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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. A study on cooling characteristics of clathrate compound as low temperature latent heat storage material

    NASA Astrophysics Data System (ADS)

    Kim, Chang Oh; Kim, Jin Heung; Chung, Nak Kyu

    2007-07-01

    Materials that can store low temperature latent heat are organic/inorganic chemicals, eutectic salt system and clathrate compound. Clathrate compound is the material that host compound in hydrogen bond forms cage and guest compound is included into it and combined. Crystallization of hydrate is generated at higher temperature than that of ice from pure water. And physical properties according to temperature are stable and congruent melting phenomenon is occurred without phase separation and it has relatively high latent heat. But clathrate compound still has supercooling problem occurred in the course of phase change and supercooling should be minimized because it affects efficiency of equipment very much. Therefore, various studies on additives to restrain this or heat storage methods are needed. Supercooling is the phenomenon that low temperature thermal storage material is not crystallized and existed as liquid for some time under phase change temperature. Because phase change into solid is delayed and it is existed as liquid due to this, heat transfer from low temperature thermal storage material is lowered. Therefore it is not crystallized at original phase change temperature and crystallized after cooled as much as supercooling degree and operation time of refrigerator is increased. In this study was investigated the cooling characteristics of the clathrate compound as a low temperature latent heat storage material. And additive was added to clathrate compound and its supercooling restrain effect was studied experimentally.

  3. Quadrupole Ordering in Clathrate Compound Ce3Pd20Si6

    NASA Astrophysics Data System (ADS)

    Goto, Terutaka; Watanabe, Tomoyuki; Tsuduku, Seiji; Kobayashi, Haruki; Nemoto, Yuichi; Yanagisawa, Tatsuya; Akatsu, Mitsuhiro; Ano, Genki; Suzuki, Osamu; Takeda, Naoya; Dönni, Andreas; Kitazawa, Hideaki

    2009-02-01

    Low-temperature elastic properties of the clathrate compound Ce3Pd20Si6 were investigated using ultrasonic measurements. Pronounced softening of elastic constants (C11-C12)/2 and C44 with decreasing temperature indicates a precursor of electric quadrupole ordering due to a Γ8 quartet ground sate with an orbital degeneracy for 8c site of a Ce ion. A minimum of (C11-C12)/2 at TC=170 mK indicates a transition from paramagnetic phase I to an ordered phase III. Applied magnetic fields induce an antiferro-quadrupole (AFQ) ordered phase II with highly anisotropic character depending on the field direction, which resembles the AFQ phase with Oxy-type order parameter in CeB6 with the Γ8 ground sate. The order paramater of the phase III may be characterized by either magnetic dipole or magnetic octupole. The Γ7 ground state at 4a site may fall into a singlet screened by conduction electrons at low temperatures without long-range magnetic ordering.

  4. 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

  5. [Pharmacological studies on the clathrate compound of mobenzoxamine with beta-cyclodextrin. (I). Effects on the digestive system].

    PubMed

    Yokochi, E; Kohno, S; Ohata, K

    1988-11-01

    Effects of the clathrate compound of mobenzoxamine (MBX) with beta-cyclodextrin (MBX-CD), a new gastro-intestinal function modulator, on the digestive system were studied in comparison with those of metoclopramide, domperidone and trimebutine. MBX-CD showed inhibitory effects that were approximately 1/4 times as potent as metoclopramide on both apomorphine- and copper sulfate-induced emesis and about 1/40 times as potent as domperidone on apomorphine-induced emesis in dogs. In rats, MBX-CD enhanced gastric emptying as potently as metoclopramide, and only MBX-CD showed a clear amelioration of the delayed gastric emptying induced by BaCl2. Similarly, only MBX-CD showed an ameliorative effect on small intestinal transport accelerated by BaCl2 in mice. Though both MBX and trimebutine inhibited spontaneous contractions of the isolated guinea pig stomach and rabbit intestine, it seemed that the properties of these effects were different from those of papaverine. On isolated guinea pig ileum, MBX inhibited contractions induced by various agonists equally to or more potently than trimebutine or papaverine. The results suggest that MBX-CD or MBX acts extensively on the gastro-intestinal system for the reason that it has not only the respective properties of the gastro-intestinal function modulators used as the standards, but also its own characteristic effects. PMID:3243512

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. Nanostructured clathrate phonon glasses: beyond the rattling concept.

    PubMed

    He, Yuping; Galli, Giulia

    2014-05-14

    Using first-principles calculations, we investigated the thermoelectric properties of a newly synthesized Si-based ternary clathrate K8Al8Si38, composed of ∼1 nm hollow cages with a metal atom inside. This compound contains solely Earth abundant elements. We found that, similar to other nanostructured type I clathrates, this system is a semiconductor and has a low thermal conductivity (∼1 W/mK). It was long believed that the mere presence of rattling centers was responsible for the low lattice thermal conductivity of type I clathrates. We found instead that the cage structural disorder induced by atomic substitution plays a crucial role in determining the conductivity of these materials, in addition to the dynamics of the guest atoms. Our calculations showed that the latter is substantially affected by the charge transfer between the metal and the cages. Our results provide design rules for the search of new types of promising nanocage structured thermoelectric materials.

  11. 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).

  12. Fully quantal calculation of H2 translation-rotation states in (H2)4@5(12)6(4) clathrate sII inclusion compounds.

    PubMed

    Felker, Peter M

    2013-05-01

    The quantal translation-rotation (TR) states of the (p-H2)4@5(12)6(4) and (o-D2)4@5(12)6(4) hydrate clathrate sII inclusion compounds have been computed by nuclear-orbital/configuration-interaction methods. The model of these compounds in a rigid, high-symmetry 5(12)6(4) cage is treated in detail. The low-energy TR level structures of both isotopomers within this model are found to consist of states that can be readily described in terms of a small number of single-H2 and double-H2 excitation modes. The use of the high-symmetry results to facilitate the calculation and interpretation of (p-H2)4 and (o-D2)4 TR states in low-symmetry physically realizable 5(12)6(4) cages is also reported.

  13. Nanostructured clathrate phonon glasses: beyond the rattling concept.

    PubMed

    He, Yuping; Galli, Giulia

    2014-05-14

    Using first-principles calculations, we investigated the thermoelectric properties of a newly synthesized Si-based ternary clathrate K8Al8Si38, composed of ∼1 nm hollow cages with a metal atom inside. This compound contains solely Earth abundant elements. We found that, similar to other nanostructured type I clathrates, this system is a semiconductor and has a low thermal conductivity (∼1 W/mK). It was long believed that the mere presence of rattling centers was responsible for the low lattice thermal conductivity of type I clathrates. We found instead that the cage structural disorder induced by atomic substitution plays a crucial role in determining the conductivity of these materials, in addition to the dynamics of the guest atoms. Our calculations showed that the latter is substantially affected by the charge transfer between the metal and the cages. Our results provide design rules for the search of new types of promising nanocage structured thermoelectric materials. PMID:24762084

  14. 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.

  15. 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

    2011-01-01

    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.

  16. 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

    2015-12-01

    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.

  17. 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

    2015-12-01

    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. PMID:26574775

  18. 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.

  19. 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.

  20. 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.

  1. 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. PMID:24940841

  2. 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.

  3. 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.

  4. 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.

  5. 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. PMID:16805702

  6. Hydrogen clusters in clathrate hydrate.

    PubMed

    Mao, Wendy L; Mao, Ho-Kwang; Goncharov, Alexander F; Struzhkin, Viktor V; Guo, Quanzhong; Hu, Jingzhu; Shu, Jinfu; Hemley, Russell J; Somayazulu, Maddury; Zhao, Yusheng

    2002-09-27

    High-pressure Raman, infrared, x-ray, and neutron studies show that H2 and H2O mixtures crystallize into the sII clathrate structure with an approximate H2/H2O molar ratio of 1:2. The clathrate cages are multiply occupied, with a cluster of two H2 molecules in the small cage and four in the large cage. Substantial softening and splitting of hydrogen vibrons indicate increased intermolecular interactions. The quenched clathrate is stable up to 145 kelvin at ambient pressure. Retention of hydrogen at such high temperatures could help its condensation in planetary nebulae and may play a key role in the evolution of icy bodies. PMID:12351785

  7. 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

  8. 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.

  9. 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.

  10. Alloys of clathrate allotropes for rechargeable batteries

    SciTech Connect

    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.

  11. Rheology and dynamics of repulsive clathrates

    NASA Astrophysics Data System (ADS)

    Eroshenko, V. A.; Lazarev, Yu. F.

    2012-01-01

    The physical and thermodynamic properties of a repulsive clathrate used as a working body for the dissipation, storage, and conversion of energy in thermomechanical systems are studied. In repulsive clathrates, use is made for the first time of the molecular repulsive forces acting in large interfacial areas in a system consisting of a fluid and a capillary-porous matrix not wetted by this fluid. Based on experimental studies of a car damper with a repulsive clathrate, a rheological model of energy dissipation was developed which can be used to design compact high-performance dampers for different purposes and anti-seismic systems of new generation.

  12. Energy landscape of clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Desmedt, A.; Bedouret, L.; Pefoute, E.; Pouvreau, M.; Say-Liang-Fat, S.; Alvarez, M.

    2012-11-01

    Clathrate hydrates are nanoporous crystalline materials made of a network of hydrogen-bonded water molecules (forming host cages) that is stabilized by the presence of foreign (generally hydrophobic) guest molecules. The natural existence of large quantities of hydrocarbon hydrates in deep oceans and permafrost is certainly at the origin of numerous applications in the broad areas of energy and environmental sciences and technologies (e.g. gas storage). At a fundamental level, their nanostructuration confers on these materials specific properties (e.g. their "glass-like" thermal conductivity) for which the host-guest interactions play a key role. These interactions occur on broad timescale and thus require the use of multi-technique approach in which neutron scattering brings unvaluable information. This work reviews the dynamical properties of clathrate hydrates, ranging from intramolecular vibrations to Brownian relaxations; it illustrates the contribution of neutron scattering in the understanding of the underlying factors governing chemical-physics properties specific to these nanoporous systems.

  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. 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.

  15. Experimental Facilities to Synthesize and Study Clathrate Hydrates: Applications to Icy Moons

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    A series of experimental investigations are being carried out on mixed CH4-N2 and CH4-CO2 clathrate hydrates, compounds of high interest for icy moons. First results on their phase diagram and their infrared and Raman signatures will be presented.

  16. 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.

  17. 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.

  18. 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.

  19. 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. PMID:27346760

  20. 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

  1. 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.

  2. Experimental evidence for empty cage methane clathrate hydrates grown using surfactants.

    NASA Astrophysics Data System (ADS)

    Botimer, Jeffrey; Dunn-Rankin, Derek; Taborek, Peter

    2015-03-01

    Clathrate hydrates are non-stochiometric ice-like crystalline compounds consisting of host water molecules forming a cage-like structure around guest molecules. The guest molecule is necessary for the stability of the hydrate. Surfactants have been shown to greatly enhance the kinetics of hydrate growth, which is important for many applications. We have built custom cells that allow in situ Raman and optical imaging of the growth of methane clathrate hydrates from liquid water. In our studies, above 0C, we observe the formation of solid that precedes the absorption of methane gas required to form clathrate hydrates. Our research shows that sodium dodecyl sulfate (SDS) causes a fundamental change in the growth mechanism of methane hydrates, creating a temporary empty cage clathrate structure. The existence of this transitional state is confirmed by in situ Raman measurements, in situ NMR. We have simultaneously monitored the gas uptake and the NMR signal of the growing hydrate in a high pressure NMR cell. The empty cage solid structure appears to be unique to surfactant assisted hydrate growth, and begins to disappear for low SDS concentrations (<25ppm). Supported by the W. M. Keck Foundation.

  3. Clathrates, Ice sheets and Global Climate Change?

    NASA Astrophysics Data System (ADS)

    Weitemeyer, K. A.; Buffett, B. A.

    2002-12-01

    Ice age cycles are associated with large fluctuations in the concentration of atmospheric methane and carbon dioxide. The cause for these fluctuations remains unexplained, although clathrates are often proposed as a potential source of methane. However, the mechanism for methane release from clathrates into the atmosphere has not been established. We examine the possiblity that clathrates accumulate below continential ice sheets during periods of glaciation, permitting substantial release of methane during deglaciation. The source of the methane is due to microbial decomposition of organic material below the ice sheet. We assume that organic material in soils ahead of the ice sheet is frozen in place due to low atmospheric temperatures. Once the ice sheet is present and sufficiently thick, the geothermal gradient adjusts to bring the sediments to the melting point of water. Assuming aneorobic conditions underneath the ice sheet, the presence of methanogens at the basal surface of the ice sheet allow for the conversion of organic carbon to methane. This methane is stored as clathrate when the temperature and pressure conditions at the basal surface permit thermodynamic stability (ice thickness in excess of 250m at 0oC). Subsequent deglaciation destabalizes clathrate causing the release of methane into the atmosphere. We use a numerical model of the Laurentide-Cascade ice sheet (Marshall et. al., 1999) for the areal extent, thickness, and the thermal conditions at the base of the ice sheet as a function of time. In order to bound the available carbon below the ice sheet, we consider two estimates of soil carbon inventory based on tundra and present potential vegetation. Our model quantifies the decrease of carbon in the soil and the accumulation of clathrate as the ice sheet advances. As the ice sheet retreats we track the amplitude and timing of methane released into the atmosphere. The amplitude of predicted fluctuations in atmospheric methane are 80-200ppbv, which

  4. High-Temperature Thermoelectric Properties of Polycrystalline Silicon Clathrate Ba8TM x Si46- x (TM = Ni, Pt)

    NASA Astrophysics Data System (ADS)

    Kikuchi, Daisuke; Fujimura, Koji; Tadokoro, Jun; Matsumoto, Miko; Yamazaki, Satoshi; Sasaki, Hirokazu; Eguchi, Tatsuhiko; Susai, Kyota

    2016-03-01

    The n-/ p-type stability of a silicon clathrate in which silicon was substituted with nickel or platinum was evaluated by density functional theory calculations. Then, Ba8Pt5Si41 and Ba8Pt1.5Ni3.5Si41 were synthesized, and their thermoelectric properties were investigated. The polycrystalline compounds, which have a type-I clathrate structure, were prepared through arc melting and spark-plasma-sintering. The crystal structures and elemental compositions of the synthesized samples were characterized via powder x-ray diffraction and electron microprobe analyses, respectively. The temperature dependence of both the electrical resistivity and the Seebeck coefficient was measured.

  5. 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.

  6. 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. PMID:25503235

  7. 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.

  8. 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

  9. 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.

  10. 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. PMID:26933681

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. Formation of bioorganic compounds in aqueous solution induced by plasma.

    PubMed

    Harada, K; Takasaki, M; Naraoka, H; Nomoto, S

    1984-01-01

    When plasma jet of Ar-arc plasma was blown into an aqueous solution containing organic compounds, oxidation reactions were induced in the solution. The plasma-induced reaction was a powerful oxidation which could convert a methyl to a carboxyl group and cleave a carbon-carbon bond without using any oxidizing reagent. This reaction could be regarded as a model for the solar plasma-induced reaction in the primitive hydrosphere.

  16. Experimental techniques to study clathrate hydrates in the context of giant icy moons

    NASA Astrophysics Data System (ADS)

    Le Menn, E.; Bezacier, L.; Bollengier, O.; Oancea, A.; Grasset, O.; Tobie, G.

    2012-09-01

    Gas clathrate hydrates probably play a key role in the storage and transport of gas compounds in water-rich environments, especially for icy moons [1]. In order to understand how they may affect the exchange processes in these objects, a series of experiments has been set up to realise controlled synthesis of mixted gas hydrates, to perform infrared and Raman diagnostics, and to constrain their phase diagram. Experiments cover a wide pressure range, from 10-2 mbar up to 30 GPa and are focused on three gas compounds of high interest for the icy satellites of the outer solar system: methane, carbon dioxide and nitrogen.

  17. 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

  18. 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.

  19. 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.

  20. Valproic Acid Induces Antimicrobial Compound Production in Doratomyces microspores.

    PubMed

    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 against antibiotic

  1. 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

  2. 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.

  3. 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.

  4. Understandng of phonon anharmonicity in thermoelectric clathrates

    NASA Astrophysics Data System (ADS)

    Tanigaki, Katsumi; Wu, Jiazhen; Shimotani, Hidekazu; Huynh, Khuong; Akagi, Kazuto; AIMR Collaboration; Department of Physics, Graduate School of Science Collaboration

    Anharmonicity in phonons, apart from the conventional Einstein- or Debye- mode harmonic phonons, is frequently observed for amorphous or glass-like materials. A frontier topic relating to anharmonic phonons revolves around the fact that they are also observed in a single crystal with a void of cage structure. Although the origin of the phonon anharmonicity has been the center of scientific debate for many years, a clear understanding has not yet been achieved. In the present study, we show that the anharmonic oscillations in thermoelectric clathrates can successfully be rationalized in terms of a single unified exponential line for a variety of clathrates by employing a new parameter associated with the freedom of space. The intrinsic nature of phonon anharmonicity is described based on the unified picture with a help of first principles calculations. Although the origin of the anharmonicity appearing in disordered materials is complex to understand due to the missing information on the real structure, the present unified picture gives important information applicable to other systems.

  5. Thermodynamic stability of clathrate hydrates relative to their separate chemical components

    NASA Astrophysics Data System (ADS)

    White, M. A.; MacLaren, D. C.; Marriott, R. A.; Zhan, B. Z.

    2003-01-01

    The thermodynamic changes (DeltaH, DeltaS, and DeltaG) for the association of several small molecules (tetrahydrofuran (THF), ethylene oxide (EO), acetone) with water to form corresponding clathrate hydrates are calculated as a function of temperature from experimental information. For THF clathrate hydrate and EO clathrate hydrate at low temperatures, the clathrate is enthalpically stabilized with respect to the components. This is also the likely case for acetone clathrate hydrate. In all the three cases, above the melting points of the guest species, the clathrate increases in enthalpic stability, but entropic factors favour the separated components. Similar changes for THF clathrate hydrate and EO clathrate hydrate occur at the melting point of ice, eventually favouring the liquid components over the clathrate.

  6. Hydrocarbon Radiolysis on Europa and the Production of Clathrates

    NASA Astrophysics Data System (ADS)

    Hand, K. P.; Carlson, R. W.

    2006-12-01

    We are studying the radiolysis of organic molecules in ice at Europa temperatures by studying both simple and complex biomolecules, including microorganisms. High energy electron irradiation is employed and the products are analyzed using infrared spectroscopy, thermal desorption mass spectroscopy, and laser desorption/ionization mass spectroscopy. Hydrocarbon radiolysis yields carbon dioxide that is trapped and methane molecules that escape and results in net loss of carbon. Aliphatic molecules with C=O bonds are also formed and thought to be polymethylene oxides (PMOs). When heated, they polymerize to form brown, high-molecular-weight refractory residues with linear, spherical, and ring-shaped macrostructures, typically many tens of micrometers in size. Laser desorption mass spectra of the residues are not overly complex and different for each initial species. During warming, CO2 spectra indicate trapping in a clathrate structure. While pure CO2 clathrates may be difficult to form on icy satellite surfaces, mixed hydrate clathrates can be formed using "helper" molecules including PMOs such as C2H4O (oxirane) and C4H8O (tetrahydrofuran). Ices containing such "helper" molecules form clathrate structures in vacuum at temperatures of about 140 K. If the original mixture contains CO2 then a mixed clathrate can be formed. In our experiments, irradiation produces both the CO2 and "helper" molecules. Clathrate hydrates may also trap O2 in similar fashion (Hand et al. 2006).

  7. Thermomechanical and thermophysical properties of repulsive clathrates

    NASA Astrophysics Data System (ADS)

    Eroshenko, V. A.; Grosu, Ya. G.

    2013-09-01

    The range of the characteristic properties of repulsive clathrates (RCs), which are new working media used for efficient energy conversion in thermomechanical systems, has been extended. The dissipation, storage, and conversion of energy by means of RCs is based on the use of the intermolecular forces acting on the interface of the system of a liquid and a nonwetting solid capillaryporous matrix and leading to ejection of the liquid from the pores of the matrix. It has been shown that it is possible to control characteristics of RCs such as compressibility, amount of the dissipated (accumulated) mechanical energy, specific heat, and thermal parameters of the compression-expansion process. The properties of RCs providing unique operation modes of power systems that are not realizable with conventional working media (gas, steam).

  8. Propane Clathrate Hydrate Formation Accelerated by Methanol.

    PubMed

    Amtawong, Jaruwan; Guo, Jin; Hale, Jared S; Sengupta, Suvrajit; Fleischer, Everly B; Martin, Rachel W; Janda, Kenneth C

    2016-07-01

    The role of methanol as both an inhibitor and a catalyst for the formation of clathrate hydrates (CHs) has been a topic of intense study. We report a new quantitative study of the kinetics of propane CH formation at 253 K from the reaction of propane gas with <75 μm ice particles that have been doped with varying amounts of methanol. We find that methanol significantly accelerates the formation reaction with quite small doping quantities. Even for only 1 methanol molecule per 10 000 water molecules, the maximum uptake rate of propane into CHs is enhanced and the initiation pressure is reduced. These results enable more efficient production of CHs for gas storage. This remarkable acceleration of the CH formation reaction by small quantities of methanol may place constraints on the mechanism of the inhibition effect observed under other conditions, usually employing much larger quantities of methanol. PMID:27275862

  9. Density driven structural transformations in amorphous semiconductor clathrates

    DOE PAGESBeta

    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 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

  10. 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.

  11. First-principles calculations for thermodynamic properties of type-I silicon clathrate intercalated by sodium atoms

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    The ground state properties of the silicon clathrate Si46 intercalated by alkali metal sodium atoms (Na8Si46) are investigated by first-principle methods. Birch-Murnaghan equation of state is fitted to two sets of the E-V data calculated by density functional theory based on the plane-wave basis set within both the local density approximation (LDA) and the generalized gradient approximation (GGA). Through quasi-harmonic Debye model, some thermodynamic properties comprise the heat capacity, the thermal expansion coefficient, Debye temperature and the Grüneisen parameter for this clathrate compounds Na8Si46 are obtained, which agree well with experimental results. Comparing the calculated heat specific in two ways with experimental results, we find that it is more accurate to describe the “rattle” modes of gust Na atoms in the cages as Einstein oscillators. Moreover, the effects of high pressure on these thermodynamic properties are also investigated which will be very helpful for a synthesis of these clathrate compounds in experiments under high pressure and high temperature condition.

  12. 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

  13. 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.

  14. 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.

  15. 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. PMID:26745181

  16. Anaphylaxis induced by ingestion of a pollen compound.

    PubMed

    Chivato, T; Juan, F; Montoro, A; Laguna, R

    1996-01-01

    We report on the case of a 32-year-old atopic patient who showed a severe anaphylactic reaction due to the ingestion of a pollen compound prepared in an herbalist's. A few minutes after ingestion, generalized pruritus, difuse erythema, facial edema, cough, hoarseness and dysphonia appeared, and the emergency administration of subcutaneous epinephrine and intravenous methylprednisolone was necessary. Skin tests with a battery of inhalants and food allergens were performed. The patient only showed sensitization to Artemisia vulgaris, Taraxacum officinalis and Salix alba. Specific IgE levels were evaluated by FEIA-CAP giving a seric level of CAP class 3 to Artemisia vulgaris and class 2 to Taraxacum officinalis and Salix alba. Samples of the pollen compound were shown in the microscopical analysis to be 93% pollens and 6% fungi. In the qualitative study Taraxacum officinalis (15%), Artemisia vulgaris (5%) and Salix alba (15%) were the main elements identified. In summary, this case study describes a food-induced systemic reaction due to a pollen compound in an atopic patient with a history of allergic rhinitis. Pollinic patients must be informed on the risks that the consumption of these compounds might cause.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

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

    PubMed

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

    1991-10-25

    The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena. PMID:11538372

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

    PubMed

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

    1991-10-25

    The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena.

  3. Clathrate desalination plant preliminary research study. Water treatment technology program report No. 5 (Final)

    SciTech Connect

    McCormack, R.A.; Andersen, R.K.

    1995-06-01

    This report presents preliminary research, design, and cost estimates for a clathrate freeze desalination method and system. A clathrate former is injected through the inner pipe of a submerged pipeline to a predetermined ocean depth at which the ocean temperture is less than the clathrate forming temperture. The agent combines with seawater within the annulus of the outer pipe to form a slurry of clathrate ice crystals and brine that is pumped to the surface. The clathrate forming agent may be recovered for reinjection or discarded. The melting of the clathrate ice and the return line of brine water to the ocean provide cold water sources that can be used to cool refrigerant in air conditioning systems in local buildings. The system depicted uses the hydrocarbon HCFC R141b (Dichloromonofluoroethane- CCl2FCH3) as the clathrate forming agent with lesser attention on HCFC R22 (Chlorodifluoromethane - CHClF2) and carbon dioxide (C02).

  4. 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.

  5. Photodynamic reactions induced by compounds derived from lichens.

    PubMed

    Wennersten, G

    1979-01-01

    Contact dermatitis from lichens is now well documented but the possible influence of exposure to sunlight is less clear. Positive reactions on photopatch testing has recently been described, but whether this represented an unspecific exacerbation or a true photoallergic response was difficult to evaluate. In this study 13 different substances derived from lichens commonly found in nature were investigated with regard to their capacity to induce photo-oxidative membrane damage, as revealed by the photohemolysis technique. It was found that the earlier suggested ability to induce photosensitization could be confirmed for several of the lichen compounds investigated. It was also shown that singlet state excited oxygen may participate to some degree in some of these reactions.

  6. 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.

  7. 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. PMID:17170301

  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. 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

  10. 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

  11. The fate of methane clathrate hydrate within Titan

    NASA Astrophysics Data System (ADS)

    Tobie, G.; Lunine, J. I.; Sotin, C.

    2004-12-01

    Titan has a thick atmosphere composed primarily of nitrogen and methane. Methane is known to be irreversibly consumed photochemically on a timescale of a few tens of million years, which implies that any replenishment process must occur to maintain the methane abundance to its current value. Methane is believed to have been trapped within clathrate hydrate, a particular structure of ice, in Saturn's subnebula environnement, and then to have been incorporated within Titan's interior. Although the major part of clathrates is likely to have been devolatilized during the late stage of Titan's accretion, a significant portion could have "survived" within the deeper interior and could have been released later in Titan's history. Through coupled thermal and orbital calculations including a full description of the tidal dissipation, the heat transfer,the H2O-NH3 phase diagram and the methane clathrate stability, we study the possible evolution of clathrate distribution within Titan's interior, its effect of the thermal evolution, and the process of degassing from the interior. We show that only models with a few percent of ammonia and a significant fraction of methane clathrate within the interior can explain both the conservation of Titan's high eccentricity over the age of the solar system and the methane replenishment of the atmosphere. In our preferred scenario, two episodes of methane degassing are predicted: one during the first billion years and a second one after 3.5-4 Ga, explaining the present-day atmospheric methane abundance. Forthcoming data from the NASA/ESA Cassini-Huygens mission will allow us to test the present predictions.

  12. EPR of CH3 Radicals in SIO2 Clathrate

    NASA Astrophysics Data System (ADS)

    Dmitriev, Yurij; Buscarino, Gianpiero; Benetis, Nikolas Ploutarch

    2016-06-01

    EPR lineshape simulations of CH3/SiO2 clathrates reveal the motional conditions of the CH3 radical up to the unusual regime of its stability, the high temperature diffusional regime. This was obvious by the isotropic magnetic interaction at the highest experimental temperatures over 140 K. Special motional and thermodynamics conditions for methyl radical may however prevail for the CH3/SiO2 clathrates system due to the limited space of the host voids, compared to solid gas isolation. The lowest temperature in the experiment was 4.1 K, while the highest one was 300 K. The EPR parameters of the radical revealed non-monotonic temperature dependence. The extremely wide temperature range of the radical stability may be attributed to the solidity of the clathrate voids and the small diameter of their channels that do not allow molecular collisions between the radical species. At the lowest sample temperatures, a portion of the radicals stopped to rotate thus indicating their attachment to specific matrix sites with large radical-host interaction. The unusual increase of the width of the CH3/SiO2 clathrate spectra with the temperature at high sample temperatures indicates resemblance to the spin-rotation interaction relaxation mechanism known only in the case of small species in non-viscous fluids, and is contrasted to the normal difussional decrease of the width in the CH3 hosted in a series of solid. The effect was explained by adopting extremely frequent radical collisions with the clathrate void walls leading to repeated angular momentum alterations, a kind of "reorientation". Yu. A. D. acknowledges support by the Russian Foundation for Basic Research (RFBR), research project 16-02-00127a.

  13. 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. PMID:26727217

  14. Crystal structures and spectroscopic properties of polycyano-polycadmate host clathrates including a CT complex guest of methylviologen dication and aromatic donor.

    PubMed

    Yoshikawa, Hirofumi; Nishikiori, Shin-ichi

    2005-09-21

    A series of polycyano-polycadmate (PCPC) host clathrates including a CT complex of methylviologen dication (MV2+) and an aromatic donor as a guest were synthesized, and their crystal structures and spectroscopic properties were investigated. The PCPC host has a framework structure built with Cd2+ ions as coordination centres and cyanides as bridging ligands. This framework host has negative charge and includes a cationic guest together with an ordinary neutral guest. MV2+, which is a strong acceptor, was included as a cationic guest and an aromatic compound, which works as a donor, was included as a neutral guest. Crystal structures of seven clathrates, whose neutral guests were o-cresol, m-cresol, p-cresol, 1-methylnaphthalene, 1,2,4-trimethoxybenzene, pyrrole and aniline, were determined by single crystal X-ray diffraction methods. In all cases MV2+ and the neutral guest formed a CT complex with a face to face stacking structure and were included as a CT complex guest. However, depending on each clathrate the ratio of aromatic donor to MV2+ was different and several variations were found in their PCPC host structures. The clathrates had their own colour depending on their neutral guest. The plot of the CT transition energies estimated from optical CT bands against the ionization potentials of the neutral guests satisfied a linear relationship predicted by Mulliken theory. However, the CT transition energies observed in the clathrates showed a shift to lower energy by ca. 0.6 eV compared with those observed in corresponding acetonitrile solutions. PMID:16127500

  15. 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

  16. 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

  17. 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.

  18. Identification of Clathrate Hydrates, Hexagonal Ice, Cubic Ice, and Liquid Water in Simulations: the CHILL+ Algorithm.

    PubMed

    Nguyen, Andrew H; Molinero, Valeria

    2015-07-23

    Clathrate hydrates and ice I are the most abundant crystals of water. The study of their nucleation, growth, and decomposition using molecular simulations requires an accurate and efficient algorithm that distinguishes water molecules that belong to each of these crystals and the liquid phase. Existing algorithms identify ice or clathrates, but not both. This poses a challenge for cases in which ice and hydrate coexist, such as in the synthesis of clathrates from ice and the formation of ice from clathrates during self-preservation of methane hydrates. Here we present an efficient algorithm for the identification of clathrate hydrates, hexagonal ice, cubic ice, and liquid water in molecular simulations. CHILL+ uses the number of staggered and eclipsed water-water bonds to identify water molecules in cubic ice, hexagonal ice, and clathrate hydrate. CHILL+ is an extension of CHILL (Moore et al. Phys. Chem. Chem. Phys. 2010, 12, 4124-4134), which identifies hexagonal and cubic ice but not clathrates. In addition to the identification of hydrates, CHILL+ significantly improves the detection of hexagonal ice up to its melting point. We validate the use of CHILL+ for the identification of stacking faults in ice and the nucleation and growth of clathrate hydrates. To our knowledge, this is the first algorithm that allows for the simultaneous identification of ice and clathrate hydrates, and it does so in a way that is competitive with respect to existing methods used to identify any of these crystals. PMID:25389702

  19. 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.

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

    PubMed

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

    2013-01-01

    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. PMID:27137391

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

    PubMed

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

    2010-03-01

    "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.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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. PMID:25139225

  8. 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.

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

    PubMed

    Mondal, Sukanta; Chattaraj, Pratim Kumar

    2014-09-01

    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. PMID:25047071

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

    DOE PAGESBeta

    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.

  11. Pressure induced phase transition in defect chalcopyrite compounds

    NASA Astrophysics Data System (ADS)

    Meenakshi, S.

    2012-07-01

    The large band gap semiconducting compounds of the type AIIB2IIIC4VI crystallizing in the defect chalcopyrite (DCP) tetragonal structure are of great technological interest and have potential applications in non linear optical and photovoltaic devices. These compounds contain a crystallographically ordered array of vacancies (stoichiometric voids) in the cation sublattice and exhibit several interesting physical and chemical properties. The presence of the vacancies facilitates the doping of these compounds by impurities and has stimulated investigations about occurrence of order-disorder effects in the cation sublattice. In this presentation our recent experimental results on the high pressure investigations on some of the defect chalcopyrite compounds would be discussed.

  12. 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.

  13. 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…

  14. Interaction of L-alanyl-L-valine and L-valyl-L-alanine with organic vapors: thermal stability of clathrates, sorption capacity and the change in the morphology of dipeptide films.

    PubMed

    Ziganshin, Marat A; Gubina, Nadezhda S; Gerasimov, Alexander V; Gorbatchuk, Valery V; Ziganshina, Sufia A; Chuklanov, Anton P; Bukharaev, Anastas A

    2015-08-21

    The strong effect of the amino acid sequence in L-alanyl-L-valine and L-valyl-L-alanine on their sorption properties toward organic compounds and water, and the thermal stability of the inclusion compounds of these dipeptides have been found. Generally, L-valyl-L-alanine has a greater sorption capacity for the studied compounds, but the thermal stability of the L-alanyl-L-valine clathrates is higher. Unusual selectivity of L-valyl-L-alanine for vapors of few chloroalkanes was observed. The correlation between the change in the surface morphology of thin film of dipeptides and stoichiometry of their clathrates with organic compounds was found. This discovery may be used to predict the influence of vapors on the morphology of films of short-chain oligopeptides.

  15. Raman Measurements of Pure Hydrogen Clathrate Formation from a Supercooled Hydrogen-Water Solution.

    PubMed

    del Rosso, Leonardo; Celli, Milva; Ulivi, Lorenzo

    2015-11-01

    The nucleation and growth of a solid clathrate hydrate from the liquid phase is a process that is even less understood and more difficult to study than the nucleation of a solid phase from a pure liquid. We have employed in situ Raman spectroscopy to study the hydrogen-water supercooled solution undergoing clathrate formation at a pressure of about 2 kbar and temperature of 263 K. Raman light scattering detects unambiguously the H2 molecules inside of clathrate crystallites, which change stoichiometry during growth. The spectral intensity of the hydrogen vibrational band shows the time evolution of the population of the large and small cages, demonstrating that, in the initial stages of clathrate formation, the occupation of the large cages is quite lower than its equilibrium value. From the measurement of the growth rate of the crystallites, we demonstrate that the growth of the clathrate in the liquid is a diffusion-limited process. PMID:26538046

  16. 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.

  17. 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

    2010-11-01

    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.

  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. High Throughput Screening Identifies a Novel Compound Protecting Cardiomyocytes from Doxorubicin-Induced Damage

    PubMed Central

    Gergely, Szabolcs; Hegedűs, Csaba; Lakatos, Petra; Kovács, Katalin; Gáspár, Renáta; Csont, Tamás; Virág, László

    2015-01-01

    Antracyclines are effective antitumor agents. One of the most commonly used antracyclines is doxorubicin, which can be successfully used to treat a diverse spectrum of tumors. Application of these drugs is limited by their cardiotoxic effect, which is determined by a lifetime cumulative dose. We set out to identify by high throughput screening cardioprotective compounds protecting cardiomyocytes from doxorubicin-induced injury. Ten thousand compounds of ChemBridge's DIVERSet compound library were screened to identify compounds that can protect H9C2 rat cardiomyocytes against doxorubicin-induced cell death. The most effective compound proved protective in doxorubicin-treated primary rat cardiomyocytes and was further characterized to demonstrate that it significantly decreased doxorubicin-induced apoptotic and necrotic cell death and inhibited doxorubicin-induced activation of JNK MAP kinase without having considerable radical scavenging effect or interfering with the antitumor effect of doxorubicin. In fact the compound identified as 3-[2-(4-ethylphenyl)-2-oxoethyl]-1,2-dimethyl-1H-3,1-benzimidazol-3-ium bromide was toxic to all tumor cell lines tested even without doxorubicine treatment. This benzimidazole compound may lead, through further optimalization, to the development of a drug candidate protecting the heart from doxorubicin-induced injury. PMID:26137186

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

    PubMed

    Nada, Hiroki

    2009-04-01

    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. Shockwave-induced compound action potentials in the peripheral nerve.

    PubMed

    Wehner, H D; Sellier, K

    1981-01-01

    To verify a presumed interaction between shockwaves arisen by impacts of high velocity projectiles and nervous tissue an electrophysiological experiment is performed with the following results: In peripheral nerves regular compound action potentials (CAPs) are provoked by shockwaves the amplitudes of which are increased corresponding to the pressure intensity of the shockwaves. The nerve shows no electrical activity below a certain pressure threshold (0.75 bar). Saturation of the CAP amplitude occurs beyond a pressure limit of 8 bar.

  3. 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.

  4. Polarization response of clathrate hydrates capsulated with guest molecules

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  5. 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. PMID:27250307

  6. 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.

  7. 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.

  8. 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.

  9. Finding New Thermoelectric Compounds Using Crystallographic Data: Atomic Displacement Parameters

    SciTech Connect

    Chakoumakos, B.C.; Mandrus, D.G.; Sales, B.C.; Sharp, J.W.

    1999-08-29

    A new structure-property relationship is discussed which links atomic displacement parameters (ADPs) and the lattice thermal conductivity of clathrate-like compounds. For many clathrate-like compounds, in which one of the atom types is weakly bound and ''rattles'' within its atomic cage, room temperature ADP information can be used to estimate the room temperature lattice thermal conductivity, the vibration frequency of the ''rattler'', and the temperature dependence of the heat capacity. Neutron data and X-ray crystallography data, reported in the literature, are used to apply this analysis to several promising classes of thermoelectric materials.

  10. 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.

  11. 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.

  12. Electronic structure and spectral characteristics of Zn-substituted clathrate silicides

    SciTech Connect

    Borshch, N. A. Pereslavtseva, N. S.; Kurganskii, S. I.

    2011-06-15

    The results of complex theoretical studies of the electron structure of Zn-substituted Si-based clathrates are reported. The calculation is carried out by the linearized augmented plane wave method. As a result, the energy band structures, the total and partial densities of electron states, and the X-ray emission spectra are obtained. The effect of the number of substitutions and their sites in the unit cell on the electron-energy spectrum of clathrates is analyzed.

  13. Monte-Carlo sorption and neutron diffraction study of the filling isotherm in clathrate hydrates

    SciTech Connect

    Klapproth, Alice; Kuhs, Werner F.; Chazallon, Bertrand

    1999-06-15

    We are interested in the thermodynamics of the gas filling of clathrate hydrates. In order to determine the pressure-dependent filling of the cages, neutron powder diffraction experiments on N{sub 2} and CO{sub 2} clathrates were performed. Interaction potentials were refined by comparing the experimentally determined fillings with those generated by MC-sorption calculations. Unsatisfactory agreement between experiment and simulation is observed when using the widely employed SPC water-water interaction potential.

  14. 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

  15. Revisiting the thermodynamic modelling of type I gas-hydroquinone clathrates.

    PubMed

    Conde, M M; Torré, J P; Miqueu, C

    2016-04-21

    Under specific pressure and temperature conditions, certain gaseous species can be engaged in a host lattice of hydroquinone molecules, forming a supramolecular entity called a gas hydroquinone clathrate. This study is devoted to the thermodynamic modelling of type I hydroquinone clathrates. The gases considered in this work are argon, krypton, xenon, methane, nitrogen, oxygen and hydrogen sulphide. The basic van der Waals and Platteeuw model, which is, for example, not able to predict well the phase equilibrium properties of such clathrates at high temperature, is modified and extended by considering first the solubility of the guest in solid HQ and then the mutual interactions between the gaseous molecules inside the clathrate structure (i.e. guest-guest interactions). Other improvements of the basic theory, such as the choice of the reference state, are proposed, and a unique set of thermodynamic parameters valid for all the studied guests are finally calculated. Very good agreement is obtained between the model predictions and the experimental data available in the literature. Our results clearly demonstrate that the highest level of theory is necessary to describe well both the triphasic equilibrium line (where the HQ clathrate, the native hydroquinone HQα and the gas coexist), the occupancy of the guest in the clathrate, and the intercalation enthalpy.

  16. 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.

  17. Tropospheric impact of methane emissions from clathrates in the Arctic Region

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    A highly potent greenhouse gas, methane, is locked in the solid phase as ice-like deposits containing a mixture of water and gas (mostly methane) called clathrates in both ocean sediments and underneath permafrost regions. Clathrates are stable under high pressures and low temperatures. In a warming climate, increases in ocean temperatures could lead to dissociation of the clathrates and release of methane into the ocean and subsequently into the atmosphere. This is of particular importance in the shallow part of the Arctic Ocean, where clathrates are expected to start outgassing abruptly at depths of around 300m. Here we present a comparison of simulations from the Community Earth System Model (CESM1) for present-day conditions with and without additional methane emissions from a plausible clathrate release scenario based on a state-of-the-art ocean sediment model. The model includes a fully interactive physical ocean and a fast atmospheric chemistry mechanism that represents methane as a fully interactive tracer (with emissions rather than concentration boundary conditions), along with the main chemical reactions for methane, ozone, and nitrous oxide. The results show that such clathrate emissions increase methane concentrations spatially non-uniformly, and that increases in surface ozone concentrations are greatest in polluted regions. We also find that the interannual variability in surface methane and ozone increases. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-ABS-570979

  18. Revisiting the thermodynamic modelling of type I gas-hydroquinone clathrates.

    PubMed

    Conde, M M; Torré, J P; Miqueu, C

    2016-04-21

    Under specific pressure and temperature conditions, certain gaseous species can be engaged in a host lattice of hydroquinone molecules, forming a supramolecular entity called a gas hydroquinone clathrate. This study is devoted to the thermodynamic modelling of type I hydroquinone clathrates. The gases considered in this work are argon, krypton, xenon, methane, nitrogen, oxygen and hydrogen sulphide. The basic van der Waals and Platteeuw model, which is, for example, not able to predict well the phase equilibrium properties of such clathrates at high temperature, is modified and extended by considering first the solubility of the guest in solid HQ and then the mutual interactions between the gaseous molecules inside the clathrate structure (i.e. guest-guest interactions). Other improvements of the basic theory, such as the choice of the reference state, are proposed, and a unique set of thermodynamic parameters valid for all the studied guests are finally calculated. Very good agreement is obtained between the model predictions and the experimental data available in the literature. Our results clearly demonstrate that the highest level of theory is necessary to describe well both the triphasic equilibrium line (where the HQ clathrate, the native hydroquinone HQα and the gas coexist), the occupancy of the guest in the clathrate, and the intercalation enthalpy. PMID:27004460

  19. 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.

  20. 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.

  1. Investigation of plasma etch induced damage in compound semiconductor devices

    SciTech Connect

    Shul, R.J.; Lovejoy, M.L.; Hetherington, D.L.; Rieger, D.J.; Vawter, G.A.; Klem, J.F.; Melloch, M.R.

    1993-11-01

    We have investigated the electrical performance of mesa-isolated GaAs pn-junction diodes to determine the plasma-induced damage effects from reactive ion and reactive ion beam etching. A variety of plasma chemistries (SiCl{sub 4}, BCl{sub 3}, BCl{sub 3}/Cl{sub 2}, and Cl{sub 2}) and ion energies ranging from 100 to 400 eV were studied. We have observed that many of the RIE BCl{sub 3}/Cl{sub 2} plasmas and RIBE Cl{sub 2} plasmas yield diodes with low reverse-bias currents that are comparable to the electrical characteristics of wet-chemical-etched devices. The reverse-bias leakage currents are independent of surface morphology and sidewall profiles.

  2. Proton diffusion in the hexafluorophosphoric acid clathrate hydrate.

    PubMed

    Bedouret, Laura; Judeinstein, Patrick; Ollivier, Jacques; Combet, Jérôme; Desmedt, Arnaud

    2014-11-26

    The hexafluorophosphoric acid clathrate hydrate is known as a "super-protonic" conductor: its proton conductivity is of the order of 0.1 S/cm at ca. room temperature. The long-range proton diffusion and the associated mechanism have been analyzed with the help of incoherent quasi-elastic neutron scattering (QENS) and proton pulsed-field-gradient nuclear magnetic resonance ((1)H PFG-NMR). The system crystallizes into the so-called type I clathrate structure (SI) at low temperature and into the type VII structure (SVII) above ca. 230 K with a melting point close to room temperature. While, in the SI phase, no long-range proton diffusion is observed (at least faster than the present measurement capabilities, i.e., 10(-7) cm(2)·s(-1)) with respect to the probed time scale, both techniques evidence a long-range proton diffusion process in the SVII phase (3.85 × 10(-6) cm(2)·s(-1) at 275 K with an activation energy of 0.19 ± 0.04 eV). QENS experiments lead to modeling the microscopic mechanism of the long-range proton diffusion by means of a Chudley-Elliot jump diffusion model with a characteristic jump distance of 2.79 ± 0.17 Å. In other words, the long-range diffusion occurs through a Grotthus mechanism with proton jumping from one water-oxygen site to another. Moreover, the analysis of the proton diffusion for hydration numbers greater than 6 (i.e., in the SVII structure) reveals that the additional water molecules coexisting with the SVII structure act as a "structural defect" barrier for the proton diffusivity, responsible for the conductivity. PMID:24941122

  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. A combination of radar and thermal approaches to search for methane clathrate in the Martian subsurface

    NASA Astrophysics Data System (ADS)

    Duxbury, N. S.; Abyzov, S. S.; Romanovsky, V. E.; Yoshikawa, K.

    2004-01-01

    It has been suggested that methane clathrate is stable in the subsurface of Mars (Max and Clifford, (J. Geophys. Res.-Planets 105 (E2) (2000) 4165). Max and Clifford (Geophys. Res. Lett. 28(9) (2001) 1787) have proposed that the Martian chaotic terrain could be a surface manifestation of the dissociation of subsurface methane clathrate hydrate. They have used the large terrestrial sub-oceanic landforms (which have formed due to dissociation of methane clathrate) as an analog. The detection of methane (either in the form of gas or in the solid form of clathrate hydrate) would be evidence of indigenous life in the Martian subsurface, since methane on Earth has mostly biogenic origin. Moreover, methane is a valuable resource for the human exploration of Mars. We propose a novel approach to search for potential Martian methane clathrate hydrate and perform related computations. Our method uses the effect of latent heat of clathrate-phase transitions on the internal heat flow, and hence on permafrost thickness above the clathrate deposit. It will allow one to extract related information out of the radar data that will be used to search for the ground ice/ground water interface. The interpretation of the radar data of ground ice/ground water boundary, which we propose here, can be used to analyze the SHARAD radar data set (Seu et al., 2003) on the Mars Reconnaissance Orbiter (MRO) 2005 mission and the potential Ground Penetrating Radar data on the Mars Science Laboratory, currently planned to be launched in 2009. From this viewpoint we make recommendations for future orbiting/landed missions to Mars.

  5. 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.

  6. New potato micro-tuber-inducing cyclohexene compounds related to theobroxide from Lasiodiplodia theobromae.

    PubMed

    Takei, Ryo; Takahashi, Kosaku; Matsuura, Hideyuki; Nabeta, Kensuke

    2008-08-01

    Two new cyclohexene compounds related to theobroxide (3) were isolated from the mycelia of Lasiodiplodia theobromae OCS71. The structures of these compounds were determined to be (4S,5S)-4,5-dihydroxy-2-methyl-cyclohex-2-enone (1) and (3aS,4R,5S,7aR)-4,5-dihydroxy-7-methyl-3a,4,5,7a-tetrahydrobenzo[1,3]dioxol-2-one (2) by means of spectroscopic analyses and chemical correlation to 3. Compound 2 was shown to take up the carbonate ion to form a carbonic acid ester non-enzymatically. The compounds also showed potato micro-tuber-inducing activities at a concentration of 10(-3) M, using a culture of single-node segments of potato stems in vitro. PMID:18685216

  7. An assessment of beclomethasone dipropionate clathrate formation in a model suspension metered dose inhaler.

    PubMed

    Bouhroum, Abdennour; Burley, Jonathan C; Champness, Neil R; Toon, Richard C; Jinks, Philip A; Williams, Philip M; Roberts, Clive J

    2010-05-31

    The aims of this study were to investigate and characterize the physico-chemical properties of beclomethasone dipropionate (BDP) crystallized from tricholoromonofluoromethane (CFC-11). Physical interactions in a model pressurised metered dose inhaler (pMDI) system and changes in surface energy after size reduction (micronization) were determined. Although CFC-11 has largely been phased out of use in pMDIs due to its ozone depletion potential, the BDP CFC-11 clathrate is a stable entity and thus suitable as a model for our initial investigations. In addition, although propellant clathrates have been known for sometime, as far as the authors are aware, their surface energies and adhesive interactions have not been reported. The structure of the clathrate was investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (X-RPD). In addition, atomic force microscopy (AFM) was employed to determine the dispersive surface free energy (SE) and force of adhesion (F(adh)) of the BDP CFC-11 clathrate with different pMDI components in a model propellant (decafluoropentane). The dispersive surface free energies for anhydrous BDP (micronized), the CFC-11 clathrate and ball-milled BDP CFC-11 clathrate are (47.5+/-4.9) mJ m(-2), (11.3+/-4.1) mJ m(-2) and (15.2+/-1.3) mJ m(-2) respectively. Force of adhesion results shows that BDP CFC-11 clathrates, even after being ball-milled for 2.5h, have a lower F(adh) compared to micronized anhydrous BDP with different pMDI components. This shows that the formation of the crystalline CFC-11 clathrate is advantageous when compared to the micronized anhydrous form, in terms of its surface energy and potential interactions within a suspension MDI formulation. In the wider context, this work has implications for the future development of HFA formulations with APIs which are prone to the formation of propellant clathrates. PMID:20184946

  8. 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.

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

    DOE PAGESBeta

    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; et al

    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

  10. 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.

  11. Estimating the potential for methane clathrate instability in the 1%-CO2 IPCC AR-4 simulations

    NASA Astrophysics Data System (ADS)

    Lamarque, Jean-François

    2008-10-01

    The recent work of Reagan and Moridis (2007) has shown that even a limited warming of 1 K over 100 years can lead to clathrate destabilization, leading to a significant flux of methane into the ocean water, at least for shallow deposits. Here we study the potential for methane clathrate destabilization by identifying the 100-year temperature increase in the available IPCC (Intergovernmental Panel on Climate Change) AR-4 1%-CO2 increase per year (up to doubling over pre-industrial conditions, which occurs after 70 years) simulations. Depending on assumptions made on the possible locations (in this case, only depth) of methane clathrates and on temperature dependence, our calculation leads to an estimated model-mean release of methane at the bottom of the ocean of approximately 560-2140 Tg(CH4)/year; as no actual geographical distribution of methane clathrates is considered here, these flux estimates must be viewed as upper bound estimates. Using an observed 1% ratio to estimate the amount of methane reaching the atmosphere, our analysis leads to a relatively small methane flux of approximately 5-21 Tg(CH4)/year, with an estimated inter-model standard deviation of approximately 30%. The role of sea-level rise by 2100 will be to further stabilize methane clathrates, albeit to a small amount as the sea-level rise is expected to be less than a few meters.

  12. First-Principles Study of Electronic Structure of Type I Hybrid Carbon-Silicon Clathrates

    NASA Astrophysics Data System (ADS)

    Chan, Kwai S.; Peng, Xihong

    2016-08-01

    A new class of type I hybrid carbon-silicon clathrates has been designed using computational methods by substituting some of the Si atoms in the silicon clathrate framework with carbon atoms. In this work, the electronic structure of hybrid carbon-silicon clathrates with and without alkaline or alkaline-earth metal guest atoms has been computed within the density functional theory framework. The theoretical calculations indicate that a small number of carbon substitutions in the Si46 framework slightly reduces the density of states (DOS) near the band edge and narrows the bandgap of carbon-silicon clathrates. Weak hybridization of the conduction band occurs when alkaline metal (Li, Na, K) atoms are inserted into the structure, while strong hybridization of the conduction band occurs when alkaline-earth metal (Mg, Ca, Ba) atoms are inserted into the hybrid structure. Empty C y Si46- y clathrates within the composition range of 2 ≤ y ≤ 15 can be tuned to exhibit indirect bandgaps of 1.5 eV or less, and may be considered as potential electronic materials.

  13. A novel prohibitin-binding compound induces the mitochondrial apoptotic pathway through NOXA and BIM upregulation.

    PubMed

    Moncunill-Massaguer, Cristina; Saura-Esteller, José; Pérez-Perarnau, Alba; Palmeri, Claudia Mariela; Núñez-Vázquez, Sonia; Cosialls, Ana M; González-Gironès, Diana M; Pomares, Helena; Korwitz, Anne; Preciado, Sara; Albericio, Fernando; Lavilla, Rodolfo; Pons, Gabriel; Langer, Thomas; Iglesias-Serret, Daniel; Gil, Joan

    2015-12-01

    We previously described diaryl trifluorothiazoline compound 1a (hereafter referred to as fluorizoline) as a first-in-class small molecule that induces p53-independent apoptosis in a wide range of tumor cell lines. Fluorizoline directly binds to prohibitin 1 and 2 (PHBs), two proteins involved in the regulation of several cellular processes, including apoptosis. Here we demonstrate that fluorizoline-induced apoptosis is mediated by PHBs, as cells depleted of these proteins are highly resistant to fluorizoline treatment. In addition, BAX and BAK are necessary for fluorizoline-induced cytotoxic effects, thereby proving that apoptosis occurs through the intrinsic pathway. Expression analysis revealed that fluorizoline induced the upregulation of Noxa and Bim mRNA levels, which was not observed in PHB-depleted MEFs. Finally, Noxa(-/-)/Bim(-/-) MEFs and NOXA-downregulated HeLa cells were resistant to fluorizoline-induced apoptosis. All together, these findings show that fluorizoline requires PHBs to execute the mitochondrial apoptotic pathway.

  14. Copper-binding compounds as proteasome inhibitors and apoptosis inducers in human cancer.

    PubMed

    Daniel, Kenyon G; Chen, Di; Yan, Bing; Dou, Q Ping

    2007-01-01

    The trace element copper is vital to the healthy functioning of organisms. Copper is used in a multitude of cellular activities including respiration, angiogenesis, and immune responses. Recently, copper has become a focus in medical research ranging from Alzheimer's disease to cancer. Copper modulation has been suggested to be a potential modality for therapy in these diseases. Several copper-binding compounds have been found to spontaneously complex with copper and form active proteasome inhibitors and apoptosis inducers. This review examines compounds in the quinoline and dithiocarbamate families and from the National Cancer Institute (NCI) Diversity Set that bind with copper and act as anticancer agents. In each case, it is shown that these compounds can bind with copper, inhibit the proteasome activity, and induce apoptosis in cancer cells. These activities are absent when copper is not present. Compounds alone, clioquinol and pyrrolidinedithiocarbamate as examples, are shown to have no effects in normal breast cells. Current research suggests that a possible therapeutic modality for cancer may be developed using the difference of high copper load in tumors versus low copper load in normal cells. This strategy would convert tumor cellular copper into a potent, specific proteasome inhibitor and apoptosis inducer. Thus, this approach could pave the way for the development of nontoxic anticancer therapy.

  15. 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.

  16. 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).

  17. 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).

  18. Spectral detectability of CH4-N2 clathrates for in-situ and remote observation of Titan and other icy moons

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    Multicomponent clathrates may be present at the surface of several icy moons, although they have not been detected yet, possibly due to the absence of reliable spectral data. In this work, w e present infrared (IR) and Raman spectral studies of CH4-N2 clathrates at low temperature and pressure, in order to identify discriminating criteria for their possible detection. These clathrates are particularly interesting for Titan and Pluto. Our experimental results indicate that identification of mixed clathrate from remote sensing is very challenging, and that only in- situ Raman spectroscopy may provide a clear identification of clathrate and co nstraints on their composition.

  19. Simulating Relaxation Channels of CO2 in Clathrate Nanocages

    NASA Astrophysics Data System (ADS)

    Dahoo, P. R.; Puig, R.; Lakhlifi, A.; Meis, C.; Gale, J. D.

    2016-08-01

    The energy levels of CO2 in the small (s) and large (l) nano-cages of cubic sI clathrates are calculated in the Born-Oppenheimer approximation using pairwise atom-atom interaction potentials. In the s cage, the centre of mass of CO2 oscillates with small amplitudes, asymmetrically about the cage center with harmonic frequencies around 100 cm-1. In the l cage, oscillations are anharmonic with large amplitude motions in a plane parallel to the hexagonal faces of the cage and the corresponding frequencies are calculated to be 55 cm-1 and 30 cm-1. Librational harmonic frequencies are calculated at 101.7 cm-1 and 56.0 cm-1 in the 5 cage and at 27.9 cm-1 and 46.4 cm-1 in the l cage. Results show that the coupling between the CO2 molecule and the nano-cage is quite different for the low frequency translational, rotational or librational modes and the high frequency vibrational modes, which consequently leads to different relaxation channels.

  20. Interpreting Temperature Strain Data from Meso-Scale Clathrate Experiments

    SciTech Connect

    Leeman, John R; Rawn, Claudia J; Ulrich, Shannon M; Elwood Madden, Megan; Phelps, Tommy Joe

    2012-01-01

    Gas hydrates are important in global climate change, carbon sequestra- tion, and seafloor stability. Currently, formation and dissociation pathways are poorly defined. We present a new approach for processing large amounts of data from meso-scale experiments, such as the LUNA distributed sensing system (DSS) in the seafloor process simulator (SPS) at Oak Ridge National Laboratory. The DSS provides a proxy for temperature measurement with a high spatial resolution allowing the heat of reaction during gas hydrate formation/dissociation to aid in locating clathrates in the vessel. The DSS fibers are placed in the sediment following an Archimedean spiral design and then the position of each sensor is solved by iterating over the arc length formula with Newtons method. The data is then gridded with 1 a natural neighbor interpolation algorithm to allow contouring of the data. The solution of the sensor locations is verified with hot and cold stimulus in known locations. An experiment was preformed with a vertically split column of sand and silt. The DSS system clearly showed hydrate forming in the sand first, then slowly creeping into the silt. Similar systems and data processing techniques could be used for monitoring of hydrates in natural environments or in any situation where a hybrid temperature/strain index is useful. Further ad- vances in fiber technology allow the fiber to be applied in any configuration and the position of each sensor to be precisely determined making practical applications easier.

  1. Nucleation and control of clathrate hydrates: insights from simulation.

    PubMed

    Moon, C; Hawtin, R W; Rodger, P Mark

    2007-01-01

    Clathrate hydrates are important in both industrial and geological settings. They give rise to many technological and environmental applications, including energy production, gas transport, global warming and CO2 capture and sequestration. In all of these applications there is a need to exert a high degree of control on the crystallisation process, either to promote or inhibit it according to the application. This crystallisation process involves the formation of a tetrahedral hydrogen bonding network (as occurs with ice), but is complicated by mass transport limitations due to the poor mixing of the common guest molecules, such as methane, and the water that forms the host lattice. The net effect is that the mechanisms for hydrate formation and growth are still poorly understood, with the consequence that development of additives to control nucleation and growth is still largely governed by trial-and-error approaches. In this paper we show how classical molecular dynamics simulations can be used to provide a direct simulation of the nucleation process for methane hydrate and consequently to allow direct simulation of the effect of additives on the nucleation and growth process. Data are presented for oligomers of PVP and compared with existing data for PDMAEMA. The results show that the two additives work by very different mechanisms, with PVP increasing the surface energy of the interfacial region and PDMAEMA adsorbing to the surface of hydrate nanocrystals. The surface energy effect is a mechanism that has not previously been considered for hydrate inhibitors.

  2. 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.

  3. Fundamental Properties of TBAF Clathrate for Usage as a Latent Heat Storage at a Room Temperature

    NASA Astrophysics Data System (ADS)

    Mizushima, Takanari; Kawamura, Hiroshi; Takao, Shingo; Yabe, Akira

    For promotion of further energy conservation, development of a coolant with a higher heat capacity regulated around a room temperature is strongly required. As a candidate of such a new coolant, we employ the clathrate hydrate, i.e., a mixture of Tetra n-butyl ammonium fluoride (TBAF) and water. This clathrate hydrate is composed of the micro crystals with an order of 100 μm in dimension. It retains fluidity and melting point at a room temperature of about 25 °C. Moreover, the melting point is able to be controlled between 25 °C and 0 °C by changing the concentration of TBAF. The temperature can be regulated by its latent heat at the melting point. Characteristics such as the latent heat and the crystal structure of the clathrate have been experimentally obtained to confirm the feasibility for its usage as the latent heat storage around a room temperature.

  4. Superconductivity in doped sp3 semiconductors: the case of the clathrates.

    PubMed

    Connétable, D; Timoshevskii, V; Masenelli, B; Beille, J; Marcus, J; Barbara, B; Saitta, A M; Rignanese, G-M; Mélinon, P; Yamanaka, S; Blase, X

    2003-12-12

    We present a joint experimental and theoretical study of the superconductivity in doped silicon clathrates. The critical temperature in Ba(8)@Si-46 is shown to strongly decrease with applied pressure. These results are corroborated by ab initio calculations using MacMillan's formulation of the BCS theory with the electron-phonon coupling constant lambda calculated from perturbative density functional theory. Further, the study of I(8)@Si-46 and of gedanken pure silicon diamond and clathrate phases doped within a rigid-band approach show that the superconductivity is an intrinsic property of the sp(3) silicon network. As a consequence, carbon clathrates are predicted to yield large critical temperatures with an effective electron-phonon interaction much larger than in C60.

  5. 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

  6. Molecular-dynamics modelling and neutron diffraction study of the site disorder in air clathrate hydrates

    SciTech Connect

    Chazallon, Bertrand; Klapproth, Alice; Kuhs, Werner F.

    1999-06-15

    We present the results of MD-simulation runs with subsequent quenches for clathrate hydrates using SPC water in order to model properly the crystallographic site disorder of the guest molecules in the water cages. A procedure is described to transform the results of the quench (symmetry P1) into the proper space-time averaged space group (Fd3-bar m) of the clathrate hydrate. The resulting disorder models are compared with the outcome of crystallographic structure refinements (R-factors, Fourier maps) from our neutron powder diffraction data. A correct description of the disorder is important for a reliable determination of the pressure-dependent cage filling.

  7. Theoretical investigation of exchange of N2 and H2 in sII clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Liu, Jinxiang; Hou, Jian; Xu, Jiafang; Liu, Haiying; Li, Shujuan; Chen, Gang; Zhang, Jun

    2016-09-01

    The replacement of N2 with H2 in sII clathrate hydrates was studied through ab initio calculations and molecular dynamics simulations. From the thermodynamic analysis, we suggest that the replacement is more likely to occur in the large cages than in the small cages. H2 and N2 can coexist in the same large cage or in the different cages, forming binary H2-N2 hydrates. Simulations show that the loading capacity of H2 can reach up to ∼4.4 wt% by the replacement method, indicating that the clathrate hydrates are a promising material for hydrogen storage under moderate conditions.

  8. 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.

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

    PubMed Central

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

    2009-01-01

    Purpose Lignans such as secoisolariciresinol diglucoside (SDG) 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 (SERM) 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. Experimental Design 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. Results Contrasts to the classical lignans, Vitexins were not metabolized to END and ENL. A mixture of Vitexins EVn-50 and purified Vitexin compound VB1 have cytotoxic effect on breast, prostate, and ovarian cancer cells and induces apoptosis with cleavage in PARP 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 demonstrated 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. Conclusion Vitexin is a class of nature lignan compounds, whose action and anticancer effect is mediated by the mechanisms different from the classical 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. PMID:19671865

  10. Preparation and antitumor effects of glaucocalyxin A-γ-cyclodextrin clathrate

    PubMed Central

    Zhang, Chong; Qu, Yan; Jia, Yan-Long; Shang, Xiao-Jun; Bai, Su-Ping

    2015-01-01

    Objective: To improve the water solubility of glaucocalyxin A (GLA) by the preparation of glaucocalyxin A γ-cyclodextrin clathrate (GLA-γ-CD) and to investigate the inhibitory effect of GLA-γ-CD on tumor growth in S180 cell xenografts. Materials and methods: GLA-γ-CD, γ-cyclodextrin (γ-CD) and GLA were combined at a mass ratio of 1:1, dissolved in 60°C water by stirring. GLA completely entrapped by the γ-CD was verified by differential thermal analysis, the GLA content was determined. Phase solubility, solubility, and in vitro dissolution rate experiments were performed. The S180 xenograft mouse model was used to observe the tumor inhibitory effects of GLA-γ-CD and GLA, and the TUNEL assay was used to detect differences in their rates of tumor cell apoptosis induction. Results: After combination with γ-CD, the solubility of GLA-γ-CD was 21.78-fold greater than that of GLA. The in vitro dissolution rate of GLA-γ-CD was significantly greater than that of GLA, and reached more than 90% in 20 min. Furthermore, GLA-γ-CD was more effective than GLA as an inhibitor of S180 tumor cells; the inhibitory rate of the high-dose group reached 57.26%, which was 54.11% greater than the inhibitory rate of the GLA group at the same dose. In addition, GLA-γ-CD induced tumor cell apoptosis more effectively than did GLA. Conclusion: The water solubility of GLA significantly increased in combination with γ-CD resulting in the production of GLA-γ-CD. Furthermore, GLA-γ-CD was more effective than GLA as an inducer of S180 tumor cell apoptosis and an inhibitor of tumor growth. PMID:26550426

  11. 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.

  12. A new method for screening potential sII and sH hydrogen clathrate hydrate promoters with model potentials.

    PubMed

    Frankcombe, Terry J; Kroes, Geert-Jan

    2011-08-01

    A new predictive computational method for classifying clathrate hydrate promoter molecules is presented, based on the interaction energies between potential promoters and the water networks of sII and sH clathrates. The motivation for this work is identifying promoters for storing hydrogen compactly in clathrate hydrates. As a first step towards achieving this goal, we have developed a general method aimed at distinguishing between molecules that form sII clathrate hydrates and molecules that can-together with a weakly interacting help gas-form sH clathrate hydrates. The new computational method calculates differences in estimated formation energies of the sII and the sH clathrate hydrate. Model interaction potentials have been used, including the electrostatic interactions with newly calculated partial charges for all the considered potential promoter molecules. The methodology can discriminate between the clathrate structure types (sII or sH) formed by each potential promoter with good selectivity, i.e., better than achieved with a simple van der Waals diameter criterion.

  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. PMID:19191246

  14. Physicochemical and structural studies of clathrate hydrates of tetrabutylammonium polyacrylates.

    PubMed

    Terekhova, Irina S; Manakov, Andrey Yu; Komarov, Vladislav Yu; Villevald, Galina V; Burdin, Alexander A; Karpova, Tamara D; Aladko, Eugeny Ya

    2013-03-01

    In this work, physicochemical and structural studies have been carried out for semiclathrate hydrates of linear (un-cross-linked) and cross-linked tetrabutylammonium polyacrylates with different degrees of cross-linking of the polymeric guest molecules (n = 0.5, 1, 2, 3%) and different degrees of substitution of proton ions of carboxylic groups in poly(acrylic acid) for TBA cations (x = 1, 0.8, 0.6). The changes in the hydrates' stability and composition depending on the outlined parameters were examined in the course of phase diagram studies of the binary systems water-tetrabutylammonium polyacrylates using differential thermal analysis method and calorimetric measurements of fusion enthalpies of the hydrates. Phase diagram studies of the binary system water-linear tetrabutylammonium polyacrylate revealed the formation of four hydrates. Based on the data of chemical analysis of hydrate crystals the compositions of all hydrates have been determined. Single-crystal X-ray diffraction studies revealed a tetragonal structure, space group 4/m, and unit cell parameters are close for different hydrates and lie in the ranges a = 23.4289-23.4713 Å and c = 12.3280-12.3651 Å (150 K). The structure can be related to tetragonal structure I typical for the clathrate hydrates of tetraalkylammonium salts with monomeric anions. Powder X-ray diffraction analyses confirmed the identity of the above crystal structure to that of the hydrates with cross-linked tetrabutylammonium polyacrylates. The behavior of TBA polyacrylate hydrates under the pressure of methane was studied and quantitative assessment of the gas content in the hydrates was made using volumetric analysis method.

  15. 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.

  16. 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.

  17. Physicochemical and structural studies of clathrate hydrates of tetrabutylammonium polyacrylates.

    PubMed

    Terekhova, Irina S; Manakov, Andrey Yu; Komarov, Vladislav Yu; Villevald, Galina V; Burdin, Alexander A; Karpova, Tamara D; Aladko, Eugeny Ya

    2013-03-01

    In this work, physicochemical and structural studies have been carried out for semiclathrate hydrates of linear (un-cross-linked) and cross-linked tetrabutylammonium polyacrylates with different degrees of cross-linking of the polymeric guest molecules (n = 0.5, 1, 2, 3%) and different degrees of substitution of proton ions of carboxylic groups in poly(acrylic acid) for TBA cations (x = 1, 0.8, 0.6). The changes in the hydrates' stability and composition depending on the outlined parameters were examined in the course of phase diagram studies of the binary systems water-tetrabutylammonium polyacrylates using differential thermal analysis method and calorimetric measurements of fusion enthalpies of the hydrates. Phase diagram studies of the binary system water-linear tetrabutylammonium polyacrylate revealed the formation of four hydrates. Based on the data of chemical analysis of hydrate crystals the compositions of all hydrates have been determined. Single-crystal X-ray diffraction studies revealed a tetragonal structure, space group 4/m, and unit cell parameters are close for different hydrates and lie in the ranges a = 23.4289-23.4713 Å and c = 12.3280-12.3651 Å (150 K). The structure can be related to tetragonal structure I typical for the clathrate hydrates of tetraalkylammonium salts with monomeric anions. Powder X-ray diffraction analyses confirmed the identity of the above crystal structure to that of the hydrates with cross-linked tetrabutylammonium polyacrylates. The behavior of TBA polyacrylate hydrates under the pressure of methane was studied and quantitative assessment of the gas content in the hydrates was made using volumetric analysis method. PMID:23383955

  18. 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.

  19. Identification of novel candidate compounds targeting TrkB to induce apoptosis in neuroblastoma.

    PubMed

    Nakamura, Yohko; Suganami, Akiko; Fukuda, Mayu; Hasan, Md Kamrul; Yokochi, Tomoki; Takatori, Atsushi; Satoh, Shunpei; Hoshino, Tyuji; Tamura, Yutaka; Nakagawara, Akira

    2014-02-01

    Neuroblastoma (NB) is one of the most frequent solid tumors in children and its prognosis is still poor. The neurotrophin receptor TrkB and its ligand brain-derived neurotrophic factor (BDNF) are expressed at high levels in high-risk NBs and are involved in defining the poor prognosis of the patients. However, the TrkB targeting therapy has never been realized in the clinic. We performed an in silico screening procedure utilizing an AutoDock/grid computing technology in order to identify novel small chemical compounds targeting the BDNF-binding domain of TrkB. For the first screening, a library of three million synthetic compounds was screened in silico and was ranked according to the Docking energy. The top-ranked 37 compounds were further functionally screened for cytotoxicity by using NB cell lines. We have finally identified seven compounds that kill NB cells with the IC50 values of 0.07-4.6 μmol/L. The terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) assay showed that these molecules induce apoptosis accompanied by p53 activation in NB cell lines. The candidate compounds and BDNF demonstrated an antagonistic effect on cell growth, invasion, and colony formation, possibly suggesting competition at the BDNF-binding site of TrkB. The candidate compounds had tumor-suppressive activity in xenograft and in vivo toxicity tests (oral and intravenous administrations) using mice, and did not show any abnormal signs. Using in silico Docking screening we have found new candidate TrkB inhibitors against high-risk NBs, which could lead to new anti-cancer drugs.

  20. 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.

  1. 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.

  2. 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.

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

    PubMed

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

    2016-05-23

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

  4. 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

  5. Surface induces different crystal structures in a room temperature switchable spin crossover compound.

    PubMed

    Gentili, Denis; Liscio, Fabiola; Demitri, Nicola; Schäfer, Bernhard; Borgatti, Francesco; Torelli, Piero; Gobaut, Benoit; Panaccione, Giancarlo; Rossi, Giorgio; Degli Esposti, Alessandra; Gazzano, Massimo; Milita, Silvia; Bergenti, Ilaria; Ruani, Giampiero; Šalitroš, Ivan; Ruben, Mario; Cavallini, Massimiliano

    2016-01-01

    We investigated the influence of surfaces in the formation of different crystal structures of a spin crossover compound, namely [Fe(L)2] (LH: (2-(pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine), which is a neutral compound thermally switchable around room temperature. We observed that the surface induces the formation of two different crystal structures, which exhibit opposite spin transitions, i.e. on heating them up to the transition temperature, one polymorph switches from high spin to low spin and the second polymorph switches irreversibly from low spin to high spin. We attributed this inversion to the presence of water molecules H-bonded to the complex tetrazolyl moieties in the crystals. Thin deposits were investigated by means of polarized optical microscopy, atomic force microscopy, X-ray diffraction, X-ray absorption spectroscopy and micro Raman spectroscopy; moreover the analysis of the Raman spectra and the interpretation of spin inversion were supported by DFT calculations.

  6. 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.

  7. 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

  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.

  9. Antiproliferative and cell apoptosis-inducing activities of compounds from Buddleja davidii in Mgc-803 cells

    PubMed Central

    2012-01-01

    Background Buddleja davidii is widely distributed in the southwestern region of China. We have undertaken a systematic analysis of B. davidii as a Chinese traditional medicine with anticancer activity by isolating natural products for their activity against the human gastric cancer cell line Mgc-803 and the human breast cancer cell line Bcap-37. Results Ten compounds were extracted and isolated from B. davidii, among which colchicine was identified in B. davidii for the first time. The inhibitory activities of these compounds were investigated in Mgc-803, Bcap-37 cells in vitro by MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay, and the results showed that luteolin and colchicine had potent inhibitory activities against the growth of Mgc-803 cells. Subsequent fluorescence staining and flow cytometry analysis indicated that these two compounds could induce apoptosis in Mgc-803 cells. The results also showed that the percentages of early apoptotic cells (Annexin V+/PI-, where PI is propidium iodide) and late apoptotic cells (Annexin V+/PI+) increased in a dose- and time-dependent manner. After 36 h of incubation with luteolin at 20 μM, the percentages of cells were approximately 15.4% in early apoptosis and 43.7% in late apoptosis; after 36 h of incubation with colchicine at 20 μM, the corresponding values were 7.7% and 35.2%, respectively. Conclusions Colchicine and luteolin from B. davidii have potential applications as adjuvant therapies for treating human carcinoma cells. These compounds could also induce apoptosis in tumor cells. PMID:22938042

  10. 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.

  11. 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

  12. 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.

  13. Can forest trees compensate for stress-generated growth losses by induced production of volatile compounds?

    PubMed

    Holopainen, Jarmo K

    2011-12-01

    Plants produce a variety of volatile organic compounds (VOCs). Under abiotic and biotic stresses, the number and amount of produced compounds can increase. Due to their long life span and large size, trees can produce biogenic VOCs (BVOCs) in much higher amounts than many other plants. It has been suggested that at cellular and tree physiological levels, induced production of VOCs is aimed at improving plant resistance to damage by reactive oxygen species generated by multiple abiotic stresses. In the few reported cases when biosynthesis of plant volatiles is inhibited or enhanced, the observed response to stress can be attributed to plant volatiles. Reported increase, e.g., in photosynthesis has mostly ranged between 5 and 50%. A comprehensive model to explain similar induction of VOCs under multiple biotic stresses is not yet available. As a result of pathogen or herbivore attack on forest trees, the induced production of VOCs is localized to the damage site but systemic induction of emissions has also been detected. These volatiles can affect fungal pathogens and the arrival rate of herbivorous insects on damaged trees, but also act as signalling compounds to maintain the trophic cascades that may improve tree fitness by improved efficiency of herbivore natural enemies. On the forest scale, biotic induction of VOC synthesis and release leads to an amplified flow of BVOCs in atmospheric reactions, which in atmospheres rich in oxides of nitrogen (NOx) results in ozone formation, and in low NOx atmospheres results in oxidation of VOCs, removal in ozone from the troposphere and the resulting formation of biogenic secondary organic aerosol (SOA) particles. I will summarize recent advances in the understanding of stress-induced VOC emissions from trees, with special focus on Populus spp. Particular importance is given to the ecological and atmospheric feedback systems based on BVOCs and biogenic SOA formation.

  14. A novel prohibitin-binding compound induces the mitochondrial apoptotic pathway through NOXA and BIM upregulation

    PubMed Central

    Moncunill-Massaguer, Cristina; Saura-Esteller, José; Pérez-Perarnau, Alba; Palmeri, Claudia Mariela; Núñez-Vázquez, Sonia; Cosialls, Ana M.; González-Gironès, Diana M.; Pomares, Helena; Korwitz, Anne; Preciado, Sara; Albericio, Fernando; Lavilla, Rodolfo; Pons, Gabriel; Langer, Thomas; Iglesias-Serret, Daniel; Gil, Joan

    2015-01-01

    We previously described diaryl trifluorothiazoline compound 1a (hereafter referred to as fluorizoline) as a first-in-class small molecule that induces p53-independent apoptosis in a wide range of tumor cell lines. Fluorizoline directly binds to prohibitin 1 and 2 (PHBs), two proteins involved in the regulation of several cellular processes, including apoptosis. Here we demonstrate that fluorizoline-induced apoptosis is mediated by PHBs, as cells depleted of these proteins are highly resistant to fluorizoline treatment. In addition, BAX and BAK are necessary for fluorizoline-induced cytotoxic effects, thereby proving that apoptosis occurs through the intrinsic pathway. Expression analysis revealed that fluorizoline induced the upregulation of Noxa and Bim mRNA levels, which was not observed in PHB-depleted MEFs. Finally, Noxa−/−/Bim−/− MEFs and NOXA-downregulated HeLa cells were resistant to fluorizoline-induced apoptosis. All together, these findings show that fluorizoline requires PHBs to execute the mitochondrial apoptotic pathway. PMID:26497683

  15. 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.

  16. Pressure-induced superconductivity in topological parent compound Bi2Te3

    SciTech Connect

    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.

    2011-01-04

    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.

  17. [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. PMID:20187500

  18. [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.

  19. 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)

  20. 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).

  1. 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

  2. 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.

  3. A novel schiff base zinc coordination compound inhibits proliferation and induces apoptosis of human osteosarcoma cells.

    PubMed

    Yan, Ming; Pang, Li; Ma, Tan-tan; Zhao, Cheng-liang; Zhang, Nan; Yu, Bing-xin; Xia, Yan

    2015-10-01

    Various kinds of schiff base metal complexes have been proven to induce apoptosis of tumor cells. However, it remains largely unknown whether schiff base zinc complexes induce apoptosis in human cancer cells. Here, we synthesized a novel schiff base zinc coordination compound (SBZCC) and investigated its effects on the growth, proliferation and apoptosis of human osteosarcoma MG-63 cells. A novel SBZCC was synthesized by chemical processes and used to treat MG-63 cells. The cell viability was determined by CCK-8 assay. The cell cycle progression, mitochondrial membrane potential and apoptotic cells were analyzed by flow cytometry. The apoptosis-related proteins levels were determined by immunoblotting. Treatment of MG-63 cells with SBZCC resulted in inhibition of cell proliferation and cell cycle arrest at G1 phase. Moreover, SBZCC significantly reduced the mitochondrial membrane potential and induced apoptosis, accompanied with increased Bax/Bcl-2 and FlasL/Fas expression as well as caspase-3/8/9 cleavage. Our results demonstrated that the synthesized novel SBZCC could inhibit the proliferation and induce apoptosis of MG-63 cells via activating both the mitochondrial and cell death receptor apoptosis pathways, suggesting that SBZCC is a promising agent for the development as anticancer drugs.

  4. 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

  5. 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

  6. 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.

  7. Electronic and optical properties of doped zeolites and clathrates: Display and thermoelectric applications. Annual report, 1 June 1997--31 May 1998

    SciTech Connect

    Metiu, H.

    1998-08-10

    Thermoelectric materials use temperature differences to produce electricity or use electrical power to produce cooling. The first property is used in energy recovery from hot gases (e.g., to make electricity from exhaust gases coming out of engines). The second is used to make refrigerators that have no moving parts, cause no pollution, and can cool microelectronic systems. Both types of devices are currently used only for special applications, since they are not economically competitive. However, they would be if some of their properties could be improved by a factor of two or more. In this work the authors use theory to anticipate which compounds, in a class of candidates called semiconductor clathrates, are likely to have superior thermoelectric properties. Such predictions help the experimentalists to focus on the synthesis and characterization of the most promising candidates.

  8. 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.

  9. Compound C inhibits in vitro angiogenesis and ameliorates thrombin-induced endothelial barrier failure.

    PubMed

    Gündüz, Dursun; Klewer, Matthias; Bauer, Pascal; Tanislav, Christian; Sedding, Daniel; Rohrbach, Susanne; Schulz, Rainer; Aslam, Muhammad

    2015-12-01

    Compound C (comp. C) is a cell-permeable pyrrazolopyrimidine derivative and widely used as adenosine monophosphate-activated protein kinase (AMPK) inhibitor to characterise the role of AMPK in various physiological processes. However, its AMPK-independent effects have also been reported. In the present study we investigated the effects of moderate dose (1-10μM) comp. C on endothelial cell (EC) proliferation, in vitro angiogenesis, and endothelial barrier function. Comp. C was unable to inhibit AMPK phosphorylation (activation) induced by metformin and A-769662 in ECs even at concentration of 10μM. At lower concentration (1μM), comp. C inhibited and potentiated the inhibitory effects of metformin and A-769662 on EC proliferation, migration, tube formation, and sprouting without inducing apoptosis. However, at higher concentration (10μM), it strongly induced apoptosis as measured by enhanced caspase 3/7 activity. Moreover, comp. C antagonised thrombin-induced EC hyperpermeability accompanied by activation of Rac1 and strengthening of adherens junctions (AJs). This EC barrier protective effect was not affected by the presence of AMPK activators. The data of the present study demonstrate that long-term treatment of ECs with low concentration comp. C inhibits EC proliferation and angiogenesis without induction of apoptosis. While short-term incubation antagonises thrombin-induced EC hyperpermeability presumably via Rac1-dependent strengthening of AJs. Furthermore, higher concentration of comp. C (10μM or above) is toxic for ECs and warns that this agent should be used with caution to demonstrate the AMPK-mediated effects. PMID:26522925

  10. 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.

  11. Rat Liver Mitochondrial Dysfunction Induced by an Organic Arsenical Compound 4-(2-Nitrobenzaliminyl) Phenyl Arsenoxide.

    PubMed

    Jiao, Yuan-Hong; Zhang, Qian; Pan, Ling-Li; Chen, Xin-You; Lei, Ke-Lin; Zhao, Jie; Jiang, Feng-Lei; Liu, Yi

    2015-12-01

    Arsenic is successfully used in cancer chemotherapy and several cancer treatments on account of its apoptogenic effects. However, it is environmentally hazardous with potential for toxicity when distributed in the soil, water, and food, and long exposure to water contaminated with Arsenic may induce cancers. Some research studies have reported that liver is the storage site and an important target organ for Arsenic toxicity. In the present work, a new kind of organic arsenic compound, 4-(2-nitrobenzaliminyl) phenyl arsenoxide (NPA), was synthesized, and its potential involvement of mitochondria was explored. The results presented that the toxicology of NPA, at least in part, mediated mitochondrial function and may thoroughly destroy mitochondrial membrane physiological functions. NPA induced mitochondrial permeability transition pore (mtPTP) opening that induces mitochondrial biochemical abnormalities as evidenced by mitochondrial swelling, mitochondrial membrane potential breakdown, membrane fluidity alterations, and the strikingly remarkable protection of CsA. Meanwhile, both the decreased respiration rate of state 4 and the increased inner membrane H(+) permeabilization revealed that the inner membrane function regarding important energy production chain was destroyed. The toxicity of NPA is due to its interaction with mitochondrial membrane thiol protein. This conclusion is based on the protective effects of RR, DTT, and MBM(+). PMID:26087905

  12. 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

  13. An antifreeze protein folds with an interior network of more than 400 semi-clathrate waters.

    PubMed

    Sun, Tianjun; Lin, Feng-Hsu; Campbell, Robert L; Allingham, John S; Davies, Peter L

    2014-02-14

    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.

  14. 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.

  15. 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.

  16. 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.

  17. Compound Poisson Processes and Clustered Damage of Radiation Induced DNA Double Strand Breaks

    NASA Astrophysics Data System (ADS)

    Gudowska-Nowak, E.; Ritter, S.; Taucher-Scholz, G.; Kraft, G.

    2000-05-01

    Recent experimental data have demonstrated that DNA damage induced by densely ionizing radiation in mammalian cells is distributed along the DNA molecule in the form of clusters. The principal constituent of DNA damage are double-strand breaks (DSB) which are formed when the breaks occur in both DNA strands and are directly opposite or separated by only a few base pairs. DSBs are believed to be most important lesions produced in chromosomes by radiation; interaction between DSBs can lead to cell killing, mutation or carcinogenesis. The paper discusses a model of clustered DSB formation viewed in terms of compound Poisson process along with the predictive essay of the formalism in application to experimental data.

  18. 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.

  19. 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.

  20. Effect of allicin and ajoene, two compounds of garlic, on inducible nitric oxide synthase.

    PubMed

    Dirsch, V M; Kiemer, A K; Wagner, H; Vollmar, A M

    1998-08-01

    Inducible nitric oxide synthase (iNOS) has recently been shown to be present in human atherosclerotic lesions and to promote the formation of deleterious peroxynitrite. Allicin and ajoene are discussed as active compounds with regard to the beneficial effects of garlic in atherosclerosis. The aim of this study was to investigate the effect of allicin and ajoene on the iNOS system in lipopolysaccharide (LPS)-stimulated RAW 264.7 macrophages. Ajoene (IC50 2.5-5 microM) and allicin (IC50 15-20 microM) dose dependently reduced nitrite accumulation, a parameter for NO synthesis, in supernatants of LPS-stimulated (1 microg/ml, 20 h) macrophages. Accordingly, reduced iNOS enzyme activities were measured by conversion of L-[3H]arginine to L-[3H]citrulline in homogenates of LPS-activated cells treated with ajoene or allicin. None of these compounds, however, showed a direct effect on the catalytic-activity of iNOS. Consequently, iNOS protein and mRNA expression in ajoene (10 microM) or allicin (50 microM) treated cells were evaluated by Western blot and Northern blot analysis, respectively. Markedly reduced iNOS protein as well as mRNA levels were demonstrated. These observations indicate that allicin and ajoene inhibit the expression of iNOS in activated macrophages. The possible link of this effect to the beneficial features attributed to garlic is discussed.

  1. 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.

  2. 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. PMID:21858698

  3. 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.

  4. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases.

    PubMed

    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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase. PMID:26827220

  5. 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.

  6. 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.

  7. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases.

    PubMed

    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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  8. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

    NASA Astrophysics Data System (ADS)

    Dureckova, Hana; Woo, Tom K.; Alavi, Saman

    2016-01-01

    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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 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 Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  9. Evidence for phase separation during the crystallization of hyperquenched glassy clathrate hydrate forming solutions

    NASA Astrophysics Data System (ADS)

    Tulk, C. A.; Ba, Y.; Klug, D. D.; McLaurin, G.; Ripmeester, J. A.

    1999-04-01

    Tetrahydrofuran, a water-soluble cyclic ether molecule, is well known for its ability to form clathrate hydrates (cubic structure II, melting point 277.5 K). An aqueous solution of THF (17:1 molecular ratio) was hyperquenched (cooled at a rate of 106Ks-1) to 77 K to give recoverable samples of ˜1 g of metastable amorphous material. The crystallization process was studied on three complementary length scales by x-ray powder diffraction, quadrupole echo double resonance (QEDOR) NMR spectroscopy, and Raman spectroscopy as the amorphous material was annealed at temperatures between 80 and 190 K. Results show that phase separation of the two components occurred predominantly during the annealing process, resulting in clusters of crystalline THF and ice Ic before clathrate hydrate crystallization was initiated. During the hyperquenching process, the decreasing molecular mobility of water molecules between room temperature and the fictive temperature (the temperature below which the solution becomes structurally immobilized upon hyperquenching) inhibits growth of the crystal nuclei that normally would result in crystalline clathrate hydrate formation. Annealing the samples between 110-140 K showed that the local hydrogen bonded O-H--O structure of the water molecules changed toward the arrangement characteristic of crystalline ice Ic. We propose that this process forces the THF out of the glassy solution, thus increasing the THF cluster size in the deposit so that these become visible to diffraction. Further annealing, above 150-160 K caused large-scale growth of crystalline clathrate hydrate material, which then could be associated with a reduction in the THF cluster size, and ice Ic.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Mutations induced by 1-nitrosopyrene and related compounds during DNA replication in human cells and induction of homologous recombination by these compounds.

    PubMed

    Maher, V M; Bhattacharyya, N P; Mah, M C; Boldt, J; Yang, J L; McCormick, J J

    1993-03-01

    The transformation of normal human cells into cancer cells is a multistep process. Evidence suggests that a minimum of five independent steps (changes) are required for the development of certain kinds of human cancer, as well as for malignant transformation of human cells in culture. Mutations are one of the mechanisms involved in bringing about such changes. A single DNA base substitution mutation can activate an oncogene or inactivate a tumor suppressor gene. Because the action of tumor suppressor genes is to prevent cells from becoming malignant, the activity of both copies of such genes must be eliminated before suppression is lifted. Homologous mitotic recombination between a mutant tumor suppressor gene allele and its non-mutant allele is one mechanism for accomplishing this. The present study was designed to investigate the mechanisms by which certain carcinogenic compounds found in diesel exhaust particles and structurally-related N-substituted aryl carcinogens induce such base substitution mutations and homologous recombination events in mammalian cells in culture, including human cells. The system we employed to determine rapidly the kinds of mutations induced by these compounds, as well as the location of the point mutations in the target gene, involved a circular DNA molecule (plasmid) carrying a small target gene, supF. The target gene was exposed in vitro to radiolabeled compounds and then was allowed to replicate in human cells where the mutations were formed. The sites of mutation induction were compared with the sites of stable binding of the carcinogens to the DNA (adducts). The system used to determine whether these agents could induce homologous recombination consisted of a thymidine kinase-deficient mouse L cell line with a recombination substrate stably integrated into the genome. To determine whether or not excision repair was involved in the mechanism by which carcinogens induced recombination, the recombination substrate was introduced

  15. Compound 331 selectively induces glioma cell death by upregulating miR-494 and downregulating CDC20.

    PubMed

    Zhang, Lei; Niu, Tianhui; Huang, Yafei; Zhu, Haichuan; Zhong, Wu; Lin, Jian; Zhang, Yan

    2015-01-01

    Malignant gliomas are the most common malignant tumors in the central nervous system (CNS). Up to date, the prognosis of glioma is still very poor, effective therapy with less side-effect is very necessary. Herein, we identify a compound named as "331" selectively induced cell death in glioma cells but not in astrocytes. Compound 331 upregulated miR-494 and downregulated CDC20 in glioma cells but not in astrocytes. These results suggest that compound 331 could be a potential drug selectively targeting glioma cells through upregulating miR-494 and downregulating CDC20. PMID:26153143

  16. Compound 331 selectively induces glioma cell death by upregulating miR-494 and downregulating CDC20

    PubMed Central

    Zhang, Lei; Niu, Tianhui; Huang, Yafei; Zhu, Haichuan; Zhong, Wu; Lin, Jian; Zhang, Yan

    2015-01-01

    Malignant gliomas are the most common malignant tumors in the central nervous system (CNS). Up to date, the prognosis of glioma is still very poor, effective therapy with less side-effect is very necessary. Herein, we identify a compound named as “331” selectively induced cell death in glioma cells but not in astrocytes. Compound 331 upregulated miR-494 and downregulated CDC20 in glioma cells but not in astrocytes. These results suggest that compound 331 could be a potential drug selectively targeting glioma cells through upregulating miR-494 and downregulating CDC20. PMID:26153143

  17. Metallomics insights into the programmed cell death induced by metal-based anticancer compounds.

    PubMed

    Tan, Cai-Ping; Lu, Yi-Ying; Ji, Liang-Nian; Mao, Zong-Wan

    2014-05-01

    Since the discovery of cisplatin more than 40 years ago, enormous research efforts have been dedicated to developing metal-based anticancer agents and to elucidating the mechanisms involved in the action of these compounds. Abnormal metabolism and the evasion of apoptosis are important hallmarks of malignant transformation, and the induction of apoptotic cell death has been considered to be a main pathway by which cytotoxic metal complexes combat cancer. However, many cancers have cellular defects involving the apoptotic machinery, which results in an acquired resistance to apoptotic cell death and therefore reduced chemotherapeutic effectiveness. Over the past decade, it has been revealed that a growing number of cell death pathways induced by metal complexes are not dependent on apoptosis. Metal complexes specifically triggering these alternative cell death pathways have been identified and explored as novel cancer treatment options. In this review, we discuss recent examples of metallomics studies on the different types of cell death induced by metal-based anticancer drugs, especially on the three major forms of programmed cell death (PCD) in mammalian cells: apoptosis, autophagy and regulated necrosis, also called necroptosis.

  18. Bond randomness induced magnon decoherence in a spin-(1)/(2) ladder compound

    NASA Astrophysics Data System (ADS)

    Náfrádi, B.; Keller, T.; Manaka, H.; Stuhr, U.; Zheludev, A.; Keimer, B.

    2013-01-01

    We have used a combination of neutron resonant spin-echo and triple-axis spectroscopies to determine the energy and linewidth of the magnon resonance in IPA-Cu(Cl0.95Br0.05)3, a model spin-1/2 ladder antiferromagnet where Br substitution induces bond randomness. We find that the bond defects induce a blue shift, δΔ, and broadening, δΓ, of the magnon gap excitation compared to the pure compound. At temperatures exceeding the energy scale of the interladder exchange interactions, δΔ and δΓ are temperature independent within the experimental error, in agreement with Matthiessen's rule according to which magnon-defect scattering yields a temperature independent contribution to the magnon mean free path. Upon cooling, δΔ and δΓ become temperature dependent and saturate at values lower than those observed at higher temperature, consistent with the crossover from one-dimensional to two-dimensional spin correlations with decreasing temperature previously observed in pure IPA-CuCl3. These results indicate limitations in the applicability of Matthiessen's rule for magnon scattering in low-dimensional magnets.

  19. Anti-amyloid compounds protect from silica nanoparticle-induced neurotoxicity in the nematode C. elegans

    PubMed Central

    Scharf, Andrea; Gührs, Karl-Heinz; von Mikecz, Anna

    2016-01-01

    Abstract Identifying nanomaterial-bio-interactions are imperative due to the broad introduction of nanoparticle (NP) applications and their distribution. Here, we demonstrate that silica NPs effect widespread protein aggregation in the soil nematode Caenorhabditis elegans ranging from induction of amyloid in nucleoli of intestinal cells to facilitation of protein aggregation in body wall muscles and axons of neural cells. Proteomic screening revealed that exposure of adult C. elegans with silica NPs promotes segregation of proteins belonging to the gene ontology (GO) group of “protein folding, proteolysis and stress response” to an SDS-resistant aggregome network. Candidate proteins in this group include chaperones, heat shock proteins and subunits of the 26S proteasome which are all decisively involved in protein homeostasis. The pathway of protein homeostasis was validated as a major target of silica NPs by behavioral phenotyping, as inhibitors of amyloid formation rescued NP-induced defects of locomotory patterns and egg laying. The analysis of a reporter worm for serotonergic neural cells revealed that silica NP-induced protein aggregation likewise occurs in axons of HSN neurons, where presynaptic accumulation of serotonin, e.g. disturbed axonal transport reduces the capacity for neurotransmission and egg laying. The results suggest that in C. elegans silica NPs promote a cascade of events including disturbance of protein homeostasis, widespread protein aggregation and inhibition of serotonergic neurotransmission which can be interrupted by compounds preventing amyloid fibrillation. PMID:26444998

  20. 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. PMID:23884575

  1. 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.

  2. A Dunnione Compound MB12662 Improves Cisplatin-Induced Tissue Injury and Emesis

    PubMed Central

    Park, Dongsun; Jo, In Geun; Jang, Ja Young; Kwak, Tae Hwan; Yoo, Sang Ku; Jeon, Jeong Hee; Choi, Ehn-Kyoung; Joo, Seong Soo; Kim, Okjin; Kim, Yun-Bae

    2015-01-01

    The present study was aimed to investigate the effects of MB12662, a synthetic dunnione compound, on cisplatin-induced vomiting reflexes and intestinal, renal, immune system, and hematopoietic toxicities in ferrets and mice, respectively. Male ICR mice were orally administered MB12662 (5, 10, 25 or 50 mg/kg) for 10 days, during which intraperitoneally challenged with cisplatin (3.5 mg/kg) from day 4 to 7, and sacrificed on day 10 for the pathological examination. Male ferrets were orally administered MB12662 (25, 50 or 100 mg/kg) for 7 days, subcutaneously challenged with cisplatin (5 mg/kg), and monitored for vomiting reflexes and survival of the animals. Four-day injection of cisplatin (3.5 mg/kg) to mice caused body weight loss and degeneration and atrophy of intestinal villi, reducing villi/crypt ratio to a half level of control animals. Cisplatin also induced renal and hepatic toxicities, and depletion of splenocytes and bone marrow progenitor cells. The systemic toxicities including decreased villi/crypt ratio, immune system atrophy, splenocyte depletion, and decreased cellularity in bone marrow were improved by MB12662. Cisplatin (5 mg/kg) induced retching and emetic responses of ferrets, which were remarkably attenuated by MB12662 in a dose-dependent manner. All the ferrets pretreated with MB12662 survived the challenge of cisplatin, in comparison with 40% mortality in vehicle-treated animals, and blood parameters of nephrotoxicity and hepatotoxicity were markedly recovered. It is expected that MB12662 could be a candidate for the body protection against burden, including emesis, of chemotherapeutic agents. PMID:26336585

  3. 3-Monoglucuronyl glycyrrhretinic acid is a possible marker compound related to licorice-induced pseudoaldosteronism.

    PubMed

    Makino, Toshiaki

    2014-01-01

    One of the most common adverse effects of traditional Japanese kampo and traditional Chinese medicine is pseudoaldosteronism caused by licorice. In this review, the authors describe the mechanisms of licorice-induced pseudoaldosteronism by the pharmacokinetics of chemical constituents and its metabolites containing licorice. Glycyrrhizin (GL), the main constituent of licorice, is absorbed as glycyrrhetinic acid (GA), which is a metabolite of GL produced by enterobacteria before its release into the circulation. Circulating GA is metabolized in the liver to become 3-monoglucuronyl-glycyrrhetinic acid (3MGA), which is excreted into the bile via multidrug resistance protein 2 (Mrp2). If Mrp2 function is damaged for some reason, 3MGA is secreted from the liver into the circulation, and excreted into the urine via organic anion transporters expressed at the basolateral side of tubular epithelial cells. Circulating GA cannot be excreted into the urine since GA binds highly to serum albumin and thus does not pass through glomerular filtration and is not a substrate of transporters expressed on tubular epithelial cells. Licorice-induced pseudoaldosteronism develops due to the inhibition of type 2 11β-hydrosteroid dehydrogenase (11β-HSD2) which results in the accumulation of cortisol in tubular epithelial cells that activate mineral corticoid receptors to stimulate the excretion of potassium that results in hypokalemia. GA, unlike 3MGA, cannot pass through tubular epithelial cells and cannot inhibit the enzyme in the cells. Therefore, 3MGA may be a genuine causative agent for licorice-induced pseudoaldosteronism. When licorice is used, 3MGA in plasma or urine could function as a marker compound to prevent the adverse effects.

  4. 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

  5. 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

  6. Methyl Radical in Clathrate Silica Voids. The Peculiar Physisorption Features of the Guest-Host Molecular Dynamics Interaction.

    PubMed

    Dmitriev, Yurij A; Buscarino, Gianpiero; Benetis, Nikolas P

    2016-08-11

    EPR line shape simulations of CH3/SiO2 clathrates and comparison to CH3/N2O and CH3/SiO2 experiments reveal the motional conditions of the CH3 radical up to the unusual regime of its stability, the high-temperature diffusional regime, at 300 K. In the low-temperature region, the CH3 in clathrates is found to rotate around the in-plane axes even at as low temperatures as 3.8 K. However, nonrotating methyls performing only libration about the C2-axes as well as around the C3-axis are also found, proving the existence of special sites in the clathrate voids that begin to accumulate a significant fraction of methyl radicals at temperatures below approximately 7 K. A distinctive feature in the spectrum anisotropy and line width temperature profiles is found nearby 25 K, which is interpreted as the radical physisorption inside the voids that occurs with the sample temperature lowering. The unusual increase of the CH3/SiO2 clathrate EPR spectral width with temperature over approximately 120 K has its origin in repeated angular momentum vector alterations due to frequent collisions with the clathrate void walls between periodical free rotation periods. This relaxation mechanism resembles to spin-rotation interaction known only for small molecular species in nonviscous fluids but unknown earlier for methyl hosted in solids. PMID:27405003

  7. 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.

  8. Methylsulfonylmethane (MSM), an organosulfur compound, is effective against obesity-induced metabolic disorders in mice.

    PubMed

    Sousa-Lima, Inês; Park, Shin-Young; Chung, Michelle; Jung, Hyun Ju; Kang, Min-Cheol; Gaspar, Joana M; Seo, Ji A; Macedo, M Paula; Park, Kyong Soo; Mantzoros, Christos; Lee, Seung-Hoon; Kim, Young-Bum

    2016-10-01

    Methylsulfonylmethane (MSM), an organosulfur compound, has been used as a dietary supplement that can improve various metabolic diseases. However, the effect of MSM on obesity-linked metabolic disorders remains unclear. The goal of the current study is to determine whether MSM has beneficial effects on glucose and lipid homeostasis in obesity-associated pathophysiologic states. High-fat diet-induced obese (DIO) and genetically obese diabetic db/db mice treated with MSM (1%-5% v/v, by drinking water) were studied. Metabolic parameters involved in glucose and lipid metabolism were determined. Treatment of DIO mice with MSM leads to a significant decrease in blood glucose levels. DIO mice treated with MSM are hypersensitive to insulin, as evidenced by decreased serum insulin and an increase in the area above the curve during an ITT. Concurrently, MSM reduces hepatic triglyceride and cholesterol contents in DIO mice. These effects are accompanied by reductions in gene expression of key molecules involved in lipogenesis and inflammation. FACS analysis reveals that MSM markedly increases the frequency of B cells and decreases the frequency of myeloid cells in peripheral blood and in bone marrow. Moreover, overnutrition-induced changes of femur microarchitecture are restored by MSM. In db/db mice, a marked impairment in glucose and lipid metabolic profiles is notably ameliorated when MSM is supplemented. These data suggest that MSM has beneficial effects on multiple metabolic dysfunctions, including hyperglycemia, hyperinsulinemia, insulin resistance, and inflammation. Thus, MSM could be the therapeutic option for the treatment of obesity-related metabolic disorders such as type 2 diabetes and fatty liver diseases. PMID:27621186

  9. Triazene compounds induce apoptosis in O6-alkylguanine-DNA alkyltransferase deficient leukemia cell lines.

    PubMed

    Tentori, L; Graziani, G; Gilberti, S; Lacal, P M; Bonmassar, E; D'Atri, S

    1995-11-01

    Previous studies demonstrated that triazene compounds (TZC) possess antitumor, antimetastatic and immunosuppressive activity, and induce novel antigenic properties in neoplastic cells. Moreover, TZC showed marked antitumor activity in patients with acute myelogenous leukemias (AML). In most cases leukemic blasts with low levels of the repair enzyme O6-alkyl-guanine-DNA alkyltransferase (OGAT) were highly susceptible to TZC. Therefore the cytotoxic effects of TZC against human leukemic cells and the influence of OGAT modulation were investigated. Five leukemia cell lines were treated with the in vitro active derivative of dacarbazine: 5-(3-methyl-1-triazeno) imidazole-4-carboxamide (MTIC), or with temozolomide (TZM), which is readily cleaved to form the linear triazene MTIC in aqueous solution. The results showed that treatment with TZC at concentrations ranging between 62.5 and 250 microM significantly inhibited cell growth of U-937 and K-562 leukemia cell lines, both with undetectable OGAT activity. Growth inhibition was accompanied by DNA fragmentation and reduction of cell volume characteristic of cell undergoing apoptosis. In contrast, Daudi, HL-60 and Jurkat leukemia cell lines, characterized by high levels of the repair enzyme, were resistant to concentrations of TZC up to 500 microM. Treatment of resistant lines with O6-benzylguanine (BG, a specific inhibitor of OGAT) rendered HL-60 and Daudi but not Jurkat cells sensitive to cytotoxic effects and apoptosis mediated by MTIC. The results presented suggest that: (1) apoptosis is involved in cytotoxic activity of TZC; (2) OGAT could have a role in preventing programmed cell death induced by TZC; and (3) treatment with BG could potentiate cytotoxic and apoptotic effects of TZC on leukemic cell lines when high level of OGAT activity is the main factor involved in resistance to TZC.

  10. Mutagenicity of nitro derivatives induced by exposure of aromatic compounds to nitrogen dioxide.

    PubMed

    Tokiwa, H; Nakagawa, R; Morita, K; Ohnishi, Y

    1981-08-01

    Mutagenic nitro derivatives were readily induced when 6 kinds of chemicals were exposed to 10 ppm of nitrogen dioxide (NO2). Single nitro derivatives were formed from pyrene, phenanthrene, fluorene or chrysene. Carbazole and fluoranthene each produced 2 derivatives substituted with nitro groups at different positions. The formation of nitro derivatives was enhanced by exposure of pyrene to NO2 containing nitric acid (HNO3, less than 100-fold enhancement) or sulphur dioxide (SO2, less than 15-fold enhancement). After 24 h of exposure the yields of the nitro derivative were 0.02% with 1 ppm of NO2 in air and 2.85% with NO2 (1 ppm) containing traces of HNO3. The nitro derivatives from all but phenanthrene and carbazole were chemically identified by means of gas chromatography (GC) and mass spectrometry (MS), and the mutagenicity of the 4 kinds of authentic nitro derivatives was tested by using Salmonella strains TA98 and TA1538 with or without the S9 fraction from rat liver treated with Aroclor 1254. The nitro derivative induced from pyrene was determined to be 1-nitropyrene; that of chrysene was 6-nitrochrysene; that of fluorene was 2-nitrofluorene; and those of fluoranthene were 3-nitrofluoranthene, and 8-nitrofluoranthene. Tested with strain TA98 in the absence of the S9 fraction, the first 4 of these derivatives yielded, respectively, 3050, 269, 433 and 13 400 revertants per nmole. Thus, each nitro derivative formed was potentially a direct-acting frameshift-type mutagen. Each compound exposed to NO2 showed a decreased mutagenic activity when tested in the presence of S9 mix. A possible explanation comes from experiments in which 1-nitropyrene was incubated with the S9 mix at 37 degree C for 10 min, and 1-aminopyrene was formed. The mutagenic activity of 1-aminopyrene was appreciable, but only about one-tenth of that of 1-nitropyrene in the Ames test. PMID:7022189

  11. 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.

  12. 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

  13. 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.

  14. Rapid composition analysis of compound semiconductor thin film solar cell by laser induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, S. H.; Kim, C. K.; In, J. H.; Jeong, S. H.

    2014-03-01

    The characteristics of laser-induced breakdown spectroscopy (LIBS) such as short measurement time and no sample preparation provide clear advantages over other analytical techniques for rapid elemental analysis at manufacturing sites where the composition of products need to be determined in real-time for process monitoring or quality control. Thin film solar cells based on CuIn1-xGaxSe2 (CIGS), polycrystalline compound semiconductor material, have unique advantages of high efficiency (>20%), long-term stability, and low manufacturing cost over other types of solar cell. The electrical and optical properties of the thin CIGS films are closely related to the concentration ratios among its major constituent elements Cu, In, Ga and Se such as Ga/(Ga + In) and Cu/(Ga + In), and thus an accurate measurement of the composition of CIGS thin films has been an issue among CIGS solar cell researchers, requiring a fast and reliable technique for composition analysis. This paper presents the results of nanosecond (ns) and femtosecond (fs) laser based LIBS analysis of thin CIGS films. The critical issues for LIBS analysis of CIGS thin films such are discussed in comparison with ns- and fs-LIBS measurement results. The calibration of LIBS signal intensity ratios with respect to reference concentration data is carried out and the results of optimal line selection for LIBS analysis, depth profiling capability, and reproducibility are discussed.

  15. 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.

  16. Proton-induced damage on 2-aminooxazole, a potential prebiotic compound.

    PubMed

    Bacchus-Montabonel, Marie-Christine

    2015-01-29

    Among the complex organic molecules detected in space, in the interstellar medium, on meteorites or comets, special interest is devoted to the potentially exobiologic-relevant species. In the hypothesis, widely discussed, of a possible exogen origin of life, the transport of such compounds and their survival is indeed a fundamental question. Recently, suggestion has been made that 2-aminooxazole could be a possible precursor of RNA nucleotides on early earth and its stability to UV radiation or to collisions may be determinant. We have thus undertaken a detailed theoretical study of the charge transfer collision dynamics induced by the impact of 2-aminooxazole with protons, which could be an important process in particular in proton-rich environments. The theoretical treatment has been developed through ab initio quantum chemistry molecular calculations followed by semiclassical collision dynamics. The results are compared to previous investigations on DNA and RNA building blocks in order to extract some qualitative trends in the damage of prebiotic species under spatial radiation. PMID:25574775

  17. 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.

  18. Proteomics Study on Nonallergic Hypersensitivity Induced by Compound 4880 and Ovalbumin

    PubMed Central

    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. PMID:26829397

  19. 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.

  20. Inhibition of Vpr-induced cell cycle abnormality by quercetin: a novel strategy for searching compounds targeting Vpr.

    PubMed

    Shimura, M; Zhou, Y; Asada, Y; Yoshikawa, T; Hatake, K; Takaku, F; Ishizaka, Y

    1999-08-01

    Vpr, an accessory gene product of HIV-1 which induces cell cycle abnormality leading to the increased HIV replication, is supposed to be a possible target for anti-AIDS drugs. We recently established a cell line (MIT-23) in which Vpr-induced cell cycle perturbation could be manipulated by a tetracycline promoter. Here, we screened anti-Vpr activity in 27 kinds of herb drugs using MIT-23 cells. One of the extracts prepared from Houttuyniae herba showed an inhibitory activity. Quercetin (QCT), a compound of this crude drug, efficiently inhibited Vpr function without affecting its expression. Furthermore, data suggested that Vpr-induced transcription from HIV-LTR was considerably abrogated by QCT. These data indicate that QCT, a flavonoid previously reported to inhibit HIV replication, also targets Vpr, implicating that MIT-23 cell provides a novel strategy for screening compounds possessing anti-Vpr activity which would be in turn utilized for clarifying the mechanism of Vpr function.

  1. 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

  2. The natural organosulfur compound dipropyltetrasulfide prevents HOCl-induced systemic sclerosis in the mouse

    PubMed Central

    2013-01-01

    Introduction The aim of this study was to test the naturally occurring organosulfur compound dipropyltetrasulfide (DPTTS), found in plants, which has antibiotic and anticancer properties, as a treatment for HOCl-induced systemic sclerosis in the mouse. Methods The prooxidative, antiproliferative, and cytotoxic effects of DPTTS were evaluated ex vivo on fibroblasts from normal and HOCl mice. In vivo, the antifibrotic and immunomodulating properties of DPTTS were evaluated in the skin and lungs of HOCl mice. Results H2O2 production was higher in fibroblasts derived from HOCl mice than in normal fibroblasts (P < 0.05). DPTTS did not increase H2O2 production in normal fibroblasts, but DPTTS dose-dependently increased H2O2 production in HOCl fibroblasts (P < 0.001 with 40 μM DPTTS). Because H2O2 reached a lethal threshold in cells from HOCl mice, the antiproliferative, cytotoxic, and proapoptotic effects of DPTTS were significantly higher in HOCl fibroblasts than for normal fibroblasts. In vivo, DPTTS decreased dermal thickness (P < 0.001), collagen content in skin (P < 0.01) and lungs (P < 0.05), αSMA (P < 0.01) and pSMAD2/3 (P < 0.01) expression in skin, formation of advanced oxidation protein products and anti-DNA topoisomerase-1 antibodies in serum (P < 0.05) versus untreated HOCl mice. Moreover, in HOCl mice, DPTTS reduced splenic B-cell counts (P < 0.01), the proliferative rates of B-splenocytes stimulated by lipopolysaccharide (P < 0.05), and T-splenocytes stimulated by anti-CD3/CD28 mAb (P < 0.001). Ex vivo, it also reduced the production of IL-4 and IL-13 by activated T cells (P < 0.05 in both cases). Conclusions The natural organosulfur compound DPTTS prevents skin and lung fibrosis in the mouse through the selective killing of diseased fibroblasts and its immunomodulating properties. DPTTS may be a potential treatment for systemic sclerosis. PMID:24286210

  3. Novel Platinum(II) compounds modulate insulin-degrading enzyme activity and induce cell death in neuroblastoma cells.

    PubMed

    Tundo, Grazia R; Sbardella, Diego; De Pascali, Sandra A; Ciaccio, Chiara; Coletta, Massimo; Fanizzi, Francesco P; Marini, Stefano

    2015-01-01

    The properties of three novel Platinum(II) compounds toward the insulin-degrading enzyme (IDE) enzymatic activity have been investigated under physiological conditions. The rationale of this study resides on previous observations that these compounds, specifically designed and synthesized by some of us, induce apoptosis in various cancer cell lines, whereas IDE has been proposed as a putative oncogene involved in neuroblastoma onset and progression. Two of these compounds, namely [PtCl(O,O'-acac)(DMSO)] and [Pt(O,O'-acac)(γ-acac)(DMS)], display a modulatory behavior, wherefore activation or inhibition of IDE activity occurs over different concentration ranges (suggesting the existence of two binding sites on the enzyme). On the other hand, [Pt(O,O'-acac)(γ-acac)(DMSO)] shows a typical competitive inhibitory pattern, characterized by a meaningful affinity constant (K i  = 0.95 ± 0.21 μM). Although all three compounds induce cell death in neuroblastoma SHSY5Y cells at concentrations exceeding 2 μM, the two modulators facilitate cells' proliferation at concentrations ≤ 1.5 μM, whereas the competitive inhibitor [Pt(O,O'-acac)(γ-acac)(DMSO)] only shows a pro-apoptotic activity at all investigated concentrations. These features render the [Pt(O,O'-acac)(γ-acac)(DMSO)] a promising "lead compound" for the synthesis of IDE-specific inhibitors (not characterized yet) with therapeutic potentiality.

  4. Desorption of low-volatility compounds induced by dynamic friction between microdroplets and an ultrasonically vibrating blade.

    PubMed

    Usmanov, D T; Hiraoka, K; Wada, H; Morita, S; Nonami, H

    2016-02-21

    Friction plays an important role in desorption and/or ionization of nonvolatile compounds in mass spectrometry, e.g., sonic spray, easy ambient sonic-spray ionization, solvent-assisted inlet ionization, desorption electrospray, etc. In our previous work, desorption of low molecular weight compounds induced by solid/solid dynamic friction was studied. The objective of this work was to investigate desorption of low-volatility compounds induced by liquid/solid friction. Water/methanol (1/1) microdroplets with ∼30 μm in diameter were generated by using a piezoelectric microdroplet generator. They were injected to analytes deposited on the flat surface of a blade vibrating ultrasonically with the frequency of 40 kHz. Neutral molecules desorbed from the blade were ionized by a helium dielectric barrier discharge (DBD), generating strong signals for samples including drugs, explosives, and insecticides. These signals were not detected when either the blade vibrator or the piezoelectric microdroplet generator was off. In contrast, for ionic compounds such as 1-butyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)imide, p-chlorobenzyl pyridinium chloride, and rhodamine B, strong ion signals were obtained when the vibrator and droplet generator were on, but DBD was off. Sub-nanogram limits of detection were attained for low-volatility compounds. PMID:26779570

  5. 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.

  6. 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.

  7. Water proton configurations in structures I, II, and H clathrate hydrate unit cells.

    PubMed

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

    2013-03-28

    Position and orientation of water protons need to be specified when the molecular simulation studies are performed for clathrate hydrates. Positions of oxygen atoms in water are experimentally determined by X-ray diffraction analysis of clathrate hydrate structures, but positions of water hydrogen atoms in the lattice are disordered. This study reports a determination of the water proton coordinates in unit cell of structure I (sI), II (sII), and H (sH) clathrate hydrates that satisfy the ice rules, have the lowest potential energy configuration for the protons, and give a net zero dipole moment. Possible proton coordinates in the unit cell were chosen by analyzing the symmetry of protons on the hexagonal or pentagonal faces in the hydrate cages and generating all possible proton distributions which satisfy the ice rules. We found that in the sI and sII unit cells, proton distributions with small net dipole moments have fairly narrow potential energy spreads of about 1 kJ∕mol. The total Coulomb potential on a test unit charge placed in the cage center for the minimum energy∕minimum dipole unit cell configurations was calculated. In the sI small cages, the Coulomb potential energy spread in each class of cage is less than 0.1 kJ∕mol, while the potential energy spread increases to values up to 6 kJ∕mol in sH and 15 kJ∕mol in the sII cages. The guest environments inside the cages can therefore be substantially different in the sII case. Cartesian coordinates for oxygen and hydrogen atoms in the sI, sII, and sH unit cells are reported for reference.

  8. 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.

  9. 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.

  10. Acting Role of Background Gas in the Emission Response of Laser-Induced Plasmas of Energetic Nitro Compounds.

    PubMed

    Delgado, Tomás; Vadillo, José M; Laserna, J Javier

    2016-08-01

    This study focuses on the analysis of the optical emission response obtained by laser-induced breakdown spectroscopy from energetic nitro compounds in condensed phase sampled in atmospheres of variable composition. The influence of different background gases was evaluated from the characteristic emissions of the excited species coexisting in the plasma plume and conclusions concerning the main pathways involved in the generation of such emission species were extracted. Different reactive (O2, N2, H2) and inert (Ar, He) gases were tested to establish the comparative emission features of organic compounds. PMID:27449368

  11. Single crystal growth of type I Na-Si clathrate by using Na-Sn flux

    NASA Astrophysics Data System (ADS)

    Morito, Haruhiko; Shimoda, Masashi; Yamane, Hisanori

    2016-09-01

    Single crystals of type I Na-Si clathrate, Na8Si46, were synthesized by heating Na, Na4Si4, and Na15Sn4 at 723 K under an Ar gas pressure of 104 Pa for 12 h. The single crystals having {110} habit planes grew up to 1.5 mm in size due to Na evaporation from a Na-Si-Sn melt with a starting compositional molar ratio of Na/Si/Sn=5.75:2:1.

  12. 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

  13. A novel kind of nitrogen heterocycle compound induces apoptosis of human chronic myelogenous leukemia K562 cells.

    PubMed

    Ding, Guoyu; Liu, Feng; Yang, Ting; Jiang, Yuyang; Fu, Hua; Zhao, Yufen

    2006-06-01

    The effects of a novel kind of nitrogen heterocycle compound, which was synthesized in our laboratory previously, on human chronic myelogenous leukemia K562 cells were investigated. The morphological changes were observed by Acridine orange (AO) staining. The screened results through DNA fragmentation and the Annexin V-FITC/PI staining assay showed that compound 8 blocked cell cycles at G(1) phase which led to apoptosis. The increase of caspase-3, 8, and 9 was detected, indicating that both of death-receptor and mitochondria-pathways were activated. Compound 8 induced a biphasic alteration in mitochondrial membrane potential of K562 cells. A dramatic elevation of Ca(2+) was also observed. In addition, a transient increase of ROS was also involved in the process. This study showed that compound 8 might be a potential chemopreventive agent for chronic myelogenous leukemia. It would guide our future work to synthesize more compounds derived from compound 8, which might have better effect, and to determine the target protein. Moreover, it might also provide a background mechanism for the introduction of this new type of promising therapeutic agent.

  14. 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

  15. 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

  16. Epitaxial strain induced ferroelectricity in rocksalt binary compound: Hybrid functional Ab initio calculation and soft mode group theory analysis

    NASA Astrophysics Data System (ADS)

    Kim, Bog G.

    2011-05-01

    We have studied the detailed mechanism of epitaxial strain induced ferroelectricity in rocksalt binary compound by ab initio calculation and soft mode group theory analysis. By applying compressive strain, cubic binary rocksalt (F m3m) transforms into tetragonal (I 4/mmm) structure. With increasing compressive strain, tetragonal structure becomes unstable against spontaneous transformation to lower symmetry tetragonal structure (I 4/mm), evident both from ab initio calculation and from soft mode group theory analysis. For the tensile strain, phase transition sequence can be cubic binary rocksalt to tetragonal (I 4/mmm) and to orthorhombic structure (I m2m). From ab initio calculation and space group analysis, we propose that the epitaxial strain induced ferroelectricity of rocksalt binary compound is the generic property.

  17. 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

  18. In situ apparatus for the study of clathrate hydrates relevant to solar system bodies using synchrotron X-ray diffraction and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Day, Sarah J.; Thompson, Stephen P.; Evans, Aneurin; Parker, Julia E.

    2015-02-01

    Context. Clathrate hydrates are believed to play a significant role in various solar system environments, e.g. comets, and the surfaces and interiors of icy satellites. However, the structural factors governing their formation and dissociation are poorly understood. Aims: We demonstrate the application of a high pressure gas cell, combined with variable temperature non-contact cooling and fast, time-resolved data collection, to the in situ study of clathrate hydrates under conditions relevant to solar system environments. Methods: Clathrates formed and processed within the sample cell are monitored in situ using time-resolved synchrotron X-ray powder diffraction and laser Raman spectroscopy. Results: X-ray diffraction allows the formation of clathrate hydrates to be observed as CO2 gas is applied to ice formed within the cell. Complete conversion is obtained by annealing at temperatures just below the ice melting point. A subsequent rise in the quantity of clathrate is observed as the cell is thermally cycled. Four regions between 100-5000 cm-1 are present in the in situ Raman spectra that carry features characteristic of both ice and clathrate formation. Conclusions: This novel experimental arrangement is well suited to studying clathrate hydrates over a wide range of temperature (80 -500 K) and pressure (1-100 bar) conditions relevant to solar system bodies and can be used with a variety of different gases and starting aqueous compositions (e.g. saline solutions). We propose the increase in clathrate formation observed during thermal cycling may be due to the formation of a quasi liquid-like phase that forms at temperatures below the ice melting point, but which allows either easier formation of new clathrate cages, or the retention and delocalisation of previously formed clathrate structures, possibly as amorphous clathrate. The structural similarities between hexagonal ice, the quasi liquid-like phase, and crystalline CO2 hydrate mean that differences in the

  19. 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.

  20. Electric double-layer capacitor based on an ionic clathrate hydrate.

    PubMed

    Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

    2013-07-01

    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 Me4NOH⋅5 H2O 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. PMID:23671039

  1. The presence of clathrates in comet 67P/Churyumov-Gerasimenko

    NASA Astrophysics Data System (ADS)

    Luspay-Kuti, A.; Mousis, O.; Hässig, M.; Fuselier, S. A.; Lunine, J. I.; Marty, B.; Mandt, K. E.; Wurz, P.; Rubin, M.

    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.

  2. Exploring Dynamics and Cage-Guest Interactions in Clathrate Hydrates Using Solid-State NMR.

    PubMed

    Sengupta, Suvrajit; Guo, Jin; Janda, Kenneth C; Martin, Rachel W

    2015-12-17

    Interactions between guest molecules and the water cages in clathrates are dominated by isotropic van der Waals forces at low temperatures because the cage structures satisfy the hydrogen bonding propensity of the water. However, above 200 K the water molecules become more labile and may interact strongly with the guests through hydrogen bonding. In this work we compare the dynamics of tetrahydrofuran (THF) and cyclopentane (CP) guests in the hydrate cages above 200 K. Since THF can form hydrogen bonds while CP cannot, the dynamics provide insight into host-guest hydrogen bonding. We use magic angle spinning (MAS) solid-state NMR to measure proton spin-lattice relaxation times (T1) of the guests as a function of temperature and find that the activation barrier to the motion of THF molecules is 4.7 kcal/mol (19.7 kJ/mol) at temperatures above 200 K. This is almost 5 times higher than the barrier at lower temperatures. In contrast, the barrier to guest motion in CP hydrate is found to be about 0.67 kcal/mol (2.8 kJ/mol), which agrees well with data at lower temperatures. These results demonstrate that hydrogen bonding interactions between the THF guest and the clathrate cage are significant above 200 K due to the host lattice mobility. PMID:26583257

  3. Possible Si-BASED Half-Metallic Materials:. MnSi46 Clathrates

    NASA Astrophysics Data System (ADS)

    Zhao, Zhi-Wei; Wang, Jing; Zhao, Hui-Yan; Liu, Ying

    The structural and magnetic properties of MSi46 (M = Mn, Fe, Co and Ni) clathrates have been studied using density functional theory calculations within the generalized gradient approximation. When the structures involve a dopant at the center of a Si20 or Si24 cage, the results show that the neighboring atoms around the dopant are drawn in toward the center. Some of the silicon clathrates with a Mn or Co dopant at the center site of a Si20 cage, or a Mn, Fe or Ni dopant at the center site of a Si24 cage are found to be half-metallic materials with large magnetic moments, and others with a Fe or Ni dopant at the center site of a Si20 cage or a Co dopant at the center site of a Si24 cage display semi-metallic characters. In particular, MnSi46 with a half-metallic gap of 0.70 eV and a magnetic moment of 5.00 μB shows promise for applications in the field of spintronics.

  4. 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

  5. Clathrate structure-type recognition: Application to hydrate nucleation and crystallisation.

    PubMed

    Lauricella, Marco; Meloni, Simone; Liang, Shuai; English, Niall J; Kusalik, Peter G; Ciccotti, Giovanni

    2015-06-28

    For clathrate-hydrate polymorphic structure-type (sI versus sII), geometric recognition criteria have been developed and validated. These are applied to the study of the rich interplay and development of both sI and sII motifs in a variety of hydrate-nucleation events for methane and H2S hydrate studied by direct and enhanced-sampling molecular dynamics (MD) simulations. In the case of nucleation of methane hydrate from enhanced-sampling simulation, we notice that already at the transition state, ∼80% of the enclathrated CH4 molecules are contained in a well-structured (sII) clathrate-like crystallite. For direct MD simulation of nucleation of H2S hydrate, some sI/sII polymorphic diversity was encountered, and it was found that a realistic dissipation of the nucleation energy (in view of non-equilibrium relaxation to either microcanonical (NVE) or isothermal-isobaric (NPT) distributions) is important to determine the relative propensity to form sI versus sII motifs.

  6. 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.

  7. Clathrate structure-type recognition: Application to hydrate nucleation and crystallisation.

    PubMed

    Lauricella, Marco; Meloni, Simone; Liang, Shuai; English, Niall J; Kusalik, Peter G; Ciccotti, Giovanni

    2015-06-28

    For clathrate-hydrate polymorphic structure-type (sI versus sII), geometric recognition criteria have been developed and validated. These are applied to the study of the rich interplay and development of both sI and sII motifs in a variety of hydrate-nucleation events for methane and H2S hydrate studied by direct and enhanced-sampling molecular dynamics (MD) simulations. In the case of nucleation of methane hydrate from enhanced-sampling simulation, we notice that already at the transition state, ∼80% of the enclathrated CH4 molecules are contained in a well-structured (sII) clathrate-like crystallite. For direct MD simulation of nucleation of H2S hydrate, some sI/sII polymorphic diversity was encountered, and it was found that a realistic dissipation of the nucleation energy (in view of non-equilibrium relaxation to either microcanonical (NVE) or isothermal-isobaric (NPT) distributions) is important to determine the relative propensity to form sI versus sII motifs. PMID:26133437

  8. 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.

  9. 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. PMID:27152351

  10. Inhibition of pokeweed mitogen-induced B cell differentiation by compounds containing primary amine or hydrazine groups.

    PubMed Central

    de Boccardo, G; Drayer, D; Rubin, A L; Novogrodsky, A; Reidenberg, M M; Stenzel, K H

    1985-01-01

    The present study examined the effect of two drugs, which contain either an aromatic amine or hydrazine moiety and are known to induce lupus like syndromes in man (procainamide and hydralazine) and an aliphatic amine (dansylcadaverine), on pokeweed mitogen (PWM)-induced B cell production of immunoglobulin G (IgG). These compounds all inhibited IgG production and generation of IgG plaque forming cells, whereas derivatives of them, without free amine groups, had little or no effect. The compounds inhibited differentiation of B cells to plasma cells, rather than production and secretion of IgG. Mitogen free culture supernatants of peripheral blood mononuclear cells (PBM) activated by the oxidizing mitogen, neuraminidase and galactose oxidase (NAGO), prevented the inhibition of B cell maturation. Moreover, incubation of NAGO treated PBM with hydralazine prevented the production of soluble factors capable of promoting B cell maturation in the presence of hydralazine. We conclude from these studies that procainamide, hydralazine and dansylcadaverine inhibit PWM-induced B cell maturation to plasma cells by an indirect mechanism, via inhibition of production of lymphokines by helper cells. The primary amine or hydrazine group appears to be required for the inhibitory effect, since analogues of the inhibitory compounds, without primary amine groups, are non-inhibitory. PMID:3882287

  11. New pathway for the formation of metallic cubic phase Ge-Sb-Te compounds induced by an electric current.

    PubMed

    Park, Yong-Jin; Cho, Ju-Young; Jeong, Min-Woo; Na, Sekwon; Joo, Young-Chang

    2016-02-23

    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/cm(2)), 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.

  12. 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

  13. Impact of metal-induced degradation on the determination of pharmaceutical compound purity and a strategy for mitigation.

    PubMed

    Dotterer, Sally K; Forbes, Robert A; Hammill, Cynthia L

    2011-04-01

    Case studies are presented demonstrating how exposure to traces of transition metals such as copper and/or iron during sample preparation or analysis can impact the accuracy of purity analysis of pharmaceuticals. Some compounds, such as phenols and indoles, react with metals in the presence of oxygen to produce metal-induced oxidative decomposition products. Compounds susceptible to metal-induced decomposition can degrade following preparation for purity analysis leading to falsely high impurity results. Our work has shown even metals at levels below 0.1 ppm can negatively impact susceptible compounds. Falsely low results are also possible when the impurities themselves react with metals and degrade prior to analysis. Traces of metals in the HPLC mobile phase can lead to chromatographic artifacts, affecting the reproducibility of purity results. To understand and mitigate the impact of metal induced decomposition, a proactive strategy is presented. The pharmaceutical would first be tested for reactivity with specific transition metals in the sample solvent/diluents and in the HPLC mobile phase. If found to be reactive, alternative sample diluents and/or mobile phases with less reactive solvents or addition of a metal chelator would be explored. If unsuccessful, glassware cleaning or sample solution refrigeration could be investigated. By employing this strategy during method development, robust purity methods would be delivered to the quality control laboratories, preventing future problems from potential sporadic contamination of glassware with metals. PMID:21163601

  14. New pathway for the formation of metallic cubic phase Ge-Sb-Te compounds induced by an electric current.

    PubMed

    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/cm(2)), 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

  15. 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

  16. 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

    2016-01-01

    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

  17. 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. PMID:26618631

  18. 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

  19. Compound 49b Prevents Diabetes-Induced Apoptosis through Increased IGFBP-3 Levels

    PubMed Central

    Zhang, Qiuhua; Guy, Kimberly; Pagadala, Jayaprakash; Jiang, Youde; Walker, Robert J; Liu, Luhong; Soderland, Carl; Kern, Timothy S; Ferry, Robert; He, Hui; Yates, C. Ryan; Miller, Duane D; Steinle, Jena J

    2012-01-01

    Purpose. To determine whether Compound 49b, a novel PKA-activating drug, can prevent diabetic-like changes in the rat retina through increased insulin-like growth factor binding protein-3 (IGFBP-3) levels. Methods. For the cell culture studies, we used both human retinal endothelial cells (REC) and retinal Müller cells in either 5 mM (normal) or 25 mM (high) glucose. Cells were treated with 50 nM Compound 49b alone of following treatment with protein kinase A (PKA) siRNA or IGFBP-3 siRNA. Western blotting and ELISA analyses were done to verify PKA and IGFBP-3 knockdown, as well as to measure apoptotic markers. For animal studies, we used streptozotocin-treated rats after 2 and 8 months of diabetes. Some rats were treated topically with 1 mM Compound 49b. Analyses were done for retinal thickness, cell numbers in the ganglion cell layer, pericyte ghosts, and numbers of degenerate capillaries, as well as electroretinogram and heart morphology. Results. Compound 49b requires active PKA and IGFBP-3 to prevent apoptosis of REC. Compound 49b significantly reduced the numbers of degenerate capillaries and pericyte ghosts, while preventing the decreased retinal thickness and loss of cells in the ganglion cell layer. Compound 49b maintained a normal electroretinogram, with no changes in blood pressure, intraocular pressure, or heart morphological changes. Conclusions. Topical Compound 49b is able to prevent diabetic-like changes in the rat retina, without producing systemic changes. Compound 49b is able to prevent REC apoptosis through increasing IGFBP-3 levels, which are reduced in response to hyperglycemia. PMID:22467575

  20. 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 are the first, to the best of our knowledge, to identify OC as a chemotherapeutic agent against human cholangiocarcinoma QBC939 cells in vitro via the regulation of autophagy and MtD. PMID:27499017

  1. 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

  2. Organic compounds characteristics associated with heat-induced increases of water repellency in Australian eucalypt forest soils

    NASA Astrophysics Data System (ADS)

    Atanassova, Irena; Doerr, Stefan H.

    2010-05-01

    Ground surface heating during wildfires often leads to increased water repellency in soils. The effect of elevated soil temperature on water repellency has been investigated in many laboratory-based studies and temperature thresholds for increases in, and destruction of, water repellency have been established. However, little is known about the changes in organic compounds patterns and their chemical structure that associated with these changes. Here we report on the characterisation of the chemical changes of organic compounds associated with heat-induced increases in water repellency in Eucalypt soils of different repellency levels. Fires are very common in eucalypt forest environments and soils under eucalypt species exhibit one of the most severe repellency levels, providing an ideal study case. Three SE Australian eucalypt forest soils from different locations (two sands and one sandy loam) were heated in the laboratory for 10 min at 300° C. Laboratory heating resulted in extreme repellency in the three soils studied. Heated and unheated control samples were then extracted by accelerated solvent extraction (ASE) with iso-propanol/ammonia mixture (IPA/NH3 95:5). Extraction led to the elimination of any water repellency present both in the original (heated) and the control samples. Organic compounds in the IPA/NH3 solvent were measured in extracts of increasing polarity in order to solubilise the residue. Before heating, the total solvent extracts from the soils with sandy texture were dominated by n-alkanols, terpenoids, C16 acid, C29 alkane, β-sitosterol and polar compounds such as glycerol, monosaccharides and glycosides. Fatty acids with chain length over C20 were detected in the sandy soils, while the soil of heavier texture (sandy loam) lacked longer than C20 fatty acids and had lower concentrations of alkanols (exceeding C26 chain lenght) and alkanes (C29, C31). Alkane patterns were characterized by the predominance of C21 - C31 homologues with a

  3. Recently Confirmed Apoptosis-Inducing Lead Compounds Isolated from Marine Sponge of Potential Relevance in Cancer Treatment

    PubMed Central

    Essack, Magbubah; Bajic, Vladimir B.; Archer, John A.C.

    2011-01-01

    Despite intense efforts to develop non-cytotoxic anticancer treatments, effective agents are still not available. Therefore, novel apoptosis-inducing drug leads that may be developed into effective targeted cancer therapies are of interest to the cancer research community. Targeted cancer therapies affect specific aberrant apoptotic pathways that characterize different cancer types and, for this reason, it is a more desirable type of therapy than chemotherapy or radiotherapy, as it is less harmful to normal cells. In this regard, marine sponge derived metabolites that induce apoptosis continue to be a promising source of new drug leads for cancer treatments. A PubMed query from 01/01/2005 to 31/01/2011 combined with hand-curation of the retrieved articles allowed for the identification of 39 recently confirmed apoptosis-inducing anticancer lead compounds isolated from the marine sponge that are selectively discussed in this review. PMID:22131960

  4. Photoperiod and aggression induce changes in ventral gland compounds exclusively in male Siberian hamsters.

    PubMed

    Rendon, Nikki M; Soini, Helena A; Scotti, Melissa-Ann L; Weigel, Ellen R; Novotny, Milos V; Demas, Gregory E

    2016-05-01

    Chemical communication is a critical component of social behavior as it facilitates social encounters, allows for evaluation of the social partner, defines territories and resources, and advertises information such as sex and physiological state of an animal. Odors provide a key source of information about the social environment to rodents; however, studies identifying chemical compounds have thus far focused primarily on few species, particularly the house mouse. Moreover, considerably less attention has been focused on how environmental factors, reproductive phenotype, and behavioral context alter these compounds outside of reproduction. We examined the effects of photoperiod, sex, and social context on chemical communication in the seasonally breeding Siberian hamster. We sampled ventral gland secretions in both male and female hamsters before and after an aggressive encounter and identified changes in a range of volatile compounds. Next, we investigated how photoperiod, reproductive phenotype, and aggression altered ventral gland volatile compound composition across the sexes. Males exhibited a more diverse chemical composition, more sex-specific volatiles, and showed higher levels of excretion compared to females. Individual volatiles were also differentially excreted across photoperiod and reproductive phenotype, as well as differentially altered in response to an aggressive encounter. Female volatile compound composition, in contrast, did not differ across photoperiods or in response to aggression. Collectively, these data contribute to a greater understanding of context-dependent changes in chemical communication in a seasonally breeding rodent.

  5. Photoperiod and aggression induce changes in ventral gland compounds exclusively in male Siberian hamsters.

    PubMed

    Rendon, Nikki M; Soini, Helena A; Scotti, Melissa-Ann L; Weigel, Ellen R; Novotny, Milos V; Demas, Gregory E

    2016-05-01

    Chemical communication is a critical component of social behavior as it facilitates social encounters, allows for evaluation of the social partner, defines territories and resources, and advertises information such as sex and physiological state of an animal. Odors provide a key source of information about the social environment to rodents; however, studies identifying chemical compounds have thus far focused primarily on few species, particularly the house mouse. Moreover, considerably less attention has been focused on how environmental factors, reproductive phenotype, and behavioral context alter these compounds outside of reproduction. We examined the effects of photoperiod, sex, and social context on chemical communication in the seasonally breeding Siberian hamster. We sampled ventral gland secretions in both male and female hamsters before and after an aggressive encounter and identified changes in a range of volatile compounds. Next, we investigated how photoperiod, reproductive phenotype, and aggression altered ventral gland volatile compound composition across the sexes. Males exhibited a more diverse chemical composition, more sex-specific volatiles, and showed higher levels of excretion compared to females. Individual volatiles were also differentially excreted across photoperiod and reproductive phenotype, as well as differentially altered in response to an aggressive encounter. Female volatile compound composition, in contrast, did not differ across photoperiods or in response to aggression. Collectively, these data contribute to a greater understanding of context-dependent changes in chemical communication in a seasonally breeding rodent. PMID:26944610

  6. Protective effects of the compounds isolated from the seed of Psoralea corylifolia on oxidative stress-induced retinal damage

    SciTech Connect

    Kim, Kyung-A; Shim, Sang Hee; Ahn, Hong Ryul; Jung, Sang Hoon

    2013-06-01

    The mechanism underlying glaucoma remains controversial, but apoptosis caused by increased levels of reactive oxygen species (ROS) is thought to play a role in its pathogenesis. We investigated the effects of compounds isolated from Psoralea corylifolia on oxidative stress-induced cell death in vitro and in vivo. Transformed retinal ganglion cells (RGC-5) were treated with L-buthione-(S,R)-sulfoximine (BSO) and glutamate in the presence or with pre-treatment with compound 6, bakuchiol isolated from P. corylifolia. We observed reduced cell death in cells pre-treated with bakuchiol. Moreover, bakuchiol inhibited the oxidative stress-induced decrease of mitochondrial membrane potential (MMP, ΔΨm). Furthermore, while intracellular Ca{sup 2+} was high in RGC-5 cells after exposure to oxidative stress, bakuchiol reduced these levels. In an in vivo study, in which rat retinal damage was induced by intravitreal injection of N-methyl-D-aspartate (NMDA), bakuchiol markedly reduced translocation of AIF and release of cytochrome c, and inhibited up-regulation of cleaved caspase-3, cleaved caspase-9, and cleaved PARP. The survival rate of retinal ganglion cells (RGCs) 7 days after optic nerve crush (ONC) in mice was significantly decreased; however, bakuchiol attenuated the loss of RGCs. Moreover, bakuchiol attenuated ONC-induced up-regulation of apoptotic proteins, including cleaved PARP, cleaved caspase-3, and cleaved caspase-9. Bakuchiol also significantly inhibited translocation of mitochondrial AIF into the nuclear fraction and release of mitochondrial cytochrome c into the cytosol. These results demonstrate that bakuchiol isolated from P. corylifolia has protective effects against oxidative stress-induced retinal damage, and may be considered as an agent for treating or preventing retinal degeneration. - Highlights: • Psoralea corylifolia have neuroprotective effects in vitro and in vivo. • Bakuchiol attenuated the increase of apoptotic proteins induced by oxidative

  7. Nanowired drug delivery of antioxidant compound H-290/51 enhances neuroprotection in hyperthermia-induced neurotoxicity.

    PubMed

    Muresanu, Dafin F; Sharma, Aruna; Tian, Z Ryan; Smith, Mark A; Sharma, Hari Shanker

    2012-02-01

    Nanoparticles from the environment or through industrial sources can induce profound alterations in human health, often leading to brain dysfunction. However, it is still unclear whether nanoparticle intoxication could also alter the physiological or pathological responses of additional brain injury, stress response or disease processes. Military personals engaged in combat or peacekeeping operations are often exposed to nanoparticles from various environmental sources, e.g., Ag, Cu, Si, C, Al. In addition, these military personals are often exposed to high environmental heat, or gun and missle explosion injury leading to head or spinal trauma. Thus it is likely that additional CNS injury or stress-induced pathophysiological processes are influenced by nanoparticle intoxication. In this situation, when a combination of nanoparticles and central nervous system (CNS) injury or stress exist together, drug therapy needed to correct these anomalies may not work as effectively as in normal situation. Previous studies from our laboratory show that nanoparticle-intoxicated animals when subjected to hyperthermia resulted in exacerbation of brain pathology. In these animals, antioxidant compounds, e.g., H-290/51 that inhibits free radical formation and induces marked neuroprotection in normal rats after heat stress, failed to protect brain damage when a combination of nanoparticles and heat exposure was used. However, nanowired H-290/51 resulted in better neuroprotection in nanoparticles intoxicated animals after heat stress. Interestingly, high doses of the normal compound induced some neuroprotection in these nanoparticle-treated, heat-stressed rats. These observations suggest that a combination of nanoparticles and heat stress is dangerous and in such situations modification of drug dosage is needed to achieve comparable neuroprotection. In this review possible mechanisms of nanoparticle-induced exacerbation of heat induced neurotoxicity and brain protection achieved by

  8. Acute photo-induced toxicity and toxicokinetics of single compounds and mixtures of polycyclic aromatic hydrocarbons in zebrafish.

    PubMed

    Willis, Alison M; Oris, James T

    2014-09-01

    The present study examined photo-induced toxicity and toxicokinetics for acute exposure to selected polycyclic aromatic hydrocarbons (PAHs) in zebrafish. Photo-enhanced toxicity from co-exposure to ultraviolet (UV) radiation and PAHs enhanced the toxicity and exhibited toxic effects at PAH concentrations orders of magnitude below effects observed in the absence of UV. Because environmental exposure to PAHs is usually in the form of complex mixtures, the present study examined the photo-induced toxicity of both single compounds and mixtures of PAHs. In a sensitive larval life stage of zebrafish, acute photo-induced median lethal concentrations (LC50s) were derived for 4 PAHs (anthracene, pyrene, carbazole, and phenanthrene) to examine the hypothesis that phototoxic (anthracene and pyrene) and nonphototoxic (carbazole and phenanthrene) pathways of mixtures could be predicted from single exposures. Anthracene and pyrene were phototoxic as predicted; however, carbazole exhibited moderate photo-induced toxicity and phenanthrene exhibited weak photo-induced toxicity. The toxicity of each chemical alone was used to compare the toxicity of mixtures in binary, tertiary, and quaternary combinations of these PAHs, and a predictive model for environmental mixtures was generated. The results indicated that the acute toxicity of PAH mixtures was additive in phototoxic scenarios, regardless of the magnitude of photo-enhancement. Based on PAH concentrations found in water and circumstances of high UV dose to aquatic systems, there exists potential risk of photo-induced toxicity to aquatic organisms.

  9. Radiation-induced crystalline-to-amorphous transition in intermetallic compounds of the Cu-Ti alloy system

    SciTech Connect

    Lam, N.Q.; Okamoto, P.R.; Devanathan, R. ); Sabochick, M.J. . Computer Applications Div.)

    1992-02-01

    Recent progress in molecular-dynamics studies of radiation-induced crystalline-to-amorphous transition in the ordered intermetallic compounds of the Cu-Ti system is discussed. The effect of irradiation was simulated by the generation of Frenkel pairs,which resulted in both the formation of stable point defects and chemical disorder upon defect recombination. The thermodynamic, structural and mechanical responses of the compounds during irradiation were determined by monitoring changes in the system potential energy, volume expansion, pair correlation function, diffraction patterns, and elastic constants. It was found that the intermetallics Cu{sub 4}Ti{sub 3}, CuTi, and CuTi{sub 2} could be rendered amorphous by the creation of Frenkel pairs, but Cu{sub 4}Ti could not, consistent with experimental observations during electron irradiation. However, the simulations showed that Cu{sub 4}Ti did become amorphous when clusters of Frenkel pairs were introduced, indicating that this compound may be susceptible to amorphization by heavy-ion bombardment. A generalization of the Lindemann criterion was used to develop a thermodynamic description of solid-state amorphization as a disorder- induced melting process.

  10. Salvinorin A analogues PR-37 and PR-38 attenuate compound 48/80-induced itch responses in mice

    PubMed Central

    Salaga, M; Polepally, P R; Zielinska, M; Marynowski, M; Fabisiak, A; Murawska, N; Sobczak, K; Sacharczuk, M; Do Rego, J C; Roth, B L; Zjawiony, J K; Fichna, J

    2015-01-01

    Background and Purpose The opioid system plays a crucial role in several physiological processes in the CNS and in the periphery. It has also been shown that selective opioid receptor agonists exert potent inhibitory action on pruritus and pain. In this study we examined whether two analogues of Salvinorin A, PR-37 and PR-38, exhibit antipruritic properties in mice. Experimental Approach To examine the antiscratch effect of PR-37 and PR-38 we used a mouse model of compound 48/80-induced pruritus. In order to elucidate the mechanism of action of tested compounds, specific antagonists of opioid and cannabinoid receptors were used. The effect of PR-37 on the CNS was assessed by measuring motor parameters and exploratory behaviours in mice. Key Results PR-37 and PR-38, jnjected s.c., significantly reduced the number of compound 48/80-induced scratching behaviours in mice in a dose- and time-dependent manner. PR-38 was also active when orally administered. The antiscratch activity of PR-37 was blocked by the selective κ opioid receptor antagonist, nor-binaltorphimine, and that of PR-38 by the selective μ opioid receptor antagonist, β-funaltrexamine. Conclusion and Implications In conclusion, a novel framework for the development of new antipruritic drugs derived from salvinorin A has been validated. PMID:26040667

  11. Synthesis of α, β-unsaturated carbonyl based compounds as acetylcholinesterase and butyrylcholinesterase inhibitors: characterization, molecular modeling, QSAR studies and effect against amyloid β-induced cytotoxicity.

    PubMed

    Bukhari, Syed Nasir Abbas; Jantan, Ibrahim; Masand, Vijay H; Mahajan, Devidas T; Sher, Muhammad; Naeem-ul-Hassan, M; Amjad, Muhammad Wahab

    2014-08-18

    A series of novel carbonyl compounds was synthesized by a simple, eco-friendly and efficient method. These compounds were screened for anti-oxidant activity, in vitro cytotoxicity and for inhibitory activity for acetylcholinesterase and butyrylcholinesterase. The effect of these compounds against amyloid β-induced cytotoxicity was also investigated. Among them, compound 14 exhibited strong free radical scavenging activity (18.39 μM) while six compounds (1, 3, 4, 13, 14, and 19) were found to be the most protective against Aβ-induced neuronal cell death in PC12 cells. Compounds 4 and 14, containing N-methyl-4-piperidone linker, showed high acetylcholinesterase inhibitory activity as compared to reference drug donepezil. Molecular docking and QSAR (Quantitative Structure-Activity Relationship) studies were also carried out to determine the structural features that are responsible for the acetylcholinesterase and butyrylcholinesterase inhibitory activity.

  12. Kinetic model of C/H/N/O emissions in laser-induced breakdown spectroscopy of organic compounds

    SciTech Connect

    Dagdigian, Paul J.; Khachatrian, Ani; Babushok, Valeri I.

    2010-05-01

    A kinetic model to predict the relative intensities of the atomic C/H/N/O emission lines in laser-induced breakdown spectroscopy (LIBS) has been developed for organic compounds. The model includes a comprehensive set of chemical processes involving both neutral and ionic chemistry and physical excitation and de-excitation of atomic levels affecting the neutral, ionic, and excited-state species concentrations. The relative excited-state atom concentrations predicted by this modeling are compared with those derived from the observed LIBS intensities for 355 nm ns laser irradiation of residues of two organic compounds on aluminum substrate. The model reasonably predicts the relative excited-state concentrations, as well as their time profiles. Comparison of measured and computed concentrations has also allowed an estimation of the degree of air entrainment.

  13. Ionic Strength-Induced Formation of Smectite Quasicrystals Enhances Nitroaromatic Compound Sorption

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The influence of ionic strength on nitroaromatic compound sorption from water by K+- and Ca2+-saturated smectite (SWy-2) was examined. The results indicated that sorption of 1,3-dinitrobenzene by K-SWy-2 increased up to 2.2 times as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorp...

  14. Pressure-induced bonding and compound formation in xenon-hydrogen solids

    SciTech Connect

    Somayazulu, Maddury; Dera, Przemyslaw; Goncharov, Alexander F; Gramsch, Stephen A; Liermann, Peter; Yang, Wenge; Liu, Zhenxian; Mao, Ho-kwang; Hemley, Russell J

    2010-11-03

    Closed electron shell systems, such as hydrogen, nitrogen or group 18 elements, can form weakly bound stoichiometric compounds at high pressures. An understanding of the stability of these van der Waals compounds is lacking, as is information on the nature of their interatomic interactions. We describe the formation of a stable compound in the Xe-H{sub 2} binary system, revealed by a suite of X-ray diffraction and optical spectroscopy measurements. At 4.8 GPa, a unique hydrogen-rich structure forms that can be viewed as a tripled solid hydrogen lattice modulated by layers of xenon, consisting of xenon dimers. Varying the applied pressure tunes the Xe-Xe distances in the solid over a broad range from that of an expanded xenon lattice to the distances observed in metallic xenon at megabar pressures. Infrared and Raman spectra indicate a weakening of the intramolecular covalent bond as well as persistence of semiconducting behaviour in the compound to at least 255 GPa.

  15. Four terpene synthases produce major compounds of the gypsy moth feeding-induced volatile blend of Populus trichocarpa.

    PubMed

    Danner, Holger; Boeckler, G Andreas; Irmisch, Sandra; Yuan, Joshua S; Chen, Feng; Gershenzon, Jonathan; Unsicker, Sybille B; Köllner, Tobias G

    2011-06-01

    After herbivore damage, many plants increase their emission of volatile compounds, with terpenes usually comprising the major group of induced volatiles. Populus trichocarpa is the first woody species with a fully sequenced genome, enabling rapid molecular approaches towards characterization of volatile terpene biosynthesis in this and other poplar species. We identified and characterized four terpene synthases (PtTPS1-4) from P. trichocarpa which form major terpene compounds of the volatile blend induced by gypsy moth (Lymantria dispar) feeding. The enzymes were heterologously expressed and assayed with potential prenyl diphosphate substrates. PtTPS1 and PtTPS2 accepted only farnesyl diphosphate and produced (-)-germacrene D and (E,E)-α-farnesene as their major products, respectively. In contrast, PtTPS3 and PtTPS4 showed both mono- and sesquiterpene synthase activity. They produce the acyclic terpene alcohols linalool and nerolidol but exhibited opposite stereospecificity. qRT-PCR analysis revealed that the expression of the respective terpene synthase genes was induced after feeding of gypsy moth caterpillars. The TPS enzyme products may play important roles in indirect defense of poplar to herbivores and in mediating intra- and inter-plant signaling.

  16. Newly synthesized bis-benzimidazole compound 8 induces apoptosis, autophagy and reactive oxygen species generation in HeLa cells.

    PubMed

    Chu, Naying; Yao, Guodong; Liu, Yuan; Cheng, Maosheng; Ikejima, Takashi

    2016-09-01

    Compound 8 (C8) is a newly synthesized bis-benzimidazole derivative and exerts significant anti-tumor activity in vitro. Previous studies demonstrated that C8 induced apoptosis and autophagy in human promyelocytic leukemia HL60 cells. However, cytotoxicity study on human peripheral blood mononuclear cells (hPBMC) showed that C8 exhibited less toxicity in normal cells. In this study, the molecular mechanism of C8 on human cervical carcinoma HeLa cells was investigated. The results showed that C8 inhibited the growth of HeLa cells and triggered both apoptotic and autophagic cell death. Subsequent experiment also indicated that reactive oxygen species (ROS) generation was induced in C8-treated HeLa cells. Since ROS scavenger decreased the ratio of apoptotic and autophagic cells, ROS generation contributed to C8-induced apoptosis and autophagy. Furthermore, inhibitors of apoptosis and autophagy also reduced ROS generation, respectively. Autophagy inhibition increased cell growth compared to C8-treated group and attenuated apoptotic cell death, indicating that C8-induced autophagy promoted apoptosis for cell death. However, the percentage of autophagic cells was enhanced when limiting apoptosis process. Taken together, C8 induced ROS-mediated apoptosis and autophagy in HeLa cells, autophagy promoted apoptosis but the former was antagonized by the latter. The data also gave us a new perspective on the anti-tumor effect of C8. PMID:27497983

  17. Newly synthesized bis-benzimidazole compound 8 induces apoptosis, autophagy and reactive oxygen species generation in HeLa cells.

    PubMed

    Chu, Naying; Yao, Guodong; Liu, Yuan; Cheng, Maosheng; Ikejima, Takashi

    2016-09-01

    Compound 8 (C8) is a newly synthesized bis-benzimidazole derivative and exerts significant anti-tumor activity in vitro. Previous studies demonstrated that C8 induced apoptosis and autophagy in human promyelocytic leukemia HL60 cells. However, cytotoxicity study on human peripheral blood mononuclear cells (hPBMC) showed that C8 exhibited less toxicity in normal cells. In this study, the molecular mechanism of C8 on human cervical carcinoma HeLa cells was investigated. The results showed that C8 inhibited the growth of HeLa cells and triggered both apoptotic and autophagic cell death. Subsequent experiment also indicated that reactive oxygen species (ROS) generation was induced in C8-treated HeLa cells. Since ROS scavenger decreased the ratio of apoptotic and autophagic cells, ROS generation contributed to C8-induced apoptosis and autophagy. Furthermore, inhibitors of apoptosis and autophagy also reduced ROS generation, respectively. Autophagy inhibition increased cell growth compared to C8-treated group and attenuated apoptotic cell death, indicating that C8-induced autophagy promoted apoptosis for cell death. However, the percentage of autophagic cells was enhanced when limiting apoptosis process. Taken together, C8 induced ROS-mediated apoptosis and autophagy in HeLa cells, autophagy promoted apoptosis but the former was antagonized by the latter. The data also gave us a new perspective on the anti-tumor effect of C8.

  18. Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures

    DOEpatents

    Lueking, Angela; Narayanan, Deepa

    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.

  19. 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.

  20. Viability of clathrate hydrates as CO2 capturing agents: a theoretical study.

    PubMed

    Srivastava, Hemant Kumar; Sastry, G Narahari

    2011-07-01

    Capture and sequestration of green house gas CO(2) is a major challenge for scientists and identifying right materials for this purpose is a task of outstanding importance. Through reliable computational studies, we have demonstrated that the clathrate cages (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) have a great potential to store CO(2). All the considered clathrates and their CO(2) inclusion complexes are optimized at B3LYP/6-31G(d) level of theory. The impact of DFT-D, M05-2X, and MP2 functionals on interaction energy were tested using various basis sets. Although different functionals and basis sets show variation in absolute IE values, the trend is consistent and does not depend on the level of the calculations. Dispersion was found important for these complexes and DFT-D shows comparable IE values with MP2 functional. The optimum and maximum cage occupancy for all the considered cages were tested on the basis of quantum chemical calculations. The maximum cage occupancy for all five considered cages (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) is one, two, two, two, and seven CO(2) molecules, respectively, and the optimum cage occupancy is one, one, one, two, and five CO(2) molecules, respectively. Thus, 5(12)6(8) cages can host up to 7 CO(2) molecules, resulting in about 32 wt %, which makes them highly promising materials.

  1. Vibrational Raman spectra of hydrogen clathrate hydrates from density functional theory.

    PubMed

    Ramya, K R; Venkatnathan, Arun

    2013-03-28

    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 (5(12)) and hexakaidecahedron (5(12)6(4)) 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 5(12)6(4)H2·THF cage is blueshifted compared to the 5(12)6(4)H2 cage. However, all vibrational modes of water molecules are redshifted which suggest reduced interaction between the H2 molecule and water molecules in the 5(12)6(4)H2·THF cage. The symmetric and asymmetric O-H stretch of water molecules in 5(12)H2, 5(12)6(4)H2, and 5(12)6(4)H2·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.

  2. Laser-induced fluorescence detection strategies for sodium atoms and compounds in high-pressure combustors

    NASA Technical Reports Server (NTRS)

    Weiland, Karen J. R.; Wise, Michael L.; Smith, Gregory P.

    1993-01-01

    A variety of laser-induced fluorescence schemes were examined experimentally in atmospheric pressure flames to determine their use for sodium atom and salt detection in high-pressure, optically thick environments. Collisional energy transfer plays a large role in fluorescence detection. Optimum sensitivity, at the parts in 10 exp 9 level for a single laser pulse, was obtained with the excitation of the 4p-3s transition at 330 nm and the detection of the 3d-3p fluorescence at 818 nm. Fluorescence loss processes, such as ionization and amplified spontaneous emission, were examined. A new laser-induced atomization/laser-induced fluorescence detection technique was demonstrated for NaOH and NaCl. A 248-nm excimer laser photodissociates the salt molecules present in the seeded flames prior to atom detection by laser-induced fluorescence.

  3. Magnetic Precursor of the Pressure-Induced Superconductivity in Fe-Ladder Compounds

    NASA Astrophysics Data System (ADS)

    Chi, Songxue; Uwatoko, Yoshiya; Cao, Huibo; Hirata, Yasuyuki; Hashizume, Kazuki; Aoyama, Takuya; Ohgushi, Kenya

    2016-07-01

    The pressure effects on the antiferromagentic orders in iron-based ladder compounds CsFe2Se3 and BaFe2S3 have been studied using neutron diffraction. With identical crystal structure and similar magnetic structures, the two compounds exhibit highly contrasting magnetic behaviors under moderate external pressures. In CsFe2Se3 the ladders are brought much closer to each other by pressure, but the stripe-type magnetic order shows no observable change. In contrast, the stripe order in BaFe2S3 undergoes a quantum phase transition where an abrupt increase of Néel temperature by more than 50% occurs at about 1 GPa, accompanied by a jump in the ordered moment. With its spin structure unchanged, BaFe2S3 enters an enhanced magnetic phase that bears the characteristics of an orbital selective Mott phase, which is the true neighbor of superconductivity emerging at higher pressures.

  4. The antitumor natural compound falcarindiol promotes cancer cell death by inducing endoplasmic reticulum stress

    PubMed Central

    Jin, H R; Zhao, J; Zhang, Z; Liao, Y; Wang, C-Z; Huang, W-H; Li, S-P; He, T-C; Yuan, C-S; Du, W

    2012-01-01

    Falcarindiol (FAD) is a natural polyyne with various beneficial biological activities. We show here that FAD preferentially kills colon cancer cells but not normal colon epithelial cells. Furthermore, FAD inhibits tumor growth in a xenograft tumor model and exhibits strong synergistic killing of cancer cells with 5-fluorouracil, an approved cancer chemotherapeutic drug. We demonstrate that FAD-induced cell death is mediated by induction of endoplasmic reticulum (ER) stress and activation of the unfolded protein response (UPR). Decreasing the level of ER stress, either by overexpressing the ER chaperone protein glucose-regulated protein 78 (GRP78) or by knockout of components of the UPR pathway, reduces FAD-induced apoptosis. In contrast, increasing the level of ER stress by knocking down GRP78 potentiates FAD-induced apoptosis. Finally, FAD-induced ER stress and apoptosis is correlated with the accumulation of ubiquitinated proteins, suggesting that FAD functions at least in part by interfering with proteasome function, leading to the accumulation of unfolded protein and induction of ER stress. Consistent with this, inhibition of protein synthesis by cycloheximide significantly decreases the accumulation of ubiquitinated proteins and blocks FAD-induced ER stress and cell death. Taken together, our study shows that FAD is a potential new anticancer agent that exerts its activity through inducing ER stress and apoptosis. PMID:22914324

  5. Gallium compound GaQ(3) -induced Ca(2+) signalling triggers p53-dependent and -independent apoptosis in cancer cells.

    PubMed

    Gogna, Rajan; Madan, Esha; Keppler, Bernhard; Pati, Uttam

    2012-05-01

    BACKGROUND AND PURPOSE A novel anti-neoplastic gallium complex GaQ(3) (KP46), earlier developed by us, is currently in phase I clinical trial. GaQ(3) induced S-phase arrest and apoptosis via caspase/PARP cleavage in a variety of cancers. However, the underlying mechanism of apoptosis is unknown. Here, we have explored the mechanism(s) of GaQ(3) -induced apoptosis in cancer cells, focusing on p53 and intracellular Ca(2+) signalling. EXPERIMENTAL APPROACH GaQ(3) -induced cytotoxicity and apoptosis were determined in cancer cell lines, with different p53 status (p53(+/+) , p53(-/-) and p53 mutant). Time course analysis of intracellular Ca(2+) calcium release, p53 promoter activation, p53-nuclear/cytoplasmic movements and reactive oxygen species (ROS) were conducted. Ca(2+) -dependent formation of the p53-p300 transcriptional complex was analysed by co-immunoprecipitation and chromatin immunoprecipitation. Ca(2+) signalling, p53, p300 and ROS were serially knocked down to study Ca(2+) -p53-ROS ineractions in GaQ(3) -induced apoptosis. KEY RESULTS GaQ(3) triggered intracellular Ca(2+) release stabilizing p53-p300 complex and recruited p53 to p53 promoter, leading to p53 mRNA and protein synthesis. p53 induced higher intracellular Ca(2+) release and ROS followed by activation of p53 downstream genes including those for the micro RNA mir34a. In p53(-/-) and p53 mutant cells, GaQ(3) -induced Ca(2+) -signalling generated ROS. ROS further increased membrane translocation of FAS and FAS-mediated extrinsic apoptosis. CONCLUSIONS AND IMPLICATIONS This study disclosed a novel mechanism of Ca(2+) -signalling-mediated p53 activation and ROS up-regulation. Understanding the mechanism of GaQ(3) -induced apoptosis will help establish this gallium-based organic compound as a potent anti-cancer drug.

  6. Effects of various chemical compounds on spontaneous and hydrogen peroxide-induced reversion in strain TA104 of Salmonella typhimurium.

    PubMed

    Han, J S

    1992-04-01

    In experiments designed to determine which active oxygen species contribute to hydrogen peroxide (HP)-induced reversion in strain TA104 of Salmonella typhimurium, 1,10-phenanthroline (an iron chelator, which prevents the formation of hydroxyl radicals from HP and DNA-bound iron by the Fenton reaction), sodium azide (a singlet oxygen scavenger), and potassium iodide (an hydroxyl radical scavenger) inhibited HP-induced reversion. These results indicate that hydroxyl radicals generated from HP by the Fenton reaction, and perhaps singlet oxygen, contribute to HP-induced reversion in TA104. However, reduced glutathione (reduces Fe3+ to Fe2+ and/or HP to water), diethyldithiocarbamic acid (an inhibitor of superoxide dismutase), diethyl maleate (a glutathione scavenger), and 3-amino-1,2,4-triazole (an inhibitor of catalase) did not inhibit HP-induced reversion in TA104. Thus, superoxide radical anions and HP itself do not appear to be the cause of HP-induced reversion in this strain. In experiments on the effect of 5 common dietary compounds (beta-carotene, retinoic acid, and vitamins A, C and E), chlorophyllin (CHL), and ergothioneine, the frequency of revertants in TA104 increased above the spontaneous frequency in the presence of beta-carotene or vitamin C (about 2-fold) or vitamin A (about 3-fold). The 5 dietary antimutagens and CHL did not inhibit HP-induced reversion in TA104. However, L-ergothioneine inhibited HP-induced reversion in this strain. Therefore, it is likely that L-ergothioneine is a scavenger of hydroxyl radicals or an inhibitor of their formation, and perhaps of singlet oxygen, at the concentrations tested in TA104.

  7. Atomic disorder induced by mechanical milling in the intermetallic compound CoAl

    NASA Astrophysics Data System (ADS)

    Di, L. M.; Bakker, H.; de Boer, F. R.

    1992-10-01

    The stoichiometric intermetallic compound CoAl with the CsCl-structure was subjected to ball milling. Structural changes during ball milling were studied by measurements of the magnetization and the lattice parameter. The behaviour of Coal upon milling turns out to be quite similar to that of CoGa. The increase of the magnetization and the decrease of the lattice parameter with the milling time show that, similar to CoGa, triple-defect disorder is generated by ball milling. By comparing the measured magnetization to the magnetization of Co xAl 100- x compounds with excess Co, the concentration of defects is derived for milled samples. In order to interpret our results, the existing experimental data of lattice parameters, X-ray densities calculated from the lattice parameters and macroscopic densities for Co xAl 100- x compounds were analyzed according to Edelin's equations. The defect volumes for vacancies and anti-site atoms obtained by fitting these experimental data have reasonable values. By means of the defect concentrations obtained from our magnetization measurements and the defect volumes by fitting the experimental data, the change of the lattice parameter was calculated by means of Edelin's equation. The agreement between the calculated lattice parameter and the measured lattice parameter is quite satisfactory.

  8. Identification of Novel Compounds Inhibiting Chikungunya Virus-Induced Cell Death by High Throughput Screening of a Kinase Inhibitor Library

    PubMed Central

    Gomes, Rafael G. B.; da Silva, Camila T.; Taniguchi, Juliana B.; No, Joo Hwan; Lombardot, Benoit; Schwartz, Olivier; Hansen, Michael A. E.; Freitas-Junior, Lucio H.

    2013-01-01

    Chikungunya virus (CHIKV) is a mosquito-borne arthrogenic alphavirus that causes acute febrile illness in humans accompanied by joint pains and in many cases, persistent arthralgia lasting weeks to years. The re-emergence of CHIKV has resulted in numerous outbreaks in the eastern hemisphere, and threatens to expand in the foreseeable future. Unfortunately, no effective treatment is currently available. The present study reports the use of resazurin in a cell-based high-throughput assay, and an image-based high-content assay to identify and characterize inhibitors of CHIKV-infection in vitro. CHIKV is a highly cytopathic virus that rapidly kills infected cells. Thus, cell viability of HuH-7 cells infected with CHIKV in the presence of compounds was determined by measuring metabolic reduction of resazurin to identify inhibitors of CHIKV-associated cell death. A kinase inhibitor library of 4,000 compounds was screened against CHIKV infection of HuH-7 cells using the resazurin reduction assay, and the cell toxicity was also measured in non-infected cells. Seventy-two compounds showing ≥50% inhibition property against CHIKV at 10 µM were selected as primary hits. Four compounds having a benzofuran core scaffold (CND0335, CND0364, CND0366 and CND0415), one pyrrolopyridine (CND0545) and one thiazol-carboxamide (CND3514) inhibited CHIKV-associated cell death in a dose-dependent manner, with EC50 values between 2.2 µM and 7.1 µM. Based on image analysis, these 6 hit compounds did not inhibit CHIKV replication in the host cell. However, CHIKV-infected cells manifested less prominent apoptotic blebs typical of CHIKV cytopathic effect compared with the control infection. Moreover, treatment with these compounds reduced viral titers in the medium of CHIKV-infected cells by up to 100-fold. In conclusion, this cell-based high-throughput screening assay using resazurin, combined with the image-based high content assay approach identified compounds against CHIKV having a novel

  9. Pain‑relieving effect of a compound isolated from white peony root oral liquid on acute radiation‑induced esophagitis.

    PubMed

    Wang, Zhiyu; Shen, Li; Li, Xing; Shu, Xin; Shan, Baoen; Zhang, Li; Gong, Yanjun; Dong, Zhiming

    2013-06-01

    Acute radiation‑induced esophagitis (ARIE) is a common complication of radiotherapy. The aim of this study was to clarify the molecular mechanism of pain relief by the compound of white peony root oral liquid (cWPROL) in ARIE. An animal model of ARIE was established and either cWPROL or a mixture of lidocaine, dexamethasone and gentamycin (mLDG) was administered. We indirectly observed rat symptoms of pain by recording the weight of food and the volume of water consumed by the rats, along with changes in body weight. Additionally, the expression levels of substance P (SP) in the esophageal tissues were detected by immunohistochemistry. It was demonstrated that cWPROL was able to release the pain of ARIE by decreasing the expression of SP; this may be one of the molecular mechanisms via which cWPROL induces pain relief.

  10. Impurity induced antiferromagnetic order in Haldane gap compound SrNi2-xMgxV2O8

    NASA Astrophysics Data System (ADS)

    Pahari, B.; Ghoshray, K.; Ghoshray, A.; Samanta, T.; Das, I.

    2007-05-01

    The effect of nonmagnetic Mg doping in SrNi2V2O8, a Haldane gap system with a disordered ground state, was investigated using DC magnetic susceptibility and heat capacity measurements in polycrystalline samples of SrNi2-xMgxV2O8 with x=0.03, 0.05, 0.07, 0.1 and 0.14. The results clearly reveal that the substitution of Ni(S=1) ion by Mg(S=0) ion induces a magnetic phase transition with the ordering temperatures lying in the range 3.4-4.3 K, for the samples with lowest and highest value of x. The intrachain exchange constant (J/kB) and the Haldane gap (Δ) for all the compounds were estimated to be ∼98±2 and 25 K, respectively, which are close to that of the undoped compound. The magnetization data further suggest that the compounds exhibit metamagnetic behavior below TN, supporting a picture of antiferromagnet with significant magnetic anisotropy and competing intrachain and interchain interactions.

  11. Time-Course of Changes in Choroidal Thickness after Complete Mydriasis Induced by Compound Tropicamide in Children

    PubMed Central

    Zeng, Junwen; Jin, Wei; Long, Wen; Lan, Weizhong; Yang, Xiao

    2016-01-01

    Purpose The aim of this study was to investigate the time-course of changes in choroidal thickness (ChT) following complete mydriasis induced by compound tropicamide. Methods ChT was measured by OCT with the enhanced-depth imaging technique (Spectralis HRA+OCT, Heidelberg Engineering, Germany) at nine locations of the fundus: subfoveal ChT (SFChT) and ChT at 1 mm and 3 mm from the fovea in four quadrants. Mydriasis was induced with compound tropicamide (0.5% tropicamide plus 0.5% phenylephrine hydrochloride, three doses at 5-minute intervals). Measurements were conducted prior to the instillation and at 0, 30, and 60 min following complete mydriasis. Results at different time-points were compared using repeated-measures ANOVA to investigate the time-course of the changes. Results Thirty-nine subjects (mean age 11.9±2 years; 16 males and 23 females) were enrolled in the study. Compound tropicamide resulted in a statistically significant decrease in SFChT at 0, 30, and 60 min after complete mydriasis, as compared to baseline (−5±4 μm, −12±4 μm, and −13±4 μm, respectively; all P<0.0001). No significant changes were detected in the parafoveal choroid except at 1 mm temporal (T1mm) and nasal (N1mm) to the fovea at 30 and 60 min (T1mm: −6±4 μm and −7±5 μm at 30 and 60 min; N1mm: −6±4 μm and −7±5 μm at 30 and 60 min, respectively; all P<0.0001). Repeated-measures ANOVA showed a significant interaction between the time after complete mydriasis and the effect of the mydriasis agent. Conclusions Complete mydriasis induced by compound tropicamide led to choroidal thinning, and the magnitude varied over time. PMID:27622495

  12. Poplar root exudates contain compounds that induce the expression of MiSSP7 in Laccaria bicolor.

    PubMed

    Plett, Jonathan M; Martin, Francis

    2012-01-01

    Communication between organisms is crucial for their survival, especially for sessile organisms such as plants that depend upon interactions with mutualistic organisms to maximize their nutrient acquisition. This communication can take the form of the exchange of volatile compounds, metabolites or effectors - small protein signals secreted from the colonizing cell that change the biology of the host cell.  We recently characterized the first mutualistic effector protein from an ectomycorrhizal fungus, a small secreted protein named MiSSP7 encoded by Laccaria bicolor.  Ectomycorrhizal fungi are soil-borne mutualistic organisms whose hyphae wrap around host roots and grow into the root apoplastic space where the fungus exchanges nutrients such as nitrogen and phosphorus in return for plant derived sugars.  The MiSSP7 protein is induced by root exudates and is highly expressed throughout the root colonization process.  Its presence was responsible for alterations to the plant transcriptomic profile, a mechanism by which MiSSP7 may aid in the formation of the symbiotic interface. Here we further discuss the implications of these findings and, further, we demonstrate that the production of MiSSP7 is induced by two flavonoids, rutin and quercitrin, a class of compounds normally found within the exudates of plant roots.  We also consider the interesting similarities between the mechanisms of effector induction and action between pathogenic and mutualistic fungi.  

  13. [Nervous system disorders induced by occupational exposure to aluminium compounds: a literature review].

    PubMed

    Sińczuk-Walczak, H

    2001-01-01

    This is a review of the literature on the effect of aluminum (Al) and its compounds on the nervous system. The role of aluminum in etiology of some degenerative diseases of the nervous system, e.g. Alzheimer disease, amyotrophic lateral sclerosis or dementia, is presented. The special attention was turned to the effects of aluminum on the nervous system functions in persons occupationally exposed to metal-containing dusts and fumes, manifested mostly by neurobehavioral disorders and changes in the brain bioelectric functions and less frequently pronounced by clinical neurological symptoms.

  14. Intercalation-induced phases in layer compounds of the A /SUP III/ B /SUP VI/ -type

    SciTech Connect

    Kovalyuk, Z.D.; Pyrlya, M.N.; Seredyuk, A.I.; Tovstyuk, K.D.

    1986-03-01

    The authors investigate the kinetics of combined electrochemical intercalation and the physicochemical properties of the introduced phases. InSe and GaSe single crystals were used in the experiments; the crystals were grown by the Bridgman method. The authors determined the concentration dependences of the electrode potentials and electrical conductivity of the compounds InSe and GaSe intercalated with lithium and lead. The results of the measurements are presented. Lithium and lead enter into the matrix of the crystals in a nonconducting state.

  15. Large drought-induced variations in oak leaf volatile organic compound emissions during PINOT NOIR 2012

    SciTech Connect

    Geron, Chris; Gu, Lianhong; Daly, Ryan; Harley, Peter; Rasmussen, Rei; Seco, Roger; Guenther, Alex; Karl, Thomas

    2015-12-17

    Here, leaf-level isoprene and monoterpene emissions were collected and analyzed from five of the most abundant oak (Quercus) species in Central Missouri's Ozarks Region in 2012 during PINOT NOIR (Particle Investigations at a Northern Ozarks Tower – NOx, Oxidants, Isoprene Research). June measurements, prior to the onset of severe drought, showed isoprene emission rates and leaf temperature responses similar to those previously reported in the literature and used in Biogenic Volatile Organic Compound (BVOC) emission models. During the peak of the drought in August, isoprene emission rates were substantially reduced, and response to temperature was dramatically altered, especially for the species in the red oak subgenus (Erythrobalanus).

  16. An Evaluation of Sensor Performance for Harmful Compounds by Using Photo-Induced Electron Transfer from Photosynthetic Membranes to Electrodes

    PubMed Central

    Kasuno, Megumi; Kimura, Hiroki; Yasutomo, Hisataka; Torimura, Masaki; Murakami, Daisuke; Tsukatani, Yusuke; Hanada, Satoshi; Matsushita, Takayuki; Tao, Hiroaki

    2016-01-01

    Rapid, simple, and low-cost screening procedures are necessary for the detection of harmful compounds in the effluent that flows out of point sources such as industrial outfall. The present study investigated the effects on a novel sensor of harmful compounds such as KCN, phenol, and herbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (atrazine), and 2-N-tert-butyl-4-N-ethyl-6-methylsulfanyl-1,3,5-triazine-2,4-diamine (terbutryn). The sensor employed an electrode system that incorporated the photocurrent of intra-cytoplasmic membranes (so-called chromatophores) prepared from photosynthetic bacteria and linked using carbon paste electrodes. The amperometric curve (photocurrent-time curve) of photo-induced electron transfer from chromatophores of the purple photosynthetic bacterium Rhodobacter sphaeroides to the electrode via an exogenous electron acceptor was composed of two characteristic phases: an abrupt increase in current immediately after illumination (I0), and constant current over time (Ic). Compared with other redox compounds, 2,5-dichloro-1,4-benzoquinone (DCBQ) was the most useful exogenous electron acceptor in this system. Photo-reduction of DCBQ exhibited Michaelis-Menten-like kinetics, and reduction rates were dependent on the amount of DCBQ and the photon flux intensity. The Ic decreased in the presence of KCN at concentrations over 0.05 μM (=μmol·dm−3). The I0 decreased following the addition of phenol at concentrations over 20 μM. The Ic was affected by terbutryn at concentrations over 10 μM. In contrast, DCMU and atrazine had no effect on either I0 or Ic. The utility of this electrode system for the detection of harmful compounds is discussed. PMID:27023553

  17. An Evaluation of Sensor Performance for Harmful Compounds by Using Photo-Induced Electron Transfer from Photosynthetic Membranes to Electrodes.

    PubMed

    Kasuno, Megumi; Kimura, Hiroki; Yasutomo, Hisataka; Torimura, Masaki; Murakami, Daisuke; Tsukatani, Yusuke; Hanada, Satoshi; Matsushita, Takayuki; Tao, Hiroaki

    2016-01-01

    Rapid, simple, and low-cost screening procedures are necessary for the detection of harmful compounds in the effluent that flows out of point sources such as industrial outfall. The present study investigated the effects on a novel sensor of harmful compounds such as KCN, phenol, and herbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (atrazine), and 2-N-tert-butyl-4-N-ethyl-6-methylsulfanyl-1,3,5-triazine-2,4-diamine (terbutryn). The sensor employed an electrode system that incorporated the photocurrent of intra-cytoplasmic membranes (so-called chromatophores) prepared from photosynthetic bacteria and linked using carbon paste electrodes. The amperometric curve (photocurrent-time curve) of photo-induced electron transfer from chromatophores of the purple photosynthetic bacterium Rhodobacter sphaeroides to the electrode via an exogenous electron acceptor was composed of two characteristic phases: an abrupt increase in current immediately after illumination (I₀), and constant current over time (Ic). Compared with other redox compounds, 2,5-dichloro-1,4-benzoquinone (DCBQ) was the most useful exogenous electron acceptor in this system. Photo-reduction of DCBQ exhibited Michaelis-Menten-like kinetics, and reduction rates were dependent on the amount of DCBQ and the photon flux intensity. The Ic decreased in the presence of KCN at concentrations over 0.05 μM (=μmol·dm(-3)). The I₀ decreased following the addition of phenol at concentrations over 20 μM. The Ic was affected by terbutryn at concentrations over 10 μM. In contrast, DCMU and atrazine had no effect on either I₀ or Ic. The utility of this electrode system for the detection of harmful compounds is discussed. PMID:27023553

  18. Experimental investigation and planetary implications of the stability of clathrate hydrates in aqueous solution at icy satellite conditions

    NASA Astrophysics Data System (ADS)

    Dunham, M.; Choukroun, M.; Barmatz, M.; Hodyss, R. P.; Smythe, W. D.

    2012-12-01

    Clathrate hydrates consist of hydrogen-bonded water molecules forming cages in which gas molecules are trapped individually. They are among the favored volatile reservoirs in solar system bodies, and are expected to play an important role in many processes: accretion of volatiles in planetesimals, outgassing on Titan, Enceladus, and comets. Their insulating thermal properties and high mechanical strength also bear important implications for understanding the evolution of icy satellites like Europa. However, the conditions allowing for their formation and/or their dissociation and the release of volatiles to the atmosphere (Titan) or the plumes (Enceladus) are still poorly understood. This is mainly because of a lack of knowledge on the stability of mixed clathrate hydrates in presence of anti-freeze agents such as ammonia. We have developed a high-pressure cryogenic calorimeter to address this deficiency in the literature. This liquid nitrogen - cooled Setaram BT2.15 calorimeter is located at the JPL Ice Physics Laboratory. The temperature range achievable with this instrument is 77-473 K. This calorimeter uses Calvet elements (3D arrays of thermocouples) to measure the heat flow required to follow a predefined heating rate within a sample and a reference cell with a resolution of 0.1 μW. A gas handling system has been designed and fabricated in house to reach pressures up to 100 bars, corresponding to several km depth in icy satellites. The thermodynamic properties of CO2 and CH4 clathrates with ammonia are under investigation, and the results will be used to constrain a statistical thermodynamic model of clathrates for applications to planetary environments. Preliminary results will be shown at the meeting. This work has been conducted at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Support from the Minnesota Space Grant Consortium, the NASA Outer Planets Research program, and government sponsorship are gratefully

  19. Electrophilic iodine(I) compounds induced semipinacol rearrangement via C-X bond cleavage.

    PubMed

    Tsuji, Nobuya; Kobayashi, Yusuke; Takemoto, Yoshiji

    2014-11-18

    Neutral electrophilic iodine(I) species proved to be efficient reagents for C-X bond cleavage of various cyclic and acyclic α-silyloxyhalides, and the induced desilylative semipinacol rearrangement provided the corresponding ketones in good yields. The reaction is operationally simple, and proceeds under mild conditions with good functional group compatibility. Mechanistic investigations, including computational studies, were also performed.

  20. Bioassay-Guided Isolation of Neuroprotective Compounds from Uncaria rhynchophylla against Beta-Amyloid-Induced Neurotoxicity

    PubMed Central

    Xian, Yan-Fang; Lin, Zhi-Xiu; Mao, Qing-Qiu; Hu, Zhen; Zhao, Ming; Che, Chun-Tao; Ip, Siu-Po

    2012-01-01

    Uncaria rhynchophylla is a component herb of many Chinese herbal formulae for the treatment of neurodegenerative diseases. Previous study in our laboratory has demonstrated that an ethanol extract of Uncaria rhynchophylla ameliorated cognitive deficits in a mouse model of Alzheimer's disease induced by D-galactose. However, the active ingredients of Uncaria rhynchophylla responsible for the anti-Alzheimer's disease activity have not been identified. This study aims to identify the active ingredients of Uncaria rhynchophylla by a bioassay-guided fractionation approach and explore the acting mechanism of these active ingredients by using a well-established cellular model of Alzheimer's disease, beta-amyloid- (Aβ-) induced neurotoxicity in PC12 cells. The results showed that six alkaloids, namely, corynoxine, corynoxine B, corynoxeine, isorhynchophylline, isocorynoxeine, and rhynchophylline were isolated from the extract of Uncaria rhynchophylla. Among them, rhynchophylline and isorhynchophylline significantly decreased Aβ-induced cell death, intracellular calcium overloading, and tau protein hyperphosphorylation in PC12 cells. These results suggest that rhynchophylline and isorhynchophylline are the major active ingredients responsible for the protective action of Uncaria rhynchophylla against Aβ-induced neuronal toxicity, and their neuroprotective effect may be mediated, at least in part, by inhibiting intracellular calcium overloading and tau protein hyperphosphorylation. PMID:22778778

  1. Magnetic Precursor of the Pressure-Induced Superconductivity in Fe-Ladder Compounds

    DOE PAGESBeta

    Chi, Songxue; Uwatoko, Yoshiya; Cao, Huibo; Hirata, Yasuyuki; Hashizume, Kazuki; Aoyama, Takuya; Ohgushi, Kenya

    2016-07-21

    We studied the pressure effects on the antiferromagentic orders in iron-based ladder compounds CsFemore » $_2$Se$_3$ and BaFe$_2$S$_3$ using single crytal neutron diffraction technique. With identical crystal structure and similar magnetic structures, the two compounds exhibit highly contrasting magnetic behaviors under moderate external pressures. In CsFe$_2$Se$_3$ the ladders are brought much closer to each other by pressure, but the stripe-type of magnetic order shows no observable change. Furthermore, the stripe order in BaFe$_2$S$_3$, undergoes a quantum phase transition where an abrupt increase of $$N\\acute{e}el$$ temperature by more than 50$$\\%$$ occurs at about 1 GPa, accompanied by a jump in ordered moment. Finally, with its spin structure unchanged, BaFe$_2$S$_3$ enters an enhanced magnetic phase that bears the characteristics of an orbital selective Mott phase, which is the true herald for superconductivity emerging at higher pressures.« less

  2. Flavonoid-induced conversion of catalase to its inactive form--Compound II.

    PubMed

    Krych, J; Gebicki, J L; Gebicka, L

    2014-11-01

    Flavonoids (FlaOHs), plant polyphenols, are ubiquitous components of human diet and are known as antioxidants. However, their prooxidant activity has also been reported. We have recently found that FlaOHs inhibit catalase, the heme enzyme which catalyzes the decomposition of hydrogen peroxide (H2O2) into water and molecular oxygen. The catalytic cycle proceeds with the formation of the intermediate, Compound I (Cpd I), an oxoferryl porphyrin π-cation radical, the two-electron oxidation product of a heme group. Under conditions of low H2O2 fluxes and in the presence of an appropriate substrate, Cpd I can undergo one-electron reduction to inactive Compound II (Cpd II), oxoferryl derivative without radical site. Here we show that in vitro, under low fluxes of H2O2, FlaOHs reduce Cpd I to inactive Cpd II. Measurable amounts of Cpd II can be formed even in the presence of reduced nicotinamide adenine dinucleotide phosphate (NADPH) at concentration comparable with the investigated FlaOHs. Possible mechanisms of electron transfer from FlaOH molecule to the heme are discussed.

  3. Magnetic Precursor of the Pressure-Induced Superconductivity in Fe-Ladder Compounds.

    PubMed

    Chi, Songxue; Uwatoko, Yoshiya; Cao, Huibo; Hirata, Yasuyuki; Hashizume, Kazuki; Aoyama, Takuya; Ohgushi, Kenya

    2016-07-22

    The pressure effects on the antiferromagentic orders in iron-based ladder compounds CsFe_{2}Se_{3} and BaFe_{2}S_{3} have been studied using neutron diffraction. With identical crystal structure and similar magnetic structures, the two compounds exhibit highly contrasting magnetic behaviors under moderate external pressures. In CsFe_{2}Se_{3} the ladders are brought much closer to each other by pressure, but the stripe-type magnetic order shows no observable change. In contrast, the stripe order in BaFe_{2}S_{3} undergoes a quantum phase transition where an abrupt increase of Néel temperature by more than 50% occurs at about 1 GPa, accompanied by a jump in the ordered moment. With its spin structure unchanged, BaFe_{2}S_{3} enters an enhanced magnetic phase that bears the characteristics of an orbital selective Mott phase, which is the true neighbor of superconductivity emerging at higher pressures. PMID:27494496

  4. Crystal structure and thermoelectric properties of KxBa8-xZnyGe46-y clathrates

    NASA Astrophysics Data System (ADS)

    Kishimoto, Kengo; Sasaki, Yuta; Koyanagi, Tsuyoshi; Ohoyama, Kenji; Akai, Koji

    2012-05-01

    Polycrystalline samples of degenerate n-type KxBa8-xZnyGe46-y (y ˜8-x/2) with the type-I clathrate structure (No. 223, Pm3¯n) were prepared by powder metallurgy to obtain a high-efficiency Ge-based clathrate. Their Zn atoms preferred to exist at the 6c site in the framework, and consequently, the samples with x around 4, such as K4Ba4Zn6Ge40, possessed highly ordered Zn/Ge atom frameworks whose 6c, 16i, and 24k sites were occupied almost solely by Zn, Ge, and Ge atoms, respectively. In spite of such ordered structures and small numbers of substituting Zn atoms, these samples exhibited carrier mobilities lower than those of Ba8Zn8Ge38 and Ba8Ga16Ge30. Band structure calculations implied that the combination of the rattler K and Ba atoms in the cages considerably modified the conduction band edge of the corresponding clathrates; such a modification is considered to strengthen alloy disorder scattering, which reduces carrier mobility. The maximum dimensionless figure-of-merit ZT was 0.51 at 1000 K for the K2Ba6Zn7Ge39 sample, which is similar to that of 0.50 at 900 K for the Ba8Zn8Ge38 sample.

  5. Systematic Studies on Anharmonicity of Rattling Phonons in Type I Clathrates by Low Temperature Heat Capacity Measurements

    NASA Astrophysics Data System (ADS)

    Tanigaki, Katsumi; Wu, Jiazhen; Tanabe, Yoichi; Heguri, Satoshi; Shiimotani, Hidekazu; Tohoku University Collaboration

    2014-03-01

    Clathrates are featured by cage-like polyhedral hosts mainly composed of the IVth group elements of Si, Ge, or Sn and alkali metal or alkaline-earth metal elements can be accommodated inside as a guest atom. One of the most intriguing issues in clathrates is their outstanding high thermoelectric performances thanks to the low thermal conductivity. Being irrespective of good electric conductivity σ, the guest atom motions provide a low-energy lying less-dispersive phonons and can greatly suppress thermal conductivity κ. This makes clathrates close to the concept of ``phonon glass electron crystal: PGEC'' and useful in thermoelectric materials from the viewpoint of the figure of merit. In the present study, we show that the local phonon anharmonicity indicated by the tunneling-term of the endohedral atoms (αT) and the itinerant-electron term (γeT), both of which show T-linear dependences in specific heat Cp, can successfully be separated by employing single crystals with various carrier concentrations in a wide range of temperture experimennts. The factors affecting on the phonon anharmonicity as well as the strength of electron-phonon interactions will be discussed based on our recent experiments. The research was financially supported by Ministry of Education, Science, Sports and Culture, Grant in Aid for Science, and Technology of Japan.

  6. Vascular relaxation induced by Eucommiae Ulmoides Oliv. and its compounds Oroxylin A and wogonin: implications on their cytoprotection action

    PubMed Central

    Akinyi, Mary; Gao, Xiu Mei; Li, Yu Hong; Wang, Bing Yao; Liu, Er Wei; Chai, Li Juan; JawoBah, Abdulai; Fan, Guan Wei

    2014-01-01

    The vascular relaxation action of Eucommiae Ulmoides Oliv. also known as Duzhong has been seen on arteries of the heart such as the aorta and the coronary artery which are elastic in nature. Duzhong is historically an active ingredient commonly used in hypertensive herbal prescriptions in China. This work investigated the vasodilating effect of Duzhong and its compounds (wogonin 10 μM and oroxylin-A) in the isolated intact rat heart, perfused retrograde according the method of Langendorff and the cytoprotective effect in EA.hy926 cell lines Coronary perfusion pressure was monitored with a pressure transducer connected to a side-arm of the aortic perfusion cannula. Duzhong induced vasorelaxation in a dose dependent manner, on precontracting the vessels with endothelin-1, Duzhong 10 mg/ml, wogonin 10 μM and oroxylin-A 10 μM could significantly lower the perfusion pressure in reference to positive control SNP, Duzhong induced vasodilation was not inhibited by L-NAME (nitric oxide inhibitor), but was significantly inhibited by Tetraethyl ammonium (TEA, a K+ channel blocker and almost abolished by potassium chloride. The underlying mechanism was carried out in EA.hy926 cell lines. When these cells were treated with H2O2, there was higher expression of NOX-4, TNF-α and COX-2 mRNA. However, wogonin treatment attenuated the mRNA of NOX-4, TNF-α and COX-2. Wogonin also upregulated the mRNA expression of CAT, SOD-1 and GSR in oxidative stress induced by H2O2 EA.hy926 cells. Duzhong and compounds can exert an in vitro relaxation effect of the coronary artery and improve the heart function in Langendorff apparatus. This action appears to be endothelium dependent but not NO mediated. Cell culture findings indicated that wogonin can exert vascular and cellular protection by scavenging Reactive Oxygen Species. PMID:25419347

  7. Disorder-induced structural transitions in topological insulating Ge-Sb-Te compounds

    SciTech Connect

    Kim, Jeongwoo; Jhi, Seung-Hoon

    2015-05-21

    The mechanism for the fast switching between amorphous, metastable, and crystalline structures in chalcogenide phase-change materials has been a long-standing puzzle. Based on first-principles calculations, we study the atomic and electronic properties of metastable Ge{sub 2}Sb{sub 2}Te{sub 5} and investigate the atomic disorder to understand the transition between crystalline hexagonal and cubic structures. In addition, we study the topological insulating property embedded in these compounds and its evolution upon structural changes and atomic disorder. We also discuss the role of the surface-like states arising from the topological insulating property in the metal-insulator transition observed in the hexagonal structure.

  8. Strain induced topological phase transitions in monolayer honeycomb structures of group-V binary compounds

    PubMed Central

    Nie, Yaozhuang; Rahman, Mavlanjan; Wang, Daowei; Wang, Can; Guo, Guanghua

    2015-01-01

    We present first-principles calculations of electronic structures of a class of two-dimensional (2D) honeycomb structures of group-V binary compounds. Our results show these new 2D materials are stable semiconductors with direct or indirect band gaps. The band gap can be tuned by applying lattice strain. During their stretchable regime, they all exhibit metal-indirect gap semiconductor-direct gap semiconductor-topological insulator (TI) transitions with increasing strain from negative (compressive) to positive (tensile) values. The topological phase transition results from the band inversion at the Γ point which is due to the evolution of bonding and anti-bonding states under lattice strain. PMID:26656257

  9. SMN-inducing compounds for the treatment of spinal muscular atrophy

    PubMed Central

    Lorson, Monique A; Lorson, Christian L

    2013-01-01

    Spinal muscular atrophy (SMA) is a leading genetic cause of infant mortality. A neurodegenerative disease, it is caused by loss of SMN1, although low, but essential, levels of SMN protein are produced by the nearly identical gene SMN2. While no effective treatment or therapy currently exists, a new wave of therapeutics has rapidly progressed from cell-based and preclinical animal models to the point where clinical trials have initiated for SMA-specific compounds. There are several reasons why SMA has moved relatively rapidly towards novel therapeutics, including: SMA is monogenic; the molecular understanding of SMN gene regulation has been building for nearly 20 years; and all SMA patients retain one or more copies of SMN2 that produces low levels of full-length, fully functional SMN protein. This review primarily focuses upon the biology behind the disease and examines SMN1- and SMN2-targeted therapeutics. PMID:23157239

  10. Large drought-induced variations in oak leaf volatile organic compound emissions during PINOT NOIR 2012

    DOE PAGESBeta

    Geron, Chris; Gu, Lianhong; Daly, Ryan; Harley, Peter; Rasmussen, Rei; Seco, Roger; Guenther, Alex; Karl, Thomas

    2015-12-17

    Here, leaf-level isoprene and monoterpene emissions were collected and analyzed from five of the most abundant oak (Quercus) species in Central Missouri's Ozarks Region in 2012 during PINOT NOIR (Particle Investigations at a Northern Ozarks Tower – NOx, Oxidants, Isoprene Research). June measurements, prior to the onset of severe drought, showed isoprene emission rates and leaf temperature responses similar to those previously reported in the literature and used in Biogenic Volatile Organic Compound (BVOC) emission models. During the peak of the drought in August, isoprene emission rates were substantially reduced, and response to temperature was dramatically altered, especially for themore » species in the red oak subgenus (Erythrobalanus).« less

  11. Active hexose correlated compound modulates LPS-induced hypotension and gut injury in rats.

    PubMed

    Doursout, Marie-Francoise; Liang, Yangyan; Sundaresan, Alamelu; Wakame, Koji; Fujii, Hajime; Takanari, Jun; Devakottai, Sundar; Kulkarni, Anil

    2016-10-01

    We hypothesized that AHCC; (Amino UP Chemical Co., Ltd., Sapporo, Japan), a mushroom mycelium extract obtained from liquid culture of Lentinula edodes, restores immune function in LPS-induced inflammation in the gut, especially when the nitric oxide signaling pathway is impaired. This is the first inter-disciplinary proposal to identify molecular mechanisms involved in LPS-induced immune dysfunction in the gut in conscious animals treated or non-treated with AHCC, a promoter of immune support. Specifically, we have tested the effects of AHCC on LPS-induced deleterious effects on blood pressure and gut injury in conscious rats. The time course of biological markers of innate/acquired immune responses, and inflammation/oxidative stress is fully described in the present manuscript. Rats were randomly assigned into 3 groups (N=6 per group). Group 1 received 10% of AHCC in drinking water for 5days; Group 2 received lipopolysaccharide (LPS; Escherichia coli 0111:B4 purchased from Sigma) only at 20mg/kg IV; Group 3 received combined treatments (AHCC + LPS). LPS was administered at 20mg/kg IV, 5days following AHCC treatment. We have demonstrated that AHCC decreased the LPS-deleterious effects of blood pressure and also decreased inflammatory markers e.g., cytokines, nitric oxide and edema formation. Finally, AHCC diminished lymphocyte infiltration, restoring gut architecture. Because AHCC was administered prior to LPS, our results indicate the potential impact of AHCC's prophylactic effects on LPS inflammation. Consequently, additional experiments are warrant to assess its therapeutic effects in sepsis-induced inflammation. PMID:27500458

  12. Pressure induced magneto-structural phase transitions in layered RMn2X2 compounds (invited)

    NASA Astrophysics Data System (ADS)

    Kennedy, Shane; Wang, Jianli; Campbell, Stewart; Hofmann, Michael; Dou, Shixue

    2014-05-01

    We have studied a range of pseudo-ternaries derived from the parent compound PrMn2Ge2, substituting for each constituent element with a smaller one to contract the lattice. This enables us to observe the magneto-elastic transitions that occur as the Mn-Mn nearest neighbour distance is reduced and to assess the role of Pr on the magnetism. Here, we report on the PrMn2Ge2-xSix, Pr1-xYxMn2Ge2, and PrMn2-xFexGe2 systems. The pressure produced by chemical substitution in these pseudo-ternaries is inherently non-uniform, with local pressure variations dependent on the local atomic distribution. We find that concentrated chemical substitution on the R or X site (e.g., in Pr0.5Y0.5Mn2Ge2 and PrMn2Ge0.8Si1.2) can produce a separation into two distinct magnetic phases, canted ferromagnetic and canted antiferromagnetic, with a commensurate phase gap in the crystalline lattice. This phase gap is a consequence of the combination of phase separation and spontaneous magnetostriction, which is positive on transition to the canted ferromagnetic phase and negative on transition to the canted antiferromagnetic phase. Our results show that co-existence of canted ferromagnetic and antiferromagnetic phases depends on chemical pressure from the rare earth and metalloid sites, on local lattice strain distributions and on applied magnetic field. We demonstrate that the effects of chemical pressure bear close resemblance to those of mechanical pressure on the parent compound.

  13. Chemotaxis of Rhizobium meliloti towards Nodulation Gene-Inducing Compounds from Alfalfa Roots

    PubMed Central

    Dharmatilake, Amitha J.; Bauer, Wolfgang D.

    1992-01-01

    Luteolin, a flavone present in seed exudates of alfalfa, induces nodulation genes (nod) in Rhizobium meliloti and also serves as a biochemically specific chemoattractant for the bacterium. The present work shows that R. meliloti RCR2011 is capable of very similar chemotactic responses towards 4′,7-dihydroxyflavone, 4′,7-Dihydroxyflavanone, and 4,4′-dihydroxy-2-methoxychalcone, the three principal nod gene inducers secreted by alfalfa roots. Chemotactic responses to the root-secreted nod inducers in capillary assays were usually two- to four-fold above background and, for the flavone and flavonone, occurred at concentrations lower than those required for half-maximal induction of the nodABC genes. Complementation experiments indicated that the lack of chemotactic responsiveness to luteolin seen in nodD1 and nodA mutants of R. meliloti was not due to mutations in the nod genes, as previously thought. Thus, while nod gene induction and flavonoid chemotaxis have the same biochemical specificity, these two functions appear to have independent receptors or transduction pathways. The wild-type strain was found to suffer selective, spontaneous loss of chemotaxis towards flavonoids during laboratory subculture. PMID:16348685

  14. Detection of Sugars via Chirality Induced in Europium(III) Compounds.

    PubMed

    Wu, Tao; Průša, Jiří; Kessler, Jiří; Dračínský, Martin; Valenta, Jan; Bouř, Petr

    2016-09-01

    Detection and resolution of simple monosaccharides are difficult tasks because their structure is quite similar. The present study shows that circularly polarized luminescence (CPL) induced in europium complexes provides very specific spectral patterns for fructose, mannose, glucose, and galactose. Differences were also observed between bare Eu(3+) ion and its complexes, when interacting with these sugars. The CPL spectra were measured on a Raman optical activity (ROA) spectrometer, which ensured high fluorescence intensity owing to the strong 532 nm laser excitation. The induced fluorescence was recorded in the same spectrum as the vibrational Raman bands. On the basis of the ligand field theory, most fluorescence spectral peaks could be assigned to f-shell europium transitions. Additional information on the interaction of the lanthanide with the sugar component was provided by measurement of time-dependent fluorescence, as formation of different complexes led to variations in fluorescence decay times. In nuclear magnetic resonance (NMR), the paramagnetic metal ion interacting with the sugars caused specific changes in (13)C chemical shifts. The spectroscopic data and molecular dynamics modeling showed that the interaction between the monosaccharides and Eu ion is rather weak due to the competition of the OH sugar groups with water molecules. However, multiple binding modes are possible, which contributes to the complexity and specificity of the spectra. The induced chirality and fluorescence spectra thus appear to be convenient means for monosaccharide detection and identification. PMID:27525502

  15. The anthracenedione compound bostrycin induces mitochondria-mediated apoptosis in the yeast Saccharomyces cerevisiae.

    PubMed

    Xu, Chunling; Wang, Jiafeng; Gao, Ye; Lin, Huangyu; Du, Lin; Yang, Shanshan; Long, Simei; She, Zhigang; Cai, Xiaoling; Zhou, Shining; Lu, Yongjun

    2010-05-01

    Bostrycin is an anthracenedione with phytotoxic and antibacterial activity that belongs to the large family of quinones. We have isolated bostrycin from the secondary metabolites of a mangrove endophytic fungus, no. 1403, collected from the South China Sea. Using the yeast Saccharomyces cerevisiae as a model, we show that bostrycin inhibits cell proliferation by blocking the cell cycle at G1 phase and ultimately leads to cell death in a time- and dose-dependent manner. Bostrycin-induced lethal cytotoxicity is accompanied with increased levels of intracellular reactive oxygen species and hallmarks of apoptosis such as chromatin condensation, DNA fragmentation and externalization of phosphatidylserine. We further show that bostrycin decreases mitochondrial membrane electric potential and causes mitochondrial destruction during the progression of cell death. Bostrycin-induced cell death was promoted in YCA1 null yeast strain but was partially rescued in AIF1 null mutant both in fermentative and respiratory media, strongly indicating that bostrycin induces apoptosis in yeast cells through a mitochondria-mediated but caspase-independent pathway.

  16. A genetically-based latitudinal cline in the emission of herbivore-induced plant volatile organic compounds.

    PubMed

    Wason, Elizabeth L; Agrawal, Anurag A; Hunter, Mark D

    2013-08-01

    The existence of predictable latitudinal variation in plant defense against herbivores remains controversial. A prevailing view holds that higher levels of plant defense evolve at low latitudes compared to high latitudes as an adaptive plant response to higher herbivore pressure on low-latitude plants. To date, this prediction has not been examined with respect to volatile organic compounds (VOCs) that many plants emit, often thus attracting the natural enemies of herbivores. Here, we compared genetically-based constitutive and herbivore-induced aboveground vegetative VOC emissions from plants originating across a gradient of more than 10° of latitude (>1,500 km). We collected headspace VOCs from Asclepias syriaca (common milkweed) originating from 20 populations across its natural range and grown in a common garden near the range center. Feeding by specialist Danaus plexippus (monarch) larvae induced VOCs, and field environmental conditions (temperature, light, and humidity) also influenced emissions. Monarch damage increased plant VOC concentrations and altered VOC blends. We found that genetically-based induced VOC emissions varied with the latitude of plant population origin, although the pattern followed the reverse of that predicted-induced VOC concentration increased with increasing latitude. This pattern appeared to be driven by a greater induction of sesquiterpenoids at higher latitudes. In contrast, constitutive VOC emission did not vary systematically with latitude, and the induction of green leafy volatiles declined with latitude. Our results do not support the prevailing view that plant defense is greater at lower than at higher latitudes. That the pattern holds only for herbivore-induced VOC emission, and not constitutive emission, suggests that latitudinal variation in VOCs is not a simple adaptive response to climatic factors.

  17. Mechanisms of G1 cell cycle arrest and apoptosis in myeloma cells induced by hybrid-compound histone deacetylase inhibitor

    SciTech Connect

    Fujii, Seiko; Okinaga, Toshinori; Ariyoshi, Wataru; Takahashi, Osamu; Iwanaga, Kenjiro; Nishino, Norikazu; Tominaga, Kazuhiro; Nishihara, Tatsuji

    2013-05-10

    Highlights: •Novel histone deacetylase inhibitor Ky-2, remarkably inhibits myeloma cell growth. •Ky-2 demonstrates no cytotoxicity against normal lymphocytic cells. •Ky-2 induces cell cycle arrest through the cell cycle-associated proteins. •Ky-2 induces Bcl-2-inhibitable apoptosis through a caspase-dependent cascade. -- Abstract: Objectives: Histone deacetylase (HDAC) inhibitors are new therapeutic agents, used to treat various types of malignant cancers. In the present study, we investigated the effects of Ky-2, a hybrid-compound HDAC inhibitor, on the growth of mouse myeloma cells. Materials and methods: Myeloma cells, HS-72, P3U1, and mouse normal cells were used in this study. Effect of HDAC inhibitors on cell viability was determined by WST-assay and trypan blue assay. Cell cycle was analyzed using flow cytometer. The expression of cell cycle regulatory and the apoptosis associated proteins were examined by Western blot analysis. Hoechst’s staining was used to detect apoptotic cells. Results: Our findings showed that Ky-2 decreased the levels of HDACs, while it enhanced acetylation of histone H3. Myeloma cell proliferation was inhibited by Ky-2 treatment. Interestingly, Ky-2 had no cytotoxic effects on mouse normal cells. Ky-2 treatment induced G1-phase cell cycle arrest and accumulation of a sub-G1 phase population, while Western blotting analysis revealed that expressions of the cell cycle-associated proteins were up-regulated. Also, Ky-2 enhanced the cleavage of caspase-9 and -3 in myeloma cells, followed by DNA fragmentation. In addition, Ky-2 was not found to induce apoptosis in bcl-2 overexpressing myeloma cells. Conclusion: These findings suggest that Ky-2 induces apoptosis via a caspase-dependent cascade and Bcl-2-inhibitable mechanism in myeloma cells.

  18. A genetically-based latitudinal cline in the emission of herbivore-induced plant volatile organic compounds.

    PubMed

    Wason, Elizabeth L; Agrawal, Anurag A; Hunter, Mark D

    2013-08-01

    The existence of predictable latitudinal variation in plant defense against herbivores remains controversial. A prevailing view holds that higher levels of plant defense evolve at low latitudes compared to high latitudes as an adaptive plant response to higher herbivore pressure on low-latitude plants. To date, this prediction has not been examined with respect to volatile organic compounds (VOCs) that many plants emit, often thus attracting the natural enemies of herbivores. Here, we compared genetically-based constitutive and herbivore-induced aboveground vegetative VOC emissions from plants originating across a gradient of more than 10° of latitude (>1,500 km). We collected headspace VOCs from Asclepias syriaca (common milkweed) originating from 20 populations across its natural range and grown in a common garden near the range center. Feeding by specialist Danaus plexippus (monarch) larvae induced VOCs, and field environmental conditions (temperature, light, and humidity) also influenced emissions. Monarch damage increased plant VOC concentrations and altered VOC blends. We found that genetically-based induced VOC emissions varied with the latitude of plant population origin, although the pattern followed the reverse of that predicted-induced VOC concentration increased with increasing latitude. This pattern appeared to be driven by a greater induction of sesquiterpenoids at higher latitudes. In contrast, constitutive VOC emission did not vary systematically with latitude, and the induction of green leafy volatiles declined with latitude. Our results do not support the prevailing view that plant defense is greater at lower than at higher latitudes. That the pattern holds only for herbivore-induced VOC emission, and not constitutive emission, suggests that latitudinal variation in VOCs is not a simple adaptive response to climatic factors. PMID:23888386

  19. Protective Effect of Total Phenolic Compounds from Inula helenium on Hydrogen Peroxide-induced Oxidative Stress in SH-SY5Y Cells

    PubMed Central

    Wang, J.; Zhao, Y. M.; Zhang, B.; Guo, C. Y.

    2015-01-01

    Inula helenium has been reported to contain a large amount of phenolic compounds, which have shown promise in scavenging free radicals and prevention of neurodegenerative diseases. This study is to investigate the neuroprotective effects of total phenolic compounds from I. helenium on hydrogen peroxide-induced oxidative damage in human SH-SY5Y cells. Antioxidant capacity of total phenolic compounds was determined by radical scavenging activity, the level of intracellular reactive oxygen species and superoxide dismutase activity. The cytotoxicity of total phenolic compounds was determined using a cell counting kit-8 assay. The effect of total phenolic compounds on cell apoptosis due to hydrogen peroxide-induced oxidative damage was detected by Hoechst 33258 and Annexin-V/PI staining using fluorescence microscope and flow cytometry, respectively. Mitochondrial function was evaluated using the mitochondrial membrane potential and mitochondrial ATP synthesis by JC-1 dye and high performance liquid chromatography, respectively. It was shown that hydrogen peroxide significantly induced the loss of cell viability, increment of apoptosis, formation of reactive oxygen species, reduction of superoxide dismutase activity, decrease in mitochondrial membrane potential and a decrease in adenosine triphosphate production. On the other hand, total phenolic compounds dose-dependently reversed these effects. This study suggests that total phenolic compounds exert neuroprotective effects against hydrogen peroxide-induced oxidative damage via blocking reactive oxygen species production and improving mitochondrial function. The potential of total phenolic compounds and its neuroprotective mechanisms in attenuating hydrogen peroxide-induced oxidative stress-related cytotoxicity is worth further exploration. PMID:26009648

  20. Cross-nucleation between clathrate hydrate polymorphs: Assessing the role of stability, growth rate, and structure matching

    SciTech Connect

    Nguyen, Andrew H.; Molinero, Valeria

    2014-02-28

    Cross-nucleation is a phenomenon where a new crystal nucleates and grows upon the surface of a different polymorph. Previous studies indicate that faster growth rate of the new crystal is a necessary but not sufficient condition for cross-nucleation. The thermodynamic stability of the different polymorphs can also affect cross-nucleation by modulating the rates of crystal growth. The interplay between thermodynamic stability of the polymorphs involved, the growth rate of the crystals, and the need for creation of an interfacial transition layer that seamlessly connects the two structures has not yet been fully elucidated. Predicting cross-nucleation is particularly challenging for clathrate hydrates, for which there are sometimes several polymorphs with similar stability and for which growth rates are not known. In this work, we use molecular dynamics simulations to investigate which factor (stability, growth rate, or formation of interfacial transition layer) controls cross-nucleation between the four known Frank-Kasper clathrate hydrate polymorphs: sI, sII, TS, and HS-I. We investigate the growth and cross-nucleation of these four hydrates filled with a set of guest molecules that produce different order of stabilities for the four crystal structures. We determine that the growth rate of sII clathrate is the fastest, followed by TS, HS-I, and sI. We find that cross-nucleation into or from sII clathrates is preceded by the formation of an interfacial transition layer at the seed crystal/liquid interface because sII does not share a crystal plane with sI, HS-I, or TS. Cross-nucleation between the latter three can occur seamlessly and is determined only by their growth rates. Our results indicate that nucleation of an interfacial transition layer between non-matching polymorphs can control cross-nucleation or lack thereof under conditions of small driving force. Under conditions of sufficient supercooling clathrate hydrate polymorphs cross-nucleate into the fastest

  1. Cross-nucleation between clathrate hydrate polymorphs: assessing the role of stability, growth rate, and structure matching.

    PubMed

    Nguyen, Andrew H; Molinero, Valeria

    2014-02-28

    Cross-nucleation is a phenomenon where a new crystal nucleates and grows upon the surface of a different polymorph. Previous studies indicate that faster growth rate of the new crystal is a necessary but not sufficient condition for cross-nucleation. The thermodynamic stability of the different polymorphs can also affect cross-nucleation by modulating the rates of crystal growth. The interplay between thermodynamic stability of the polymorphs involved, the growth rate of the crystals, and the need for creation of an interfacial transition layer that seamlessly connects the two structures has not yet been fully elucidated. Predicting cross-nucleation is particularly challenging for clathrate hydrates, for which there are sometimes several polymorphs with similar stability and for which growth rates are not known. In this work, we use molecular dynamics simulations to investigate which factor (stability, growth rate, or formation of interfacial transition layer) controls cross-nucleation between the four known Frank-Kasper clathrate hydrate polymorphs: sI, sII, TS, and HS-I. We investigate the growth and cross-nucleation of these four hydrates filled with a set of guest molecules that produce different order of stabilities for the four crystal structures. We determine that the growth rate of sII clathrate is the fastest, followed by TS, HS-I, and sI. We find that cross-nucleation into or from sII clathrates is preceded by the formation of an interfacial transition layer at the seed crystal/liquid interface because sII does not share a crystal plane with sI, HS-I, or TS. Cross-nucleation between the latter three can occur seamlessly and is determined only by their growth rates. Our results indicate that nucleation of an interfacial transition layer between non-matching polymorphs can control cross-nucleation or lack thereof under conditions of small driving force. Under conditions of sufficient supercooling clathrate hydrate polymorphs cross-nucleate into the fastest

  2. Effects of Water in Synthetic Lubricant Systems and Clathrate Formation: A Literature Search and Review

    SciTech Connect

    Rohatgi, Ngoc Dung T.

    2001-08-08

    An extensive literature search and a confidential survey were critically analyzed to determine the effects of water on the stability of hydrofluorocarbon/synthetic lubricant systems and to identify key areas requiring further investigation. Following are highlights from the analysis: Clathrate hydrates are solid solutions formed when water molecules are linked through hydrogen bonding creating cavities that can enclose various guest molecules from hydrate formers, such as hydrofluorocarbons R-32, R-125, R-134a, R-407C and R-410A. The four methods for preventing clathrate formation were drying the gas, heating it, reducing its pressure, or using inhibitors. The hydrolysis of polyolester lubricants was mostly acid-catalyzed and its reaction rate constant typically followed the Arrhenius equation of an activated process. Hydrolytic stability improved with hindered molecular structures, and with the presence of acid catcher additives and desiccants. Water vapor can effect the adsorption of long-chain fatty acids and the chemistry of formation of protective oxide film. However, these effects on lubrication can be either positive or negative. Fifty to sixty percent of the moisture injected into an air-conditioning system remained in the refrigerant and the rest mixed with the compressor oil. In an automotive air-conditioning system using R-134a, ice would form at 0 C evaporating temperature when the water content in the vapor refrigerant on the low-pressure side was more than 350 ppm. Moisture would cause the embrittlement of polyethylene terephthalate and the hydrolysis of polyesters, but would reduce the effect of amine additives on fluoroelastomer rubbers. The reactions of water with refrigerants and lubricants would cause formicary and large-pit corrosion in copper tubes, as well as copper plating and sludge formation. Moreover, blockage of capillary tubes increased rapidly in the presence of water. Twenty-four companies responded to the survey. From the responses

  3. Bioactive compounds from crocodile (Crocodylus siamensis) white blood cells induced apoptotic cell death in hela cells.

    PubMed

    Patathananone, Supawadee; Thammasirirak, Sompong; Daduang, Jureerut; Chung, Jing Gung; Temsiripong, Yosapong; Daduang, Sakda

    2016-08-01

    Crocodile (Crocodylus siamensis) white blood cell extracts (WBCex) were examined for anticancer activity in HeLa cell lines using the MTT assay. The percentage viability of HeLa cells significantly deceased after treatment with WBCex in a dose- and time-dependent manner. The IC50 dose was suggested to be approximately 225 μg/mL protein. Apoptotic cell death occurred in a time-dependent manner based on investigation by flow cytometry using annexin V-FITC and PI staining. DAPI nucleic acid staining indicated increased chromatin condensation. Caspase-3, -8 and -9 activities also increased, suggesting the induction of the caspase-dependent apoptotic pathway. Furthermore, the mitochondrial membrane potential (ΔΨm ) of HeLa cells was lost as a result of increasing levels of Bax and reduced levels of Bcl-2, Bcl-XL, Bcl-Xs, and XIAP. The decreased ΔΨm led to the release of cytochrome c and the activation of caspase-9 and -3. Apoptosis-inducing factor translocated into the nuclei, and endonuclease G (Endo G) was released from the mitochondria. These results suggest that anticancer agents in WBCex can induce apoptosis in HeLa cells via both caspase-dependent and -independent pathways. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 986-997, 2016.

  4. Utilizing small nutrient compounds as enhancers of exercise-induced mitochondrial biogenesis

    PubMed Central

    Craig, Daniel M.; Ashcroft, Stephen P.; Belew, Micah Y.; Stocks, Ben; Currell, Kevin; Baar, Keith; Philp, Andrew

    2015-01-01

    Endurance exercise, when performed regularly as part of a training program, leads to increases in whole-body and skeletal muscle-specific oxidative capacity. At the cellular level, this adaptive response is manifested by an increased number of oxidative fibers (Type I and IIA myosin heavy chain), an increase in capillarity and an increase in mitochondrial biogenesis. The increase in mitochondrial biogenesis (increased volume and functional capacity) is fundamentally important as it leads to greater rates of oxidative phosphorylation and an improved capacity to utilize fatty acids during sub-maximal exercise. Given the importance of mitochondrial biogenesis for skeletal muscle performance, considerable attention has been given to understanding the molecular cues stimulated by endurance exercise that culminate in this adaptive response. In turn, this research has led to the identification of pharmaceutical compounds and small nutritional bioactive ingredients that appear able to amplify exercise-responsive signaling pathways in skeletal muscle. The aim of this review is to discuss these purported exercise mimetics and bioactive ingredients in the context of mitochondrial biogenesis in skeletal muscle. We will examine proposed modes of action, discuss evidence of application in skeletal muscle in vivo and finally comment on the feasibility of such approaches to support endurance-training applications in humans. PMID:26578969

  5. Giant rotating magnetocaloric effect induced by highly texturing in polycrystalline DyNiSi compound.

    PubMed

    Zhang, Hu; Li, YaWei; Liu, Enke; Ke, YaJiao; Jin, JinLing; Long, Yi; Shen, BaoGen

    2015-01-01

    Large rotating magnetocaloric effect (MCE) has been observed in some single crystals due to strong magnetocrystalline anisotropy. By utilizing the rotating MCE, a new type of rotary magnetic refrigerator can be constructed, which could be more simplified and efficient than the conventional one. However, compared with polycrystalline materials, the high cost and complexity of preparation for single crystals hinder the development of this novel magnetic refrigeration technology. For the first time, here we observe giant rotating MCE in textured DyNiSi polycrystalline material, which is larger than those of most rotating magnetic refrigerants reported so far. This result suggests that DyNiSi compound could be attractive candidate of magnetic refrigerants for novel rotary magnetic refrigerator. By considering the influence of demagnetization effect on MCE, the origin of large rotating MCE in textured DyNiSi is attributed to the coexistence of strong magnetocrystalline anisotropy and highly preferred orientation. Our study on textured DyNiSi not only provides a new magnetic refrigerant with large rotating MCE for low temperature magnetic refrigeration, but also opens a new way to exploit magnetic refrigeration materials with large rotating MCE, which will be highly beneficial to the development of rotating magnetic refrigeration technology. PMID:26159558

  6. Giant rotating magnetocaloric effect induced by highly texturing in polycrystalline DyNiSi compound

    NASA Astrophysics Data System (ADS)

    Zhang, Hu; Li, Yawei; Liu, Enke; Ke, Yajiao; Jin, Jinling; Long, Yi; Shen, Baogen

    2015-07-01

    Large rotating magnetocaloric effect (MCE) has been observed in some single crystals due to strong magnetocrystalline anisotropy. By utilizing the rotating MCE, a new type of rotary magnetic refrigerator can be constructed, which could be more simplified and efficient than the conventional one. However, compared with polycrystalline materials, the high cost and complexity of preparation for single crystals hinder the development of this novel magnetic refrigeration technology. For the first time, here we observe giant rotating MCE in textured DyNiSi polycrystalline material, which is larger than those of most rotating magnetic refrigerants reported so far. This result suggests that DyNiSi compound could be attractive candidate of magnetic refrigerants for novel rotary magnetic refrigerator. By considering the influence of demagnetization effect on MCE, the origin of large rotating MCE in textured DyNiSi is attributed to the coexistence of strong magnetocrystalline anisotropy and highly preferred orientation. Our study on textured DyNiSi not only provides a new magnetic refrigerant with large rotating MCE for low temperature magnetic refrigeration, but also opens a new way to exploit magnetic refrigeration materials with large rotating MCE, which will be highly beneficial to the development of rotating magnetic refrigeration technology.

  7. Protection of Erwinia amylovora bacteriophage Y2 from UV-induced damage by natural compounds

    PubMed Central

    Born, Yannick; Bosshard, Lars; Duffy, Brion; Loessner, Martin J.; Fieseler, Lars

    2015-01-01

    Bacteriophages have regained much attention as biocontrol agents against bacterial pathogens. However, with respect to stability, phages are biomolecules and are therefore sensitive to a number of environmental influences. UV-irradiation can readily inactivate phage infectivity, which impedes their potential application in the plant phyllosphere. Therefore, phages for control of Erwinia amylovora, the causative agent of fire blight, need to be protected from UV-damage by adequate measures. We investigated the protective effect of different light-absorbing substances on phage particles exposed to UV-light. For this, natural extracts from carrot, red pepper, and beetroot, casein and soy peptone in solution, and purified substances such as astaxanthin, aromatic amino acids, and Tween 80 were prepared and tested as natural sunscreens for phage. All compounds were found to significantly increase half-life of UV-irradiated phage particles and they did not negatively affect phage viability or infectivity. Altogether, a range of readily available, natural substances are suitable as UV-protectants to prevent phage particles from UV-light damage. PMID:26904378

  8. Protective Actions of 17β-Estradiol and Progesterone on Oxidative Neuronal Injury Induced by Organometallic Compounds

    PubMed Central

    Ishihara, Yasuhiro; Takemoto, Takuya; Yamazaki, Takeshi

    2015-01-01

    Steroid hormones synthesized in and secreted from peripheral endocrine glands pass through the blood-brain barrier and play a role in the central nervous system. In addition, the brain possesses an inherent endocrine system and synthesizes steroid hormones known as neurosteroids. Increasing evidence shows that neuroactive steroids protect the central nervous system from various harmful stimuli. Reports show that the neuroprotective actions of steroid hormones attenuate oxidative stress. In this review, we summarize the antioxidative effects of neuroactive steroids, especially 17β-estradiol and progesterone, on neuronal injury in the central nervous system under various pathological conditions, and then describe our recent findings concerning the neuroprotective actions of 17β-estradiol and progesterone on oxidative neuronal injury induced by organometallic compounds, tributyltin, and methylmercury. PMID:25815107

  9. On the suitability of partially clathrated ice for analysis of concentration and δ 13C of palaeo-atmospheric CO 2

    NASA Astrophysics Data System (ADS)

    Schaefer, Hinrich; Lourantou, Anna; Chappellaz, Jérôme; Lüthi, Dieter; Bereiter, Bernhard; Barnola, Jean-Marc

    2011-07-01

    The stable carbon isotopic signature of carbon dioxide (δ 13CO 2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric δ 13CO 2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO 2 concentration values, presenting a worst-case test for δ 13CO 2 reconstructions. Even so, the reconstructed atmospheric δ 13CO 2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16‰ magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of δ 13CO 2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

  10. CO 2 and O 2/N 2 variations in and just below the bubble-clathrate transformation zone of Antarctic ice cores

    NASA Astrophysics Data System (ADS)

    Lüthi, Dieter; Bereiter, Bernhard; Stauffer, Bernhard; Winkler, Renato; Schwander, Jakob; Kindler, Philippe; Leuenberger, Markus; Kipfstuhl, Sepp; Capron, Emilie; Landais, Amaelle; Fischer, Hubertus; Stocker, Thomas F.

    2010-08-01

    CO 2 measurements on the EPICA (European Project for Ice Coring in Antarctica) DML ice core in depth levels just below the bubble ice-clathrate ice transformation zone (1230-2240 m depth) were performed. In the youngest part (1230-1600 m), they reveal variations of up to 25 ppmv around the mean atmospheric concentration within centimetres, corresponding to a snow deposition interval of a few years. Similar results are found at corresponding depth regions of the Dome C and the Talos Dome ice cores. Since we can exclude all hitherto known processes altering the concentration of CO 2 in ice cores, we present a hypothesis about spatial fractionation of air components related to episodically increasing clathrate formation followed by diffusion processes from bubbles to clathrates. This hypothesis is supported by optical line-scan observations and by O 2/N 2 measurements at the same depth where strong CO 2 variations are detected. Below the clathrate formation zone, this small-scale fractionation process is slowly smoothed out, most likely by diffusion, regaining the initial mean atmospheric concentration. Although this process compromises the representativeness of a single CO 2 measurement on small ice samples in the clathrate formation zone of an ice core, it does not affect the mean atmospheric CO 2 concentration if CO 2 values are averaged over a sufficiently long depth scale (> 10 cm in case of the EPICA DML ice core).

  11. Highly confined water: two-dimensional ice, amorphous ice, and clathrate hydrates.

    PubMed

    Zhao, Wen-Hui; Wang, Lu; Bai, Jaeil; Yuan, Lan-Feng; Yang, Jinlong; Zeng, Xiao Cheng

    2014-08-19

    Understanding phase behavior of highly confined water, ice, amorphous ice, and clathrate hydrates (or gas hydrates), not only enriches our view of phase transitions and structures of quasi-two-dimensional (Q2D) solids not seen in the bulk phases but also has important implications for diverse phenomena at the intersection between physical chemistry, cell biology, chemical engineering, and nanoscience. Relevant examples include, among others, boundary lubrication in nanofluidic and lab-on-a-chip devices, synthesis of antifreeze proteins for ice-growth inhibition, rapid cooling of biological suspensions or quenching emulsified water under high pressure, and storage of H2 and CO2 in gas hydrates. Classical molecular simulation (MD) is an indispensable tool to explore states and properties of highly confined water and ice. It also has the advantage of precisely monitoring the time and spatial domains in the sub-picosecond and sub-nanometer scales, which are difficult to control in laboratory experiments, and yet allows relatively long simulation at the 10(2) ns time scale that is impractical with ab initio molecular dynamics simulations. In this Account, we present an overview of our MD simulation studies of the structures and phase behaviors of highly confined water, ice, amorphous ice, and clathrate, in slit graphene nanopores. We survey six crystalline phases of monolayer (ML) ice revealed from MD simulations, including one low-density, one mid-density, and four high-density ML ices. We show additional supporting evidence on the structural stabilities of the four high-density ML ices in the vacuum (without the graphene confinement), for the first time, through quantum density-functional theory optimization of their free-standing structures at zero temperature. In addition, we summarize various low-density, high-density, and very-high-density Q2D bilayer (BL) ice and amorphous ice structures revealed from MD simulations. These simulations reinforce the notion that

  12. Mycofumigation by the Volatile Organic Compound-Producing Fungus Muscodor albus Induces Bacterial Cell Death through DNA Damage

    PubMed Central

    Alpha, Cambria J.; Campos, Manuel; Jacobs-Wagner, Christine

    2014-01-01

    Muscodor albus belongs to a genus of endophytic fungi that inhibit and kill other fungi, bacteria, and insects through production of a complex mixture of volatile organic compounds (VOCs). This process of mycofumigation has found commercial application for control of human and plant pathogens, but the mechanism of the VOC toxicity is unknown. Here, the mode of action of these volatiles was investigated through a series of genetic screens and biochemical assays. A single-gene knockout screen revealed high sensitivity for Escherichia coli lacking enzymes in the pathways of DNA repair, DNA metabolic process, and response to stress when exposed to the VOCs of M. albus. Furthermore, the sensitivity of knockouts involved in the repair of specific DNA alkyl adducts suggests that the VOCs may induce alkylation. Evidence of DNA damage suggests that these adducts lead to breaks during DNA replication or transcription if not properly repaired. Additional cytotoxicity profiling indicated that during VOC exposure, E. coli became filamentous and demonstrated an increase in cellular membrane fluidity. The volatile nature of the toxic compounds produced by M. albus and their broad range of inhibition make this fungus an attractive biological agent. Understanding the antimicrobial effects and the VOC mode of action will inform the utility and safety of potential mycofumigation applications for M. albus. PMID:25452287

  13. Mycofumigation by the volatile organic compound-producing Fungus Muscodor albus induces bacterial cell death through DNA damage.

    PubMed

    Alpha, Cambria J; Campos, Manuel; Jacobs-Wagner, Christine; Strobel, Scott A

    2015-02-01

    Muscodor albus belongs to a genus of endophytic fungi that inhibit and kill other fungi, bacteria, and insects through production of a complex mixture of volatile organic compounds (VOCs). This process of mycofumigation has found commercial application for control of human and plant pathogens, but the mechanism of the VOC toxicity is unknown. Here, the mode of action of these volatiles was investigated through a series of genetic screens and biochemical assays. A single-gene knockout screen revealed high sensitivity for Escherichia coli lacking enzymes in the pathways of DNA repair, DNA metabolic process, and response to stress when exposed to the VOCs of M. albus. Furthermore, the sensitivity of knockouts involved in the repair of specific DNA alkyl adducts suggests that the VOCs may induce alkylation. Evidence of DNA damage suggests that these adducts lead to breaks during DNA replication or transcription if not properly repaired. Additional cytotoxicity profiling indicated that during VOC exposure, E. coli became filamentous and demonstrated an increase in cellular membrane fluidity. The volatile nature of the toxic compounds produced by M. albus and their broad range of inhibition make this fungus an attractive biological agent. Understanding the antimicrobial effects and the VOC mode of action will inform the utility and safety of potential mycofumigation applications for M. albus.

  14. High-temperature- and high-pressure-induced formation of the Laves-phase compound XeS2

    NASA Astrophysics Data System (ADS)

    Yan, Xiaozhen; Chen, Yangmei; Xiang, Shikai; Kuang, Xiaoyu; Bi, Yan; Chen, Haiyan

    2016-06-01

    We explore the reactivity of xenon with sulfur under high pressure, using unbiased structure searching techniques combined with first-principles calculations, which identify a stable XeS2 compound crystallized in a Laves phase with hypercoordinated (16-fold) Xe at 191 GPa and 0 K. Taking the thermal effects into account, we find that increasing the temperature could further stabilize it. The formation of XeS2 is a consequence of pressure-induced charge transfer from Xe to S atoms and the delocalization of Xe 5 p and S 3 p electrons. Meanwhile, the stabilization into a Laves phase of XeS2 is the result of delocalized chemical bonding and the need for optimum structure packing. The present discussion of the formation mechanism in XeS2 is general, and conclusions can be used to understand the formation of other Laves-phase compounds and the Xe chemistry that allows closed-shell Xe to participate in chemical reactions.

  15. A novel platinum compound inhibits constitutive Stat3 signaling and induces cell cycle arrest and apoptosis of malignant cells.

    PubMed

    Turkson, James; Zhang, Shumin; Mora, Linda B; Burns, Audrey; Sebti, Said; Jove, Richard

    2005-09-23

    Previous studies have established constitutive activation of Stat3 protein as one of the molecular changes required for tumorigenesis. To develop novel therapeutics for tumors harboring constitutively active Stat3, compounds from the NCI 2000 diversity set were evaluated for inhibition of Stat3 DNA-binding activity in vitro. Of these, a novel platinum (IV) compound, IS3 295, interacted with Stat3 and inhibited its binding to specific DNA-response elements. Further analysis suggested noncompetitive-type kinetics for the inhibition of Stat3 binding to DNA. In human and mouse tumor cell lines with constitutively active Stat3, IS3 295 selectively attenuated Stat3 signaling, thereby inducing cell growth arrest at G0/G1 phase and apoptosis. Moreover, in transformed cells, IS3 295 repressed expression of cyclin D1 and bcl-xL, two of the known Stat3-regulated genes that are overexpressed in malignant cells, suggesting that IS3 295 mediates anti-tumor cell activity in part by blocking Stat3-mediated sub-version of cell growth and apoptotic signals. Together, our findings provide evidence for the inhibition of Stat3 activity and biological functions by IS3 295 through interaction with Stat3 protein. This study represents a significant advance in small molecule-based approaches to target Stat3 and suggests potential new applications for platinum (IV) complexes as modulators of the Stat3 pathway for cancer therapy.

  16. Production of organic compounds in plasmas: A comparison among electric sparks, laser-induced plasmas and UV light

    NASA Technical Reports Server (NTRS)

    Scattergood, T. W.; Mckay, C. P.; Borucki, W. J.; Giver, L. P.; Vanghyseghem, H.; Parris, J. E.; Miller, S. L.

    1991-01-01

    In order to study the production of organic compounds in plasmas (and shocks), various mixtures of N2, CH4, and H2, modeling the atmosphere of Titan, were exposed to discrete sparks, laser-induced plasmas (LIP) and ultraviolet light. The yields of HCN and simple hydrocarbons were measured and compared to those calculated from a simple quenched thermodynamic equilibrium model. The agreement between experiment and theory was fair for HCN and C2H2. However, the yields of C2H6 and other hydrocarbons were much higher than those predicted by the model. Our experiments suggest that photolysis by ultraviolet light from the plasma is an important process in the synthesis. This was confirmed by the photolysis of gas samples exposed to the light, but not to the plasma or shock waves. The results of these experiments demonstrate that, in addition to the well-known efficient synthesis of organic compounds in plasmas, the yields of saturated species, e.g., ethane, may be higher than predicted by theory and that LIP provide a convenient and clean way of simulating planetary lightning and impact plasmas in the laboratory.

  17. [Black water bloom induced by different types of organic matters and forming mechanisms of major odorous compounds].

    PubMed

    Lu, Xin; Feng, Zi-Yan; Shang, Jing-Ge; Fan, Cheng-Xin; Deng, Jian-Cai

    2012-09-01

    Self-made glass reactors were employed to study the occurrence of black water bloom induced by different types of organic matters, to clarify the precursor of volatile organic sulfur compounds (VOSCs), and then to preliminarily study its degradation mechanisms under laboratory-controlled conditions. Our research indicated that provided organic matrix were as high as 1.0 g x L(-1), all organic matters could blacken the lake water regardless of sulfur appearance or not. However, compared with sulfur-free compounds that took more than 13 d to blacken the water, sulfur containing materials could accelerate the occurrence of black color to 7-13 d and increase the water chromaticity to above 410 which causing offensive odor consisted chiefly of DMDS, DMTS and DMTeS. Based on the function of methionine on the production of VOSCs, methionine was identified to be the precursors of VOSCs. Methionine was readily broke down by sulfate-reducing bacteria (SRB) (also other bacteria) (at 95% with the duration of 35 d) to produce hydrogen sulfide, methanethiol, and dominantly dimethylpolysulfides such as DMDS, DMTS and DMTeS. And the occurrence of black color had been advanced from 13 d to 8 d. Methanogenic bacteria slightly inhibited the degradation of methionine and reduced the evolution of sulfide. Therefore, the addition of methanogenic bacteria inhibitor set the formation of black color ahead by 1 d. Methionine was also degraded by nonbiodegradation, but it was a secondary pathway and cannot completely degrade methionine to blacken the water.

  18. Apoptosis of cerebellar granule cells induced by organotin compounds found in drinking water: involvement of MAP kinases.

    PubMed

    Mundy, William R; Freudenrich, Theresa M

    2006-01-01

    Mono- and dialkyl organotin compounds are used primarily as heat stabilizers in polyvinyl chloride (PVC) plastics. Recently, monomethyltin (MMT), dimethyltin (DMT), monobutyltin (MBT), and dibutyltin (DBT) have been detected in water from homes and businesses served by PVC pipes. While trialkyl organotins such as trimethyltin (TMT) and triethyltin (TET) are well known neurotoxicants, the toxicity of the mono- and dialkyl organotins is not well described. The present study compared the cytotoxicity of organotins found in drinking water with the known neurotoxicant TMT in primary cultures of cerebellar granule cells, and examined the role of MAP kinase signaling in organotin-induced cell death. Twenty-four hour exposure to TMT resulted in a concentration-dependent decrease in cell viability with an EC(50) of 3 microM. Exposure to MMT, DMT, and MBT at concentrations up to 10 microM had no effect. DBT, however, was very potent, and decreased cell viability with an EC(50) of 0.3 microM. Staining of organotin-treated cerebellar granule cells with the nuclear dye Syto-13 revealed that TMT and DBT, but not MMT, DMT, or MBT, produced condensation and fragmentation of chromatin characteristic of apoptosis. TMT- and DBT-induced apoptosis was confirmed using TUNEL staining and measurement of PARP cleavage. Activation of MAP kinase pathways was examined after 6 h of exposure to the organotins which induced apoptosis. Both TMT and DBT activated ERK1/2, but only TMT activated the JNK/c-Jun and p38 pathways. Pharmacologic blockade of JNK/c-Jun and p38 activation significantly decreased apoptosis produced by TMT, but not by DBT. These results show that DBT is a potent neurotoxicant in vitro, but unlike TMT, does not induce cell death via activation of MAP kinase signaling.

  19. A novel isoquinoline compound abolishes chronic unpredictable mild stress-induced depressive-like behavior in mice.

    PubMed

    Pesarico, Ana Paula; Sartori, Gláubia; Brüning, César A; Mantovani, Anderson C; Duarte, Thiago; Zeni, Gilson; Nogueira, Cristina Wayne

    2016-07-01

    Chronic unpredictable mild stress (CUMS) elicits aspects of cognitive and behavioral alterations that can be used to model comparable aspects of depression in humans. The aim of the present study was to investigate the antidepressant-like potential of 7-fluoro-1,3-diphenylisoquinoline-1-amine (FDPI), a novel isoquinoline compound, in CUMS, a model that meets face, construct and predictive criteria for validity. Swiss mice were subjected to different stress paradigms daily for a period of 35 days to induce the depressive-like behavior. The animals received concomitant FDPI (0.1 and 1mg/kg, intragastric) or paroxetine (8mg/kg, intraperitoneal) and CUMS. The behavioral tests (splash test, tail suspension test, modified forced swimming test and locomotor activity) were performed. The levels of cytokines, corticosterone and adrenocorticotropic (ACTH) hormones were determined in the mouse prefrontal cortex and serum. The synaptosomal [(3)H] serotonin (5-HT) uptake, nuclear factor (NF)-κB, tyrosine kinase receptor (TrkB) and pro-brain-derived neurotrophic factor (BDNF) levels were determined in the mouse prefrontal cortex. CUMS induced a depressive-like behavior in mice, which was demonstrated in the modified forced swimming, tail suspension and splash tests. FDPI at both doses prevented depressive-like behavior induced by CUMS, without altering the locomotor activity of mice. FDPI at the highest dose prevented the increase in the levels of NF-kB, pro-inflammatory cytokines, corticosterone and ACTH and modulated [(3)H]5-HT uptake and the proBDNF/TrkB signaling pathway altered by CUMS. The present findings demonstrated that FDPI elicited an antidepressant-like effect in a model of stress-induced depression. PMID:27036647

  20. Production of organic compounds in plasmas: a comparison among electric sparks, laser-induced plasmas, and UV light.

    PubMed

    Scattergood, T W; McKay, C P; Borucki, W J; Giver, L P; Van Ghyseghem, H; Parris, J E; Miller, S L

    1989-01-01

    The chemistry in planetary atmospheres that is induced by processes associated with high-temperature plasmas is of broad interest because such processes may explain many of the chemical species observed. There are at least two important phenomena that are known to generate plasmas (and shocks) in planetary atmospheres: lightning and meteor impacts. For both phenomena, rapid heating of atmospheric gases leads to formation of a high-temperature plasma which emits radiation and produces shock waves that propagate through the surrounding atmosphere. These processes initiate chemical reactions that can transform simple gases into more complex compounds. In order to study the production of organic compounds in plasmas (shocks), various mixtures of N2, CH4, and H2, modeling the atmosphere of Titan, were exposed to discrete sparks, laser-induced plasmas (LIP), an ultraviolet radiation. The yields of HCN and several simple hydrocarbons were measured by gas chromatography and compared to those calculated from a simple quenched thermodynamic equilibrium model. The agreement between experiment and theory was fair for HCN and C2H2. However, the agreement for C2H6 and the other hydrocarbons was poor, indicating that a more comprehensive theory is needed. Our experiments suggest that photolysis by ultraviolet light from the plasma is an important process in the synthesis. This was confirmed by the photolysis of gas samples exposed to the light but not to the shock waves emitted by the sparks. Hence, the results of these experiments demonstrate that the thermodynamic equilibrium theory does not adequately model lightning and meteor impacts and that photolysis must be included. Finally, the similarity in yields between the spark and the LIP experiments suggest that LIP provide valid and clean simulations of lightning and meteor impacts and that photolysis must be included. Finally, the similarity in yields between the spark and the LIP experiments suggests that LIP provide valid

  1. Lysergic acid diethylamide antagonizes shaking induced in rats by five chemically different compounds.

    PubMed

    Cowan, A; Watson, T

    1978-04-14

    Thyrotropin-releasing hormone (TRH), sodium valproate, AF-3-5 (1-[2-hydroxyphenyl]-4-[3-nitrophenyl]-1,2,3,6-tetrahydropyrimidine-2-one), RX336-M (7,8-dihydro-5',6'-dimethylcyclohex-5'-eno-1',2',8',14 codeinone), and Sgd 8473 (alpha-[4-chlorobenzylideneamino)-oxy]-isobutyric acid) each induced repetitive shaking of the body of rats after intraperitoneal injection. This action of the five diverse chemicals appears to be subserved by a common pharmacological component, because pretreatment with d-lysergic acid diethylamide (0.03--1.0 mg kg-1, s.c.) attenuated the shaking behavior in a dose-related manner, and cross tolerance was found between RX336-M and TRH, sodium valproate, and AG-3-5.

  2. Kinetic model of atomic and molecular emissions in laser-induced breakdown spectroscopy of organic compounds.

    PubMed

    Ma, Qianli; Dagdigian, Paul J

    2011-07-01

    A kinetic model previously developed to predict the relative intensities of atomic emission lines in laser-induced breakdown spectroscopy has been extended to include processes related to CN and C(2) molecular emissions. Simulations with this model were performed to predict the relative excited-state populations. The results from the simulations are compared with experimentally determined excited-state populations from 1,064 nm laser irradiation of organic residues on aluminum foil. The model reasonably predicts the relative intensity of the molecular emissions. Significantly, the model reproduces the vastly different temporal profiles of the atomic and molecular emissions. The latter are found to extend to much longer times after the laser pulse, and this appears to be due to the increasing concentration of the molecules versus time. From the simulations, the important processes affecting the CN and C(2) concentrations are identified.

  3. Epicoccum nigrum P16, a Sugarcane Endophyte, Produces Antifungal Compounds and Induces Root Growth

    PubMed Central

    Fávaro, Léia Cecilia de Lima; Sebastianes, Fernanda Luiza de Souza; Araújo, Welington Luiz

    2012-01-01

    Background Sugarcane is one of the most important crops in Brazil, mainly because of its use in biofuel production. Recent studies have sought to determine the role of sugarcane endophytic microbial diversity in microorganism-plant interactions, and their biotechnological potential. Epicoccum nigrum is an important sugarcane endophytic fungus that has been associated with the biological control of phytopathogens, and the production of secondary metabolites. In spite of several studies carried out to define the better conditions to use E. nigrum in different crops, little is known about the establishment of an endophytic interaction, and its potential effects on plant physiology. Methodology/Principal Findings We report an approach based on inoculation followed by re-isolation, molecular monitoring, microscopic analysis, plant growth responses to fungal colonization, and antimicrobial activity tests to study the basic aspects of the E. nigrum endophytic interaction with sugarcane, and the effects of colonization on plant physiology. The results indicate that E. nigrum was capable of increasing the root system biomass and producing compounds that inhibit the in vitro growth of sugarcane pathogens Fusarium verticillioides, Colletotrichum falcatum, Ceratocystis paradoxa, and Xanthomomas albilineans. In addition, E. nigrum preferentially colonizes the sugarcane surface and, occasionally, the endophytic environment. Conclusions/Significance Our work demonstrates that E. nigrum has great potential for sugarcane crop application because it is capable of increasing the root system biomass and controlling pathogens. The study of the basic aspects of the interaction of E. nigrum with sugarcane demonstrated the facultative endophytism of E. nigrum and its preference for the phylloplane environment, which should be considered in future studies of biocontrol using this species. In addition, this work contributes to the knowledge of the interaction of this ubiquitous endophyte

  4. Large drought-induced variations in oak leaf volatile organic compound emissions during PINOT NOIR 2012.

    PubMed

    Geron, Chris; Daly, Ryan; Harley, Peter; Rasmussen, Rei; Seco, Roger; Guenther, Alex; Karl, Thomas; Gu, Lianhong

    2016-03-01

    Leaf-level isoprene and monoterpene emissions were collected and analyzed from five of the most abundant oak (Quercus) species in Central Missouri's Ozarks Region in 2012 during PINOT NOIR (Particle Investigations at a Northern Ozarks Tower - NOx, Oxidants, Isoprene Research). June measurements, prior to the onset of severe drought, showed isoprene emission rates and leaf temperature responses similar to those previously reported in the literature and used in Biogenic Volatile Organic Compound (BVOC) emission models. During the peak of the drought in August, isoprene emission rates were substantially reduced, and response to temperature was dramatically altered, especially for the species in the red oak subgenus (Erythrobalanus). Quercus stellata (in the white oak subgenus Leucobalanus), on the other hand, increased its isoprene emission rate during August, and showed no decline at high temperatures during June or August, consistent with its high tolerance to drought and adaptation to xeric sites at the prairie-deciduous forest interface. Mid-late October measurements were conducted after soil moisture recharge, but were affected by senescence and cooler temperatures. Isoprene emission rates were considerably lower from all species compared to June and August data. The large differences between the oaks in response to drought emphasizes the need to consider BVOC emissions at the species level instead of just the whole canopy. Monoterpene emissions from Quercus rubra in limited data were highest among the oaks studied, while monoterpene emissions from the other oak species were 80-95% lower and less than assumed in current BVOC emission models. Major monoterpenes from Q. rubra (and in ambient air) were p-cymene, α-pinene, β-pinene, d-limonene, γ-terpinene, β-ocimene (predominantly1,3,7-trans-β-ocimene, but also 1,3,6-trans-β-ocimene), tricyclene, α-terpinene, sabinene, terpinolene, and myrcene. Results are discussed in the context of canopy flux studies

  5. Large drought-induced variations in oak leaf volatile organic compound emissions during PINOT NOIR 2012.

    PubMed

    Geron, Chris; Daly, Ryan; Harley, Peter; Rasmussen, Rei; Seco, Roger; Guenther, Alex; Karl, Thomas; Gu, Lianhong

    2016-03-01

    Leaf-level isoprene and monoterpene emissions were collected and analyzed from five of the most abundant oak (Quercus) species in Central Missouri's Ozarks Region in 2012 during PINOT NOIR (Particle Investigations at a Northern Ozarks Tower - NOx, Oxidants, Isoprene Research). June measurements, prior to the onset of severe drought, showed isoprene emission rates and leaf temperature responses similar to those previously reported in the literature and used in Biogenic Volatile Organic Compound (BVOC) emission models. During the peak of the drought in August, isoprene emission rates were substantially reduced, and response to temperature was dramatically altered, especially for the species in the red oak subgenus (Erythrobalanus). Quercus stellata (in the white oak subgenus Leucobalanus), on the other hand, increased its isoprene emission rate during August, and showed no decline at high temperatures during June or August, consistent with its high tolerance to drought and adaptation to xeric sites at the prairie-deciduous forest interface. Mid-late October measurements were conducted after soil moisture recharge, but were affected by senescence and cooler temperatures. Isoprene emission rates were considerably lower from all species compared to June and August data. The large differences between the oaks in response to drought emphasizes the need to consider BVOC emissions at the species level instead of just the whole canopy. Monoterpene emissions from Quercus rubra in limited data were highest among the oaks studied, while monoterpene emissions from the other oak species were 80-95% lower and less than assumed in current BVOC emission models. Major monoterpenes from Q. rubra (and in ambient air) were p-cymene, α-pinene, β-pinene, d-limonene, γ-terpinene, β-ocimene (predominantly1,3,7-trans-β-ocimene, but also 1,3,6-trans-β-ocimene), tricyclene, α-terpinene, sabinene, terpinolene, and myrcene. Results are discussed in the context of canopy flux studies

  6. Recurrent phagocytosis-induced apoptosis in the cyclical generation change of the compound ascidian Botryllus schlosseri.

    PubMed

    Franchi, Nicola; Ballin, Francesca; Manni, Lucia; Schiavon, Filippo; Basso, Giuseppe; Ballarin, Loriano

    2016-09-01

    Colonies of the marine, filter-feeding ascidian Botryllus schlosseri undergo cyclical generation changes or takeovers. These events are characterised by the progressive resorption of adult zooids and their replacement by their buds that grow to adult size, open their siphons and start filtering. During the take-over, tissues of adult zooids undergo extensive apoptosis; circulating, spreading phagocytes enter the effete tissues, ingest dying cells acquiring a giant size and a round morphology. Then, phagocytes re-enter the circulation where they represent a considerable fraction (more than 20%) of circulating haemocytes. In this study, we evidence that most of these circulating phagocytes show morphological and biochemical signs of apoptosis. Accordingly, these phagocytes express transcripts of orthologues of the apoptosis-related genes Bax, AIF1 and PARP1. Electron microscopy shows that giant phagocytes contain apoptotic phagocytes inside their own phagocytic vacuole. The transcript of the orthologues of the anti-apoptotic gene IAP7 was detected only in spreading phagocytes, mostly abundant in phases far from the take-over. Therefore, the presented data suggest that, at take-over, phagocytes undergo phagocytosis-induced apoptosis (PIA). In mammals, PIA is assumed to be a process assuring the killing and the complete elimination of microbes, by promoting the disposal of terminally differentiated phagocytes and the resolution of infection. In B. schlosseri, PIA assumes a so far undescribed role, being required for the control of asexual development and colony homeostasis.

  7. Gene expression profiling in rat liver treated with compounds inducing phospholipidosis

    SciTech Connect

    Hirode, Mitsuhiro |; Ono, Atsushi |; Miyagishima, Toshikazu; Nagao, Taku; Ohno, Yasuo; Urushidani, Tetsuro |

    2008-06-15

    We have constructed a large-scale transcriptome database of rat liver treated with various drugs. In an effort to identify a biomarker for diagnosis of hepatic phospholipidosis, we extracted 78 probe sets of rat hepatic genes from data of 5 drugs, amiodarone, amitriptyline, clomipramine, imipramine, and ketoconazole, which actually induced this phenotype. Principal component analysis (PCA) using these probes clearly separated dose- and time-dependent clusters of treated groups from their controls. Moreover, 6 drugs (chloramphenicol, chlorpromazine, gentamicin, perhexiline, promethazine, and tamoxifen), which were reported to cause phospholipidosis but judged as negative by histopathological examination, were designated as positive by PCA using these probe sets. Eight drugs (carbon tetrachloride, coumarin, tetracycline, metformin, hydroxyzine, diltiazem, 2-bromoethylamine, and ethionamide), which showed phospholipidosis-like vacuolar formation in the histopathology, could be distinguished from the typical drugs causing phospholipidosis. Moreover, the possible induction of phospholipidosis was predictable by the expression of these genes 24 h after single administration in some of the drugs. We conclude that these identified 78 probe sets could be useful for diagnosis of phospholipidosis, and that toxicogenomics would be a promising approach for prediction of this type of toxicity.

  8. Rhododendrol, a depigmentation-inducing phenolic compound, exerts melanocyte cytotoxicity via a tyrosinase-dependent mechanism.

    PubMed

    Sasaki, Minoru; Kondo, Masatoshi; Sato, Kohji; Umeda, Mai; Kawabata, Keigo; Takahashi, Yoshito; Suzuki, Tamio; Matsunaga, Kayoko; Inoue, Shintaro

    2014-09-01

    Rhododendrol, an inhibitor of melanin synthesis developed for lightening/whitening cosmetics, was recently reported to induce a depigmentary disorder principally at the sites of repeated chemical contact. Rhododendrol competitively inhibited mushroom tyrosinase and served as a good substrate, while it also showed cytotoxicity against cultured human melanocytes at high concentrations sufficient for inhibiting tyrosinase. The cytotoxicity was abolished by phenylthiourea, a chelator of the copper ions at the active site, and by specific knockdown of tyrosinase with siRNA. Hence, the cytotoxicity appeared to be triggered by the enzymatic conversion of rhododendrol to active product(s). No reactive oxygen species were detected in the treated melanocytes, but up-regulation of the CCAAT-enhancer-binding protein homologous protein gene responsible for apoptosis and/or autophagy and caspase-3 activation were found to be tyrosinase dependent. These results suggest that a tyrosinase-dependent accumulation of ER stress and/or activation of the apoptotic pathway may contribute to the melanocyte cytotoxicity. PMID:24890809

  9. Novel piperazine core compound induces death in human liver cancer cells: possible pharmacological properties

    PubMed Central

    Samie, Nima; Muniandy, Sekaran; Kanthimathi, M. S.; Haerian, Batoul Sadat; Raja Azudin, Raja Elina

    2016-01-01

    The current study evaluates the cytotoxic mechanism of a novel piperazine derivate designated as PCC against human liver cancer cells. In this context, human liver cancer cell lines, SNU-475 and 243, human monocyte/macrophage cell line, CRL-9855, and human B lymphocyte cell line, CCL-156, were used to determine the IC50 of PCC using the standard MTT assay. PCC displayed a strong suppressive effect on SNU-475 and SNU-423 cells with an IC50 value of 6.98 ± 0.11 μg/ml and 7.76 ± 0.45 μg/ml respectively, after 24 h of treatment. Significant dipping in the mitochondrial membrane potential and elevation in the released of cytochrome c from the mitochondria indicated the induction of the intrinsic apoptosis pathway by PCC. Activation of this pathway was further evidenced by significant activation of caspase 3/7 and 9. PCC was also shown to activate the extrinsic pathways of apoptosis via activation of caspase-8 which is linked to the suppression of NF-ƙB translocation to the nucleus. Cell cycle arrest in the G1 phase was confirmed by flow cytometry and up-regulation of glutathione reductase expression was quantified by qPCR. This study suggests that PCC is a simultaneous inducer of intrinsic and extrinsic pathways of apoptosis in liver cancer cell lines. PMID:27072064

  10. Neurosupportive Role of Vanillin, a Natural Phenolic Compound, on Rotenone Induced Neurotoxicity in SH-SY5Y Neuroblastoma Cells

    PubMed Central

    Dhanalakshmi, Chinnasamy; Manivasagam, Thamilarasan; Nataraj, Jagatheesan; Justin Thenmozhi, Arokiasamy; Essa, Musthafa Mohamed

    2015-01-01

    Vanillin, a phenolic compound, has been reported to offer neuroprotection against experimental Huntington's disease and global ischemia by virtue of its antioxidant, anti-inflammatory, and antiapoptotic properties. The present study aims to elucidate the underlying neuroprotective mechanism of vanillin in rotenone induced neurotoxicity. Cell viability was assessed by exposing SH-SY5Y cells to various concentrations of rotenone (5–200 nM) for 24 h. The therapeutic effectiveness of vanillin against rotenone was measured by pretreatment of vanillin at various concentrations (5–200 nM) and then incubation with rotenone (100 nM). Using effective dose of vanillin (100 nM), mitochondrial membrane potential, levels of reactive oxygen species (ROS), and expression patterns of apoptotic markers were assessed. Toxicity of rotenone was accompanied by the loss of mitochondrial membrane potential, increased ROS generation, release of cyt-c, and enhanced expressions of proapoptotic and downregulation of antiapoptotic indices via the upregulation of p38 and JNK-MAPK pathway proteins. Our results indicated that the pretreatment of vanillin attenuated rotenone induced mitochondrial dysfunction, oxidative stress, and apoptosis. Thus, vanillin may serve as a potent therapeutic agent in the future by virtue of its multiple pharmacological properties in the treatment of neurodegenerative diseases including PD. PMID:26664453

  11. Neurosupportive Role of Vanillin, a Natural Phenolic Compound, on Rotenone Induced Neurotoxicity in SH-SY5Y Neuroblastoma Cells.

    PubMed

    Dhanalakshmi, Chinnasamy; Manivasagam, Thamilarasan; Nataraj, Jagatheesan; Justin Thenmozhi, Arokiasamy; Essa, Musthafa Mohamed

    2015-01-01

    Vanillin, a phenolic compound, has been reported to offer neuroprotection against experimental Huntington's disease and global ischemia by virtue of its antioxidant, anti-inflammatory, and antiapoptotic properties. The present study aims to elucidate the underlying neuroprotective mechanism of vanillin in rotenone induced neurotoxicity. Cell viability was assessed by exposing SH-SY5Y cells to various concentrations of rotenone (5-200 nM) for 24 h. The therapeutic effectiveness of vanillin against rotenone was measured by pretreatment of vanillin at various concentrations (5-200 nM) and then incubation with rotenone (100 nM). Using effective dose of vanillin (100 nM), mitochondrial membrane potential, levels of reactive oxygen species (ROS), and expression patterns of apoptotic markers were assessed. Toxicity of rotenone was accompanied by the loss of mitochondrial membrane potential, increased ROS generation, release of cyt-c, and enhanced expressions of proapoptotic and downregulation of antiapoptotic indices via the upregulation of p38 and JNK-MAPK pathway proteins. Our results indicated that the pretreatment of vanillin attenuated rotenone induced mitochondrial dysfunction, oxidative stress, and apoptosis. Thus, vanillin may serve as a potent therapeutic agent in the future by virtue of its multiple pharmacological properties in the treatment of neurodegenerative diseases including PD.

  12. Effects of Anthocyanin and Flavanol Compounds on Lipid Metabolism and Adipose Tissue Associated Systemic Inflammation in Diet-Induced Obesity

    PubMed Central

    Morrison, Martine C.; Sheedfar, Fareeba; Mulder, Petra; Schreurs, Marijke; Hommelberg, Pascal P. H.; Hofker, Marten H.; Schalkwijk, Casper; Kleemann, Robert; Tietge, Uwe J. F.; Koonen, Debby P. Y.; Heeringa, Peter

    2016-01-01

    Background. Naturally occurring substances from the flavanol and anthocyanin family of polyphenols have been proposed to exert beneficial effects in the course of obesity. We hypothesized that their effects on attenuating obesity-induced dyslipidemia as well as the associated inflammatory sequelae especially have health-promoting potential. Methods. Male C57BL/6J mice (n = 52) received a control low-fat diet (LFD; 10 kcal% fat) for 6 weeks followed by 24 weeks of either LFD (n = 13) or high-fat diet (HFD; 45 kcal% fat; n = 13) or HFD supplemented with 0.1% w/w of the flavanol compound epicatechin (HFD+E; n = 13) or an anthocyanin-rich bilberry extract (HFD+B; n = 13). Energy substrate utilization was determined by indirect calorimetry in a subset of mice following the dietary switch and at the end of the experiment. Blood samples were collected at baseline and at 3 days and 4, 12, and 20 weeks after dietary switch and analyzed for systemic lipids and proinflammatory cytokines. Adipose tissue (AT) histopathology and inflammatory gene expression as well as hepatic lipid content were analyzed after sacrifice. Results. The switch from a LFD to a HFD lowered the respiratory exchange ratio and increased plasma cholesterol and hepatic lipid content. These changes were not attenuated by HFD+E or HFD+B. Furthermore, the polyphenol compounds could not prevent HFD-induced systemic rise of TNF-α levels. Interestingly, a significant reduction in Tnf gene expression in HFD+B mice was observed in the AT. Furthermore, HFD+B, but not HFD+E, significantly prevented the early upregulation of circulating neutrophil chemoattractant mKC. However, no differences in AT histopathology were observed between the HFD types. Conclusion. Supplementation of HFD with an anthocyanin-rich bilberry extract but not with the flavanol epicatechin may exert beneficial effects on the systemic early inflammatory response associated with diet-induced obesity. These systemic effects were transient and

  13. Effects of Anthocyanin and Flavanol Compounds on Lipid Metabolism and Adipose Tissue Associated Systemic Inflammation in Diet-Induced Obesity.

    PubMed

    van der Heijden, Roel A; Morrison, Martine C; Sheedfar, Fareeba; Mulder, Petra; Schreurs, Marijke; Hommelberg, Pascal P H; Hofker, Marten H; Schalkwijk, Casper; Kleemann, Robert; Tietge, Uwe J F; Koonen, Debby P Y; Heeringa, Peter

    2016-01-01

    Background. Naturally occurring substances from the flavanol and anthocyanin family of polyphenols have been proposed to exert beneficial effects in the course of obesity. We hypothesized that their effects on attenuating obesity-induced dyslipidemia as well as the associated inflammatory sequelae especially have health-promoting potential. Methods. Male C57BL/6J mice (n = 52) received a control low-fat diet (LFD; 10 kcal% fat) for 6 weeks followed by 24 weeks of either LFD (n = 13) or high-fat diet (HFD; 45 kcal% fat; n = 13) or HFD supplemented with 0.1% w/w of the flavanol compound epicatechin (HFD+E; n = 13) or an anthocyanin-rich bilberry extract (HFD+B; n = 13). Energy substrate utilization was determined by indirect calorimetry in a subset of mice following the dietary switch and at the end of the experiment. Blood samples were collected at baseline and at 3 days and 4, 12, and 20 weeks after dietary switch and analyzed for systemic lipids and proinflammatory cytokines. Adipose tissue (AT) histopathology and inflammatory gene expression as well as hepatic lipid content were analyzed after sacrifice. Results. The switch from a LFD to a HFD lowered the respiratory exchange ratio and increased plasma cholesterol and hepatic lipid content. These changes were not attenuated by HFD+E or HFD+B. Furthermore, the polyphenol compounds could not prevent HFD-induced systemic rise of TNF-α levels. Interestingly, a significant reduction in Tnf gene expression in HFD+B mice was observed in the AT. Furthermore, HFD+B, but not HFD+E, significantly prevented the early upregulation of circulating neutrophil chemoattractant mKC. However, no differences in AT histopathology were observed between the HFD types. Conclusion. Supplementation of HFD with an anthocyanin-rich bilberry extract but not with the flavanol epicatechin may exert beneficial effects on the systemic early inflammatory response associated with diet-induced obesity. These systemic effects were transient and

  14. Clathrate eustasy: Methane hydrate melting as a mechanism for geologically rapid sea-level fall

    USGS Publications Warehouse

    Bratton, J.F.

    1999-01-01

    Although submarine methane hydrates or clathrates have been highlighted as potential amplifiers of modern global climate change and associated glacio-eustatic sea-level rise, their potential role in sea-level fall has not been appreciated Recent estimates of the total volume occupied by gas hydrates in marine sediments vary 20-fold, from 1.2 ?? 1014 to 2.4 ?? 1015 m3. Using a specific volume change on melting of-21%, dissociation of the current global inventory of hydrate would result in a decrease of submarine hydrate volume of 2.4 ?? 1013 to 5.0??1014 m3. Release of free gas bubbles present beneath hydrates would increase these volumes by 1.1-2.0 ?? 1013 m3. The combined effects of hydrate melting and subhydrate gas release would result conservatively in a global sea-level fall of 10-146 cm. Such a mechanism may offset some future sea-level rise associated with thermal expansion of the oceans. It could also explain anomalous sea-level drops during ice-free periods such as the early Eocene, the Cretaceous, and the Devonian.

  15. Weak interactions between water and clathrate-forming gases at low pressures

    DOE PAGESBeta

    Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; Kay, Bruce D.; Smith, R. Scott

    2015-07-17

    Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10–1 mbar methane or 10–5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10–5 mbar methane does not alter their morphology, suggesting that the presence ofmore » the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.« less

  16. Weak interactions between water and clathrate-forming gases at low pressures

    SciTech Connect

    Thurmer, Konrad; Yuan, Chunqing; Kimmel, Gregory A.; Kay, Bruce D.; Smith, R. Scott

    2015-11-01

    Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10-1 mbar methane or 10-5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10-5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water-gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~43 K and isobutane desorbs near ~100 K. Similar desorption temperatures were observed for desorption from amorphous solid water.

  17. Clathrate eustasy: Methane hydrate melting as a mechanism for geologically rapid sea-level fall

    SciTech Connect

    Bratton, J.F.

    1999-10-01

    Although submarine methane hydrates or clathrates have been highlighted as potential amplifiers of modern global climate change and associated glacio-eustatic sea-level rise, their potential role in sea-level fall has not been appreciated. Recent estimates of the total volume occupied by gas hydrates in marine sediments vary 20-fold, from 1.2 x 10{sup 14} to 2.4 x 10{sup 15} m{sup 3}. Using a specific volume change on melting of {minus}21%, dissociation of the current global inventory of hydrate would result in a decrease of submarine hydrate volume of 2.4 x 10{sup 13} to 5.0 x 10{sup 14} m{sup 3}. Release of free gas bubbles present beneath hydrates would increase these volumes by 1.1 --2.0 x 10{sup 13} m{sup 3}. The combined effects of hydrate melting and subhydrate gas release would result conservatively in a global sea-level fall of 10--146 cm. Such a mechanism may offset some future sea-level rise associated with thermal expansion of the oceans. It could also explain anomalous sea-level drops during ice-free periods such as the early Eocene, the Cretaceous, and the Devonian.

  18. Major occurrences and reservoir concepts of marine clathrate hydrates: implications of field evidence

    USGS Publications Warehouse

    Booth, J.S.; Winters, W.J.; Dillon, William P.; Clennell, M.B.; Rowe, M.M.

    1998-01-01

    This paper is part of the special publication Gas hydrates: relevance to world margin stability and climatic change (eds J.P. Henriet and J. Mienert). Questions concerning clathrate hydrate as an energy resource, as a factor in modifying global climate and as a triggering mechanism for mass movements invite consideration of what factors promote hydrate concentration, and what the quintessential hydrate-rich sediment may be. Gas hydrate field data, although limited, provide a starting point for identifying the environments and processes that lead to more massive concentrations. Gas hydrate zones are up to 30 m thick and the vertical range of occurrence at a site may exceed 200 m. Zones typically occur more than 100m above the phase boundary. Thicker zones are overwhelmingly associated with structural features and tectonism, and often contain sand. It is unclear whether an apparent association between zone thickness and porosity represents a cause-and-effect relationship. The primary control on the thickness of a potential gas hydrate reservoir is the geological setting. Deep water and low geothermal gradients foster thick gas hydrate stability zones (GHSZs). The presence of faults, fractures, etc. can favour migration of gas-rich fluids. Geological processes, such as eustacy or subsidence, may alter the thickness of the GHSZ or affect hydrate concentratiion. Tectonic forces may promote injection of gas into the GHSZ. More porous and permeable sediment, as host sediment properties, increase storage capacity and fluid conductivity, and thus also enhance reservoir potential.

  19. Constraints on sea to air emissions from methane clathrates in the vicinity of Svalbard

    NASA Astrophysics Data System (ADS)

    Pisso, Ignacio; Vadakkepuliyambatta, Sunil; Platt, Stephen Matthew; Eckhardt, Sabine; Allen, Grant; Pitt, Joseph; Silyakova, Anna; Hermansen, Ove; Schmidbauer, Norbert; Mienert, Jurgen; Myhre, Cathrine Lund; Stohl, Andreas

    2016-04-01

    Methane stored in the seabed in the form of clathrates has the potential to be released into the atmosphere due to ongoing ocean warming. The Methane Emissions from Arctic Ocean to Atmosphere (MOCA, http://moca.nilu.no/) proje sct conducted measurement campaigns in the vicinity of Svalbard during the summers of 2014 and 2015 in collaboration with the Centre for Arctic Gas Hydrate, Environment and Climate (CAGE, https://cage.uit.no/) and the MAMM (https://arcticmethane.wordpress.com) project . The extensive set of measurements includes air (BAe 146) and ship (RV Helmer Hansen) borne methane concentrations, complemented with the nearby monitoring site at Zeppelin mountain. In order to assess the atmospheric impact of emissions from seabed methane hydrates, we characterised the local and long range atmospheric transport during the aircraft campaign and different scenarios for the emission sources. We present a range of upper bounds for the CH4 emissions during the campaign period as well as the methodologies used to obtain them. The methodologies include a box model, Lagrangian transport and elementary inverse modelling. We emphasise the analysis of the aircraft data. We discuss in detail the different methodologies used for determining the upper flux bounds as well as its uncertainties and limitations. The additional information provided by the ship and station observations will be briefly mentioned.

  20. Weak interactions between water and clathrate-forming gases at low pressures

    SciTech Connect

    Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; Kay, Bruce D.; Smith, R. Scott

    2015-07-17

    Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10–1 mbar methane or 10–5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10–5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.

  1. Molecular Modes and Dynamics of HCl and DCl Guests of Gas Clathrate Hydrates.

    PubMed

    Uras-Aytemiz, Nevin; Balcı, F Mine; Maşlakcı, Zafer; Özsoy, Hasan; Devlin, J Paul

    2015-08-27

    Recent years have yielded advances in the placement of unusual molecules as guests within clathrate hydrates (CHs) without severe distortion of the classic lattice structures. Reports describing systems for which observable but limited distortion does occur are available for methanol, ammonia, acetone, and small ether molecules. In these particular examples, the large-cage molecules often participate as non-classical guests H-bonded to the cage walls. Here, we expand the list of such components to include HCl/DCl and HBr as small-cage guests. Based on FTIR spectra of nanocrystalline CHs from two distinct preparative methods combined with critical insights derived from on-the-fly molecular dynamics and ab initio computational data, a coherent argument emerges that these strong acids serve as a source of molecular small-cage guests, ions, and orientational defects. Depending on the HCl/DCl content the ions, defects and molecular guests determine the CH structures, some of which form in sub-seconds via an all-vapor preparative method.

  2. Encapsulation of saline solution by tetrahydrofuran clathrate hydrates and inclusion migration by recrystallization.

    PubMed

    Nagashima, Kazushige; Orihashi, Suguru; Yamamoto, Yoshitaka; Takahashi, Masayoshi

    2005-05-26

    Encapsulation of saline solution as an impurity in tetrahydrofuran clathrate hydrates grown in a stoichiometric solution with 3 wt % NaCl and the release of a saline solution during melting along with inclusion migration by hydrate recrystallization during annealing are studied using a directional growth apparatus in combination with a Mach-Zender interferometer. Interferometric observation revealed that the salt concentration increased locally in the solution near the growth interface. The time evolution of salt concentration in the solution was in accordance with the numerical results obtained from the diffusion equation for salt, assuming perfect rejection of salt by the hydrate. However, after the interfacial pattern developed into a serrated pattern (periodical array of trough and crest), the salt concentration in the solution ceased to increase, deviating from the theoretical value. This indicates that the saline solution was encapsulated by the growth hydrate. On the other hand, upon melting of the slowly grown hydrate, the salt concentration near the interface was observed to be locally high at the location of the trough during growth, whereas it was dilute at the location of the growth crest. Furthermore, when the hydrate was annealed under an applied temperature gradient, the inclusions (encapsulated saline solution) in the hydrate migrated toward the bulk solution and were finally expelled by hydrate recrystallization. The migration speed of the inclusions increased with a larger temperature gradient. By melting the sample over a sufficiently long anneal time, the melt was determined to be completely desalinated.

  3. Influence of combining rules on the cavity occupancy of clathrate hydrates by Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Papadimitriou, Nikolaos I.; Tsimpanogiannis, Ioannis N.; Economou, Ioannis G.; Stubos, Athanassios K.

    2014-09-01

    Assessing the exact amount of gas stored in clathrate-hydrate structures can be addressed by either molecular-level simulations (e.g. Monte Carlo) or continuum-level modelling (e.g. van der Waals-Platteeuw-theory-based models). In either case, the Lorentz-Berthelot (LB) combining rules are by far the most common approach for the evaluation of the parameters between the different types of atoms that form the hydrate structure. The effect of combining rules on the calculations has not been addressed adequately in the hydrate-related literature. Only recently the use of the LB combining rules in hydrate studies has been questioned. In the current study, we report an extensive series of Grand Canonical Monte Carlo simulations along the three-phase (H-Lw-V) equilibrium curve. The exact geometry of hydrate crystals is known from diffraction experiments and, therefore, the formation of hydrates can be simulated as a process of gas adsorption in a solid porous material. We examine the effect of deviations from the LB combining rules on the cavity occupancy of argon hydrates and work towards quantifying it. The specific system is selected as a result of the characteristic behaviour of argon to form hydrates of different structures depending on the prevailing pressure. In particular, an sII hydrate is formed at lower pressures, while an sI hydrate is formed at intermediate pressures, and finally an sH hydrate is formed at higher pressures.

  4. Ternary clathrates Ba Cd Ge: phase equilibria, crystal chemistry and physical properties

    NASA Astrophysics Data System (ADS)

    Melnychenko-Koblyuk, N.; Grytsiv, A.; Berger, St.; Kaldarar, H.; Michor, H.; Röhrbacher, F.; Royanian, E.; Bauer, E.; Rogl, P.; Schmid, H.; Giester, G.

    2007-01-01

    The present paper describes the formation, phase relations at subsolidus temperatures and at 800 °C, crystal chemistry and physical properties of a series of ternary clathrates as part of the solid solution {\\mathrm {Ba_{8}Cd}}_{x}\\mathrm {Ge}_{43-5x/8}\\square _{3-3x/8} , derived from binary {\\mathrm {Ba_{8}Ge_{43}}}\\square_{3} with a solubility limit of 8 Cd per formula unit at 800 °C. Structural investigations in all cases confirm cubic primitive symmetry with a lattice parameter aap1.1 nm, consistent with the space group type Pm{\\bar {3}}n . Both the temperature dependent x-ray spectra and the heat capacity define a low-lying, almost localized, phonon branch. Studies of transport properties show electrons to be the majority charge carriers in the systems. As the Cd content increases, the system is driven towards a metal-to-insulator transition, causing \\mathrm {Ba_{8}Cd_{4.7}Ge_{40.3}}\\square_{1.0} , for example, to show metallic behaviour at low temperatures while at high temperatures semiconducting features become obvious. A model based on a gap of the electronic density of states slightly above the Fermi energy perfectly explains such a scenario. Thermal conductivity exhibits a pronounced low temperature maximum, dominated by the lattice contribution, while at higher temperatures the electronic part becomes more important.

  5. Hydrate-phobic surfaces: fundamental studies in clathrate hydrate adhesion reduction.

    PubMed

    Smith, J David; Meuler, Adam J; Bralower, Harrison L; Venkatesan, Rama; Subramanian, Sivakumar; Cohen, Robert E; McKinley, Gareth H; Varanasi, Kripa K

    2012-05-01

    Clathrate hydrate formation and subsequent plugging of deep-sea oil and gas pipelines represent a significant bottleneck for deep-sea oil and gas operations. Current methods for hydrate mitigation are expensive and energy intensive, comprising chemical, thermal, or flow management techniques. In this paper, we present an alternate approach of using functionalized coatings to reduce hydrate adhesion to surfaces, ideally to a low enough level that hydrodynamic shear stresses can detach deposits and prevent plug formation. Systematic and quantitative studies of hydrate adhesion on smooth substrates with varying solid surface energies reveal a linear trend between hydrate adhesion strength and the practical work of adhesion (γ(total)[1 + cos θ(rec)]) of a suitable probe liquid, that is, one with similar surface energy properties to those of the hydrate. A reduction in hydrate adhesion strength by more than a factor of four when compared to bare steel is achieved on surfaces characterized by low Lewis acid, Lewis base, and van der Waals contributions to surface free energy such that the practical work of adhesion is minimized. These fundamental studies provide a framework for the development of hydrate-phobic surfaces, and could lead to passive enhancement of flow assurance and prevention of blockages in deep-sea oil and gas operations.

  6. Structural, Electronic and Vibrational Properties of Nax Si 136(0 < x < 24) Clathrates

    NASA Astrophysics Data System (ADS)

    Higgins, Craig; Nenghabi, Emmanuel; Myles, Charles; Biswas, Koushik; Beekman, Matt; Nolas, George

    2011-03-01

    CRAIG HIGGINS, EMMANUEL NENGHA BI† , CHARLES W. MYLES, Texas Tech U.; KOUSHIK BISWAS, Oak Ridge National Lab; MATT BEEKMAN, U. of Oregon; GEORGE S. NOLAS, U. of South Florida - Na x Si 136 is a Type II clathrate with important thermoelectric properties. It's face-centered cubic lattice contains polyhedral ``cages'' of silicon atoms with Na atom ``guests'' in the cages. This material is very interesting because powder X-ray diffraction experiments 1 for differing Na content x have shown that, for increasing x in the range 0

  7. Weak interactions between water and clathrate-forming gases at low pressures

    NASA Astrophysics Data System (ADS)

    Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; Kay, Bruce D.; Scott Smith, R.

    2015-11-01

    Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10- 1 mbar methane or 10- 5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10- 5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water-gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. Similar desorption temperatures were observed for desorption from amorphous solid water.

  8. Roasting coffee beans produces compounds that induce prophage lambda in E. coli and are mutagenic in E. coli and S. typhimurium.

    PubMed

    Kosugi, A; Nagao, M; Suwa, Y; Wakabayashi, K; Sugimura, T

    1983-03-01

    Freshly brewed blended coffee, instant coffee and instant caffeine-free coffee induced prophage lambda in lysogenic E. coli K12, strain GY5027. Because coffee prepared from green beans by the same extraction method as used for freshly brewed blended coffee had no prophage-inducing activity, this activity may be attributed to compounds produced in the roasting process. Roasting also produced compounds that were mutagenic in S. typhimurium TA100 and E. coli WP2 uvrA/pKM101. PMID:6220221

  9. cis-Jasmone induces accumulation of defence compounds in wheat, Triticum aestivum.

    PubMed

    Moraes, Maria C Blassioli; Birkett, Michael A; Gordon-Weeks, Ruth; Smart, Lesley E; Martin, Janet L; Pye, Barry J; Bromilow, Richard; Pickett, John A

    2008-01-01

    Liquid phase extraction (LPE) and vapor phase extraction (VPE) methodologies were used to evaluate the impact of the plant activator, cis-jasmone, on the secondary metabolism of wheat, Triticum aestivum, var. Solstice. LPE allowed the measurement of benzoxazinoids, i.e. 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (DIMBOA), 2-hydroxy-7-methoxy-1,4-benzoxazin-3-one (HMBOA) and 6-methoxy-benzoxazolin-2-one (MBOA), and phenolic acids such as trans-p-coumaric acid, syringic acid, p-hydroxybenzoic acid, vanillic acid and cis- and trans-ferulic acid. Using LPE, a significantly higher level of DIMBOA was found in aerial parts and roots of T. aestivum following treatment with cis-jasmone, when compared with untreated plants. Similar results were obtained for phenolic acids, such as trans-ferulic acid and vanillic acid in roots. Using VPE, it was possible to measure levels of 2-hydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (HBOA), benzoxazolin-2(3H)-one (BOA), ferulic acid, syringic acid and coumaric acid. The levels of HBOA in aerial parts and roots were significantly greater in cis-jasmone treated plants compared to untreated plants. cis-Jasmone is known to be a plant activator in terms of production of defence-related volatile semiochemicals that repel aphids and increase the foraging activity of aphid parasitoids. These results show, for the first time, that cis-jasmone also induces selective production of secondary metabolites that are capable of directly reducing development of pests, diseases and weeds.

  10. Low-temperature laser-induced selective area growth of compound semiconductor

    NASA Astrophysics Data System (ADS)

    Uppili, Sudarsan

    Laser induced epitaxial growth of gallium phosphide was investigated as a low temperature, spatially selective process using both pyrolytic and photolytic reaction. A focussed beam from an argon ion laser operating at 514.5 nm was used to direct-write epitaxial microstructures of homoepitaxial GaP using a pyrolytic process. The precursors were trimethyl gallium (TMG) and tertiary butylphosphine (TBP). Dependence of the epitaxial growth on several deposition parameters was examined. An ArF excimer laser was also used to achieve homoepitaxy and heteroepitaxy of gallium phosphide on gallium arsenide at 500 C using TMG and TBP as the precusor gases. Dependence of homoepitaxial growth of GaP on several parameters is examined. The crystalline properties of the film were determined using transmission electron microscopy (TEM). Electrical properties of p-n diodes fabricated via Zn doping were also examined. Defect structures in excimer laser-assisted epitaxial GaP on (100) GaP and (100) GaAs were examined using TEM. Periodic structures were obtained using nominally unpolarized excimer laser radiation, during heteroepitaxial growth of GaP on GaAs. Both crystalline properties and chemical composition of these structures were examined. Microanalysis showed modulation in composition in the ripple structure resulting from the thermal variation caused by the optical interference during growth. Electrical conductivity measurements of GaP during pulsed lasers irradiation indicated that in the absence of gases, there was appreciable heating of the semiconductor. However, a very small quantity of hydrogen or helium cooled the substrate appreciably. This suggested that the average temperature rise of the substrate was not an important factor in the temperature calculations used in the present investigation.

  11. Pyranocycloartobiloxanthone A, a novel gastroprotective compound from Artocarpus obtusus Jarret, against ethanol-induced acute gastric ulcer in vivo.

    PubMed

    Sidahmed, Heyam M A; Hashim, Najihah Mohd; Amir, Junaidah; Abdulla, Mahmood Ameen; Hadi, A Hamid A; Abdelwahab, Siddig Ibrahim; Taha, Manal Mohamed Elhassan; Hassandarvish, Pouya; Teh, Xinsheng; Loke, Mun Fai; Vadivelu, Jamuna; Rahmani, Mawardi; Mohan, Syam

    2013-07-15

    Pyranocycloartobiloxanthone A (PA), a xanthone derived from the Artocarpus obtusus Jarret, belongs to the Moraceae family which is native to the tropical forest of Malaysia. In this study, the efficacy of PA as a gastroprotective compound was examined against ethanol-induced ulcer model in rats. The rats were pretreated with PA and subsequently exposed to acute gastric lesions induced by absolute ethanol. The ulcer index, gastric juice acidity, mucus content, histological analysis, glutathione (GSH) levels, malondialdehyde level (MDA), nitric oxide (NO) and non-protein sulfhydryl group (NP-SH) contents were evaluated in vivo. The activities of PA as anti-Helicobacter pylori, cyclooxygenase-2 (COX-2) inhibitor and free radical scavenger were also investigated in vitro. The results showed that the oral administration of PA protects gastric mucosa from ethanol-induced gastric lesions. PA pretreatment significantly (p<0.05) restored the depleted GSH, NP-SH and NO levels in the gastric homogenate. Moreover, PA significantly (p<0.05) reduced the elevated MDA level due to ethanol administration. The gastroprotective effect of PA was associated with an over expression of HSP70 and suppression of Bax proteins in the ulcerated tissue. In addition, PA exhibited a potent FRAP value and significant COX-2 inhibition. It also showed a significant minimum inhibitory concentration (MIC) against H. pylori bacterium. The efficacy of PA was accomplished safely without the presence of any toxicological parameters. The results of the present study indicate that the gastroprotective effect of PA might contribute to the antioxidant and anti-inflammatory properties as well as the anti-apoptotic mechanism and antibacterial action against Helicobacter pylori.

  12. STX, a novel nonsteroidal estrogenic compound, induces rapid action in primate GnRH neuronal calcium dynamics and peptide release.

    PubMed

    Kenealy, B P; Keen, K L; Rønnekleiv, O K; Terasawa, E

    2011-08-01

    Previously, we reported that 1 nM 17ß-estradiol (E(2)) induces a rapid action, which is, in part, mediated through the G protein-coupled receptor GPR30 in primate GnRH neurons. Because it has been reported that the diphenylacrylamide compound, STX, causes estrogenic action in the mouse and guinea pig hypothalamus, the present study examined effects of STX in primate GnRH neurons and whether there is an action independent of GPR30. Results are summarized as follows. STX (10 nM) exposure increased 1) the oscillation frequency of intracellular calcium concentration ([Ca(2+)](i)), 2) the percentage of cells stimulated, and 3) the synchronization frequency of [Ca(2+)](i) oscillations. STX (10-100 nM) also stimulated GnRH release. The effects of STX on both [Ca(2+)](i) oscillations and GnRH release were similar to those caused by E(2) (1 nM), although with less magnitude. STX (10 nM)-induced changes in [Ca(2+)](i) oscillations were not altered by GPR30 small interfering RNA transfection, indicating that STX-sensitive receptors differ from GPR30. Finally, a higher dose of E(2) (10 nM) induced a larger change in [Ca(2+)](i) oscillations than that with a smaller dose of E(2) (1 nM), and the effects of 10 nM E(2) were reduced but not completely blocked by GPR30 small interfering RNA transfection, indicating that the effects of 10 nM E(2) in primate GnRH neurons are mediated by multiple membrane receptors, including GPR30 and STX-sensitive receptors. Collectively, the rapid action of E(2) mediated through GPR30 differs from that mediated through STX-sensitive receptors. The molecular structure of the STX-sensitive receptor remains to be identified.

  13. Effects of organosulfur compounds from garlic and onions on benzo[a]pyrene-induced neoplasia and glutathione S-transferase activity in the mouse.

    PubMed

    Sparnins, V L; Barany, G; Wattenberg, L W

    1988-01-01

    In the present study, eight organosulfur compounds from garlic and onions were studied for their inhibitory effects on benzo[a]pyrene (BP)-induced neoplasia of forestomach and lung of female A/J mice when administered 96 and 48 h prior to carcinogen challenge. These compounds had one, two or three linearly connected sulfur atoms. They included the four allyl group-containing derivatives: allyl methyl trisulfide (AMT), allyl methyl disulfide (AMD), diallyl trisulfide (DAT), and diallyl sulfide (DAS), and also four corresponding saturated compounds in which propyl groups were substituted for the allyl groups. All four allylic compounds inhibited BP-induced neoplasia of the forestomach. The saturated analogs were almost without inhibitory activity, indicating the importance of the allyl groups. DAT, which contains two allyl groups, was more potent than AMT, which contains only one allyl group, thus providing further evidence for the role of allyl groups in the inhibitory effects observed. DAS and AMD, but not DAT or AMT, inhibited pulmonary adenoma formation. The fact that in the lung the monosulfide and disulfide inhibited, but the trisulfide did not inhibit, indicates that the number of sulfur atoms in the molecule can control the organ sites at which protection against carcinogenesis will occur. All four allylic compounds induced increased glutathione S-transferase (GST) activity in the forestomach, but varied in their capacity to induce GST in lung, liver and small bowel. Their saturated analogs produced little or no induction. In evaluating relationships between diet and cancer, it would be useful to consider the possible role of garlic and onion organosulfur compounds as protective agents. In addition, further studies of this class of chemicals might lead to the identification and development of useful new chemopreventive compounds. PMID:3335037

  14. Flavonoid Compound Icariin Activates Hypoxia Inducible Factor-1α in Chondrocytes and Promotes Articular Cartilage Repair.

    PubMed

    Wang, Pengzhen; Zhang, Fengjie; He, Qiling; Wang, Jianqi; Shiu, Hoi Ting; Shu, Yinglan; Tsang, Wing Pui; Liang, Shuang; Zhao, Kai; Wan, Chao

    2016-01-01

    Articular cartilage has poor capability for repair following trauma or degenerative pathology due to avascular property, low cell density and migratory ability. Discovery of novel therapeutic approaches for articular cartilage repair remains a significant clinical need. Hypoxia is a hallmark for cartilage development and pathology. Hypoxia inducible factor-1alpha (HIF-1α) has been identified as a key mediator for chondrocytes to response to fluctuations of oxygen availability during cartilage development or repair. This suggests that HIF-1α may serve as a target for modulating chondrocyte functions. In this study, using phenotypic cellular screen assays, we identify that Icariin, an active flavonoid component from Herba Epimedii, activates HIF-1α expression in chondrocytes. We performed systemic in vitro and in vivo analysis to determine the roles of Icariin in regulation of chondrogenesis. Our results show that Icariin significantly increases hypoxia responsive element luciferase reporter activity, which is accompanied by increased accumulation and nuclear translocation of HIF-1α in murine chondrocytes. The phenotype is associated with inhibiting PHD activity through interaction between Icariin and iron ions. The upregulation of HIF-1α mRNA levels in chondrocytes persists during chondrogenic differentiation for 7 and 14 days. Icariin (10-6 M) increases the proliferation of chondrocytes or chondroprogenitors examined by MTT, BrdU incorporation or colony formation assays. Icariin enhances chondrogenic marker expression in a micromass culture including Sox9, collagen type 2 (Col2α1) and aggrecan as determined by real-time PCR and promotes extracellular matrix (ECM) synthesis indicated by Alcian blue staining. ELISA assays show dramatically increased production of aggrecan and hydroxyproline in Icariin-treated cultures at day 14 of chondrogenic differentiation as compared with the controls. Meanwhile, the expression of chondrocyte catabolic marker genes

  15. Flavonoid Compound Icariin Activates Hypoxia Inducible Factor-1α in Chondrocytes and Promotes Articular Cartilage Repair

    PubMed Central

    He, Qiling; Wang, Jianqi; Shiu, Hoi Ting; Shu, Yinglan; Tsang, Wing Pui; Liang, Shuang; Zhao, Kai; Wan, Chao

    2016-01-01

    Articular cartilage has poor capability for repair following trauma or degenerative pathology due to avascular property, low cell density and migratory ability. Discovery of novel therapeutic approaches for articular cartilage repair remains a significant clinical need. Hypoxia is a hallmark for cartilage development and pathology. Hypoxia inducible factor-1alpha (HIF-1α) has been identified as a key mediator for chondrocytes to response to fluctuations of oxygen availability during cartilage development or repair. This suggests that HIF-1α may serve as a target for modulating chondrocyte functions. In this study, using phenotypic cellular screen assays, we identify that Icariin, an active flavonoid component from Herba Epimedii, activates HIF-1α expression in chondrocytes. We performed systemic in vitro and in vivo analysis to determine the roles of Icariin in regulation of chondrogenesis. Our results show that Icariin significantly increases hypoxia responsive element luciferase reporter activity, which is accompanied by increased accumulation and nuclear translocation of HIF-1α in murine chondrocytes. The phenotype is associated with inhibiting PHD activity through interaction between Icariin and iron ions. The upregulation of HIF-1α mRNA levels in chondrocytes persists during chondrogenic differentiation for 7 and 14 days. Icariin (10−6 M) increases the proliferation of chondrocytes or chondroprogenitors examined by MTT, BrdU incorporation or colony formation assays. Icariin enhances chondrogenic marker expression in a micromass culture including Sox9, collagen type 2 (Col2α1) and aggrecan as determined by real-time PCR and promotes extracellular matrix (ECM) synthesis indicated by Alcian blue staining. ELISA assays show dramatically increased production of aggrecan and hydroxyproline in Icariin-treated cultures at day 14 of chondrogenic differentiation as compared with the controls. Meanwhile, the expression of chondrocyte catabolic marker genes

  16. The angular structure of ONC201, a TRAIL pathway-inducing compound, determines its potent anti-cancer activity

    PubMed Central

    Wagner, Jessica; Kline, Christina Leah; Pottorf, Richard S.; Nallaganchu, Bhaskara Rao; Olson, Gary L.; Dicker, David T.; Allen, Joshua E.; El-Deiry, Wafik S.

    2014-01-01

    We previously identified TRAIL-inducing compound 10 (TIC10), also known as NSC350625 or ONC201, from a NCI chemical library screen as a small molecule that has potent anti-tumor efficacy and a benign safety profile in preclinical cancer models. The chemical structure that was originally published by Stahle, et. al. in the patent literature was described as an imidazo[1,2-a]pyrido[4,3-d]pyrimidine derivative. The NCI and others generally accepted this as the correct structure, which was consistent with the mass spectrometry analysis outlined in the publication by Allen et. al. that first reported the molecule's anticancer properties. A recent publication demonstrated that the chemical structure of ONC201 material from the NCI is an angular [3,4-e] isomer of the originally disclosed, linear [4,3-d] structure. Here we confirm by NMR and X-ray structural analysis of the dihydrochloride salt form that the ONC201 material produced by Oncoceutics is the angular [3,4-e] structure and not the linear structure originally depicted in the patent literature and by the NCI. Similarly, in accordance with our biological evaluation, the previously disclosed anti-cancer activity is associated with the angular structure and not the linear isomer. Together these studies confirm that ONC201, produced by Oncoceutics or obtained from the NCI, possesses an angular [3,4-e] structure that represents the highly active anti-cancer compound utilized in prior preclinical studies and now entering clinical trials in advanced cancers. PMID:25587031

  17. Systemic resistance induced by volatile organic compounds emitted by plant growth-promoting fungi in Arabidopsis thaliana.

    PubMed

    Naznin, Hushna Ara; Kiyohara, Daigo; Kimura, Minako; Miyazawa, Mitsuo; Shimizu, Masafumi; Hyakumachi, Mitsuro

    2014-01-01

    Volatile organic compounds (VOC) were extracted and identified from plant growth-promoting fungi (PGPF), Phoma sp., Cladosporium sp. and Ampelomyces sp., using gas chromatography-mass spectrometry (GC-MS). Among the three VOC extracted, two VOC blends (emitted from Ampelomyces sp. and Cladosporium sp.) significantly reduced disease severity in Arabidopsis plants against Pseudomonas syringae pv. tomato DC3000 (Pst). Subsequently, m-cresol and methyl benzoate (MeBA) were identified as major active volatile compounds from Ampelomyces sp. and Cladosporium sp., respectively, and found to elicit induced systemic resistance (ISR) against the pathogen. Molecular signaling for disease suppression by the VOC were investigated by treating different mutants and transgenic Arabidopsis plants impaired in salicylic acid (SA) or Jasmonic acid (JA)/ethylene (ET) signaling pathways with m-cresol and MeBA followed by challenge inoculation with Pst. Results show that the level of protection was significantly lower when JA/ET-impaired mutants were treated with MeBA, and in SA-, and JA/ET-disrupted mutants after m-cresol treatment, indicating the involvement of these signal transduction pathways in the ISR primed by the volatiles. Analysis of defense-related genes by real-time qRT-PCR showed that both the SA-and JA-signaling pathways combine in the m-cresol signaling of ISR, whereas MeBA is mainly involved in the JA-signaling pathway with partial recruitment of SA-signals. The ET-signaling pathway was not employed in ISR by the volatiles. Therefore, this study identified two novel volatile components capable of eliciting ISR that may be promising candidates in biological control strategy to protect plants from diseases. PMID:24475190

  18. High-pressure/low-temperature neutron scattering of gas inclusion compounds: progress and prospects.

    PubMed

    Zhao, Yusheng; Xu, Hongwu; Daemen, Luke L; Lokshin, Konstantin; Tait, Kimberly T; Mao, Wendy L; Luo, Junhua; Currier, Robert P; Hickmott, Donald D

    2007-04-01

    Alternative energy resources such as hydrogen and methane gases are becoming increasingly important for the future economy. A major challenge for using hydrogen is to develop suitable materials to store it under a variety of conditions, which requires systematic studies of the structures, stability, and kinetics of various hydrogen-storing compounds. Neutron scattering is particularly useful for these studies. We have developed high-pressure/low-temperature gas/fluid cells in conjunction with neutron diffraction and inelastic neutron scattering instruments allowing in situ and real-time examination of gas uptake/release processes. We studied the formation of methane and hydrogen clathrates, a group of inclusion compounds consisting of frameworks of hydrogen-bonded H(2)O molecules with gas molecules trapped inside the cages. Our results reveal that clathrate can store up to four hydrogen molecules in each of its large cages with an intermolecular H(2)-H(2) distance of only 2.93 A. This distance is much shorter than that in the solid/metallic hydrogen (3.78 A), suggesting a strong densification effect of the clathrate framework on the enclosed hydrogen molecules. The framework-pressurizing effect is striking and may exist in other inclusion compounds such as metal-organic frameworks (MOFs). Owing to the enormous variety and flexibility of their frameworks, inclusion compounds may offer superior properties for storage of hydrogen and/or hydrogen-rich molecules, relative to other types of compounds. We have investigated the hydrogen storage properties of two MOFs, Cu(3)[Co(CN)(6)](2) and Cu(3)(BTC)(2) (BTC = benzenetricarboxylate), and our preliminary results demonstrate that the developed neutron-scattering techniques are equally well suited for studying MOFs and other inclusion compounds. PMID:17389387

  19. Compound 13, an α1-selective small molecule activator of AMPK, inhibits Helicobacter pylori-induced oxidative stresses and gastric epithelial cell apoptosis

    SciTech Connect

    Zhao, Hangyong; Zhu, Huanghuang; Lin, Zhou; Lin, Gang; Lv, Guoqiang

    2015-08-07

    Half of the world's population experiences Helicobacter pylori (H. pylori) infection, which is a main cause of gastritis, duodenal and gastric ulcer, and gastric cancers. In the current study, we investigated the potential role of compound 13 (C13), a novel α1-selective small molecule activator of AMP-activated protein kinase (AMPK), against H. pylori-induced cytotoxicity in cultured gastric epithelial cells (GECs). We found that C13 induced significant AMPK activation, evidenced by phosphorylation of AMPKα1 and ACC (acetyl-CoA carboxylase), in both primary and transformed GECs. Treatment of C13 inhibited H. pylori-induced GEC apoptosis. AMPK activation was required for C13-mediated GEC protection. Inhibition of AMPK kinase activity by the AMPK inhibitor Compound C, or silencing AMPKα1 expression by targeted-shRNAs, alleviated C13-induced GEC protective activities against H. pylori. Significantly, C13 inhibited H. pylori-induced reactive oxygen species (ROS) production in GECs. C13 induced AMPK-dependent expression of anti-oxidant gene heme oxygenase (HO-1) in GECs. Zinc protoporphyrin (ZnPP) and tin protoporphyrin (SnPP), two HO-1 inhibitors, not only suppressed C13-mediated ROS scavenging activity, but also alleviated its activity in GECs against H. pylori. Together, these results indicate that C13 inhibits H. pylori-induced ROS production and GEC apoptosis through activating AMPK–HO–1 signaling. - Highlights: • We synthesized compound 13 (C13), a α1-selective small molecule AMPK activator. • C13-induced AMPK activation requires α1 subunit in gastric epithelial cells (GECs). • C13 enhances Helicobacter pylori-induced pro-survival AMPK activation to inhibit GEC apoptosis. • C13 inhibits H. pylori-induced reactive oxygen species (ROS) production in GECs. • AMPK-heme oxygenase (HO-1) activation is required for C13-mediated anti-oxidant activity.

  20. In vitro evaluation of candidate pretreatment and treatment compounds against sulfur mustard (HD) -induced human mononuclear leukocyte toxicity using a dye exclusion cell viability assay

    SciTech Connect

    Starner, R.A.; Blank, J.A.; Hobson, D.W.; Menton, R.G.; Meier, H.L.

    1993-05-13

    An assay measuring propidium iodide (PI) incorporation into nonviable human peripheral blood mononuclear leukocytes (PBML) was established at the U.S. Army Medical Research Institute of Chemical Defense (USAMRICD), and the technology transferred and implemented at Battelle's Medical Research and Evaluation Facility (MREF) for use as a screen to evaluate candidate compounds for direct cytotoxicity as well as for efficacy in preventing HD-induced cytotoxicity. For assay transition, studies were performed to establish a fixed HD challenge concentration; to develop a positive and negative control dataset; and to establish the reproducibility in obtaining an EC50 (concentration of candidate compound required to provide 50 percent protection against the fixed HD concentration) for niacinamide (NM). Various concentrations of candidate compounds were preincubated for 15 to 30 min with PBML prior to adding the fixed HD challenge. At 24 hr after exposure, PI was added to the cultures and the number of nonviable (PI positive) cells was determined by flow cytometry. Positive (NM pretreated) and negative (HD only) controls were examined concurrently and used to maintain data quality. From this dataset, candidate compounds were evaluated for direct cytotoxic effects and for efficacy in preventing HD-induced cytotoxicity. EC50 values for effective candidate compounds were estimated and reported for ranking compound effectiveness. Results from these studies demonstrate assay function and reproducibility during routine screening operations.

  1. A New High-pressure System to Investigate Clathrate Hydrates Stability and Role in Volatile Outgassing on Titan and Enceladus

    NASA Astrophysics Data System (ADS)

    Smythe, W. D.; Choukroun, M.; Elliott, J.; Barmatz, M.; Hodyss, R. P.

    2011-12-01

    The origin of Titan's atmospheric methane and of the volatiles measured in Enceladus' south pole plumes remain, to this day, unresolved. Clathrate hydrates are among the favored deep-seated reservoir candidates. However, the conditions allowing for their dissociation and the release of volatiles to the atmosphere (Titan) or the plumes (Enceladus) are still poorly constrained. This is mainly because there is a lack of knowledge on the stability of mixed clathrate hydrates in presence of anti-freeze agents such as ammonia. We present a new high-pressure system, a high-pressure cryogenic calorimeter, currently being developed at JPL that is designed to address this deficiency in the literature. We use a liquid nitrogen - cooled Setaram BT2.15 calorimeter, located at the Ice Physics Laboratory, JPL (see Figure 1). The temperature range achievable with this instrument is 77-473 K. This calorimeter uses Calvet elements (3D arrays of thermocouples), to measure the heat flux required to follow a predefined heating rate within a sample and a reference cell with a resolution of 0.1 μW. A high-pressure system is being implemented in order to develop the capability of investigating the pressure range 0-100 bars. This system includes: high-pressure cells with a gas flow system (from Setaram), a gas handling system to deliver the gas from 1K bottles of CH4, CO2, and N2, a vacuum system, and a vent system. With the calorimeter, clathrate hydrates will be synthesized within the cells from an H2O-NH3 aqueous solution. Then, cooling and heating tests will be conducted for several gas pressures in order to measure simultaneously the dissociation curve and thermodynamic properties (heat capacity, latent heat). Similarly, clathrate hydrates will be synthesized from the solution of interest within the fluid pressure cell. Dissociation curves will be measured by varying temperature, and following optically and via Raman and diffuse reflectance infrared spectroscopy the samples

  2. Olive oil compounds inhibit the paracrine regulation of TNF-α-induced endothelial cell migration through reduced glioblastoma cell cyclooxygenase-2 expression.

    PubMed

    Lamy, Sylvie; Ben Saad, Aroua; Zgheib, Alain; Annabi, Borhane

    2016-01-01

    The established causal relationship between the chronic inflammatory microenvironment, tumor development and cancer recurrence has provided leads for developing novel preventive strategies. Accumulating experimental, clinical and epidemiological data has provided support for the chemopreventive properties of olive oil compounds traditionally found within the Mediterranean diet. In this study, we investigated whether tyrosol (Tyr), hydroxytyrosol, oleuropein and oleic acid (OA), four compounds contained in extra virgin olive oil, can prevent tumor necrosis factor (TNF)-α-induced expression of cyclooxygenase (COX)-2 (an inflammation biomarker) in a human glioblastoma cell (U-87 MG) model. We found that Tyr and OA significantly inhibited TNF-α-induced COX-2 gene and protein expression, as well as PGE2 secretion. Both compounds also inhibited TNF-α-induced JNK and ERK phosphorylation, whereas only Tyr inhibited TNF-α-induced NF-κB phosphorylation. Paracrine-regulated migration of human brain microvascular endothelial cells (HBMECs) was assessed using growth factor-enriched conditioned media (CM) isolated from U-87 MG cells. We found that while PGE2 triggered HBMEC migration, the CM isolated from U-87 MG cells, where either COX-2 or NF-κB had been silenced or had been treated with Tyr or OA, exhibited decreased chemotactic properties. These observations demonstrate that olive oil compounds inhibit the effect of the chronic inflammatory microenvironment on glioblastoma progression through TNF-α actions and may be useful in cancer chemoprevention.

  3. Ferromagnetic coupling mediated by Coπ non-covalent contacts in a pentacoordinate Co(ii) compound showing field-induced slow relaxation of magnetization.

    PubMed

    Nemec, I; Herchel, R; Trávníček, Z

    2016-08-01

    [Co(II)(dpt)(NCS)2], where dpt = bis(3-aminopropyl)amine, was identified as a pentacoordinate Co(II) compound showing field-induced slow relaxation of magnetization. Furthermore, intermolecular ferromagnetic coupling mediated by Coπ non-covalent contacts, where π orbitals originate from the thiocyanato ligand, is reported for the first time. PMID:27435418

  4. Alliin, a Garlic (Allium sativum) Compound, Prevents LPS-Induced Inflammation in 3T3-L1 Adipocytes

    PubMed Central

    Quintero-Fabián, Saray; Ortuño-Sahagún, Daniel; Vázquez-Carrera, Manuel; López-Roa, Rocío Ivette

    2013-01-01

    Garlic (Allium sativum L.) has been used to alleviate a variety of health problems due to its high content of organosulfur compounds and antioxidant activity. The main active component is alliin (S-allyl cysteine sulfoxide), a potent antioxidant with cardioprotective and neuroprotective actions. In addition, it helps to decrease serum levels of glucose, insulin, triglycerides, and uric acid, as well as insulin resistance, and reduces cytokine levels. However its potential anti-inflammatory effect is unknown. We examined the effects of alliin in lipopolysaccharide- (LPS-) stimulated 3T3-L1 adipocytes by RT-PCR, Western blot, and microarrays analysis of 22,000 genes. Incubation of cells for 24 h with 100 μmol/L alliin prevented the increase in the expression of proinflammatory genes, IL-6, MCP-1, and Egr-1 in 3T3-L1 adipocytes exposed to 100 ng/mL LPS for 1 h. Interestingly, the phosphorylation of ERK1/2, which is involved in LPS-induced inflammation in adipocytes, was decreased following alliin treatment. Furthermore, the gene expression profile by microarrays evidentiate an upregulation of genes involved in immune response and downregulation of genes related with cancer. The present results have shown that alliin is able to suppress the LPS inflammatory signals by generating an anti-inflammatory gene expression profile and by modifying adipocyte metabolic profile. PMID:24453416

  5. Volatile organic compounds from fungi isolated after hurricane katrina induce developmental defects and apoptosis in a Drosophila melanogaster model.

    PubMed

    Inamdar, Arati A; Bennett, Joan W

    2015-05-01

    In previous work, our laboratory developed a Drosophila model for studying the adverse effects of fungal volatile organic compounds (VOCs) emitted by growing cultures of molds. In this report, we have extended these studies and compared the toxic effects of fungal VOCs emitted from living cultures of four molds isolated after Hurricane Katrina from a flooded home in New Orleans. Strains of Aspergillus, Mucor, Penicillium, and Trichoderma were grown with wild-type larvae and the toxic effects of volatile products on the developmental stages of Drosophila larvae were evaluated. Furthermore, heterozygous mutants of Drosophila carrying the apoptotic genes, reaper and dronc, were used to assess the role of apoptosis in fungal VOCs mediated toxicity. Third-instar larvae of Drosophila carrying these apoptotic genes were exposed to fungal VOCs emitted from growing mold cultures for 10 days. The larval strains carrying apoptopic genes survived longer than the control wild type larvae; moreover, of those that survived, heterozygous reaper and dronc strains progressed to pupae and adult phases more rapidly, suggesting that fungal VOCs may induce apoptotic changes in flies. These data lend support to the use of Drosophila as an inexpensive and genetically versatile toxicological model to investigate the mechanistic basis for some of the human illnesses/symptoms associated with exposure to mold-contaminated indoor air, especially after hurricanes.

  6. Alliin, a garlic (Allium sativum) compound, prevents LPS-induced inflammation in 3T3-L1 adipocytes.

    PubMed

    Quintero-Fabián, Saray; Ortuño-Sahagún, Daniel; Vázquez-Carrera, Manuel; López-Roa, Rocío Ivette

    2013-01-01

    Garlic (Allium sativum L.) has been used to alleviate a variety of health problems due to its high content of organosulfur compounds and antioxidant activity. The main active component is alliin (S-allyl cysteine sulfoxide), a potent antioxidant with cardioprotective and neuroprotective actions. In addition, it helps to decrease serum levels of glucose, insulin, triglycerides, and uric acid, as well as insulin resistance, and reduces cytokine levels. However its potential anti-inflammatory effect is unknown. We examined the effects of alliin in lipopolysaccharide- (LPS-) stimulated 3T3-L1 adipocytes by RT-PCR, Western blot, and microarrays analysis of 22,000 genes. Incubation of cells for 24 h with 100 μmol/L alliin prevented the increase in the expression of proinflammatory genes, IL-6, MCP-1, and Egr-1 in 3T3-L1 adipocytes exposed to 100 ng/mL LPS for 1 h. Interestingly, the phosphorylation of ERK1/2, which is involved in LPS-induced inflammation in adipocytes, was decreased following alliin treatment. Furthermore, the gene expression profile by microarrays evidentiate an upregulation of genes involved in immune response and downregulation of genes related with cancer. The present results have shown that alliin is able to suppress the LPS inflammatory signals by generating an anti-inflammatory gene expression profile and by modifying adipocyte metabolic profile.

  7. Volatile organic compounds from fungi isolated after hurricane katrina induce developmental defects and apoptosis in a Drosophila melanogaster model.

    PubMed

    Inamdar, Arati A; Bennett, Joan W

    2015-05-01

    In previous work, our laboratory developed a Drosophila model for studying the adverse effects of fungal volatile organic compounds (VOCs) emitted by growing cultures of molds. In this report, we have extended these studies and compared the toxic effects of fungal VOCs emitted from living cultures of four molds isolated after Hurricane Katrina from a flooded home in New Orleans. Strains of Aspergillus, Mucor, Penicillium, and Trichoderma were grown with wild-type larvae and the toxic effects of volatile products on the developmental stages of Drosophila larvae were evaluated. Furthermore, heterozygous mutants of Drosophila carrying the apoptotic genes, reaper and dronc, were used to assess the role of apoptosis in fungal VOCs mediated toxicity. Third-instar larvae of Drosophila carrying these apoptotic genes were exposed to fungal VOCs emitted from growing mold cultures for 10 days. The larval strains carrying apoptopic genes survived longer than the control wild type larvae; moreover, of those that survived, heterozygous reaper and dronc strains progressed to pupae and adult phases more rapidly, suggesting that fungal VOCs may induce apoptotic changes in flies. These data lend support to the use of Drosophila as an inexpensive and genetically versatile toxicological model to investigate the mechanistic basis for some of the human illnesses/symptoms associated with exposure to mold-contaminated indoor air, especially after hurricanes. PMID:24307503

  8. A new V-shaped organic fluorescent compound integrated with crystallization-induced emission enhancement and intramolecular charge transfer.

    PubMed

    Gu, Pei-Yang; Zhang, You-Hao; Liu, Gao-Yan; Ge, Jian-Feng; Xu, Qing-Feng; Zhang, Qichun; Lu, Jian-Mei

    2013-09-01

    The emission behavior of a new V-shaped organic fluorescent compound (p,p′-bis(2-aryl-1,3,4-oxadiazol-5-yl)diphenyl sulfone (OZA-SO)), consisting of diethylamino (donor) and sulfone (acceptor) units, has been studied in various polar solvents and with different morphologies. As expected, there is the gradual transition from the locally excited state to the intramolecular charge-transfer (ICT) state with the increasing solvent polarity. The photoluminescence intensity of OZA-SO initially decreases with a low water fraction (f(w)), owing to ICT effect, and then increases with a high f(w), owing to crystallization-induced emission enhancement. At the same time, the fluorescence lifetime of OZA-SO increases from 0.062 ns in dimethylformamide (DMF) to 5.80 ns in a solution containing 90 % water, and then to 7.49 ns in a solution containing 60 % water. Furthermore, the solid-state emission of OZA-SO can be tuned reversibly from green to yellow by fuming/grinding or fuming/heating owing to morphological changes. This color-switchable feature of OZA-SO may have potential applications in optical-recording and temperature-sensing materials.

  9. Magnetically-induced ferroelectricity in the (ND4)2[FeCl5(D2O)] molecular compound

    PubMed Central

    Alberto Rodríguez-Velamazán, José; Fabelo, Óscar; Millán, Ángel; Campo, Javier; Johnson, Roger D.; Chapon, Laurent

    2015-01-01

    The number of magnetoelectric multiferroic materials reported to date is scarce, as magnetic structures that break inversion symmetry and induce an improper ferroelectric polarization typically arise through subtle competition between different magnetic interactions. The (NH4)2[FeCl5(H2O)] compound is a rare case where such improper ferroelectricity has been observed in a molecular material. We have used single crystal and powder neutron diffraction to obtain detailed solutions for the crystal and magnetic structures of (NH4)2[FeCl5(H2O)], from which we determined the mechanism of multiferroicity. From the crystal structure analysis, we observed an order-disorder phase transition related to the ordering of the ammonium counterion. We have determined the magnetic structure below TN, at 2 K and zero magnetic field, which corresponds to a cycloidal spin arrangement with magnetic moments contained in the ac-plane, propagating parallel to the c-axis. The observed ferroelectricity can be explained, from the obtained magnetic structure, via the inverse Dzyaloshinskii-Moriya mechanism. PMID:26417890

  10. Identification of an immediate-early salicylic acid-inducible tobacco gene and characterization of induction by other compounds.

    PubMed

    Horvath, D M; Chua, N H

    1996-08-01

    Tobacco genes that are induced in response to salicylic acid (SA) treatment with immediate-early kinetics were identified by differential mRNA display. Detailed analysis of IS10a, one cDNA clone identified by this method, revealed induction within 30 min of treatment, with a peak of expression at 3 h, that decayed rapidly thereafter. Treatment with the protein synthesis inhibitor, cycloheximide (CHX), also caused induction of IS10a mRNA to comparable levels, but the IS10a mRNA continued to accumulate after 3 h of induction. In combination, CHX and SA led to a superinduction of IS10a mRNA levels that was also sustained. Half-maximal induction was evident at ca. 100-150 microM SA. In addition to SA, induction of IS10a occurred to varying degrees upon treatment with acetylsalicylic acid, benzoic acid, 2,4-dichlorophenoxyacetic acid, methyl jasmonate, and hydrogen peroxide, whereas treatment with other compounds had no effect. The proteins encoded by IS10a and a second highly homologous cDNA show sequence similarity to UDP-glucose: flavonoid glucosyltransferases.

  11. Thermoelectric material including a multiple transition metal-doped type I clathrate crystal structure

    DOEpatents

    Yang, Jihui; Shi, Xun; Bai, Shengqiang; Zhang, Wenqing; Chen, Lidong; Yang, Jiong

    2012-01-17

    A thermoelectric material includes a multiple transition metal-doped type I clathrate crystal structure having the formula A.sub.8TM.sub.y.sub.1.sup.1TM.sub.y.sub.2.sup.2 . . . TM.sub.y.sub.n.sup.nM.sub.zX.sub.46-y.sub.1.sub.-y.sub.2.sub.- . . . -y.sub.n.sub.-z. In the formula, A is selected from the group consisting of barium, strontium, and europium; X is selected from the group consisting of silicon, germanium, and tin; M is selected from the group consisting of aluminum, gallium, and indium; TM.sup.1, TM.sup.2, and TM.sup.n are independently selected from the group consisting of 3d, 4d, and 5d transition metals; and y.sub.1, y.sub.2, y.sub.n and Z are actual compositions of TM.sup.1, TM.sup.2, TM.sup.n, and M, respectively. The actual compositions are based upon nominal compositions derived from the following equation: z=8q.sub.A-|.DELTA.q.sub.1|y.sub.1-|.DELTA.q.sub.2|y.sub.2- . . . -|.DELTA.q.sub.n|y.sub.n, wherein q.sub.A is a charge state of A, and wherein .DELTA.q.sub.1, .DELTA.q.sub.2, .DELTA.q.sub.n are, respectively, the nominal charge state of the first, second, and n-th TM.

  12. Chemically Homogenous Compounds with Antagonistic Properties at All α1-Adrenoceptor Subtypes but not β1-Adrenoceptor Attenuate Adrenaline-Induced Arrhythmia in Rats

    PubMed Central

    Pytka, Karolina; Lustyk, Klaudia; Żmudzka, Elżbieta; Kotańska, Magdalena; Siwek, Agata; Zygmunt, Małgorzata; Dziedziczak, Agnieszka; Śniecikowska, Joanna; Olczyk, Adrian; Gałuszka, Adam; Śmieja, Jarosław; Waszkielewicz, Anna M.; Marona, Henryk; Filipek, Barbara; Sapa, Jacek; Mogilski, Szczepan

    2016-01-01

    Studies proved that among all α1-adrenoceptors, cardiac myocytes functionally express only α1A- and α1B-subtype. Scientists indicated that α1A-subtype blockade might be beneficial in restoring normal heart rhythm. Therefore, we aimed to determine the role of α1-adrenoceptors subtypes (i.e., α1A and α1B) in antiarrhythmic effect of six structurally similar derivatives of 2-methoxyphenylpiperazine. We compared the activity of studied compounds with carvedilol, which is β1- and α1-adrenoceptors blocker with antioxidant properties. To evaluate the affinity for adrenergic receptors, we used radioligand methods. We investigated selectivity at α1-adrenoceptors subtypes using functional bioassays. We tested antiarrhythmic activity in adrenaline-induced (20 μg/kg i.v.), calcium chloride-induced (140 and 25 mg/kg i.v.) and barium chloride-induced (32 and 10 mg/kg i.v.) arrhythmia models in rats. We also evaluated the influence of studied compounds on blood pressure in rats, as well as lipid peroxidation. All studied compounds showed high affinity toward α1-adrenoceptors but no affinity for β1 receptors. Biofunctional studies revealed that the tested compounds blocked α1A-stronger than α1B-adrenoceptors, but except for HBK-19 they antagonized α1A-adrenoceptor weaker than α1D-subtype. HBK-19 showed the greatest difference in pA2 values—it blocked α1A-adrenoceptors around seven-fold stronger than α1B subtype. All compounds showed prophylactic antiarrhythmic properties in adrenaline-induced arrhythmia, but only the activity of HBK-16, HBK-17, HBK-18, and HBK-19 (ED50 = 0.18–0.21) was comparable to that of carvedilol (ED50 = 0.36). All compounds reduced mortality in adrenaline-induced arrhythmia. HBK-16, HBK-17, HBK-18, and HBK-19 showed therapeutic antiarrhythmic properties in adrenaline-induced arrhythmia. None of the compounds showed activity in calcium chloride- or barium chloride-induced arrhythmias. HBK-16, HBK-17, HBK-18, and HBK-19 decreased heart

  13. Chemically Homogenous Compounds with Antagonistic Properties at All α1-Adrenoceptor Subtypes but not β1-Adrenoceptor Attenuate Adrenaline-Induced Arrhythmia in Rats.

    PubMed

    Pytka, Karolina; Lustyk, Klaudia; Żmudzka, Elżbieta; Kotańska, Magdalena; Siwek, Agata; Zygmunt, Małgorzata; Dziedziczak, Agnieszka; Śniecikowska, Joanna; Olczyk, Adrian; Gałuszka, Adam; Śmieja, Jarosław; Waszkielewicz, Anna M; Marona, Henryk; Filipek, Barbara; Sapa, Jacek; Mogilski, Szczepan

    2016-01-01

    Studies proved that among all α1-adrenoceptors, cardiac myocytes functionally express only α1A- and α1B-subtype. Scientists indicated that α1A-subtype blockade might be beneficial in restoring normal heart rhythm. Therefore, we aimed to determine the role of α1-adrenoceptors subtypes (i.e., α1A and α1B) in antiarrhythmic effect of six structurally similar derivatives of 2-methoxyphenylpiperazine. We compared the activity of studied compounds with carvedilol, which is β1- and α1-adrenoceptors blocker with antioxidant properties. To evaluate the affinity for adrenergic receptors, we used radioligand methods. We investigated selectivity at α1-adrenoceptors subtypes using functional bioassays. We tested antiarrhythmic activity in adrenaline-induced (20 μg/kg i.v.), calcium chloride-induced (140 and 25 mg/kg i.v.) and barium chloride-induced (32 and 10 mg/kg i.v.) arrhythmia models in rats. We also evaluated the influence of studied compounds on blood pressure in rats, as well as lipid peroxidation. All studied compounds showed high affinity toward α1-adrenoceptors but no affinity for β1 receptors. Biofunctional studies revealed that the tested compounds blocked α1A-stronger than α1B-adrenoceptors, but except for HBK-19 they antagonized α1A-adrenoceptor weaker than α1D-subtype. HBK-19 showed the greatest difference in pA2 values-it blocked α1A-adrenoceptors around seven-fold stronger than α1B subtype. All compounds showed prophylactic antiarrhythmic properties in adrenaline-induced arrhythmia, but only the activity of HBK-16, HBK-17, HBK-18, and HBK-19 (ED50 = 0.18-0.21) was comparable to that of carvedilol (ED50 = 0.36). All compounds reduced mortality in adrenaline-induced arrhythmia. HBK-16, HBK-17, HBK-18, and HBK-19 showed therapeutic antiarrhythmic properties in adrenaline-induced arrhythmia. None of the compounds showed activity in calcium chloride- or barium chloride-induced arrhythmias. HBK-16, HBK-17, HBK-18, and HBK-19 decreased heart

  14. Preparation and Thermoelectric Properties of Sn-Based Type VIII Single-Crystalline Clathrate Via a-Sn Flux Method

    NASA Astrophysics Data System (ADS)

    Cheng, Feng; Shen, Lanxian; Li, Decong; Liu, Hongxia; Wang, Jinsong; Deng, Shukang

    2016-06-01

    In this study, type VIII Ba8Ga16Sn30 single-crystal clathrates with different stoichiometric ratios were prepared using the a-Sn self-flux method. The structures of the samples were also investigated. Results indicate that n-/p-type single-crystal clathrates can be obtained by adjusting the initial content of Ga. Samples were determined to be n-type when the initial Ga content was X = 12, 13, and 14; and p-type when X = 16 and 18. The samples exhibited high melting points and large lattice parameters, as well as increasing Ga content. The electrical conductivities of the samples were lower than those prepared using the Sn self-flux method because of the low carrier concentration. The elemental composition of the sample was near the theoretical value when the Ga content was X = 14 and 16, which also yielded the highest Seebeck values of -523 μV/K and 331 V/K, respectively. Finally, the sample with X = 14 and 18 exhibited the highest ZT values of 0.82 and 0.46, respectively, at a temperature of 480 K in n-/p-type.

  15. The clathrate Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y}: Phase equilibria and crystal structure

    SciTech Connect

    Melnychenko-Koblyuk, Nataliya; Grytsiv, Andriy; Rogl, Peter; Schmid, Harald; Giester, Gerald

    2009-07-15

    Phase relations at 700 deg. C, 800 deg. C and solidus temperatures have been derived for the clathrate system Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y} via X-ray single crystal and powder diffractometry combined with electron probe micro analysis and differential thermal analysis. The ternary clathrate phase derives from binary Ba{sub 8}Ge{sub 43}square{sub 3} and extends up to x=6. Structure investigations define cubic primitive symmetry with the space group type Pm3-barn consistent with a clathrate type I structure throughout the entire homogeneity region 0=5.5. - Graphical Abstract: Cages and atom thermal displacement parameters in clathrate Ba{sub 8}Cu{sub x}Ge{sub 46-x-y}square{sub y} for Ba{sub 8}Cu{sub 2}Ge{sub 42}square{sub 2} and Ba{sub 8}Cu{sub 6}Ge{sub 40}.

  16. Climate change-induced vegetation change as a driver of increased subarctic biogenic volatile organic compound emissions

    PubMed Central

    Valolahti, Hanna; Kivimäenpää, Minna; Faubert, Patrick; Michelsen, Anders; Rinnan, Riikka

    2015-01-01

    Emissions of biogenic volatile organic compounds (BVOCs) have been earlier shown to be highly temperature sensitive in subarctic ecosystems. As these ecosystems experience rapidly advancing pronounced climate warming, we aimed to investigate how warming affects the BVOC emissions in the long term (up to 13 treatment years). We also aimed to assess whether the increased litterfall resulting from the vegetation changes in the warming subarctic would affect the emissions. The study was conducted in a field experiment with factorial open-top chamber warming and annual litter addition treatments on subarctic heath in Abisko, northern Sweden. After 11 and 13 treatment years, BVOCs were sampled from plant communities in the experimental plots using a push–pull enclosure technique and collection into adsorbent cartridges during the growing season and analyzed with gas chromatography–mass spectrometry. Plant species coverage in the plots was analyzed by the point intercept method. Warming by 2 °C caused a 2-fold increase in monoterpene and 5-fold increase in sesquiterpene emissions, averaged over all measurements. When the momentary effect of temperature was diminished by standardization of emissions to a fixed temperature, warming still had a significant effect suggesting that emissions were also indirectly increased. This indirect increase appeared to result from increased plant coverage and changes in vegetation composition. The litter addition treatment also caused significant increases in the emission rates of some BVOC groups, especially when combined with warming. The combined treatment had both the largest vegetation changes and the highest BVOC emissions. The increased emissions under litter addition were probably a result of a changed vegetation composition due to alleviated nutrient limitation and stimulated microbial production of BVOCs. We suggest that the changes in the subarctic vegetation composition induced by climate warming will be the major factor

  17. Effects of benzodiazepines and non-benzodiazepine compounds on the GABA-induced response in frog isolated sensory neurones.

    PubMed Central

    Yakushiji, T.; Fukuda, T.; Oyama, Y.; Akaike, N.

    1989-01-01

    1. The effects of benzodiazepines and non-benzodiazepine compounds on the gamma-aminobutyric acid (GABA)-induced chloride current (ICl) were studied in frog isolated sensory neurones by use of a concentration-jump (termed 'concentration-clamp') technique, under single-electrode voltage-clamp conditions. The drugs used were classified into four categories as follows: full benzodiazepine receptor agonists (diazepam, clonazepam, nitrazepam, midazolam, clotiazepam and etizolam), partial agonists (CL 218,872, Ro 16-6028, Ro 17-1812 and Ro 23-0364), inverse agonists (Ro 15-3505, FG 7142 and beta-CCE) and a benzodiazepine receptor antagonist, Ro 15-1788 (flumazenil). 2. All full agonists at concentrations of 3 x 10(-6) M or less increased dose-dependently the peak amplitude of ICl elicited by 3 x 10(-6) M GABA to twice to three times larger than the control. However, no further augmentation of the GABA response was observed at concentrations of 1 x 10(-5) M or higher. Partial agonists also showed a dose-dependent augmentation of the GABA response at concentrations ranging from 3 x 10(-8) M to 3 x 10(-5) M, but their efficacies of augmentation of the GABA response were only about half or less of those of full agonists. Of the inverse agonists, beta-CCE had a unique dose-dependent effect on the GABA response. Beta-CCE reduced dose-dependently the GABA response at concentrations of less than 3 x 10(-6) M, but augmented it at concentrations of 3 x 10(-5) M and 6 x 10(-5) M. The inverse agonists reduced dose-dependently the GABA response.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2574062

  18. Vitis thunbergii var. taiwaniana Extracts and Purified Compounds Ameliorate Obesity in High-Fat Diet-Induced Obese Mice.

    PubMed

    Lin, Shyr-Yi; Huang, Guan-Cheng; Hsieh, Ying-Ying; Lin, Yin-Shiou; Han, Chuan-Hsiao; Wen, Chi-Luan; Chang, Chi-I; Hou, Wen-Chi

    2015-10-28

    The increasing prevalence of obesity continues to gain more attention worldwide. In this study, diet-induced obese mice were used to evaluate the antiobesity effects of extracts, fractions, and purified compounds from Vitis thunbergii var. taiwaniana (VTT). The C57BL/6J mice were fed a 5-week high-fat diet (HF) concurrently with ethanol extracts (Et-ext, 80 mg/kg) from roots (R), stems (S), and leaves (L) by oral gavage daily. Only R-Et-ext interventions showed significant weight reduction in mice compared with those in the HF group; however, mouse plasma contents of total cholesterols (TC), total triglycerides (TG) and low-density lipoproteins (LDL) of all three Et-ext intervened groups showed significant reductions compared with those in the HF group. Furthermore, intervention with the ethyl acetate-partitioned fraction (EA-fra, 60 mg/kg) from R-Et-ext but not the n-butanol-partitioned fraction or water fraction from R-Et-ext showed significant weight reduction in mice compared with those in the HF group. The same molecular weights of three resveratrol tetramers, (+)-hopeaphenol, (+)-vitisin A, and (-)-vitisin B, were isolated from the EA-fra of VTT-R. The (+)-vitisin A and fenofibrate (25 mg/kg) but not the (+)-hopeaphenol and (-)-vitisin B interventions showed significant weight reduction in mice compared with those in the HF group. The total feed intake among the HF groups with or without interventions showed no significant differences. The mouse plasma contents of TC, TG, LDL, free fatty acid, and plasma lipase activity of the three resveratrol tetramer-intervened groups showed reductions in the mice compared with those in the HF group. It was proposed that the lipase inhibitory activities of VTT extracts and purified resveratrol tetramers might contribute in part to the antiobesity effect, and these results suggested that VTT may be developed as functional food for achieving antiobesity objectives and requires further investigation.

  19. Climate change-induced vegetation change as a driver of increased subarctic biogenic volatile organic compound emissions.

    PubMed

    Valolahti, Hanna; Kivimäenpää, Minna; Faubert, Patrick; Michelsen, Anders; Rinnan, Riikka

    2015-09-01

    Emissions of biogenic volatile organic compounds (BVOCs) have been earlier shown to be highly temperature sensitive in subarctic ecosystems. As these ecosystems experience rapidly advancing pronounced climate warming, we aimed to investigate how warming affects the BVOC emissions in the long term (up to 13 treatment years). We also aimed to assess whether the increased litterfall resulting from the vegetation changes in the warming subarctic would affect the emissions. The study was conducted in a field experiment with factorial open-top chamber warming and annual litter addition treatments on subarctic heath in Abisko, northern Sweden. After 11 and 13 treatment years, BVOCs were sampled from plant communities in the experimental plots using a push-pull enclosure technique and collection into adsorbent cartridges during the growing season and analyzed with gas chromatography-mass spectrometry. Plant species coverage in the plots was analyzed by the point intercept method. Warming by 2 °C caused a 2-fold increase in monoterpene and 5-fold increase in sesquiterpene emissions, averaged over all measurements. When the momentary effect of temperature was diminished by standardization of emissions to a fixed temperature, warming still had a significant effect suggesting that emissions were also indirectly increased. This indirect increase appeared to result from increased plant coverage and changes in vegetation composition. The litter addition treatment also caused significant increases in the emission rates of some BVOC groups, especially when combined with warming. The combined treatment had both the largest vegetation changes and the highest BVOC emissions. The increased emissions under litter addition were probably a result of a changed vegetation composition due to alleviated nutrient limitation and stimulated microbial production of BVOCs. We suggest that the changes in the subarctic vegetation composition induced by climate warming will be the major factor

  20. Mitochondrial dysfunction, impaired oxidative-reduction activity, degeneration, and death in human neuronal and fetal cells induced by low-level exposure to thimerosal and other metal compounds

    PubMed Central

    Geier, D.A.; King, P.G.; Geier, M.R.

    2009-01-01

    Thimerosal (ethylmercurithiosalicylic acid), an ethylmercury (EtHg)-releasing compound (49.55% mercury (Hg)), was used in a range of medical products for more than 70 years. Of particular recent concern, routine administering of Thimerosal-containing biologics/childhood vaccines have become significant sources of Hg exposure for some fetuses/infants. This study was undertaken to investigate cellular damage among in vitro human neuronal (SH-SY-5Y neuroblastoma and 1321N1 astrocytoma) and fetal (nontransformed) model systems using cell vitality assays and microscope-based digital image capture techniques to assess potential damage induced by Thimerosal and other metal compounds (aluminum (Al) sulfate, lead (Pb)(II) acetate, methylmercury (MeHg) hydroxide, and mercury (Hg)(II) chloride) where the cation was reported to exert adverse effects on developing cells. Thimerosal-associated cellular damage was also evaluated for similarity to pathophysiological findings observed in patients diagnosed with autistic disorders (ADs). Thimerosal-induced cellular damage as evidenced by concentration- and time-dependent mitochondrial damage, reduced oxidative–reduction activity, cellular degeneration, and cell death in the in vitro human neuronal and fetal model systems studied. Thimerosal at low nanomolar (nM) concentrations induced significant cellular toxicity in human neuronal and fetal cells. Thimerosal-induced cytoxicity is similar to that observed in AD pathophysiologic studies. Thimerosal was found to be significantly more toxic than the other metal compounds examined. Future studies need to be conducted to evaluate additional mechanisms underlying Thimerosal-induced cellular damage and assess potential co-exposures to other compounds that may increase or decrease Thimerosal-mediated toxicity. PMID:24532866

  1. Quinazoline-based tricyclic compounds that regulate programmed cell death, induce neuronal differentiation, and are curative in animal models for excitotoxicity and hereditary brain disease

    PubMed Central

    Vainshtein, A; Veenman, L; Shterenberg, A; Singh, S; Masarwa, A; Dutta, B; Island, B; Tsoglin, E; Levin, E; Leschiner, S; Maniv, I; Pe’er, L; Otradnov, I; Zubedat, S; Aga-Mizrachi, S; Weizman, A; Avital, A; Marek, I; Gavish, M

    2015-01-01

    Expanding on a quinazoline scaffold, we developed tricyclic compounds with biological activity. These compounds bind to the 18 kDa translocator protein (TSPO) and protect U118MG (glioblastoma cell line of glial origin) cells from glutamate-induced cell death. Fascinating, they can induce neuronal differentiation of PC12 cells (cell line of pheochromocytoma origin with neuronal characteristics) known to display neuronal characteristics, including outgrowth of neurites, tubulin expression, and NeuN (antigen known as ‘neuronal nuclei’, also known as Rbfox3) expression. As part of the neurodifferentiation process, they can amplify cell death induced by glutamate. Interestingly, the compound 2-phenylquinazolin-4-yl dimethylcarbamate (MGV-1) can induce expansive neurite sprouting on its own and also in synergy with nerve growth factor and with glutamate. Glycine is not required, indicating that N-methyl-D-aspartate receptors are not involved in this activity. These diverse effects on cells of glial origin and on cells with neuronal characteristics induced in culture by this one compound, MGV-1, as reported in this article, mimic the diverse events that take place during embryonic development of the brain (maintenance of glial integrity, differentiation of progenitor cells to mature neurons, and weeding out of non-differentiating progenitor cells). Such mechanisms are also important for protective, curative, and restorative processes that occur during and after brain injury and brain disease. Indeed, we found in a rat model of systemic kainic acid injection that MGV-1 can prevent seizures, counteract the process of ongoing brain damage, including edema, and restore behavior defects to normal patterns. Furthermore, in the R6-2 (transgenic mouse model for Huntington disease; Strain name: B6CBA-Tg(HDexon1)62Gpb/3J) transgenic mouse model for Huntington disease, derivatives of MGV-1 can increase lifespan by >20% and reduce incidence of abnormal movements. Also in vitro

  2. Experimental Studies of the Growth Kinetics of Methane Clathrate Hydrates & Superfluid Hydrodynamics on the Nanoscale

    NASA Astrophysics Data System (ADS)

    Botimer, Jeffrey David

    This thesis details the experimental findings of three distinct research projects. The first studies the growth kinetics of methane clathrate hydrates grown under the influence of multiple factors including surfactants, porous media, substrate wetting properties, and salt content. The second investigates the flow behaviors of superfluid helium through single, high aspect ratio nanopipes. The third models the frequency response of a quartz tuning fork in high pressure normal and superfluid helium and demonstrates how quartz tuning forks can be used as cheap, small, in situ, cryogenic pressure gauges. The first project reports studies of the kinetics of growth of methane hydrates from liquid water containing small amounts of surfactant (<500 ppm of sodium dodecyl sulfate, SDS). The kinetics are monitored using simultaneous measurements of the uptake of methane detected by a pressure drop in the gas phase, and either visual observations of the amount of liquid water and solid phase in the reaction vessel, or in situ micro-Raman measurements or in situ NMR measurements. These diagnostics show that the uptake of methane and the conversion of liquid water to a solid phase do not occur simultaneously; the uptake of gas always lags the visual and spectroscopic signatures of the disappearance of liquid water and the formation of solid. The evidence suggests that the SDS causes water to form an intermediate immobile solid-like state before combining with the methane to form hydrate. The growth mechanism is related to the surfactant and disappears for low SDS concentrations (<25 ppm). Also reported are studies of the growth rates of methane hydrates as a function of substrate wetting properties, driving force, and growth media. The second project studies pressure driven flow of superfluid helium through single high aspect ratio glass nanopipes into a vacuum has been studied for a wide range of pressure drop (0--30 atm), reservoir temperature (0.8--2.5K), pipe lengths (1-30mm

  3. Cytotoxic Compounds from Juglans sinensis Dode Display Anti-Proliferative Activity by Inducing Apoptosis in Human Cancer Cells.

    PubMed

    Lee, Yoo Jin; Cui, Jun; Lee, Jun; Han, Ah-Reum; Lee, Eun Byul; Jang, Ho Hee; Seo, Eun Kyoung

    2016-01-01

    Phytochemical investigation of the bark of Juglans sinensis Dode (Juglandaceae) led to the isolation of two active compounds, 8-hydroxy-2-methoxy-1,4-naphthoquinone (1) and 5-hydroxy-2-methoxy-1,4-naphthoquinone (2), together with 15 known compounds 3-17. All compounds were isolated from this plant for the first time. The structures of 1 and 2 were elucidated by spectroscopic data analysis, including 1D and 2D NMR experiments. Compounds 1-17 were tested for their cytotoxicity against the A549 human lung cancer cell line; compounds 1 and 2 exhibited significant cytotoxicity and additionally had potent cytotoxicity against six human cancer cell lines, MCF7 (breast cancer), SNU423 (liver cancer), SH-SY5Y (neuroblastoma), HeLa (cervical cancer), HCT116 (colorectal cancer), and A549 (lung cancer). In particular, breast, colon, and lung cancer cells were more sensitive to the treatment using compound 1. In addition, compounds 1 and 2 showed strong cytotoxic activity towards human breast cancer cells MCF7, HS578T, and T47D, but not towards MCF10A normal-like breast cells. They also inhibited the colony formation of MCF7, A549, and HCT116 cells in a dose-dependent manner. Flow cytometry analysis revealed that the percentage of apoptotic cells significantly increased in MCF7 cells upon the treatment with compounds 1 and 2. The mechanism of cell death caused by compounds 1 and 2 may be attributed to the upregulation of Bax and downregulation of Bcl2. These findings suggest that compounds 1 and 2 may be regarded as potential therapeutic agents against cancer.

  4. Classification of compounds for prevention of NMDLA-induced seizures/mortality, or maximal electroshock and pentylenetetrazol seizures in mice and antagonism of MK801 binding in vitro.

    PubMed

    Palmer, G C; Harris, E W; Ray, R; Stagnitto, M L; Schmiesing, R J

    1992-01-01

    Intravenous injection of N-methyl-D,L-aspartic acid (NMDLA) into mice produces characteristic convulsions followed by death. The present study was designed to determine the degree of blockade of these seizures/mortality by compounds acting at various subsites on the N-methyl-D-aspartic acid (NMDA) receptor complex (competitive and noncompetitive antagonists, as well as inhibitors of the strychnine-insensitive glycine subsite, and Zn++ subsite agonists), and also calcium channel blockers, clinically used anticonvulsants, plus selected compounds with activities or structures similar to specific agents chosen. Activity among compounds was correlated to in vitro potency regarding inhibition of binding of MK801 to the ionic channel subsite associated with the NMDA receptor. Furthermore, all compounds were examined for antiseizure properties with respect to tonic hindlimb extension elicited by maximal electroshock (MES) and clonus induced by pentylenetetrazol (PTZ). Drugs were subsequently classified according to their spectra of efficacy in these tests. The following characteristics emerged: 1) agents active at all 3 NMDA mechanisms (convulsions/mortality/MK801 binding) plus MES and PTZ, were MK801 and CPP [3-(2-carboxypiperazin-4-yl) propyl-1-phosphonic acid]; 2) active at all the NMDA mechanisms and MES were ketamine and dextromethorphan; 3) active against NMDLA-induced convulsions/mortality, MES and PTZ, but not MK801 binding, were doxepin, desipramine and diazepam; 4) active against NMDLA-induced convulsions/mortality and MES were des-Me-doxepin, flunarizine and remacemide; 5) active against NMDLA-induced convulsions/mortality and PTZ was nisoldipine; 6) active against only NMDLA-induced convulsions/mortality were chlorpheniramine and iproniazid; 7) active in the MES and PTZ tests were phenobarbital, pentobarbital and valproate; 8) active in the MES test alone were phenytoin and carbamazepine; 9) active against PTZ only was ethosuximide; 10) active only in the in

  5. Ajoene, a compound of garlic, induces apoptosis in human promyeloleukemic cells, accompanied by generation of reactive oxygen species and activation of nuclear factor kappaB.

    PubMed

    Dirsch, V M; Gerbes, A L; Vollmar, A M

    1998-03-01

    The pharmacological role of garlic in prevention and treatment of cancer has received increasing attention, but thorough investigations into the molecular mechanisms of action of garlic compounds are rare. The present study demonstrates that ajoene, a major compound of garlic induces apoptosis in human leukemic cells, but not in peripheral mononuclear blood cells of healthy donors. The effect was dose and time dependent. Apoptosis was judged by three criteria, morphology of cells, quantification of subdiploid DNA content by flow cytometry, and detection of DNA fragmentation by gel electrophoresis. Ajoene increased the production of intracellular peroxide in a dose- and time-dependent fashion, which could be partially blocked by preincubation of the human leukemic cells with the antioxidant N-acetylcysteine. Interestingly, N-acetylcysteine-treated cells showed a 50% loss of ajoene-induced apoptosis. Moreover, ajoene was demonstrated to activate nuclear translocation of the transcription factor nuclear factor kappaB, an effect that was abrogated in N-acetylcysteine-loaded cells. These results suggested that ajoene might induce apoptosis in human leukemic cells via stimulation of peroxide production and activation of nuclear factor kappaB. This is a novel aspect in the biological profile of this garlic compound and an important step in elucidating the underlying molecular mechanisms of its antitumor action.

  6. Induction of aromatic amino acids and phenylpropanoid compounds in Scrophularia striata Boiss. cell culture in response to chitosan-induced oxidative stress.

    PubMed

    Kamalipourazad, Maryam; Sharifi, Mohsen; Maivan, Hassan Zare; Behmanesh, Mehrdad; Chashmi, Najmeh Ahmadian

    2016-10-01

    Manipulation of cell culture media by elicitors is one of most important strategies to inducing secondary metabolism for the production of valuable metabolites. In this investigation, inducing effect of chitosan on physiological, biochemical, and molecular parameters were investigated in cell suspension cultures of Scrophularia striata Boiss. The results showed that chitosan concentration and time of elicitation are determinants of the effectiveness of the elicitor. Accumulation of aromatic amino acids (phenylalanine [Phe] and tyrosine [Tyr]), phenylpropanoid compounds (phenolic acids [PAs] and echinacoside [ECH]), hydrogen peroxide (H2O2) production, phenylalanine ammonia-lyase (PAL) activity and gene expression, and antioxidant enzymes (superoxide dismutase [SOD], peroxidase [POX], catalase [CAT]) activities were altered by changing the exposure time of elicitation. Results showed that, upon elicitation with chitosan, oxidative events were induced, antioxidant responses of S. striata cells were boosted through enhanced activity of an effective series of scavenging enzymes (SOD, CAT, and POX), and biosynthesis of non-enzymatic antioxidants (ECH and PAs [cinnamic, p-coumaric and, caffeic acids]). The increase in amino acid content and PAL activity at early days of exposure to chitosan was related with rises in phenolic compounds. These results provide evidence that chitosan by up-regulation of PAL gene differentially improves the production of phenylpropanoid compounds, which are of medical commercial value with good biotechnological prospects. PMID:27392152

  7. The Mechanism of Melanocytes-Specific Cytotoxicity Induced by Phenol Compounds Having a Prooxidant Effect, relating to the Appearance of Leukoderma

    PubMed Central

    Ito, Shinobu; Kanazawa, Hideko; Masaki, Hitoshi

    2015-01-01

    Specific phenol compounds including rhododendrol (RD), a skin-brightening ingredient in cosmetics, are reported to induce leukoderma, inducing a social problem, and the elucidation of mechanism of leukoderma is strongly demanded. This study investigated the relationship among the cytotoxicities of six phenol compounds on B16F10 melanoma cells and HaCaT keratinocytes and generated reactive oxygen species (ROS). As a result, the cytotoxicity of RD on B16F10 cells was higher than that on HaCaT cells, and RD significantly increased intracellular ROS and hydrogen peroxide (H2O2) levels in B16F10 cells. Furthermore, although raspberry ketone (RK), RD derivative, also increased intracellular ROS in B16F10 cells, increase in ROS was suppressed by disodium dihydrogen ethylenediaminetetraacetate dehydrate (EDTA). The amounts of increased ROS with RK in HaCaT cells without melanocyte were further increased by tyrosinase. Therefore, tyrosinase, a metalloprotein having copper, was speculated to be one of causative agents allowing phenol compounds to work as a prooxidant. Hydroxyl radical was generated by adding a mixture of tyrosinase and H2O2 to RD, and the amount of the radical was further increased by UVB, indicating that RD cytotoxicity was caused by intracellularly increased ROS, which possibly related to phenol induced prooxidants. PMID:25861631

  8. Induction of aromatic amino acids and phenylpropanoid compounds in Scrophularia striata Boiss. cell culture in response to chitosan-induced oxidative stress.

    PubMed

    Kamalipourazad, Maryam; Sharifi, Mohsen; Maivan, Hassan Zare; Behmanesh, Mehrdad; Chashmi, Najmeh Ahmadian

    2016-10-01

    Manipulation of cell culture media by elicitors is one of most important strategies to inducing secondary metabolism for the production of valuable metabolites. In this investigation, inducing effect of chitosan on physiological, biochemical, and molecular parameters were investigated in cell suspension cultures of Scrophularia striata Boiss. The results showed that chitosan concentration and time of elicitation are determinants of the effectiveness of the elicitor. Accumulation of aromatic amino acids (phenylalanine [Phe] and tyrosine [Tyr]), phenylpropanoid compounds (phenolic acids [PAs] and echinacoside [ECH]), hydrogen peroxide (H2O2) production, phenylalanine ammonia-lyase (PAL) activity and gene expression, and antioxidant enzymes (superoxide dismutase [SOD], peroxidase [POX], catalase [CAT]) activities were altered by changing the exposure time of elicitation. Results showed that, upon elicitation with chitosan, oxidative events were induced, antioxidant responses of S. striata cells were boosted through enhanced activity of an effective series of scavenging enzymes (SOD, CAT, and POX), and biosynthesis of non-enzymatic antioxidants (ECH and PAs [cinnamic, p-coumaric and, caffeic acids]). The increase in amino acid content and PAL activity at early days of exposure to chitosan was related with rises in phenolic compounds. These results provide evidence that chitosan by up-regulation of PAL gene differentially improves the production of phenylpropanoid compounds, which are of medical commercial value with good biotechnological prospects.

  9. Methods of thermoelectric enhancement in silicon-germanium alloy type I clathrates and in nanostructured lead chalcogenides

    NASA Astrophysics Data System (ADS)

    Martin, Joshua

    The rapid increase in thermoelectric (TE) materials R&D is a consequence of the growing need to increase energy efficiency and independence through waste heat recovery. TE materials enable the direct solid-state conversion of heat into electricity, with little maintenance, noise, or cost. In addition, these compact devices can be incorporated into existing technologies to increase the overall operating efficiency. High efficiency TE materials would enable the practical solid-state conversion of thermal to electrical energy. Optimizing the interdependent physical parameters to achieve acceptable efficiencies requires materials exhibiting a unique combination of properties. This research reports two methods of thermoelectric enhancement: lattice strain effects in silicon-germanium alloy type I clathrates and the nanostructured enhancement of lead chalcogenides. The synthesis and chemical, structural, and transport properties characterization of Ba8Ga16SixGe30-x type I clathrates with similar Ga-to-group IV element ratios but with increasing Si substitution (4 < x < 14) is reported. Substitution of Si within the Ga-Ge lattice framework of the type I clathrate Ba8Ga16Ge30 results in thermoelectric performance enhancement. The unique dependences of carrier concentration, electrical resistivity, Seebeck coefficient, and carrier effective mass on Si substitution level, may imply a modified band structure with Si substitution. These materials were then further optimized by adjusting the Ga-to-group IV element ratios. Recent progress in a number of higher efficiency TE materials can be attributed to nanoscale enhancement. Many of these materials demonstrate increased Seebeck coefficient and decreased thermal conductivity due to the phenomenological properties of nanometer length scales. To satisfy the demands of bulk industrial applications requires additional synthesis techniques to incorporate nanostructure directly within a bulk matrix. This research investigates, for

  10. Unusual high fluorescence of two nitro-distyrylbenzene-like compounds induced by CT processes affecting the fluorescence/intersystem-crossing competition.

    PubMed

    Carlotti, B; Elisei, F; Mazzucato, U; Spalletti, A

    2015-06-14

    Two nitro-substituted 1,4-distyrylbenzene-like compounds have been investigated using stationary and time-resolved (ns/fs) spectrometric techniques as a function of solvent polarity. In the two compounds the central benzene ring is substituted with a p-nitrostyryl group at one side while, at the other side, compound 1 (asymmetric) bears a pyrid-4-ylethenyl group and compound 2 (symmetric) another p-nitrostyryl group. The solvent dependent intramolecular charge transfer (ICT) in the singlet manifold was found to strongly affect the competition among fluorescence, intersystem crossing and trans-cis photoisomerization. The presence of nitro-groups in the 1,4-distyrylbenzene skeleton causes the usual strong decrease of fluorescence in favour of intersystem crossing to a reactive triplet state. However, the favoured formation of the ICT state in polar solvents induces an unexpected important increase of the fluorescence quantum yield (three/two order of magnitude for the nitro and dinitro derivatives, respectively). The ultrafast spectral transients helped to understand the solvent effects measured by stationary techniques and gave information on the dynamics of the locally excited singlet state ((1)LE*) and the (1)ICT* state, fast produced in polar solvents. Evidence of dual fluorescence in a limited range of solvent polarity, particularly for compound 1, is also reported. The role of an upper triplet state in a non-polar solvent is discussed also based on quantum-mechanical calculations (TD-DFT method) and temperature effects on the photophysical parameters. PMID:25975235

  11. Unusual high fluorescence of two nitro-distyrylbenzene-like compounds induced by CT processes affecting the fluorescence/intersystem-crossing competition.

    PubMed

    Carlotti, B; Elisei, F; Mazzucato, U; Spalletti, A

    2015-06-14

    Two nitro-substituted 1,4-distyrylbenzene-like compounds have been investigated using stationary and time-resolved (ns/fs) spectrometric techniques as a function of solvent polarity. In the two compounds the central benzene ring is substituted with a p-nitrostyryl group at one side while, at the other side, compound 1 (asymmetric) bears a pyrid-4-ylethenyl group and compound 2 (symmetric) another p-nitrostyryl group. The solvent dependent intramolecular charge transfer (ICT) in the singlet manifold was found to strongly affect the competition among fluorescence, intersystem crossing and trans-cis photoisomerization. The presence of nitro-groups in the 1,4-distyrylbenzene skeleton causes the usual strong decrease of fluorescence in favour of intersystem crossing to a reactive triplet state. However, the favoured formation of the ICT state in polar solvents induces an unexpected important increase of the fluorescence quantum yield (three/two order of magnitude for the nitro and dinitro derivatives, respectively). The ultrafast spectral transients helped to understand the solvent effects measured by stationary techniques and gave information on the dynamics of the locally excited singlet state ((1)LE*) and the (1)ICT* state, fast produced in polar solvents. Evidence of dual fluorescence in a limited range of solvent polarity, particularly for compound 1, is also reported. The role of an upper triplet state in a non-polar solvent is discussed also based on quantum-mechanical calculations (TD-DFT method) and temperature effects on the photophysical parameters.

  12. Gastroprotective effects of goniothalamin against ethanol and indomethacin-induced gastric lesions in rats: Role of prostaglandins, nitric oxide and sulfhydryl compounds.

    PubMed

    Vendramini-Costa, Débora Barbosa; Monteiro, Karin Maia; Iwamoto, Leilane Hespporte; Jorge, Michelle Pedroza; Tinti, Sirlene Valério; Pilli, Ronaldo Aloise; de Carvalho, João Ernesto

    2014-12-01

    Goniothalamin (GTN), a styryl-lactone, is a secondary metabolite naturally found in its enantiomeric form (R) in plants of the genus Goniothalamus (Annonaceae). The antiproliferative activity against human tumor cell lines reported in several studies suggest that the α,β-unsaturated δ-lactone moiety emerges as a key Michael acceptor for cysteine residues or other nucleophilic biological molecules. Our group reported on the in vivo activity of (R)- and (S)-GTN as well as its racemic form (rac-GTN) in both Ehrlich solid tumor and carrageenan-induced paw edema in mice, without side effects in the effective doses. Despite the rich body of data on the in vitro GTN biological activity, much less is known about its in vivo pharmacological action. Herein we describe the gastroprotective activity of rac-GTN on chemical-induced gastric ulcers models in rats. GTN has a potent gastroprotective effect on ethanol-induced ulcers (effective dose50=18mg/kg) and this activity is dependent on sulfhydryl compounds and prostaglandins generation, but independent of nitric oxide (NO), gastric secretion and mucus production. We hypothesize that goniothalamin may act as a mild irritant, inducing the production of sulfhydryl compounds and prostaglandins, in a process known as adaptive cytoprotection. This hypothesis is supported by the fact that Michael acceptors are the most potent inducers of antioxidant response (as activation of Nrf2 pathway) through generation of mild oxidative stress and that gastroprotective activity of goniothalamin is inhibited after pre-treatment with NEM (N-ethylmaleimide) and NSAID (non-steroidal anti-inflammatory drugs), highlighting the importance of sulfhydryl compounds and prostaglandins on GTN activity.

  13. Thermoelectric and transport properties of sintered n-type K{sub 8}Ba{sub 16}Ga{sub 40}Sn{sub 96} with type-II clathrate structure

    SciTech Connect

    Koda, Shota; Kishimoto, Kengo Asada, Hironori; Koyanagi, Tsuyoshi; Akai, Koji

    2014-07-14

    This clathrate had a maximum dimensionless figure-of-merit, ZT, of 0.93 at 637 K, which was slightly higher than that of 0.83 for the sintered type-VIII clathrate Ba{sub 8}Ga{sub 16}Sn{sub 30}. We investigated the high-temperature thermoelectric properties, transport properties, electronic structures, and thermal stabilities of the clathrates. The type-II clathrate was found to be superior to the type-VIII clathrate as a thermoelectric material; it had a high thermal stability and melting point, 859 K, high mobility, 141 cm{sup 2}V{sup −1}s{sup −1} at 300 K, because of its low inertial mass, and low high-temperature lattice thermal conductivity, approximately 4 mW cm{sup −1}K{sup −1}, resulting from a larger unit cell and weaker bipolar thermal conduction. We discuss these properties in terms of the electronic structure and the differences between the two types of clathrate.

  14. Anti-Inflammatory Activity of a Novel Family of Aryl Ureas Compounds in an Endotoxin-Induced Airway Epithelial Cell Injury Model

    PubMed Central

    Cabrera-Benitez, Nuria E.; Pérez-Roth, Eduardo; Casula, Milena; Ramos-Nuez, Ángela; Ríos-Luci, Carla; Rodríguez-Gallego, Carlos; Sologuren, Ithaisa; Jakubkiene, Virginija; Slutsky, Arthur S.; Padrón, José M.; Villar, Jesús

    2012-01-01

    Background Despite our increased understanding of the mechanisms involved in acute lung injury (ALI) and the acute respiratory distress syndrome (ARDS), there is no specific pharmacological treatment of proven benefit. We used a novel screening methodology to examine potential anti-inflammatory effects of a small structure-focused library of synthetic carbamate and urea derivatives in a well established cell model of lipopolysaccharide (LPS)-induced ALI/ARDS. Methodology/Principal Findings After a pilot study to develop an in vitro LPS-induced airway epithelial cell injury model, a library of synthetic carbamate and urea derivates was screened against representative panels of human solid tumor cell lines and bacterial and fungal strains. Molecules that were non-cytotoxic and were inactive in terms of antiproliferative and antimicrobial activities were selected to study the effects on LPS-induced inflammatory response in an in vitro cell culture model using A549 human alveolar and BEAS-2B human bronchial cells. These cells were exposed for 18 h to LPS obtained from Escherichia coli, either alone or in combination with the test compounds. The LPS antagonists rhein and emodin were used as reference compounds. The most active compound (CKT0103) was selected as the lead compound and the impact of CKT0103 on pro-inflammatory IL-6 and IL-8 cytokine levels, expression of toll-like receptor-4 (TLR4) and nuclear factor kappa B inhibitor alpha (IκBα) was measured. CKT0103 significantly inhibited the synthesis and release of IL-6 and IL-8 induced by LPS. This suppression was associated with inhibition of TLR4 up-regulation and IκBα down-regulation. Immunocytochemical staining for TLR4 and IκBα supported these findings. Conclusions/Significance Using a novel screening methodology, we identified a compound – CKT0103 – with potent anti-inflammatory effects. These findings suggest that CKT0103 is a potential target for the treatment of the acute phase of sepsis and

  15. Crystal structure, characterization and thermoelectric properties of the type-I clathrate Ba{sub 8-y}Sr{sub y}Al{sub 14}Si{sub 32} (0.6{<=}y{<=}1.3) prepared by aluminum flux

    SciTech Connect

    Roudebush, John H.; Toberer, Eric S.; Hope, Hakon; Jeffrey Snyder, G.; Kauzlarich, Susan M.

    2011-05-15

    The title compound was prepared as single crystals using an aluminum flux technique. Single crystal and powder X-ray diffraction indicate that this composition crystallizes in the clathrate type-I structure, space group Pm3-bar n. Electron microprobe characterization indicates the composition to be Ba{sub 8-y}Sr{sub y}Al{sub 14.2(2)}Si{sub 31.8(2)} (0.77clathrate phase with nominal composition Ba{sub 7}Sr{sub 1}Al{sub 14}Si{sub 32} has been prepared by Al flux. Single crystal diffraction at 90 and 12 K reveal that the framework is fully occupied with the cation sites nearly fully occupied. The lattice thermal conductivity is low thereby suggesting further optimization of the carrier concentration will lead to a high zT. Display Omitted Highlights: {yields} Ba{sub 7}Sr{sub 1}Al{sub 14}Si{sub 32} is a light element phase ideal for thermoelectric power generation. {yields} Ba{sub 7}Sr{sub 1}Al{sub 14}Si{sub 32} is a high melting point cubic

  16. A novel anti-inflammatory compound, artonkin-4'-O-glucoside, from the leaves of Artocarpus tonkinensis suppresses experimentally induced arthritis.

    PubMed

    Dang, D T N; Eriste, E; Liepinsh, E; Trinh, T T; Erlandsson-Harris, H; Sillard, R; Larsson, P

    2009-02-01

    Artocarpus tonkinenesis (Moraceae) has been used in Vietnamese traditional medicine for the treatment of backache and joint diseases since many 100 years. We have previously shown that a crude extract of A. tonkinensis elicited anti-inflammatory effects in rat collagen-induced arthritis (CIA), with significant improvement of disease symptoms. However, the pharmacological basis of the bioactivity of A. tonkinensis extract is not known. In the present study, we have isolated four individual active components from A. tonkinensis extract by reverse phase high-pressure liquid chromatography. The structures of the compounds were determined by nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry and their biological effects investigated. A novel biologically active flavonoid glucoside (5-hydroxy-8-hydroxymethyl-8-methyl-2-[4-(3,4,5-trihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yloxy)-phenyl]-8H-pyrano[3,2-g]chromen-4-one) with an average molecular mass of 514.49 Da was isolated.We have named the compound artonkin-4'-O-glucoside. The name 'artonkin' for the novel flavonoid part of the compound was coined from the Latin name of its source Artocarpus tonkinensis. The three other active flavonoid glucosides isolated and characterized were alphitonin-4-O-beta-D-glucoside, maesopsin-4-O-beta-D-glucoside and kaempherol-3-O-beta-D-glucoside. All four compounds were found to cause anti-inflammatory effect with different potencies. The anti-inflammatory effects demonstrated in the rat model of arthritis correlate well with the inhibition of mitogen-induced T-cell proliferation. Furthermore, the compounds inhibit production of cytokines, such as tumour necrosis factor-a and interferon-c, in mitogen-stimulated T cells in a concentration-dependent manner. We postulate that the isolated flavonoids suppress T-cell proliferation as well as cytokine expression and thereby contribute to an amelioration of arthritis severity in CIA.

  17. Quantifying the flux and fate of methane into the Hudson Canyon at the edge of methane clathrate hydrate stability

    NASA Astrophysics Data System (ADS)

    Kessler, J. D.; Leonte, M.; Garcia-Tigreros Kodovska, F.; Chan, E. W.; Valentine, D. L.; Kellermann, M. Y.; Arrington, E. C.; Navarrete, L. C.; Weinstein, A.; Chepigin, A.; Weber, T.; Ruppel, C. D.; Scranton, M. I.

    2015-12-01

    Methane seeps were investigated in the Hudson Canyon, along the northern US Atlantic Margin on the R/V Endeavor in July 2014. These seeps are located along the upper feather-edge of the methane clathrate hydrate stability zone. Water column samples were collected guided by the acoustic identification of bubble streams in a 32 km2 region. This presentation details the measurements of dissolved methane concentration, natural stable isotopes, potential methane oxidation rates, and current velocity which were used in chemical and isotopic models to quantify (1) the total emission of methane to the water column in this region and (2) the extent of aerobic methane oxidation. In addition, the timing, efficiency, and kinetics of aerobic methane oxidation were investigated with mesocosm incubations of seawater in a unique experimental design that enabled high temporal resolution data acquisition. Finally, the ultimate fate of methane carbon was assessed with high precision measurements of pH.

  18. Thermoelectric properties of polycrystalline type-I germanium clathrates Ba8Ga16-xGe30+x

    NASA Astrophysics Data System (ADS)

    Leszczynski, J.; Kolezynski, A.; Wojciechowski, K. T.

    2012-06-01

    Samples of germanium clathrates A8Ga16-xGe30+x (A=Ba, K) filled with Ba and K were prepared using standard powder metallurgy methods. The structure and phase composition of the prepared samples were analyzed by powder x-ray diffraction XRD. Due to experimental problems we were unable to synthesize K containing samples with the desired quality. Preliminary electronic band structure calculations were performed for two compositions of Ba8Ga16-xGe30+x (x=0; 10) based on the DTF theory. Electrical conductivity, Seebeck coefficient and thermal conductivity were measured in the temperature range 20 - 450°C. The observed properties were compared with the electronic band structure calculations, showing good qualitative correlation between measured transport properties and theoretical predictions.

  19. Observations of CO{sub 2} clathrate hydrate formation and dissolution under deep-ocean disposal conditions

    SciTech Connect

    Warzinski, R.P.; Cugini, A.V.; Holder, G.D.

    1995-11-01

    Disposal of anthropogenic emissions of CO{sub 2} may be required to mitigate rises in atmospheric levels of this greenhouse gas if other measures are ineffective and the worst global warming scenarios begin to occur. Long-term storage of large quantities of CO{sub 2} has been proposed, but the feasibility of large land and ocean disposal options remains to be established. Determining the fate of liquid CO{sub 2} injected into the ocean at depths greater than 500 m is complicated by uncertainties associated with the physical behavior of CO{sub 2} under these conditions, in particular the possible formation of the ice-like CO{sub 2} clathrate hydrate. Resolving this issue is key to establishing the technical feasibility of this option. Experimental and theoretical work in this area is reported.

  20. Anomalous Infrared Spectra of Hybridized Phonons in Type-I Clathrate Ba8Ga16Ge30

    NASA Astrophysics Data System (ADS)

    Iwamoto, Kei; Kushibiki, Shunsuke; Honda, Hironori; Kajitani, Shuhei; Mori, Tatsuya; Matsumoto, Hideki; Toyota, Naoki; Suekuni, Koichiro; Avila, Marcos A.; Takabatake, Toshiro

    2013-02-01

    The optical conductivity spectra of the rattling phonons in the clathrate Ba8Ga16Ge30 are investigated in detail by use of the terahertz time-domain spectroscopy. The experiment has revealed that the lowest-lying vibrational mode of Ba(2)2+ ions consist of a sharp Lorentzian peak at 1.2 THz superimposed on a broad tail weighted in the lower frequency regime around 1.0 THz. With decreasing temperature, an unexpected linewidth broadening of the phonon peak is observed, together with monotonic softening of the phonon peak and enhancement of the tail structure. These observed anomalies are discussed in terms of impurity scattering effects on the hybridized phonon system of rattling and acoustic phonons.

  1. The false-positive responses of analgesic drugs to the intradermal serotonin- and compound 48/80-induced scratches as an animal model of itch.

    PubMed

    Ilkaya, Fatih; Yesilyurt, Ozgur; Seyrek, Melik; Gunduz, Ozgur; Ide, Tayfun; Akar, Ahmet; Ulugol, Ahmet; Guzel, Hasan; Dogrul, Ahmet; Ucar, Durmus; Gunaydin, Caner

    2016-01-01

    Intradermal injection of pruritogens such as serotonin, histamine and compound 48/80 into the skin and then, the evaluation of the scratching behavior is the commonly used animal model to advance pruritic research and drug development. However, predictive validity of this model is poorly documented. There is a close interaction between itch and pain sensations with regard to mediation through an anatomically and functionally identical neuronal pathway. One approach is whether the existing animal model of itch differentiates itch or pain to show efficacy of clinically effective analgesic drugs as a back translation. In this study, we explored the effects of different group of analgesic drugs on serotonin and compound 48/80-induced scratching behavior in Balb-C mice. Serotonin (25 μg) and compound 48/80 (100 μg) was injected intradermally in a volume of 50 μl into the rostral part of skin on the back of male mice and scratches were counted for a 30-min observation period. Morphine (1, 3, 10 mg/kg), tramadol (20, 40, 80 mg/kg), cannabinoid agonist CP 55,940 (0.1, 0.3, 1 mg/kg), paracetamol (100, 200, 300 mg/kg) and diclofenac (50, 100, 200 mg/kg) were given intraperitoneally 30 min prior to pruritogen injection. The analgesic drugs dose dependently blocked serotonin and compound 48/80-induced straching behavior with exerting complete inhibition at certain doses. Our data suggests that intradermal pruritogen-induced scratching models may not discriminate pain and itch sensations and give false positive results when standard analgesic drugs are used. PMID:27685776

  2. Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

    PubMed

    Shin, Kyuchul; Udachin, Konstantin A; Moudrakovski, Igor L; Leek, Donald M; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

    2013-05-21

    One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests.

  3. Screening a Small Library of Xanthones for Antitumor Activity and Identification of a Hit Compound which Induces Apoptosis.

    PubMed

    Barbosa, João; Lima, Raquel T; Sousa, Diana; Gomes, Ana Sara; Palmeira, Andreia; Seca, Hugo; Choosang, Kantima; Pakkong, Pannee; Bousbaa, Hassan; Pinto, Madalena M; Sousa, Emília; Vasconcelos, M Helena; Pedro, Madalena

    2016-01-13

    Our previous work has described a library of thioxanthones designed to have dual activity as P-glycoprotein modulators and antitumor agents. Some of these compounds had shown a significant cell growth inhibitory activity towards leukemia cell lines, without affecting the growth of non-tumor human fibroblasts. However, their effect in cell lines derived from solid tumors has not been previously studied. The present work aimed at: (i) screening this small series of compounds from an in-house library, for their in vitro cell growth inhibitory activity in human tumor cell lines derived from solid tumors; and (ii) initiate a study of the effect of the most potent compound on apoptosis. The tumor cell growth inhibitory effect of 27 compounds was first analysed in different human tumor cell lines, allowing the identification of a hit compound, TXA1. Its hydrochloride salt TXA1·HCl was then synthesized, to improve solubility and bioavailability. Both TXA1 and TXA1·HCl inhibited the growth of MCF-7, NCI-H460, A375-C5, HeLa, 786-O, Caki-2 and AGS cell lines. The effect of TXA1·HCl in MCF-7 cells was found to be irreversible and was associated, at least in part, with an increase in cellular apoptosis.

  4. Screening a Small Library of Xanthones for Antitumor Activity and Identification of a Hit Compound which Induces Apoptosis.

    PubMed

    Barbosa, João; Lima, Raquel T; Sousa, Diana; Gomes, Ana Sara; Palmeira, Andreia; Seca, Hugo; Choosang, Kantima; Pakkong, Pannee; Bousbaa, Hassan; Pinto, Madalena M; Sousa, Emília; Vasconcelos, M Helena; Pedro, Madalena

    2016-01-01

    Our previous work has described a library of thioxanthones designed to have dual activity as P-glycoprotein modulators and antitumor agents. Some of these compounds had shown a significant cell growth inhibitory activity towards leukemia cell lines, without affecting the growth of non-tumor human fibroblasts. However, their effect in cell lines derived from solid tumors has not been previously studied. The present work aimed at: (i) screening this small series of compounds from an in-house library, for their in vitro cell growth inhibitory activity in human tumor cell lines derived from solid tumors; and (ii) initiate a study of the effect of the most potent compound on apoptosis. The tumor cell growth inhibitory effect of 27 compounds was first analysed in different human tumor cell lines, allowing the identification of a hit compound, TXA1. Its hydrochloride salt TXA1·HCl was then synthesized, to improve solubility and bioavailability. Both TXA1 and TXA1·HCl inhibited the growth of MCF-7, NCI-H460, A375-C5, HeLa, 786-O, Caki-2 and AGS cell lines. The effect of TXA1·HCl in MCF-7 cells was found to be irreversible and was associated, at least in part, with an increase in cellular apoptosis. PMID:26771595

  5. Parasitic Wasps Aphidius ervi are More Attracted to a Blend of Host-Induced Plant Volatiles than to the Independent Compounds.

    PubMed

    Takemoto, Hiroyuki; Takabayashi, Junji

    2015-09-01

    Arthropodal natural enemies respond to volatiles from plants infested by their prey/host herbivores (herbivore-induced plant volatiles; HIPVs). However, the relative importance of HIPV blends vs. each compound in the blend in attracting natural enemies is not fully understood. In this study, we investigated the response of a parasitic wasp, Aphidius ervi, to HIPVs that were specific or nonspecific to infestations by its host aphid, Acyrthosiphon pisum. To select such compounds, we compared the volatiles emitted from broad bean plants infested by either A. pisum (host) or by Aphis craccivora (nonhost), and selected the host-specific HIPVs β-myrcene, n-octanal, and α-phellandrene, and host-nonspecific HIPVs (E)-β-ocimene, γ-terpinene, and linalool as test compounds. For each compound, we used a range that covered the amounts emitted from infested broad bean plants for bioassays. Female wasps preferred n-octanal and (E)-β-ocimene at 10-ng and 30-ng doses over clean air. Interestingly, the wasps preferred α-phellandrene at 0.1-ng and 30-ng doses, but not at 1-ng and 10-ng doses. The wasps repelled linalool over clean air at 1-ng and 0.1-ng doses. We then mixed the equivalent amounts of the six compounds to test the effect of the blend. The wasps responded to a blend of six HIPV components at all concentrations tested (0.001 ng each to 5 ng each). These results suggested that the blend provided more useful information for female wasps than the individual compounds. The possible use of the single component and the blend for the biological control of A. ervi is discussed.

  6. Prevention and treatment of non-steroidal anti-inflammatory drug-induced gastro-duodenal damage: rationale for the use of antisecretory compounds.

    PubMed

    Scarpignato, C; Pelosini, I

    1999-01-01

    Gastro-duodenal mucosa possesses an array of defensive mechanisms and non-steroidal anti-inflammatory drugs have a deleterious effect on most of them. This results in a mucosa less able to cope with even a reduced acid load. The presence of acid appears to be a conditio sine qua non for non-steroidal anti-inflammatory drug-injury, which is in fact pH-dependent. The acute damage induced by acid non-steroidal anti-inflammatory drugs, like aspirin, can be markedly reduced or even prevented by raising intragastric pH with antacids or antisecretory compounds. Animal studies have clearly shown that not only the degree, but also the duration, of acid inhibition is an important factor for prevention of non-steroidal anti-inflammatory drug-induced mucosal damage. As a consequence, proton pump inhibitors (PPIs) appear to be more effective that H2-receptor antagonists both in preventing and treating gastro-duodenal lesions. While acid suppression seems to be the only effective mechanism for ulcer healing, prevention of non-steroidal anti-inflammatory drug-injury might also rely on the mucosal protective activity of these compounds. Clinical pharmacological studies, performed in healthy volunteers, have shown that--as in laboratory animals--elevation of intragastric pH by means of antacids or antisecretory compounds protects against acute NSAID-induced damage. Unlike H2-blockers, PPIs protect from non-steroidal anti-inflammatory drug-injury not only the duodenum, but also the stomach, where the majority of mucosal lesions are usually located. Although elevation of intragastric pH affects non-steroidal anti-inflammatory drug pharmacokinetics and pharmacodynamics in laboratory animals, a lack of drug-to-drug interaction between PPIs and some of these compounds has been reported in humans. To summarize, clinical and experimental pharmacology support the use of PPIs for the prevention and treatment of non-steroidal anti-inflammatory drug-induced gastro-duodenal damage. Acid

  7. A novel compound DSC suppresses lipopolysaccharide-induced inflammatory responses by inhibition of Akt/NF-κB signalling in macrophages.

    PubMed

    Liu, Xin-Hua; Pan, Li-Long; Jia, Yao-Ling; Wu, Dan; Xiong, Qing-Hui; Wang, Yang; Zhu, Yi-Zhun

    2013-05-15

    A novel compound [4-(2-acetoxy-3-((R)-3-(benzylthio)-1-methoxy-1-oxopropan-2-ylamino)-3-oxopropyl)-1,2-phenylene diacetate (DSC)], derived from Danshensu, exerted cytoprotective effects by anti-oxidative and anti-apoptotic activities in vitro. Herein, we reported the protective effects of DSC on lipopolysaccharide (LPS)-induced inflammatory responses in murine RAW264.7 macrophages and the underlying mechanisms. We showed that DSC concentration-dependently attenuated nitric oxide (NO) production and inducible nitric oxide synthase (iNOS) expression with less cytotoxicity. Signal transduction studies indicated that DSC significantly inhibited LPS-induced phosphorylation of Akt, but not c-Jun N-terminal kinase 1/2, p38, or extracellular signal-regulated kinase 1/2. Meanwhile, LPS-induced nuclear translocation of nuclear factor-κB (NF-κB) p65 was decreased by DSC. Furthermore, a phosphatidylinositol 3-kinase (PI3K) inhibitor LY294002 significantly suppressed LPS-induced NF-κB p65 nuclear translocation, iNOS expression, and NO production, which was also mimicked by pretreatment with DSC. These results suggested that DSC attenuated LPS-induced inflammatory response in macrophages, at least in part, through suppression of PI3K/Akt signaling and NF-κB activation.

  8. Post-exposure treatment with ginsenoside compound K ameliorates auditory functional injury associated with noise-induced hearing loss in mice.

    PubMed

    Hong, Bin Na; Kim, Se Young; Yi, Tae Hoo; Kang, Tong Ho

    2011-01-01

    Noise-induced hearing loss (NIHL) is thought to primarily involve damage to the sensory hair cells of the cochlea via mechanical and metabolic mechanisms. Unfortunately, initial studies assessing the effectiveness of post-exposure treatment after hearing loss have yielded largely disappointing results. This study explored the effects of oral treatment with Korean red ginseng (RG) and with two bioavailable ginsenoside metabolites, ginsenoside Rh1 and ginsenoside compound K (GCK), in response to NIHL in a murine model. Pharmacological treatments began 24h after noise exposure and were continued once daily for 7 days. Central auditory function was evaluated using auditory middle latency responses, and cochlear function was determined based on transient evoked otoacoustic emissions. Additionally, cochlear hair cell morphology was investigated after noise exposure. Both Korean red ginseng and compound K reduced threshold shifts, central auditory function damage, and cochlear functional and morphological deficits. In contrast, treatment with ginsenoside Rh1 did not result in recovery of NIHL in mice. These results suggest that consumption of Korean red ginseng may facilitate recovery from noise-induced hearing loss. Furthermore, one of the active constituents in ginseng is likely ginsenoside compound K. PMID:20969919

  9. Discovery of Plant Phenolic Compounds That Act as Type III Secretion System Inhibitors or Inducers of the Fire Blight Pathogen, Erwinia amylovora

    PubMed Central

    Khokhani, Devanshi; Zhang, Chengfang; Li, Yan; Wang, Qi; Zeng, Quan; Yamazaki, Akihiro; Hutchins, William; Zhou, Shan-Shan

    2013-01-01

    Erwinia amylovora causes a devastating disease called fire blight in rosaceous plants. The type III secretion system (T3SS) is one of the important virulence factors utilized by E. amylovora in order to successfully infect its hosts. By using a green fluorescent protein (GFP) reporter construct combined with a high-throughput flow cytometry assay, a library of phenolic compounds and their derivatives was studied for their ability to alter the expression of the T3SS. Based on the effectiveness of the compounds on the expression of the T3SS pilus, the T3SS inhibitors 4-methoxy-cinnamic acid (TMCA) and benzoic acid (BA) and one T3SS inducer, trans-2-(4-hydroxyphenyl)-ethenylsulfonate (EHPES), were chosen for further study. Both the T3SS inhibitors (TMCA and BA) and the T3SS inducer (EHPES) were found to alter the expression of T3SS through the HrpS-HrpL pathway. Additionally, TMCA altered T3SS expression through the rsmBEa-RsmAEa system. Finally, we found that TMCA and BA weakened the hypersensitive response (HR) in tobacco by suppressing the T3SS of E. amylovora. In our study, we identified phenolic compounds that specifically targeted the T3SS. The T3SS inhibitor may offer an alternative approach to antimicrobial therapy by targeting virulence factors of bacterial pathogens. PMID:23770912

  10. A Soft Coral-Derived Compound, 11-epi-Sinulariolide Acetate Suppresses Inflammatory Response and Bone Destruction in Adjuvant-Induced Arthritis

    PubMed Central

    Lee, Hsin-Pai; Chen, Wu-Fu; Sun, Yu-Min; Su, Jui-Hsin; Lu, Yi; Huang, Shi-Ying; Hung, Han-Chun; Sung, Ping-Jyun; Sheu, Jyh-Horng; Wen, Zhi-Hong

    2013-01-01

    In recent years, a significant number of metabolites with potent anti-inflammatory properties have been discovered from marine organisms, and several of these compounds are now under clinical trials. In the present study, we isolated 11-epi-sinulariolide acetate (Ya-s11), a cembrane-type compound with anti-inflammatory effects, from the Formosa soft coral Sinularia querciformis. Preliminary screening revealed that Ya-s11 significantly inhibited the expression of the proinflammatory proteins induced nitric oxide synthase and cyclooxygenase-2 in lipopolysaccharide-stimulated murine macrophages. We also examined the therapeutic effects of Ya-s11 on adjuvant-induced arthritis (AIA) in female Lewis rats, which demonstrate features similar to human rheumatoid arthritis (RA). Animal experiments revealed that Ya-s11 (subcutaneously 9 mg/kg once every 2 days from day 7 to day 28 postimmunization) significantly inhibited AIA characteristics. Moreover, Ya-s11 also attenuated protein expression of cathepsin K, matrix metalloproteinases-9 (MMP-9), tartrate-resistant acid phosphatase (TRAP), and tumor necrosis factor-α (TNF-α) in ankle tissues of AIA-rats. Based on its attenuation of the expression of proinflammatory proteins and disease progression in AIA rats, the marine-derived compound Ya-s11 may serve as a useful therapeutic agent for the treatment of RA. PMID:23675440

  11. Discovery of plant phenolic compounds that act as type III secretion system inhibitors or inducers of the fire blight pathogen, Erwinia amylovora.

    PubMed

    Khokhani, Devanshi; Zhang, Chengfang; Li, Yan; Wang, Qi; Zeng, Quan; Yamazaki, Akihiro; Hutchins, William; Zhou, Shan-Shan; Chen, Xin; Yang, Ching-Hong

    2013-09-01

    Erwinia amylovora causes a devastating disease called fire blight in rosaceous plants. The type III secretion system (T3SS) is one of the important virulence factors utilized by E. amylovora in order to successfully infect its hosts. By using a green fluorescent protein (GFP) reporter construct combined with a high-throughput flow cytometry assay, a library of phenolic compounds and their derivatives was studied for their ability to alter the expression of the T3SS. Based on the effectiveness of the compounds on the expression of the T3SS pilus, the T3SS inhibitors 4-methoxy-cinnamic acid (TMCA) and benzoic acid (BA) and one T3SS inducer, trans-2-(4-hydroxyphenyl)-ethenylsulfonate (EHPES), were chosen for further study. Both the T3SS inhibitors (TMCA and BA) and the T3SS inducer (EHPES) were found to alter the expression of T3SS through the HrpS-HrpL pathway. Additionally, TMCA altered T3SS expression through the rsmBEa-RsmAEa system. Finally, we found that TMCA and BA weakened the hypersensitive response (HR) in tobacco by suppressing the T3SS of E. amylovora. In our study, we identified phenolic compounds that specifically targeted the T3SS. The T3SS inhibitor may offer an alternative approach to antimicrobial therapy by targeting virulence factors of bacterial pathogens.

  12. A soft coral-derived compound, 11-epi-sinulariolide acetate suppresses inflammatory response and bone destruction in adjuvant-induced arthritis.

    PubMed

    Lin, Yen-You; Jean, Yen-Hsuan; Lee, Hsin-Pai; Chen, Wu-Fu; Sun, Yu-Min; Su, Jui-Hsin; Lu, Yi; Huang, Shi-Ying; Hung, Han-Chun; Sung, Ping-Jyun; Sheu, Jyh-Horng; Wen, Zhi-Hong

    2013-01-01

    In recent years, a significant number of metabolites with potent anti-inflammatory properties have been discovered from marine organisms, and several of these compounds are now under clinical trials. In the present study, we isolated 11-epi-sinulariolide acetate (Ya-s11), a cembrane-type compound with anti-inflammatory effects, from the Formosa soft coral Sinularia querciformis. Preliminary screening revealed that Ya-s11 significantly inhibited the expression of the proinflammatory proteins induced nitric oxide synthase and cyclooxygenase-2 in lipopolysaccharide-stimulated murine macrophages. We also examined the therapeutic effects of Ya-s11 on adjuvant-induced arthritis (AIA) in female Lewis rats, which demonstrate features similar to human rheumatoid arthritis (RA). Animal experiments revealed that Ya-s11 (subcutaneously 9 mg/kg once every 2 days from day 7 to day 28 postimmunization) significantly inhibited AIA characteristics. Moreover, Ya-s11 also attenuated protein expression of cathepsin K, matrix metalloproteinases-9 (MMP-9), tartrate-resistant acid phosphatase (TRAP), and tumor necrosis factor-α (TNF-α) in ankle tissues of AIA-rats. Based on its attenuation of the expression of proinflammatory proteins and disease progression in AIA rats, the marine-derived compound Ya-s11 may serve as a useful therapeutic agent for the treatment of RA.

  13. Superoxide radical-generating compounds activate a predicted promoter site for paraquat-inducible genes of the Chromobacterium violaceum bacterium in a dose-dependent manner.

    PubMed

    Gabriel, J E; Guerra-Slompo, E P; de Souza, E M; de Carvalho, F A L; Madeira, H M F; de Vasconcelos, A T R

    2015-01-01

    The purpose of the present study was to functionally evaluate the influence of superoxide radical-generating compounds on the heterologous induction of a predicted promoter region of open reading frames for paraquat-inducible genes (pqi genes) revealed during genome annotation analyses of the Chromobacterium violaceum bacterium. A 388-bp fragment corresponding to a pqi gene promoter of C. violaceum was amplified using specific primers and cloned into a conjugative vector containing the Escherichia coli lacZ gene without a promoter. Assessments of the expression of the β-galactosidase enzyme were performed in the presence of menadione (MEN) and phenazine methosulfate (PMS) compounds at different final concentrations to evaluate the heterologous activation of the predicted promoter region of interest in C. violaceum induced by these substrates. Under these experimental conditions, the MEN reagent promoted highly significant increases in the expression of the β-galactosidase enzyme modulated by activating the promoter region of the pqi genes at all concentrations tested. On the other hand, significantly higher levels in the expression of the β-galactosidase enzyme were detected exclusively in the presence of the PMS reagent at a final concentration of 50 μg/mL. The findings described in the present study demonstrate that superoxide radical-generating compounds can activate a predicted promoter DNA motif for pqi genes of the C. violaceum bacterium in a dose-dependent manner. PMID:26345950

  14. Fabrication of FeSi and Fe3Si compounds by electron beam induced mixing of [Fe/Si]2 and [Fe3/Si]2 multilayers grown by focused electron beam induced deposition

    NASA Astrophysics Data System (ADS)

    Porrati, F.; Sachser, R.; Gazzadi, G. C.; Frabboni, S.; Huth, M.

    2016-06-01

    Fe-Si binary compounds have been fabricated by focused electron beam induced deposition by the alternating use of iron pentacarbonyl, Fe(CO)5, and neopentasilane, Si5H12 as precursor gases. The fabrication procedure consisted in preparing multilayer structures which were treated by low-energy electron irradiation and annealing to induce atomic species intermixing. In this way, we are able to fabricate FeSi and Fe3Si binary compounds from [Fe/Si]2 and [Fe3/Si]2 multilayers, as shown by transmission electron microscopy investigations. This fabrication procedure is useful to obtain nanostructured binary alloys from precursors which compete for adsorption sites during growth and, therefore, cannot be used simultaneously.

  15. Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

    PubMed

    Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

    2015-07-28

    The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy.

  16. Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

    PubMed

    Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

    2015-07-28

    The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy. PMID:26085288

  17. Anticancer compound Oplopantriol A kills cancer cells through inducing ER stress and BH3 proteins Bim and Noxa

    PubMed Central

    Jin, H R; Liao, Y; Li, X; Zhang, Z; Zhao, J; Wang, C-Z; Huang, W-H; Li, S-P; Yuan, C-S; Du, W

    2014-01-01

    Oplopantriol-A (OPT) is a natural polyyne from Oplopanax horridus. We show here that OPT preferentially kills cancer cells and inhibits tumor growth. We demonstrate that OPT-induced cancer cell death is mediated by excessive endoplasmic reticulum (ER) stress. Decreasing the level of ER stress either by inactivating components of the unfolded protein response (UPR) pathway or by expression of ER chaperone protein glucose-regulated protein 78 (GRP78) decreases OPT-induced cell death. We show that OPT induces the accumulation of ubiquitinated proteins and the stabilization of unstable proteins, suggesting that OPT functions, at least in part, through interfering with the ubiquitin/proteasome pathway. In support of this, inhibition of protein synthesis significantly decreased the accumulation of ubiquitinated proteins, which is correlated with significantly decreased OPT-induced ER stress and cell death. Finally, we show that OPT treatment significantly induced the expression of BH3-only proteins, Noxa and Bim. Knockdown of both Noxa and Bim significantly blocked OPT-induced cell death. Taken together, our results suggest that OPT is a potential new anticancer agent that induces cancer cell death through inducing ER stress and BH3 proteins Noxa and Bim. PMID:24763047

  18. Bioactive compounds in green tea leaves attenuate the injury of retinal ganglion RGC-5 cells induced by H2O2 and ultraviolet radiation.

    PubMed

    Jin, Jianchang; Ying, Hao; Huang, Meirong; Du, Qizhen

    2015-11-01

    The Chinese commonly believe that tea helps maintain clear vision. This viewpoint has been recorded in Chinese medical books also. The key bioactive compounds in green tea leaves, (-)-epigallocatechin gallate (EGCG), L-theanine (theanine) and caffeine, were investigated for their abilities to attenuate the injury of retinal ganglion cells (RGC-5) induced by H2O2 and ultraviolet radiation. Theanine and caffeine promoted cell growth while concentrations of EGCG greater than 10μg/ml inhibited cell growth. The nine and caffeine both protected RGC-5 cells from injury as well as enhanced their recovery, while EGCG only protected the cells from injury and did not help them to recover. Tea is a unique drink, which is simultaneously enriched with EGCG, theanine and caffeine. The role of these compounds in optic nerve protection may partially explain why some tea drinkers feel enhanced vision. PMID:26687755

  19. Electrocatalytic Production of C3-C4 Compounds by Conversion of CO2 on a Chloride-Induced Bi-Phasic Cu2O-Cu Catalyst.

    PubMed

    Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung

    2015-12-01

    Electrocatalytic conversion of carbon dioxide (CO2) has recently received considerable attention as one of the most feasible CO2 utilization techniques. In particular, copper and copper-derived catalysts have exhibited the ability to produce a number of organic molecules from CO2. Herein, we report a chloride (Cl)-induced bi-phasic cuprous oxide (Cu2O) and metallic copper (Cu) electrode (Cu2OCl) as an efficient catalyst for the formation of high-carbon organic molecules by CO2 conversion, and identify the origin of electroselectivity toward the formation of high-carbon organic compounds. The Cu2OCl electrocatalyst results in the preferential formation of multi-carbon fuels, including n-propanol and n-butane C3-C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface. PMID:26473324

  20. Cold-induced activities of cytochromes P450 1A1 and 1A2 in rat liver: putative role of endogenous compounds in induction mechanism.

    PubMed

    Perepechaeva, M L; Grishanova, A Yu

    2013-03-01

    Adaptation to cold includes adaptive changes at the organism and molecular levels. One of the interesting facts is induction of cytochromes P450 subfamily 1A (CYP1A) in the liver of rats, inducible enzymes participating in biotransformation of procarcinogenic xenobiotics, under the effect of moderate cold exposure. Cold activation of CYP1A can be mediated by adaptive changes and the resultant redistribution or intensification of the synthesis of mediator compounds. This hypothesis is verified in the present study. The role of bilirubin, tocopherol, and corticosterone as mediators of cold induction of CYP1A in the rat liver was evaluated. The results indicate that these compounds can be involved in cold induction of CYP1A, but none of them is the only mediator in this process.

  1. Electrocatalytic Production of C3-C4 Compounds by Conversion of CO2 on a Chloride-Induced Bi-Phasic Cu2O-Cu Catalyst.

    PubMed

    Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung

    2015-12-01

    Electrocatalytic conversion of carbon dioxide (CO2) has recently received considerable attention as one of the most feasible CO2 utilization techniques. In particular, copper and copper-derived catalysts have exhibited the ability to produce a number of organic molecules from CO2. Herein, we report a chloride (Cl)-induced bi-phasic cuprous oxide (Cu2O) and metallic copper (Cu) electrode (Cu2OCl) as an efficient catalyst for the formation of high-carbon organic molecules by CO2 conversion, and identify the origin of electroselectivity toward the formation of high-carbon organic compounds. The Cu2OCl electrocatalyst results in the preferential formation of multi-carbon fuels, including n-propanol and n-butane C3-C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface.

  2. The hydrogen sulfide releasing compounds ATB-346 and diallyl trisulfide attenuate streptozotocin-induced cognitive impairment, neuroinflammation, and oxidative stress in rats: involvement of asymmetric dimethylarginine.

    PubMed

    Mostafa, Dalia K; El Azhary, Nesrine M; Nasra, Rasha A

    2016-07-01

    Hydrogen sulfide (H2S) has attracted interest as a gaseous mediator involved in diverse processes in the nervous system, particularly with respect to learning and memory. However, its therapeutic potential in Alzheimer disease (AD) is not fully explored. Therefore, the effects of H2S-releasing compounds against AD-like behavioural and biochemical abnormalities were investigated. Memory deficit was induced by intracerberoventicular injection of streptozotocin (STZ, 3 mg·kg(-1)). Animals were randomly assigned into 5 groups (12 rats each): normal control, STZ treated, and 3 drug-treated groups receiving naproxen, H2S-releasing naproxen (ATB-346), and diallyl trisulfide in 20, 32, 40 mg·kg(-1)·day(-1), respectively. Memory function was assessed by passive avoidance and T-maze tasks. After 21 days, hippocampal IL-6, malondialdehyde, reduced glutathione (GSH), asymmetric dimethylarginine (ADMA), and acetylcholinestrase activity were determined. ATB-346 and diallyl trisulfide ameliorated behavioural performance and reduced malondialdehyde, ADMA, and acetylcholinestrase activity while increasing GSH. This study demonstrates the beneficial effects of H2S release in STZ-induced memory impairment by modulation of neuroinflammation, oxidative stress, and cholinergic function. It also delineates the implication of ADMA to the cognitive impairment induced by STZ. These findings draw the attention to H2S-releasing compounds as new candidates for treating neurodegenerative disorders that have prominent oxidative and inflammatory components such as AD.

  3. Lazaroid compounds prevent early but not late stages of oxidant-induced cell injury: potential explanation for the lack of efficacy of lazaroids in clinical trials.

    PubMed

    Huang, H; Patel, P B; Salahudeen, A K

    2001-01-01

    Earlier in vitro studies demonstrated the remarkable potency of the lazaroid compounds to prevent oxidant-induced early cell injury. However, the ability of lazaroid compounds to limit oxidative injury in vivo(including renal ischemia-reperfusion) has been less certain, and the early clinical trials using lazaroids to limit CNS injury or organ injury in the setting of transplantation have not been promising. Lazaroid compounds are potent inhibitors of lipid peroxidation, and their inability to influence other key injury processes, particularly during the late stages of cell injury, might partly explain the limited clinical efficacy. To test this, renal tubular (LLC-PK1) cells were incubated with 250 micromH(2)O(2)for 135 min, in the presence or absence of 2-methyl aminochroman (2-MAC, U-83836E), a lazaroid with potent ability to inhibit lipid peroxidation, or desferrioxamine, (DFO) an iron chelator with broader antioxidant efficacy. Cell injury, lipid peroxidation, DNA damage and ATP depletion were measured in the early (immediately after H(2)O(2)incubation) and late (24 h after H(2)O(2)incubation) stages of cell injury. In the early stage, 2-MAC suppressed H(2)O(2)-induced lipid peroxidation and LDH release, but not the DNA damage, ATP depletion or loss of cell replication. In contrast, DFO suppressed all of the measurements. In the late stages, despite continued suppression of lipid peroxidation, only DFO maintained significant cytoprotection against H(2)O(2), and this was accompanied by reduced DNA damage, higher ATP levels and preservation of cell proliferation. Thus, the inability of the lazaroid compound 2-MAC to sustain cytoprotection in the later stages of cell injury might provide at least a partial explanation for the inefficiency of lazaroids to limit tissue injury in clinical and certain in vivo settings. PMID:11207066

  4. Potent organometallic osmium compounds induce mitochondria-mediated apoptosis and S-phase cell cycle arrest in A549 non-small cell lung cancer cells.

    PubMed

    van Rijt, Sabine H; Romero-Canelón, Isolda; Fu, Ying; Shnyder, Steve D; Sadler, Peter J

    2014-05-01

    The problems of acquired resistance associated with platinum drugs may be addressed by chemotherapeutics based on other transition metals as they offer the possibility of novel mechanisms of action. In this study, the cellular uptake and induction of apoptosis in A549 human non-small cell lung cancer cells of three promising osmium(II) arene complexes containing azopyridine ligands, [Os(η(6)-arene)(p-R-phenylazopyridine)X]PF6, where arene is p-cymene or biphenyl, R is OH or NMe2, and X is Cl or I, were investigated. These complexes showed time-dependent (4–48 h) potent anticancer activity with highest potency after 24 h (IC50 values ranging from 0.1 to 3.6 μM). Cellular uptake of the three compounds as quantified by ICP-MS, was independent of their logP values (hydrophobicity). Furthermore, maximum cell uptake was observed after 24 h, with evident cell efflux of the osmium after 48 and 72 h of exposure, which correlated with the corresponding IC50 values. The most active compound 2, [Os(η(6)-p-cymene)(NMe2-phenylazopyridine)I]PF6, was taken up by lung cancer cells predominately in a temperature-dependent manner indicating that energy-dependent mechanisms are important in the uptake of 2. Cell fractionation studies showed that all three compounds accumulated mainly in cellular membranes. Furthermore, compound 2 induced apoptosis and caused accumulation in the S-phase of the cell cycle. In addition, 2 induced cytochrome c release and alterations in mitochondrial membrane potential even after short exposure times, indicating that mitochondrial apoptotic pathways are involved. This study represents th