which are lower than that of diamond structured Si by two orders of magnitude. The suitable bandgaps, small effective masses, and low thermal conductivity of our new silicon allotropes are anticipated to find applications in photovoltaic and thermoelectric devices.

  2. Effect of ammonia on the stability of clathrate hydrates: experimental study and implications for Titan

    NASA Astrophysics Data System (ADS)

    Choukroun, M.; Ibourichene, A.; Smythe, W. D.; Mielke, R. E.; Barmatz, M.; Hodyss, R. P.

    2013-12-01

    The likely presence of clathrate hydrates on Titan has long been inferred from cosmochemical, thermal, and thermodynamic models. As gas-laden icy structures (up to 15 mol%), they may be internal reservoirs of methane and other atmospheric gasses, and their dissociation during cryovolcanic activity could be a main contributor to the replenishment of Titan's atmospheric methane. However, the controversial nature of the few cryovolcanic features tentatively detected on Titan by the Cassini spacecraft questions our current understanding of the modalities of outgassing processes. The paucity of data on the stability of clathrate hydrates in presence of ammonia (likely source of Titan's atmospheric nitrogen) hinders our capability to address outgassing processes. We are conducting an experimental study in the ternary systems H2O-CH4-NH3 and H2O-THF-NH3. Phase diagrams of the former are constructed under pressures up to 100 bars using a high-pressure cryogenic calorimeter, while the latter is investigated at atmospheric pressure using a liquid nitrogen cooled cryostage coupled to a microscope and a Raman spectrometer. The main preliminary results are: 1/ although ammonia does affect the stability of clathrate hydrates, its influence appears lower than on the melting of water ice; 2/ the dissociation proceeds incongruently, similarly to the incongruent melting of water ice in the H2O-NH3 system. These results and their implications will be presented at the meeting. This work has been conducted at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Copyright 2013, Caltech. Support by the NASA Outer Planets Research Program and government sponsorship acknowledged.

  3. Global-density fluctuations in methane clathrate hydrates in externally applied electromagnetic fields.

    PubMed

    Waldron, Conor J; English, Niall J

    2017-07-14

    Non-equilibrium molecular-dynamics simulations of bulk methane clathrate hydrates have been conducted in a range of externally applied electromagnetic (e/m) fields. Studies into frequencies of system(or "global")-mass-density fluctuations showed that these clathrates have three major modes: the dominant one is attributable to water molecules' librations and occurs at 720 cm(-1), regardless of any applied e/m fields. One of the more minor system-density fluctuations arises at 10-12 cm(-1) and is caused by the propagation of local-density fluctuations; again, this is independent of e/m fields. The final density fluctuation is caused by e/m fields, and it only becomes apparent for field strengths of 1.2 V/nm or higher. The frequency of this mode is always twice the frequency of the applied e/m field. It was shown that the main qualitative features of the translational and librational densities of states (DOSs) were unaffected by the application of e/m fields; however, a slight coupling effect was observed, producing a peak in all DOSs at the frequency of the applied field. This study showed that e/m fields below a certain intensity threshold do not lead to any marked structural distortion or dissociation effect on pre-existing bulk clathrates, in which the hydrogen-bonding structure of the lattice remains intact. This is verified by system-density and configurational-energy values as well as radial distribution functions.

  4. Catalytic activity of methanol in all-vapor subsecond clathrate-hydrate formation

    NASA Astrophysics Data System (ADS)

    Devlin, J. Paul

    2014-04-01

    Methanol's property as a catalyst in the formation of gas clathrate hydrates has been recognized for several years and was recently employed in a broad ranging study [K. Shin, K. A. Udachin, I. L. Moudrakovski, D. M. Leek, S. Alavi, C. I. Ratcliffe, and J. A. Ripmeester, Proc. Natl. Acad. Sci. U.S.A. 110, 8437 (2013)]. A new measure of that activity is offered here from comparative rates of formation of methanol (MeOH) clathrate hydrates within our all-vapor aerosol methodology for which tetrahydrofuran (THF) and other small ethers have set a standard for catalytic action. We have previously described numerous examples of the complete conversion of warm all-vapor mixtures to aerosols of gas clathrate hydrates on a sub-second time scale, generally with the catalyst confined primarily to the large cage of either structure-I (s-I) or structure-II (s-II) hydrates. THF has proven to be the most versatile catalyst for the complete subsecond conversion of water to s-II hydrate nanocrystals that follows pulsing of appropriate warm vapor mixtures into a cold chamber held in the 140-220 K range. Here, the comparative ability of MeOH to catalyze the formation of s-I hydrates in the presence of a small-cage help-gas, CO2 or acetylene, is examined. The surprising result is that, in the presence of either help gas, CH-formation rates appear largely unchanged by a complete replacement of THF by MeOH in the vapor mixtures for a chamber temperature of 170 K. However, as that temperature is increased, the dependence of effective catalysis by MeOH on the partial pressure of help gases also increases. Nevertheless, added MeOH is shown to markedly accelerate the s-II THF-CO2 CH formation rate at 220 K.

  5. The effect of topically applied salicylic compounds on serotonin-induced scratching behaviour in hairless rats.

    PubMed

    Thomsen, J S; Simonsen, L; Benfeldt, E; Jensen, S B; Serup, J

    2002-08-01

    There is a strong need for antipruritic substances for treating itch in clinical dermatology. In one recent human study, topically applied acetylsalicylic acid has been described to rapidly decrease histamine-induced itch. We have established a model for periferally elicited pruritus by injecting serotonin into the rostral back area (neck) in rats. Using this model, we aimed to investigate the antipruritic potential of four different salicylic compounds, which all possess different skin penetration characteristics. Eighteen rats were studied for 6 weeks. Prior to serotonin injections (2 mg/ml, 50 micro l), 10 micro l of test substances was applied to a circular area 18 mm in diameter. The four substances were salicylic acid, butyl salicylate, diethylamine salicylate and salicylamide, all solubilized in dimethyl isosorbide to a concentration of 5% w/w. Diethylamine salicylate and salicylamide were previously shown to be slowly absorbed through rat skin in contrast to salicylic acid and butyl salicylate. After serotonin injections, scratching was monitored by video recording for 1.5 h. Compared with the vehicle, a lower number of scratch sequences were seen when diethylamine salicylate (P < 0.001) and salicylamide (P = 0.005) had been applied. The numbers of scratch sequences were lower with diethylamine salicylate and salicylamide than with the vehicle throughout the 1.5-h study period. We conclude that topical application of diethylamine salicylate and salicylamide could suppress serotonin-induced scratching in rats. The antipruritic effect seems to be related to the slow drug release of the two substances. The results may be clinically relevant as serotonin induces itch in humans.

  6. Organophosphorus compound-induced delayed neurotoxicity in white leghorn hens assessed by Fluoro-Jade.

    PubMed

    Carlson, Kent; Ehrich, Marion

    2004-01-01

    Certain organophosphorus (OP) compounds can induce a delayed neuropathy, termed OPIDN, that involves central and peripheral nervous system axons, terminals, and perikarya. Historically, OPIDN has been characterized by staining neural sections with silver or hematoxylin and eosin (H and E). This study utilized a novel staining method, Fluoro-Jade, for evaluating the distribution and extent of OPIDN in the central nervous system of hens. Results were then compared to synoptically sectioned and stained H and E preparations. White Leghorn hens were injected with phenyl saligenin phosphate (PSP, 2.5 mg/kg, intramuscular [im]), triphenyl phosphite (TPPi, 500 mg/kg, subcutaneous [sc]), or dimethyl sulfoxide vehicle (DMSO, 0.5 ml/kg, im or sc) and evaluated clinically for signs of neurological dysfunction associated with OPIDN. Hens were sacrificed 7, 14, and 21 days post dosing. Brains and spinal cords were removed immediately following sacrifice, fixed in formalin, and embedded in paraffin. Microtome-cut sections (7 micro m) were then stained with Fluoro-Jade (0.001%, w/v) or H&E. Staining with Fluoro-Jade revealed time-dependent degeneration of nerve fibers and terminals (with PSP and TPPi), or cell bodies (with TPPi) in lamina VII, spinocerebellar, and medial pontine-spinal tracts of the lumbar spinal cord, in white matter and mossy fibers of foliae I-V and IX of the cerebellum, and in medullary, pontine, and midbrain nuclei and paleostriatal fibers surrounding the optic tract. TPPi-induced degeneration was more extensive than that induced by PSP and affected additional cerebellar folia, medullary, pontine, midbrain, and forebrain nuclei and fiber tracts. H&E-stained sections revealed fewer sites of neurodegeneration when compared to Fluoro-Jade. These results demonstrate that Fluoro-Jade is a sensitive method for staining neural tissue affected by OPIDN.

  7. Enhancement of fracture healing in the rat, modulated by compounds that stimulate inducible nitric oxide synthase

    PubMed Central

    Rajfer, R. A.; Kilic, A.; Neviaser, A. S.; Schulte, L. M.; Hlaing, S. M.; Landeros, J.; Ferrini, M. G.; Ebramzadeh, E.

    2017-01-01

    Objectives We investigated the effects on fracture healing of two up-regulators of inducible nitric oxide synthase (iNOS) in a rat model of an open femoral osteotomy: tadalafil, a phosphodiesterase inhibitor, and the recently reported nutraceutical, COMB-4 (consisting of L-citrulline, Paullinia cupana, ginger and muira puama), given orally for either 14 or 42 days. Materials and Methods Unilateral femoral osteotomies were created in 58 male rats and fixed with an intramedullary compression nail. Rats were treated daily either with vehicle, tadalafil or COMB-4. Biomechanical testing of the healed fracture was performed on day 42. The volume, mineral content and bone density of the callus were measured by quantitative CT on days 14 and 42. Expression of iNOS was measured by immunohistochemistry. Results When compared with the control group, the COMB-4 group exhibited 46% higher maximum strength (t-test, p = 0.029) and 92% higher stiffness (t-test, p = 0.023), but no significant changes were observed in the tadalafil group. At days 14 and 42, there was no significant difference between the three groups with respect to callus volume, mineral content and bone density. Expression of iNOS at day 14 was significantly higher in the COMB-4 group which, as expected, had returned to baseline levels at day 42. Conclusion This study demonstrates an enhancement in fracture healing by an oral natural product known to augment iNOS expression. Cite this article: R. A. Rajfer, A. Kilic, A. S. Neviaser, L. M. Schulte, S. M. Hlaing, J. Landeros, M. G. Ferrini, E. Ebramzadeh, S-H. Park. Enhancement of fracture healing in the rat, modulated by compounds that stimulate inducible nitric oxide synthase: Acceleration of fracture healing via inducible nitric oxide synthase. Bone Joint Res 2017:6:–97. DOI: 10.1302/2046-3758.62.BJR-2016-0164.R2. PMID:28188129

  8. THz frequency dynamics of network/guest atom systems : liquid water, clathrates, and network glasses.

    SciTech Connect

    Nakayama, T.; Materials Science Division

    2009-02-01

    Network/guest atom systems show peculiar dynamic behaviors at THz frequency region such as the plateau of thermal conductivities and the broad band spectra called the Boson peak. These are commonly realized in network/guest atom systems such as glasses, clathrates and even for liquid water. Though the phenomena are universal, there is no consistent view to explain these on the same basis. This paper, pointing out similar behaviors for these different systems, tries to present a unified view for these peculiar dynamics.

  9. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

    SciTech Connect

    Dureckova, Hana Woo, Tom K.; Alavi, Saman

    2016-01-28

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  10. Dietary Compound Kaempferol Inhibits Airway Thickening Induced by Allergic Reaction in a Bovine Serum Albumin-Induced Model of Asthma.

    PubMed

    Shin, Daekeun; Park, Sin-Hye; Choi, Yean-Jung; Kim, Yun-Ho; Antika, Lucia Dwi; Habibah, Nurina Umy; Kang, Min-Kyung; Kang, Young-Hee

    2015-12-16

    Asthma is characterized by aberrant airways including epithelial thickening, goblet cell hyperplasia, and smooth muscle hypertrophy within the airway wall. The current study examined whether kaempferol inhibited mast cell degranulation and prostaglandin (PG) release leading to the development of aberrant airways, using an in vitro model of dinitrophenylated bovine serum albumin (DNP-BSA)-sensitized rat basophilic leukemia (RBL-2H3) mast cells and an in vivo model of BSA-challenged asthmatic mice. Nontoxic kaempferol at 10-20 μM suppressed β-hexosaminidase release and cyclooxygenase 2 (COX2)-mediated production of prostaglandin D2 (PGD2) and prostaglandin F2α (PGF2α) in sensitized mast cells. Oral administration of ≤20 mg/kg kaempferol blocked bovine serum albumin (BSA) inhalation-induced epithelial cell excrescence and smooth muscle hypertrophy by attenuating the induction of COX2 and the formation of PGD2 and PGF2α, together with reducing the anti-α-smooth muscle actin (α-SMA) expression in mouse airways. Kaempferol deterred the antigen-induced mast cell activation of cytosolic phospholipase A2 (cPLA2) responsive to protein kinase Cμ (PKCμ) and extracellular signal-regulated kinase (ERK). Furthermore, the antigen-challenged activation of Syk-phospholipase Cγ (PLCγ) pathway was dampened in kaempferol-supplemented mast cells. These results demonstrated that kaempferol inhibited airway wall thickening through disturbing Syk-PLCγ signaling and PKCμ-ERK-cPLA2-COX2 signaling in antigen-exposed mast cells. Thus, kaempferol may be a potent anti-allergic compound targeting allergic asthma typical of airway hyperplasia and hypertrophy.

  11. The ginsenoside metabolite compound K, a novel agonist of glucocorticoid receptor, induces tolerance to endotoxin-induced lethal shock.

    PubMed

    Yang, Chul-Su; Ko, Sung-Ryong; Cho, Byung-Goo; Shin, Dong-Min; Yuk, Jae-Min; Li, Shengjin; Kim, Jin-Man; Evans, Ronald M; Jung, Jun-Sub; Song, Dong-Keun; Jo, Eun-Kyeong

    2008-01-01

    Compound K (C-K), a protopanaxadiol ginsenoside metabolite, was previously shown to have immunomodulatory effects. Here, we describe a novel therapeutic role for C-K in the treatment of lethal sepsis through the modulation of Toll-like receptor (TLR) 4-associated signalling via glucocorticoid receptor (GR) binding. In mononuclear phagocytes, C-K significantly repressed the activation of TLR4/lipopolysaccharide (LPS)-induced NF-kappaB and mitogen-activated protein kinases (MAPKs), as well as the secretion of pro-inflammatory cytokines. However C-K did not affect the TLR3-mediated expression of interferon-beta or the nuclear translocation of IRF-3. C-K competed with the synthetic glucocorticoid dexamethasone for binding to GR and activated glucocorticoid responsive element (GRE)-containing reporter plasmids in a dose-dependent manner. In addition, the blockade of GR with either the GR antagonist RU486 or a siRNA against GR substantially reversed the anti-inflammatory effects of C-K. Furthermore, TLR4-dependent repression of inflammatory response genes by C-K was mediated through the disruption of p65/interferon regulatory factor complexes. Importantly, pre- or post-treatment with C-K significantly rescued mice from Gram-negative bacterial LPS-induced lethal shock by lowering their systemic inflammatory cytokine levels and by reversing the lethal sequelae of sepsis. Collectively, these results demonstrate that C-K, as a functional ligand of GR, regulates distinct TLR4-mediated inflammatory responses, and suggest a novel therapy for Gram-negative septic shock.

  12. Antibacterial active compounds from Hypericum ascyron L. induce bacterial cell death through apoptosis pathway.

    PubMed

    Li, Xiu-Mei; Luo, Xue-Gang; Si, Chuan-Ling; Wang, Nan; Zhou, Hao; He, Jun-Fang; Zhang, Tong-Cun

    2015-01-01

    Hypericum ascyron L. has been used as a traditional medicine for the treatment of wounds, swelling, headache, nausea and abscesses in China for thousands of years. However, modern pharmacological studies are still necessary to provide a scientific basis to substantiate their traditional use. In this study, the mechanism underlying the antimicrobial effect of the antibacterial activity compounds from H. ascyron L. was investigated. Bioguided fractionation of the extract from H. ascyron L. afforded antibacterial activity fraction 8. The results of cup plate analysis and MTT assay showed that the MIC and MBC of fraction 8 is 5 mg/mL. Furthermore, using Annexin V-FITC/PI, TUNEL labeling and DNA gel electrophoresis, we found that cell death with apoptosis features similar to those in eucaryon could be induced in bacteria strains after exposure to the antibacterial activity compounds from H. ascyron L. at moderate concentration. In addition, we further found fraction 8 could disrupt the cell membrane potential indicate that fraction 8 exerts pro-apoptotic effects through a membrane-mediated apoptosis pathway. Finally, quercetin and kaempferol 3-O-β-(2″-acetyl)-galactopyranoside, were identified from fraction 8 by means of Mass spectrometry and Nuclear magnetic resonance. To our best knowledge, this study is the first to show that Kaempferol 3-O-β-(2″-acetyl)-galactopyranoside coupled with quercetin had significant antibacterial activity via apoptosis pathway, and it is also the first report that Kaempferol 3-O-β-(2″-acetyl)-galactopyranoside was found in clusiacea. Our data might provide a rational base for the use of H. ascyron L. in clinical, and throw light on the development of novel antibacterial drugs. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  13. Quinones and aromatic chemical compounds in particulate matter induce mitochondrial dysfunction: implications for ultrafine particle toxicity.

    PubMed

    Xia, Tian; Korge, Paavo; Weiss, James N; Li, Ning; Venkatesen, M Indira; Sioutas, Constantinos; Nel, Andre

    2004-10-01

    Particulate pollutants cause adverse health effects through the generation of oxidative stress. A key question is whether these effects are mediated by the particles or their chemical compounds. In this article we show that aliphatic, aromatic, and polar organic compounds, fractionated from diesel exhaust particles (DEPs), exert differential toxic effects in RAW 264.7 cells. Cellular analyses showed that the quinone-enriched polar fraction was more potent than the polycyclic aromatic hydrocarbon (PAH)-enriched aromatic fraction in O2 .- generation, decrease of membrane potential (Delta-Psi m), loss of mitochondrial membrane mass, and induction of apoptosis. A major effect of the polar fraction was to promote cyclosporin A (CsA)-sensitive permeability transition pore (PTP) opening in isolated liver mitochondria. This opening effect is dependent on a direct effect on the PTP at low doses as well as on an effect on Delta-Psi m at high doses in calcium (Ca2+)-loaded mitochondria. The direct PTP effect was mimicked by redox-cycling DEP quinones. Although the aliphatic fraction failed to perturb mitochondrial function, the aromatic fraction increased the Ca2+ retention capacity at low doses and induced mitochondrial swelling and a decrease in Delta-Psi m at high doses. This swelling effect was mostly CsA insensitive and could be reproduced by a mixture of PAHs present in DEPs. These chemical effects on isolated mitochondria could be reproduced by intact DEPs as well as ambient ultrafine particles (UFPs). In contrast, commercial polystyrene nanoparticles failed to exert mitochondrial effects. These results suggest that DEP and UFP effects on the PTP and Delta-Psi m are mediated by adsorbed chemicals rather than the particles themselves.

  14. Comparative efficacy of systemic acquired resistance-inducing compounds against rust infection in sunflower plants.

    PubMed

    Amzalek, Esther; Cohen, Yigal

    2007-02-01

    ABSTRACT Four inducers of systemic acquired resistance (SAR) were examined for their efficacy in controlling rust infection caused by Puccinia helianthi in sunflower plants. Of the four compounds, DL-3-amino-n-butanoic acid (DL-beta-aminobutyric acid [BABA]) was the most effective and sodium salicylate (NaSA) was the least effective in protecting against rust. In leaf disk assays, full protection was obtained with BABA at 25 mug/ml, benzodiathiazol-S-methyl ester (BTH) at 100 mug/ml, 2,6-di-chloroisonicotinic acid (INA) at 100 mug/ml, and NaSA at >200 mug/ml. L-2-amino-n-butanoic acid (AABA) was partially effective, whereas N-methyl-BABA and 4-aminobutnoic acid (GABA) were ineffective. The R-enantiomer of BABA, but not the S-enantiomer, was more effective than the racemic mixture. In intact plants, BABA applied as a foliar spray or a root dip, before or after (up to 48 h) inoculation, provided significant protection for 8 days. BTH, INA, and NaSA were less protective and more phytotoxic compared with BABA. BABA did not affect urediospore germination, germ tube growth, appressorial formation, or initial ingress of P. helianthi, but strongly suppressed mycelial colonization in the mesophyll and, consequently, pustule and urediospore formation. No accumulation of defense compounds (phenolics, lignin, or callose) was detected in BABA-treated inoculated or noninoculated plants. This is the first report on the activity of BABA against an obligate Basidomycete pathogen in planta.

  15. Quinones and Aromatic Chemical Compounds in Particulate Matter Induce Mitochondrial Dysfunction: Implications for Ultrafine Particle Toxicity

    PubMed Central

    Xia, Tian; Korge, Paavo; Weiss, James N.; Li, Ning; Venkatesen, M. Indira; Sioutas, Constantinos; Nel, Andre

    2004-01-01

    Particulate pollutants cause adverse health effects through the generation of oxidative stress. A key question is whether these effects are mediated by the particles or their chemical compounds. In this article we show that aliphatic, aromatic, and polar organic compounds, fractionated from diesel exhaust particles (DEPs), exert differential toxic effects in RAW 264.7 cells. Cellular analyses showed that the quinone-enriched polar fraction was more potent than the polycyclic aromatic hydrocarbon (PAH)–enriched aromatic fraction in O2•− generation, decrease of membrane potential (ΔΨm), loss of mitochondrial membrane mass, and induction of apoptosis. A major effect of the polar fraction was to promote cyclosporin A (CsA)–sensitive permeability transition pore (PTP) opening in isolated liver mitochondria. This opening effect is dependent on a direct effect on the PTP at low doses as well as on an effect on ΔΨm at high doses in calcium (Ca2+)-loaded mitochondria. The direct PTP effect was mimicked by redox-cycling DEP quinones. Although the aliphatic fraction failed to perturb mitochondrial function, the aromatic fraction increased the Ca2+ retention capacity at low doses and induced mitochondrial swelling and a decrease in ΔΨm at high doses. This swelling effect was mostly CsA insensitive and could be reproduced by a mixture of PAHs present in DEPs. These chemical effects on isolated mitochondria could be reproduced by intact DEPs as well as ambient ultrafine particles (UFPs). In contrast, commercial polystyrene nanoparticles failed to exert mitochondrial effects. These results suggest that DEP and UFP effects on the PTP and ΔΨm are mediated by adsorbed chemicals rather than the particles themselves. PMID:15471724

  16. EQCM Measurements: Redox-Induced Changes in Solvent and Ion Content in Anchored Redox Monolayers of Organosulfur Compounds and Their Electrocatalysis on Gold Electrodes

    DTIC Science & Technology

    1990-08-01

    EQCM Mwasurements: Redox-Induced Changes in Solvent and M0 Content in Anchored Redox Monolayers of Organosulfur CD Compounds and their Electrocatalysis ...REDOX-INDUCED CHANGES IN SOLVENT AND ION CONTENT IN ANCHORED REDOX MONOLAYERS OF ORGANOSULFUR COMPOUNDS AND THEIR ELECTROCATALYSIS ON GOLD...Measurements: Redox-Induced Changes in Solvent and Ion Content in Anchored Redox Monolayers of Organosulfur Compounds and their Electrocatalysis on

  17. Purified vitexin compound 1 suppresses tumor growth and induces cell apoptosis in a mouse model of human choriocarcinoma.

    PubMed

    Tan, Zhihui; Zhang, Yi; Deng, Jun; Zeng, Guangyao; Zhang, Yu

    2012-03-01

    In our previous study, we had isolated a series of lignan compounds, termed vitexins, from the seed of Chinese herb Vitex negundo and found broad antitumor activities of these compounds in many cancer xenograft models and cell lines. This study was aimed to determine the antitumor effect of purified vitexin compound 1 (VB1) on choriocarcinoma in vitro and in vivo. The severe combined immunodeficiency mouse model of choriocarcinoma was established to investigate the in vivo effect of VB1. Its effect on proliferation and apoptosis in JEG-3 cell line was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, colony formation assay and flow cytometry, respectively. The expression of caspase-3, Bcl-2, and some molecules involved in the mammalian target of rapamycin (mTOR) signaling was detected by Western blot. Vitexin compound 1 significantly inhibited the growth of choriocarcinoma in severe combined immunodeficient mice and reduced the serum β-human chorionic gonadotropin level. Vitexin compound 1 inhibited cell proliferation, induced apoptosis, and inhibited the mTOR signaling in JEG-3 cell line. Vitexin compound 1 could inhibit choriocarcinoma via inducing cell apoptosis and suppressing the mTOR pathway.

  18. Development of Novel Bifunctional Compounds that Induce Apoptosis in Prostate Cancer Cells

    DTIC Science & Technology

    2007-03-01

    as well as clues to the reasons why the 11β compound is able to trigger apoptosis while other aniline mustard compounds such as chlorambucil do not. REFERENCES None included. APPENDICIES None included.

  19. Compound C induces protective autophagy in cancer cells through AMPK inhibition-independent blockade of Akt/mTOR pathway.

    PubMed

    Vucicevic, Ljubica; Misirkic, Maja; Janjetovic, Kristina; Vilimanovich, Urosh; Sudar, Emina; Isenovic, Esma; Prica, Marko; Harhaji-Trajkovic, Ljubica; Kravic-Stevovic, Tamara; Bumbasirevic, Vladimir; Trajkovic, Vladimir

    2011-01-01

    In the present study, we report that compound C, an inhibitor of a key intracellular energy sensor AMP-activated protein kinase (AMPK), can induce autophagy in cancer cells. The induction of autophagy in U251 human glioma cell line was demonstrated by acridine orange staining of intracellular acidic vesicles, Beclin 1 induction, p62 decrease and conversion of LC3-I to autophagosome-associated LC3-II in the presence of proteolysis inhibitors. The presence of autophagosome-like vesicles was confirmed by transmission electron microscopy. Compound C-mediated inhibition of AMPK and raptor in U251 cells was associated with paradoxical decrease in phosphorylation of AMPK/raptor-repressed mTOR, a major negative regulator of autophagy, and its downstream target p70S6K. The phosphorylation of an mTOR activator Akt and the PI3K-activating kinase Src was also impaired in compound C-treated cells. The siRNA-mediated AMPK silencing did not reduce the activity of the Akt/mTOR/p70S6K pathway and AMPK activators metformin and AIC AR failed to block compound C-induced autophagy. Autophagy inhibitors bafilomycin and chloroquine significantly increased the cytotoxicity of compound C towards U251 cells, as confirmed by increase in lactate dehydrogenase release, DNA fragmentation and caspase-3 activation. Similar effects of compound C were also observed in C6 rat glioma, L929 mouse fibrosarcoma and B16 mouse melanoma cell lines. Since compound C has previously been reported to suppress AMPK-dependent autophagy in different cell types, our findings suggest that the effects of compound C on autophagy might be dose-, cell type- and/or context-dependent. By demonstrating the ability of compound C to induce autophagic response in cancer cells via AMPK inhibition-independent downregulation of Akt/mTOR pathway, our results warrant caution when using compound C to inhibit AMPK-dependent cellular responses, but also support further exploration of compound C and related molecules as potential

  20. Elicitation of induced resistance against Pectobacterium carotovorum and Pseudomonas syringae by specific individual compounds derived from native Korean plant species.

    PubMed

    Song, Geun Cheol; Ryu, Shi Yong; Kim, Young Sup; Lee, Ji Young; Choi, Jung Sup; Ryu, Choong-Min

    2013-10-16

    Plants have developed general and specific defense mechanisms for protection against various enemies. Among the general defenses, induced resistance has distinct characteristics, such as broad-spectrum resistance and long-lasting effectiveness. This study evaluated over 500 specific chemical compounds derived from native Korean plant species to determine whether they triggered induced resistance against Pectobacterium carotovorum supsp. carotovorum (Pcc) in tobacco (Nicotiana tabacum) and Pseudomonas syringae pv. tomato (Pst) in Arabidopsis thaliana. To select target compound(s) with direct and indirect (volatile) effects, a new Petri-dish-based in vitro disease assay system with four compartments was developed. The screening assay showed that capsaicin, fisetin hydrate, jaceosidin, and farnesiferol A reduced the disease severity significantly in tobacco. Of these four compounds, capsaicin and jaceosidin induced resistance against Pcc and Pst, which depended on both salicylic acid (SA) and jasmonic acid (JA) signaling, using Arabidopsis transgenic and mutant lines, including npr1 and NahG for SA signaling and jar1 for JA signaling. The upregulation of the PR2 and PDF1.2 genes after Pst challenge with capsaicin pre-treatment indicated that SA and JA signaling were primed. These results demonstrate that capsaicin and jaceosidin can be effective triggers of strong induced resistance against both necrotrophic and biotrophic plant pathogens.

  1. Compound 19e, a Novel Glucokinase Activator, Protects against Cytokine-Induced Beta-Cell Apoptosis in INS-1 Cells

    PubMed Central

    Oh, Yoon Sin; Seo, Eunhui; Park, Kaapjoo; Jun, Hee-Sook

    2017-01-01

    Previously, compound 19e, a novel heteroaryl-containing benzamide derivative, was identified as a potent glucokinase activator (GKA) and showed a glucose-lowering effect in diabetic mice. In this study, the anti-apoptotic actions of 19e were evaluated in INS-1 pancreatic beta-cells co-treated with TNF-α and IL-1β to induce cell death. Compound 19e protected INS-1 cells from cytokine-induced cell death, and the effect was similar to treatment with another GKA or exendin-4. Compound 19e reduced annexin-V stained cells and the expression of cleaved caspase-3 and poly (ADP-ribose) polymerase protein, as well as upregulated the expression of B-cell lymphoma-2 protein. Compound 19e inhibited apoptotic signaling via induction of the ATP content, and the effect was correlated with the downregulation of nuclear factor-κB p65 and inducible nitric oxide synthase. Further, 19e increased NAD-dependent protein deacetylase sirtuin-1 (SIRT1) deacetylase activity, and the anti-apoptotic effect of 19e was attenuated by SIRT1 inhibitor or SIRT1 siRNA treatment. Our results demonstrate that the novel GKA, 19e, prevents cytokine-induced beta-cell apoptosis via SIRT1 activation and has potential as a therapeutic drug for the preservation of pancreatic beta-cells. PMID:28405188

  2. Gadolinium-based Compounds Induce NLRP3-dependent IL-1β Production and Peritoneal Inflammation

    PubMed Central

    Schmidt-Lauber, Christian; Bossaller, Lukas; Abujudeh, Hani H.; Vladimer, Gregory I.; Christ, Anette; Fitzgerald, Katherine A.; Latz, Eicke; Gravallese, Ellen M.; Marshak-Rothstein, Ann; Kay, Jonathan

    2015-01-01

    Objective Nephrogenic systemic fibrosis (NSF) is a progressive fibrosing disorder that may develop in patients with chronic kidney disease (CKD) after administration of gadolinium-based contrast agents (GBCAs). In the setting of impaired renal clearance of GBCAs, gadolinium (Gd) deposits in various tissues and fibrosis subsequently develops. However, the precise mechanism by which fibrosis occurs in NSF is incompletely understood. Because other profibrotic agents, such silica or asbestos, activate the NOD-like receptor protein 3 (NLRP3) inflammasome and initiate IL-1β release with the subsequent development of fibrosis, we evaluated the effects of GBCAs on inflammasome activation. Methods Bone marrow derived macrophages (BMDM) from C57BL/6, Nlrp3−/− and Asc−/− mice were incubated with three Gd-containing compounds and IL-1β activation and secretion was detected by ELISA and Western blot analysis. Inflammasome activation and regulation was investigated in IL-4- and IFNγ-polarized macrophages by ELISA, qRT-PCR and NanoString nCounter analysis. Furthermore, C57BL/6 and Nlrp3−/− mice were injected i.p. with GBCA and recruitment of inflammatory cells to the peritoneum was analyzed by FACS. Results Both free Gd and GBCAs activate the NLRP3 inflammasome and induce IL-1β secretion in vitro. Gd-DTPA also induces the recruitment of neutrophils and inflammatory monocytes to the peritoneum in vivo. Gd activated IL-4-polarized macrophages more effectively than IFNγ-polarized macrophages, which preferentially expressed genes known to downregulate inflammasome activity. Conclusion These data suggest that Gd released from GBCAs triggers a NLRP3 inflammasome-dependent inflammatory response that leads to fibrosis in an appropriate clinical setting. The preferential activation of IL-4-differentiated macrophages is consistent with the predominantly fibrotic presentation of NSF. PMID:24914072

  3. Bioactive compounds isolated from apple, tea, and ginger protect against dicarbonyl induced stress in cultured human retinal epithelial cells.

    PubMed

    Sampath, Chethan; Zhu, Yingdong; Sang, Shengmin; Ahmedna, Mohamed

    2016-02-15

    Methylglyoxal (MGO) is known to be a major precursor of advanced glycation end products (AGEs) which are linked to diabetes and its related complications. Naturally occurring bioactive compounds could play an important role in countering AGEs thereby minimizing the risk associated with their formation. In this study, eight specific bioactive compounds isolated from apple, tea and ginger were evaluated for their AGEs scavenging activity using Human Retinal Pigment Epithelial (H-RPE) cells treated with MGO. Among the eight specific compounds evaluated, (-)-epigallocatechin 3-gallate (EGCG) from tea, phloretin in apple, and [6]-shogaol and [6]-gingerol from ginger were found to be most effective in preventing MGO-induced cytotoxicity in the epithelial cells. Investigation of possible underlying mechanisms suggests that that these compounds could act by modulating key regulative detoxifying enzymes via modifying nuclear factor-erythroid 2-related factor 2 (Nrf2) function. MGO-induced cytotoxicity led to increased levels of AGEs causing increase in Nε-(Carboxymethyl) lysine (CML) and glutathione (GSH) levels and over expression of receptor for advanced glycation end products (RAGE). Data also showed that translocation of Nrf2 from cytosol to nucleus was inhibited, which decreased the expression of detoxifying enzyme like heme oxygenase-1 (HO-1). The most potent bioactive compounds scavenged dicarbonyl compounds, inhibited AGEs formation and significantly reduced carbonyl stress by Nrf2 related pathway and restoration of HO-1 expression. These findings demonstrated the protective effect of bioactive compounds derived from food sources against MGO-induced carbonyl stress through activation of the Nrf2 related defense pathway, which is of significant importance for therapeutic interventions in complementary treatment/management of diabetes-related complications. Copyright © 2016. Published by Elsevier GmbH.

  4. Electron density topology of cubic structure I Xe clathrate hydrate at high pressure

    NASA Astrophysics Data System (ADS)

    Flacau, Roxana; Desgreniers, Serge; Tse, John S.

    2008-12-01

    In this report, we present a detailed powder x-ray diffraction study of the structural properties and charge density topology of structure I Xe clathrate hydrate under high pressure and room temperature. The pressure dependence of the structural parameters was determined by applying a Rietveld analysis to the experimental data. The combined Rietveld/maximum entropy method was used to derive the most probable charge density distribution at each pressure. Our results show that the charge density distribution of the encaged Xe atoms differs depending on the type of host cage at all pressures. Spherical electron density distributions were observed for the Xe atoms in the small cages while the atoms in the large cages showed longitudinal elongated electronic distributions. Along with the observed cage deformations, the change in electronic density distribution represents a clear indication that the guest-host interaction differs significantly between the small and large cages at high pressures. A similar behavior has been previously reported in low-temperature studies of methane clathrate hydrate.

  5. Electron density topology of cubic structure I Xe clathrate hydrate at high pressure.

    PubMed

    Flacau, Roxana; Desgreniers, Serge; Tse, John S

    2008-12-28

    In this report, we present a detailed powder x-ray diffraction study of the structural properties and charge density topology of structure I Xe clathrate hydrate under high pressure and room temperature. The pressure dependence of the structural parameters was determined by applying a Rietveld analysis to the experimental data. The combined Rietveld/maximum entropy method was used to derive the most probable charge density distribution at each pressure. Our results show that the charge density distribution of the encaged Xe atoms differs depending on the type of host cage at all pressures. Spherical electron density distributions were observed for the Xe atoms in the small cages while the atoms in the large cages showed longitudinal elongated electronic distributions. Along with the observed cage deformations, the change in electronic density distribution represents a clear indication that the guest-host interaction differs significantly between the small and large cages at high pressures. A similar behavior has been previously reported in low-temperature studies of methane clathrate hydrate.

  6. High pressure synthesis and in situ Raman spectroscopy of H2 and HD clathrate hydrates.

    PubMed

    Zaghloul, Mohamed A S; Celli, Milva; Salem, N M; Elsheikh, S M; Ulivi, Lorenzo

    2012-10-28

    By means of a newly constructed high pressure and low temperature optical apparatus we have measured the Raman spectra of H(2) and HD simple clathrate hydrates, synthesized in situ by the application of more than 2500 bar gas pressure on solid water. High resolution spectra of the molecular vibration have been measured at low temperature (about 20 K). In the case of HD this band is simpler than in the case of H(2), where the presence of the ortho- and para-species complicated the interpretation of the spectrum. We have determined frequency positions of the bands arising from multiple occupancy of the large cages of the sII clathrate, some of which are almost superimposed. The intensity of the bands gives information on the average and distribution of cage occupation, and of the ortho-para (o-p) ratio of H(2) molecules. Hydrogen o-p conversion rate is measured, for molecules in the small cages and in the large cages, and it is observed that these are different. A model considering both intrinsic and extrinsic conversion processes is applied to the measured data. The intrinsic conversion rate so derived is compared favorably to that measured for pure hydrogen in different situations.

  7. Vibrational Raman spectra of hydrogen clathrate hydrates from density functional theory

    NASA Astrophysics Data System (ADS)

    Ramya, K. R.; Venkatnathan, Arun

    2013-03-01

    Hydrogen clathrate hydrates are promising sources of clean energy and are known to exist in a sII hydrate lattice, which consists of H2 molecules in dodecahedron (512) and hexakaidecahedron (51264) water cages. The formation of these hydrates which occur in extreme thermodynamic conditions is known to be considerably reduced by an inclusion of tetrahydrofuran (THF) in cages of these hydrate lattice. In this present work, we employ the density functional theory with a dispersion corrected (B97-D) functional to characterize vibrational Raman modes in the cages of pure and THF doped hydrogen clathrate hydrates. Our calculations show that the symmetric stretch of the H2 molecule in the 51264H2.THF cage is blueshifted compared to the 51264H2 cage. However, all vibrational modes of water molecules are redshifted which suggest reduced interaction between the H2 molecule and water molecules in the 51264H2.THF cage. The symmetric and asymmetric O-H stretch of water molecules in 512H2, 51264H2, and 51264H2.THF cages are redshifted compared with the corresponding guest free cages due to interactions between encapsulated H2 molecules and water molecules of the cages. The low frequency modes contain contributions from contraction and expansion of water cages and vibration of water molecules due to hydrogen bonding and these modes could possibly play an important role in the formation of the hydrate lattice.

  8. The presence of clathrates in comet 67P/Churyumov-Gerasimenko

    PubMed Central

    Luspay-Kuti, Adrienn; Mousis, Olivier; Hässig, Myrtha; Fuselier, Stephen A.; Lunine, Jonathan I.; Marty, Bernard; Mandt, Kathleen E.; Wurz, Peter; Rubin, Martin

    2016-01-01

    Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate. PMID:27152351

  9. High pressure synthesis and in situ Raman spectroscopy of H2 and HD clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Zaghloul, Mohamed A. S.; Celli, Milva; Salem, N. M.; Elsheikh, S. M.; Ulivi, Lorenzo

    2012-10-01

    By means of a newly constructed high pressure and low temperature optical apparatus we have measured the Raman spectra of H2 and HD simple clathrate hydrates, synthesized in situ by the application of more than 2500 bar gas pressure on solid water. High resolution spectra of the molecular vibration have been measured at low temperature (about 20 K). In the case of HD this band is simpler than in the case of H2, where the presence of the ortho- and para-species complicated the interpretation of the spectrum. We have determined frequency positions of the bands arising from multiple occupancy of the large cages of the sII clathrate, some of which are almost superimposed. The intensity of the bands gives information on the average and distribution of cage occupation, and of the ortho-para (o-p) ratio of H2 molecules. Hydrogen o-p conversion rate is measured, for molecules in the small cages and in the large cages, and it is observed that these are different. A model considering both intrinsic and extrinsic conversion processes is applied to the measured data. The intrinsic conversion rate so derived is compared favorably to that measured for pure hydrogen in different situations.

  10. The presence of clathrates in comet 67P/Churyumov-Gerasimenko.

    PubMed

    Luspay-Kuti, Adrienn; Mousis, Olivier; Hässig, Myrtha; Fuselier, Stephen A; Lunine, Jonathan I; Marty, Bernard; Mandt, Kathleen E; Wurz, Peter; Rubin, Martin

    2016-04-01

    Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate.

  11. Experimental inelastic neutron scattering spectrum of hydrogen hexagonal clathrate-hydrate compared with rigorous quantum simulations

    NASA Astrophysics Data System (ADS)

    Celli, Milva; Powers, Anna; Colognesi, Daniele; Xu, Minzhong; Bačić, Zlatko; Ulivi, Lorenzo

    2013-10-01

    We have performed high-resolution inelastic neutron scattering (INS) measurements on binary hydrogen clathrate hydrates exhibiting the hexagonal structure (sH). Two samples, differing only in the ortho/para fraction of hydrogen, were prepared using heavy water and methyl tert-butyl ether as the promoter in its perdeuterated form. The INS spectrum of the translation-rotation (TR) excitations of the guest H2 molecule was obtained by subtracting the very weak signal due to the D2O lattice modes. By means of a subtraction procedure, it has been possible to obtain separately the spectra of caged p-H2 and o-H2. sH clathrates are comprised of three distinct types of cages, two of which, differing in shape and size, are each occupied by one H2 molecule only. Both contribute to the measured INS spectrum which is, therefore, rather complex and challenging to assign unambiguously. To assist with the interpretation, the INS spectra are calculated accurately utilizing the quantum methodology which incorporates the coupled five-dimensional TR energy levels and wave functions of the H2 molecule confined in each type of nanocage. The computed INS spectra are highly realistic and reflect the complexity of the coupled TR dynamics of the guest H2 in the anisotropic confining environment. The simulated INS spectra of p-H2 and o-H2 in the small and medium cages are compared with the experimental data, and are indispensable for their interpretation.

  12. NH3 as unique non-classical content-former within clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Maşlakcı, Zafer; Devlin, J. Paul; Uras-Aytemiz, Nevin

    2017-06-01

    High quality FTIR spectra of aerosols of NH3-THF and NH3-TMO binary clathrate hydrates (CHs) have been measured. Our recently developed all-vapor sub-second approach to clathrate-hydrate formation combined with computational studies has been used to identify vibrational spectroscopic signatures of NH3 within the gas hydrates. The present study shows that there are three distinct NH3 types, namely, classical small-cage NH3, nonclassical small-cage NH3, and NH3 within the hydrate network. The network ammonia does not directly trigger the non-classical CH structure. Rather, the ammonia within the network structure perturbs the water bonding, introducing orientational defects that are stabilized by small and/or large cage guest molecules through H-bonding. This unusual behavior of NH3 within CHs opens a possibility for catalytic action of NH3 during CH-formation. Furthermore, impacts over time of the small-cage NH3-replacement molecules CO2 and CH4 on the structure and composition of the ternary CHs have been noted.

  13. Copper position in type-I Ba 8Cu 4Si 42 clathrate

    NASA Astrophysics Data System (ADS)

    Yang, L.; Wang, Y.; Liu, T.; Hu, T. D.; Li, B. X.; Ståhl, K.; Chen, S. Y.; Li, M. Y.; Shen, P.; Lu, G. L.; Wang, Y. W.; Jiang, J. Z.

    2005-06-01

    Local structure of Cu in a type-I Ba 8Cu 4Si 42 clathrate has been investigated by synchrotron X-ray powder diffraction, Cu K-edge extended X-ray absorption fine spectroscopy, X-ray absorption near edge spectroscopy (XANES) and theoretical calculation. It is found that XANES spectra cannot be explained by the substitution of Cu atoms at Si16 i, and Si24 k positions. Our calculations show that the binding energies of the Si atom in Si16 i, Si24 k and Si6 c positions are 9.000, 9.495 and 8.911 eV, respectively. Both experimental and theoretical results support that Cu atoms in the type-I Ba 8Cu 4Si 42 clathrate, as a doped element, prefer to occupy the least-binding Si, i.e., the Si6 c sites. No structural change between 112 and 300 K was observed and the (100)-faceted cubic crystal has negligible distortion/ordering according to transmission electron microscopy.

  14. Electric Double-Layer Capacitor Based on an Ionic Clathrate Hydrate

    SciTech Connect

    Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

    2013-05-13

    Herein, we suggest a new approach to an electric double-layer capacitor (EDLC) that is based on a proton-conducting ionic clathrate hydrate (ICH). The ice-like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me{sub 4}NOH[DOT OPERATOR]5H{sub 2}O show a high specific capacitance, reversible charge–discharge behavior, and a long cycle life. The ionic-hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1)The ICH does not cause leakage problems under normal EDLC operating conditions. 2)The hydrate material can be utilized itself, without requiring any pre-treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3)The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4)The hydrate solid electrolyte exhibits more-favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems.

  15. Paeonol, a Major Compound of Moutan Cortex, Attenuates Cisplatin-Induced Nephrotoxicity in Mice

    PubMed Central

    Lee, Hyojung; Lee, Gihyun; Kim, Hyunseong; Bae, Hyunsu

    2013-01-01

    Cisplatin is an effective chemotherapeutic agent that is used for the treatment of a variety of cancers; however, its nephrotoxicity limits the use of this drug. In the present study, we examined whether paeonol, a major compound of Moutan Cortex, has protective effects on cisplatin-induced acute renal failure in mice. To accomplish this, Balb/c mice (6 to 8 wk of age, weighing 20 to 25 g) were administered, Moutan Cortex (300 mg/kg) or paeonol (20 mg/kg) once a day. At day 4, mice received cisplatin (30, 20, or 10 mg/kg) intraperitoneally. The paeonol-treated group showed marked attenuation of serum creatine and blood urea nitrogen levels as well as reduced levels of proinflammatory cytokines and nitric oxide when compared to the control group. In addition, the paeonol-treated group showed prolonged survival and marked attenuation of renal tissue injury. Taken together, these results demonstrated that paeonol can prevent the renal toxic effects of cisplatin. PMID:24171038

  16. Gene expression for peroxisome-associated enzymes in hepatocellular carcinomas induced by ciprofibrate, a hypolipidemic compound

    SciTech Connect

    Rao, M.S.; Nemali, M.R.; Reddy, J.K.

    1986-03-05

    Administration of hypolipidemic compounds leads to marked proliferation of peroxisomes and peroxisome-associated enzymes (PAE) in the livers of rodents and non-rodent species. The increase peroxisome-associated enzymes such as fatty acid ..beta..-oxidation system and catalase is shown to be due to an increase in the levels of mRNA. In this experiment they have examined hepatocellular carcinomas (HCC), induced in male F-344 rats by ciprofibrate (0.025%, w/w for 60 weeks), for gene expression of PAE. Total RNA was purified from HCC as well as from control and ciprofibrate (0.025% for 2 weeks) fed rat livers. Northern blot analysis was performed using (32/sub p/)cDNA probes for albumin, fatty acetyl-CoA oxidase, enoyl-CoA hydratase 3-hydroxyacyl-CoA dehydrogenase bifunctional enzyme and catalase. mRNA levels in HCC for albumin, fatty acid ..beta..-oxidation enzymes and catalase were comparable with those levels observed in the livers of rats given ciprofibrate for 2 weeks. In control livers the mRNAs for ..beta..-oxidation enzymes were low. Albumin mRNA levels in all the 3 groups were comparable. Additional studies are necessary to determine whether the increased level of mRNAs for the ..beta..-oxidation enzymes in HCC is due to the effect of ciprofibrate or to the gene amplification.

  17. Structural and functional alterations of catalase induced by acriflavine, a compound causing apoptosis and necrosis.

    PubMed

    Attar, Farnoosh; Khavari-Nejad, Sarah; Keyhani, Jacqueline; Keyhani, Ezzatollah

    2009-08-01

    Acriflavine is an antiseptic agent causing both apoptosis and necrosis in yeast. In this work, its effect on the structure and function of catalase, a vital enzyme actively involved in protection against oxidative stress, was investigated. In vitro kinetic studies showed that acriflavine inhibited the enzymatic activity in a competitive manner. The residual activity detectable after preincubation of catalase (1.5 nmol/L) with various concentrations of acriflavine went from 50% to 20% of the control value as the acriflavine concentration increased from 30 to 90 micromol/L. Correlatively with the decrease in activity, alterations in the enzyme's conformation were observed as indicated by fluorescence spectroscopy, circular dichroism spectroscopy, and electronic absorption spectroscopy. The enzyme's intrinsic fluorescence obtained upon excitation at either 297 nm (tryptophan residues) or 280 nm (tyrosine and tryptophan residues) decreased as a function of acriflavine concentration. Circular dichroism studies showed alterations of the protein structure by acriflavine with up to 13% decrease in alpha helix, 16% increase in beta-sheet content, 17% increase in random coil, and 4% increase in beta turns. Spectrophotometric studies showed a blueshift and modifications in the chromicity of catalase at 405 nm, corresponding to an absorbance band due to the enzyme's prosthetic group. Thus, acriflavine induced in vitro a profound change in the structure of catalase so that the enzyme could no longer function. Our results showed that acriflavine, a compound producing apoptosis and necrosis, can have a direct effect on vital functions in cells by disabling key enzymes.

  18. Reduction in hypericin-induced phototoxicity by Hypericum perforatum extracts and pure compounds

    PubMed Central

    Schmitt, Laura A.; Liu, Yi; Murphy, Patricia A.; Petrich, Jacob W.; Dixon, Philip M.; Birt, Diane F.

    2006-01-01

    Clinical evidence suggests that administration of Hypericum perforatum (Hp) extracts containing the photo-activated hypericin compounds may cause fewer skin photosensitization reactions than administration of pure hypericin. This study was conducted to determine whether the phototoxicity of hypericin in HaCaT keratinocytes could be attenuated by H. perforatum extracts and constituents. Two extracts, when supplemented with 20 μM hypericin: (1) an ethanol re-extraction of residue following a chloroform extraction (denoted ethanol(-chloroform)) (3.35 μM hypericin and 124.0 μM total flavonoids); and (2) a chloroform extract (hypericin and flavonoids not detected), showed 25% and 50% (p < 0.0001) less phototoxicity than 20 μM hypericin alone. Two H. perforatum constituents, when supplemented with 20 μM hypericin: (1) 10 μM chlorogenic acid; and (2) 0.25 μM pyropheophorbide, exhibited 24% (p < 0.05) and 40% (p < 0.05) less phototoxicity than 20 μM hypericin alone. The peroxidation of arachidonic acid was assessed as a measure of oxidative damage by photo-activated hypericin, but this parameter of lipid peroxidation was not influenced by the extracts or constituents. However α-tocopherol, a known antioxidant also did not influence the amount of lipid peroxidation induced in this system. These observations indicate that hypericin combined with H. perforatum extracts or constituents may exert less phototoxicity than pure hypericin, but possibly not through a reduction in arachidonic acid peroxidation. PMID:16859921

  19. Spiral magnetic order and pressure-induced superconductivity in transition metal compounds

    NASA Astrophysics Data System (ADS)

    Wang, Yishu; Feng, Yejun; Cheng, J.-G.; Wu, W.; Luo, J. L.; Rosenbaum, T. F.

    2016-10-01

    Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity.

  20. Proteomics Study on Nonallergic Hypersensitivity Induced by Compound 4880 and Ovalbumin.

    PubMed

    Xu, Yubin; Guo, Na; Dou, Deqiang; Ran, Xiaoku; Ma, Xiande; Kuang, Haixue

    2016-01-01

    Nonallergic hypersensitivity reaction (NHR) accounts for more than 77% of all immune-mediated immediate hypersensitivity reactions and has become a serious threat to public health. Here, proteomics was used to study the NHR mechanism of two typical substances, the compound 4880 and ovalbumin. Twelve different proteins were suggested as potential biomarkers for examining the NHR mechanism, and our results revealed that the mechanism mainly encompassed 2 processes, i.e., generation and effect processes. The generation process could be classified as direct stimulation, complement (classical and alternative), coagulation, kallikrein-kinin, and integrated pathways. Thus glutathione peroxidase 1, terminal complement complex (complement factor 4d and Bb), coagulation 13, kininogen-1, and IgE could be used as candidate biomarkers for the indication of the corresponding pathways respectively, the proteins were further confirmed by ELISA. And the effect process was mainly composed of histamine as well as proteins such as DCD and MYLPF, which could be used as important indices for the symptoms of NHR. Our study differs from previous studies in that C4880 was found to not only be involved in the direct stimulation pathway, but also in the activated complement and kallikrein-kinin pathways through the coagulation pathway. We also report for the first time that ovalbumin-induced NHR could be a combination of the coagulation, classical complement, and integrated pathways.

  1. Spiral magnetic order and pressure-induced superconductivity in transition metal compounds

    PubMed Central

    Wang, Yishu; Feng, Yejun; Cheng, J.-G.; Wu, W.; Luo, J. L.; Rosenbaum, T. F.

    2016-01-01

    Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity. PMID:27708255

  2. Spiral magnetic order and pressure-induced superconductivity in transition metal compounds.

    PubMed

    Wang, Yishu; Feng, Yejun; Cheng, J-G; Wu, W; Luo, J L; Rosenbaum, T F

    2016-10-06

    Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity.

  3. The natural compound forskolin synergizes with dexamethasone to induce cell death in myeloma cells via BIM.

    PubMed

    Follin-Arbelet, Virginie; Misund, Kristine; Naderi, Elin Hallan; Ugland, Hege; Sundan, Anders; Blomhoff, Heidi Kiil

    2015-08-26

    We have previously demonstrated that activation of the cyclic adenosine monophosphate (cAMP) pathway kills multiple myeloma (MM) cells both in vitro and in vivo. In the present study we have investigated the potential of enhancing the killing of MM cell lines and primary MM cells by combining the cAMP-elevating compound forskolin with the commonly used MM therapeutic drugs melphalan, cyclophosphamide, doxorubicin, bortezomib and dexamethasone. We observed that forskolin potentiated the killing induced by all the tested agents as compared to treatment with the single agents alone. In particular, forskolin had a synergistic effect on the dexamethasone-responsive cell lines H929 and OM-2. By knocking down the proapoptotic BCL-2 family member BIM, we proved this protein to be involved in the synergistic induction of apoptosis by dexamethasone and forskolin. The ability of forskolin to maintain the killing of MM cells even at lower concentrations of the conventional agents suggests that forskolin may be used to diminish treatment-associated side effects. Our findings support a potential role of forskolin in combination with current conventional agents in the treatment of MM.

  4. Adrenocorticotropin-induced hypertension in rats: role of ouabain-like compound.

    PubMed

    Yamada, K; Goto, A; Omata, M

    1997-04-01

    We examined the role of ouabain-like compound (OLC) in hypertension associated with corticotropin (ACTH) excess in rats. Physiological saline solution (1 mL/kg) or synthetic ACTH-Z (0.5 mg/kg) was injected intramuscularly for 15 days to 14 control and 13 male Wistar rats. Significant increases in blood pressure and plasma sodium/potassium ratio, and decreases in plasma potassium concentration and urinary sodium/potassium ratio were observed in ACTH-treated rats. The plasma OLC level was higher in ACTH-treated group (control; 76 +/- 13, ACTH; 202 +/- 48 pmol/L, P < .05). Plasma OLC level correlated with systolic blood pressure (SPB; r = 0.53, P < .01). Urinary OLC excretion was also higher in ACTH-treated group (control; 0.95 +/- 0.01, ACTH; 3.32 +/- 0.67 pmol/day, P < .01). A significant relation was also found between urinary OLC excretion and SBP (r = 0.66, P < .01). Plasma potassium concentration negatively correlated with SBP (r = -0.48, P < .01) and urinary sodium/potassium ratio also correlated inversely with urinary OLC excretion (r = -0.55, P < .01). Measurement of OLC levels after the fractionation of urine by reverse-phase high performance liquid chromatography showed that the major OLC peak in urine from both groups coincided with that of authentic ouabain. These results suggest the contribution of OLC to ACTH-induced hypertension in rats.

  5. Laser- and UV-LED-induced fluorescence detection of dissolved organic compounds in water

    NASA Astrophysics Data System (ADS)

    Sharikova, Anna V.; Killinger, Dennis K.

    2010-04-01

    We have developed a laser-induced fluorescence (LIF) system to detect and continuously observe in real time the levels of colored dissolved organic matter (CDOM) or Dissolved Organic Compounds (DOCs) in water from various sources, such as tap water and reverse osmosis processed water. At the same time, we have studied deep-UV light emitting diodes (LEDs) as alternative light sources for our system, which would make the apparatus cheaper and more compact. Our portable LIF system had two interchangeable microchip Nd:YAG lasers, operating at 266 nm and 355 nm, as UV sources, and fluorescence was measured over the range of 260-680 nm. The fluorescence was collected at 90º to the laser beam. We have also studied deep-UV LEDs emitting between 265 nm and 355 nm as alternative sources of fluorescence excitation. The average laser power was approximately 30 times that of the LED. Fluorescence spectra from sea water, tap water, and reverse osmosis water for both excitation sources were also measured, and similar spectra were observed. Differences in the signal intensity due to the difference in the laser and LED excitation intensity were consistent with theory.

  6. Studies on the role of neurotoxic esterase in organophosphorous compound-induced delayed neurotoxicity

    SciTech Connect

    Carrington, C.D.

    1984-01-01

    Neurotoxic esterase (NTE) is a protein with esterase activity that is proposed to be the site at which organophosphorus compound (OP) induced delayed neurotoxicity (OPIDIN) is initiated. The role of NTE in OPIDIN in unknown. The studies described in this dissertation were designed to further elucidate potential mechanisms underlying the involvement of NTE in OPIDN. The prophylactic effect of phenylmethylsulfonyl fluoride (PMSF) was found to be correlated with the time course of inhibition of NTE by PMSF and two neurotoxic OPs, and is therefore most likely to be due to the prevention of the binding of the OP to the initiation site. A membrane bound protein labelled with /sup 3/H-diisopropyl phosphorofluoridate (DiFP) with an apparent molecular weight of 160 K was the major binding site with a specificity similar to that of NTE. Recovery of NTE activity following in vivo inhibition by DiFP was found to be slower in hen brain when compared to chicks or rats. Differences in recovery in peripheral nerve were not found to be correlated with differences in susceptibility between species or between young and adult animals. The anterograde transport rate for NTE was estimated to be about 300 mm/day. Since exchange between mobile and stationary transport pools appeared to be rapid, it is concluded that the proximodistal delay in NTE recovery is due to a dilution of newly synthesized NTE by inhibited NTE as it is transported down the nerve.

  7. Spiral Magnetic Order and Pressure-Induced Superconductivity in Transition Metal Compounds

    SciTech Connect

    Wang, Yishu; Feng, Yejun; Cheng, J.-G.; Wu, W.; Luo, J. L.; Rosenbaum, T. F.

    2016-01-01

    Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity.

  8. Large Drought-induced Variations in Oak Leaf Volatile Organic Compound Emissions during PINOT NOIR 2012

    EPA Pesticide Factsheets

    Leaf level oak isoprene emissions and co2/H2O exchange in the Ozarks, USABAGeron.csv is the speciated biomass displayed in Figure 1.Biomass Dry Weights.xlsx is used to convert leaf area to dry leaf biomass and is used in Figure 2.Daly Ozarks leaf ISOP.txt and MOFLUX_Isoprene Summary_refined Tcurve data.xlsx are the leaf isoprene emission rate files shown in Figure 2.Harley Aug12_Chris.xls is the leaf isoprene emission rate file shown in Figure 3.Daly Ozarks leaf.txt is the BVOC emissions file used for Figure 7 and Table 4.Drought IS.txt is the review data given in Table 2.Fig4 Aug10 2012 Harley.txt is shown in Figure 4.Fig 5 Aug14 2012 Harley.txt is shown in Figure 5.Daly Ozarks Leaf.txt is used in Fig 7.Drought IS.txt is used in Fig 8.This dataset is associated with the following publication:Geron , C., R. Daly , P. Harley, R. Rasmussen, R. Seco, A. Guenther, T. Karl, and L. Gu. Large Drought-Induced Variations in Oak Leaf Volatile Organic Compound Emissions during PINOT NOIR 2012. CHEMOSPHERE. Elsevier Science Ltd, New York, NY, USA, 146: 8-21, (2016).

  9. Strain induced superconductivity in the parent compound BaFe2As2.

    PubMed

    Engelmann, J; Grinenko, V; Chekhonin, P; Skrotzki, W; Efremov, D V; Oswald, S; Iida, K; Hühne, R; Hänisch, J; Hoffmann, M; Kurth, F; Schultz, L; Holzapfel, B

    2013-01-01

    The discovery of superconductivity with a transition temperature, Tc, up to 65 K in single-layer FeSe (bulk Tc=8 K) films grown on SrTiO3 substrates has attracted special attention to Fe-based thin films. The high Tc is a consequence of the combined effect of electron transfer from the oxygen-vacant substrate to the FeSe thin film and lattice tensile strain. Here we demonstrate the realization of superconductivity in the parent compound BaFe2As2 (no bulk Tc) just by tensile lattice strain without charge doping. We investigate the interplay between strain and superconductivity in epitaxial BaFe2As2 thin films on Fe-buffered MgAl2O4 single crystalline substrates. The strong interfacial bonding between Fe and the FeAs sublattice increases the Fe-Fe distance due to the lattice misfit, which leads to a suppression of the antiferromagnetic spin density wave and induces superconductivity with bulk Tc≈10 K. These results highlight the role of structural changes in controlling the phase diagram of Fe-based superconductors.

  10. Hydration of krypton and consideration of clathrate models of hydrophobic effects from the perspective of quasi-chemical theory.

    PubMed

    Ashbaugh, Henry S; Asthagiri, D; Pratt, Lawrence R; Rempe, Susan B

    2003-09-01

    Ab initio molecular dynamics (AIMD) results on a krypton-water liquid solution are presented and compared to recent XAFS results for the radial hydration structure for a Kr atom in liquid water solution. Though these AIMD calculations have important limitations of scale, the comparisons with the liquid solution results are satisfactory and significantly different from the radial distributions extracted from the data on the solid Kr/H(2)O clathrate hydrate phase. The calculations also produce the coordination number distribution that can be examined for metastable coordination structures suggesting possibilities for clathrate-like organization; none are seen in these results. Clathrate pictures of hydrophobic hydration are discussed, as is the quasi-chemical theory that should provide a basis for clathrate pictures. Outer shell contributions are discussed and estimated; they are positive and larger than the positive experimental hydration free energy of Kr(aq), implying that inner shell contributions must be negative and of comparable size. Clathrate-like inner shell hydration structures on a Kr atom solute are obtained for some, but not all, of the coordination number cases observed in the simulation. The structures found have a delicate stability. Inner shell coordination structures extracted from the simulation of the liquid, and then subjected to quantum chemical optimization, always decomposed. Interactions with the outer shell material are decisive in stabilizing coordination structures observed in liquid solution and in clathrate phases. The primitive quasi-chemical estimate that uses a dielectric model for the influence of the outer shell material on the inner shell equilibria gives a contribution to hydration free energy that is positive and larger than the experimental hydration free energy. The 'what are we to tell students' question about hydrophobic hydration, often answered with structural clathrate pictures, is then considered; we propose an

  11. Methylene blue administration in the compound 48/80-induced anaphylactic shock: hemodynamic study in pigs.

    PubMed

    Menardi, Antonio Carlos; Capellini, Verena Kise; Celotto, Andrea Carla; Albuquerque, Agnes Afrodite Sumarelli; Viaro, Fernanda; Vicente, Walter Vilella A; Rodrigues, Alfredo José; Evora, Paulo Roberto Barbosa

    2011-12-01

    To verify if the methylene blue (MB) administration prevents and/or reverses the compound 48/80 (C48/80)-induced anaphylactic shock in pigs. Female Dalland pigs were anesthetized and had the hemodynamic parameters recorded during the necessary time to administer some drugs and observe their effect. The animals were randomly assigned to one of the five groups: 1) control; 2) MB: the animals received a bolus injection of MB (2 mg/kg) followed by continuous infusion of MB (2.66 mg/Kg/h delivered by syringe infusion pump); 3) C48/80: the animals received a bolus injection of C48/80 (4 mg/kg); 4) C48/80+MB: the animals received a bolus injection of C48/80 (4 mg/kg) and 10 minutes after the C48/80 administration the animals received a bolus injection of MB (2 mg/kg) followed by continuous infusion of MB (2.66 mg/Kg/h delivered by syringe infusion pump); 5) MB+C48/80: the animals received a bolus injection of MB (2 mg/kg) and 3 minutes later they received a bolus injection of C48/80 (4 mg/kg). The intravenous infusion of MB alone caused no changes in the mean arterial pressure (MAP) showing that the administered MB dose was safe in this experimental model. The C48/80 was effective in producing experimental anaphylactic shock since it was observed a decrease in both MAP and cardiac output (CO) after its administration. The MB did not prevent or reverse the C48/80-induced anaphylactic shock in this model. In fact, the MAP of the animals with anaphylactic shock treated with MB decreased even more than the MAP of the animals from the C48/80 group. On the other hand, the C48/80-induced epidermal alterations disappeared after the MB infusion. Despite our data, the clinical manifestations improvement brings some optimism and does not allow excluding the MB as a possible therapeutic option in the anaphylactic shock.

  12. The compound Chinese medicine "Kang Fu Ling" protects against high power microwave-induced myocardial injury.

    PubMed

    Zhang, Xueyan; Gao, Yabing; Dong, Ji; Wang, Shuiming; Yao, Binwei; Zhang, Jing; Hu, Shaohua; Xu, Xinping; Zuo, Hongyan; Wang, Lifeng; Zhou, Hongmei; Zhao, Li; Peng, Ruiyun

    2014-01-01

    The prevention and treatment of Microwave-caused cardiovascular injury remains elusive. This study investigated the cardiovascular protective effects of compound Chinese medicine "Kang Fu Ling" (KFL) against high power microwave (HPM)-induced myocardial injury and the role of the mitochondrial permeability transition pore (mPTP) opening in KFL protection. Male Wistar rats (100) were divided into 5 equal groups: no treatment, radiation only, or radiation followed by treatment with KFL at 0.75, 1.5, or 3 g/kg/day. Electrocardiography was used to Electrophysiological examination. Histological and ultrastructural changes in heart tissue and isolated mitochondria were observed by light microscope and electron microscopy. mPTP opening and mitochondrial membrane potential were detected by confocal laser scanning microscopy and fluorescence analysis. Connexin-43 (Cx-43) and endothelial nitric oxide synthase (eNOS) were detected by immunohistochemistry. The expression of voltage-dependent anion channel (VDAC) was detected by western blotting. At 7 days after radiation, rats without KFL treatment showed a significantly lower heart rate (P<0.01) than untreated controls and a J point shift. Myocyte swelling and rearrangement were evident. Mitochondria exhibited rupture, and decreased fluorescence intensity, suggesting opening of mPTP and a consequent reduction in mitochondrial membrane potential. After treatment with 1.5 g/kg/day KFL for 7 d, the heart rate increased significantly (P<0.01), and the J point shift was reduced flavorfully (P<0.05) compared to untreated, irradiated rats; myocytes and mitochondria were of normal morphology. The fluorescence intensities of dye-treated mitochondria were also increased, suggesting inhibition of mPTP opening and preservation of the mitochondrial membrane potential. The microwave-induced decrease of Cx-43 and VDAC protein expression was significantly reversed. Microwave radiation can cause electrophysiological, histological and

  13. Neuroprotective Properties of Compounds Extracted from Dianthus superbus L. against Glutamate-induced Cell Death in HT22 Cells

    PubMed Central

    Yun, Bo-Ra; Yang, Hye Jin; Weon, Jin Bae; Lee, Jiwoo; Eom, Min Rye; Ma, Choong Je

    2016-01-01

    Background: Dianthus superbus L. has been used in Chinese herbal medicine as a diuretic and anti-inflammatory agent. Objective: In this study, we isolated ten bioactive compounds from D. superbus and evaluated their neuroprotective activity against glutamate-induced cell death in the hippocampal neuronal HT22 cells. Materials and Methods: New compound, (E)-methyl-4-hydroxy-4-(8a-methyl-3-oxodecahydronaphthalen-4a-yl) (1) and, nine known compounds, diosmetin-7-O (2’’,6’’-di-O-α-L-rhamnopyranosyl)-β-D-glucopyranoside (2), 4-hydroxy-3-methoxy-pentyl ester benzenepropanoic acid (3), vanillic acid (4), 4-hydroxy-benzeneacetic acid (5), 4-methoxybenzeneacetic acid (6), (E)-4-methoxycinnamic acid (7), 3-methoxy-4-hydroxyphenylethanol (8), hydroferulic acid (9), and methyl hydroferulate (10), were isolated by bioactivity-guided separation. Structures of the isolated compounds were identified on the basis of 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional NMR spectra, while their neuroprotective properties were evaluated by performing the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. Results: D. superbus extract had a neuroprotective effect and isolated 10 compounds. Among the compounds, compounds 5 and 6 effectively protected HT22 cells against glutamate toxicity. Conclusion: In conclusion, the extract of D. superbus and compounds isolated from it exhibited neuroprotective properties, suggesting therapeutic potential for applications in neurotoxic diseases. SUMMARY D. superbus extract significantly protected on glutamate-induced cell death in HT22 cellsNew compound, (E)-methyl-4-hydroxy-4-(8a-methyl-3-oxodecahydronaphthalen-4a-yl) (1) and, nine known compounds, diosmetin-7-O(2’’,6’’-di-O-α-L-rhamnopyranosyl)-β-D-glucopyranoside (2), 4-hydroxy-3-methoxy-pentyl ester benzenepropanoic acid (3), vanillic acid (4), 4-hydroxy-benzeneacetic acid (5), 4-methoxybenzeneacetic acid (6), (E)-4-methoxycinnamic acid (7), 3

  14. Superconductive sodalite-like clathrate calcium hydride at high pressures

    PubMed Central

    Wang, Hui; Tse, John S.; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-01-01

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H2 fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH6 a body-centered cubic structure with hydrogen that forms unusual “sodalite” cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H2 of electrons donated by Ca forming an “H4” unit as the building block in the construction of the three-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone center. The resultant dynamic Jahn–Teller effect helps to enhance electron–phonon coupling and leads to superconductivity of CaH6. A superconducting critical temperature (Tc) of 220–235 K at 150 GPa obtained from the solution of the Eliashberg equations is the highest among all hydrides studied thus far. PMID:22492976

  15. Superconductive sodalite-like clathrate calcium hydride at high pressures.

    PubMed

    Wang, Hui; Tse, John S; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-04-24

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H(2) fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH(6) a body-centered cubic structure with hydrogen that forms unusual "sodalite" cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H(2) of electrons donated by Ca forming an "H(4)" unit as the building block in the construction of the three-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone center. The resultant dynamic Jahn-Teller effect helps to enhance electron-phonon coupling and leads to superconductivity of CaH(6). A superconducting critical temperature (T(c)) of 220-235 K at 150 GPa obtained from the solution of the Eliashberg equations is the highest among all hydrides studied thus far.

  16. Dual actions of a novel bifunctional compound to lower glucose in mice with diet-induced insulin resistance.

    PubMed

    Chen, Katherine; Jih, Alice; Kavaler, Sarah T; Lagakos, William S; Oh, Dayoung; Watkins, Steven M; Kim, Jane J

    2015-08-01

    Docosahexaenoic acid (DHA 22:6n-3) and salicylate are both known to exert anti-inflammatory effects. This study investigated the effects of a novel bifunctional drug compound consisting of DHA and salicylate linked together by a small molecule that is stable in plasma but hydrolyzed in the cytoplasm. The components of the bifunctional compound acted synergistically to reduce inflammation mediated via nuclear factor κB in cultured macrophages. Notably, oral administration of the bifunctional compound acted in two distinct ways to mitigate hyperglycemia in high-fat diet-induced insulin resistance. In mice with diet-induced obesity, the compound lowered blood glucose by reducing hepatic insulin resistance. It also had an immediate glucose-lowering effect that was secondary to enhanced glucagon-like peptide-1 (GLP-1) secretion and abrogated by the administration of exendin(9-39), a GLP-1 receptor antagonist. These results suggest that the bifunctional compound could be an effective treatment for individuals with type 2 diabetes and insulin resistance. This strategy could also be employed in other disease conditions characterized by chronic inflammation.

  17. Dual actions of a novel bifunctional compound to lower glucose in mice with diet-induced insulin resistance

    PubMed Central

    Chen, Katherine; Jih, Alice; Kavaler, Sarah T.; Lagakos, William S.; Oh, Dayoung; Watkins, Steven M.

    2015-01-01

    Docosahexaenoic acid (DHA 22:6n-3) and salicylate are both known to exert anti-inflammatory effects. This study investigated the effects of a novel bifunctional drug compound consisting of DHA and salicylate linked together by a small molecule that is stable in plasma but hydrolyzed in the cytoplasm. The components of the bifunctional compound acted synergistically to reduce inflammation mediated via nuclear factor κB in cultured macrophages. Notably, oral administration of the bifunctional compound acted in two distinct ways to mitigate hyperglycemia in high-fat diet-induced insulin resistance. In mice with diet-induced obesity, the compound lowered blood glucose by reducing hepatic insulin resistance. It also had an immediate glucose-lowering effect that was secondary to enhanced glucagon-like peptide-1 (GLP-1) secretion and abrogated by the administration of exendin(9–39), a GLP-1 receptor antagonist. These results suggest that the bifunctional compound could be an effective treatment for individuals with type 2 diabetes and insulin resistance. This strategy could also be employed in other disease conditions characterized by chronic inflammation. PMID:26058862

  18. X-ray Inducible Luminescence and Singlet Oxygen Sensitization by an Octahedral Molybdenum Cluster Compound: A New Class of Nanoscintillators.

    PubMed

    Kirakci, Kaplan; Kubát, Pavel; Fejfarová, Karla; Martinčík, Jiří; Nikl, Martin; Lang, Kamil

    2016-01-19

    Newly synthesized octahedral molybdenum cluster compound (n-Bu4N)2[Mo6I8(OOC-1-adamantane)6] revealed uncharted features applicable for the development of X-ray inducible luminescent materials and sensitizers of singlet oxygen, O2((1)Δg). The compound exhibits a red-NIR luminescence in the solid state and in solution (e.g., quantum yield of 0.76 in tetrahydrofuran) upon excitation by UV-vis light. The luminescence originating from the excited triplet states is quenched by molecular oxygen to produce O2((1)Δg) with a high quantum yield. Irradiation of the compound by X-rays generated a radioluminescence with the same emission spectrum as that obtained by UV-vis excitation. It proves the formation of the same excited triplet states regardless of the excitation source. By virtue of the described behavior, the compound is suggested as an efficient sensitizer of O2((1)Δg) upon X-ray excitation. The luminescence and radioluminescence properties were maintained upon embedding the compound in polystyrene films. In addition, polystyrene induced an enhancement of the radioluminescence intensity via energy transfer from the scintillating polymeric matrix. Sulfonated polystyrene nanofibers were used for the preparation of nanoparticles which form stable dispersions in water, while keeping intact the luminescence properties of the embedded compound over a long time period. Due to their small size and high oxygen diffusivity, these nanoparticles are suitable carriers of sensitizers of O2((1)Δg). The presented results define a new class of nanoscintillators with promising properties for X-ray inducible photodynamic therapy.

  19. A study of the xenon effect in type-II clathrate hydrate synthesis; Commencing with hydrogen, argon and xenon uptake into a propane clathrate hydrate

    NASA Astrophysics Data System (ADS)

    Abbondondola, Joanne Angela

    It has been proposed that clathrate hydrates can be a possible storage medium for alternative fuels, such as hydrogen. The type-II propane gas hydrate is a viable choice because there are twice as many small cages as large cages and the small cavities are available for hydrogen storage. However, propane hydrate formation is a kinetically slow process which makes it commercially unattractive. Our objectives were twofold; (1) to quantify hydrogen, argon and xenon sorption into a preformed type-II propane hydrate at near-ambient conditions and (2) to investigate the effect of xenon on the rate of type-II propane hydrate formation. The propane hydrate is synthesized from 250 mum ice grains, and is estimated to have a porosity of 65 %. Hydrogen is rapidly absorbed by the hydrate sample and approaches the equilibrium vapor pressure in an hour before a very slow residual absorption process ensues. For an initial hydrogen pressure of 1.5 MPa, about 4.5 % of the available 512 cages are occupied by hydrogen after one hour, and 4.9 % after 18 hours. In contrast, for both argon and xenon significantly more gas is absorbed by the hydrate, but at a much slower rate: about 5% as fast for xenon and 1% as fast for argon. We conclude that hydrogen readily diffuses through the propane hydrate microcrystal structure, while argon and xenon are probably absorbed by growing new double hydrate while consuming the propane hydrate. Thus, although considerably higher pressures would be required to store significant quantities of hydrogen in propane hydrate, it appears that the crystal can be loaded and emptied in relatively short amounts of time. Experimental results show that propane is incorporated into clathrate hydrate cages more rapidly using propane-xenon mixtures than for pure propane gas. For a 0.92 xenon: propane mix, 60% of the theoretical yield of propane enclathration is achieved in 20 minutes, versus several days for pure propane. It appears that xenon serves to nucleate the

  20. A synthetic compound that potentiates bone morphogenetic protein-2-induced transdifferentiation of myoblasts into the osteoblastic phenotype.

    PubMed

    Kato, Satoshi; Sangadala, Sreedhara; Tomita, Katsuro; Titus, Louisa; Boden, Scott D

    2011-03-01

    There is an urgent need to develop methods that lower costs of using recombinant human bone morphogenetic proteins (BMPs) to promote bone induction. In this study, we demonstrate the osteogenic effect of a low-molecular weight compound, SVAK-12, that potentiated the effects of BMP-2 in inducing transdifferentiation of C2C12 myoblasts into the osteoblastic phenotype. Here, we report a specific compound, SVAK-12, which was selected based on in silico screenings of small-molecule databases using the homology modeled interaction motif of Smurf1-WW2 domain. The enhancement of BMP-2 activity by SVAK-12 was characterized by evaluating a BMP-specific reporter activity and by monitoring the BMP-2-induced expression of mRNA for osteocalcin and alkaline phosphatase (ALP), which are widely accepted marker genes of osteoblast differentiation. Finally, we confirmed these results by also measuring the enhancement of BMP-2-induced activity of ALP. Smurf1 is an E3 ligase that targets osteogenic Smads for ubiquitin-mediated proteasomal degradation. Smurf1 is an interesting potential target to enhance bone formation based on the positive effects on bone of proteins that block Smurf1-binding to Smad targets or in Smurf1-/- knockout mice. Since Smads bind Smurf1 via its WW2 domain, we performed in silico screening to identify compounds that might interact with the Smurf1-WW2 domain. We recently reported the activity of a compound, SVAK-3. However, SVAK-3, while exhibiting BMP-potentiating activity, was not stable and thus warranted a new search for a more stable and efficacious compound among a selected group of candidates. In addition to being more stable, SVAK-12 exhibited a dose-dependent activity in inducing osteoblastic differentiation of myoblastic C2C12 cells even when multiple markers of the osteoblastic phenotype were parallelly monitored.

  1. A synthetic compound that potentiates bone morphogenetic protein-2-induced transdifferentiation of myoblasts into the osteoblastic phenotype

    PubMed Central

    Kato, Satoshi; Tomita, Katsuro; Titus, Louisa; Boden, Scott D.

    2011-01-01

    There is an urgent need to develop methods that lower costs of using recombinant human bone morphogenetic proteins (BMPs) to promote bone induction. In this study, we demonstrate the osteogenic effect of a low-molecular weight compound, SVAK-12, that potentiated the effects of BMP-2 in inducing transdifferentiation of C2C12 myoblasts into the osteoblastic phenotype. Here, we report a specific compound, SVAK-12, which was selected based on in silico screenings of small-molecule databases using the homology modeled interaction motif of Smurf1-WW2 domain. The enhancement of BMP-2 activity by SVAK-12 was characterized by evaluating a BMP-specific reporter activity and by monitoring the BMP-2-induced expression of mRNA for osteocalcin and alkaline phosphatase (ALP), which are widely accepted marker genes of osteoblast differentiation. Finally, we confirmed these results by also measuring the enhancement of BMP-2-induced activity of ALP. Smurf1 is an E3 ligase that targets osteogenic Smads for ubiquitin-mediated proteasomal degradation. Smurf1 is an interesting potential target to enhance bone formation based on the positive effects on bone of proteins that block Smurf1-binding to Smad targets or in Smurf1−/− knockout mice. Since Smads bind Smurf1 via its WW2 domain, we performed in silico screening to identify compounds that might interact with the Smurf1-WW2 domain. We recently reported the activity of a compound, SVAK-3. However, SVAK-3, while exhibiting BMP-potentiating activity, was not stable and thus warranted a new search for a more stable and efficacious compound among a selected group of candidates. In addition to being more stable, SVAK-12 exhibited a dose-dependent activity in inducing osteoblastic differentiation of myoblastic C2C12 cells even when multiple markers of the osteoblastic phenotype were parallelly monitored. PMID:21110071

  2. Production of organic compounds in plasmas - A comparison among electric sparks, laser-induced plasmas, and UV light

    NASA Technical Reports Server (NTRS)

    Scattergood, Thomas W.; Mckay, Christopher P.; Borucki, William J.; Giver, Lawrence P.; Van Ghyseghem, Hilde

    1989-01-01

    In order to ascertain the features of organic compound-production in planetary atmospheres under the effects of plasmas and shocks, various mixtures of N2, CH4, and H2 modeling the atmosphere of Titan were subjected to discrete sparks, laser-induced plasmas, and UV radiation. The experimental results obtained suggest that UV photolysis from the plasma is an important organic compound synthesis process, as confirmed by the photolysis of gas samples that were exposed to the light but not to the shock waves emitted by the sparks. The thermodynamic equilibrium theory is therefore incomplete in the absence of photolysis.

  3. Production of organic compounds in plasmas - A comparison among electric sparks, laser-induced plasmas, and UV light

    NASA Astrophysics Data System (ADS)

    Scattergood, T. W.; McKay, C. P.; Borucki, W. J.; Giver, L. P.; van Ghyseghem, H.; Parris, J. E.; Miller, S. L.

    1989-10-01

    In order to ascertain the features of organic compound-production in planetary atmospheres under the effects of plasmas and shocks, various mixtures of N2, CH4, and H2 modeling the atmosphere of Titan were subjected to discrete sparks, laser-induced plasmas, and UV radiation. The experimental results obtained suggest that UV photolysis from the plasma is an important organic compound synthesis process, as confirmed by the photolysis of gas samples that were exposed to the light but not to the shock waves emitted by the sparks. The thermodynamic equilibrium theory is therefore incomplete in the absence of photolysis.

  4. Surface topographical and ultrastructural alterations of Raillietina echinobothrida and Ascaridia galli induced by a compound isolated from Acacia oxyphylla.

    PubMed

    Roy, B; Dasgupta, S; Manivel, V; Parameswaran, P S; Giri, B R

    2012-04-30

    The stem bark of Acacia oxyphylla Graham ex Bentham is used as an anthelmintic by the natives of Mizoram (North-East India). Therefore, the aim of the study was to assess the effect of the active compound isolated from A. oxyphylla on the tegument of adult Raillietina echinobothrida and Ascaridia galli. The test parasites R. echinobothrida and A. galli were incubated in physiological buffered saline containing 0.0005, 0.001, 0.05, 0.1 and 1mg/ml of the isolated compound. The alterations in the tegument of the parasites post paralysis were examined using electron microscopes. The compound reduced the cestode's motility soon after incubation, but did not induce paralysis in the nematodes till about 11-14 h at highest concentration. The compound caused extensive digestion of cestode tegument as evident by electron microscopy. Disorganization of muscle bundles, loss of cell-cell contact, extreme vacuolization and oedema were some of the changes observed. Loss of cellular organelles combined with distortion of those present was markedly noted throughout the parasite tissue. Deformation and disorganization of epicuticle, disruption of mitochondrial and nuclear membrane were also observed in nematode exposed to the active compound of the plant. Substantial structural deformities in the treated parasites are indicative of an efficient vermicidal activity of the isolated compound against cestodes and nematodes. Copyright © 2012. Published by Elsevier B.V.

  5. The novel compound OSI-461 induces apoptosis and growth arrest in human acute myeloid leukemia cells.

    PubMed

    Singh, Raminder; Fröbel, Julia; Cadeddu, Ron-Patrick; Bruns, Ingmar; Schroeder, Thomas; Brünnert, Daniela; Wilk, Christian Matthias; Zerbini, Luiz Fernando; Haas, Rainer; Czibere, Akos

    2012-02-01

    Acute myeloid leukemia (AML) is a heterogeneous hematological malignancy. Treatment of patients suffering from high-risk AML as defined by clinical parameters, cytogenetics, and/or molecular analyses is often unsuccessful. OSI-461 is a pro-apoptotic compound that has been proposed as a novel therapeutic option for patients suffering from solid tumors like prostate or colorectal carcinoma. But little is known about its anti-proliferative potential in AML. Hence, we treated bone marrow derived CD34(+) selected blast cells from 20 AML patients and the five AML cell lines KG-1a, THP-1, HL-60, U-937, and MV4-11 with the physiologically achievable concentration of 1 μM OSI-461 or equal amounts of DMSO as a control. Following incubation with OSI-461, we found a consistent induction of apoptosis and an accumulation of cells in the G2/M phase of the cell cycle. In addition, we demonstrate that the OSI-461 mediated anti-proliferative effects observed in AML are associated with the induction of the pro-apoptotic cytokine mda-7/IL-24 and activation of the growth arrest and DNA-damage inducible genes (GADD) 45α and 45γ. Furthermore, OSI-461 treated leukemia cells did not regain their proliferative potential for up to 8 days after cessation of treatment following the initial 48 h treatment period with 1 μM OSI-461. This indicates sufficient targeting of the leukemia-initiating cells in our in vitro experiments through OSI-461. The AML samples tested in this study included samples from patients who were resistant to conventional chemotherapy and/or had FLT3-ITD mutations demonstrating the high potential of OSI-461 in human AML.

  6. Macroalgal Morphogenesis Induced by Waterborne Compounds and Bacteria in Coastal Seawater

    PubMed Central

    Grueneberg, Jan; Engelen, Aschwin H.; Costa, Rodrigo; Wichard, Thomas

    2016-01-01

    Axenic gametes of the marine green macroalga Ulva mutabilis Føyn (Ria Formosa, locus typicus) exhibit abnormal development into slow-growing callus-like colonies with aberrant cell walls. Under laboratory conditions, it was previously demonstrated that all defects in growth and thallus development can be completely abolished when axenic gametes are inoculated with a combination of two specific bacterial strains originally identified as Roseobacter sp. strain MS2 and Cytophaga sp. strain MS6. These bacteria release diffusible morphogenetic compounds (= morphogens), which act similar to cytokinin and auxin. To investigate the ecological relevance of the waterborne bacterial morphogens, seawater samples were collected in the Ria Formosa lagoon (Algarve, Southern Portugal) at 20 sampling sites and tidal pools to assess their morphogenetic effects on the axenic gametes of U. mutabilis. Specifically the survey revealed that sterile-filtered seawater samples can completely recover growth and morphogenesis of U. mutabilis under axenic conditions. Morphogenetic activities of free-living and epiphytic bacteria isolated from the locally very abundant Ulva species (i.e., U. rigida) were screened using a multiwell-based testing system. The most represented genera isolated from U. rigida were Alteromonas, Pseudoalteromonas and Sulfitobacter followed by Psychrobacter and Polaribacter. Several naturally occurring bacterial species could emulate MS2 activity (= induction of cell divisions) regardless of taxonomic affiliation, whereas the MS6 activity (= induction of cell differentiation and cell wall formation) was species-specific and is probably a feature of difficult-to-culture bacteria. Interestingly, isolated bacteroidetes such as Algoriphagus sp. and Polaribacter sp. could individually trigger complete Ulva morphogenesis and thus provide a novel mode of action for bacterial-induced algal development. This study also highlights that the accumulation of algal growth factors in

  7. Macroalgal Morphogenesis Induced by Waterborne Compounds and Bacteria in Coastal Seawater.

    PubMed

    Grueneberg, Jan; Engelen, Aschwin H; Costa, Rodrigo; Wichard, Thomas

    2016-01-01

    Axenic gametes of the marine green macroalga Ulva mutabilis Føyn (Ria Formosa, locus typicus) exhibit abnormal development into slow-growing callus-like colonies with aberrant cell walls. Under laboratory conditions, it was previously demonstrated that all defects in growth and thallus development can be completely abolished when axenic gametes are inoculated with a combination of two specific bacterial strains originally identified as Roseobacter sp. strain MS2 and Cytophaga sp. strain MS6. These bacteria release diffusible morphogenetic compounds (= morphogens), which act similar to cytokinin and auxin. To investigate the ecological relevance of the waterborne bacterial morphogens, seawater samples were collected in the Ria Formosa lagoon (Algarve, Southern Portugal) at 20 sampling sites and tidal pools to assess their morphogenetic effects on the axenic gametes of U. mutabilis. Specifically the survey revealed that sterile-filtered seawater samples can completely recover growth and morphogenesis of U. mutabilis under axenic conditions. Morphogenetic activities of free-living and epiphytic bacteria isolated from the locally very abundant Ulva species (i.e., U. rigida) were screened using a multiwell-based testing system. The most represented genera isolated from U. rigida were Alteromonas, Pseudoalteromonas and Sulfitobacter followed by Psychrobacter and Polaribacter. Several naturally occurring bacterial species could emulate MS2 activity (= induction of cell divisions) regardless of taxonomic affiliation, whereas the MS6 activity (= induction of cell differentiation and cell wall formation) was species-specific and is probably a feature of difficult-to-culture bacteria. Interestingly, isolated bacteroidetes such as Algoriphagus sp. and Polaribacter sp. could individually trigger complete Ulva morphogenesis and thus provide a novel mode of action for bacterial-induced algal development. This study also highlights that the accumulation of algal growth factors in

  8. Effect of resveratrol, a natural polyphenolic compound, on platelet activation induced by endotoxin or thrombin.

    PubMed

    Olas, Beata; Wachowicz, Barbara; Saluk-Juszczak, Joanna; Zieliński, Tomasz

    2002-08-15

    Resveratrol (3, 4', 5-trihydroxystilbene), a natural polyphenol, is found in some plants that are used in human nutrition. Grapes are a major source for resveratrol, and a significant amount can also be found in red wine. Several experimental studies have demonstrated biological properties of resveratrol, especially its anti-inflammatory, antioxidant, anti-platelet and antitumor effects. In the present study, we investigated the first step of platelet activation-platelet adhesion stimulated by lipopolysaccharide (LPS) from Proteus mirabilis (weak stimulator) and thrombin (strong activator) in the presence of resveratrol. Our studies show that endotoxin (0.3 microg/10(8) platelets), like thrombin (0.2 U/10(8) platelets), induced the adhesion of platelets (expressed as absorbance of cell attached proteins) to collagen and fibrinogen. Preincubation of washed platelets with resveratrol at physiological plasma concentrations (25-100 microg/ml, 30 min, 37 degrees C) had an inhibitory effect on adhesion of platelets to collagen after activation by LPS alone or LPS with thrombin. The strongest effect on this process was caused by resveratrol at the concentration of 100 microg/ml. Pretreatment of platelets with resveratrol (25-100 microg/ml, 30 min, 37 degrees C) had also inhibitory effects on adhesion of platelets to fibrinogen after stimulation of these cells by LPS alone or by LPS with thrombin at the same concentration. In conclusion, we suggest that resveratrol present in human diet may be an important compound responsible for the reduction of platelet adhesion and changed reactivity of blood platelets in inflammatory process.

  9. Experimental Study of Flows Induced Scour around compound Vegetation Patch in Different Densities

    NASA Astrophysics Data System (ADS)

    Chan, Hsun-Chuan; Huang, Tai-Ran

    2015-04-01

    In the natural rivers, woody vegetation commonly grows along the riverbank. When flows run through the woody vegetation zones, the stream processes are markedly affected. Previous studies were to explore Single-density vegetation group. This study used a combination of dual-density vegetation group. We experimentally investigated the flows induced scour around vegetation patch in different density. Since vegetation grows along the nature bank, so the vegetation model is arranged along one side of the flume wall. The experiments were expected to simulate the near bank scour in the jointed effects of vegetation and levee. The woody vegetation was set in 10 square centimeters. Modelled vegetation was simulated by the steel columns in the emergent flow conditions. Uniform sand with a median size of 0.88 mm was used as the bed sediment. The experimental flow was steady and flow velocity was adopted to close to the initiation of sediment motion. It was observed sediment erosion phenomenon around the vegetation zone. The bed morphology of equilibrium scour condition was measured by a Laser Distance Meter in the cases of vegetation density equal to 0.03, 0.04, 0.05, 0.07, 0.09, 0.12, 0.15,0.2, and 0.3. Test result of the vegetation group compound arrangement made by a combination of density 0.03, 0.05, 0.09, and 0.12. The difference between double density and single density of the vegetation was compared. Vegetation densities were used to research the effects of vegetation on the maximum scour depth of the scour hole. Near the vegetation zone, the size of the scour hole increased as the vegetation density increased. However, the height of depositing dune is in a low correlation with vegetation density. Location of Maximum scour depth and the maximum accumulation will move upstream with the density increase.

  10. Protective effect of bioactive compounds from Lonicera japonica Thunb. against H2O2-induced cytotoxicity using neonatal rat cardiomyocytes

    PubMed Central

    Wang, Chen; Wang, Gang; Liu, Hong; Hou, Yun-long

    2016-01-01

    Objective(s): Pharmacological studies showed that the extracts of Jin Yin Hua and its active constituents have lipid lowering, antipyretic, hepatoprotective, cytoprotective, antimicrobial, antibiotic, antioxidative, antiviral, and anti-inflammatory effects. The purpose of the present study was to investigate the protective effects of caffeoylquinic acids (CQAs) from Jin Yin Hua against hydrogen peroxide (H2O2)-induced and hypoxia-induced cytotoxicity using neonatal rat cardiomyocytes. Materials and Methods: Seven CQAs (C1 to C7) isolated and identified from Jin Yin Hua were used to examine the effects of H2O2-induced and hypoxia-induced cytotoxicity. We studied C4 and C6 as preventative bioactive compounds of the reactive oxygen species (ROS) production, apoptotic pathway, and apoptosis-related gene expression. Results: C4 and C6 were screened as bioactive compounds to exert a cytoprotective effect against oxidative injury. Pretreatment with C4 and C6, dose-dependently attenuated hypoxia-induced ROS production and reduced the ratio of GSSG/GStotal. Western blot data revealed that the inhibitory effect of C4 on H2O2-induced up and down-regulation of Bcl-2, Bax, caspase-3, and cleaved caspase-3. Apoptosis was evaluated by detection of DNA fragmentation using TUNEL assay, and quantified with Annexin V/PI staining. Conclusion: In vitro experiments revealed that both C4 and C6 protect cardiomyocytes from necrosis and apoptosis during H2O2-induced injury, via inhibiting the generation of ROS and activation of caspase-3 apoptotic pathway. These results demonstrated that CQAs might be a class of compounds which possess potent myocardial protective activity against the ischemic heart diseases related to oxidative stress. PMID:27096070

  11. Effects of Constituent Compounds of Smilax china on Nicotine-Induced Endothelial Dysfunction in Human Umbilical Vein Endothelial Cells.

    PubMed

    Lincha, Victor Ruberio; Zhao, Bing-Tian; Woo, Mi-Hee; Yang, In-Jun; Shin, Heung-Mook

    2016-01-01

    This study investigated the effects of compounds isolated from 70% ethanol (EtOH) extraction of Smilax china L. (SCE), a plant belonging to the family Smilacaceae on nicotine-induced endothelial dysfunction (ED) in human umbilical vein endothelial cells. We isolated 10 compounds from ethyl acetate (EtOAc) fraction of 70% EtOH extract of SCE and investigated their inhibitory effect on nicotine-induced ED in endothelial cells. Kaempferol, kaempferol 7-O-α-L-rhamnopyranoside, puerarin and ferulic acid showed strong inhibition of nicotine-induced vascular cell adhesion molecule (VCAM-1) expression while kaempferol, kaempferin, and caffeic acid attenuated intercellular adhesion molecule (ICAM-1) expression. Lepidoside, caffeic acid and methylsuccinic acid caused the highest up-regulated expression of endothelial nitric oxide synthase at the protein level with caffeic acid and ferulic acid showing strong inhibitory effects on inducible nitric oxide synthase (iNOS) expression. In addition, ferulic acid and kaempferol showed inhibition against interleukin-8 (IL-8) and interleukin-1β (IL-1β) expression while ferulic acid and caffeic acid showed comparatively higher inhibition of ED associated tumor necrosis factor-α (TNF-α) expression. These results show the potential of the aforementioned compounds to reverse the toxic effects of nicotine on the endothelium.

  12. Food-associated estrogenic compounds induce estrogen receptor-mediated luciferase gene expression in transgenic male mice.

    PubMed

    Ter Veld, Marcel G R; Zawadzka, E; van den Berg, J H J; van der Saag, Paul T; Rietjens, Ivonne M C M; Murk, Albertinka J

    2008-07-30

    The present paper aims at clarifying to what extent seven food-associated compounds, shown before to be estrogenic in vitro, can induce estrogenic effects in male mice with an estrogen receptor (ER)-mediated luciferase (luc) reporter gene system. The luc induction was determined in different tissues 8h after dosing the ER-luc male mice intraperitoneally (IP) or 14h after oral dosing. Estradiol-propionate (EP) was used as a positive control at 0.3 and 1mg/kg bodyweight (bw), DMSO as solvent control. The food-associated estrogenic compounds tested at non-toxic doses were bisphenol A (BPA) and nonylphenol (NP) (both at 10 and 50mg/kgbw), dichlorodiphenyldichloroethylene (p,p'-DDE; at 5 and 25mg/kgbw), quercetin (at 1.66 and 16.6mg/kgbw), di-isoheptyl phthalate (DIHP), di-(2-ethylhexyl) phthalate (DEHP) and di-(2-ethylhexyl) adipate (DEHA) all at 30 and 100mg/kgbw. In general IP dosing resulted in higher luc inductions than oral dosing. EP induced luc activity in the liver in a statistically significant dose-related way with the highest induction of all compounds tested which was 20,000 times higher than the induction by the DMSO-control. NP, DDE, DEHA and DIHP did not induce luc activity in any of the tissues tested. BPA induced luc in the liver up to 420 times via both exposure routes. BPA, DEHP and quercetin induced luc activity in the liver after oral exposure. BPA (50mg/kgbw IP) also induced luc activity in the testis, kidneys and tibia. The current study reveals that biomarker-responses in ER-luc male mice occur after a single oral exposure to food-associated estrogenic model compounds at exposure levels 10 to 10(4) times higher than the established TDI's for some of these compounds. Given the facts that (i) the present study did not include chronic exposure and that (ii) simultaneous exposure to multiple estrogenic compounds may be a realistic exposure scenario, it remains to be seen whether this margin is sufficiently high.

  13. Evidence for the encagement of alkali metal ions through the formation of gas-phase clathrates: Cs sup + in water clusters

    SciTech Connect

    Selinger, A.; Castleman, A.W. Jr. )

    1991-10-31

    Reported herein is the first evidence for the encagement of an atomic ion in a cluster leading to the formation of a gas-phase clathrate, namely Cs{sup +} contained within a complex comprised of 20 water molecules. Evidence is also presented for the encagement of Cs{sup +} by other (distorted) clathrates involving 18, 22, 24, 27 and 29 water molecules. All of these species were reduced under thermal reaction conditions in a fast-flow reactor.

  14. DJ-1-binding compounds prevent oxidative stress-induced cell death and movement defect in Parkinson's disease model rats.

    PubMed

    Miyazaki, Shin; Yanagida, Takashi; Nunome, Kana; Ishikawa, Shizuma; Inden, Masatoshi; Kitamura, Yoshihisa; Nakagawa, Shinsuke; Taira, Takahiro; Hirota, Kosaku; Niwa, Masami; Iguchi-Ariga, Sanae M M; Ariga, Hiroyoshi

    2008-06-01

    Parkinson's disease (PD) is caused by neuronal cell death. Although a precursor of dopamine and inhibitors of dopamine degradation have been used for PD therapy, cell death progresses during treatment. DJ-1, a causative gene product of a familial form of PD, PARK7, plays roles in transcriptional regulation and anti-oxidative stress, and loss of its function is thought to result in the onset of PD. Superfluous oxidation of cysteine at amino acid 106 (C106) of DJ-1 renders DJ-1 inactive, and such oxidized DJ-1 has been observed in patients with the sporadic form of PD. In this study, we isolated compounds that bind to the region at C106 by a virtual screening. These compounds prevented oxidative stress-induced death of SH-SY5Y cells, embryonic stem cell-derived dopaminergic cells and primary neuronal cells of the ventral mesencephalon, but not that of DJ-1-knockdown cells of SH-SY5Y and NIH3T3 cells, indicating that the effect of the compounds is specific to DJ-1. These compounds inhibited production of reactive oxygen species and restored activities of mitochondrial complex I and tyrosine hydroxylase that had been compromised by oxidative stress. These compounds prevented dopaminergic cell death in the substantia nigra and restored movement abnormality in 6-hydroxyldopamine-injected PD model rats. One mechanism of action of these compounds is prevention of superfluous oxidation of DJ-1, and the compounds passed through the blood-brain barrier in vitro. Taken together, the results indicate that these compounds should become fundamental drugs for PD therapy.

  15. Soil aeration to achieve co-metabolic biodegradation of chlorinated solvents in the presence of inducer compounds

    SciTech Connect

    Eisenbeis, J.J.; Bourquin, A.W.

    1995-12-31

    A chemical distribution facility in Denver has been found to have soil and ground water contaminated with a wide variety of organic compounds, primarily toluene and chlorinated solvents, and their breakdown products. Since toluene and chlorobenzenes (both present at the site) have been shown to be inducers for an aerobic enzyme pathway that can degrade trichloroethene (TCE), 1,2-dichloroethene (DCE) and vinyl chloride, field and laboratory studies are being conducted to determine if cometabolic aerobic biodegradation of these and other compounds is occurring in soils that have been aerated with soil vapor extraction (SVE). Studies summarized in this paper include in situ respiration tests to estimate overall biodegradation rate in aerated soils within the influence of a SVE system, sampling to determine if in situ biodegradation of chlorinated volatile organic compounds in ground water has occurred, and a laboratory column study simulating bioventing of unremediated soils.

  16. First Principles Study of the Properties of the Type II Clathrate Alloy Si136-xGex(x = 8, 32, 96)

    NASA Astrophysics Data System (ADS)

    Xue, Dong; Myles, Charles

    The Type-II clathrate materials based on Si, Ge, and Sn have ``open-framework'' lattices consisting of large ``cages'' of atoms covalently bonded together. Due primarily to their potential thermoelectric applications, there has been considerable research on these materials with various guest atoms in the cages and with various substitutional atoms on the lattice framework. Also of interest are the pure Type II clathrates M136 (M = Si, Ge, Sn) with neither framework substitution nor guest atoms in the cages. A fundamental understanding of the intrinsic properties of these ``guest-free'' clathrates is therefore also needed. Mixtures or ``alloys'' of two different Type II clathrate materials are also potentially interesting. For example, Moriguchi et al. have reported the successful synthesis of Type II clathrates with mixtures of Si and Ge on the framework lattice. Motivated by these experiments, we have carried out a computational and theoretical study the properties of the Type II clathrate ``alloy'' Si136-xGex. We report the results of DFT-based first-principles calculations of the structural, electronic, vibrational, and thermal properties of Si136-xGex for x = 8, 32, 96. Our calculations have assumed that the ideal lattice symmetry is unaffected by the mixing of Si and Ge. Among other results, we predict that Si136-xGex should have a direct band gap ranging from 1.2 to 2.0 eV.

  17. Development of gallium compounds for treatment of lymphoma: gallium maltolate, a novel hydroxypyrone gallium compound, induces apoptosis and circumvents lymphoma cell resistance to gallium nitrate.

    PubMed

    Chitambar, Christopher R; Purpi, David P; Woodliff, Jeffrey; Yang, Meiying; Wereley, Janine P

    2007-09-01

    Clinical studies have shown gallium nitrate to have significant antitumor activity against non-Hodgkin's lymphoma and bladder cancer, thus indicating that gallium-based drugs have potential for further development as antineoplastic agents. In this study, we compared the cytotoxicity of gallium maltolate, a novel gallium compound, with gallium nitrate in lymphoma cell lines, including p53 variant and unique gallium nitrate-resistant cells. We found that gallium maltolate inhibited cell proliferation and induced apoptosis through the mitochondrial pathway at lower concentrations and more rapidly than gallium nitrate. Gallium maltolate produced an increase in intracellular reactive oxygen species (ROS) within 2 h of incubation with cells; this effect could be blocked by mitoquinone, a mitochondria-targeted antioxidant. The role of the transferrin receptor (TfR) in gallium maltolate's action was examined using monoclonal antibody (MoAb) 42/6 to block TfR function. However, although MoAb 42/6 reduced gallium maltolate-induced caspase-3 activity, it had only a minor effect on cell growth inhibition. Importantly, gallium maltolate induced apoptosis in cells resistant to gallium nitrate, and, unlike gallium nitrate, its cytotoxicity was not affected by cellular p53 status. Cellular gallium uptake was greater with gallium maltolate than with gallium nitrate. We conclude that gallium maltolate inhibits cell proliferation and induces apoptosis more efficiently than gallium nitrate. Gallium maltolate is incorporated into lymphoma cells to a greater extent than gallium nitrate via both TfR-independent and -dependent pathways; it has significant activity against gallium nitrate-resistant cells and acts independently of p53. Further studies to evaluate its antineoplastic activity in vivo are warranted.

  18. Potential for ion-induced nucleation of volatile organic compounds by radon decay in indoor environments

    SciTech Connect

    Daisey, J.M. ); Hopke, P.K. )

    1993-07-01

    The theoretical potential for the formation of clusters of vapor-phase organic compounds found in indoor air around the [sup 218]PoO[sub x][sup +] ion was investigated as well as which compounds were most likely to form clusters. A compilation of measurements of indoor organic compounds has been made for future experiments and theoretical calculations by the radon research community. Forty-four volatile and semivolatile organic compounds out of the more than 300 that have been reported in indoor air were investigated. Water vapor was included for comparison. The results indicate that there is a potential for the formation of clusters of organic compounds around the [sup 218]PoO[sub x][sup +] ion. The compounds with the greatest potential for cluster formation are the volatile oxidized hydrocarbons (e.g., n-butanol, phenol, hexanal, nonanal, benzaldehyde, the ketones, and the acetates) and the semivolatile organic compounds (pentachlorophenol, nicotine, chlordane, chlorpyrifos). Although the estimated diameters are consistent with the measured diameters for the unattached fraction, the state of experimental and theoretical knowledge in this area is not sufficiently developed to judge the quantitative validity of these predictions. 48 refs., 1 fig., 5 tabs.

  19. Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures

    DOEpatents

    Lueking, Angela [State College, PA; Narayanan, Deepa [Redmond, WA

    2011-03-08

    A process for making a hydrogenated carbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenated carbon material. A hydrogenated carbon material including a hydrogen carbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.

  20. The atmosphere of a dirty-clathrate cometary nucleus - A two-phase, multifluid model

    NASA Technical Reports Server (NTRS)

    Marconi, M. L.; Mendis, D. A.

    1983-01-01

    The dynamical and thermal structure of a dirty-clathrate cometary nucleus' gas atmosphere is presently given a self-consistent, transonic multifluid solution in which, although the heavy neutron and ion species are treated as a single fluid in the collision-dominated region, the photoproduced H is treated separately. The thermal profile of the atmosphere thus obtained is entirely different from those predicted by the earlier, single-fluid models as well as the multifluid models which assumed equipartition of energy between electrons and ions. While the electron gas, like the neutrals and the ions, cools due to expansion, its main mode of energy loss in the inner coma is by way of inelastic collisions with the predominant H2O molecule. The high electron temperature in the outer coma also decreases the efficiency of electron removal by dissociative recombination, thereby increasing electron density throughout the coma.

  1. Order-disorder transition in clathrate Ba6Ge25 studied by positron annihilation

    NASA Astrophysics Data System (ADS)

    Li, X. F.; Zhao, B.; Zhang, T.; He, H. F.; Zhang, Q.; Yang, D. W.; Chen, Z. Q.; Tang, X. F.

    2015-07-01

    Clathrate Ba6Ge25 is prepared by melt method and spark plasma sintering. Structural transition below room temperature is studied by positron annihilation and X-ray diffraction measurements. There is a pronounced transition in the temperature range of 200-250 K which might be involved with the movement of Ba atoms in Ge cages and result in disordered structure. This transition is further confirmed by the theoretical calculation of positron annihilation states. Thus our results confirm the structural models proposed by Carrillo-Cabrera et al. (2005). The measured specific heat capacity, electric resistivity and magnetic susceptibility all show anomalous transition in the same temperature range, indicating that the movement of Ba atoms in the cage has influence on the thermal, electric as well as magnetic properties of Ba6Ge25.

  2. The Promoter of Rv0560c Is Induced by Salicylate and Structurally-Related Compounds in Mycobacterium tuberculosis

    PubMed Central

    Schuessler, Dorothée L.; Parish, Tanya

    2012-01-01

    Mycobacterium tuberculosis, the causative agent of tuberculosis (TB), is a major global health threat. During infection, bacteria are believed to encounter adverse conditions such as iron depletion. Mycobacteria synthesize iron-sequestering mycobactins, which are essential for survival in the host, via the intermediate salicylate. Salicylate is a ubiquitous compound which is known to induce a mild antibiotic resistance phenotype. In M. tuberculosis salicylate highly induces the expression of Rv0560c, a putative methyltransferase. We identified and characterized the promoter and regulatory elements of Rv0560c. PRv0560c activity was highly inducible by salicylate in a dose-dependent manner. The induction kinetics of PRv0560c were slow, taking several days to reach maximal activity, which was sustained over several weeks. Promoter activity could also be induced by compounds structurally related to salicylate, such as aspirin or para-aminosalicylic acid, but not by benzoate, indicating that induction is specific to a structural motif. The −10 and −35 promoter elements were identified and residues involved in regulation of promoter activity were identified in close proximity to an inverted repeat spanning the −35 promoter element. We conclude that Rv0560c expression is controlled by a yet unknown repressor via a highly-inducible promoter. PMID:22485172

  3. Growth inhibition and apoptosis in cancer cells induced by polyphenolic compounds of Acacia hydaspica: Involvement of multiple signal transduction pathways

    PubMed Central

    Afsar, Tayyaba; Trembley, Janeen H.; Salomon, Christine E.; Razak, Suhail; Khan, Muhammad Rashid; Ahmed, Khalil

    2016-01-01

    Acacia hydaspica R. Parker is known for its medicinal uses in multiple ailments. In this study, we performed bioassay-guided fractionation of cytotoxic compounds from A. hydaspica and investigated their effects on growth and signaling activity in prostate and breast cancer cell lines. Four active polyphenolic compounds were identified as 7-O-galloyl catechin (GC), catechin (C), methyl gallate (MG), and catechin-3-O-gallate (CG). The four compounds inhibited prostate cancer PC-3 cell growth in a dose-dependent manner, whereas CG and MG inhibited breast cancer MDA-MB-231 cell growth. All tested compounds inhibited cell survival and colony growth in both cell lines, and there was evidence of chromatin condensation, cell shrinkage and apoptotic bodies. Further, acridine orange, ethidium bromide, propidium iodide and DAPI staining demonstrated that cell death occurred partly via apoptosis in both PC-3 and MDA-MB-231 cells. In PC-3 cells treatment repressed the expression of anti-apoptotic molecules Bcl-2, Bcl-xL and survivin, coupled with down-regulation of signaling pathways AKT, NFκB, ERK1/2 and JAK/STAT. In MDA-MB-231 cells, treatment induced reduction of CK2α, Bcl-xL, survivin and xIAP protein expression along with suppression of NFκB, JAK/STAT and PI3K pathways. Our findings suggest that certain polyphenolic compounds derived from A. hydaspica may be promising chemopreventive/therapeutic candidates against cancer. PMID:26975752

  4. Growth inhibition and apoptosis in cancer cells induced by polyphenolic compounds of Acacia hydaspica: Involvement of multiple signal transduction pathways.

    PubMed

    Afsar, Tayyaba; Trembley, Janeen H; Salomon, Christine E; Razak, Suhail; Khan, Muhammad Rashid; Ahmed, Khalil

    2016-03-15

    Acacia hydaspica R. Parker is known for its medicinal uses in multiple ailments. In this study, we performed bioassay-guided fractionation of cytotoxic compounds from A. hydaspica and investigated their effects on growth and signaling activity in prostate and breast cancer cell lines. Four active polyphenolic compounds were identified as 7-O-galloyl catechin (GC), catechin (C), methyl gallate (MG), and catechin-3-O-gallate (CG). The four compounds inhibited prostate cancer PC-3 cell growth in a dose-dependent manner, whereas CG and MG inhibited breast cancer MDA-MB-231 cell growth. All tested compounds inhibited cell survival and colony growth in both cell lines, and there was evidence of chromatin condensation, cell shrinkage and apoptotic bodies. Further, acridine orange, ethidium bromide, propidium iodide and DAPI staining demonstrated that cell death occurred partly via apoptosis in both PC-3 and MDA-MB-231 cells. In PC-3 cells treatment repressed the expression of anti-apoptotic molecules Bcl-2, Bcl-xL and survivin, coupled with down-regulation of signaling pathways AKT, NFκB, ERK1/2 and JAK/STAT. In MDA-MB-231 cells, treatment induced reduction of CK2α, Bcl-xL, survivin and xIAP protein expression along with suppression of NFκB, JAK/STAT and PI3K pathways. Our findings suggest that certain polyphenolic compounds derived from A. hydaspica may be promising chemopreventive/therapeutic candidates against cancer.

  5. S-52, a novel nootropic compound, protects against β-amyloid induced neuronal injury by attenuating mitochondrial dysfunction.

    PubMed

    Gao, Xin; Zheng, Chun Yan; Qin, Guo Wei; Tang, Xi Can; Zhang, Hai Yan

    2012-10-01

    Accumulating evidence suggests that β-amyloid (Aβ)-induced oxidative DNA damage and mitochondrial dysfunction may initiate and contribute to the progression of Alzheimer's disease (AD). This study evaluated the neuroprotective effects of S-52, a novel nootropic compound, on Aβ-induced mitochondrial failure. In an established paradigm of moderate cellular injury induced by Aβ, S-52 was observed to attenuate the toxicity of Aβ to energy metabolism, mitochondrial membrane structure, and key enzymes in the electron transport chain and tricarboxylic acid cycle. In addition, S-52 also effectively inhibited reactive oxygen species accumulation dose dependently not only in Aβ-harmed cells but also in unharmed, normal cells. The role of S-52 as a scavenger of free radicals is involved in the antioxidative effect of this compound. The beneficial effects on mitochondria and oxidative stress extend the neuroprotective effects of S-52. The present study provides crucial information for better understanding the beneficial profiles of this compound and discovering novel potential drug candidates for AD therapy.

  6. New pathway for the formation of metallic cubic phase Ge-Sb-Te compounds induced by an electric current

    PubMed Central

    Park, Yong-Jin; Cho, Ju-Young; Jeong, Min-Woo; Na, Sekwon; Joo, Young-Chang

    2016-01-01

    The novel discovery of a current-induced transition from insulator to metal in the crystalline phase of Ge2Sb2Te5 and GeSb4Te7 have been studied by means of a model using line-patterned samples. The resistivity of cubic phase Ge-Sb-Te compound was reduced by an electrical current (~1 MA/cm2), and the final resistivity was determined based on the stress current density, regardless of the initial resistivity and temperature, which indicates that the conductivity of Ge-Sb-Te compound can be modulated by an electrical current. The minimum resistivity of Ge-Sb-Te materials can be achieved at high kinetic rates by applying an electrical current, and the material properties change from insulating to metallic behavior without a phase transition. The current-induced metal transition is more effective in GeSb4Te7 than Ge2Sb2Te5, which depends on the intrinsic vacancy of materials. Electromigration, which is the migration of atoms induced by a momentum transfer from charge carriers, can easily promote the rearrangement of vacancies in the cubic phase of Ge-Sb-Te compound. This behavior differs significantly from thermal annealing, which accompanies a phase transition to the hexagonal phase. This result suggests a new pathway for modulating the electrical conductivity and material properties of chalcogenide materials by applying an electrical current. PMID:26902593

  7. Adsorption sites and rotational tunneling of methyl groups in cubic I methyl fluoride water clathrate.

    PubMed

    Prager, M; Baumert, J; Press, W; Plazanet, M; Tse, J S; Klug, D D

    2005-03-21

    Neutron spectroscopy in the microeV and meV regime and quasielastic scattering is applied to characterize the dynamics of methyl groups of methyl fluoride guest molecules in cubic I CH3F-water clathrate. Only above T approximately 60 K quasielastic spectra are unaffected by quantum effects. They are well described by two Lorentzians representing the CH3F species in the small and large cages of the structure. The intensities show that both cages are completely filled. The linear broadenings with temperature follow the model of rotational diffusion. Two clearly separated tunneling bands were observed at T = 4.2 K and are also assigned to the two types of water cages. Disorder of the environment (H-bonds) is reflected in the shape of the bands. For the less hindered species housing the large cages the tunneling band can be quantitatively converted into a potential distribution function within the model of single particle rotation. Transitions to excited rotational states show the dominance of a sixfold potential term V6 = 13 meV modified by a weak threefold term distributed around a characteristic value V3 = 0.9 meV. The potential distribution of V3 influences the barrier for classical reorientation only weakly in agreement with the results from quasielastic data. Adsorption sites with the guest molecules oriented towards a hydrogen bond along one of twelve local twofold axes of the cage are proposed. Such sites are consistent with the sixfold rotational potential and earlier results from methyl iodide clathrate. Rotation-translation coupling as an alternative dynamical process is excluded.

  8. CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Synthesis and high temperature thermoelectric transport properties of Si-based type-I clathrates

    NASA Astrophysics Data System (ADS)

    Deng, Shu-Kang; Tang, Xin-Feng; Tang, Run-Sheng

    2009-07-01

    N-type Si-based type-I clathrates with different Ga content were synthesized by combining the solid-state reaction method, melting method and spark plasma sintering (SPS) method. The effects of Ga composition on high temperature thermoelectric transport properties were investigated. The results show that at room temperature, the carrier concentration decreases, while the carrier mobility increases slightly with increasing Ga content. The Seebeck coefficient increases with increasing Ga content. Among all the samples, Ba7.93Ga17.13Si28.72 exhibits higher Seebeck coefficient than the others and reaches -135 μV.K-1 at 1000 K. The sample prepared by this method exhibits very high electrical conductivity, and reaches 1.95×105 S.m-1 for Ba8.01Ga16.61Si28.93 at room temperature. The thermal conductivity of all samples is almost temperature independent in the temperature range of 300-1000 K, indicating the behaviour of a typical metal. The maximum ZT value of 0.75 is obtained at 1000 K for the compound Ba7.93Ga17.13Si28.72.

  9. Guest Molecular Dynamics in Superconducting Clathrates Ag6O8AgX (X=NO3 and HF2): NMR Investigation

    NASA Astrophysics Data System (ADS)

    Kanetake, Fumiya; Naruwa, Hirofumi; Mukuda, Hidekazu; Kitaoka, Yoshio; Kawashima, Kenji; Ishii, Masaru; Akimitsu, Jun

    2011-07-01

    We report a microscopic investigation of the superconducting clathrates Ag6O8AgX (X=NO3 and HF2), which are composed of Ag6O8 polyhedral cages and a guest molecule X inside the cages. Site-selective NMR measurements have revealed that the trigonal planar NO3 molecule in Ag6O8AgNO3 is confined in the (001) plane in a low-temperature tetragonal phase, while the uniaxial HF2 molecule in Ag6O8AgHF2 is preferentially directed along the c-axis in a low-temperature phase. These results point to the fact that the distortion of the cages takes place so as to minimize the entropy of the molecular motions of the guest ions inside the cages as the cage volume contracts thermally upon cooling. Note that the difference in Tc between these compounds may be primarily ascribed to a difference in their Debye frequencies, but neither to anharmonic vibrations of the guest molecules called rattling nor to other possible remaining degrees of freedom in the molecular dynamics.

  10. Novel therapeutic compound tuftsin-phosphorylcholine attenuates collagen-induced arthritis.

    PubMed

    Bashi, T; Shovman, O; Fridkin, M; Volkov, A; Barshack, I; Blank, M; Shoenfeld, Y

    2016-04-01

    Treatment with helminthes and helminthes ova improved the clinical symptoms of several autoimmune diseases in patients and in animal models. Phosphorylcholine (PC) proved to be the immunomodulatory molecule. We aimed to decipher the tolerogenic potential of tuftsin-PC (TPC), a novel helminth-based compound in collagen-induced arthritis (CIA) a mouse model of rheumatoid arthritis (RA). CIA DBA/1 mice were treated with TPC subcutaneously (5 µg/0.1 ml) or orally (250 µg/0.1 ml), starting prior to disease induction. The control groups were treated with PBS. Collagen antibodies were tested by enzyme-linked immunosorbent assay (ELISA), cytokine protein levels by ELISA kits and regulatory T (Treg ) and regulatory B (Breg ) cell phenotypes by fluorescence-activated cell sorter (FACS). TPC-treated mice had a significantly lower arthritis score of 1.5 in comparison with control mice 11.8 (P < 0.0001) in both subcutaneous and orally treated groups at day 31. Moreover, histology analysis demonstrated highly inflamed joints in control mice, whereas TPC-treated mice maintained normal joint structure. Furthermore, TPC decreased the titres of circulating collagen II antibodies in mice sera (P < 0.0001), enhanced expression of IL-10 (P < 0.0001) and inhibited production of tumour necrosis factor (TNF)-α, interleukin (IL)-17 and IL-1β (P < 0.0001). TPC significantly expanded the CD4(+) CD25(+) forkhead box protein 3 (FoxP3(+) ) Treg cells and CD19(+) IL-10(+) CD5(high) CD1d(high) T cell immunoglobulin mucin-1 (TIM-1(+) ) Breg cell phenotypes (P < 0.0001) in treated mice. Our data indicate that treatment with TPC attenuates CIA in mice demonstrated by low arthritic score and normal joints histology. TPC treatment reduced proinflammatory cytokines and increased anti-inflammatory cytokine expression, as well as expansion of Treg and Breg cells. Our results may lead to a new approach for a natural therapy for early rheumatoid arthritis onset.

  11. Development of Novel Bifunctional Compounds that Induce Apoptosis in Prostate Cancer Cells

    DTIC Science & Technology

    2008-03-01

    adducts respectively. 7 could be administered orally. This series of experiments is based upon the knowledge that chlorambucil , which is...whereas other aniline mustard compounds such as chlorambucil do not. REFERENCES None included. APPENDICIES None included.

  12. Development of Novel Bifunctional Compounds that Induce Apoptosis in Prostate Cancer Cells

    DTIC Science & Technology

    2005-02-01

    have administered the compound dissolved in a vehicle containing Cremophor EL, a polyoxyethylated castor oil. The availability of radiolabeled...seeking an improved vehicle in which to administer the compound. One reason for this was that Cremophor EL in our current vehicle poses potential problems...effective and have fewer adverse side effects formulations in which these drugs are administered in Cremophor EL or other 7 vehicles. Selective

  13. Tracking "apolar" NMe4+ ions within two polyoxothiomolybdates that have the same pores: smaller clathrate and larger highly porous clusters in action.

    PubMed

    Korenev, Vladimir S; Boulay, Antoine G; Haouas, Mohamed; Bannani, Fatma; Fedin, Vladimir P; Sokolov, Maxim N; Terazzi, Emmanuel; Garai, Somenath; Müller, Achim; Taulelle, Francis; Marrot, Jérôme; Leclerc, Nathalie; Floquet, Sébastien; Cadot, Emmanuel

    2014-03-10

    Two nanosized polyoxothiometalates were synthesized based on linking oxomolybdate building blocks with {Mo2O2S2}(2+) groups. Remarkably, both compounds are formed selectively primarily upon changing the related concentrations in a logical way; they exhibit common structural features based on the same {Mo9O6S3}-type pores, which result in connections between {Mo6O21} pentagons and {Mo2O2S2}(2+) linkers. Whereas the much larger spherical Mo132-type Keplerate contains twenty pores, the smaller Mo63 -type cluster remarkably contains only two. The two compounds and a similar Keplerate exhibit interesting supramolecular properties related to interactions with the unusual predominantly apolar NMe4(+) cations. Structural characterization of the Mo63 -type compound reveals in the solid state a clathrate-like species that contains four NMe4(+) cations embedded in two types of structurally well-adapted pockets. Related NMR spectroscopic investigations in solution using NMe4(+) as the NMR spectroscopic probe are in agreement with the solid-state description. (1)H NMR spectroscopic experiments (1D variable-temperature, 2D total correlation spectroscopy (TOCSY), exchange spectroscopy (EXSY), and diffusion-ordered spectroscopy (DOSY)) feature firmly immobilized and mobile NMe4(+) ions in relationship with the type of host-guest arrangements. The use of the (1)H NMR DOSY spectroscopic methodology has been successfully applied to track the interactions of the NMe4(+) cations with the {Mo9O6S3} pores of a sulfurated Keplerate, thereby allowing the first quantitative analysis of this type of plugging process. The stability constant K=(210±20) mol(-1)  L is discussed related to the character of the process.

  14. Properties of CO2 clathrate hydrates formed in the presence of MgSO4 solutions with implications for icy moons

    NASA Astrophysics Data System (ADS)

    Safi, E.; Thompson, S. P.; Evans, A.; Day, S. J.; Murray, C. A.; Parker, J. E.; Baker, A. R.; Oliveira, J. M.; van Loon, J. Th.

    2017-04-01

    Context. There is evidence to suggest that clathrate hydrates have a significant effect on the surface geology of icy bodies in the solar system. However the aqueous environments believed to be present on these bodies are likely to be saline rather than pure water. Laboratory work to underpin the properties of clathrate hydrates in such environments is generally lacking. Aims: We aim to fill this gap by carrying out a laboratory investigation of the physical properties of CO2 clathrate hydrates produced in weak aqueous solutions of MgSO4. Methods: We use in situ synchrotron X-ray powder diffraction to investigate clathrate hydrates formed at high CO2 pressure in ice that has formed from aqueous solutions of MgSO4 with varying concentrations. We measure the thermal expansion, density and dissociation properties of the clathrates under temperature conditions similar to those on icy solar system bodies. Results: We find that the sulphate solution inhibits the formation of clathrates by lowering their dissociation temperatures. Hysteresis is found in the thermal expansion coefficients as the clathrates are cooled and heated; we attribute this to the presence of the salt in solution. We find the density derived from X-ray powder diffraction measurements is temperature and pressure dependent. When comparing the density of the CO2 clathrates to that of the solution in which they were formed, we conclude that they should sink in the oceans in which they form. We also find that the polymorph of ice present at low temperatures is Ih rather than the expected Ic, which we tentatively attribute to the presence of the MgSO4. Conclusions: We (1) conclude that the density of the clathrates has implications for their behaviour in satellite oceans as their sinking and floating capabilities are temperature and pressure dependent; (2) conclude that the presence of MgSO4 inhibits the formation of clathrates and in some cases may even affect their structure and (3) report the dominance

  15. Conformational restriction of aryl thiosemicarbazones produces potent and selective anti-Trypanosoma cruzi compounds which induce apoptotic parasite death.

    PubMed

    Magalhaes Moreira, Diogo Rodrigo; de Oliveira, Ana Daura Travassos; Teixeira de Moraes Gomes, Paulo André; de Simone, Carlos Alberto; Villela, Filipe Silva; Ferreira, Rafaela Salgado; da Silva, Aline Caroline; dos Santos, Thiago André Ramos; Brelaz de Castro, Maria Carolina Accioly; Pereira, Valéria Rego Alves; Leite, Ana Cristina Lima

    2014-03-21

    Chagas disease, caused by Trypanosoma cruzi, is a life-threatening infection leading to approximately 12,000 deaths per year. T. cruzi is susceptible to thiosemicarbazones, making this class of compounds appealing for drug development. Previously, the homologation of aryl thiosemicarbazones resulted in an increase in anti-T. cruzi activity in comparison to aryl thiosemicarbazones without a spacer group. Here, we report the structural planning, synthesis and anti-T. cruzi evaluation of new aryl thiosemicarbazones (9a-x), designed as more conformationally restricted compounds. By varying substituents attached to the phenyl ring, substituents were observed to retain, enhance or greatly increase the anti-T. cruzi activity, in comparison to the nonsubstituted derivative. In most cases, hydrophobic and bulky substituents, such as bromo, biphenyl and phenoxyl groups, greatly increased antiparasitic activity. Specifically, thiosemicarbazones were identified that inhibit the epimastigote proliferation and were toxic for trypomastigotes without affecting mouse splenocytes viability. The most potent anti-T. cruzi thiosemicarbazones were evaluated against cruzain. However, inhibition of this enzyme was not observed, suggesting that the compounds work through another mechanism. In addition, examination of T. cruzi cell death showed that these thiosemicarbazones induce apoptosis. In conclusion, the structural design executed within the series of aryl thiosemicarbazones (9a-x) led to the identification of new potent anti-T. cruzi agents, such as compounds (9h) and (9r), which greatly inhibited epimastigote proliferation, and demonstrated a toxicity for trypomastigotes, but not for splenocytes. Mechanistically, these compounds do not inhibit the cruzain, but induce T. cruzi cell death by an apoptotic process. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  16. Restraint stress-induced central monoaminergic & oxidative changes in rats & their prevention by novel Ocimum sanctum compounds

    PubMed Central

    Ahmad, Ausaf; Rasheed, Naila; Chand, Kailash; Maurya, Rakesh; Banu, Naheed; Palit, Gautam

    2012-01-01

    Background & objectives: Ocimum sanctum (OS) is known to possess various therapeutic properties. We have earlier isolated and characterized three OS compounds; Ocimarin, Ocimumoside A and Ocimumoside B. However, their role in modulating stress-induced central changes is unexplored. Thus, the present study was aimed to investigate the effect of these OS compounds on restraint stress (RS)-induced changes in the monoaminergic and antioxidant systems in the frontal cortex, striatum and hippocampus of rats. Methods: RS was produced by immobilizing (restraining) the Sprague Dawley rats for a period of 2.5 h inside cylindrical steel tubes. The monoamine levels and the in vivo antioxidant status in brain regions were evaluated by HPLC-EC and spectrophotometric assays, respectively. Results: RS significantly increased the dopamine levels in the frontal cortex and decreased in the striatum and hippocampus, and accompanied with selective increase of dopamine metabolites compared to the NS control group. The serotonin and its metabolite levels were significantly increased, while noradrenaline levels were decreased by RS in the three brain regions studied. The activities of superoxide dismutase and glutathione peroxidase in the frontal cortex and striatum were significantly increased by RS with decreased glutathione levels and increased lipid peroxidation. Pre-treatment with Ocimumoside A and B (40 mg/kg po) for a period of 3 days prevented the RS-induced changes with an efficacy similar to that of standard anti-stress (Panax quinquefolium; 100 mg/kg po) and antioxidant (Melatonin; 20 mg/kg ip) drugs, while, Ocimarin failed to modulate these changes. OS compounds per se had no effect on these parameters. Interpretation & conclusions: The present findings showed the anti-stress potential of Ocimumoside A and B in relation to their simultaneous modulatory effects on the central monoaminergic and antioxidant systems implicating their therapeutic importance in stress

  17. Restraint stress-induced central monoaminergic & oxidative changes in rats & their prevention by novel Ocimum sanctum compounds.

    PubMed

    Ahmad, Ausaf; Rasheed, Naila; Chand, Kailash; Maurya, Rakesh; Banu, Naheed; Palit, Gautam

    2012-04-01

    Ocimum sanctum (OS) is known to possess various therapeutic properties. We have earlier isolated and characterized three OS compounds; Ocimarin, Ocimumoside A and Ocimumoside B. However, their role in modulating stress-induced central changes is unexplored. Thus, the present study was aimed to investigate the effect of these OS compounds on restraint stress (RS)-induced changes in the monoaminergic and antioxidant systems in the frontal cortex, striatum and hippocampus of rats. RS was produced by immobilizing (restraining) the Sprague Dawley rats for a period of 2.5 h inside cylindrical steel tubes. The monoamine levels and the in vivo antioxidant status in brain regions were evaluated by HPLC-EC and spectrophotometric assays, respectively. RS significantly increased the dopamine levels in the frontal cortex and decreased in the striatum and hippocampus, and accompanied with selective increase of dopamine metabolites compared to the NS control group. The serotonin and its metabolite levels were significantly increased, while noradrenaline levels were decreased by RS in the three brain regions studied. The activities of superoxide dismutase and glutathione peroxidase in the frontal cortex and striatum were significantly increased by RS with decreased glutathione levels and increased lipid peroxidation. Pre-treatment with Ocimumoside A and B (40 mg/kg po) for a period of 3 days prevented the RS-induced changes with an efficacy similar to that of standard anti-stress (Panax quinquefolium; 100 mg/kg po) and antioxidant (Melatonin; 20 mg/kg ip) drugs, while, Ocimarin failed to modulate these changes. OS compounds per se had no effect on these parameters. The present findings showed the anti-stress potential of Ocimumoside A and B in relation to their simultaneous modulatory effects on the central monoaminergic and antioxidant systems implicating their therapeutic importance in stress-related disorders. Further studies are required to understand the mechanism of action

  18. Anti-aphrodisiac compounds of male butterflies increase the risk of egg parasitoid attack by inducing plant synomone production.

    PubMed

    Fatouros, Nina E; Pashalidou, Foteini G; Aponte Cordero, Wilma V; van Loon, Joop J A; Mumm, Roland; Dicke, Marcel; Hilker, Monika; Huigens, Martinus E

    2009-11-01

    During mating in many butterfly species, males transfer spermatophores that contain anti-aphrodisiacs to females that repel conspecific males. For example, males of the large cabbage white, Pieris brassicae (Lepidoptera: Pieridae), transfer the anti-aphrodisiac, benzyl cyanide (BC) to females. Accessory reproductive gland (ARG) secretion of a mated female P. brassicae that is deposited with an egg clutch contains traces of BC, inducing Brussels sprouts plants (Brassica oleracea var. gemmifera) to arrest certain Trichogramma egg parasitoids. Here, we assessed whether deposition of one egg at a time by the closely related small cabbage white, Pieris rapae, induced B. oleracea var. gemmifera to arrest Trichogramma wasps, and whether this plant synomone is triggered by substances originating from male P. rapae seminal fluid. We showed that plants induced by singly laid eggs of P. rapae arrest T. brassicae wasps three days after butterfly egg deposition. Elicitor activity was present in ARG secretion of mated female butterflies, whereas the secretion of virgin females was inactive. Pieris rapae used a mixture of methyl salicylate (MeSA) and indole as an anti-aphrodisiac. We detected traces of both anti-aphrodisiacal compounds in the ARG secretion of mated female P. rapae, whereas indole was lacking in the secretion of virgin female P. rapae. When applied onto the leaf, indole induced changes in the foliar chemistry that arrested T. brassicae wasps. This study shows that compounds of male seminal fluid incur possible fitness costs for Pieris butterflies by indirectly promoting egg parasitoid attack.

  19. Natural compound oblongifolin C inhibits autophagic flux, and induces apoptosis and mitochondrial dysfunction in human cholangiocarcinoma QBC939 cells

    PubMed Central

    Zhang, Aiqing; He, Wei; Shi, Huimin; Huang, Xiaodan; Ji, Guozhong

    2016-01-01

    The compounds, which are obtained from natural plants or microbes may offer potential as one of the strategies for the management of cholangiocarcinoma. Oblongifolin C (OC), a natural small molecule compound extracted and purified from Garcinia yunnanensis Hu, can activate the mitochondrial apoptotic pathway in human cervical cancer cells. However, the direct effects of OC on cholangiocarcinoma cells are not well defined. The effect of OC on cell apoptosis and its underlying mechanisms were investigated in cultured QBC939 cells by the methyl thiazol tetrazolium assay, mitochondrial membrane potential, ATP content and western blot analysis. The present study reported that the in vitro treatment of human cholangiocarcinoma QBC939 cells with different concentrations (5, 10, 20 and 40 μM) of OC decreased cell viability and induced apoptosis in a dose-dependent manner. The results of the present study also showed that OC-induced QBC939 cell apoptosis was mediated through the inhibition of autophagy and mitochondrial dysfunction (MtD). Additionally, inhibiting autophagy increased OC-induced apoptosis and MtD, whereas exposure to the autophagy inducer, rapmycin, attenuated these changes. Together, the results of the present study