Sample records for ph 13-8 mo

  1. Effects of Mo Content on Microstructure and Mechanical Property of PH13-8Mo Martensitic Precipitation-Hardened Stainless Steel

    NASA Astrophysics Data System (ADS)

    Yubing, Pei; Tianjian, Wang; Zhenhuan, Gao; Hua, Fan; Gongxian, Yang

    This paper introduces the effects of Mo content on microstructure and mechanical property of PH13-8Mo martensitic precipitation-hardened stainless steel which is used for LP last stage blade in steam turbine. Thermodynamic software Thermo-Calc has been used to calculate precipitation temperature and the mass fraction of precipitated phases in PH13-8Mo steel with different Mo content. The result shows that when the mass of Mo is below 0.6wt.%, chi-phase mu-phase and sigma-phase could disappear. The microstructure and mechanical property of high Mo PH13-8Mo (Mo=0.57wt.%) and low Mo PH13-8Mo (Mo=2.15wt.%)have been investigated in different heat treatments. The investigations reveal that austenitizing temperature decrease with the reduce of Mo content, so the optimum solution temperature for low Mo PH13-8Mo is lower than that for high Mo PH13-8Mo.The influence of solution temperature on grain size is weakened with the increase of Mo content, Mo rich carbides could retard coarsening of grain. An enormous amount of nano-size uniformly distributed β-NiAl particles are found in both kinds of steels using transmission electron microscopy, they are the most important strengthening phase in PH13-8Mo.

  2. Vacuum investment cast PH13-8Mo corrosion resistant steel. (SAE standard)

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

    NONE

    1991-07-01

    An industry-wide interest has arisen with regards to the properties and capabilities of investment cast PH 13-8Mo corrosion resistant steel. Specifically of interest are the structural applications in the aerospace industry for this product heat treated to the H1000 condition. The objective of this AMEC cooperative test program was to generate and compile useful data for aerospace structural evaluation of investment cast PH 13-8Mo heat treated to H1000. The determination was made of overall mechanical properties, fatigue, fracture toughness, and crack growth data along with basic microstructural evaluation of the investment cast material. The evaluation of mechanical property variations betweenmore » cast and machined tensile specimens and evaluation of microstructural constituents. PH 13-8Mo, H1000 investment castings for use in the aerospace industry is included.« less

  3. Stress corrosion study of PH13-8Mo stainless steel using the Slow Strain Rate Technique

    NASA Technical Reports Server (NTRS)

    Torres, Pablo D.

    1989-01-01

    The need for a fast and reliable method to study stress corrosion in metals has caused increased interest in the Slow Strain Rate Technique (SSRT) during the last few decades. PH13-8MoH950 and H1000 round tensile specimens were studied by this method. Percent reduction-in-area, time-to-failure, elongation at fracture, and fracture energy were used to express the loss in ductility, which has been used to indicate susceptibility to stress corrosion cracking (SCC). Results from a 3.5 percent salt solution (corrosive medium) were compared to those in air (inert medium). A tendency to early failure was found when testing in the vicinity of 1.0 x 10(-6) mm/mm/sec in the 3.5 percent salt solution. PH13-8Mo H1000 was found to be less likely to suffer SCC than PH13-8Mo H950. This program showed that the SSRT is promising for the SCC characterization of metals and results can be obtained in much shorter times (18 hr for PH steels) than those required using conventional techniques.

  4. Machining-induced deformation in stepped specimens of PH 13-8 Mo, 18 nickel maraging steel grade 200T1 and grain-refined HP 9-4-20

    NASA Technical Reports Server (NTRS)

    Wigley, D. A.

    1985-01-01

    The results of a study to evaluate the dimensional changes created during machining and subsequent cycling to cryogenic temperatures for three different metallic alloys are presented. Experimental techniques are described and results presented for 18 Ni Grade 200 maraging steel, PH-13-8 Mo stainless steel, and Grain-refined HP 9-4-20.

  5. The dimensional stability analysis of seventeen stepped specimens of 18Ni 200 grade, PH13-8Mo and A-286

    NASA Technical Reports Server (NTRS)

    Wigley, D. A.

    1983-01-01

    This report documents the results of a dimensional stability analysis of seventeen stepped specimens that were used in the evaluation of factors influencing warpage in metallic alloys being used for cryogenic wind tunnel models. Specimens used in the analysis were manufactured from 18Ni 200 Grade Maaraging steel, PH13-8Mo, and A-286 stainless steel. Quantitative data are provided on the behavior of the specimens due to the effects of both machining and cryogenic cycling effects.

  6. Stress corrosion cracking evaluation of martensitic precipitation hardening stainless steels

    NASA Technical Reports Server (NTRS)

    Humphries, T. S.; Nelson, E. E.

    1980-01-01

    The resistance of the martensitic precipitation hardening stainless steels PH13-8Mo, 15-5PH, and 17-4PH to stress corrosion cracking was investigated. Round tensile and c-ring type specimens taken from several heats of the three alloys were stressed up to 100 percent of their yield strengths and exposed to alternate immersion in salt water, to salt spray, and to a seacoast environment. The results indicate that 15-5PH is highly resistant to stress corrosion cracking in conditions H1000 and H1050 and is moderately resistant in condition H900. The stress corrosion cracking resistance of PH13-8Mo and 17-4PH stainless steels in conditions H1000 and H1050 was sensitive to mill heats and ranged from low to high among the several heats included in the tests. Based on a comparison with data from seacoast environmental tests, it is apparent that alternate immersion in 3.5 percent salt water is not a suitable medium for accelerated stress corrosion testing of these pH stainless steels.

  7. Metal-templated synthesis of macrocyclic (triphosphine)molybdenum complexes

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

    Diel, B.N.; Brandt, P.F.; Haltiwanger, R.C.

    1989-07-12

    Reaction of CH{sub 2}=CHCH{sub 2}PH{sub 2}, CH{sub 2}=CHCH{sub 2}CH{sub 2}PH{sub 2}, and CH{equivalent to}CCH{sub 2}PPH{sub 2} with (mesitylene)Mo(CO){sub 3} or (cycloheptatriene)Mo(CO){sub 3} yields the complexes (CH{sub 2}=CHCH{sub 2}PH{sub 2}){sub 3} (1), (CH{sub 2}=CHCH{sub 2}CH{sub 2}PH{sub 2}){sub 3}Mo(CO){sub 3} (2), and (CH{equivalent to}CCH{sub 2}PH{sub 2}){sub 3}Mo(CO){sub 3}, (3), respectively. Reaction of CH{sub 2}=CHCH{sub 2}PH{sub 2} and CH{equivalent to}CCH{sub 2}PH{sub 2} with cis-(piperidine){sub 2}Mo(CO){sub 4} yields cis-(CH{sub 2}=CHCH{sub 2}PH{sub 2}){sub 2}Mo(CO){sub 4} (4) and cis-(CH{equivalent to}CCH{sub 2}PH{sub 2}){sub 2}Mo(CO){sub 4} (5). Free-radical-initiated cyclooligomerization of 1 and 2 yields the triligated macrocyclic secondary-phosphine complexes fac-(HP(CH{sub 2}){sub 3}){sub 3}Mo(CO){sub 3} (6) and fac-(HP-(CH{sub 2}){submore » 4}){sub 3}Mo(CO){sub 3} (7). Under similar conditions, reaction of 4 yields an acyclic diphosphine complex characterized tentatively as cis-(H{sub 2}P(CH{sub 2}){sub 3}PH(CH{sub 2}CH=CH{sub 2}))Mo(CO){sub 4} (8). Compounds 1-7 and 10 have been characterized by spectral ({sup 31}P, {sup 13}C, and {sup 1}H, NMR and IR and mass) data. 6 has been characterized in the solid state by single-crystal x-ray analysis, and the results are reported. {sup 31}P NMR spectra studies of the cyclooligomerization of 1 show the partially cyclized intermediates formed prior to 6. The macrocyclic complexes 6 and 7 are kinetically stable, showing no sign of ligand displacement in reactions with pH{sub 3}P, PF{sub 3}, KCN, or P(OMe){sub 3}. 44 refs., 4 figs., 4 tabs.« less

  8. Gaseous hydrogen embrittlement of PH 13-8 Mo steel

    NASA Astrophysics Data System (ADS)

    Ding, Y. S.; Tsay, L. W.; Chiang, M. F.; Chen, C.

    2009-04-01

    In this study, notched tensile and fatigue crack growth tests in gaseous hydrogen were performed on PH 13-8 Mo stainless steel specimens at room temperature. These specimens were susceptible to hydrogen embrittlement (HE), but at different degrees, depending on the aging conditions or the microstructures of the alloys. In hydrogen, the accelerated fatigue crack growth rate (FCGR) usually accompanied a reduced notched tensile strength (NTS) of the specimens, i.e., the faster the FCGR the lower the NTS. It was proposed that the same fracture mechanism could be applied to these two different types of specimens, regardless of the loading conditions. Rapid fatigue crack growth and high NTS loss were found in the H800 (426 °C under-aged) and H900 (482 °C peak-aged) specimens. The HE susceptibility of the steel was reduced by increasing the aging temperature above 593 °C, which was attributed to the increased amount of austenite in the structure. Extensive quasi-cleavage fracture was observed for the specimens that were deteriorated severely by HE.

  9. Effect of Microstructure on Stress Corrosion Cracking Behaviour of High Nitrogen Stainless Steel Gas Tungsten Arc Welds

    NASA Astrophysics Data System (ADS)

    Mohammed, Raffi; Srinivasa Rao, K.; Madhusudhan Reddy, G.

    2018-03-01

    Present work is aimed to improve stress corrosion cracking resistance of high nitrogen steel and its welds. An attempt to weld high nitrogen steel of 5 mm thick plate using gas tungsten arc welding (GTAW) with three high strength age hardenable fillers i.e., 11-10 PH filler, PH 13- 8Mo and maraging grade of MDN 250 filler is made. Welds were characterized by optical microscopy and scanning electron microscopy. Vickers hardness testing of the welds was carried out to study the mechanical behaviour of welds. Potentio-dynamic polarization studies were done to determine pitting corrosion resistance in aerated 3.5% NaCl solution. Stress corrosion cracking (SCC) testing was carried out using constant load type machine with applied stress of 50% yield strength and in 45% MgCl2 solution boiling at 155°C. The results of the present investigation established that improvement in resistance to stress corrosion cracking was observed for PH 13- 8Mo GTA welds when compared to 11-10 PH and MDN 250 GTA welds. However, All GTA welds failed in the weld interface region. This may be attributed to relatively lower pitting potential in weld interface which acts as active site and the initiation source of pitting.

  10. Aircraft Steels

    DTIC Science & Technology

    2009-02-19

    component usage. PH 13-8Mo is a precipitation-hardenable martensitic stainless steel combining excellent corrosion resistance with strength. Custom 465 is...a martensitic , age-hardenable stainless steel capable of about 1,724 MPa (250 ksi) UTS when peak-aged (H900 condition). Especially, this steel can...NOTES 14. ABSTRACT Five high strength steels (4340, 300M, AerMet 100, Ferrium S53, and Hy-Tuf) and four stainless steels (High Nitrogen, 13

  11. Heat treatment of investment cast PH 13-8 Mo stainless steel: Part II. Isothermal aging kinetics

    NASA Astrophysics Data System (ADS)

    Robino, C. V.; Cieslak, M. J.; Hochanadel, P. W.; Edwards, G. R.

    1994-04-01

    The hardening response of investment cast PH 13-8 Mo stainless steel has been evaluated by hardness measurements following aging in the temperature range normally specified for this alloy (510 °C to 593 °C). A new relationship between fraction transformed and hardness was developed, and analysis of the data in terms of the kinetics of precipitation, in a manner similar to that frequently applied to other precipitation-hardenable martensitic steels, yielded low time exponents and a low value for the apparent activation energy. The values of the time exponents were 0.49, 0.37, 0.56, and 0.53 at 510 °C, 538 °C, 566 °C, and 593 °C, respectively, and that for the apparent activation energy was 139 kJ/mole. As has been proposed for other maraging type steels, these estimates suggest that Β-NiAl precipitates along or near dislocations and that growth of the precipitates is dominated by dislocation pipe diffusion. However, these predictions were neither supported nor refuted by transmission electron microscopy (TEM) because of difficulties in imaging the Β-NiAl precipitates at the aging times and temperatures used. Further, analysis of the data using the formalism of Wert and Zener for the growth of precipitates with interfering diffusion fields indicated that the estimates of fraction transformed from hardness data are not fully appropriate for maraging type steels. Consideration of the nature of the Avrami analysis and the electron microscopy results suggests that other phenomena, including dislocation recovery and reversion of martensite to austenite, occur at rates sufficient to convolute the Avrami analysis. It is further suggested that these results cast doubt on the fundamental implications of previous analyses of precipitation kinetics in age-hardening martensitic steels. Although the Avrami analysis was found not to provide a tenable description of the precipitation kinetics, it does provide a reasonable methodology for portrayal of the hardening response of PH 13-8 Mo stainless steel.

  12. Influence of Soil Solution Salinity on Molybdenum Adsorption by Soils

    USDA-ARS?s Scientific Manuscript database

    Molybdenum (Mo) adsorption on five arid-zone soils from California was investigated as a function of equilibrium solution Mo concentration (0-30 mg L-1), solution pH (4-8), and electrical conductivity (EC = 0.3 or 8 dS m-1). Molybdenum adsorption decreased with increasing pH. An adsorption maximum...

  13. Potential for use of industrial waste materials as filter media for removal of Al, Mo, As, V and Ga from alkaline drainage in constructed wetlands--adsorption studies.

    PubMed

    Hua, T; Haynes, R J; Zhou, Y-F; Boullemant, A; Chandrawana, I

    2015-03-15

    The potential to remove Al, Mo, V, As and Ga from alkaline (pH 8.0-8.6) drainage originating from seawater neutralized bauxite processing residue storage areas using constructed wetland technology was studied in a laboratory study. Bauxite processing residue sand, bauxite, alum water treatment sludge and blast furnace slag were investigated as potential active filter materials. Al was shown to precipitate as Al(OH)3 in the pH range 7.0-8.0 in aqueous solution and 6.0-8.5 in the presence of silica sand particles that provided a surface for nucleation. For V As Mo and Ga, adsorption to the surfaces of the adsorbents decreased greatly at elevated pH values (>pH 6-9). Water treatment sludge and bauxite had a greater ability to adsorb V, As and Mo at high pH (As and V at pH 7-9 and Mo at pH 5-7) than processing sand and slag. Adsorption isotherm data for As and V onto all four adsorbent than processing sand and slag. Adsorption isotherm data for As and V onto all four adsorbent materials fitted equally well to the Langmuir and Freundlich equations but for Ga, and to a lesser extent Mo, the Freundlich equation gave higher R(2) values. For all four ions, the maximum adsorption capacity (Langmuir value qmax) was greatest for water treatment sludge. Bauxite adsorbed more Mo, Ga and V than residue sand or slag. The pseudo-second order equation gave a better fit to the experimental kinetic data than the pseudo-first order model suggesting that chemisorption rather than diffusion/exchange was the rate limiting step to adsorption. It was concluded that water treatment sludge and bauxite were the most effective adsorbents and that for effective removal of the target ions the pH of the drainage water needs to be decreased to 6.0-7.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. {Mo96La8} eggshell ring and self-assembly to {Mo132} Keplerate through Mo-blue intermediate, involved in UV-photolysis of [Mo7O24](6-)/carboxylic acid system at pH 4.

    PubMed

    Yamase, Toshihiro; Kumagai, Shun; Prokop, Petra V; Ishikawa, Eri; Tomsa, Adrian-Raul

    2010-10-18

    The prolonged UV-photolysis of aqueous solutions containing [Mo(7)O(24)](6-) and C(2)H(5)CO(2)H (as electron donor) at pH 3.9-4.1 generates the carboxylate-coordinated {Mo(132)} Keplerate (1a) isolated as a formamidinium/ammonium-mixed salt, [HC(NH(2))(2)](26)(NH(4))(28)[Mo(V)(60)Mo(VI)(72)O(372)(H(2)O)(48)(C(2)H(5)CO(2))(36)((i)C(3)H(7)CO(2))(6)]·16H(2)O (1), through the Mo-blue intermediate (2). The coordination of 2 to La(3+) gives rise to the formation of the chain structure of the C(2)-symmetric {Mo(96)La(8)} eggshell rings, formulated by H(22)[Mo(V)(20)Mo(VI)(76)O(301)(H(2)O)(29){La(H(2)O)(6)}(2)]{La(H(2)O)(5)}(6)]·54.5H(2)O (3). The eggshell-ring geometry results from the insertion of [Mo(VI)(2)O(7)(H(2)O)](2-) (spacer) into the equator outer ring of the wheel-shaped Mo-blue, and 10 {(Mo(VI))(Mo(VI)(5))} pentagonal subunits alternately above and below the equator outer ring are connected by eight La(3+) and two {Mo(VI)(2)} linkers within two inner rings. The neighboring eggshell rings are linked through two Mo-O-Mo bonds formed by dehydrative condensation between the {Mo(VI)(2)} linkers to result in the chain structure. Together with the results of the elemental analysis and IR, electronic absorption, (13)C NMR, and ESI-MS spectra for 2, the ring profile analysis of 3 let us identify 2 with a carbolylate-coordinated Mo-blue ring of high nuclearity. The Mo(VI)→Mo(V) photoreductive change of 2 to the 60-electron reduced Keplerate in the presence of C(2)H(5)CO(2)H involves both degradation of the outer ring and splitting of the binuclear linkers, which leads to the formation of [(Mo(VI))Mo(VI)(5)O(21)(H(2)O)(4)(carboxylate)](7-) pentagonal subunits and [Mo(V)(2)O(4)(carboxylate)](+)/[Mo(V)O(2)(carboxylate)(1/2)](0.5+)-mixed linkers for 1.

  15. Turnover-Dependent Inactivation of the Nitrogenase MoFe-Protein at High pH

    PubMed Central

    2013-01-01

    Proton uptake accompanies the reduction of all known substrates by nitrogenase. As a consequence, a higher pH should limit the availability of protons as a substrate essential for turnover, thereby increasing the proportion of more highly reduced forms of the enzyme for further study. The utility of the high-pH approach would appear to be problematic in view of the observation reported by Pham and Burgess [(1993) Biochemistry 32, 13725–13731] that the MoFe-protein undergoes irreversible protein denaturation above pH 8.65. In contrast, we found by both enzyme activity and crystallographic analyses that the MoFe-protein is stable when incubated at pH 9.5. We did observe, however, that at higher pHs and under turnover conditions, the MoFe-protein is slowly inactivated. While a normal, albeit low, level of substrate reduction occurs under these conditions, the MoFe-protein undergoes a complex transformation; initially, the enzyme is reversibly inhibited for substrate reduction at pH 9.5, yet in a second, slower process, the MoFe-protein becomes irreversibly inactivated as measured by substrate reduction activity at the optimal pH of 7.8. The final inactivated MoFe-protein has an increased hydrodynamic radius compared to that of the native MoFe-protein, yet it has a full complement of iron and molybdenum. Significantly, the modified MoFe-protein retains the ability to specifically interact with its nitrogenase partner, the Fe-protein, as judged by the support of ATP hydrolysis and by formation of a tight complex with the Fe-protein in the presence of ATP and aluminum fluoride. The turnover-dependent inactivation coupled to conformational change suggests a mechanism-based transformation that may provide a new probe of nitrogenase catalysis. PMID:24392967

  16. Turnover-dependent inactivation of the nitrogenase MoFe-protein at high pH.

    PubMed

    Yang, Kun-Yun; Haynes, Chad A; Spatzal, Thomas; Rees, Douglas C; Howard, James B

    2014-01-21

    Proton uptake accompanies the reduction of all known substrates by nitrogenase. As a consequence, a higher pH should limit the availability of protons as a substrate essential for turnover, thereby increasing the proportion of more highly reduced forms of the enzyme for further study. The utility of the high-pH approach would appear to be problematic in view of the observation reported by Pham and Burgess [(1993) Biochemistry 32, 13725-13731] that the MoFe-protein undergoes irreversible protein denaturation above pH 8.65. In contrast, we found by both enzyme activity and crystallographic analyses that the MoFe-protein is stable when incubated at pH 9.5. We did observe, however, that at higher pHs and under turnover conditions, the MoFe-protein is slowly inactivated. While a normal, albeit low, level of substrate reduction occurs under these conditions, the MoFe-protein undergoes a complex transformation; initially, the enzyme is reversibly inhibited for substrate reduction at pH 9.5, yet in a second, slower process, the MoFe-protein becomes irreversibly inactivated as measured by substrate reduction activity at the optimal pH of 7.8. The final inactivated MoFe-protein has an increased hydrodynamic radius compared to that of the native MoFe-protein, yet it has a full complement of iron and molybdenum. Significantly, the modified MoFe-protein retains the ability to specifically interact with its nitrogenase partner, the Fe-protein, as judged by the support of ATP hydrolysis and by formation of a tight complex with the Fe-protein in the presence of ATP and aluminum fluoride. The turnover-dependent inactivation coupled to conformational change suggests a mechanism-based transformation that may provide a new probe of nitrogenase catalysis.

  17. Toxicity of the molybdate anion in soil is partially explained by effects of the accompanying cation or by soil pH.

    PubMed

    Buekers, Jurgen; Mertens, Jelle; Smolders, Erik

    2010-06-01

    Previous studies have shown that toxicity of cationic trace metals in soil is partially confounded by effects of the accompanying anions. A similar assessment is reported here for toxicity of an oxyanion, i.e., molybdate (MoO(4) (2-)), the soil toxicity of which is relatively unexplored. Solubility and toxicity were compared between the soluble sodium molybdate (Na(2)MoO(4)) and the sparingly soluble molybdenum trioxide (MoO(3)). Confounding effects of salinity were excluded by referencing the Na(2)MoO(4) effect to that of sodium chloride (NaCl). The pH decrease from the acid MoO(3) amendment was equally referenced to a hydrochloric (HCl) treatment or a lime-controlled MoO(3) treatment. The concentrations of molybdenum (Mo) in soil solution or calcium chloride (CaCl(2)) 0.01 M extracts were only marginally affected by either MoO(3) or Na(2)MoO(4) as an Mo source after 10 to 13 days of equilibration. Effects of Mo on soil nitrification were fully confounded by associated changes in salinity or pH. Effects of Mo on growth of wheat seedlings (Triticum aestivum L) were more pronounced than those on nitrification, and toxicity thresholds were unaffected by the form of added Mo. The Mo thresholds for wheat growth were not confounded by pH or salinity at incipient toxicity. It is concluded that oxyanion toxicity might be confounded in relatively insensitive tests for which reference treatments should be included. Copyright 2010 SETAC.

  18. An intermetallic forming steel under radiation for nuclear applications

    NASA Astrophysics Data System (ADS)

    Hofer, C.; Stergar, E.; Maloy, S. A.; Wang, Y. Q.; Hosemann, P.

    2015-03-01

    In this work we investigated the formation and stability of intermetallics formed in a maraging steel PH 13-8 Mo under proton radiation up to 2 dpa utilizing nanoindentation, microcompression testing and atom probe tomography. A comprehensive discussion analyzing the findings utilizing rate theory is introduced, comparing the aging process to radiation induced diffusion. New findings of radiation induced segregation of undersize solute atoms (Si) towards the precipitates are considered.

  19. Spirochaeta psychrophila sp. nov., a psychrophilic spirochaete isolated from subseafloor sediment, and emended description of the genus Spirochaeta.

    PubMed

    Miyazaki, Masayuki; Sakai, Sanae; Yamanaka, Yuko; Saito, Yumi; Takai, Ken; Imachi, Hiroyuki

    2014-08-01

    An obligately anaerobic, psychrophilic spirochaete, strain MO-SPC1(T), was isolated from a methanogenic microbial community grown in a continuous-flow bioreactor. Originally, this community was obtained from subseafloor sediments off the Shimokita Peninsula of Japan in the north-western Pacific Ocean. The cells were motile, Gram-stain-negative, helical, 0.25-0.55×3.6-15 µm, with a wavelength of approximately 0.5-0.6 µm. Strain MO-SPC1(T) grew at 0-18 °C (optimally at 15 °C), at pH 6.0-7.5 (optimally at pH 6.8-7.0) and in 20-70 g NaCl l(-1) (optimally at 30-40 NaCl l(-1)). The strain grew chemo-organotrophically with mono-, di- and polysaccharides. The major end products of glucose fermentation were acetate, ethanol, hydrogen and carbon dioxide. The abundant polar lipids of strain MO-SPC1(T) were diphosphatidylglycerol, phosphatidylglycerol, unknown phospholipids and an unknown lipid. The major cellular fatty acids (>5% of the total) were C(14 : 0), C(16 : 0), iso-C(13 : 0), iso-C(14 : 0), iso-C(15 : 0), anteiso-C(13 : 0) and anteiso-C(15 : 0). To the best of our knowledge, this is the first report of the fatty acids iso-C(13 : 0) and anteiso-C(13 : 0) from a species of the genus Spirochaeta. Isoprenoid quinones were not found. The G+C content of the genomic DNA was 39.8 mol%. 16S rRNA gene sequence-based phylogenetic analysis showed that strain MO-SPC1(T) was affiliated with the genus Spirochaeta, and its closest relatives were Spirochaeta isovalerica MA-2(T) (95.6% sequence identity) and Spirochaeta litoralis R1(T) (89.4%). Based on its phenotypic characteristics and phylogenetic traits, strain MO-SPC1(T) is placed in a separate taxon at the level of a novel species within the genus Spirochaeta, for which the name Spirochaeta psychrophila sp. nov. is proposed, reflecting its true psychrophilic physiology. The type strain is MO-SPC1(T) ( = JCM 17280(T) = DSM 23951(T)). To our knowledge, this is the first report of an isolate of the phylum Spirochaetes from a deep-sea sedimentary environment, and of an obligately psychrophilic nature. © 2014 IUMS.

  20. Surface modification of superaustenitic and maraging stainless steels by low-temperature gas-phase carburization

    NASA Astrophysics Data System (ADS)

    Gentil, Johannes

    Low-temperature gas-phase carburization of 316L austenitic stainless steel was developed in recent years by the Swagelok company. This process generates great mechanical and electrochemical surface properties. Hardness, wear resistance, fatigue behavior, and corrosion resistance are dramatically improved, while the formation of carbides is effectively suppressed. This new technique is of technical, economical, but especially of scientific interest because the surface properties of common stainless steel can be enhanced to a level of more sophisticated and more expensive superalloys. The consequential continuation of previous research is the application of the carburization process to other steel grades. Differences in chemical composition, microstructure, and passivity between the various alloys may cause technical problems and it is expected that the initial process needs to be optimized for every specific material. This study presents results of low-temperature carburization of AL-6XN (superaustenitic stainless steel) and PH13-8Mo (precipitation-hardened martensitic stainless steel). Both alloys have been treated successfully in terms of creating a hardened surface by introducing high amounts of interstitially dissolved carbon. The surface hardness of AL-6XN was increased to 12GPa and is correlated with a colossal carbon supersaturation at the surface of up to 20 at.%. The hardened case develops a carburization time-dependent thickness between 10mum after one carburization cycle and up to 35mum after four treatments and remains highly ductile. Substantial broadening of X-ray diffraction peaks in low-temperature carburized superaustenitic stainless steels are attributed to the generation of very large compressive biaxial residual stresses. Those large stresses presumably cause relaxations of the surface, so-called undulations. Heavily expanded regions of carburized AL-6XN turn ferromagnetic. Non-carburized AL-6XN is known for its outstanding corrosion resistance, which is not impaired upon carburization. The passive film as analyzed by XPS is fully intact. Carbon concentration levels in PH13-8Mo reach 10 at.% and correlate with a surface hardness of up to 14GPa. Indication for the transformation from martensite to austenite during the process are observed. In this context, the shape of the carbon concentration-depth profile can be explained. Also the absence of carbides, as analyzed by TEM, can be rationalized. Upon cooling to room temperature, most of the austenite backtransforms into martensite and the surface regains its ferromagnetic properties. Compressive biaxial residual stresses in carburized PH13-8Mo are measured around (2--2.5)GPa. The applied low-temperature carburization process gives rise to a substantial loss in corrosion resistance of PH13-8Mo. Possible reasons including the observed formation of internal and external oxides as well as the change in alloy composition are discussed. Due to the penetration depth of X-rays into the probed specimen surface, a carbon concentration gradient may cause detectable asymmetry of diffraction peaks for certain alloys and under certain conditions. For the first time, this effect is rationalized, explained, and demonstrated on the basis of measured data.

  1. Synthesis and Photoluminescence Characteristics of Eu(3+)-Doped Molybdates Nanocrystals.

    PubMed

    Li, Fuhai; Yu, Lixin; Wei, Shuilin; Sun, Jiaju; Chen, Weiqing; Sun, Wei

    2015-12-01

    In this paper, the Eu(3+)-doped molybdate (CaMoO4, ZnMoO4 and BaMoO4) phosphors have been prepared by a hydrothermal method through modulating the pH value of the precursor solution (pH = 8, 10, and 12, respectively). The crystalline phase, morphology, photoluminescent properties of the prepared samples were systematically characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and photoluminescence (PL) spectra. The results indicate that the photoluminescence and morphology can be affected by the precursor solution. And the growth of the ZnMoO4 crystals also can be affected by the pH value of the precursor solution.

  2. Azo compound degradation kinetics and halonitromethane formation kinetics during chlorination.

    PubMed

    Fu, Jing; Wang, Xiaomao; Bai, Weiliang; Yang, Hongwei; Xie, Yuefeng F

    2017-05-01

    The chlorination of azo compounds can produce halonitromethanes (HNMs), which have attracted increasing concern due to their high genotoxicity. By impacting the speciation of chlorine and azo compounds, pH impacts apparent second-order rate constants of Methyl Orange (MO, 27.5-1.4 × 10 3  M -1  s -1 ), Acid Orange II (AO, 16.7-99.3 M -1  s -1 ), and Acid Red 1 (AR 1, 3.7-72.5 M -1  s -1 ) (pH range 6.3-9.0). The two-compartment first-order model successfully described the chloropicrin (TCNM) formation kinetics, suggesting that both fast- and slow-reacting precursors of TCNM are generated from the chlorination of azo compounds. The ratios between fast and slow formation rate constants for MO and AO were 15.6-5.4 × 10 2 , while that of AR 1 was 9.8-19.4 (pH range 6.5-9.0). The fraction of the fast-reacting TCNM precursors decreased with increasing pH for MO and AO; while that for AR 1 decreased when pH increased from 6.5 to 8.0, and then increased when pH increased from 8.0 to 9.0. The impact of pH on TCNM formation was also precursor-specific. The highest molar yields of TCNM predicted from the model in this study were 2.4%, 2.5%, and 1.5% for MO, AO, and AR 1, respectively. The study demonstrates that azo compounds are important HNM precursors, and pose a potential threat to drinking water safety. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Computer-Assisted Optimization of Electrodeposited Hydroxyapatite Coating Parameters on Medical Alloys

    NASA Astrophysics Data System (ADS)

    Coşkun, M. İbrahim; Karahan, İsmail H.; Yücel, Yasin; Golden, Teresa D.

    2016-04-01

    CoCrMo bio-metallic alloys were coated with a hydroxyapatite (HA) film by electrodeposition using various electrochemical parameters. Response surface methodology and central composite design were used to optimize deposition parameters such as electrolyte pH, deposition potential, and deposition time. The effects of the coating parameters were evaluated within the limits of solution pH (3.66 to 5.34), deposition potential (-1.13 to -1.97 V), and deposition time (6.36 to 73.64 minutes). A 5-level-3-factor experimental plan was used to determine ideal deposition parameters. Optimum conditions for the deposition parameters of the HA coating with high in vitro corrosion performance were determined as electrolyte pH of 5.00, deposition potential of -1.8 V, and deposition time of 20 minutes.

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

    Vogel, E.A.F.

    A series of new tetranuclear molybdenum(II) nitrile cluster derivatives is reported. Improvements in the synthetic routes to these and other derivatives is also reported. The single crystal x-ray structure of Mo/sub 4/Cl/sub 12//sup 4/minus// is modeled. New tetrameric nitrile derivatives with the stoichiometry Mo/sub 4/Cl/sub 8/(RCN)/sub 4/ (R = Pr/sup n/, Pr/sup i/, Bu/sup t/, PhCH/sub 2/) have been isolated by ligand exchange from Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/ and/or direct synthesis from Mo/sub 4/Cl/sub 8/(PBu/sup n/sub 3//)/sub 4/. Mo/sub 4/Cl/sub 8/(Pr/sup n/CN)/sub 4/ was synthesized with higher yields and with simpler reaction conditions than Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/. Improved syntheticmore » routes for R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N) have been developed. (Et/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ can be directly synthesized from the phosphine tetramer, circumventing the preparation of the reactive species-Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/, which is the most difficult precursor to prepare. A change in reaction solvent, from dichloromethane or dichloroethane to chlorobenzene, in the preparation of (Pr/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ has permitted its isolation under less rigorous conditions and in high yield. A single crystal structure determination has been done on a sample of (Ph/sub 4/P)/sub 4/Mo/sub 4/Cl/sub 12/. Although, the quality of the data is poor, the structure of the Mo/sub 4/Cl/sub 12/ cluster core was refined. Four complex types have been found to fit the data. 22 refs., 12 figs., 7 tabs.« less

  5. Molybdenum isotope fractionation during complexation with organic matter in the Critical Zone

    NASA Astrophysics Data System (ADS)

    King, E. K.; Pett-Ridge, J. C.; Perakis, S. S.

    2016-12-01

    Molybdenum (Mo) is a micronutrient and a redox sensitive trace metal that also forms strong complexes with organic matter (OM). The fractionation of Mo in sediments associated with adsorption onto both iron (Fe) and manganese (Mn) (oxyhydr)oxides under oxic conditions and sulfide phases under euxinic conditions has been used to constrain redox conditions in the ocean. Additionally, Mo isotope dynamics in terrestrial systems can shed light on the pedogenic mechanisms driving the riverine Mo isotopic composition and how atmospheric inputs alter the trace metal budget and isotopic composition of soils. As a result of these studies, it has been hypothesized that multiple mechanisms are responsible for fractionating Mo isotopes. In particular, Mo fractionation during adsorption onto OM is unknown, despite the fact this mechanism is 3x to more than 20x greater than adsorption onto Fe- and Mn- (oxyhydr)oxides across a range of soil types from Oregon, Iceland, and Hawaii1-3 (Marks et al., 2015; Siebert et al., 2015; King et al., 2016). In this study, we measured Mo adsorption and isotopic fractionation onto insolubilized humic acid (IHA), a proxy for OM, as a function of both adsorption time (2-170 h) and pH (2-7). Preliminary results suggest that for the time series experiment, Mo adsorption onto IHA increased from 35% to 64% and a plateau was reached after 24 hours. The average Mo isotope fractionation between the solution and the IHA was Δ98Mosolution-IHA = 1.8 ± 0.3‰. For the pH series experiment, the average Mo isotope fractionation was Δ98Mosolution-IHA = 2.0 ± 0.2‰. Next, we compared the Mo isotopic composition of foliage, O-horizon, and surface soil from 12 sites in the Oregon Coast Range to better understand the impact of OM on Mo isotope dynamics in natural samples. The potential isotopic offset between dissolved and adsorbed Mo onto OM is of the same order of magnitude and direction as fractionation onto Fe- and Mn- (oxyhydr)oxides such as ferrihydrite, hematite, and birnessite which have Δ98Mosolution-oxide values of 1.1‰, 2.2‰, and 1.8‰, respectively (Goldberg et al., 2009; Wasylenki et al., 2011). These results have important implications for the interpretation of the sedimentary Mo record, its use as a paleoredox tracer, and its potential to record changes in the terrestrial weathering environment.

  6. Removal of methyl orange and methylene blue dyes from aqueous solution using lala clam (Orbicularia orbiculata) shell

    NASA Astrophysics Data System (ADS)

    Eljiedi, Arwa Alseddig Ahmed; Kamari, Azlan

    2017-05-01

    Textile effluents are considered as potential sources of water pollution because they contain toxic dyes. In the present study, lala clam shell was used as an alternative low-cost adsorbent for the removal of two harmful dyes, namely methyl orange (MO) and methylene blue (MB) from aqueous solution. Batch adsorption studies were carried out by varying experimental parameters such as solution pH, initial concentration and adsorbent dosage. The optimum pH values for MO and MB removal were pH 2.0 and pH 8.0, respectively. At an initial MO and MB concentration of 20 mg/L, the maximum removal percentage of MO and MB were 18.9 % and 81.3 %, respectively. The adsorption equilibrium data were correlated with both Langmuir and Freundlich isotherm models. The biomass adsorbent was characterised using Field Emission Scanning Electron Microscope (FESEM) and Fourier Transform Infrared Spectrometer (FTIR). Results from this study suggest that lala clam shell, a fishery waste, can be beneficial for water treatment.

  7. Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility.

    PubMed

    Lehoux, Alizée P; Lockwood, Cindy L; Mayes, William M; Stewart, Douglas I; Mortimer, Robert J G; Gruiz, Katalin; Burke, Ian T

    2013-10-01

    Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m(3) of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 → 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5-8.5. This effect was attributed to the reaction of Ca(2+) supplied by the gypsum with OH(-) and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.

  8. A novel two-level dielectric barrier discharge reactor for methyl orange degradation.

    PubMed

    Tao, Xumei; Wang, Guowei; Huang, Liang; Ye, Qingguo; Xu, Dongyan

    2016-12-15

    A novel pilot two-level dielectric barrier discharge (DBD) reactor has been proposed and applied for degradation of continuous model wastewater. The two-level DBD reactor was skillfully realized with high space utilization efficiency and large contact area between plasma and wastewater. Various conditions such as applied voltage, initial concentration and initial pH value on methyl orange (MO) model wastewater degradation were investigated. The results showed that the appropriate applied voltage was 13.4 kV; low initial concentration and low initial pH value were conducive for MO degradation. The percentage removal of 4 L MO with concentration of 80 mg/L reached 94.1% after plasma treatment for 80min. Based on ultraviolet spectrum (UV), Infrared spectrum (IR), liquid chromatography-mass spectrometry (LC-MS) analysis of degradation intermediates and products, insights in the degradation pathway of MO were proposed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Prevention and treatment of Nitrite toxicity in juvenile steelhead trout (Salmo gairdneri)

    USGS Publications Warehouse

    Wedemeyer, Gary A.; Yasutake, W.T.

    1978-01-01

    The efficacy of mineral salts, pH, and tetramethylthianine (methylene blue) treatment in reducing the acute toxicity of nitrite to fingerling steelhead trout (Salmo gairdneri) was determined using a static bioassay system at 10 °C. The acute toxicity (96-h LC50) was reduced by a factor of about 24 for 5-g steelhead and 13 for 10-g fish when the total water hardness was increased from 25 to 300 mg/L (as CaCO3). NaCl or CaCl2 additions (0–200 mg/L) reduced toxicity by a factor of up to 3 for NaCl and 50 for CaCl2. Increasing the pH from 6.0 to 8.0 decreased toxicity by a factor of about 8 for the smaller and 3 for the larger fish. Methylene blue at 0.1 or 1.0 mg/L was effective in decreasing acute toxicity. For alleviating methemoglobinemia, removing the fish to freshwater for 48 h was about as effective as 1.0 mg/L methylene blue. Chronic exposure in soft water to 0.03 mg/L NO2-N for 6 mo caused no significant growth reduction, gill histological changes, hematological dyscrasias, or impaired ability of the smolts to adapt to 30‰ seawater and grow for an additional 2 mo. Key words: nitrite, toxicity, fish, methylene blue, pH, salts, acute toxicity, chronic toxicity

  10. 35 GHz ENDOR characterization of the "very rapid" signal of xanthine oxidase reacted with 2-hydroxy-6-methylpurine (13C8): evidence against direct Mo-C8 interaction.

    PubMed

    Manikandan, P; Choi, E Y; Hille, R; Hoffman, B M

    2001-03-21

    Xanthine oxidase is a molybdenum-containing enzyme that catalyzes the hydroxylation of xanthine and a wide variety of other aromatic heterocycles. In the course of the reaction with xanthine and substrates such as 2-hydroxy-6-methylpurine (HMP), the enzyme gives rise to a Mo(V) EPR signal, denoted "very rapid", that arises from an authentic catalytic intermediate. The two alternative catalytic mechanisms proposed for this enzyme differ critically in whether the distance between Mo and C8 of the purine nucleus in this intermediate is short enough to admit a direct bonding interaction. To examine this distance, we have performed 13C ENDOR measurements of the "very rapid" EPR signal generated by xanthine oxidase during reaction with 13C8-HMP. The resulting (13)C8 hyperfine tensor, A = [10.2(1), 7.0(1), 6.5(1)] MHz, is discussed in the framework of a detailed consideration of factors involved in extracting metrical parameters from an anisotropic hyperfine interaction composed of contributions from multiple sources, in particular, the effect of the local contributions from spin density on (13)C8. The analysis presented here gives a Mo...C distance whose value is expected to be ca. 2.7-2.9 A in the "very rapid" intermediates formed with both xanthine and HMP, consistent with plausible bond lengths for a Mo-O-C8 fragment where C8 is a trigonal-planar aromatic carbon. The difference from earlier conclusions is explained. The data thus do not support the existence of a direct Mo-C bond in the signal-giving species. This conclusion supports a mechanism that does not involve such an interaction and which begins with base-assisted nucleophilic attack of the Mo(VI)-OH group on the C-8 of substrate, with concomitant hydride transfer to the Mo=S group to give Mo(IV)-SH; the EPR-active "very rapid" species then forms by one-electron oxidation and deprotonation to yield the EPR-detectable Mo(V)OS(OR) species. We further discuss the complexities and limitations of the semiempirical method used to arrive at these conclusions.

  11. Industry Funding Among Leadership in Medical Oncology and Radiation Oncology in 2015.

    PubMed

    Yoo, Stella K; Ahmed, Awad A; Ileto, Jan; Zaorsky, Nicholas G; Deville, Curtiland; Holliday, Emma B; Wilson, Lynn D; Jagsi, Reshma; Thomas, Charles R

    2017-10-01

    To quantify and determine the relationship between oncology departmental/division heads and private industry vis-à-vis potential financial conflict of interests (FCOIs) as publicly reported by the Centers for Medicare and Medicaid Services Open Payments database. We extracted the names of the chairs/chiefs in medical oncology (MO) and chairs of radiation oncology (RO) for 81 different institutions with both RO and MO training programs as reported by the Association of American Medical Colleges. For each leader, the amount of consulting fees and research payments received in 2015 was determined. Logistic modeling was used to assess associations between the 2 endpoints of receiving a consulting fee and receiving a research payment with various institution-specific and practitioner-specific variables included as covariates: specialty, sex, National Cancer Institute designation, PhD status, and geographic region. The majority of leaders in MO were reported to have received consulting fees or research payments (69.5%) compared with a minority of RO chairs (27.2%). Among those receiving payments, the average (range) consulting fee was $13,413 ($200-$70,423) for MO leaders and $6463 ($837-$16,205) for RO chairs; the average research payment for MO leaders receiving payments was $240,446 ($156-$1,234,762) and $295,089 ($160-$1,219,564) for RO chairs. On multivariable regression when the endpoint was receipt of a research payment, those receiving a consulting fee (odds ratio [OR]: 5.34; 95% confidence interval [CI]: 2.22-13.65) and MO leaders (OR: 5.54; 95% CI: 2.62-12.18) were more likely to receive research payments. Examination of the receipt of consulting fees as the endpoint showed that those receiving a research payment (OR: 5.41; 95% CI: 2.23-13.99) and MO leaders (OR: 3.06; 95% CI: 1.21-8.13) were more likely to receive a consulting fee. Leaders in academic oncology receive consulting or research payments from industry. Relationships between oncology leaders and industry can be beneficial, but guidance is needed to develop consistent institutional policies to manage FCOIs. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Molybdenum and zinc stable isotope variation in mining waste rock drainage and waste rock at the Antamina mine, Peru.

    PubMed

    Skierszkan, E K; Mayer, K U; Weis, D; Beckie, R D

    2016-04-15

    The stable isotope composition of molybdenum (Mo) and zinc (Zn) in mine wastes at the Antamina Copper-Zn-Mo mine, Peru, was characterized to investigate whether isotopic variation of these elements indicated metal attenuation processes in mine drainage. Waste rock and ore minerals were analyzed to identify the isotopic composition of Mo and Zn sources, namely molybdenites (MoS2) and sphalerites (ZnS). Molybdenum and Zn stable isotope ratios are reported relative to the NIST-SRM-3134 and PCIGR-1 Zn standards, respectively. δ(98)Mo among molybdenites ranged from -0.6 to +0.6‰ (n=9) while sphalerites showed no δ(66)Zn variations (0.11±0.01‰, 2 SD, n=5). Mine drainage samples from field waste rock weathering experiments were also analyzed to examine the extent of isotopic variability in the dissolved phase. Variations spanned 2.2‰ in δ(98)Mo (-0.1 to +2.1‰) and 0.7‰ in δ(66)Zn (-0.4 to +0.3‰) in mine drainage over a wide pH range (pH2.2-8.6). Lighter δ(66)Zn signatures were observed in alkaline pH conditions, which was consistent with Zn adsorption and/or hydrozincite (Zn5(OH)6(CO3)2) formation. However, in acidic mine drainage Zn isotopic compositions reflected the value of sphalerites. In addition, molybdenum isotope compositions in mine drainage were shifted towards heavier values (0.89±1.25‰, 2 SD, n=16), with some overlap, in comparison to molybdenites and waste rock (0.13±0.82‰, 2 SD, n=9). The cause of heavy Mo isotopic signatures in mine drainage was more difficult to resolve due to isotopic heterogeneity among ore minerals and a variety of possible overlapping processes including dissolution, adsorption and secondary mineral precipitation. This study shows that variation in metal isotope ratios are promising indicators of metal attenuation. Future characterization of isotopic fractionation associated to key environmental reactions will improve the power of Mo and Zn isotope ratios to track the fate of these elements in mine drainage. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Utilization of cross-linked chitosan/bentonite composite in the removal of methyl orange from aqueous solution.

    PubMed

    Huang, Ruihua; Liu, Qian; Zhang, Lujie; Yang, Bingchao

    2015-01-01

    A kind of biocomposite was prepared by the intercalation of chitosan in bentonite and the cross-linking reaction of chitosan with glutaraldehyde, which was referred to as cross-linked chitosan/bentonite (CCS/BT) composite. Adsorptive removal of methyl orange (MO) from aqueous solutions was investigated by batch method. The adsorption of MO onto CCS/BT composite was affected by the ratio of chitosan to BT and contact time. pH value had only a minor impact on MO adsorption in a wide pH range. Adsorption kinetics was mainly controlled by the pseudo-second-order kinetic model. The adsorption of MO onto CCS/BT composite followed the Langmuir isotherm model, and the maximum adsorption capacity of CCS/BT composite calculated by the Langmuir model was 224.8 mg/g. Experimental results indicated that this adsorbent had a potential for the removal of MO from aqueous solutions.

  14. The physiology of the Tambaqui (Colossoma macropomum) at pH 8.0.

    PubMed

    Wood, Chris M; Gonzalez, R J; Ferreira, Márcio Soares; Braz-Mota, Susana; Val, Adalberto Luis

    2018-05-01

    The Tambaqui is a model neotropical teleost which is of great economic and cultural importance in artisanal fisheries and commercial aquaculture. It thrives in ion-poor, often acidic Amazonian waters and exhibits excellent regulation of physiology down to water pH 4.0. Curiously, however, it is reported to perform poorly in aquaculture at pH 8.0, an only slightly alkaline pH which would be benign for most freshwater fish. In initial experiments with Tambaqui of intermediate size (30-50 g), we found that ammonia excretion rate was unchanged at pH 4, 5, 6, and 7, but elevated after 20-24 h at pH 8, exactly opposite the pattern seen in most teleosts. Subsequent experiments with large Tambaqui (150-300 g) demonstrated that only ammonia, and not urea excretion was increased at pH 8.0, and that the elevation was proportional to a general increase in MO 2 . There was an accompanying elevation in net acidic equivalent excretion and/or basic equivalent uptake which occurred mainly at the gills. Net Na + balance was little affected while Cl - balance became negative, implicating a disturbance of Cl - versus base exchange rather than Na + versus acid exchange. Arterial blood pH increased by 0.2 units at pH 8.0, reflecting combined metabolic and respiratory alkaloses. Most parameters recovered to control levels by 18-24 h after return to pH 6.0. With respect to large Tambaqui, we conclude that a physiology adapted to acidic pH performs inappropriately at moderately alkaline pH. In small Tambaqui (4-15 g), the responses were very different, with an initial inhibition of ammonia excretion rate at pH 8.0 followed by a subsequent restoration of control levels. Elevated ammonia excretion rate occurred only after return to pH 6.0. Furthermore, MO 2 , plasma cortisol, and branchial vH + ATPase activities all declined during pH 8.0 exposure in small Tambaqui, in contrast to the responses in larger fish. Overall, small Tambaqui appear to cope better at pH 8.0, a difference that may correlate with their natural history in the wild.

  15. ZnMoO4:Er3+,Yb3+ phosphor with controlled morphology and enhanced upconversion through alkali ions doping

    NASA Astrophysics Data System (ADS)

    Luitel, Hom Nath; Chand, Rumi; Watari, Takanori

    2018-04-01

    A facile hydrothermal method was used to synthesize ZnMoO4:Er3+,Yb3+ nanoparticles. The shapes and sizes of the nanoparticles were well tuned by simply monitoring the pH of the starting solution. Microballs consisting of agglomerated nanograins were observed at strong acidic condition. At mild pH, plates and rectangular particles were realized, while strong basic pH stabilized rods. Further increasing pH to extremely basic conditions (pH > 13), rods changed to fragile hairy structures. The nucleation and growth mechanism of nanograins to form different morphology nanoparticles were studied and illustrated. XRD patterns confirmed well crystalline, triclinic structure despite small amount of aliovalent metal ions doping. Under 980 nm excitation, the ZnMoO4:Er3+,Yb3+ nanophosphor exhibited strong green (centered at 530 and 560 nm) and weak red (centered at 660 nm) upconversion (UC) emissions. Substitution of part of the Zn2+ ions by monovalent alkali ions intensified the UC emission intensities drastically. The order of intensification was K+>Na+>Li+>Rb+>no alkali ion. When Zn2+ ions were substituted with 10 at% K+ ions, the green and red UC emissions intensities increased by more than 50 and 15 folds, respectively. Time dependent measurements confirmed efficient Yb to Er energy transfer in the ZnMoO4:Er3+,Yb3+,K+ nanophosphor. The optimized ZnMoO4:Er3+,Yb3+,K+ phosphor exhibited intense UC emissions with 0.31% quantum yield. The upconverted light is visible to naked eye while pumping by laser of less than 1 mW power and opens door for variety of novel applications.

  16. Damage Tolerant Design Handbook. A Compilation of Fracture and Crack- Growth Data for High-Strength Alloys. Volume 1

    DTIC Science & Technology

    1983-12-01

    34. Report MCR -74-43, Martin Marietta Corp.. Denver Division, Deaver, CO. Contract HAS 9-13599 (Jamnary 1974). 0981" T!-6AL-IV da/dN ’ rI-6L-6V-2Sn KIc...34Lockheed-Palo Alto M. J. Rebholz Martin Marietta Alumi•um D. Mellem Materials Laboratory C. Harmsworth, J. Larsen, and T. Nicholas (Wright-Patterson AFB...Applications,’ Report AFML- TR-73-182, Boeing Comercial Airplane Co., Seattle, WA., Contract ?33615- 71 -C-1550, September 1973. 88136 PH 13-8 Mo KIc Dill

  17. Initation of pitting corrosion in martensitic stainless steels. [17-4PH; 13-8Mo; Custom 450

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

    Cieslak, W.R.; Semarge, R.E.; Bovard, F.S.

    1986-01-01

    The form of localized corrosion known as pitting often initiates preferentially at microstructural inhomogeneities. The pit initiation resistance, therefore, is controlled by the characteristics of the initiation sites, rather than by the bulk material composition. This investigation correlates the pit initiation resistance, as measured by critical pitting potentials, with preferred pit initiation sites for 3 martensitic stainless steels. Pit initiation sites are determined by secondary electron (SE) and backscattered electron (BSE) imaging and energy dispersive and wavelength dispersive spectrometries (EDS and WDS) with a scalling electron microscope (SEM) and an electron probe microanalyzer (EPMA).

  18. Precipitation of molybdenum(V) as the hydroxide and its separation from rhenium.

    PubMed

    Yatirajam, V; Ahuja, U; Kakkar, L R

    1975-03-01

    A study of the conditions for precipitation of molybdenum(V) hydroxide shows that for Mo concentration 1 mg ml about 97.5% of the Mo can be precipitated between pH 5 and 5.8. Lower concentrations of molybdenum(V) or molybdenum(VI) can be precipitated quantitatively by using 20 times the amount of zirconium as collector, at the same pH. On this basis, a simple method is given for quantitative separation of rhenium from large amounts of molybdenum and is attested by analysis of synthetic and molybdenite samples.

  19. Heterometallic niobium complexes containing the {open_quotes}CpNb{close_quotes} unit. X-ray crystal structures of CpNbCl{sub 2}({mu}-SEt){sub 2}NiCp and CpNb(PhCCPh)({mu}-SPr{sup 1}){sub 2}Mo(CO){sub 4}

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

    Woodward, S.; Curtis, M.D.; Rheingold, A.L.

    1992-06-01

    Cp{sub 2}Nb{sub 2}Cl{sub 2}({mu}-Cl{sub 2})(CO){sub 4} reacts with Cp{sub 2}Ni{sub 2}({mu}-SEt){sub 2} to yield paramagnetic CpNbCl{sub 2}({mu}-SEt){sub 2}NiCp: (g) = 2.004, A = 129 G; space group = P2{sub 1}/c,a = 7.466 (1) {Angstrom}, b = 28.427 (5) {Angstrom}, c = 8.620 (2) {Angstrom}, {beta} = 104.81 (1){degree}. CpNb(PhCCPh)({mu}-SPr{sup i}){sub 2}Mo(CO){sub 4} is synthesized by the addition of LiSPr{sup i} to CpNbCl{sub 2}PhCCPh resulting in formation of CpNb(SPr{sup i}){sub 2}(PhCCPh) followed by the reaction of the thiolate complex with Mo(MeCN){sub 3}(CO){sub 3} and CO (1 equiv). The crystal structure for CpNb(PhCCPh)({mu}-SPr{sup i}){sub 2}Mo(CO){sub 4} is reported and EHMO calculations ofmore » the bonding in CpNbCl{sub 2}({mu}-SEt{sub 2})NiCp were discussed. 27 refs., 5 figs., 5 tabs.« less

  20. Octahedral d[sup 6] Bis(maleimide) and Bis(maleic anhydride) complexes of molybdenum

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

    Lai, Chen-Hsing; Cheng, Chien-Hong; Liao, Fen-Ling

    1993-12-08

    Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] reacts with 2 equiv of alkene, where the alkene is maleimide (MI), N-phenylmaleimide (PhMI), or N-methylmaleimide, to give the corresponding Mo(CO)[sub 2](alkene)[sub 2](CH[sub 3]CN)[sub 2] complex (1a-c, respectively) in excellent yield. Dissolution of 1 in DMSO led to the substitution of acetonitrile ligands by DMSO to form the corresponding cis bis(DMSO) complexes 2a-c. Addition of 1 equiv of NN to 1 yields MO(CO)[sub 2](alkene)[sub 2](alkene)[sub 2](NN) (NN = en, alkene = PhMI (3b), MeMI (3c); NN = o-phenylenediamine, alkene = PhMI (4)). Treatment of Mo-(CO)[sub 4](NN) (NN = phen or bpy), with 2 equiv of alkenemore » in refluxed acetonitrile for 2 h gave Mo(CO)[sub 2]-(alkene)[sub 2](NN) (NN = phen, alkene = MI (5a), PhMI (5b); NN = bpy, alkene = MI (6a), PhMI (6b)). Treatment of Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] with 2 equiv of maleic anhydride (MA) gave Mo(CO)[sub 2](MA)[sub 2](CH[sub 3]CN)[sub 2] (7). The acetonitrile ligands in 7 were replaced by DMSO molecules to give complex 8 as 7 was dissolved in DMSO. Similarly, the reaction of 7 with a bidentate ligand NN (phen or bpy) gave the substituted product Mo(CO)[sub 2](MA)[sub 2](NN) (9 or 10). The structures and conformations of 1b and 7 were determined by X-ray diffraction. Both molecules adopt an octahedral geometry with mutually perpendicular trans alkene ligands and each alkene ligand eclipses a N-Mo-CO vector. Each PhMI or MA is oriented so that the central nitrogen or oxygen atom points to a carbonyl group. 1b crystallizes in triclinic space group P1. There are three possible conformations for a trans bis(maleimide) or bis(maleic anhydride) complex (I-III). The results of X-ray and NMR studies indicated that the main conformation of complexes 1-10 is I both in the solid state and in solution.« less

  1. Electrophysiological signs of supplementary-motor-area deficits in high-functioning autism but not Asperger syndrome: an examination of internally cued movement-related potentials.

    PubMed

    Enticott, Peter G; Bradshaw, John L; Iansek, Robert; Tonge, Bruce J; Rinehart, Nicole J

    2009-10-01

    Motor dysfunction is common to both autism and Asperger syndrome, but the underlying neurophysiological impairments are unclear. Neurophysiological examinations of motor dysfunction can provide information about likely sites of functional impairment and can contribute to the debate about whether autism and Asperger syndrome are variants of the same disorder or fundamentally distinct neurodevelopmental conditions. We investigated the neurophysiology of internally determined motor activity in autism and Asperger syndrome via examination of movement-related potentials (MRPs). We used electroencephalography to investigate MRPs, via an internally cued movement paradigm, in the following three groups: (1) individuals with high-functioning autism (14 males, one female; mean age 13 y 1 mo, SD 4 y 2 mo, range 7 y 8 mo to 20 y 9 mo; mean Full-scale IQ 93.40, SD 20.72); (2) individuals with Asperger syndrome (10 males, two females; mean age 13 y 7 mo, SD 3 y 9 mo, range 8 y 11 mo to 20 y 4 mo; mean Full-scale IQ 103.25, SD 19.37), and (3) a healthy control group (13 males, seven females; mean age 14 y 0 mo, SD 3 y 11 mo; range 8 y 4 mo to 21 y 0 mo; mean Full-scale IQ 114.25, SD 11.29). Abnormal MRPs can reflect disruption of motor-related neural networks involving the basal ganglia, thalamus, and supplementary motor area. There was evidence for abnormal MRPs in autism (e.g. increased post-movement cortical activity, abnormal peak time) but not in Asperger syndrome. The results support basal ganglia, thalamus, and supplementary motor area involvement as a likely source of motor dysfunction in autism, and provide further evidence for the neurobiological separateness of autism and Asperger syndrome.

  2. Water Quality Criteria for Nitrocellulose

    DTIC Science & Technology

    1986-06-01

    38 . 6. REFERENCES. .................................................... 40 ’ 7. GLOSSARY...Flexible "collodion, FM--NIS, Guncotton, IX 3/5, Kodak Li 115, LR 115, Nitrocel- lulose E950, Nitrocotton, Nitron , Nixon N/C, NTs 62, Nrs 218, Nrs 222...0OCf 38.79 15.8 40 ,827h 24 mo 1 42.69 6.5 1,526 24 mo 3 NAI 6.7 NDJ 24 mo 10 38.35 13.8 36,031k Mouse 24 mo 0 37 6.2 0 (female) 24 ma 1of 34.2 12.8

  3. Fabrications of some kinds of 2-D frameworks consisting of nanosized polyoxomolybdate anion [Mo 36O 112(H 2O) 16] 8- via condensation processes

    NASA Astrophysics Data System (ADS)

    Eda, Kazuo; Iriki, Yuichi; Kawamura, Kenjiro; Ikuki, Takeshi; Hayashi, Masahiko

    2007-12-01

    We succeeded to prepare novel [Mo 36O 112(H 2O) 16] 8- ({Mo 36}) compounds by using 1,3-diamino-2-propanol ( βOHC 3-DA) and 1,3,5-tris(aminomethyl)benzene (MES-TA)+1,3-diaminopropane (C 3-DA) as linkers, and determined their crystal structures. We have confirmed they have unique two-dimensional (2-D) molybdenum oxide frameworks, which are formed by condensation of {Mo 36}s. Side-staggered arrays of {Mo 36}s, connected in lying position by eight bridges per a {Mo 36}, are formed in the compound with βOHC 3-DA, while herringbone arrays of {Mo 36}s, connected in standing position by four bridges per a {Mo 36}, are built in the compound with MES-TA+C 3-DA. The latter compound exhibited non-stoichiometric property, and its composition and cell parameters varied depending on the relative concentration of MES-TA in the mother solution.

  4. Preparation of transition metal composite graphite felt cathode for efficient heterogeneous electro-Fenton process.

    PubMed

    Liang, Liang; Yu, Fangke; An, Yiran; Liu, Mengmeng; Zhou, Minghua

    2017-01-01

    A composite graphite felt (GF) modified with transition metal was fabricated and used as cathode in heterogeneous electro-Fenton (EF) for methyl orange (MO) degradation. Characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), the morphology and surface physicochemical properties of the cathodes after modification were observed considerably changed. After loading metals, the current response became higher, the accumulation of H 2 O 2 and the degradation efficiency of MO were improved. Under the same conditions, GF-Co had the highest catalytic activity for electro-reduction of O 2 to H 2 O 2 and MO degradation. At pH 3, 99 % of MO degradation efficiency was obtained using GF-Co after 120 min treatment and even at initial pH 9, 82 % of that was obtained. TOC removal efficiency reached 93.8 % using GF-Co at pH 3 after 120 min treatment while that was 12.3 % using GF. After ten-time runs, the mineralization ratio of the GF-Co was still 89.5 %, suggesting that GF-Co was very promising for wastewater treatment. The addition of isopropanol proved that · OH played an important role in degradation of MO.

  5. A Comparative Analysis of the Corrosive Effect of Artificial Saliva of Variable pH on DMLS and Cast Co-Cr-Mo Dental Alloy

    PubMed Central

    Puskar, Tatjana; Jevremovic, Danimir; Williams, Robert J.; Eggbeer, Dominic; Vukelic, Djordje; Budak, Igor

    2014-01-01

    Dental alloys for direct metal laser sintering (DMLS) are available on the market today, but there is little scientific evidence reported on their characteristics. One of them is the release of ions, as an indicator of the corrosion characteristics of a dental alloy. Within this research, the difference in the elution of metals from DMLS and cast (CM) samples of Co-Cr-Mo dental alloy in saliva-like medium of three different pH was examined by inductively-coupled plasma mass spectrometry (ICP-MS). The obtained results show that the metal elution in artificial saliva from the DMLS alloy was lower than the elution from the CM alloy. The release of all investigated metal ions was influenced by the acidity, both from the DMLS and CM alloy, throughout the investigated period of 30 days. The change in acidity from a pH of 6.8 to a pH of 2.3 for the cast alloy led to a higher increase of the elution of Co, Cr and Mo from CM than from the DMLS alloy. The greatest release out of Co, Cr and Mo was for Co for both tested alloys. Further, the greatest release of all ions was measured at pH 2.3. In saliva of pH 2.3 and pH 4.5, the longer the investigated period, the higher the difference between the total metal ion release from the CM and DMLS alloys. Both alloys showed a safe level of elution according to the ISO definition in all investigated acidic environments. PMID:28788197

  6. A Comparative Analysis of the Corrosive Effect of Artificial Saliva of Variable pH on DMLS and Cast Co-Cr-Mo Dental Alloy.

    PubMed

    Puskar, Tatjana; Jevremovic, Danimir; Williams, Robert J; Eggbeer, Dominic; Vukelic, Djordje; Budak, Igor

    2014-09-11

    Dental alloys for direct metal laser sintering (DMLS) are available on the market today, but there is little scientific evidence reported on their characteristics. One of them is the release of ions, as an indicator of the corrosion characteristics of a dental alloy. Within this research, the difference in the elution of metals from DMLS and cast (CM) samples of Co-Cr-Mo dental alloy in saliva-like medium of three different pH was examined by inductively-coupled plasma mass spectrometry (ICP-MS). The obtained results show that the metal elution in artificial saliva from the DMLS alloy was lower than the elution from the CM alloy. The release of all investigated metal ions was influenced by the acidity, both from the DMLS and CM alloy, throughout the investigated period of 30 days. The change in acidity from a pH of 6.8 to a pH of 2.3 for the cast alloy led to a higher increase of the elution of Co, Cr and Mo from CM than from the DMLS alloy. The greatest release out of Co, Cr and Mo was for Co for both tested alloys. Further, the greatest release of all ions was measured at pH 2.3. In saliva of pH 2.3 and pH 4.5, the longer the investigated period, the higher the difference between the total metal ion release from the CM and DMLS alloys. Both alloys showed a safe level of elution according to the ISO definition in all investigated acidic environments.

  7. Effect of castration and slaughter age on performance, carcass, and meat quality traits of Holstein calves fed a high-concentrate diet.

    PubMed

    Marti, S; Realini, C E; Bach, A; Pérez-Juan, M; Devant, M

    2013-03-01

    The aim of this study was to evaluate the effect of castration and slaughter age on performance and meat quality of Holstein bulls fed a high-concentrate diet. A total of 132 animals (116 ± 3.7 kg of BW and 97 ± 2.4 d of age) were randomly allocated in 6 pens using a 3 × 3 factorial arrangement of treatments. Three castration ages [bulls, animals castrated at 3 mo (CAS3), and animals castrated at 8 mo of age (CAS8)] and 3 slaughter ages (10, 12, and 14 mo of age) were evaluated. Feed intake was recorded daily using a computerized concentrate feeder, and BW was recorded every 14 d. The 9th to 11th rib section was removed at 24 h postmortem and dissected into lean, fat, and bone, and meat quality was evaluated on the LM. Castration, at 3 or 8 mo of age, reduced (P < 0.001) ADG and muscle pH and impaired (P < 0.01) feed efficiency. As slaughter age increased, concentrate consumption increased linearly (P < 0.001) and feed efficiency was reduced linearly (P < 0.001). Slaughter age also affected (P < 0.001) meat pH. Significant interactions between castration and slaughter ages were also observed in carcass conformation (P < 0.05), fatness (P < 0.001), percentage of subcutaneous fat (P < 0.01), carcass dressing percentage (P < 0.05), and intramuscular fat (P < 0.05) and tended to be significant in intermuscular fat (P = 0.09). In Holstein animals, castration age affects performance and meat pH regardless of slaughter age, and slaughter age affects performance and meat pH independently of castration. However, in Holstein animals, castration affects several characteristics related to fat deposition differently depending on slaughter age, such as carcass fat cover and intramuscular, intermuscular, and subcutaneous fat.

  8. Mammary Tumor Development: Stromal-Epithelial Interactions in Oncogenesis.

    DTIC Science & Technology

    1996-09-01

    differentiation, prolif- erative preneoplastic lesions, or invasive adenocarcinomas , depending on the promoter con- struct used and the animal’s age when...Zn). Virgin RSV-SGF transgenic mice showed marked preneoplastic MG ductal proliferation by 6 mo. By 8 mo., 1/3 had developed adenocarcinoma . Virgin...fat pRSGF Constitutively expressed Highly abnormal. None Normal Observed at 8 1/3 of mice show months of age invasive secretory adenocarcinoma SGF

  9. A new series of HAPs as anti-HBV agents targeting at capsid assembly.

    PubMed

    Yang, Xiu-yan; Xu, Xiao-qian; Guan, Hua; Wang, Li-li; Wu, Qin; Zhao, Guo-ming; Li, Song

    2014-09-01

    A series of novel Heteroaryldihydropyrimidines (HAPs) derivatives were designed and synthesized as potent inhibitors of HBV capsid assembly. These compounds were prepared from efforts to optimize an earlier series of HAPs, and compounds Mo1, Mo7, Mo8, Mo10, Mo12, and Mo13 demonstrated potent inhibition of HBV DNA replication at submicromolar range. Copyright © 2014. Published by Elsevier Ltd.

  10. Therapeutic and prognostic value of chromosomal AP classification at the blastic phase of Ph-positive chronic myeloid leukemia: comparison of data from Nagasaki University, Japan and Roswell Park Memorial Institute, U.S.A.

    PubMed

    Sadamori, N; Yao, E; Mine, M; Tokunaga, S; Matsunaga, M; Nakamura, H; Sasagawa, I; Itoyama, T; Kawachi, T; Sandberg, A A

    1991-01-01

    To assess parameters of therapeutic response and survival after the onset of the blastic phase (BP) in 47 patients with Philadelphia chromosome (Ph)-positive chronic myeloid leukemia (CML), a number of clinical hematologic, and cytogenetic data at the BP were evaluated. Among the eleven parameters examined, only the chromosomal findings correlated with the therapeutic response and survival after onset of the BP. The patients were divided into three groups on the basis of the chromosome findings in the bone marrow: one, with only a Ph (PP), another with two different clones, i.e., one clone with Ph only and another with additional karyotypic changes (AP), and a third group with only abnormal clones containing karyotypic abnormalities in addition to the Ph (AA). The number of patients with AA was 12, 18 with AP, and 17 with PP. The results were as follows: (1) The percentage of patients with a good therapeutic response was 25% (3/12) in AA, 22% (4/18) in AP, and 76% (13/17) in PP; (2) The median survival after the onset of the BP was 1.5 mo for AA, 2.4 mo for AP, and 7.3 mo for PP. Statistically, there was a significant difference between PP and the other two groups (p < 0.05). These data were reevaluated and compared to those of 64 patients with Ph-positive CML in Roswell Park Memorial Institute (RPMI) who had been reported earlier in 1983.

  11. Absolute rate expressions for hydrogen atom abstraction from molybdenum hydrides by carbon-centered radicals

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

    Franz, J.A.; Linehan, J.C.; Birnbaum, J.C.

    1999-10-27

    A new family of basis rate expressions for hydrogen atom abstraction by primary, secondary, and tertiary alkyl radicals in dodecane and benzyl radical in benzene from the molybdenum hydride Cp*Mo-(CO){sub 3}H and for reactions of a primary alkyl radical with CpMo(CO){sub 3}H in dodecane are reported (Cp* = {eta}{sup 5}-pentamethylcyclopentadienyl, Cp = {eta}{sup 5}-cyclopentadienyl). Rate expressions for reaction of primary, secondary, and tertiary radical clocks with Cp*Mo(CO){sub 3}H were as follows: for hex-5-enyl, log(k/M{sup {minus}1} s{sup {minus}1}) = (9.27 {+-} 0.13) {minus} (1.36 {+-} 0.22)/{theta}, {theta} = 2.303RT kcal/mol; for hept-6-en-2-yl, log(k/M{sup {minus}1} s{sup {minus}1}) = (9.12 {+-} 0.42) {minus}more » (1.91 {+-} 0.74)/{theta}; and for 2-methylhept-6-en-2-yl, log(k/M{sup {minus}1} s{sup {minus}1}) = (9.36 {+-} 0.18) {minus} (3.19 {+-} 0.30)/{theta} (errors are 2{sigma}). Hydrogen atom abstraction from CpMo(CO){sub 3}H by hex-5-enyl is described by log(k/M{sup {minus}1} s{sup {minus}1}) = (9.53 {+-} 0.34) {minus} (1.24 {+-} 0.62)/{theta}. Relative rate constants for 1{degree}:2{degree}:3{degree} alkyl radicals were found to be 26:7:1 at 298 K. Benzyl radical was found to react 1.4 times faster than tertiary alkyl radical. The much higher selectivities for CP*Mo(CO){sub 3}H than those observed for main group hydrides (Bu{sub 3}SnH, PhSeH, PhSH) with alkyl radicals, together with the very fast benzyl hydrogen-transfer rate, suggest the relative unimportance of simple enthalpic effects and the dominance of steric effects for the early transition-state hydrogen transfers. Hydrogen abstraction from Cp*Mo(CO){sub 3}H by benzyl radicals is described by log(k/M{sup {minus}1} s{sup {minus}1}) = (8.89 {+-} 0.22) {minus} (2.31 {+-} 0.33)/{theta}.« less

  12. Passivation Characteristics of Alloy Corrosion-Resistant Steel Cr10Mo1 in Simulating Concrete Pore Solutions: Combination Effects of pH and Chloride

    PubMed Central

    Ai, Zhiyong; Sun, Wei; Jiang, Jinyang; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

    2016-01-01

    The electrochemical behaviour for passivation of new alloy corrosion-resistant steel Cr10Mo1 immersed in alkaline solutions with different pH values (13.3, 12.0, 10.5, and 9.0) and chloride contents (0.2 M and 1.0 M), was investigated by various electrochemical techniques: linear polarization resistance, electrochemical impedance spectroscopy and capacitance measurements. The chemical composition and structure of passive films were determined by XPS. The morphological features and surface composition of the immersed steel were evaluated by SEM together with EDS chemical analysis. The results evidence that pH plays an important role in the passivation of the corrosion-resistant steel and the effect is highly dependent upon the chloride contents. In solutions with low chloride (0.2 M), the corrosion-resistant steel has notably enhanced passivity with pH falling from 13.3 to 9.0, but does conversely when in presence of high chloride (1.0 M). The passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer enriched in Fe oxides and hydroxides, and an inner layer, rich in Cr species. The film composition varies with pH values and chloride contents. As the pH drops, more Cr oxides are enriched in the film while Fe oxides gradually decompose. Increasing chloride promotes Cr oxides and Fe oxides to transform into their hydroxides with little protection, and this is more significant at lower pH (10.5 and 9.0). These changes annotate passivation characteristics of the corrosion-resistant steel in the solutions of different electrolyte. PMID:28773867

  13. Passivation Characteristics of Alloy Corrosion-Resistant Steel Cr10Mo1 in Simulating Concrete Pore Solutions: Combination Effects of pH and Chloride.

    PubMed

    Ai, Zhiyong; Sun, Wei; Jiang, Jinyang; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

    2016-09-01

    The electrochemical behaviour for passivation of new alloy corrosion-resistant steel Cr10Mo1 immersed in alkaline solutions with different pH values (13.3, 12.0, 10.5, and 9.0) and chloride contents (0.2 M and 1.0 M), was investigated by various electrochemical techniques: linear polarization resistance, electrochemical impedance spectroscopy and capacitance measurements. The chemical composition and structure of passive films were determined by XPS. The morphological features and surface composition of the immersed steel were evaluated by SEM together with EDS chemical analysis. The results evidence that pH plays an important role in the passivation of the corrosion-resistant steel and the effect is highly dependent upon the chloride contents. In solutions with low chloride (0.2 M), the corrosion-resistant steel has notably enhanced passivity with pH falling from 13.3 to 9.0, but does conversely when in presence of high chloride (1.0 M). The passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer enriched in Fe oxides and hydroxides, and an inner layer, rich in Cr species. The film composition varies with pH values and chloride contents. As the pH drops, more Cr oxides are enriched in the film while Fe oxides gradually decompose. Increasing chloride promotes Cr oxides and Fe oxides to transform into their hydroxides with little protection, and this is more significant at lower pH (10.5 and 9.0). These changes annotate passivation characteristics of the corrosion-resistant steel in the solutions of different electrolyte.

  14. The effect of application of cold natural smoke on the ripening of Cheddar cheese.

    PubMed

    Shakeel-Ur-Rehman; Farkye, N Y; Drake, M A

    2003-06-01

    The present study was undertaken to study the effects of application of natural wood smoke on ripening of Cheddar cheese, and to determine the effects of smoking before or after ripening on cheese quality. A 20-kg block of Cheddar cheese obtained immediately after pressing was divided into six approximately 3-kg blocks and ripened at 8 degrees C for up to 270 d. One 3-kg block was taken after 1 d, 1, 3, 6, or 9 mo and smoked for 20 min, then returned to the ripening room for further ripening. Cheeses were sampled at intervals for lactobacilli counts, moisture, pH, and proteolysis. Sensory analysis was conducted on 6 and 9-mo-old cheeses by a trained sensory panel (n = 7). Results show that application of natural wood smoke did not significantly affect cheese pH or primary proteolysis during ripening. However, secondary proteolysis as assessed by the concentrations of free amino acids was generally higher in smoked cheeses than in control cheeses after 6 mo of ripening. Cheese smoked after 6 mo of ripening had better smoked flavor than that smoked after 9 mo of ripening. Cheese smoked after 3 mo of age and further ripened for 6 mo had the highest smoked flavor intensity. It is concluded that it is best to smoke cheese after ripening for at least 3 mo.

  15. Enzymatic decolourisation of Methyl Orange and Bismarck Brown using crude peroxidase from Armoracia rusticana

    NASA Astrophysics Data System (ADS)

    Ambatkar, Mugdha; Mukundan, Usha

    2015-12-01

    The decolourisation of Methyl Orange (MO) and Bismarck Brown (BB) by crude peroxidase from Armoracia rusticana (Horseradish) was studied by varying different reaction parameters. The pH of the reaction mixture, initial dye concentration, amount of enzyme and hydrogen peroxide concentration were optimised for ambient temperatures (30 ± 2 °C). The optimum pH for decolourisation was 4.0 (72.95 %) and 3.0 (79.24 %) for MO and BB, respectively. Also it was found that the Chemical Oxygen Demand of the enzyme-treated sample was significantly lower than that of the untreated controls for both dyes. The addition of a complex iron salt like Ferric EDTA was found to enhance the decolourisation of both dyes at pH 6.0, showing an increase of 8.69 % and 14.17 % in the decolourisation of MO and of BB, respectively. The present study explores the potential of crude peroxidase from horseradish to decolourise representative monoazo and diazo dyes, MO and BB, respectively. An attempt has been made to utilise a crude enzyme with appreciable activity obtained after minimal processing for the decolourisation of the aforesaid dyes. The findings of this study would find application in the enzymatic treatment of wastewater containing azo dyes.

  16. Poly[bis­{3,3′-[(biphenyl-4,4′-di­yl)dimethyl­ene]diimidazol-1-ium} γ-octa­molybdate(VI)

    PubMed Central

    Liu, Hongsheng; Su, Lianjiang; Wang, Limin; Li, Weihong

    2010-01-01

    In the title compound, {(C20H20N4)2[Mo8O26]}n, the asymmetric unit contains half of an [Mo8O26]4− anion and one 3,3′-[(biphenyl-4,4′-di­yl)dimethyl­ene]diimidazol-1-ium dication. In the anion, four distorted [MoO6] octa­hedra are connected via edge-sharing, forming an [Mo4O13]2− building block, composed of Mo—O(t), Mo—O(μ2), Mo—O(μ3) and Mo—O(μ4) units, with Mo—O distances ranging from 1.6858 (15) to 2.4785 (13) Å. The γ-type [Mo8O26]4− anion is completed by crystallographic inversion symmetry and is linked into an infinite chain along [100] by corner-sharing. The anionic chains and the cations are joined by N—H⋯O hydrogen bonds, generating layers extending parallel to (001). PMID:21580534

  17. Structural and Computational Studies of Cp(CO)2(PCy3)MoFBF3, a Complex with a Bound BF4- Ligand

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

    Cheng, Tan-Yun; Szalda, David J.; Franz, James A.

    2010-02-15

    Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BF4 gives Cp(CO)2(PCy3)MoFBF3, and the crystal structure of this complex was determined. In the weakly bound FBF3 ligand, the B-F(bridging) bond length is 1.475(8) Å, which is 0.15 Å longer than the average length of the three B-F(terminal) bonds. The PCy3 and FBF3 ligands are cis to each other in the four-legged piano stool structure. Electronic structure (DFT) calculations predict the trans isomer of Cp(CO)2(PCy3)MoFBF3 to be 9.5 kcal/mol (in ΔGog,298)) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BAr'4 [Ar' = 3,5-bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp(CO)2(PCy3)Mo(ClCH2Cl)]+[BAr'4]more » , in which CH2Cl2 is coordinated to the metal. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

  18. Photo Degradation of Methyl Orange by Persulfate Activated with Zero Valent Iron

    NASA Astrophysics Data System (ADS)

    Munkoeva, V. A.; Sizykh, M. R.; Batoeva, A. A.

    2017-11-01

    The oxidative degradation of Methyl Orange (MO) subjected to direct photolysis (Solar) and various oxidative systems was studied. The comparative experiments have shown that MO conversion and mineralization increases in the following order: Solar ∼ Solar/Fe0 ∼ Solar/S2O82- < S2O82-/Fe0 < Solar/S2O82-/Fe0. The influence of the main factors (duration of exposure, the ratio of initial concentrations of MO:S2O82-:Fe0, pH and temperature of the reaction medium) on the degree of MO conversion and mineralization was studied. The optimal pH and temperature of the reaction medium were 5.8 and 25°C, respectively. The rate of MO decomposition and mineralization increased proportionally to the initial concentration of the oxidant at the molar ratios [S2O82-] :[MO] ≤ 12. Judging by the nature of the kinetic curves, a further increase of this ratio is impractical. However, an increase in the oxidant concentration had a positive effect on the degrees of conversion and mineralization of total organic carbon (TOC). Thus, at the ratios of 12:1 and 48:1, the conversion efficiency of TOC was 23 and 60 %, respectively. The optimal concentration of Fe0 was 100 mg/l.

  19. Fractionation analysis of oxyanion-forming metals and metalloids in leachates of cement-based materials using ion exchange solid phase extraction.

    PubMed

    Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Lund, Walter

    2009-05-15

    A simple and versatile solid phase extraction (SPE) method has been developed to determine the anionic species of As, Cr, Mo, Sb, Se and V in leachates of cement mortar and concrete materials in the pH range 3-13. The anionic fractions of these elements were extracted using a strong anion exchanger (SAX) and their concentrations were determined as the difference in element concentration between the sample and the SAX effluent. Inductively coupled plasma mass spectrometry (ICP-MS) was used off-line to analyse solutions before and after passing through the SAX. The extraction method has been developed by optimizing sorbent type, sorbent conditioning and sample percolation rate. Breakthrough volumes and effect of matrix constituents were also studied. It was found that a polymer-based SAX conditioned with a buffer close to the sample pH or in some cases deionised water gave the best retention of the analytes. Optimal conditions were also determined for the quantitative elution of analytes retained on the SAX. Extraction of the cement mortar and concrete leachates showed that most of the elements had similar distribution of anions in both leachate types, and that the distribution was strongly pH dependent. Cr, Mo and V exist in anionic forms in strongly basic leachates (pH>12), and significant fractions of anionic Se were also detected in these solutions. Cr, Mo, Se and V were not determined as anions by the present method in the leachates of pH<12. Anionic As and Sb were found in small fractions in most of the leachates.

  20. Microstructural Evolution and Mechanical Properties of Simulated Heat-Affected Zones in Cast Precipitation-Hardened Stainless Steels 17-4 and 13-8+Mo

    NASA Astrophysics Data System (ADS)

    Hamlin, Robert J.; DuPont, John N.

    2017-01-01

    Cast precipitation-hardened (PH) stainless steels 17-4 and 13-8+Mo are used in applications that require a combination of high strength and moderate corrosion resistance. Many such applications require fabrication and/or casting repair by fusion welding. The purpose of this work is to develop an understanding of microstructural evolution and resultant mechanical properties of these materials when subjected to weld thermal cycles. Samples of each material were subjected to heat-affected zone (HAZ) thermal cycles in the solution-treated and aged condition (S-A-W condition) and solution-treated condition with a postweld thermal cycle age (S-W-A condition). Dilatometry was used to establish the onset of various phase transformation temperatures. Light optical microscopy (LOM), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS) were used to characterize the microstructures, and comparisons were made to gas metal arc welds that were heat treated in the same conditions. Tensile testing was also performed. MatCalc thermodynamic and kinetic modeling software was used to predict the evolution of copper (Cu)-rich body center cubic precipitates in 17-4 and β-NiAl precipitates in 13-8+Mo. The yield strength was lower in the simulated HAZ samples of both materials prepared in the S-A-W condition when compared to their respective base metals. Samples prepared in the S-W-A condition had higher and more uniform yield strengths for both materials. Significant changes were observed in the matrix microstructure of various HAZ regions depending on the peak temperature, and these microstructural changes were interpreted with the aid of dilatometry results, LOM, SEM, and EDS. Despite these significant changes to the matrix microstructure, the changes in mechanical properties appear to be governed primarily by the precipitation behavior. The decrease in strength in the HAZ samples prepared in the S-A-W condition was attributed to the dissolution of precipitates, which was supported by the MatCalc modeling results. MatCalc modeling results for samples in the S-W-A condition predicted uniform size of precipitates across all regions of the HAZ, and these predictions were supported by the observed trends in mechanical properties. Cross-weld tensile tests performed on GMA welds showed the same trends in mechanical behavior as the simulated HAZ samples. Welding in the S-W-A condition resulted in over 90 pct retention in yield strength when compared to base metal strengths. These findings indicate that welding these PH stainless steels in the solution-treated condition and using a postweld age will provide better and more uniform mechanical properties in the HAZ that are more consistent with the base metal properties.

  1. Effect of electrical stimulation of the lower esophageal sphincter in gastroesophageal reflux disease patients refractory to proton pump inhibitors

    PubMed Central

    Soffer, Edy; Rodríguez, Leonardo; Rodriguez, Patricia; Gómez, Beatriz; Neto, Manoel G; Crowell, Michael D

    2016-01-01

    AIM: To evaluate the efficacy of lower esophageal sphincter (LES)-electrical stimulation therapy (EST) in a subgroup of patients that reported only partial response to proton pump inhibitors (PPIs) therapy, compared to a group of patient with complete response. METHODS: Bipolar stitch electrodes were laparoscopically placed in the LES and connected to an implantable pulse generator (EndoStim BV, the Hague, the Netherlands), placed subcutaneously in the anterior abdominal wall. Stimulation at 20 Hz, 215 μsec, 3-8 mAmp in 30 min sessions was delivered starting on day 1 post-implant. Patients were evaluated using gastroesophageal reflux disease (GERD)-HRQL, symptom diaries; esophageal pH and esophageal manometry before and up to 24 mo after therapy and results were compared between partial and complete responders. RESULTS: Twenty-three patients with GERD on LES-EST were enrolled and received continuous per-protocol stimulation through 12 mo and 21 patients completed 24 mo of therapy. Of the 23 patients, 16 (8 male, mean age 52.1 ± 12 years) had incomplete response to PPIs prior to LES-EST, while 7 patients (5 male, mean age 52.7 ± 4.7) had complete response to PPIs. In the sub-group with incomplete response to PPIs, median (IQR) composite GERD-HRQL score improved significantly from 9.5 (9.0-10.0) at baseline on-PPI and 24.0 (20.8-26.3) at baseline off-PPI to 2.5 (0.0-4.0) at 12-mo and 0.0 (0.0-2.5) at 24-mo follow-up (P < 0.05 compared to on-and off-PPI at baseline). Median (IQR) % 24-h esophageal pH < 4.0 at baseline in this sub-group improved significantly from 9.8% (7.8-11.5) at baseline to 3.0% (1.9-6.3) at 12 mo (P < 0.001) and 4.6% (2.0-5.8) at 24 mo follow-up (P < 0.01). At their 24-mo follow-up, 9/11 patients in this sub-group were completely free of PPI use. These results were comparable to the sub-group that reported complete response to PPI therapy at baseline. No unanticipated implantation or stimulation-related adverse events, or any untoward sensation due to stimulation were reported in either group and LES-EST was safely tolerated by both groups. CONCLUSION: LES-EST is safe and effective in controlling symptoms and esophageal acid exposure in GERD patients with incomplete response to PPIs. These results were comparable to those observed PPI responders. PMID:26855821

  2. Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

    NASA Astrophysics Data System (ADS)

    Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

    2018-06-01

    As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during chemical weathering in terrestrial environments where the role of secondary processes such as adsorption is significant.

  3. Government stewardship of the for-profit private health sector in Afghanistan

    PubMed Central

    Sayedi, Omarzaman; Irani, Laili; Archer, Lauren C.; Sears, Kathleen; Sharma, Suneeta

    2017-01-01

    Abstract Background: Since 2003, Afghanistan's largely unregulated for-profit private health sector has grown at a rapid pace. In 2008, the Ministry of Public Health (MoPH) launched a long-term stewardship initiative to oversee and regulate private providers and align the sector with national health goals. Aim: We examine the progress the MoPH has made towards more effective stewardship, consider the challenges and assess the early impacts on for-profit performance. Methods: We reviewed publicly available documents, publications and the grey literature to analyse the development, adoption and implementation of strategies, policies and regulations. We carried out a series of key informant/participant interviews, organizational capacity assessments and analyses of hospital standards checklists. Using a literature review of health systems strengthening, we proposed an Afghan-specific definition of six key stewardship functions to assess progress towards MoPH stewardship objectives. Results: The MoPH and its partners have achieved positive results in strengthening its private sector stewardship functions especially in generating actionable intelligence and establishing strategic policy directions, administrative structures and a legal and regulatory framework. Progress has also been made on improving accountability and transparency, building partnerships and applying minimum required standards to private hospitals. Procedural and operational issues still need resolution and the MoPH is establishing mechanisms for resolving them. Conclusions: The MoPH stewardship initiative is notable for its achievements to date under challenging circumstances. Its success is due to the focus on developing a solid policy framework and building institutions and systems aimed at ensuring higher quality private services, and a rational long-term and sustainable role for the private sector. Although the MoPH stewardship initiative is still at an early stage, the evidence suggests that enhanced stewardship functions in the MoPH are leading to a more efficient and effective for-profit private sector. These successful early efforts offer high-leverage potential to rapidly scale up going forward. PMID:27683341

  4. Government stewardship of the for-profit private health sector in Afghanistan.

    PubMed

    Cross, Harry E; Sayedi, Omarzaman; Irani, Laili; Archer, Lauren C; Sears, Kathleen; Sharma, Suneeta

    2017-04-01

    Since 2003, Afghanistan's largely unregulated for-profit private health sector has grown at a rapid pace. In 2008, the Ministry of Public Health (MoPH) launched a long-term stewardship initiative to oversee and regulate private providers and align the sector with national health goals. We examine the progress the MoPH has made towards more effective stewardship, consider the challenges and assess the early impacts on for-profit performance. We reviewed publicly available documents, publications and the grey literature to analyse the development, adoption and implementation of strategies, policies and regulations. We carried out a series of key informant/participant interviews, organizational capacity assessments and analyses of hospital standards checklists. Using a literature review of health systems strengthening, we proposed an Afghan-specific definition of six key stewardship functions to assess progress towards MoPH stewardship objectives. The MoPH and its partners have achieved positive results in strengthening its private sector stewardship functions especially in generating actionable intelligence and establishing strategic policy directions, administrative structures and a legal and regulatory framework. Progress has also been made on improving accountability and transparency, building partnerships and applying minimum required standards to private hospitals. Procedural and operational issues still need resolution and the MoPH is establishing mechanisms for resolving them. The MoPH stewardship initiative is notable for its achievements to date under challenging circumstances. Its success is due to the focus on developing a solid policy framework and building institutions and systems aimed at ensuring higher quality private services, and a rational long-term and sustainable role for the private sector. Although the MoPH stewardship initiative is still at an early stage, the evidence suggests that enhanced stewardship functions in the MoPH are leading to a more efficient and effective for-profit private sector. These successful early efforts offer high-leverage potential to rapidly scale up going forward. © VC The Author 2016. Published by Oxford University Press in association with The London School of Hygiene and Tropical Medicine.

  5. Leaching and geochemical behavior of fired bricks containing coal wastes.

    PubMed

    Taha, Yassine; Benzaazoua, Mostafa; Edahbi, Mohamed; Mansori, Mohammed; Hakkou, Rachid

    2018-03-01

    High amounts of mine wastes are continuously produced by the mining industry all over the world. Recycling possibility of some wastes in fired brick making has been investigated and showed promising results. However, little attention is given to the leaching behavior of mine wastes based fired bricks. The objective of this paper is to evaluate the geochemical behavior of fired bricks containing different types of coal wastes. The leachates were analyzed for their concentration of As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Zn and sulfates using different leaching tests; namely Tank Leaching tests (NEN 7375), Toxicity Characteristic Leaching Procedure (TCLP) and pH dependence test (EPA, 1313). The results showed that the release of constituents of potential interest was highly reduced after thermal treatment and were immobilized within the glassy matrix of the fired bricks. Moreover, it was also highlighted that the final pH of all fired samples changed and stabilized around 8-8.5 when the initial pH of leaching solution was in the range 2.5-11.5. The release of heavy metals and metalloids (As) tended to decrease with the increase of pH from acidic to alkaline solutions while Mo displayed a different trend. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Ambulatory Activity of Children with Cerebral Palsy: Which Characteristics Are Important?

    ERIC Educational Resources Information Center

    van Wely, Leontien; Becher, Jules G.; Balemans, Astrid C. J.; Dallmeijer, Annet J.

    2012-01-01

    Aim: To assess ambulatory activity of children with cerebral palsy (CP), aged 7 to 13 years, and identify associated characteristics. Method: Sixty-two children with spastic CP (39 males, 23 females; mean age 10y 1mo, SD 1y 8mo; age range 7-13y), classified as Gross Motor Function Classification System (GMFCS) levels I to III, participated.…

  7. Molybdenum isotope fractionation during adsorption to organic matter

    NASA Astrophysics Data System (ADS)

    King, E. K.; Perakis, S. S.; Pett-Ridge, J. C.

    2018-02-01

    Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2-170 h) and pH (2-7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (±0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

  8. Rates of arsenopyrite oxidation by oxygen and Fe(III) at pH 1.8-12.6 and 15-45 degrees C.

    PubMed

    Yu, Yunmei; Zhu, Yongxuan; Gao, Zhenmin; Gammons, Christopher H; Li, Denxian

    2007-09-15

    The oxidation rate of arsenopyrite by dissolved oxygen was measured using a mixed flow reactor at dissolved O2 concentrations of 0.007-0.77 mM, pH 1.8-12.6, and temperatures of 15-45 degrees C. As(III) was the dominant redox species (>75%) in the experimental system, and the As(III)/As(V) ratio of effluent waters did not change with pH. The results were used to derive the following rate law expression (valid between pH 1.8 and 6.4): r = 10((-2211 +/- 57)T) (mO2)(0.45 +/- 0.05), where r is the rate of release of dissolved As in mol m(-2) s(-1) and T is in Kelvin. Activation energies (Ea) for oxidation of arsenopyrite by 02 at pH 1.8 and 5.9 are 43 and 57 kJ/mol, respectively, and they compare to an Ea value of 16 kJ/mol for oxidation by Fe(III) at pH 1.8. Apparent As release rates passed through a minimum in the pH range 7-8, which may have been due to oxidation of Fe2+ to hydrous ferric oxide (HFO) with attenuation of dissolved As onto the freshly precipitated HFO.

  9. Porous p-NiO/n-Nb2O5 nanocomposites prepared by an EISA route with enhanced photocatalytic activity in simultaneous Cr(VI) reduction and methyl orange decolorization under visible light irradiation.

    PubMed

    Hashemzadeh, Fatemeh; Gaffarinejad, Ali; Rahimi, Rahmatollah

    2015-04-09

    Porous NiO/Nb2O5 nanocomposites with Ni/Nb molar ratio of 0.4, 0.8 and 1.2 have been obtained via the EISA route using P123 copolymer as organic template, and are assigned as NiNb0.4, NiNb0.8 and NiNb1.2, respectively. For comparison, pure Nb2O5 sample assigned as NiNb0.0 was also synthesized by the same method. Structural and textural features of the as prepared samples were investigated by XRD, FTIR, FE-SEM, EDX, UV-vis DRS and BET techniques. The results indicated that the porous p-NiO/n-Nb2O5 junction nanocomposites were formed and coupling of NiO with Nb2O5 resulted a remarkable red shift in the optical response of the nanocomposite samples. The photocatalytic properties of the nanocomposite samples, and also synthesized pure Nb2O5 (NiNb0.0) and commercial Nb2O5 as reference catalysts were evaluated for the first time by simultaneous Cr(VI) reduction and MO decolorization in aqueous suspension under visible light irradiation at pH 2. NiNb0.4 was found to be the most active photocatalyst, which might be attributed to the extended absorption in the visible light region and the effective photogenerated electron-hole separation by the photosynergistic effects of the p-NiO/n-Nb2O5 composite powder. The photocatalytic efficiency of the most active photocatalyst, NiNb0.4, was found to be rather low for either single Cr(VI) solution or single MO solution. However, the photocatalytic reduction of Cr(VI) and photocatalytic decolorization of MO proceed more rapidly for the coexistence system of Cr(VI) and MO than for the single process, showing synergetic effect between the reduction and decolorization reactions. The effects of initial concentration of Cr(VI), MO and the initial pH value on the rate of simultaneous photoreactions over NiNb0.4 sample, were also investigated. The Cr(VI) and MO removal rates were further enhanced by increasing MO and Cr (VI) concentration to an optimal value, respectively, and/or decreasing solution pH. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Survival After Relapse of Medulloblastoma.

    PubMed

    Koschmann, Carl; Bloom, Karina; Upadhyaya, Santhosh; Geyer, J Russell; Leary, Sarah E S

    2016-05-01

    Survival after recurrence of medulloblastoma has not been reported in an unselected cohort of patients in the contemporary era. We reviewed 55 patients diagnosed with medulloblastoma between 2000 and 2010, and treated at Seattle Children's Hospital to evaluate patterns of relapse treatment and survival. Fourteen of 47 patients (30%) over the age of 3 experienced recurrent or progressive medulloblastoma after standard therapy. The median time from diagnosis to recurrence was 18.0 months (range, 3.6 to 62.6 mo), and site of recurrence was metastatic in 86%. The median survival after relapse was 10.3 months (range, 1.3 to 80.5 mo); 3-year survival after relapse was 18%. There were trend associations between longer survival and having received additional chemotherapy (median survival 12.8 vs. 1.3 mo, P=0.16) and radiation therapy (15.4 vs. 5.9 mo, P=0.20). Isolated local relapse was significantly associated with shorter survival (1.3 vs. 12.8 mo, P=0.009). Recurrence of medulloblastoma is more likely to be metastatic than reported in previous eras. Within the limits of our small sample, our data suggest a potential survival benefit from retreatment with cytotoxic chemotherapy and radiation even in heavily pretreated patients. This report serves as a baseline against which to evaluate novel therapy combinations.

  11. Photochemical studies of alkylammonium molybdates. Part 12. O→Mo charge-transfer triplet-states-initiated self-assembly to {Mo154} ring- and tube-molybdenum-blues

    NASA Astrophysics Data System (ADS)

    Yamase, T.; Prokop, P.; Arai, Y.

    2003-08-01

    The chemically induced dynamic electron-spin-polarization technique is employed in order to investigate the primary steps of the photoredox reaction between polyoxomolybdates and alkylammonium cations as both proton and electron-donors in solutions. An observation of emissive electron-spin-polarization signals of alkylamino radical cations for the photoredox reaction between polyoxomolybdates and alkylammonium cations in solutions reveals that the O→Mo ligand-to-metal charge-transfer triplet states are involved in the transfers of both proton and electron from alkylammonium cation to polyoxomolybdate anions. Prolonged photolysis of aqueous solutions containing [Mo36O112(H2O)16]8-, [iPrNH3]+, and LaCl3 at pH 1.0 leads to formation of two kinds of {Mo154} molybdenum-blues, [Mo28VMo126VIO462H28(H2O)70]·156.5H2O (1) and [iPrNH3]8 [Mo28VMo126VIO458H12(H2O)66]·127H2O (2), which were X-ray crystallographically characterized. The former exhibits the intact car-tire-shaped {Mo154} ring structure (with thickness of about 1.1 nm and with outer- and inner-rings of approximately 3.5- and 2.3-nm diameters, respectively) derived formally from the dehydrated cyclic heptamerization of four-electron reduced building blocks of {Mo22} (≡[Mo4VMo18VIO70H12(H2O)10]) with overall symmetry of D7d. The anion for the latter, [Mo28VMo126VIO458H12(H2O)66]8- (2a), exhibits a nanotube structure of {Mo154} rings, each inner ring of which contains a bis(μ-oxo)-linkaged [MoO2(μ-O)(μ-H2O)MoO2]2+ unit replacing one of seven [Mo(H2O)O2(μ-O)Mo(H2O)O2]2+linker units. The neighboring {Mo154} rings are connected by six Mo-O-Mo bridge between inner-rings consisting of 7 head- and 14 linkers-MoO6 octahedra for each.

  12. Isoelectric focusing-affinity immunoblot analysis of mouse monoclonal antibodies to the four human IgG subclasses

    NASA Technical Reports Server (NTRS)

    Hamilton, Robert G.; Roebber, Marianne; Rodkey, L. Scott; Reimer, Charles B.

    1987-01-01

    Isoelectric focusing (IEF)/affinity immunoblotting and enzyme-linked immunosorbent assay (ELISA) were used for parallel analysis of murine monoclonal antihuman IgG-subclass antisera (MoAbs). Coomassie Blue-stained protein bands in the pH region 5.5-8.0 were shown to be murine IgG by direct blotting onto nitrocellulose followed by detection with conjugated antimouse IgG. Use of IgG myeloma antigen-coated nitrocellulose in the IEF-affinity immunoblot allowed detection of the charge microheterogeneity of MoAbs. The MoAb group contained one to five major dense bands flanked by up to four minor fainter bands, all with pIs ranging from 6.1 to 7.8. Semiquantitative estimates of binding specificity in the IEF-affinity blot compared well with cross-reactivity data obtained from a quantitative ELISA.

  13. Selective synthesis and characterization of single-crystal silver molybdate/tungstate nanowires by a hydrothermal process.

    PubMed

    Cui, Xianjin; Yu, Shu-Hong; Li, Lingling; Biao, Liu; Li, Huabin; Mo, Maosong; Liu, Xian-Ming

    2004-01-05

    Selective synthesis of uniform single crystalline silver molybdate/tungstate nanorods/nanowires in large scale can be easily realized by a facile hydrothermal recrystallization technique. The synthesis is strongly dependent on the pH conditions, temperature, and reaction time. The phase transformation was examined in details. Pure Ag(2)MoO(4) and Ag(6)Mo(10)O(33) can be easily obtained under neutral condition and pH 2, respectively, whereas other mixed phases of Mo(17)O(47), Ag(2)Mo(2)O(7,) Ag(6)Mo(10)O(33) were observed under different pH conditions. Ag(6)Mo(10)O(33) nanowires with uniform diameter 50-60 nm and length up to several hundred micrometers were synthesized in large scale for the first time at 140 degrees C. The melting point of Ag(6)Mo(10)O(33) nanowires were found to be about 238 degrees C. Similarly, Ag(2)WO(4), and Ag(2)W(2)O(7) nanorods/nanowires can be selectively synthesized by controlling pH value. The results demonstrated that this route could be a potential mild way to selectively synthesize various molybdate nanowires with various phases in large scale.

  14. Microcapsules Containing pH-Responsive, Fluorescent Polymer-Integrated MoS2: An Effective Platform for in Situ pH Sensing and Photothermal Heating.

    PubMed

    Park, Chan Ho; Lee, Sangmin; Pornnoppadol, Ghasidit; Nam, Yoon Sung; Kim, Shin-Hyun; Kim, Bumjoon J

    2018-03-14

    We report the design of a novel microcapsule platform for in situ pH sensing and photothermal heating, which involves the encapsulation of pH-responsive polymer-coated molybdenum disulfide (MoS 2 ) nanosheets (NSs) in microcapsules with an aqueous core and a semipermeable polymeric shell. The MoS 2 NSs were functionalized with pH-responsive polymers having fluorescent groups at the distal end to provide pH-sensitive Förster resonance energy transfer (FRET) effect. The pH-responsive polymers were carefully designed to produce a dramatic change in the polymer conformation, which translated to a change in the FRET efficiency near pH 7.0 in response to subtle pH changes, enabling the detection of cancer cells. The pH-sensitive MoS 2 NSs were microfluidically encapsulated within semipermeable membranes to yield microcapsules with a uniform size and composition. The microcapsules retained the MoS 2 NSs without leakage while allowing the diffusion of small ions and water through the membrane. At the same time, the membranes excluded adhesive proteins and lipids in the surrounding media, protecting the encapsulated MoS 2 NSs from deactivation and enabling in situ pH monitoring. Moreover, the encapsulated MoS 2 NSs showed high-performance photothermal heating, rendering the dual-functional microcapsules highly suitable for cancer diagnosis and treatment.

  15. Spectrophotometric determination of fluoxetine hydrochloride in bulk and in pharmaceutical formulations.

    PubMed

    Prabhakar, A H; Patel, V B; Giridhar, R

    1999-07-01

    Two new rapid, sensitive and economical spectrophotometric methods are described for the determination of fluoxetine hydrochloride in bulk and in pharmaceutical formulations. Both methods are based on the formation of a yellow ion-pair complex due to the action of methyl orange (MO) and thymol blue (TM) on fluoxetine in acidic (pH 4.0) and basic (pH 8.0) medium, respectively. Under optimised conditions they show an absorption maxima at 433 nm (MO) and 410 nm (TB), with molar absorptivities of 2.12 x 10(-4) and 4.207 x 10(-3) l mol(-1) cm(-1) and Sandell's Sensitivities of 1.64 x 10(-2) and 0.082 microg cm(-2) per 0.001 absorbance unit for MO and TB, respectively. The colour is stable for 5 min after extraction. In both cases Beer's Law is obeyed at 1-20 microg mol(-1) with MO and 4-24 microg mol(-1) with TB. The proposal method was successfully extended to pharmaceutical preparations capsules. The results obtained by both the agreement and E.P. (3rd edition) were in good agreement and statistical comparison by Student's t-test and variance ratio F-test showed no significant difference in the three methods.

  16. Stabilization of Reduced Molybdenum-Iron-Sulfur Single and Double Cubane Clusters by Cyanide Ligation

    PubMed Central

    Pesavento, Russell P.; Berlinguette, Curtis P.; Holm, R. H.

    2008-01-01

    Recent work has shown that cyanide ligation increases the redox potentials of Fe4S4 clusters, enabling the isolation of [Fe4S4(CN)4]4−, the first synthetic Fe4S4 cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C., Proc. Natl. Acad. Sci. USA 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe3S4 clusters. Reaction of single cubane [(Tp)MoFe3S4(PEt3)3]1+ and edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] with cyanide in acetonitrile affords [(Tp)MoFe3S4(CN)3]2− (2) and [(Tp)2Mo2Fe6S8(CN)4]4− (5), respectively. Reduction of 2 with KC14H10 yields [(Tp)MoFe3S4(CN)3]3− (3). Clusters were isolated in ca. 70–90% yields as Et4N+ or Bu4N+ salts; Clusters 3 and 5 contain all-ferrous cores; 3 is the first [MoFe3S4]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe4S4 and MFe3S4 clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe3S4L3]2−,3 and [(Tp)2Mo2Fe6S8L4]4−,3− clusters with L = CN, PhS, halide, and PEt3 are compared. Clusters with π-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials while π-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less negative) redox potentials. When potentials of 3/2 and [(Tp)MoFe3S4(SPh)3]3−/2− are compared, cyanide stabilizes 3 by 270 mV vs. the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe4S4(CN)4]4− vs. [Fe4S4(SPh)4]4− where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1−)). PMID:17279830

  17. Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation.

    PubMed

    Pesavento, Russell P; Berlinguette, Curtis P; Holm, R H

    2007-01-22

    Recent work has shown that cyanide ligation increases the redox potentials of Fe(4)S(4) clusters, enabling the isolation of [Fe(4)S(4)(CN)4]4-, the first synthetic Fe(4)S(4) cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe(3)S(4) clusters. Reaction of single-cubane [(Tp)MoFe(3)S(4)(PEt(3))3]1+ and edge-bridged double-cubane [(Tp)2Mo(2)Fe(6)S(8)(PEt(3))4] with cyanide in acetonitrile affords [(Tp)MoFe(3)S(4)(CN)3]2- (2) and [(Tp)2Mo(2)Fe(6)S(8)(CN)4]4- (5), respectively. Reduction of 2 with KC(14)H(10) yields [(Tp)MoFe(3)S(4)(CN)3]3- (3). Clusters were isolated in approximately 70-90% yields as Et(4)N+ or Bu(4)N+ salts; clusters 3 and 5 contain all-ferrous cores, and 3 is the first [MoFe(3)S(4)]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe(4)S(4) and MFe(3)S(4) clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe(3)S(4)L3]2-,3- and [(Tp)2Mo(2)Fe(6)S(8)L(4)]4-,3- clusters with L = CN-, PhS-, halide, and PEt3 are compared. Clusters with pi-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials, while pi-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less-negative) redox potentials. When the potentials of 3/2 and [(Tp)MoFe(3)S(4)(SPh)3]3-/2- are compared, cyanide stabilizes 3 by 270 mV versus the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe(4)S(4)(CN)4]4- versus [Fe(4)S(4)(SPh)4]4- where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1-)).

  18. Molybdenum isotope fractionation during adsorption to organic matter

    USGS Publications Warehouse

    King, Elizabeth K.; Perakis, Steven; Pett-Ridge, Julie C.

    2018-01-01

    Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (± 0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

  19. Deposition and separation of W and Mo from aqueous solutions with simultaneous hydrogen production in stacked bioelectrochemical systems (BESs): Impact of heavy metals W(VI)/Mo(VI) molar ratio, initial pH and electrode material.

    PubMed

    Huang, Liping; Li, Ming; Pan, Yuzhen; Quan, Xie; Yang, Jinhui; Puma, Gianluca Li

    2018-04-16

    The deposition and separation of W and Mo from aqueous solutions with simultaneous hydrogen production was investigated in stacked bioelectrochemical systems (BESs) composed of microbial electrolysis cell (1#) serially connected with parallel connected microbial fuel cell (2#). The impact of W/Mo molar ratio (in the range 0.01 mM : 1 mM and vice-versa), initial pH (1.5 to 4.0) and cathode material (stainless steel mesh (SSM), carbon rod (CR) and titanium sheet (TS)) on the BES performance was systematically investigated. The concentration of Mo(VI) was more influential than W(VI) in determining the rate of deposition of both metals and the rate of hydrogen production. Complete metal recovery was achieved at equimolar W/Mo ratio of 0.05 mM : 0.05 mM. The rates of metal deposition and hydrogen production increased at acidic pH, with the fastest rates at pH 1.5. The morphology of the metal deposits and the valence of the Mo were correlated with W/Mo ratio and pH. CR cathodes (2#) coupled with SSM cathodes (1#) achieved a significant rate of hydrogen production (0.82 ± 0.04 m 3 /m 3 /d) with W and Mo deposition (0.049 ± 0.003 mmol/L/h and 0.140 ± 0.004 mmol/L/h (1#); 0.025 ± 0.001 mmol/L/h and 0.090 ± 0.006 mmol/L/h (2#)). Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon.

    PubMed

    Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C

    2010-12-20

    The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).

  1. Recycling 100Mo for direct production of 99mTc on medical cyclotrons

    NASA Astrophysics Data System (ADS)

    Kumlin, Joel O.; Zeisler, Stefan K.; Hanemaayer, Victoire; Schaffer, Paul

    2018-05-01

    A scalable recycling technique for the recovery of 100Mo from previously irradiated and chemically processed targets is described. A combined process for both Cu and Ta supported targets and the respective `waste' solutions has been developed. This process involves selectively dissolving Cu target backings from undissolved portions of 100Mo pellets; precipitating Cu(OH)2 at pH 9; electrochemical removal of Cu traces; precipitating (NH4)2MoO4 at pH 2.5-3; thermally decomposing (NH4)2MoO4; and H2 reduction of MoO3 to Mo metal. Radionuclidic decontamination by a factor of 100 is observed, while overall 100Mo recovery from initial target plating to recycled Mo metal of 96% is achieved.

  2. Exploring the Effect of Surface Functionality on the Self-Assembly of Polyoxopalladate Macroions

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

    Haso, Fadi; Yang, Peng; Gao, Yunyi

    2015-05-12

    The solution behavior of the two polyoxo-13-palladates(II) ([Pd(II) 13 As(V) 8 O34 (OH)6 ](8-) and [Pd(II) 13 (As(V) Ph)8 O32 ](6-) ) was studied in detail. We discovered that the countercation-mediated attraction is the driving force for their self-assembly into larger architectures. However, the presence of phenyl groups in the periphery of [Pd(II) 13 (As(V) Ph)8 O32 ](6-) results in an enhanced attraction among these polyanions through hydrophobic interactions, which leads to completely different trends of assembly size for these two very similar clusters when decreasing solvent polarity. An increase of assembly size with increasing solvent polarity was observed formore » [Pd(II) 13 (As(V) Ph)8 O32 ](6-) , whereas for [Pd(II) 13 As (V) 8 O34 (OH)6 ](8-) it was the opposite, due to the absence of hydrophobic interactions.« less

  3. Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution.

    PubMed

    Korenev, Vladimir S; Floquet, Sébastien; Marrot, Jérôme; Haouas, Mohamed; Mbomekallé, Israël-Martyr; Taulelle, Francis; Sokolov, Maxim N; Fedin, Vladimir P; Cadot, Emmanuel

    2012-02-20

    Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

  4. Syntheses, structures and properties of two new organic-inorganic hybrid materials based on ε-Zn Keggin units {ε-PMo(V)8Mo(VI)4O(40-x)(OH)(x)Zn4}.

    PubMed

    Miao, Hao; Hu, Gonghao; Guo, Jiuyu; Wan, Hongxiang; Mei, Hua; Zhang, Yu; Xu, Yan

    2015-01-14

    Two novel organic-inorganic hybrids, Na[PMo(V)8Mo(VI)4O38(OH)2Zn4][pyim]2·1.5H2O [ε(pyim)2] (pyim = 2-(2-pyridyl)-imidazole) and [PMo(V)8Mo(VI)4O37(OH)3Zn4]2[pyim]6·4H2O [ε2(pyim)6], based on ε-Zn Keggin units {ε-PMo(V)8Mo(VI)4O(40-x)(OH)(x)Zn4}, have been successfully synthesized under hydrothermal conditions by controlling the pH values. Structural analysis indicates that the framework of ε(pyim)2 is a 1D chain constructed by monomeric ε-Zn units modified by pyim ligands, while ε2(pyim)6 is an isolated structural compound with dimeric ε-Zn units modified by pyim ligands. This is the first isolated structure of the ε-Keggin POMs system. The luminescent and electrochemical properties of ε(pyim)2 and ε2(pyim)6 were investigated. ε2(pyim)6 also shows high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester (MAP).

  5. Sphaerochaeta multiformis sp. nov., an anaerobic, psychrophilic bacterium isolated from subseafloor sediment, and emended description of the genus Sphaerochaeta.

    PubMed

    Miyazaki, Masayuki; Sakai, Sanae; Ritalahti, Kirsti M; Saito, Yayoi; Yamanaka, Yuko; Saito, Yumi; Tame, Akihiko; Uematsu, Katsuyuki; Löffler, Frank E; Takai, Ken; Imachi, Hiroyuki

    2014-12-01

    An anaerobic, psychrophilic bacterium, strain MO-SPC2(T), was isolated from a methanogenic microbial community in a continuous-flow bioreactor that was established from subseafloor sediments collected from off the Shimokita Peninsula of Japan in the north-western Pacific Ocean. Cells were pleomorphic: spherical, annular, curved rod, helical and coccoid cell morphologies were observed. Motility only occurred in helical cells. Strain MO-SPC2(T) grew at 0-17 °C (optimally at 9 °C), at pH 6.0-8.0 (optimally at pH 6.8-7.2) and in 20-40 g NaCl l(-1) (optimally at 20-30 NaCl l(-1)). The strain grew chemo-organotrophically with mono-, di- and polysaccharides. The major end products of glucose fermentation were acetate, ethanol, hydrogen and carbon dioxide. The abundant polar lipids of strain MO-SPC2(T) were phosphatidylglycolipids, phospholipids and glycolipids. The major cellular fatty acids were C14 : 0, C16 : 0 and C16 : 1ω9. Isoprenoid quinones were not detected. The G+C content of the DNA was 32.3 mol%. 16S rRNA gene-based phylogenetic analysis showed that strain MO-SPC2(T) was affiliated with the genus Sphaerochaeta within the phylum Spirochaetes, and its closest relatives were Sphaerochaeta pleomorpha Grapes(T) (88.4 % sequence identity), Sphaerochaeta globosa Buddy(T) (86.7 %) and Sphaerochaeta coccoides SPN1(T) (85.4 %). Based on phenotypic characteristics and phylogenetic traits, strain MO-SPC2(T) is considered to represent a novel species of the genus Sphaerochaeta, for which the name Sphaerochaeta multiformis sp. nov. is proposed. The type strain is MO-SPC2(T) ( = JCM 17281(T) = DSM 23952(T)). An emended description of the genus Sphaerochaeta is also proposed. © 2014 IUMS.

  6. Scandium complexes with the tetraphenylethylene and anthracene dianions.

    PubMed

    Ellis, John E; Minyaev, Mikhail E; Nifant'ev, Ilya E; Churakov, Andrei V

    2018-06-01

    The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η 6 -1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C 4 H 8 O) 2 (C 12 H 24 O 6 )][Sc(C 26 H 20 ) 2 ]·2C 4 H 8 O or [Na(18-crown-6)(THF) 2 ][Sc(η 6 -C 2 Ph 4 ) 2 ]·2(THF), (1b), (η 5 -1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η 6 -1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C 17 H 13 )(C 26 H 20 )(C 4 H 8 O)]·0.5C 7 H 8 or [(η 5 -1,3-Ph 2 C 5 H 3 )Sc(η 6 -C 2 Ph 4 )(THF)]·0.5(toluene), (5b), poly[[(μ 2 -η 3 :η 3 -anthracenediyl)bis(η 6 -anthracenediyl)bis(η 5 -1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K 2 Sc 2 (C 14 H 10 ) 3 (C 17 H 13 ) 2 (C 4 H 8 O) 4 ]·C 4 H 8 O} n or [K(THF) 2 ] 2 [(1,3-Ph 2 C 5 H 3 ) 2 Sc 2 (C 14 H 10 ) 3 ]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C 17 H 14 , (3a), have been established. The [Sc(η 6 -C 2 Ph 4 ) 2 ] - complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η 3 -allyl coordination mode. The complex homoleptic [Sc(η 6 -C 2 Ph 4 ) 2 ] - anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The 1D 1 H and 13 C{ 1 H}, and 2D COSY 1 H- 1 H and 13 C- 1 H NMR data are presented for M[Sc(Ph 4 C 2 ) 2 ]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d 8 media. Complex (5b) exhibits an unsymmetrical bis-η 3 -allyl coordination mode of the dianion, but this changes to a η 4 coordination mode for (1,3-Ph 2 C 5 H 3 )Sc(Ph 4 C 2 )(THF) 2 , (5a), in THF-d 8 solution. A 45 Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph 4 C 2 bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η 6 -coordination mode for two bent ligands and a μ 2 -η 3 :η 3 -bridging mode of a flat ligand. Each [(1,3-Ph 2 C 5 H 3 ) 2 Sc 2 (C 14 H 10 ) 3 ] 2- dianionic unit is connected to four neighbouring units via short contacts with [K(THF) 2 ] + cations, forming a two-dimensional coordination polymer framework parallel to (001).

  7. Comparison of a modified phenol/chloroform and commercial-kit methods for extracting DNA from horse fecal material.

    PubMed

    Janabi, Ali H D; Kerkhof, Lee J; McGuinness, Lora R; Biddle, Amy S; McKeever, Kenneth H

    2016-10-01

    There are many choices for methods of extracting bacterial DNA for Next Generation Sequencing (NGS) from fecal samples. Here, we compare our modifications of a phenol/chloroform extraction method plus an inhibitor removal solution (C3) (ph/Chl+C3) to the PowerFecal® DNA Isolation Kit (MoBio-K). DNA quality and quantity coupled to NGS results were used to assess differences in relative abundance, Shannon diversity index, unique species, and principle coordinate analysis (PCoA) between biological replicates. Six replicate samples, taken from a single ball of horse feces manually collected from the rectum, were subjected to each extraction method. The Ph/Chl+C3 method produced 100× higher DNA yields with less shearing than the MoBio-K method. To assess the methods, the two method samples were sent for sequencing of the bacterial V3-V4 region of 16S rRNA gene using the Illumina MiSeq platform. The relative abundance of Bacteroidetes was greater and there were more unique species assigned to this group in MoBio-K than in Ph/Chl+C3 (P<0.05). In contrast, Firmicutes had greater relative abundance and more unique species in Ph/Chl+C3 extracts than in MoBio-K (P<0.05). The other major bacterial phyla were equally abundant in samples using both extraction methods. Alpha diversity and Shannon Weaver indices showed greater evenness of bacterial distribution in Ph/Chl+C3 compared with MoBio-K (P<0.05), but there was no difference in the OTU richness. Principle coordinate analysis (PCoA) indicated a distinct separation between the two methods (P<0.05) and tighter clustering (less variability) in Ph/Chl+C3 than in MoBio-K. These results suggest that the Ph/Chl+C3 may be preferred for research to identify specific Firmicutes taxa such as Clostridium, and Bacillus. However; MoBio-K may be a better choice for projects focusing on Bacteroidetes abundance. The Ph/Chl+C3 method required less time, but has some safety concerns associated with exposure and disposal of phenol and chloroform. While the MoBio-K may be better choice for researchers with less access to safety equipment like a fume hood. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Effect of atorvastatin on progression of sensorineural hearing loss and tinnitus in the elderly: results of a prospective, randomized, double-blind clinical trial.

    PubMed

    Olzowy, Bernhard; Canis, Martin; Hempel, John-Martin; Mazurek, Birgit; Suckfüll, Markus

    2007-06-01

    To test whether the 3-hydroxy-3-methylglutaryl- coenzyme A reductase inhibitor atorvastatin can slow down the progression of presbycusis. Fifty patients 60- to 75-years-old with presbycusis and moderately elevated serum cholesterol. In a double-blind design, patients were randomly assigned to treatment with either atorvastatin (40 mg/d orally) or placebo. Pure-tone audiometry and tinnitus evaluation at enrolment and after 7 and 13 months. Development of hearing thresholds after 7 and 13 months showed no significant differences between the groups. Tinnitus score continuously improved in the atorvastatin group (34.8 at 7 and 27.6 at 13 mo), whereas it slightly deteriorated in the placebo group (24.8 at 7 and 26.8 at 13 mo). The effect on tinnitus was a tendency without statistic significance (p = 0.0833). Atorvastatin had no effect on the development of hearing thresholds, but resulted in a trend toward a relief of tinnitus.

  9. Corrosion fatigue of high strength fastener materials in seawater

    NASA Technical Reports Server (NTRS)

    Tipton, D. G.

    1983-01-01

    Environmental effects which significantly reduce the fatigue life of metals are discussed. Corrosion fatigue is a major concern in the engineering application of high strength fasteners in marine environments. The corrosion fatigue failure of an AISI 41L4O high strength steel blade to hub attachment bolt at the MOD-OA 200 kW wind turbine generator was investigated. The reduction of fatigue strength of AISI 41L4O in marine environments and to obtain similar corrosion fatigue data for candidate replacement materials was studied. The AISI 4140, PH 13-8Mo stainless steel, alloy 718 and alloy MP-35N were tested in axial fatigue at a frequency of 20 Hz in dry air and natural seawater. The fatigue data are fitted by regression equations to allow determination of fatigue strength for a given number of cycles to failure.

  10. Corrosion fatigue of high strength fastener materials in seawater

    NASA Astrophysics Data System (ADS)

    Tipton, D. G.

    1983-12-01

    Environmental effects which significantly reduce the fatigue life of metals are discussed. Corrosion fatigue is a major concern in the engineering application of high strength fasteners in marine environments. The corrosion fatigue failure of an AISI 41L4O high strength steel blade to hub attachment bolt at the MOD-OA 200 kW wind turbine generator was investigated. The reduction of fatigue strength of AISI 41L4O in marine environments and to obtain similar corrosion fatigue data for candidate replacement materials was studied. The AISI 4140, PH 13-8Mo stainless steel, alloy 718 and alloy MP-35N were tested in axial fatigue at a frequency of 20 Hz in dry air and natural seawater. The fatigue data are fitted by regression equations to allow determination of fatigue strength for a given number of cycles to failure.

  11. Self-Recognition Between Two Almost Identical Macroions During Their Assembly: The Effects of pH and Temperature.

    PubMed

    Haso, Fadi; Li, Dong; Garai, Somenath; Pigga, Joseph M; Liu, Tianbo

    2015-09-14

    Two Keplerate-type macroions, [Mo(VI) 72 Fe(III) 30 O252 - (CH3 COO)12 {Mo2 O7 (H2 O)}2 {H2 Mo2 O8 (H2 O)}(H2 O)91 ]⋅ca. 150 H2 O= {Mo72 Fe30 } and [{Na(H2 O)12 }⊂{Mo(VI) 72 Cr(III) 30 O252 (CH3 COO)19 - (H2 O)94 }]⋅ca. 120 H2 O={Mo72 Cr30 }, with identical size and shape but different charge density, can self-assemble into spherical "blackberry"-like structures in aqueous solution by means of electrostatic interactions. These two macroanions can self-recognize each other and self-assemble into two separate types of homogeneous blackberries in their mixed dilute aqueous solution, in which they carry -7 and -5 net charges, respectively. Either adjusting the solution pH or raising temperature is expected to make the self-recognition more difficult, by making the charge densities of the two clusters closer, or by decreasing the activation energy barrier for the blackberry formation, respectively. Amazingly, the self-recognition behavior remains, as confirmed by dynamic and static light scattering, TEM, and energy dispersive spectroscopy techniques. The results prove that the self-recognition behavior of the macroions due to the long-range electrostatic interaction is universal and can be achieved when only minimum differences exist between two types of macroanions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. High efficient removal of molybdenum from water by Fe2(SO4)3: Effects of pH and affecting factors in the presence of co-existing background constituents.

    PubMed

    Zhang, Xiang; Ma, Jun; Lu, Xixin; Huangfu, Xiaoliu; Zou, Jing

    2015-12-30

    Comparatively investigated the different effects of Fe2(SO4)3 coagulation-filtration and FeCl3 coagulation-filtration on the removal of Mo (VI). And the influence of calcium, sulfate, silicate, phosphate and humic acid (HA) were also studied. The following conclusions can be obtained: (1) compared with the case of FeCl3, Fe2(SO4)3 showed a higher Mo (VI) removal efficiency at pH 4.00-5.00, but an equal removal efficiency at pH 6.00-9.00. (2) The optimum Mo (VI) removal by Fe2(SO4)3 was achieved at pH 5.00-6.00; (3) The presence of calcium can reduce the removal of Mo (VI) over the entire pH range in the present study; (4) The effect of co-existing background anions (including HA) was dominated by three factors: Firstly the influence of co-existing background anions on the content of Fe intercepted from water (intercepted Fe). Secondly the competition of co-existing anions with Mo (VI) for adsorption sites. Thirdly the influence of co-existing background anions on the Zeta potential of the iron flocs. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Hydroxyproline Metabolism and Oxalate Synthesis in Primary Hyperoxaluria.

    PubMed

    Fargue, Sonia; Milliner, Dawn S; Knight, John; Olson, Julie B; Lowther, W Todd; Holmes, Ross P

    2018-06-01

    Background Endogenous oxalate synthesis contributes to calcium oxalate stone disease and is markedly increased in the inherited primary hyperoxaluria (PH) disorders. The incomplete knowledge regarding oxalate synthesis complicates discovery of new treatments. Hydroxyproline (Hyp) metabolism results in the formation of oxalate and glycolate. However, the relative contribution of Hyp metabolism to endogenous oxalate and glycolate synthesis is not known. Methods To define this contribution, we performed primed, continuous, intravenous infusions of the stable isotope [ 15 N, 13 C 5 ]-Hyp in nine healthy subjects and 19 individuals with PH and quantified the levels of urinary 13 C 2 -oxalate and 13 C 2 -glycolate formed using ion chromatography coupled to mass detection. Results The total urinary oxalate-to-creatinine ratio during the infusion was 73.1, 70.8, 47.0, and 10.6 mg oxalate/g creatinine in subjects with PH1, PH2, and PH3 and controls, respectively. Hyp metabolism accounted for 12.8, 32.9, and 14.8 mg oxalate/g creatinine in subjects with PH1, PH2, and PH3, respectively, compared with 1.6 mg oxalate/g creatinine in controls. The contribution of Hyp to urinary oxalate was 15% in controls and 18%, 47%, and 33% in subjects with PH1, PH2, and PH3, respectively. The contribution of Hyp to urinary glycolate was 57% in controls, 30% in subjects with PH1, and <13% in subjects with PH2 or PH3. Conclusions Hyp metabolism differs among PH types and is a major source of oxalate synthesis in individuals with PH2 and PH3. In patients with PH1, who have the highest urinary excretion of oxalate, the major sources of oxalate remain to be identified. Copyright © 2018 by the American Society of Nephrology.

  14. Mechanistic studies on the reactions of PhS(-) or [MoS(4)](2)(-) with [M(4)(SPh)(10)](2)(-) (M = Fe or Co).

    PubMed

    Cui, Zhen; Henderson, Richard A

    2002-08-12

    Kinetic studies, using stopped-flow spectrophotometry, on the reactions of [M(4)(SPh)(10)](2)(-) (M = Fe or Co) with PhS(-) to form [M(SPh)(4)](2)(-) are described, as are the reactions between [M(4)(SPh)(10)](2)(-) and [MoS(4)](2)(-) to form [S(2)MoS(2)Fe(SPh)(2)](2)(-) or [S(2)MoS(2)CoS(2)MoS(2)](2)(-). The kinetics of the reactions with PhS(-) are consistent with an initial associative substitution mechanism involving attack of PhS(-) at one of the tetrahedral M sites of [M(4)(SPh)(10)](2)(-) to form [M(4)(SPh)(11)](3)(-). Subsequent or concomitant cleavage of a micro-SPh ligand, at the same M, initiates a cascade of rapid reactions which result ultimately in the complete rupture of the cluster and formation of [M(SPh)(4)](2)(-). The kinetics of the reaction between [M(4)(SPh)(10)](2)(-) and [MoS(4)](2)(-) indicate an initial dissociative substitution mechanism at low concentrations of [MoS(4)](2)(-), in which rate-limiting dissociation of a terminal thiolate from [M(4)(SPh)(10)](2)(-) produces [M(4)(SPh)(9)](-) and the coordinatively unsaturated M site is rapidly attacked by a sulfido group of [MoS(4)](2)(-). It is proposed that subsequent chelation of the MoS(4) ligand results in cleavage of an M-micro-SPh bond, initiating a cascade of reactions which lead to the ultimate break-up of the cluster and formation of the products, [S(2)MoS(2)Fe(SPh)(2)](2)(-) or [S(2)MoS(2)CoS(2)MoS(2)](2)(-). With [Co(4)(SPh)(10)](2)(-), at higher concentrations of [MoS(4)](2)(-), a further substitution pathway is evident which exhibits a second order dependence on the concentration of [MoS(4)](2)(-). The mechanistic picture of cluster disruption which emerges from these studies rationalizes the "all or nothing" reactivity of [M(4)(SPh)(10)](2)(-).

  15. Effects of hot-salt stress corrosion on titanium alloys.

    NASA Technical Reports Server (NTRS)

    Gray, H. R.

    1972-01-01

    Susceptibility of titanium alloys to hot-salt stress-corrosion cracking increased as follows: Ti-2Al-11Sn-5Zr-1Mo-0.2Si (679), Ti-6Al-2Sn-4Zr-2Mo (6242), Ti-6Al-4V (64), Ti-6Al-4V-3Co (643), Ti-8Al-1Mo-1V (811), and Ti-13V-11Cr-3Al (13-11-3). The Ti-5Al-6Sn-2Zr-1Mo-0.25Si (5621S) alloy was both the least and most susceptible, depending on heat treatment. Such rankings can be drastically altered by heat-to-heat variations and processing conditions. Residual compressive stresses reduce susceptibility to stress-corrosion. Detection of substantial concentrations of hydrogen in all corroded alloys confirmed the generality of a previously proposed hydrogen embrittlement mechanism.

  16. Design Strategies for CeO2-MoO3 Catalysts for DeNOx and Hg(0) Oxidation in the Presence of HCl: The Significance of the Surface Acid-Base Properties.

    PubMed

    Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Mingguan; Sun, Xiaoxu; Li, Junhua; Duan, Lei; Hao, Jiming

    2015-10-20

    A series of CeMoOx catalysts with different surface Ce/Mo ratios was synthesized by a coprecipitation method via changing precipitation pH value. The surface basicity on selective catalytic reduction (SCR) catalysts (CeMoOx and VMo/Ti) was characterized and correlated to the durability and activity of catalyst for simultaneous elimination of NOx and Hg(0). The pH value in the preparation process affected the surface concentrations of Ce and Mo, the Brunauer-Emmett-Teller (BET) specific surface area, and the acid-base properties over the CeMoOx catalysts. The O 1s X-ray photoelectron spectroscopy (XPS) spectra and CO2-temperature programmed desorption (TPD) suggested that the surface basicity increased as the pH value increased. The existence of strong basic sites contributed to the deactivation effect of HCl over the VMo/Ti and CeMoOx catalysts prepared at pH = 12. For the CeMoOx catalysts prepared at pH = 9 and 6, the appearance of surface molybdena species replaced the surface -OH, and the existence of appropriate medium-strength basic sites contributed to their resistance to HCl poisoning in the SCR reaction. Moreover, these sites facilitated the adsorption and activation of HCl and enhanced Hg(0) oxidation. On the other hand, the inhibitory effect of NH3 on Hg(0) oxidation was correlated with the competitive adsorption of NH3 and Hg(0) on acidic surface sites. Therefore, acidic surface sites may play an important role in Hg(0) adsorption. The characterization and balance of basicity and acidity of an SCR catalyst is believed to be helpful in preventing deactivation by acid gas in the SCR reaction and simultaneous Hg(0) oxidation.

  17. Molybdenum Enrichment in the 3.2 Ga old Black Shales Recovered by Dixon Island-Cleaverville Drilling Project (DXCL-DP) in Northwestern Pilbara, Western Australia

    NASA Astrophysics Data System (ADS)

    Yamaguchi, K. E.; Kiyokawa, S.; Naraoka, H.; Ikehara, M.; Ito, T.; Suganuma, Y.; Sakamoto, R.; Hosoi, K.

    2010-12-01

    To obtain drillcores of Mesoarchean black shales with negligible modern weathering, we conducted continental drilling at Cleaverville coast in Pilbara, Western Australia. We recovered 3.2Ga sulfidic black shales of the Cleaverville Group from three drillholes (~200m in total), namely DX, CL1, and CL2. Information on the geology of the drilling site has been reported [1, 2]. Here we report the discovery of Mo enrichment in the 3.2Ga DXCL-DP black shales. We analyzed total chemical compositions of forty black shale samples from drillcore DX and fifty-six of those from CL1 and CL2. Molybdenum concentrations for DX samples ranged from 0.3 to 12.9ppm (Avg±1σ= 1.8±1.9ppm), and those for CL1 and CL2 (combined) ranged from 0.8 to 3.3ppm (Avg±1σ= 1.4±0.4ppm). The highest concentration of Mo occurs in Corg-rich sample, and is comparable to that of the contemporaneous Fig Tree Group in South Africa [3, 4]. The highest concentration of Mo in the DXCL-DP samples, ~13ppm, is lower than that found in the 2.5 Ga Mt. McRae Shale of the Hamersley Group, Western Australia (maximums are ~17ppm [5], and ~40ppm [6]). However, it is much higher, by thirteen times, than the average Mo concentration in the Phanerozoic shales (1ppm [7]). No significant enrichment of Mo was expected to occur in the before-GOE black shales if pO2 was as low as <10-6 PAL. Sulfur isotope analysis revealed, based on the variable δ34S values (-1.9 ~ +26.8‰), that bacterial sulfate reduction was so extensive in the 3.2Ga deep marine environments that sulfate utilization by sulfate-reducers was near completion [8]. Production of bacteriogenic sulfide would have enhanced fixation of dissolved Mo into sulfide minerals in sediments. This is rather a common process occurring in oxygen-depleted environments in the modern ocean ([9]). A combined enrichment of Mo, Corg, and S, together with high δ34S values for a sedimentary formation may be used as a strong evidence for operation of modern-day style sedimentary Mo enrichment. This further implies that oxygenation of the atmosphere and (at least the surface) oceans was significant during deposition of the sediments, ~800Ma earlier than commonly thought ([10]). Operation of present-day style geochemical cycle of Mo in the Mesoarchean surface environments suggests early evolution of atmosphere, oceans, and microbial biosphere. References: [1] Kiyokawa et al, 2006, GSAB 118: 3-22. [2] Yamaguchi et al, 2009, Sci. Drill. 7: 34-37. [3] Yamaguchi, 2002, Ph.D. dissertation, Penn State Univ. [4] Yamaguchi & Ohmoto, 2002, GSA Abstract [5] Naraoka et al, 2001, 4th Int'l Archaean Symp., Perth. [6] Anbar et al, 2007, Science 317: 1903-1906. [7] Vine & Tourtelot, 1970, Econ. Geol. 65: 253-272. [8] Sakamoto et al, 2010, Fall AGU Mtg. [9] Morford & Emerson, 1999, GCA 63: 1735-1750. [10] Bekker et al, 2004, Nature 427: 117-120.

  18. A Simplified Extemporaneously Prepared Potassium Chloride Oral Solution.

    PubMed

    Tannous, Elias; Tal, Yana; Amarny, Kamal

    2016-01-01

    Although commercial preparations of oral potassium supplements are usually available, there are times when our Medical Center is faced with situations in which the oral solution of potassium chloride is not available. This solution is necessary for our pediatric outpatients who cannot swallow tablets and need an oral solution. Moreover, there are no studies available which describe an extemporaneously prepared potassium chloride oral solution on which we can rely for assigning a beyond-use date. The aim of this study was to formulate an extemporaneous pediatric oral solution of potassium chloride and to determine the physical and chemical stability of this preparation. We prepared 1 mMoL/mL by withdrawing 25 mL of potassium chloride 14.9%. Ora-Sweet SF was added to 50 mL in a metered flask. The solution was kept refrigerated (2°C to 8°C). Samples were withdrawn to measure potassium concentration, pH, and microbial overgrowth. The test was performed by our biochemical laboratory. The oral solution of potassium chloride 1 mMoL/mL stored at 2°C to 8°C maintained at least 91% of the initial concentration for 28 days. There were no notable changes in pH, and the solution remained physically stable with no visual microbial growth. The oral solution of potassium chloride 1 mMoL/mL prepared in Ora-Sweet and stored at 2°C to 8°C in amber glass bottles is expected to remain stable for 28 days. Copyright© by International Journal of Pharmaceutical Compounding, Inc.

  19. Activation of persulfate/copper by hydroxylamine via accelerating the cupric/cuprous redox couple.

    PubMed

    Zhou, Peng; Zhang, Jing; Liang, Juan; Zhang, Yongli; Liu, Ya; Liu, Bei

    2016-01-01

    Cuprous copper [Cu(I)] reacts with sodium persulfate (PDS) to generate sulfate radical SO4(-)•, but it has been seldom investigated owing to its instability and difficulty in dissolving it. This study proposes a new method to regenerate Cu(I) from cupric copper [Cu(II)] by addition of hydroxylamine (HA) to induce the continuous production of radicals through active PDS, and investigates the resulting enhanced methyl orange (MO) degradation efficiency and mechanism in the new system. HA accelerated the degradation of MO markedly in the pH range from 6.0 to 8.0 in the HA/Cu(II)/PDS process. Both SO4(-)• and hydroxyl radicals (•OH) were considered as the primary reactive radicals in the process. The MO degradation in the HA/Cu(II)/PDS process can be divided into three stages: the fast stage, the transitory stage, and the low stage. MO degradation was enhanced with increased dosage of PDS. Although high dosage of HA could accelerate the transformation of the Cu(II)/Cu(I) cycle to produce more reactive radicals, excess HA can quench the reactive radicals. This study indicates that through a copper-redox cycling mechanism by HA, the production of SO4(-)• and •OH can be strongly enhanced, and the effective pH range can be expanded to neutral conditions.

  20. Increased risk of revision of cementless stemmed total hip arthroplasty with metal-on-metal bearings

    PubMed Central

    Pedersen, Alma B; Mäkelä, Keijo; Eskelinen, Antti; Havelin, Leif Ivar; Furnes, Ove; Kärrholm, Johan; Garellick, Göran; Overgaard, Søren

    2015-01-01

    Background and purpose Data from the national joint registries in Australia and England and Wales have revealed inferior medium-term survivorship for metal-on-metal (MoM) total hip arthroplasty (THA) than for metal-on-polyethylene (MoP) THA. Based on data from the Nordic Arthroplasty Register Association (NARA), we compared the revision risk of cementless stemmed THA with MoM and MoP bearings and we also compared MoM THA to each other. Patients and methods We identified 32,678 patients who were operated from 2002 through 2010 with cementless stemmed THA with either MoM bearings (11,567 patients, 35%) or MoP bearings (21,111 patients, 65%). The patients were followed until revision, death, emigration, or the end of the study period (December 31, 2011), and median follow-up was 3.6 (interquartile range (IQR): 2.4–4.8) years for MoM bearings and 3.4 (IQR: 2.0–5.8) years for MoP bearings. Multivariable regression in the presence of competing risk of death was used to assess the relative risk (RR) of revision for any reason (with 95% confidence interval (CI)). Results The cumulative incidence of revision at 8 years of follow-up was 7.0% (CI: 6.0–8.1) for MoM bearings and 5.1% (CI: 4.7–5.6) for MoP bearings. At 6 years of follow-up, the RR of revision for any reason was 1.5 (CI: 1.3–1.7) for MoM bearings compared to MoP bearings. The RR of revision for any reason was higher for the ASR (adjusted RR = 6.4, CI: 5.0–8.1), the Conserve Plus (adjusted RR = 1.7, CI: 1.1–2.5) and “other” acetabular components (adjusted RR = 2.4, CI: 1.5–3.9) than for MoP THA at 6 years of follow-up. Interpretation At medium-term follow-up, the survivorship for cementless stemmed MoM THA was inferior to that for MoP THA, and metal-related problems may cause higher revision rates for MoM bearings with longer follow-up. PMID:25715878

  1. Catalytic mechanism of cationic red GTL at wide pH using the Mo-Zn-Al-O nanocatalyst under room conditions.

    PubMed

    Xu, Yin; Li, Xiaoyi; Sun, Dezhi

    2014-09-01

    Catalytic mechanism of cationic red GTL at wide pH using the Mo-Zn-Al-O nanocatalyst under room conditions was investigated. The experimental results indicate that initial pH significantly affected the removal of cationic red GTL, the removal of COD, the pH value and residual oxygen in the reaction. In the range of pH value from 4 to 10, decolorization of cationic red GTL was almost above 90%. COD removal efficiency was enhanced with the decrease of pH in CWAO process and 79% of the COD was removed at pH 4.0, whereas only 57% COD removal was observed at pH 10.0. The terminal pH was in the range of 5.0-6.0 and the highest terminal concentrations of aqueous oxygen with 5.5 mg/L were observed at pH = 4.0. The radical inhibition experiments also carried out and the generation of *OH and 1O2 in catalytic wet air oxidation process were detected. It was found that the degradation of cationic red GTL occurs mainly via oxidation by 1O2 radical generated by Mo-Zn-Al-O nanocatalyst under acid conditions and *OH radical under alkaline conditions.

  2. Ductile failure X-prize.

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

    Cox, James V.; Wellman, Gerald William; Emery, John M.

    2011-09-01

    Fracture or tearing of ductile metals is a pervasive engineering concern, yet accurate prediction of the critical conditions of fracture remains elusive. Sandia National Laboratories has been developing and implementing several new modeling methodologies to address problems in fracture, including both new physical models and new numerical schemes. The present study provides a double-blind quantitative assessment of several computational capabilities including tearing parameters embedded in a conventional finite element code, localization elements, extended finite elements (XFEM), and peridynamics. For this assessment, each of four teams reported blind predictions for three challenge problems spanning crack initiation and crack propagation. After predictionsmore » had been reported, the predictions were compared to experimentally observed behavior. The metal alloys for these three problems were aluminum alloy 2024-T3 and precipitation hardened stainless steel PH13-8Mo H950. The predictive accuracies of the various methods are demonstrated, and the potential sources of error are discussed.« less

  3. Soya, maize, and sorghum-based ready-to-use therapeutic food with amino acid is as efficacious as the standard milk and peanut paste-based formulation for the treatment of severe acute malnutrition in children: a noninferiority individually randomized controlled efficacy clinical trial in Malawi.

    PubMed

    Bahwere, Paluku; Akomo, Peter; Mwale, Mwawi; Murakami, Hitoshi; Banda, Chrissy; Kathumba, Sylvester; Banda, Chimwemwe; Jere, Solomon; Sadler, Kate; Collins, Steve

    2017-10-01

    Background: Development of more cost-effective ready-to-use therapeutic food (RUTF) is a global public health priority. To date, previous lower-cost recipes have been less effective than the standard peanut and milk (PM)-based RUTF, particularly in children aged <24 mo. Objective: We aimed to compare the efficacy of the PM-RUTF to a milk-free soya, maize, and sorghum (FSMS)-RUTF enriched with crystalline amino acids without cow milk powder and a milk, soya, maize, and sorghum (MSMS)-RUTF containing 9.3% skim cow milk powder. Design: This nonblinded, 3-arm, parallel-group, simple randomized controlled trial enrolled Malawian children with severe acute malnutrition. Results: In intention-to-treat analyses, FSMS-RUTF showed noninferiority for recovery rates in children aged 24-59 mo (Δ: -1.9%; 95% CI: -9.5%, 5.6%) and 6-23 mo (Δ: -0.2%; 95% CI: -7.5%, 7.1%) compared with PM-RUTF. MSMS-RUTF also showed noninferiority for recovery rates in children aged 24-59 mo (Δ: 0.0%; 95% CI: -7.3%, 7.4%) and 6-23 mo (Δ: 0.6%; 95% CI: -4.3%, 5.5%). Noninferiority in recovery rates was also observed in per-protocol analyses. For length of stay in the program (time to cure), both FSMS-RUTF in children aged 24-59 mo (Δ: 2.8 d; 95% CI: -0.8, 6.5 d) and 6-23 mo (Δ: 3.4 d; 95% CI: -1.2, 8.0 d) and MSMS-RUTF in children aged 24-59 mo (Δ: 0.2 d; 95% CI: -3.1, 3.6 d) and 6-23 mo (Δ: 1.2 d; 95% CI: -3.4, 5.8 d) were not inferior to PM-RUTF. FSMS-RUTF was also significantly better than PM-RUTF at increasing hemoglobin and body iron stores in anemic children, with mean hemoglobin increases of 2.1 (95% CI: 1.6, 2.6) and 1.3 (95% CI: 0.9, 1.8) and mean body iron store increases of 2.0 (95% CI: 0.8, 3.3) and 0.1 (95% CI: -1.1, 1.3) for FSMS-RUTF and PM-RUTF, respectively. Conclusions: FSMS-RUTF without milk is efficacious in the treatment of severe acute malnutrition in children aged 6-23 and 24-59 mo. It is also better at correcting iron deficiency anemia than PM-RUTF. This trial was registered at www.pactr.org as PACTR201505001101224. © 2017 American Society for Nutrition.

  4. Influence of sodium chloride, pH, and lactic acid bacteria on anaerobic lactic acid utilization during fermented cucumber spoilage.

    PubMed

    Johanningsmeier, Suzanne D; Franco, Wendy; Perez-Diaz, Ilenys; McFeeters, Roger F

    2012-07-01

    Cucumbers are preserved commercially by natural fermentations in 5% to 8% sodium chloride (NaCl) brines. Occasionally, fermented cucumbers spoil after the primary fermentation is complete. This spoilage has been characterized by decreases in lactic acid and a rise in brine pH caused by microbial instability. Objectives of this study were to determine the combined effects of NaCl and pH on fermented cucumber spoilage and to determine the ability of lactic acid bacteria (LAB) spoilage isolates to initiate lactic acid degradation in fermented cucumbers. Cucumbers fermented with 0%, 2%, 4%, and 6% NaCl were blended into slurries (FCS) and adjusted to pH 3.2, 3.8, 4.3, and 5.0 prior to centrifugation, sterile-filtration, and inoculation with spoilage organisms. Organic acids and pH were measured initially and after 3 wk, 2, 6, 12, and 18 mo anaerobic incubation at 25 °C. Anaerobic lactic acid degradation occurred in FCS at pH 3.8, 4.3, and 5.0 regardless of NaCl concentration. At pH 3.2, reduced NaCl concentrations resulted in increased susceptibility to spoilage, indicating that the pH limit for lactic acid utilization in reduced NaCl fermented cucumbers is 3.2 or lower. Over 18 mo incubation, only cucumbers fermented with 6% NaCl to pH 3.2 prevented anaerobic lactic acid degradation by spoilage bacteria. Among several LAB species isolated from fermented cucumber spoilage, Lactobacillus buchneri was unique in its ability to metabolize lactic acid in FCS with concurrent increases in acetic acid and 1,2-propanediol. Therefore, L. buchneri may be one of multiple organisms that contribute to development of fermented cucumber spoilage. Microbial spoilage of fermented cucumbers during bulk storage causes economic losses for producers. Current knowledge is insufficient to predict or control these losses. This study demonstrated that in the absence of oxygen, cucumbers fermented with 6% sodium chloride to pH 3.2 were not subject to spoilage. However, lactic acid was degraded by spoilage microorganisms in reduced salt, even with pH as low as 3.2. Efforts to reduce salt in commercial brining operations will need to include control measures for this increased susceptibility to spoilage. Lactobacillus buchneri was identified as a potential causative agent and could be used as a target in development of such control measures. Journal of Food Science © 2012 Institute of Food Technologists® No claim to original US government works.

  5. The Synthesis and Characterization of Aromatic Hybrid Anderson–Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions

    PubMed Central

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

    2015-01-01

    Four aromatic hybrid Anderson polyoxomolybdates with Fe3+ or Mn3+ as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, 1H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3[FeMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-FeMo6-bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRIS–R=(HOCH2)3C–R)), (TBA)3[FeMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-FeMo6-cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3[MnMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-MnMo6-bzn), and (TBA)3[MnMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-MnMo6-cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mm) sodium salts Na3[FeMo6O18{(OCH2)3CNHCOC6H5}2] (Na-FeMo6-bzn), Na3[FeMo6O18{(OCH2)3CNHCOC8H7}2] (Na-FeMo6-cin), Na3[MnMo6O18{(OCH2)3CNHCOC6H5}2] (Na-MnMo6-bzn), and Na3[MnMo6O18{(OCH2)3CNHCOC8H7}2] (Na-MnMo6-cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate–polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern–Volmer analysis, which suggested the formation of a 1:1 POM–protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. PMID:26527418

  6. Synthesis of 1,4,7-triphenyl-1,4,7-triphosphacyclononane: the first metal-free synthesis of a [9]-aneP(3)R(3) ring.

    PubMed

    Lowry, Daniel J; Helm, Monte L

    2010-06-07

    The 1,4,7-triphenyl-1,4,7-triphosphacyclononane ([9]-aneP(3)Ph(3)) macrocycle was synthesized through the reaction of lithium bis(2-phenylphosphidoethyl)phenylphosphine with 1,2-dichloroethane. [9]-aneP(3)Ph(3) was subsequently coordinated to a Mo(0) metal center and isolated as the fac-Mo([9]-aneP(3)Ph(3))(CO)(3) metal complex.

  7. A cost and technical efficiency analysis of two alternative models for implementing the basic package of health services in Afghanistan.

    PubMed

    Blaakman, Aaron Philip; Salehi, Ahmad Shah; Boitard, Romain

    2014-01-01

    Since 2003, the Afghan Ministry of Public Health (MoPH) and international partners have directed a contracting-out model through which non-governmental organisations (NGOs) deliver the Basic Package of Health Services (BPHS) in 31 of the 34 Afghan provinces. The MoPH also managed health service delivery in three provinces under an alternative initiative entitled Strengthening Mechanisms (SM). In 2011, under the authority of the MoPH and Delegation of the European Union to Afghanistan, EPOS Health Management conducted a cost and technical efficiency study of the contracting-out and SM mechanisms in six provinces to examine economic trade-offs in the provision of the BPHS. The study provides analyses of all resource inputs and primary outputs of the BPHS in the six provinces during 2008 and 2009. The authors examined technical efficiency using Data Envelopment Analysis (DEA) at the BPHS facility level. Cost analysis results indicate that the weighted average cost per BPHS outpatient visit totalled $3.41 in the SM provinces and $5.39 in the NGO-led provinces in 2009. Furthermore, the data envelopment analyses (DEAs) indicate that facilities in the three NGO-led provinces scored 0.168 points higher on the DEA scale (0-1) than SM facilities. The authors conclude that an approximate 60% increase in costs yielded a 16.8% increase in technical efficiency in the delivery of the BPHS during 2009 in the six provinces.

  8. Low Temperature Reactive Sputtering of Thin Aluminum Nitride Films on Metallic Nanocomposites

    PubMed Central

    Ramadan, Khaled Sayed Elbadawi; Evoy, Stephane

    2015-01-01

    Piezoelectric aluminum nitride thin films were deposited on aluminum-molybdenum (AlMo) metallic nanocomposites using reactive DC sputtering at room temperature. The effect of sputtering parameters on film properties was assessed. A comparative study between AlN grown on AlMo and pure aluminum showed an equivalent (002) crystallographic texture. The piezoelectric coefficients were measured to be 0.5±0.1 C m-2 and 0.9±0.1 C m-2, for AlN deposited on Al/0.32Mo and pure Al, respectively. Films grown onto Al/0.32Mo however featured improved surface roughness. Roughness values were measured to be 1.3nm and 5.4 nm for AlN films grown on AlMo and on Al, respectively. In turn, the dielectric constant was measured to be 8.9±0.7 for AlN deposited on Al/0.32Mo seed layer, and 8.7±0.7 for AlN deposited on aluminum; thus, equivalent within experimental error. Compatibility of this room temperature process with the lift-off patterning of the deposited AlN is also reported. PMID:26193701

  9. Influence of the Additives and The pH On the Cobalt-Molybdenum (Co-Mo) Alloy Electrodeposited On n-TypeSilicon

    NASA Astrophysics Data System (ADS)

    Fekih, Z.; Ghellai, N.; Fortas, G.; Chiboub, N.; Sam, S.; Chabanne-sari, N. E.; Gabouze, N.

    In this work, thin films of metal alloys (Co-Mo) have been electrodeposited onto silicon (Si) surface. The effects of two different additives (H3BO3 and Na2CO3) and the pH of the solution on the electrochemically deposited films (morphology, stochiometry…) have been investigated. The properties of the deposits were characterized by using X-Rays Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The results show that the morphology and the film composition depend on both the pH of the solution and the additives. The presence of boric acid favors the Mo deposition. Crack-free homogeneous deposits with a low percentage of molybdenum can be easily obtained from high pH bath. The deposits were shown to exhibits a good crystalline structure.

  10. PLANE STRAIN FRACTURE TOUGHNESS DATA FOR HANDBOOK PRESENTATION

    DTIC Science & Technology

    An experimental program was conducted to determine the plane strain fracture toughness (K sub IC) of the following classes of: (1) AISI Alloy Steels...4340, 4140 ); (2) 5Cr-Mo-V Steels; (3) Precipitation-Hardening Stainless Steels (17-7 PH, PH 15-7 Mo, 17-4, AM355); (4) Titanium Alloy, Ti-6Al-4V. The

  11. Tunable Quantum Spin Liquidity in Mo3O13 Cluster Mott Insulators

    NASA Astrophysics Data System (ADS)

    Akbari-Sharbaf, Arash; Ziat, Djamel; Verrier, Aime; Quilliam, Jeffrey A.; Sinclair, Ryan; Zhou, Haidong D.; Sun, Xuefeng F.

    A study of a tunable quantum spin liquid (QSL) phase in the compound Li2In1- x ScxMo3O8 (x = 0.2, 0.4, 0.6, 0.8, 1) will be presented. Crystal structure of these compounds can be viewed as Mo ions arranged on an asymmetric Kagome lattice (KL), with two different Mo-Mo bond lengths, separated by nonmagnetic layers composed of Li, In, and Sc ions. Using X-ray diffraction spectroscopy, muon spin relaxation spectroscopy, bulk magnetic susceptibility and specific heat measurements we show that by changing the composition of the nonmagnetic layers we can drive the system from an ordered antiferromagnetic state to a quantum spin liquid state. The mechanism responsible for the tunability of the magnetic phase in this class of materials may be associated with the degree of asymmetry of the KL controlled by the composition of the nonmagnetic layers. For high degree of asymmetry the constraint on the electronic distribution leads to a configuration of Mo3O8 clusters with net spin-1/2 per cluster arrange on a triangular lattice and long range antiferromagnetic order. For low degree of asymmetry the electronic distribution leads to a magnetic phase with QSL character. We acknowledge support from NSERC and CFREF.

  12. Revised Space Groups for Three Molybdenum(V) Phosphate Compounds

    NASA Astrophysics Data System (ADS)

    Leclaire, A.; Borel, M. M.; Guesdon, A.; Marsh, Richard E.

    2001-06-01

    The space groups of three previously described Mo(V) phosphate structures are revised. (1) δ-KMo2P3O13, originally reported as triclinic, Poverline1, is revised to monoclinic, C2/c; it is identical to the compound previously identified as K4Mo8P12O52. (2) The compound formulated as [Mo12CdP8O50(OH)12]Cd [N(CH3)4]2(H3O)6·5H2O, originally described as monoclinic, Pn, is revised to P21/n (also monoclinic). (3) Rb3O2(MoO)4(PO4)4, originally reported as orthorhombic, C2221, is revised to tetragonal, P43212. The general descriptions of the structures are unchanged; however, for compound 2 the revision involves the addition of a center of symmetry and, as a result, there are significant changes in the interatomic distances and angles.

  13. Investigation of Local Hydrogen Uptake in Rescaled Model Occluded Sites Using Crevice Scaling Laws

    DTIC Science & Technology

    2005-04-01

    13- 8 Mo . Under anodic polarization, there is a combination of x and G in a crevice or crack where the stainless steel would be passive and remain...2004). 8 . G.A. Young, Jr., J.R. Scully, "The Effects of Test Temperature , Temper and Alloyed Copper on Hydrogen Controlled Crack Growth of an A1-Zn-Mg...sharp crack tip.[16] Precipitation-aged hardened martensitic stainless steels (i.e., Fe-Cr-Ni- Mo alloys) that release hydrolysable Cr and Fe cations

  14. Duration of breast-feeding and adiposity in adult life.

    PubMed

    O'Tierney, Perrie F; Barker, David J P; Osmond, Clive; Kajantie, Eero; Eriksson, Johan G

    2009-02-01

    Few studies have examined whether the duration of breast-feeding is associated with BMI in adult life. In the past, the heights and weights of infants and the duration of breast-feeding were routinely recorded at infant welfare clinics in Helsinki, Finland. Most infants in the city were taken to these free clinics. The Helsinki Birth Cohort comprises 13,345 people born in the city during 1934-1944; 84% were breast-fed. In 2001, a questionnaire was sent to members of the cohort asking about their weight and height. A random sample of 2003 men and women attended a clinic at which height, weight, and body composition were measured. We studied sibships that included 2 or more people from the cohort. There were 1823 subjects: 831 had completed the questionnaire; 129 had attended the clinic. We grouped the subjects according to duration of breast-feeding: 0-2 mo, 3-4 mo, 5-7 mo, and 8 mo or more. We compared siblings who were discordant for duration of breast-feeding. We found that a longer period of breast-feeding was associated with lower BMI at 1 y of age (P = 0.04 for a linear trend). This relation disappeared by the age of 7 y. People breast-fed for 5-7 mo had the lowest reported BMI at age 60 y, although this was not statistically significant; 8.8% more people breast-fed for 8 mo or more had reported BMIs that were overweight (25 to 30 kg/m(2)) compared with those breast-fed for shorter periods (P = 0.06). Breast-feeding for <2 mo or 8 mo or more was associated with an increased BMI and percentage body fat in later life, measured at the clinic (P = 0.08 and P = 0.03 for quadratic trends). We conclude that breast-feeding for <2 mo may be deleterious, possibly because of lack of exposure to protective factors in breast milk. Breast-feeding beyond 8 mo may be deleterious because mother's hormones in breast milk reset the infant's hypothalamic-pituitary-thyroid axis.

  15. Mastery motivation as a predictor of occupational performance following upper limb intervention for school-aged children with congenital hemiplegia.

    PubMed

    Miller, Laura; Ziviani, Jenny; Ware, Robert S; Boyd, Roslyn N

    2014-10-01

    To determine the extent to which children's mastery motivation predicts occupational performance outcomes following upper limb intervention (ULI). In this cohort study, participants received 45 hours of ULI, either in an intensive group-based or distributed individualized model. The Dimensions of Mastery Questionnaire (DMQ) measured mastery motivation at baseline. Occupational performance outcomes were assessed at baseline and 13 weeks' post-intervention using the Canadian Occupational Performance Measure (COPM). Multivariable models determined the contribution of mastery motivation to COPM outcome irrespective of group membership. Forty-two children with congenital hemiplegia (29 males, 13 females; mean age 7y 8mo [SD 2y 2mo]; range 5y 1mo-12y 8mo; Manual Ability Classification System [MACS] I=20 and II=22; predominant motor type unilateral spastic n=41) participated in the study. Significant gains were seen in COPM performance and satisfaction scores (p<0.001) post-intervention with no between group differences. Children who had greater persistence with object-oriented tasks (p=0.02) and better manual ability (p=0.03) achieved higher COPM performance scores at 13 weeks. Children's persistence on object-oriented tasks was the strongest predictor of COPM satisfaction (p=0.01). Children's persistence with object-oriented tasks as well as manual abilities needs to be considered when undertaking ULI. Predetermining children's motivational predispositions can assist clinicians to tailor therapy sessions individually based on children's strengths, contributing to effective engagement in ULI. © 2014 Mac Keith Press.

  16. High temperature deformation of hot-pressed polycrystalline orthoenstatite. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Dehghan-Banadaki, A.

    1983-01-01

    Artificial hot pressed polycrystalline samples were prepared from purified powder of Bamble, Norway, orthoenstatite, (Mg0.86Fe0.14)SiO3. The uniaxial creep behavior of the polycrystalline orthoenstatite was studied over stress ranges of 10-180 MPa and temperatures of 1500-1700 K (0.82-0.93 T sub m) under two different oxygen fugacities, namely equilibrium (Mo-MoO2 buffer) and a reducing (graphite heating element) atmosphere, respectively. An intergranular glassy phase of different compositions with a cavitational creep deformation were observed. In the Mo-MoO2 buffer atmosphere with PO2 approx. 10 to the minus 11 power - 10 to the minus 13 power atmospheres, the results of an analytical electron microscopy analysis indicate that the glassy phases are richer in Ca and Al due to the residual impurities after hot pressing. In the reducing atmosphere with an oxygen fugacity of PO2 approx. 10 to the minus 3 power - 10 to the minus 25 power atmospheres, the results of analytical electron microscopy analysis indicate that the glassy phase is almost pure silica with the presence of free iron precipitate on grain facets and at triple junctions due to the reduction of bulk materials.

  17. Electrodeposition of Zn-Co-Mo Alloy on the Steel Substrate from Citrate Bath and Its Corrosion Behavior in the Chloride Media

    NASA Astrophysics Data System (ADS)

    Keyvani, A.; Yeganeh, M.; Rezaeyan, H.

    2017-04-01

    In this study, Zn-Co-Mo coatings were deposited on the steel substrate from a citrate bath after adjusting pH, concentration, and current density. The morphology, the content of alloying elements, and the thickness of deposits were studied. Deposition behavior of these ternary coatings was examined by cathodic polarization and cyclic voltammetry (CV) techniques. The synthesized deposits were investigated by scanning electron microscopy (SEM), energy-dispersive x-ray (EDX) analysis, x-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization methods. The results showed that the deposition potential of Zn-Co-Mo alloy was feasible in negative potentials higher than about -1.25 V versus Ag/AgCl. Moreover, the corrosion behavior of these coatings was found to be related to the extent of Mo as well as the local anodes and cathodes. The amount of molybdenum in the Zn-Co-Mo coating varied from 2.6 to 14 wt.% as a result of changing the pH. Based on the experimental findings, a narrow range of pH values between 5 and 5.5 could contribute to the high quality of coating in conjunction with the corrosion resistant alloy. Besides, the coatings with Mo element could show a passive-like behavior in the anodic region.

  18. The effect of pH on the corrosion behavior of intermetallic compounds Ni{sub 3}(Si,Ti) and Ni{sub 3}(Si,Ti) + 2Mo in sodium chloride solutions

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

    Priyotomo, Gadang, E-mail: gada001@lipi.go.id; Nuraini, Lutviasari, E-mail: Lutviasari@gmail.com; Kaneno, Yasuyuki, E-mail: kaneno@mtr.osakafu-u.ac.id

    The corrosion behavior of the intermetallic compounds, Ni{sub 3}(Si,Ti) (L1{sub 2}: single phase) and Ni{sub 3}(Si,Ti) + 2Mo (L1{sub 2} and (L12 + Ni{sub ss}) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EDAX: Energy Dispersive X-ray) in 0.5 kmol/m{sup 3} NaCl solutions at various pH. The corrosion behavior of nickel alloy C-276 was studied under the same experimental conditions as a reference. It was found that the uniform attack was observed on Ni{sub 3}(Si,Ti) for the immersion test at lower pH, while the pitting attack was observedmore » on this compound for this test at neutral solution. Furthermore, Ni{sub 3}(Si,Ti)+2Mo had the preferential dissolution of L1{sub 2} compared to (L1{sub 2} + Ni{sub ss}) mixture region at lower pH, while pitting attack occurred in (L1{sub 2} + Ni{sub ss}) mixture region at neutral solution. For both intermetallic compounds, the magnitude of pitting and uniform attack decrease with increasing pH of solutions. From the immersion test and polarization curves, the corrosion resistance of Ni{sub 3}(Si,Ti)+2Mo is lower than that of Ni{sub 3}(Si,Ti), while the nickel alloy C-276 is the highest one at various pH of solutions. On the other hand, in the lower pH of solutions, the corrosion resistance of tested materials decreased significantly compared to those in neutral and higher pH of solutions.« less

  19. Kinetic analysis of the combustion synthesis of molybdenum and titanium silicides

    NASA Astrophysics Data System (ADS)

    Wang, Lily L.; Munir, Z. A.

    1995-05-01

    The temperature profiles associated with the passage of self-propagating combustion waves during the synthesis of MoSi2 and Ti5Si3 were determined. From these profiles, kinetic analyses of the combustion synthesis process for these two silicides were made. The synthesis is associated with high heating rates: 1.3 × 104 and 4.9 × 104 K·s-1 for MoSi2 and Ti5Si3, respectively. The width of the combustion zone was determined as 1.3 and 1.8 mm for the silicides of Mo and Ti, respectively. The degree of conversion, η, and its spatial distribution and the conversion rate, ∂η/∂t, were determined. However, because of the inherent characteristics of wave propagation in MoSi2, only in the case of Ti5Si3 could the activation energy be calculated. An average value of 190 kJ µ mol-1 was determined for titanium suicide.

  20. An unexpected mechanism of hydrosilylation by a silyl hydride complex of molybdenum.

    PubMed

    Khalimon, Andrey Y; Ignatov, Stanislav K; Simionescu, Razvan; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

    2012-01-16

    Carbonyl hydrosilylation catalyzed by (ArN)Mo(H)(SiH(2)Ph)(PMe(3))(3) (3) is unusual in that it does not involve the expected Si-O elimination from intermediate (ArN)Mo(SiH(2)Ph)(O(i)Pr)(PMe(3))(2) (7). Instead, 7 reversibly transfers β-CH hydrogen from the alkoxide ligand to metal.

  1. Degradable Molybdenum Oxide Nanosheets with Rapid Clearance and Efficient Tumor Homing Capabilities as a Therapeutic Nanoplatform.

    PubMed

    Song, Guosheng; Hao, Jiali; Liang, Chao; Liu, Teng; Gao, Min; Cheng, Liang; Hu, Junqing; Liu, Zhuang

    2016-02-05

    Molybdenum oxide (MoOx) nanosheets with high near-infrared (NIR) absorbance and pH-dependent oxidative degradation properties were synthesized, functionalized with polyethylene glycol (PEG), and then used as a degradable photothermal agent and drug carrier. The nanosheets, which are relatively stable under acidic pH, could be degraded at physiological pH. Therefore, MoOx-PEG distributed in organs upon intravenous injection would be rapidly degraded and excreted without apparent in vivo toxicity. MoOx-PEG shows efficient accumulation in tumors, the acidic pH of which then leads to longer tumor retention of those nanosheets. Along with the capability of acting as a photothermal agent for effective tumor ablation, MoOx-PEG can load therapeutic molecules with high efficiencies. This concept of inorganic theranostic nanoagent should be relatively stable in tumors to allow imaging and treatment, while being readily degradable in normal organs to enable rapid excretion and avoid long-term retention/toxicity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Search for Magnetic Monopoles with the MoEDAL Forward Trapping Detector in 13 TeV Proton-Proton Collisions at the LHC

    NASA Astrophysics Data System (ADS)

    Acharya, B.; Alexandre, J.; Baines, S.; Benes, P.; Bergmann, B.; Bernabéu, J.; Branzas, H.; Campbell, M.; Caramete, L.; Cecchini, S.; de Montigny, M.; De Roeck, A.; Ellis, J. R.; Fairbairn, M.; Felea, D.; Flores, J.; Frank, M.; Frekers, D.; Garcia, C.; Hirt, A. M.; Janecek, J.; Kalliokoski, M.; Katre, A.; Kim, D.-W.; Kinoshita, K.; Korzenev, A.; Lacarrère, D. H.; Lee, S. C.; Leroy, C.; Lionti, A.; Mamuzic, J.; Margiotta, A.; Mauri, N.; Mavromatos, N. E.; Mermod, P.; Mitsou, V. A.; Orava, R.; Parker, B.; Pasqualini, L.; Patrizii, L.; Pǎvǎlaş, G. E.; Pinfold, J. L.; Popa, V.; Pozzato, M.; Pospisil, S.; Rajantie, A.; Ruiz de Austri, R.; Sahnoun, Z.; Sakellariadou, M.; Sarkar, S.; Semenoff, G.; Shaa, A.; Sirri, G.; Sliwa, K.; Soluk, R.; Spurio, M.; Srivastava, Y. N.; Suk, M.; Swain, J.; Tenti, M.; Togo, V.; Tuszyński, J. A.; Vento, V.; Vives, O.; Vykydal, Z.; Whyntie, T.; Widom, A.; Willems, G.; Yoon, J. H.; Zgura, I. S.; MoEDAL Collaboration

    2017-02-01

    MoEDAL is designed to identify new physics in the form of long-lived highly ionizing particles produced in high-energy LHC collisions. Its arrays of plastic nuclear-track detectors and aluminium trapping volumes provide two independent passive detection techniques. We present here the results of a first search for magnetic monopole production in 13 TeV proton-proton collisions using the trapping technique, extending a previous publication with 8 TeV data during LHC Run 1. A total of 222 kg of MoEDAL trapping detector samples was exposed in the forward region and analyzed by searching for induced persistent currents after passage through a superconducting magnetometer. Magnetic charges exceeding half the Dirac charge are excluded in all samples and limits are placed for the first time on the production of magnetic monopoles in 13 TeV p p collisions. The search probes mass ranges previously inaccessible to collider experiments for up to five times the Dirac charge.

  3. Sorption of Th (IV) to silica as a function of pH, humic/fulvic acid, ionic strength, electrolyte type.

    PubMed

    Chen, Changlun; Wang, Xiangke

    2007-02-01

    The removal behavior of thorium (Th(IV)) has been investigated in multicomponent systems containing silica (SiO2) as the model of inorganic particles because of its widespread presence in the earth's crust and soil humic acid (HA)/fulvic acid (FA) by batch experiments. The influence of pH from 2 to 12, ionic strength from 0.02 to 0.2 M KNO3, soil HA/FA concentration from 8.3 to 22.5 mg/L, and foreign cations (Li+, Na+, K+) and anions (NO3(-), Cl-) on the sorption of Th(IV) onto SiO2 was also tested. The sorption isotherms of Th(IV) at approximately constant pH (3.50+/-0.02) were determined and analyzed regressively with three kinds of sorption isotherm models, i.e., linear, Langmuir, and Freundlich models. The results demonstrated that the sorption of Th(IV) onto SiO2 increased steeply with increasing pH from 2 to 4. Generally, humic substances (HSs) were shown to enhance Th(IV) sorption at low pH, but to reduce Th(IV) sorption at intermediate and high pH. It was a hypothesis that the significantly positive influence of HA/FA at pH from 2 to 4 on the sorption of Th(IV) onto SiO2 was attributed to strong surface binding of HA/FA on SiO2 and subsequently the formation of ternary surface complexes such as [triple bond]MO-O-HA-Th or [triple bond]MO-O-FA-Th. The results also demonstrated that the sorption was strongly dependent on the concentration of HA/FA, and independent of ionic strength and foreign ions under our experimental conditions.

  4. The effect of turbidity levels and Moringa oleifera concentration on the effectiveness of coagulation in water treatment.

    PubMed

    Nkurunziza, T; Nduwayezu, J B; Banadda, E N; Nhapi, I

    2009-01-01

    Laboratory experiments were carried out to assess the water purification and antimicrobial properties of Moringa oleifera (MO). Hence different concentrations (25 to 300 mg/L) were prepared from a salt (1 M NaCl) extract of MO fine powder and applied to natural surface water whose turbidity levels ranged from 50 to 450 NTU. The parameters determined before and after coagulation were turbidity, pH, colour, hardness, iron, manganese and Escherichia coli. The experiments showed that turbidity removal is influenced by the initial turbidity since the lowest turbidity removal of 83.2% was observed at 50 NTU, whilst the highest of 99.8% was obtained at 450 NTU. Colour removal followed the same trend as the turbidity. The pH exhibited slight variations through the coagulation. The hardness removal was very low (0 to 15%). However, high removals were achieved for iron (90.4% to 100%) and manganese (93.1% to 100%). The highest E. coli removal achieved was 96.0%. Its removal was associated with the turbidity removal. The optimum MO dosages were 150 mg/L (50 NTU and 150 NTU) and 125 mg/L for the rest of the initial turbidity values. Furthermore all the parameters determined satisfied the WHO guidelines for drinking water except for E. coli.

  5. The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions.

    PubMed

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

    2015-12-01

    Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  6. Sources and distribution of trace elements in Estonian peat

    NASA Astrophysics Data System (ADS)

    Orru, Hans; Orru, Mall

    2006-10-01

    This paper presents the results of the distribution of trace elements in Estonian mires. Sixty four mires, representative of the different landscape units, were analyzed for the content of 16 trace elements (Cr, Mn, Ni, Cu, Zn, and Pb using AAS; Cd by GF-AAS; Hg by the cold vapour method; and V, Co, As, Sr, Mo, Th, and U by XRF) as well as other peat characteristics (peat type, degree of humification, pH and ash content). The results of the research show that concentrations of trace elements in peat are generally low: V 3.8 ± 0.6, Cr 3.1 ± 0.2, Mn 35.1 ± 2.7, Co 0.50 ± 0.05, Ni 3.7 ± 0.2, Cu 4.4 ± 0.3, Zn 10.0 ± 0.7, As 2.4 ± 0.3, Sr 21.9 ± 0.9, Mo 1.2 ± 0.2, Cd 0.12 ± 0.01, Hg 0.05 ± 0.01, Pb 3.3 ± 0.2, Th 0.47 ± 0.05, U 1.3 ± 0.2 μg g - 1 and S 0.25 ± 0.02%. Statistical analyses on these large database showed that Co has the highest positive correlations with many elements and ash content. As, Ni, Mo, ash content and pH are also significantly correlated. The lowest abundance of most trace elements was recorded in mires fed only by precipitation (ombrotrophic), and the highest in mires fed by groundwater and springs (minerotrophic), which are situated in the flood plains of river valleys. Concentrations usually differ between the superficial, middle and bottom peat layers, but the significance decreases depending on the type of mire in the following order: transitional mires - raised bogs - fens. Differences among mire types are highest for the superficial but not significant for the basal peat layers. The use of peat with high concentrations of trace elements in agriculture, horticulture, as fuel, for water purification etc., may pose a risk for humans: via the food chain, through inhalation, drinking water etc.

  7. Long-term outcomes of uveitic glaucoma treated with Ahmed valve implant in a series of Chinese patients.

    PubMed

    Bao, Ning; Jiang, Zheng-Xuan; Coh, Paul; Tao, Li-Ming

    2018-01-01

    To report long-term outcomes of secondary glaucoma due to uveitis treated with Ahmed glaucoma valve (AGV) implantation in a series of Chinese patients. The retrospective study included 67 eyes from 56 patients with uveitic glaucoma who underwent AGV implantation. Success of the treatment was defined as patients achieving intraocular pressure (IOP) levels between 6 and 21 mm Hg with or without additional anti-glaucoma medications and/or a minimum of 20% reduction from baseline IOP. The main outcome measurements included IOP, the number of glaucoma medications at 1, 3, 6, 12, 24, 36, 48 and 60mo after surgery, surgical complications, final best-corrected vision acuity (BCVA), visual field (VF) and retinal nerve fiber layer (RNFL). The mean follow-up was 53.3±8.5 (range 48 to 60)mo. The cumulative probability of success rate was 98.5%, 95.5%, 89.6%, 83.6%, 76.1%, 70.1%, 65.7% and 61.2% at 1, 3, 6, 12, 24, 36, 48 and 60mo, respectively. IOP was reduced from a baseline of 30.8±6.8 to 9.9±4.1, 10.1±4.2, 10.9±3.7, 12.9±4.6, 13.8±3.9, 13.2±4.6, 12.3±3.5 and 13.1±3.7 mm Hg at 1, 3, 6, 12, 24, 36, 48 and 60mo, respectively ( P <0.01). The number of postoperative glaucoma medications was significantly decreased compared with baseline at all time points during the study period ( P <0.05). There was no significant difference between preoperative and postoperative BCVA. Remarkable surgical complications were not found after surgery. The VF and RNFL of the patients were stable after the surgery. AGV implantation is safe and effect in terms of reducing IOP, decreasing the number of glaucoma medications, and preserving vision for patients with uveitic glaucoma.

  8. Three 3D hybrid networks based on octamolybdates and different Cu{sup I}/Cu{sup II}-bis(triazole) motifs

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

    Zhang, Chun-Jing; Pang, Hai-Jun; Tang, Qun

    2010-12-15

    Three 3D compounds based on octamolybdate clusters and various Cu{sup I}/Cu{sup II}-bis(triazole) motifs, [Cu{sup I}{sub 2}btb][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (1), [Cu{sup I}{sub 2}btpe][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (2), and [Cu{sup II}(btpe){sub 2}][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (3) [btb=1,4-bis(1,2,4-triazol-1-yl)butane, btpe=1,5-bis(1,2,4-triazol-1-yl)pentane], were isolated via tuning flexible ligand spacer length and metal coordination preferences. In 1, the copper(I)-btb motif is a one-dimensional (1D) chain which is further linked by hexadentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters via coordinating to Cu{sup I} cations giving a 3D structure. In 2, the copper(I)-btpe motif exhibits a 'stairs'-like [Cu{sup I}{sub 2}btpe]{sup 2+} sheet, and the tetradentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-}more » clusters interact with two neighboring [Cu{sup I}{sub 2}btpe]{sup 2+} sheets constructing a 3D framework. In 3, the copper(II)-btpe motif possesses a novel (2D{yields}3D) interdigitated structure, which is further connected by the tetradentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters forming a 3D framework. The thermal stability and luminescent properties of 1-3 are investigated in the solid state. -- Graphical abstract: Three 3D compounds based on {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters with different Cu{sup I}/Cu{sup II}-bis(triazole) motifs were synthesized by regularly tuning flexible ligand spacer length and metal coordination preferences. Display Omitted« less

  9. Molybdenum isotope fractionation in scleractinian corals and its implications on biological activities

    NASA Astrophysics Data System (ADS)

    Wei, G.; Wang, Z.; Li, J.; Deng, W.; Chen, X.; Ma, J.; Zeng, T.

    2017-12-01

    Molybdenum can actively involve in many biological processes on coral reefs, and its isotope fractionation in coral skeleton is possibly linked to some biological activities. We have performed a 3-days' time-series observation in a time interval of 4 hours on both Mo concentrations and δ98/85Mo of the seawater of the Luhuitou Reef in Sanya of Southern Hainan Islands in the northern South China Sea. Both Mo concentrations and δ98/85Mo show in pace diurnal variations with temperature, pH, dissolved oxygen (DO) contents, dissolved inorganic carbon (DIC) contents and its δ13C. High Mo concentrations and low δ98/85Mo generally occur during day time, and low Mo concentrations and high δ98/85Mo occur at night, suggesting that respiration of coral dominated at night tends to uptake more Mo from seawater. A further analysis on the Mo isotopic compositions of 6 different coral species on the Luhuitou Reef indicates that different coral species has different δ98/85Mo values in their skeleton. The lowest δ98/85Mo value occurs in Fungia of 0.34 ‰, and the highest occurs in Acropora sp of 1.91 ‰. These are all lower than that of the seawater, 2.04 ‰, suggesting a specie-depended Mo fractionation on coral skeleton. Meanwhile, we measured a 32-year time series of both Mo concentrations and δ98/85Mo of a Porites coral from the Great Barrier Reefs of Australia in annual resolution. The Mo concentrations vary from 12.5 to 78.0 ng/g, with an average of 21.4 ± 0.02 ng/g, and the δ98/95Mo values change from 0.46 to 1.83‰, with an average of 1.34 ± 0.09‰. A significant negative correlation occurs between the δ98/95Mo and the Mo concentration, and a positive correlation occurs between the δ98/95Mo and the seawater surface temperature. All these suggest that Mo isotope fractionation in coral skeleton is associated with biological activities of coral, such as respiration, and the δ98/95Mo values may be used to indicate changes in the related biological activities.

  10. One-step hydrothermal synthesis of feather duster-like NiS@MoS2 with hierarchical array structure for the Pt-free dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Su, Lijun; Xiao, Yaoming; Han, Gaoyi; Lin, Jeng-Yu

    2018-04-01

    Novel feather duster-like nickel sulfide (NiS) @ molybdenum sulfide (MoS2) with hierarchical array structure is synthesized via a simple one-step hydrothermal method, in which a major structure of rod-like NiS in the center and a secondary structure of MoS2 nanosheets with a thickness of about 15-55 nm on the surface. The feather duster-like NiS@MoS2 is employed as the counter electrode (CE) material for the dye-sensitized solar cell (DSSC), which exhibits superior electrocatalytic activity due to its feather duster-like hierarchical array structure can not only support the fast electron transfer and electrolyte diffusion channels, but also can provide high specific surface area (238.19 m2 g-1) with abundant active catalytic sites and large electron injection efficiency from CE to electrolyte. The DSSC based on the NiS@MoS2 CE achieves a competitive photoelectric conversion efficiency of 8.58%, which is higher than that of the NiS (7.13%), MoS2 (7.33%), and Pt (8.16%) CEs under the same conditions. [Figure not available: see fulltext.

  11. Spray and Combustion of Gelled Hypergolic Propellants

    DTIC Science & Technology

    2014-10-20

    Anderson Postdoc tlnu 2/09 Ast:I·ium Mau DeRidder Anderson Postdoc tlnu 5110 Spacex Chenzhou Lian Merkle Postdoc tlnu 8/10 IBM Watson Labs Changjin Yoon...Heister PhD, 1211 1 GE Global Research Center - 5 - - 6 - Erik Dambach Heister/Pourpoint PhD, 5/11 SpaceX Paulo Santos Campanella PhD, 8/11...Yair Solomon Anderson MS, 8/12 Technion Jordan Forness Heister/Pourpoint MS, 5/13 SpaceX Jennifer Mallory Sojka PhD, 5/12 Western New England

  12. Use of spectroscopic technique to develop a reagent for Mo(VI) utilizing micellar effects on complex formation

    NASA Astrophysics Data System (ADS)

    Taşcioğlu, Sülin; Kaki, E.; Taşcioğlu, Senay

    2012-09-01

    Ultraviolet and visible spectral properties of aqueous solutions of molybdenum(VI) (Mo), gallic acid (GA), Lalanine (Ala), and L-Phenylalanine (Phe), and of their binary and ternary solutions were investigated in the absence and presence of anionic, cationic, and nonionic surfactant micelles. Evaluation of the spectra in a comparative way revealed that both Ala and Phe form ternary complexes with Mo and GA. The formation of a quaternary complex between Mo, GA, Phe, and cetyltrimethylammonium bromide at pH 4.5 provided a reagent system with a strikingly high sensitivity (1.2•106 l/(mol•cm)) for use in the spectrophotometric determination of Mo. A mechanism of micellar effects was discussed in terms of the substrate molecular charge and hydrophobicity, and rationalized on the basis of the spectral data obtained above and below the isoelectric pH of the amino acids.

  13. Soil organic matter regulates molybdenum storage and mobility in forests

    USGS Publications Warehouse

    Marks, Jade A; Perakis, Steven; King, Elizabeth K.; Pett-Ridge, Julie

    2015-01-01

    The trace element molybdenum (Mo) is essential to a suite of nitrogen (N) cycling processes in ecosystems, but there is limited information on its distribution within soils and relationship to plant and bedrock pools. We examined soil, bedrock, and plant Mo variation across 24 forests spanning wide soil pH gradients on both basaltic and sedimentary lithologies in the Oregon Coast Range. We found that the oxidizable organic fraction of surface mineral soil accounted for an average of 33 %of bulk soil Mo across all sites, followed by 1.4 % associated with reducible Fe, Al, and Mn-oxides, and 1.4 % in exchangeable ion form. Exchangeable Mo was greatest at low pH, and its positive correlation with soil carbon (C) suggests organic matter as the source of readily exchangeable Mo. Molybdenum accumulation integrated over soil profiles to 1 m depth (τMoNb) increased with soil C, indicating that soil organic matter regulates long-term Mo retention and loss from soil. Foliar Mo concentrations displayed no relationship with bulk soil Mo, and were not correlated with organic horizon Mo or soil extractable Mo, suggesting active plant regulation of Mo uptake and/or poor fidelity of extractable pools to bioavailability. We estimate from precipitation sampling that atmospheric deposition supplies, on average, over 10 times more Mo annually than does litterfall to soil. In contrast, bedrock lithology had negligible effects on foliar and soil Mo concentrations and on Mo distribution among soil fractions. We conclude that atmospheric inputs may be a significant source of Mo to forest ecosystems, and that strong Mo retention by soil organic matter limits ecosystem Mo loss via dissolution and leaching pathways.

  14. Oxidation-reduction potentials of molybdenum, flavin and iron-sulphur centres in milk xanthine oxidase.

    PubMed Central

    Cammack, R; Barber, M J; Bray, R C

    1976-01-01

    1. The mid-point reduction potentials of the various groups in xanthine oxidase from bovine milk were determined by potentiometric titration with dithionite in the presence of dye mediators, removing samples for quantification of the reduced species by e.p.r. (electron-paramagnetic-resonance) spectroscopy. The values obtained for the functional enzyme in pyrophosphate buffer, pH8.2, are: Fe/S centre I, -343 +/- 15mV; Fe/S II, -303 +/- 15mV; FAD/FADH-; -351 +/- 20mV; FADH/FADH2, -236 +/-mV; Mo(VI)/Mo(V) (Rapid), -355 +/- 20mV; Mo(V) (Rapid)/Mo(IV), -355 +/- 20mV. 2. Behaviour of the functional enzyme is essentially ideal in Tris but less so in pyrophosphate. In Tris, the potential for Mo(VI)/Mo(V) (Rapid) is lowered relative to that in pyrophosphate, but the potential for Fe/S II is raised. The influence of buffer on the potentials was investigated by partial-reduction experiments with six other buffers. 3. Conversion of the enzyme with cyanide into the non-functional form, which gives the Slow molybdenum signal, or alkylation of FAD, has little effect on the mid-point potentials of the other centres. The potentials associated with the Slow signal are: Mo(VI)/Mo(V) (Slow), -440 +/- 25mV; Mo(V) (Slow)/Mo(IV), -480 +/- 25 mV. This signal exhibits very sluggish equilibration with the mediator system. 4. The deviations from ideal behaviour are discussed in terms of possible binding of buffer ions or anti-co-operative interactions amongst the redox centres. PMID:183752

  15. First Trimester Maternal Serum PP13 in the Risk Assessment for Preeclampsia

    PubMed Central

    ROMERO, Roberto; KUSANOVIC, Juan Pedro; THAN, Nandor Gabor; EREZ, Offer; GOTSCH, Francesca; ESPINOZA, Jimmy; EDWIN, Samuel; CHEFETZ, Ilana; GOMEZ, Ricardo; NIEN, Jyh Kae; SAMMAR, Marei; PINELES, Beth; HASSAN, Sonia S.; MEIRI, Hamutal; TAL, Yossi; KUHNREICH, Ido; PAPP, Zoltan; CUCKLE, Howard S.

    2008-01-01

    Objective To determine whether first trimester maternal serum Placental Protein 13 (PP13) concentrations can be used in the risk assessment for preeclampsia. Study Design This case-control study included 50 patients with preeclampsia and 250 patients with normal pregnancies. Samples were collected between 8-13 weeks of gestation. Serum PP13 concentrations were measured by ELISA and expressed as medians and multiples of the median (MoM) for gestational age. Sensitivity and specificity were derived from receiver operating characteristic curve analysis. Results 1) Serum PP13 concentration in the first trimester was significantly lower in patients who developed preterm and early-onset preeclampsia than in those with normal pregnancies; and 2) At 80% specificity, a cutoff of 0.39 MoM had a sensitivity of 100% for early-onset preeclampsia and 85% for preterm preeclampsia. Conclusion Maternal serum first trimester PP13 appears to be a reasonable marker for risk assessment, but a weak marker for severe preeclampsia at term, and ineffective for identifying mild preeclampsia at term. PMID:18539259

  16. Enhanced decolorization of methyl orange in aqueous solution using iron-carbon micro-electrolysis activation of sodium persulfate.

    PubMed

    Li, Peng; Liu, Zhipeng; Wang, Xuegang; Guo, Yadan; Wang, Lizhang

    2017-08-01

    Reactivity of sodium persulfate (PS) in the decolorization of methyl orange (MO) in aqueous solution using an iron-carbon micro-electrolysis (ICE) method was investigated. The effects of sodium persulfate doses, pH, Fe-to-C mass ratios, initial MO concentration as well as the reaction temperature were comprehensively studied in batch experiments. The ICE-PS coupled process was more suitable for wide ranges of pH, initial MO concentration and reaction temperature, accompanied by the reduction of Fe compared ICE. The MO removal efficiency improved substantially by ICE-PS technique, 76.03% for ICE and 91.27% for ICE-PS at experimental conditions of pH 3.0, Fe-to-C mass ratio 3:1, PS addition 10 mM and initial MO concentration 0.61 mM. Furthermore, the biodegradability index (BI) dramatically increased from 0.26 to 0.65. The binary hydroxyl and sulfate radicals that non-selectively degrade MO to the derivatives with small molecules are ascribed to ICE-PS method as detected by the UV-vis spectra. The PS activation resource was Fe 2+ through the hydroxyl radical quenching reaction by the additive tert-butanol (TBA). This study provides an in-depth theoretical understanding of the development and wide commercial application of the ICE technology to refractory industrial dye wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Characterization of hierarchical α-MoO3 plates toward resistive heating synthesis: electrochemical activity of α-MoO3/Pt modified electrode toward methanol oxidation at neutral pH

    NASA Astrophysics Data System (ADS)

    Filippo, Emanuela; Baldassarre, Francesca; Tepore, Marco; Guascito, Maria Rachele; Chirizzi, Daniela; Tepore, Antonio

    2017-05-01

    The growth of MoO3 hierarchical plates was obtained by direct resistive heating of molybdenum foils at ambient pressure in the absence of any catalysts and templates. Plates synthesized after 60 min resistive heating typically grow in an single-crystalline orthorhombic structure that develop preferentially in the [001] direction, and are characterized by high resolution transmission electron microscopy, selected area diffraction pattern and Raman-scattering measurements. They are about 100-200 nm in thickness and a few tens of micrometers in length. As heating time proceeds to 80 min, plates of α-MoO3 form a branched structure. A more attentive look shows that primary plates formed at until 60 min could serve as substrates for the subsequent growth of secondary belts. Moreover, a full electrochemical characterization of α-MoO3 plates on platinum electrodes was done by cyclic voltammetric experiments, at pH 7 in phosphate buffer, to probe the activity of the proposed composite material as anode to methanol electro-oxidation. Reported results indicate that Pt MoO3 modified electrodes are appropriate to develop new an amperometric non-enzymatic sensor for methanol as well as to make anodes suitable to be used in direct methanol fuel cells working at neutral pH.

  18. An electrochemical investigation of TMJ implant metal alloys in an artificial joint fluid environment: the influence of pH variation.

    PubMed

    Royhman, Dmitry; Radhakrishnan, Rashmi; Yuan, Judy Chia-Chun; Mathew, Mathew T; Mercuri, Louis G; Sukotjo, Cortino

    2014-10-01

    To investigate the corrosion behaviour of commonly used TMJ implants alloys (CoCrMo and Ti6Al4V) under simulated physiological conditions. Corrosion behaviour was evaluated using standard electrochemical corrosion techniques and galvanic corrosion techniques as per ASTM standards. Standard electrochemical tests (E(corr), I(corr), R(p) and C(f)) were conducted in bovine calf serum (BCS), as a function of alloys type and different pHs. Galvanic corrosion tests were conducted in BCS at a pH of 7.6. Alloy surfaces were characterized using white-light interferometry (WLI) and scanning electron microscopy (SEM). The potentiodynamic test results exhibited the enhanced passive layer growth and a better corrosion resistance of Ti6Al4V compared to CoCrMo. Electrochemical impedance spectroscopy measurements demonstrated the influence of protein as a function of pH on corrosion mechanisms/kinetics. Galvanic coupling was not a major contributor to corrosion. SEM and WLI images demonstrated a significantly higher in surface roughness in CoCrMo after corrosion. The results of this study suggest that Ti6Al4V shows superior corrosion behaviour to CoCrMo due to its strong passive layer, simulated joint fluid components can affect the electrochemical nature of the metal/electrolyte interface as a function of pH, and the galvanic effect of coupling CoCrMo and Ti6Al4V in a single joint is weak. Published by Elsevier Ltd.

  19. Kinetic studies of the acylation of pig muscle–d-glyceraldehyde 3-phosphate dehydrogenase by 1,3-diphosphoglycerate and of proton uptake and release in the overall enzyme mechanism

    PubMed Central

    Harrigan, P. J.; Trentham, D. R.

    1973-01-01

    In the presence of NAD+ the acylation by 1,3-diphosphoglycerate of the four active sites of pig muscle d-glyceraldehyde 3-phosphate dehydrogenase can be monitored at 365nm by the disappearance of the absorption band present in the binary complex of NAD+ and the enzyme. A non-specific salt effect decreased the acylation rate 25-fold when the ionic strength was increased from 0.10 to 1.0. This caused acylation to be the rate-limiting process in the enzyme-catalysed reductive dephosphorylation of 1,3-diphosphoglycerate at high ionic strength at pH8. The salt effect permitted investigation of the acylation over a wide range of conditions. Variation of pH from 5.4 to 8.6 produced at most a two-fold change in the acylation rate. One proton was taken up per site acylated at pH8.0. By using a chromophoric H+ indicator the rate of proton uptake could be monitored during the acylation and was also almost invariant in the pH range 5.5–8.5. Transient kinetic studies of the overall enzyme-catalysed reaction indicated that acylation was the process involving proton uptake at pH8.0. The enzyme mechanism is discussed in the light of these results. PMID:4360248

  20. Impact of saline aquifer water on surface and shallow pit corrosion of martensitic stainless steels during exposure to CO2 environment (CCS)

    NASA Astrophysics Data System (ADS)

    Pfennig, Anja; Kranzmann, Axel

    2018-05-01

    Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Main corrosion products are FeCO3 and FeOOH. Corrosion rates obtained at 100 bar are generally much lower than those measured at ambient pressure. Highest surface corrosion rates are 0.8 mm/year for 42CrMo4 and lowest 0.01 mm/year for X5CrNiCuNb16-4 in the vapour phase at ambient pressure. At 100 bar the highest corrosion rates are 0.01 mm/year for 42CrMo4, X20Cr13 (liquid phase), X46Cr13 and less than 0.01 mm/year for X35CrMo4 and X5CrNiCuNb16-4 after 8000 h of exposure with no regard to atmosphere. Martensitic microstructure offers good corrosion resistance.

  1. Performance comparison of protonic and sodium phosphomolybdovanadate polyoxoanion catholytes within a chemically regenerative redox cathode polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Ward, David B.; Gunn, Natasha L. O.; Uwigena, Nadine; Davies, Trevor J.

    2018-01-01

    The direct reduction of oxygen in conventional polymer electrolyte fuel cells (PEFCs) is seen by many researchers as a key challenge in PEFC development. Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells offer an alternative approach via the indirect reduction of oxygen, improving durability and reducing cost. These systems substitute gaseous oxygen for a liquid catalyst that is reduced at the cathode then oxidised in a regeneration vessel via air bubbling. A key component of a CRRC system is the liquid catalyst or catholyte. To date, phosphomolybdovanadium polyoxometalates with empirical formula H3+nPVnMo12-nO40 have shown the most promise for CRRC PEFC systems. In this work, four catholyte formulations are studied and compared against each other. The catholytes vary in vanadium content, pH and counter ion, with empirical formulas H6PV3Mo9O40, H7PV4Mo8O40, Na3H3PV3Mo9O40 and Na4H3PV4Mo8O40. Thermodynamic properties, cell performance and regeneration rates are measured, generating new insights into how formulation chemistry affects the components of a CRRC system. The results include the best CRRC PEFC performance reported to date, with noticeable advantages over conventional PEFCs. The optimum catholyte formulation is then determined via steady state tests, the results of which will guide further optimization of the catholyte formulation.

  2. Syntheses and characterization of phosphonates and diphosphonates of molybdenum, A4[(MoO3)5(O3PR)2]·xH2O, A2[Mo2O5(O3PR)2] and A2[Mo2O5(O3P-R-PO3)] (A = K, Rb, Cs, Tl, NH4).

    PubMed

    Elias Jesu Packiam, D; Vidyasagar, Kanamaluru

    2017-11-28

    Twenty new molybdenum phosphonates and diphosphonates have been synthesized and structurally characterized by single crystal and powder X-ray diffraction, CHN analyses, spectroscopic and thermal studies. Four of them are molecular phenyl- and benzyl-phosphonates containing discrete [(MoO 3 ) 5 (O 3 PR) 2 ] 4- (R = Ph or CH 2 Ph) cyclic anions. The sixteen non-molecular compounds are layered isostructural phenylphosphonates, A 2 [Mo 2 O 5 (O 3 PPh) 2 ] (A = NH 4 , Tl, Rb, Cs) and K 1.5 (H 3 O) 0.5 [Mo 2 O 5 (O 3 PPh) 2 ] and the corresponding diphosphonate compounds with pillared anionic layers, A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 3 PO 3 )], A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 4 PO 3 )] and A 2 [Mo 2 O 5 (O 3 P(C 6 H 4 )PO 3 )]. The A + ions reside in the interlayer region as well as in the cavities within the anionic layers.

  3. Changes in hip abductor moment 3 or more years after femoral derotation osteotomy among individuals with cerebral palsy.

    PubMed

    Boyer, Elizabeth R; Novacheck, Tom F; Schwartz, Michael H

    2017-09-01

    To examine the effect of femoral derotation osteotomy (FDO) on dimensionless hip abductor moment during gait in children with cerebral palsy. We retrospectively analyzed data from independent ambulators within our database. Postoperative visits 1 year (short-term) and at least 3 years (mid-term) were analyzed. We estimated the coronal plane hip abductor moment arm based on musculoskeletal modeling that accounted for anteversion and hip rotation. There were 140 individuals with a short-term analysis (77 males, 63 females; age at surgery 9y 11mo [range 4y 5mo-17y 5mo]) and 29 with mid-term analysis (15 males, 14 females; age at surgery 8y 7mo [range 4y 5mo-13y 1mo]). At short-term, anteversion and internal hip rotation decreased 35° and 13° respectively, which increased median (IQR) moment arms from 20 (23) per cent below normal to 2 (12) per cent above normal. Dimensionless mean hip abductor moment remained unchanged at short-term. Mid-term anteversion did not change but hip rotation increased 8° and hip abductor moment increased to 0.040 (0.029). There was no change in pelvic and trunk obliquity, although hip abductor strength increased and walking velocity decreased at mid-term. The unexpected lack of improvement in hip abductor moment from pre- to short-term may be caused by gait compensations that unload the hip. The increase in hip abductor moment beyond 3 years postoperatively underscores the benefits of an FDO into adolescence for independent ambulating individuals with cerebral palsy. © 2017 Mac Keith Press.

  4. Validation of reaching in a virtual environment in typically developing children and children with mild unilateral cerebral palsy.

    PubMed

    Robert, Maxime T; Levin, Mindy F

    2018-04-01

    To compare three reaching movements made in two planes between a low-cost, game-based virtual reality and a matched physical environment in typically developing children and children with cerebral palsy (CP). To determine if differences in kinematics are related to sensory deficits. An observational study in which 27 children (typically developing, n=17, mean age 13y, [SD] 2y 2mo, range 9y 3mo-17y 2mo; CP, n=10, mean age 13y 8mo, [SD] 1y 8mo, range 11y 1mo-17y 1mo, Manual Ability Classification System levels I-II) performed 15 trials of three gestures in each of a virtual reality and a matched physical environment. Upper-limb and trunk kinematics were recorded using an electromagnetic system (G4, Polhemus, six markers, 120Hz). Compared to the physical environment, movements in virtual reality made by typically developing children were slower (p=0.002), and involved less trunk flexion (p=0.002) and rotation (p=0.026). Children with CP had more curved trajectories (p=0.005) and used less trunk flexion (p=0.003) and rotation (p=0.005). Elbow and shoulder kinematics differed from 2.8% to 155.4% between environments in both groups. Between groups, there were small, clinically insignificant differences with only the vertical gesture being longer in typically developing children. Children with CP who had greater tactile impairment used more trunk displacement. Clinicians and researchers need to be aware of differences in movement variables when setting goals or designing protocols for improving reaching in children with CP using low-cost, game-based virtual reality systems. Upper-limb kinematics differed in each group when reaching in physical versus virtual environments. There were small differences in movements made by children with mild unilateral cerebral palsy (CP) compared to typically developing children. Differences in reaching kinematics should be considered when goal setting using virtual reality interventions for children with mild unilateral CP. © 2018 Mac Keith Press.

  5. The effect of redox-active cyanomanganese(I) ligands on intramolecular electron transfer to, and alkyne alignment in, M(CO)(RC[triple bond, length as m-dash]CR)Tp' (M = Mo or W) units.

    PubMed

    Adams, Christopher J; Connelly, Neil G; Onganusorn, Sriwipha

    2009-04-28

    The complexes [(eta-C(5)Me(5))(ON)LMn(micro-CN)M(CO)(RC[triple bond, length as m-dash]CR)Tp'](+) (L = CNXyl, M = Mo; L = CNBu(t), M = Mo or W, R = Ph or Me) and trans- or cis-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-CN)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+), and their linkage isomers [(eta-C(5)Me(5))(ON)LMn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) and trans- or cis-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+), undergo two one-electron oxidations. The complexes [(eta-C(5)Me(5))(ON)LMn(micro-XY)M(CO)(RC[triple bond, length as m-dash]CR)Tp'](+) (XY = CN or NC) are oxidised first at the N-bound metal centre and then at the C-bound centre. For [(dppm){(EtO)(3)P}(OC)(2)Mn(micro-XY)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+), the trans isomers are first oxidised at manganese whereas the cis isomers are first oxidised at M. Thus, the order of one-electron oxidation of the two series of binuclear monocations is influenced by linkage isomerisation of the cyanide bridge and cis-trans isomerisation of the Mn(CO)(2) group. IR spectroscopic changes on reaction of Ag(+) with [(eta-C(5)Me(5))(ON)(Bu(t)NC)Mn(micro-CN)W(CO)(MeC[triple bond, length as m-dash]CMe)Tp'](+) are consistent with one-electron at the N-bound tungsten centre. Likewise, trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) (M = Mo or W) give the stable dications [(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)M(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](2+). Significantly longer Mn-P bond distances in trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)Mo(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](2+) than in trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)Mo(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) are consistent with one-electron oxidation first at Mn(I); the alignment of the (CN)Mn(CO)(2){P(OEt)(3)}(dppm) fragment relative to the alkyne in trans-[(dppm){(EtO)(3)P}(OC)(2)Mn(micro-NC)Mo(CO)(PhC[triple bond, length as m-dash]CPh)Tp'](+) suggests it acts as a pi-acceptor, in contrast to related species such as trans-(NC)Mn(CO)(2){P(OEt)(3)}(dppm) and (NC)Mn(NO){P(OPh)(3)}(pi-C(5)H(4)Me) which behave as simple N-donors.

  6. Controllable synthesis of Bi2MoO6 nanosheets and their facet-dependent visible-light-driven photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Yang, Zixin; Shen, Min; Dai, Ke; Zhang, Xuehao; Chen, Hao

    2018-02-01

    Bi2MoO6 nanosheets with exposed {010} facets were selectively synthesized through hydrothermal method by adjusting the pH value in the presence of cetyltrimethyl ammonium bromide (CTAB) as the templates. The effects of CTAB content and hydrothermal conditions on the morphologies and crystal phases of the products were determined by using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-vis diffuse reflectance spectroscopy (DRS), Fourier-transform infrared spectroscopy (FTIR), Raman spectrometry, and Brunauer-Emmett-Teller surface area analyses. It is found that Bi2MoO6 nanosheets with relatively large particle sizes (plate length 0.5-3 μm) and special anisotropic growth along the {010} plane can be obtained from an alkaline hydrothermal environment. The band gap of Bi2MoO6 can be fine-tuned from 2.30 to 2.57 eV by adjusting the pH value of hydrothermal solution. The pH value has a significant effect on the composition of hydrothermal precursors, which results in Bi2MoO6 nanosheets with different ratio of {010} faces, especially the formation of Bi2O3 in the primary stage of the hydrothermal treatment is a key factor for the exposure of {010} facets. The visible-light-driven photocatalytic activities of the Bi2MoO6 products with different ratio of {010} facets exposed are investigated through the degradation of Rhodamine B, oxytetracycline, and tetracycline. Bi2MoO6 nanosheets synthesized at pH 10.0 with highest {010} facet exposed ratio exhibited highly efficient visible light photocatalytic activity for pollutant decomposition, which can be mainly attributed to the flake structures, the crystallinity and most importantly, the exposed {010} facet which generate high concentration of rad O2-.

  7. Kinetically designed conditions for the catalytic formation of disfavored products. The reaction of ({eta}{sup 5}-C{sub 5}H{sub 5})Mo(CO){sub 3}* with N,N,N{prime},N{prime}-tetramethyl-1,4-phenylenediamine

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

    Balla, J.; Espenson, J.H.; Bakac, A.

    1995-03-16

    In the absence of other reagents, the 17e molybdenum radical, ($eta{sup 5}-C{sub 5}H{sub 5})Mo(CO){sub 3}*, combines to form the stable dimer, [CpMo(CO){sub 3}]{sub 2}. In the presence of TMPD, however, an electron transfer process ensues, in which the normally persistent radical TMPD*{sup +} is produced. Under these conditions, the absorbance of the TMPD*{sup +} radical disappear shortly thereafter. Various kinetic tests have been applied to show that this is the result of a sequence of two electron transfer steps. One is the reaction between CpMo(CO){sub 3}* (Mo*) and TMPD, and the other is the reaction between Mo* and TMPD*{sup +}.more » The net result of the two reactions occurring in sequence is the disproportionation of the molybdenum radical, rather than the combination reaction that occurs in the absence of this redox-active amine. To the contrary, PhNMe{sub 2} shows no such effect, confirming that these observations are correctly attributed to electron transfer and not to ligand-catalyzed disproportionation. That the TMPD-catalyzed sequence really is disproportionation was confirmed by the chemical identification of the products, CpMo(CO){sub 3}{sup -} and CpMo(CO){sub 3}NCCH{sub 3}{sup +}. 40 refs., 8 figs., 1 tab.« less

  8. Application of ESI-HRMS for molybdenum speciation in natural waters: An investigation of molybdate-halide reactions.

    PubMed

    Dang, Duc Huy; Evans, R Douglas

    2018-03-01

    High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO 3 Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO 4 2- to HMoO 4 - ) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Enhanced field emission performance of NiMoO4 nanosheets by tuning the phase

    NASA Astrophysics Data System (ADS)

    Bankar, Prashant K.; Ratha, Satyajit; More, Mahendra A.; Late, Dattatray J.; Rout, Chandra Sekhar

    2017-10-01

    In this paper we report, large scale synthesis of α and β-NiMoO4 by a facile hydrothermal method and we observed that urea plays important role on the growth of β-NiMoO4 nanosheets. We have also carried out field emission (FE) investigations of α and β-NiMoO4 at a base pressure of ∼1 × 10-8 mbar. The obtained turn-on field at emission current density of 1 μA/cm2 for β-NiMoO4 nanosheets and α -NiMoO4 is 1.3 V/μm and 2.2 V/μm respectively were observed. The maximum field emission current density of 1.006 mA/cm2at an applied electric field of 2.7 V/μm was achieved for β-NiMoO4 nanosheets. Furthermore, we found that the β-NiMoO4 nanosheets possess good field emission performance compared to α-NiMoO4. The results indicate that NiMoO4can be used as a promising material in FE applications with possibility of tuning field emission performance by controlling the phase.

  10. Excellent mechanical properties and resistance to cavitation erosion for an ultra-low carbon CrMnN stainless steel through quenching and partitioning treatment

    NASA Astrophysics Data System (ADS)

    Zhou, Ze-an; Fu, Wan-tang; Zhu, Zhe; Li, Bin; Shi, Zhong-ping; Sun, Shu-hua

    2018-05-01

    The retained austenite content (RAC), the mechanical properties, and the resistance to cavitation erosion (CE) of the 00Cr13Mn8MoN steel after quenching and partitioning (Q&P) processing were investigated. The results show that the Q&P process affected the RAC, which reached the maximum value after partitioning at 400°C for 10 min. The tensile strength of the steel slightly decreased with increasing partitioning temperature and time. However, the elongation and product of strength and elongation first increased and then decreased. The sample partitioned at 400°C for 10 min exhibited the optimal property: a strength-ductility of 23.8 GPa·%. The resistance to CE for the 00Cr13Mn8MoN steel treated by the Q&P process was improved due to work hardening, spalling, and cavitation-induced martensitic transformation of the retained austenite.

  11. NTF: Soldering Technology Development for Cryogenics

    NASA Technical Reports Server (NTRS)

    Hall, E. T., Jr.

    1985-01-01

    The advent of the National Transonic Facility (NTF) brought about a new application for an old joining method, soldering. Soldering for use at cryogenic temperatures requires that solders remain ductile and free from tin-pest (grey tin), have toughness to withstand aerodynamic loads associated with flight research, and maintain their surface finishes. Solders are used to attach 347 Stainless-Steel tubing in surface grooves of models. The solder must fill up the gap and metallurgically bound to the tubing and model. Cryogenic temperatures require that only specific materials for models can be used, including: Vasco Max 200 CVM, lescalloy A-286 Vac Arc, pH 13-8 Mo. Solders identified for testing at this time are: 50% Sn - 49.5% Pb - 0.5% Sb, 95% Sn - 5% Sb, 50% In 50% Pb, and 37.5% Sn - 37.5% Pb - 25% In. With these materials and solders, it is necessary to determine their solderability. After solderability is determined, tube/groove specimens are fabricated and stressed under cryogenic temperatures. Compatible solders are then used for acutual models.

  12. Corrosion fatigue of high strength fastener materials in seawater. Final report

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

    Tipton, D.G.

    1983-12-01

    Environmental effects can significantly reduce the fatigue life of metals. As such, corrosion fatigue is a major concern in the engineering application of high strength fasteners in marine environments. The corrosion fatigue failure of an AISI 41L40 high strength steel blade-to-hub attachment bolt at the MOD-0A 200 kW wind turbine generator in Oahu, Hawaii prompted the current test program. Tests were undertaken to confirm the dramatic reduction of fatigue strength of AISI 41L40 in marine environments and to obtain similar corrosion fatigue data for candidate replacement materials. AISI 41L40, AISI 4140, PH 13-8Mo stainless steel, alloy 718 and alloy MP-35Nmore » were tested in axial fatigue at a frequency of 20 Hz in dry air and natural seawater. The fatigue data were fitted by regression equations to allow determination of fatigue strength for a given number of cycles to failure.« less

  13. [Study of the stability of pyrimido-[5,4-e]-1,2,4-triazine antibiotics in acid-base media by NMR spectroscopy].

    PubMed

    Esipov, S E; Chernyshev, A I; Shorshnev, S V; Iakushkina, N I; Antonovskiĭ, V L

    1985-02-01

    A comparative study of the NMR 1H and 13C spectra of reumycin, fervenulin and xanthothricin in aqueous acid-base media showed that at pH or pD ranging from 8.0 to 1.0 the antibiotics were chemically stable. By the ratio of the 1H and 13C chemical shifts of reumycin at pH 4.0-10.0 the pKa values of this antibiotic were determined: 6.7 in aqueous (D2O) solution and 8.76 in dimethylsulfoxide media. Alkalization of the solutions of reumycin (pH 12.0), fervenulin (pH 9.0) and xanthothricin (pH 8.0) resulted in irreversible chemical transformation of the antibiotics. The analysis of the chemical shifts in the PMR spectra of the transformation products revealed transformation of the uracil ring in reumycin and uracil and triazine rings in fervenulin and xanthothricin. Alkalization of the xanthothricin solutions resulted also in demethylation with formation of reumycin.

  14. Infrequent composted biosolids applications affect semi-arid grassland soils and vegetation.

    PubMed

    Ippolito, J A; Barbarick, K A; Paschke, M W; Brobst, R B

    2010-05-01

    Monitoring of repeated composted biosolids applications is necessary for improving beneficial reuse program management strategies, because materials will likely be reapplied to the same site at a future point in time. A field trial evaluated a single and a repeated composted biosolids application in terms of long-term (13-14 years) and short-term (2-3 years) effects, respectively, on soil chemistry and plant community in a Colorado semi-arid grassland. Six composted biosolids rates (0, 2.5, 5, 10, 21, 30 Mg ha(-1)) were surface applied in a split-plot design study with treatment (increasing compost rates) as the main factor and co-application time (1991, or 1991 and 2002) as the split factor applications. Short- and long-term treatment effects were evident in 2004 and 2005 for soil 0-8 cm depth pH, EC, NO(3)-N, NH(4)-N, total N, and AB-DTPA soil Cd, Cu, Mo, Zn, P, and Ba. Soil organic matter increases were still evident 13 and 14 years following composted biosolids application. The repeated composted biosolids application increased soil NO(3)-N and NH(4)-N and decreased AB-DTPA extractable Ba as compared to the single composted biosolids application in 2004; differences between short- and long-term applications were less evident in 2005. Increasing biosolids rates resulted in increased native perennial grass cover in 2005. Plant tissue Cu, Mo, Zn, and P concentrations increased, while Ba content decreased depending on specific plant species and year. Overall, the lack of many significant negative effects suggests that short- or long-term composted biosolids application at the rates studied did not adversely affect this semi-arid grassland ecosystem. Published by Elsevier Ltd.

  15. Extraordinary selectivity of CoMo{sub 3}S{sub 13} chalcogel for C{sub 2}H{sub 6} and CO{sub 2} adsorption.

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

    Shafaei-Fallah, M.; Rothenberger, Z.; Katsoulidis, A. P.

    The chalcogel CoMo{sub 3}S{sub 13} is obtained from the reaction of (NH{sub 4}){sub 2}[Mo{sub 3}S{sub 13}] with cobalt acetate in solution. The chalcogel has a BET surface area of 570 m{sup 2} g{sup -1}, and pair distribution function analysis (PDF) and infrared spectroscopy indicate that the [Mo{sub 3}S{sub 13}]{sup 2-} cluster is a building block in the porous network. The CoMo{sub 3}S{sub 13} chalcogel exhibits high selectivity for separating ethane and carbon dioxide from hydrogen and methane.

  16. Performance and Metabolism of Calves Fed Starter Feed Containing Sugarcane Molasses or Glucose Syrup as a Replacement for Corn.

    PubMed

    Oltramari, C E; Nápoles, G G O; De Paula, M R; Silva, J T; Gallo, M P C; Pasetti, M H O; Bittar, C M M

    2016-07-01

    The aim of this study was to evaluate the effect of replacing corn grain for sugar cane molasses (MO) or glucose syrup (GS) in the starter concentrate on performance and metabolism of dairy calves. Thirty-six individually housed Holstein male calves were blocked according to weight and date of birth and assigned to one of the starter feed treatments, during an 8 week study: i) starter containing 65% corn with no MO or GS (0MO); ii) starter containing 60% corn and 5% MO (5MO); iii) starter containing 55% corn and 10% MO (10MO); and iv) starter containing 60% corn and 5% GS (5GS). Animals received 4 L of milk replacer daily (20 crude protein, 16 ether extract, 12.5% solids), divided in two meals (0700 and 1700 h). Starter and water were provided ad libitum. Starter intake and fecal score were monitored daily until animals were eight weeks old. Body weight and measurements (withers height, hip width and heart girth) were measured weekly before the morning feeding. From the second week of age, blood samples were collected weekly, 2 h after the morning feeding, for glucose, β-hydroxybutyrate and lactate determination. Ruminal fluid was collected at 4, 6, and 8 weeks of age using an oro-ruminal probe and a suction pump for determination of pH and short-chain fatty acids (SCFA). At the end of the eighth week, animals were harvested to evaluate development of the proximal digestive tract. The composition of the starter did not affect (p>0.05) concentrate intake, weight gain, fecal score, blood parameters, and rumen development. However, treatment 5MO showed higher (p<0.05) total concentration of SCFAs, acetate and propionate than 0MO, and these treatments did not differ from 10MO and 5GS (p>0.05). Thus, it can be concluded that the replacement of corn by 5% or 10% sugar cane molasses or 5% GS on starter concentrate did not impact performance, however it has some positive effects on rumen fermentation which may be beneficial for calves with a developing rumen.

  17. SHINE and Mini-SHINE Column Designs for Recovery of Mo from 140 g-U/L Uranyl Sulfate

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

    Stepinski, Dominique C.; Vandegrift, George F.

    Argonne is assisting SHINE Medical Technologies (SHINE) in their efforts to develop an accelerator-driven process that utilizes a uranyl-sulfate solution for the production of fission Mo-99. In an effort to design a Mo-recovery system for the SHINE project using low-enriched uranium (LEU), we conducted batch, breakthrough, and pulse tests to determine the Mo isotherm, mass-transfer zone (MTZ), and system parameters for a 130 g-U/L uranyl sulfate solution at pH 1 and 80°C, as described previously. The VERSE program was utilized to calculate the MTZ under various loading times and velocities. The results were then used to design Mo separation andmore » recovery columns employing a pure titania sorbent (110-μm particles, S110, and 60 Å pore size). The plant-scale column designs assume Mo will be separated from 271 L of a 141 g-U/L uranyl sulfate solution, pH 1, containing 0.0023 mM Mo. The VERSE-designed recovery systems have been tested and verified in laboratory-scale experiments, and this approach was found to be very successful.« less

  18. Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

    DOE PAGES

    Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie; ...

    2017-09-22

    Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

  19. Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

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

    Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie

    Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

  20. Search for Magnetic Monopoles with the MoEDAL Forward Trapping Detector in 13 TeV Proton-Proton Collisions at the LHC.

    PubMed

    Acharya, B; Alexandre, J; Baines, S; Benes, P; Bergmann, B; Bernabéu, J; Branzas, H; Campbell, M; Caramete, L; Cecchini, S; de Montigny, M; De Roeck, A; Ellis, J R; Fairbairn, M; Felea, D; Flores, J; Frank, M; Frekers, D; Garcia, C; Hirt, A M; Janecek, J; Kalliokoski, M; Katre, A; Kim, D-W; Kinoshita, K; Korzenev, A; Lacarrère, D H; Lee, S C; Leroy, C; Lionti, A; Mamuzic, J; Margiotta, A; Mauri, N; Mavromatos, N E; Mermod, P; Mitsou, V A; Orava, R; Parker, B; Pasqualini, L; Patrizii, L; Păvălaş, G E; Pinfold, J L; Popa, V; Pozzato, M; Pospisil, S; Rajantie, A; Ruiz de Austri, R; Sahnoun, Z; Sakellariadou, M; Sarkar, S; Semenoff, G; Shaa, A; Sirri, G; Sliwa, K; Soluk, R; Spurio, M; Srivastava, Y N; Suk, M; Swain, J; Tenti, M; Togo, V; Tuszyński, J A; Vento, V; Vives, O; Vykydal, Z; Whyntie, T; Widom, A; Willems, G; Yoon, J H; Zgura, I S

    2017-02-10

    MoEDAL is designed to identify new physics in the form of long-lived highly ionizing particles produced in high-energy LHC collisions. Its arrays of plastic nuclear-track detectors and aluminium trapping volumes provide two independent passive detection techniques. We present here the results of a first search for magnetic monopole production in 13 TeV proton-proton collisions using the trapping technique, extending a previous publication with 8 TeV data during LHC Run 1. A total of 222 kg of MoEDAL trapping detector samples was exposed in the forward region and analyzed by searching for induced persistent currents after passage through a superconducting magnetometer. Magnetic charges exceeding half the Dirac charge are excluded in all samples and limits are placed for the first time on the production of magnetic monopoles in 13 TeV pp collisions. The search probes mass ranges previously inaccessible to collider experiments for up to five times the Dirac charge.

  1. [The design of Co-Cr-Mo alloy combining the framework with porcelain fused to metal restorations and determination of the mechanical properties].

    PubMed

    Chao, Yong-lie; Lui, Chang-hong; Li, Ning; Yang, Xiao-yu

    2005-02-01

    To investigate a kind of Co-Cr-Mo alloys used for both porcelain fused to metal (PFM) restorations and casting framework of removable partial dentures. The Co-Cr-Mo alloy underwent the design for elementary compositions of the alloys and the production from the raw materials by means of a vacuum melt furnace. The strength, hardness, plasticity and casting ability of the alloy were examined with metal tensile test. Vickers hardness test and grid casting were examined respectively. The microstructure of the Co-Cr-Mo alloy was also inspected by scanning electron microscope and X-ray diffraction analysis. The elementary composition of DA9-4 alloy mainly consisted of Co 54%-67%, Cr 21%-26%, Mo 5%-8%, W 5%-8%, Si 1%-3%, Mn 0.1%-0.25% and trace elements. The yield strength of the alloy was 584 MPa, while the tensile strength was 736 MPa. The coefficient of expansion was 15.0%, the Vickers hardness reached 322, and the casting ratio exibited 100%. The DA9-4 Co-Cr-Mo alloy used for PFM and framework shown in this paper can meet the clinical demands and have reached the objects of the experiment plan.

  2. Defective motion processing in children with cerebral visual impairment due to periventricular white matter damage.

    PubMed

    Weinstein, Joel M; Gilmore, Rick O; Shaikh, Sumera M; Kunselman, Allen R; Trescher, William V; Tashima, Lauren M; Boltz, Marianne E; McAuliffe, Matthew B; Cheung, Albert; Fesi, Jeremy D

    2012-07-01

    We sought to characterize visual motion processing in children with cerebral visual impairment (CVI) due to periventricular white matter damage caused by either hydrocephalus (eight individuals) or periventricular leukomalacia (PVL) associated with prematurity (11 individuals). Using steady-state visually evoked potentials (ssVEP), we measured cortical activity related to motion processing for two distinct types of visual stimuli: 'local' motion patterns thought to activate mainly primary visual cortex (V1), and 'global' or coherent patterns thought to activate higher cortical visual association areas (V3, V5, etc.). We studied three groups of children: (1) 19 children with CVI (mean age 9y 6mo [SD 3y 8mo]; 9 male; 10 female); (2) 40 neurologically and visually normal comparison children (mean age 9y 6mo [SD 3y 1mo]; 18 male; 22 female); and (3) because strabismus and amblyopia are common in children with CVI, a group of 41 children without neurological problems who had visual deficits due to amblyopia and/or strabismus (mean age 7y 8mo [SD 2y 8mo]; 28 male; 13 female). We found that the processing of global as opposed to local motion was preferentially impaired in individuals with CVI, especially for slower target velocities (p=0.028). Motion processing is impaired in children with CVI. ssVEP may provide useful and objective information about the development of higher visual function in children at risk for CVI. © The Authors. Journal compilation © Mac Keith Press 2011.

  3. Selective Electrocatalytic Reduction of Nitrite to Dinitrogen Based on Decoupled Proton-Electron Transfer.

    PubMed

    He, Daoping; Li, Yamei; Ooka, Hideshi; Go, Yoo Kyung; Jin, Fangming; Kim, Sun Hee; Nakamura, Ryuhei

    2018-02-14

    The development of denitrification catalysts which can reduce nitrate and nitrite to dinitrogen is critical for sustaining the nitrogen cycle. However, regulating the selectivity has proven to be a challenge, due to the difficulty of controlling complex multielectron/proton reactions. Here we report that utilizing sequential proton-electron transfer (SPET) pathways is a viable strategy to enhance the selectivity of electrochemical reactions. The selectivity of an oxo-molybdenum sulfide electrocatalyst toward nitrite reduction to dinitrogen exhibited a volcano-type pH dependence with a maximum at pH 5. The pH-dependent formation of the intermediate species (distorted Mo(V) oxo species) identified using operando electron paramagnetic resonance (EPR) and Raman spectroscopy was in accord with a mathematical prediction that the pK a of the reaction intermediates determines the pH-dependence of the SPET-derived product. By utilizing this acute pH dependence, we achieved a Faradaic efficiency of 13.5% for nitrite reduction to dinitrogen, which is the highest value reported to date under neutral conditions.

  4. Roles of Bridging Ligand Topology and Conformation in Controlling Exchange Interactions between Paramagnetic Molybdenum Fragments in Dinuclear and Trinuclear Complexes.

    PubMed

    Ung VÂ, V&acaron;n Ân; Cargill Thompson, Alexander M. W.; Bardwell, David A.; Gatteschi, Dante; Jeffery, John C.; McCleverty, Jon A.; Totti, Federico; Ward, Michael D.

    1997-07-30

    The magnetic properties of two series of dinuclear complexes, and one trinuclear complex, have been examined as a function of the bridging pathway between the metal centers. The first series of dinuclear complexes is [{Mo(V)(O)(Tp)Cl}(2)(&mgr;-OO)], where "OO" is [1,4-O(C(6)H(4))(n)O](2)(-) (n = 1, 1; n = 2, 3), [4,4'-O(C(6)H(3)-2-Me)(2)O](2)(-) (4), or [1,3-OC(6)H(4)O](2)(-) (2) [Tp = tris(3,5-dimethylpyrazolyl)hydroborate]. The second series of dinuclear complexes is [{Mo(I)(NO)(Tp)Cl}(2)(&mgr;-NN)], where "NN" is 4,4'-bipyridyl (5), 3,3'-dimethyl-4,4'-bipyridine (6), 3,8-phenanthroline (7), or 2,7-diazapyrene (8). The trinuclear complex is [{Mo(V)(O)(Tp)Cl}(3)(1,3,5-C(6)H(3)O(3))] (9), whose crystal structure was determined [9.5CH(2)Cl(2): C(56)H(81)B(3)Cl(13)Mo(3)N(18)O(6); monoclinic, P2(1)/n; a = 13.443, b = 41.46(2), c = 14.314(6) Å; beta = 93.21(3) degrees; V = 7995(5) Å(3); Z = 4; R(1) = 0.106]. In these complexes, the sign and magnitude of the exchange coupling constant J is clearly related to both the topology and the conformation of the bridging ligand [where J is derived from H = -JS(1)().S(2)() for 1-8 and H = -J(S(1)().S(2)() + S(2)().S(3)() + S(1)().S(3)()) for 9]. The values are as follows: 1, -80 cm(-)(1); 2, +9.8 cm(-)(1); 3, -13.2 cm(-)(1); 4, -2.8 cm(-)(1); 5, -33 cm(-)(1); 6, -3.5 cm(-)(1); 7, -35.6 cm(-)(1); 8, -35.0 cm(-)(1); 9, +14.4 cm(-)(1). In particular the following holds: (1) J is negative (antiferromagnetic exchange) across the para-substituted bridges ligands of 1 and 3-8 but positive (ferromagnetic exchange) across the meta-substituted bridging ligands of 2 and 9. (2) J decreases in magnitude dramatically as the bridging ligand conformation changes from planar to twisted (compare 3 and 4, or 6 and 8). These observations are consistent with a spin-polarization mechanism for the exchange interaction, propagated across the pi-system of the bridging ligand by via overlap of bridging ligand p(pi) orbitals with the d(pi) magnetic orbitals of the metals. The EPR spectrum of 9 is characteristic of a quartet species and shows weak Deltam(s) = 2 and Deltam(s) = 3 transitions at one-half and one-third, respectively, of the field strength of the principal Deltam(s) = 1 component.

  5. Thermal conduction properties of Mo/Si multilayers for extreme ultraviolet optics

    NASA Astrophysics Data System (ADS)

    Bozorg-Grayeli, Elah; Li, Zijian; Asheghi, Mehdi; Delgado, Gil; Pokrovsky, Alexander; Panzer, Matthew; Wack, Daniel; Goodson, Kenneth E.

    2012-10-01

    Extreme ultraviolet (EUV) lithography requires nanostructured optical components, whose reliability can be influenced by radiation absorption and thermal conduction. Thermal conduction analysis is complicated by sub-continuum electron and phonon transport and the lack of thermal property data. This paper measures and interprets thermal property data, and their evolution due to heating exposure, for Mo/Si EUV mirrors with 6.9 nm period and Mo/Si thickness ratios of 0.4/0.6 and 0.6/0.4. We use time-domain thermoreflectance and the 3ω method to estimate the thermal resistance between the Ru capping layer and the Mo/Si multilayers (RRu-Mo/Si = 1.5 m2 K GW-1), as well as the out-of-plane thermal conductivity (kMo/Si 1.1 W m-1 K-1) and thermal anisotropy (η = 13). This work also reports the impact of annealing on thermal conduction in a co-deposited MoSi2 layer, increasing the thermal conductivity from 1.7 W m-1 K-1 in the amorphous phase to 2.8 W m-1 K-1 in the crystalline phase.

  6. Bis­[4,4′-(propane-1,3-di­yl)­dipiperidin­ium] β-octa­molybdate(VI)

    PubMed Central

    Driss, Mohamed; Ksiksi, Rekaya; Ben Amor, Fatma; Zid, Mohamed Faouzi

    2010-01-01

    The title compound, bis­[4,4′-(propane-1,3-di­yl)­dipiperidin­ium] β-octa­molybdate(VI), (C13H28N2)2[Mo8O26], was produced by hydro­thermal reaction of an acidified aqueous solution of Na2MoO4·2H2O and 4,4′-trimethyl­ene­dipiperidine (L). The structure of the title compound consists of β-octa­molybdate(VI) anion clusters and protonated [H2 L]2+ cations. The octa­molybdate anion is located around an inversion center. N—H⋯O hydrogen bonds between the cations and anions ensure the cohesion of the structure and result in a three-dimensional network. PMID:21579027

  7. (Pentamethylcyclopentadienyl)molybdenum(IV) chloride. Synthesis, structure, and properties

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

    Abugideiri, F.; Desai, J.U.; Gordon, J.C.

    1994-08-17

    Three different syntheses of trichloro(pentamethylcyclopentadienyl)molybdenum(IV) are described, I.E. (1) thermal decarbonylation of Cp{sup *}MoCl{sub 3}(CO){sub 2}, (2) reduction of Cp{sup *}MoCl{sub 4}, and (3) chlorination of [Cp{sup *}MoCl{sub 2}]{sub 2}. A fourth route (conproportionation of [Cp{sup *}MoCl{sub 2}]{sub 2} and Cp{sup *}MoCl{sub 4}) has been investigated by {sup 1}H-NMR. The product has a dinuclear, dichloro-bridged structure with a four-legged piano stool geometry around each metal atom; the two piano stools have a mutual anti arrangement and the two metals are 3.888(1) {Angstrom} from each other, indicating the absence of a direct metal-metal bonding interaction. Crystal data: monoclinic, space group P2{submore » 1}/n, a = 8.424(1) {Angstrom}, b = 13.323(4) {Angstrom}, c = 11.266(2) {Angstrom}, {beta} = 93.87(1){degrees}, V = 1261.6(8) {Angstrom}{sup 3}, Z = 2, R = 0.038, R{sub w} = 0.057 for 127 parameters and 1350 observed reflections with F{sub o}{sup 2} > 3{sigma}(F{sub o}{sup 2}). The temperature dependent magnetic moment of the material could be fit to the sum of two Bleany-Bowers equations. [Cp{sup *}MoCl{sub 3}]{sub 2} reacts readily with CO, Cl{sup {minus}}, and PMe{sub 3} to afford Cp{sup *}MoCl{sub 3}(CO){sub 2}, [Cp{sup *}MoCl{sub 4}]{sup {minus}}, and Cp{sup *}MoCl{sub 3}(PMe{sub 3}), respectively, while the reaction with 1,2-bis(diphenylphosphino)ethane (dppe) affords the reduction product Cp{sup *}MoCl{sub 2}(dppe).« less

  8. Breastfeeding in Mexico was stable, on average, but deteriorated among the poor, whereas complementary feeding improved: results from the 1999 to 2006 National Health and Nutrition Surveys.

    PubMed

    González de Cossío, Teresita; Escobar-Zaragoza, Leticia; González-Castell, Dinorah; Reyes-Vázquez, Horacio; Rivera-Dommarco, Juan A

    2013-05-01

    We present: 1) indicators of infant and young child feeding practices (IYCFP) and median age of introduction of foods analyzed by geographic and socioeconomic variables for the 2006 national probabilistic Health Nutrition Survey (ENSANUT-2006); and 2) changes in IYCFP indicators between the 1999 national probabilistic Nutrition Survey and ENSANUT-2006, analyzed by the same variables. Participants were women 12-49 y and their <2-y-old children (2953 in 2006 and 3191 in 1999). Indicators were estimated with the status quo method. The median age of introduction of foods was calculated by the Kaplan-Meier method using recall data. The national median duration of breastfeeding was similar in both surveys, 9.7 mo in 1999 and 10.4 mo in 2006, but decreased in the vulnerable population. In 1999 indigenous women breastfed 20.8 mo but did so for only 13.0 mo in 2006. The national percentage of those exclusively breastfeeding <6 mo also remained stable: 20% in 1999 and 22.3% in 2006. Nevertheless, exclusively breastfeeding <6 mo changed within the indigenous population, from 46% in 1999 to 34.5% in 2006. Between surveys, most breastfeeding indicators had lower values in vulnerable populations than in those better-off. Complementary feeding, however, improved overall. Complementary feeding was inadequately timed: median age of introduction of plain water was 3 mo, formula and non-human milk was 5 mo, and cereals, legumes, and animal foods was 5 mo. Late introduction of animal foods occurred among vulnerable indigenous population when 50% consumed these products at 8 mo. Mexican IYCFP indicate that public policy must protect breastfeeding while promoting the timely introduction of complementary feeding.

  9. Controllable synthesis of organic-inorganic hybrid MoOx/polyaniline nanowires and nanotubes.

    PubMed

    Wang, Sinong; Gao, Qingsheng; Zhang, Yahong; Gao, Jing; Sun, Xuhui; Tang, Yi

    2011-02-01

    A novel chemical oxidative polymerization approach has been proposed for the controllable preparation of organic-inorganic hybrid MoO(x)/polyaniline (PANI) nanocomposites based on the nanowire precursor of Mo(3)O(10)(C(6)H(8)N)(2)·2H(2)O with sub-nanometer periodic structures. The nanotubes, nanowires, and rambutan-like nanoparticles of MoO(x)/PANI were successfully obtained through simply modulating the pH values to 2.5-3.5, ≈2.0 and ≈1.0, respectively. Through systematic physicochemical characterization, such as scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and so forth, the composition and structure of MoO(x)/PANI hybrid nanocomposites are well confirmed. It is found that the nanowire morphology of the precursor is the key to achieve the one-dimensional (1D) structures of final products. A new polymerization-dissolution mechanism is proposed to explain the formation of such products with different morphologies, in which the match between polymerization and dissolution processes of the precursor plays the important role. This approach will find a new way to controllably prepare various organic-inorganic hybrid 1D nanomaterials especially for polymer-hybrid nanostructures. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Early breakthrough of molybdenum and uranium in a permeable reactive barrier.

    PubMed

    Morrison, Stan J; Mushovic, Paul S; Niesen, Preston L

    2006-03-15

    A permeable reactive barrier (PRB) using zerovalent iron (ZVI) was installed at a site near Cañon City, CO, to treat molybdenum (Mo) and uranium (U) in groundwater. The PRB initially decreased Mo concentrations from about 4.8 to less than 0.1 mg/L; however, Mo concentrations in the ZVI increased to 2.0 mg/L after about 250 days and continued to increase until concentrations in the ZVI were about 4 times higherthan in the influent groundwater. Concentrations of U were reduced from 1.0 to less than 0.02 mg/L during the same period. Investigations of solid-phase samples indicate that (1) calcium carbonate, iron oxide, and sulfide minerals had precipitated in pores of the ZVI; (2) U and Mo were concentrated in the upgradient 5.1 cm of the ZVI; and (3) calcium was present throughout the ZVI accounting for up to 20.5% of the initial porosity. Results of a column test indicated that the ZVI from the PRB was still reactive for removing Mo and that removal rates were dependenton residence time and pH. The chemical evolution of the PRB is explained in four stages that present a progression from porous media flow through preferential flow and, finally, complete bypass of the ZVI.

  11. Safety Evaluation of Green Tea Polyphenols Consumption in Middle-aged Ovariectomized Rat Model.

    PubMed

    Shen, Chwan-Li; Brackee, Gordon; Song, Xiao; Tomison, Michael D; Finckbone, VelvetLee; Mitchell, Kelly T; Tang, Lili; Chyu, Ming-Chien; Dunn, Dale M; Wang, Jia-Sheng

    2017-09-01

    This work evaluates chronic safety in middle-aged ovariectomized rats supplemented with different dosages of green tea polyphenols (GTP) in drinking water. The experiment used 6-mo-old sham (n = 39) and ovariectomized (OVX, n = 143) female rats. All sham (n = 39) and 39 of the OVX animals received no GTP treatment and their samples were collected for outcome measures at baseline, 3 mo, and 6 mo (n = 13 per group for each). The remaining OVX animals were randomized into 4 groups receiving 0.15%, 0.5%, 1%, and 1.5% (n = 26 for each) of GTP (wt/vol), respectively, in drinking water for 3 and 6 mo. No mortality or abnormal treatment-related findings in clinical observations or ophthalmologic examinations were noted. No treatment-related macroscopic or microscopic findings were noted for animals administered 1.5% GTP supplementation. Throughout the study, there was no difference in the body weight among all OVX groups. In all OVX groups, feed intake and water consumption significantly decreased with GTP dose throughout the study period. At 6 mo, GTP intake did not affect hematology, clinical chemistry, and urinalysis, except for phosphorus and blood urea nitrogen (increased), total cholesterol, lactate dehydrogenase, and urine pH (decreased). This study reveals that the no-observed-adverse-effect level (NOAEL) of GTP is 1.5% (wt/vol) in drinking water, the highest dose used in this study. © 2017 Institute of Food Technologists®.

  12. NADiA ProsVue prostate-specific antigen slope is an independent prognostic marker for identifying men at reduced risk of clinical recurrence of prostate cancer after radical prostatectomy.

    PubMed

    Moul, Judd W; Lilja, Hans; Semmes, O John; Lance, Raymond S; Vessella, Robert L; Fleisher, Martin; Mazzola, Clarisse; Sarno, Mark J; Stevens, Barbara; Klem, Robert E; McDermed, Jonathan E; Triebell, Melissa T; Adams, Thomas H

    2012-12-01

    To validate the hypothesis that men displaying serum prostate-specific antigen (PSA) slopes ≤ 2.0 pg/mL/mo after prostatectomy, measured using a new immuno-polymerase chain reaction diagnostic test (NADiA ProsVue), have a reduced risk of clinical recurrence as determined by positive biopsy, imaging findings, or death from prostate cancer. From 4 clinical sites, we selected a cohort of 304 men who had been followed up for 17.6 years after prostatectomy for clinical recurrence. We assessed the prognostic value of a PSA slope cutpoint of 2.0 pg/mL/mo against established risk factors to identify men at low risk of clinical recurrence using uni- and multivariate Cox proportional hazards regression and Kaplan-Meier analyses. The univariate hazard ratio of a PSA slope >2.0 pg/mL/mo was 18.3 (95% confidence interval 10.6-31.8) compared with a slope ≤ 2.0 pg/mL/mo (P <.0001). The median disease-free survival interval was 4.8 years vs >10 years in the 2 groups (P <.0001). The multivariate hazard ratio for PSA slope with the covariates of preprostatectomy PSA, pathologic stage, and Gleason score was 9.8 (95% confidence interval 5.4-17.8), an 89.8% risk reduction for men with PSA slopes ≤ 2.0 pg/mL/mo (P <.0001). The Gleason score (<7 vs ≥ 7) was the only other significant predictor (hazard ratio 5.4, 95% confidence interval 2.1-13.8, P = .0004). Clinical recurrence after radical prostatectomy is difficult to predict using established risk factors. We have demonstrated that a NADiA ProsVue PSA slope of ≤ 2.0 pg/mL/mo after prostatectomy is prognostic for a reduced risk of prostate cancer recurrence and adds predictive power to the established risk factors. Copyright © 2012 Elsevier Inc. All rights reserved.

  13. Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H Activation.

    PubMed

    Handford, Rex C; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter

    2017-03-20

    Treatment of CH 2 Cl 2 solutions of Cp*M(NO)Cl 2 (Cp* = η 5 -C 5 (CH 3 ) 5 ; M = Mo, W) first with 2 equiv of AgSbF 6 in the presence of PhCN and then with 1 equiv of Ph 2 PCH 2 CH 2 PPh 2 affords the yellow-orange salts [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 with 2 equiv of Cp 2 Co in C 6 H 6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) which have been isolated as analytically pure orange-red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf) 3 , to solutions of Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes in which one of the phenyl substituents of the Ph 2 PCH 2 CH 2 PPh 2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF 3 produces the analogous Cp*M(NO→BF 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes. In contrast, B(C 6 F 5 ) 3 forms the 1:1 Lewis acid-base adducts, Cp*M(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) in CH 2 Cl 2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) converts cleanly to the orthometalated product Cp*Mo(NO→B(C 6 F 5 ) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ), but Cp*W(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph 2 PCH 2 PPh 2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

  14. [Determination of total mass and morphology analysis of heavy metal in soil with potassium biphthalate-sodium hydroxide by ICP-AES].

    PubMed

    Qu, Jiao; Yuan, Xing; Cong, Qiao; Wang, Shuang

    2008-11-01

    Blank soil was used as quality controlling samples, soil sample dealt by potassium biphthalate-sodium hydroxide buffer solution was used as check sample, mixed acid HNO3-HF-HClO4 was chosen to nitrify soil samples, and plasma emission spectrometer (ICP-AES) was used as detecting method. The authors determined the total metal mass of Mo, Pb, As, Hg, Cr, Cd, Zn, Cu and Ni in the extracted and dealt soil samples, and determined the mass of Mo, Pb, As, Hg, Cr, Cd, Zn, Cu and Ni in the three chemical morphologies, including acid extractable morphology, oxide associated morphology, and organics associated modality. The experimental results indicated that the different pH of potassium biphthalate-sodium hydroxide buffer solution had obvious influence on the total mass of heavy metal and morphology transformation. Except for metal element Pb and Zn, the addition of different pH potassium dihydrogen phosphate-sodium hydroxide buffer solution could accelerate the soil samples nitrification and the total mass determination of heavy metal in the soil samples. The potassium biphthalate-sodium hydroxide buffer solution could facilitate the acid extractable morphology of Cr, Cu, Hg and Pb, oxidation associated morphology of As, Hg, Pb and Zn and the organic associated morphology transforming of As and Hg. At pH 5.8, the maximum acid extractable morphology contents of Cu and Hg were 2.180 and 0.632 mg x kg(-1), respectively; at pH 6.2, the maximal oxidation associated morphology content of Pb could achieve 27.792 mg x kg(-1); at pH 6.0, the maximum organic associated morphology content of heavy metal Hg was 4.715 mg x kg(-1).

  15. Sugar beet factory lime affects the mobilization of Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn under dynamic redox conditions in a contaminated floodplain soil.

    PubMed

    Shaheen, Sabry M; Rinklebe, Jörg

    2017-01-15

    The impact of sugar beet factory lime (SBFL) on the release dynamics and mobilization of toxic metals (TMs) under dynamic redox conditions in floodplain soils has not been studied up to date. Therefore, the aim of this study was to verify the scientific hypothesis that SBFL is able to immobilize Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn under different redox potentials (E H ) in a contaminated floodplain soil. For this purpose, the non-treated contaminated soil (CS) and the same soil treated with SBFL (CS+SBFL) were flooded in the laboratory using a highly sophisticated automated biogeochemical microcosm apparatus. The experiment was conducted stepwise from reducing (-13 mV) to oxidizing (+519 mV) soil conditions. Soil pH decreased under oxic conditions in CS (from 6.9 to 4.0) and in CS+SBFL (from 7.5 to 4.4). The mobilization of Cu, Cr, Pb, and Fe were lower in CS+SBFL than in CS under both reducing/neutral and oxic/acidic conditions. Those results demonstrate that SBFL is able to decrease concentrations of these elements under a wide range of redox and pH conditions. The mobilization of Cd, Co, Mn, Mo, Ni, and Zn were higher in CS+SBFL than in CS under reducing/neutral conditions; however, these concentrations showed an opposite behavior under oxic/acidic conditions and were lower in CS+SBFL than in CS. We conclude that SBFL immobilized Cu, Cr, Pb, and Fe under dynamic redox conditions and immobilized Cd, Co, Mn, Mo, Ni, and Zn under oxic acidic conditions; however, the latter elements were mobilized under reducing neutral conditions in the studied soil. Therefore, the addition of SBFL to acid floodplain soils contaminated with TMs might be an important alternative for ameliorating these soils with view to a sustainable management of these soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Quantified pH imaging with hyperpolarized (13) C-bicarbonate.

    PubMed

    Scholz, David Johannes; Janich, Martin A; Köllisch, Ulrich; Schulte, Rolf F; Ardenkjaer-Larsen, Jan H; Frank, Annette; Haase, Axel; Schwaiger, Markus; Menzel, Marion I

    2015-06-01

    Because pH plays a crucial role in several diseases, it is desirable to measure pH in vivo noninvasively and in a spatially localized manner. Spatial maps of pH were quantified in vitro, with a focus on method-based errors, and applied in vivo. In vitro and in vivo (13) C mapping were performed for various flip angles for bicarbonate (BiC) and CO2 with spectral-spatial excitation and spiral readout in healthy Lewis rats in five slices. Acute subcutaneous sterile inflammation was induced with Concanavalin A in the right leg of Buffalo rats. pH and proton images were measured 2 h after induction. After optimizing the signal to noise ratio of the hyperpolarized (13) C-bicarbonate, error estimation of the spectral-spatial excited spectrum reveals that the method covers the biologically relevant pH range of 6 to 8 with low pH error (< 0.2). Quantification of pH maps shows negligible impact of the residual bicarbonate signal. pH maps reflect the induction of acute metabolic alkalosis. Inflamed, infected regions exhibit lower pH. Hyperpolarized (13) C-bicarbonate pH mapping was shown to be sensitive in the biologically relevant pH range. The mapping of pH was applied to healthy in vivo organs and interpreted within inflammation and acute metabolic alkalosis models. © 2014 Wiley Periodicals, Inc.

  17. Comparison of oral and intramuscular recombinant canine distemper vaccination in African wild dogs (Lycaon pictus).

    PubMed

    Connolly, Maren; Thomas, Patrick; Woodroffe, Rosie; Raphael, Bonnie L

    2013-12-01

    A series of three doses of recombinant canary-pox-vectored canine distemper virus vaccine was administered at 1-mo intervals, orally (n = 8) or intramuscularly (n = 13), to 21 previously unvaccinated juvenile African wild dogs (Lycaon pictus) at the Wildlife Conservation Society's Bronx Zoo. Titers were measured by serum neutralization at each vaccination and at intervals over a period of 3.5-21.5 mo after the initial vaccination. All postvaccination titers were negative for orally vaccinated animals at all sampling time points. Of the animals that received intramuscular vaccinations, 100% had presumed protective titers by the end of the course of vaccination, but only 50% of those sampled at 6.5 mo postvaccination had positive titers. None of the three animals sampled at 21.5 mo postvaccination had positive titers.

  18. MnMoO4 nanosheet array: an efficient electrocatalyst for hydrogen evolution reaction with enhanced activity over a wide pH range.

    PubMed

    Wen, Lulu; Sun, Yiqiang; Zhang, Tao; Bai, Yu; Li, Xinyang; Lyu, Xianjun; Cai, Weiping; Li, Yue

    2018-08-17

    We report the preparation of MnMoO 4 nanosheet array on nickel foam (MnMoO 4 NSA/NF) as an excellent 3D hydrogen evolution reaction (HER) electrocatalyst with good catalytic performance applied under basic, acidic and neutral conditions. In 0.5 M H 2 SO 4 , this MnMoO 4 NSA/NF electrode needs an overpotential of 89 mV to drive current densities of 10 mA cm -2 , to achieve the same current density, it demands overpotentials of 105 mV in 1.0 M KOH, 161 mV in 1.0 M PBS (pH = 7), respectively. After continuous CV scanning for 1000 cycles under different pH conditions, it also demonstrates an excellent stability with ignorable activity decrease. Such preeminent HER performance may be derived from the synergistic effect between manganese (Mn) and molybdenum (Mo) atoms, exposure of more active sites on the nanosheets and effective electron transport along the nanosheets. This MnMoO 4 NSA/NF electrocatalyst provides us a highly efficient material for water splitting devices for industrial hydrogen production.

  19. Systematic study on the influence of the morphology of α-MoO{sub 3} in the selective oxidation of propylene

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

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin

    2015-08-15

    A variety of morphologically different α-MoO{sub 3} samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO{sub 3} prepared by flame spray pyrolysis (FSP) and a classical synthesis route. Hydrothermal synthesis from ammonium heptamolybdate (AHM) and nitric acid at pH 1–2 led to ammonium containing molybdenum oxide phases that were completely transformed into α-MoO{sub 3} after calcination at 550 °C. A one-step synthesis of α-MoO{sub 3} rods was possible starting from MoO{sub 3}·2H{sub 2}O with acetic acid or nitric acid and from AHM with nitric acid at 180 °C.more » Particularly, if nitric acid was used during synthesis, the rod-like morphology of the samples could be stabilized during calcination at 550 °C and the following catalytic activity tests, which was beneficial for the catalytic performance in propylene oxidation. Characterization studies using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy showed that those samples, which retained their rod-like morphology during the activity tests, yielded the highest propylene conversion. - Graphical abstract: Hydrothermal synthesis from MoO{sub 3}·2H{sub 2}O in the presence of HNO{sub 3} led to rod-shaped particles which mainly expose (1 0 0) facets which are the most active surfaces. - Highlights: • Hydrothermal synthesis of MoO3 resulted in either rod or slab shaped particles depending on pH. • At pH<0 rods stable towards calcination and catalytic activity testing were formed. • Rod shaped particles had significantly higher activity than slab shaped ones. • The rod shaped particles mainly expose the (1 0 0) facets which are the most active surfaces. • Total surface area is not main determining factor for catalytic activity.« less

  20. Corrosion behavior of Alloy 22 in heated surface test conditions in simulated Yucca Mountain Nuclear Repository environment

    NASA Astrophysics Data System (ADS)

    Badwe, Sunil

    In the nuclear repository conditions, the nuclear waste package wall surfaces will be at elevated temperatures because of the heat generated by fission reactions within the waste. It is anticipated that the ground water may contain varying levels of anions such as chloride, nitrate, sulfate picked up from the rocks. The ground waters could seep through the rock faults and drip on to the waste packages. The dripped water will evaporate due to the heat from the nuclear waste leaving behind concentrated brine which eventually becomes dry salt deposit. The multi-ionic salts in the ground water are expected to be hygroscopic in nature. The next drop of water falling at the same place or the humidity in the repository will transform the hygroscopic salt deposit into a more concentrated brine. This cycle will continue for years and eventually a potentially corrosive brine will be formed on the waste package surface. Hence the waste package surface goes through the alternate wet-dry cycles. These conditions indicate that the concentration and pH of the environment in the repository vary considerably. The conventional corrosion tests hardly simulate these varying environmental conditions. Hence there has been a need to develop an electrochemical test that could closely simulate the anticipated repository conditions stated above. In this research, a new electrochemical method, called as Heated Surface Corrosion testing (HSCT) has been devised and tested. In the conventional testing the electrolyte is heated and in HSCT the working electrode is heated. The present study employs the temperature of 80°C which may be one of the temperatures of the waste package surface. The new HSCT was validated by testing stainless steel type 304. The HSCT was observed to be more aggressive than the conventional tests. Initiation of pitting of SS 304 in chloride solution (pH 3) occurred at much shorter exposure times in the HSCT condition than the exposure time required for pitting in conventional testing. The reduced time to pitting demonstrated the capability of HSCT to impose repository more corrosive conditions. The stability of the passive film of stainless alloys under the hygroscopic salt layers could be determined using this technique. Alloy 22, a nickel base Ni-22Cr-13Mo-3W alloy has an excellent corrosion resistance in oxidizing and reducing environments. Corrosion behavior of Alloy 22 was evaluated using the newly devised HSCT method in simulated acidified water (SAW), simulated concentrated water (SCW) and in pure chloride (pH 3 and 8) environments. In this method, the concentration of the environment varied with test duration. Alloy 22 was evaluated in four different heat treated conditions viz. (a) mill annealed, (b) 610°C/1 h-representing Cr depletion, (c) 650°C/100 h-representing Mo+Cr depletion, (d) 800°C/100 h-representing Mo depletion. The corrosion rate of mill annealed Alloy 22 was not affected by the continuous increase in ionic strength of the SAW (pH 3) environment. Passivation kinetics was faster with increase in concentration of the electrolytes. The major difference between the conventional test and HSCT was the aging characteristics of the passive film of Alloy 22. Cyclic polarization was carried out on Alloy 22 in conventional ASTM G61 and HSCT method to compare. The electrochemical response of Alloy 22 was the same by heating the electrolyte or heating the electrode. The corrosion behavior of Alloy 22 was investigated in three different aged conditions using HSCT approach in two different electrolytes. The thermal aging conditions of the specimens introduced depletion of chromium and molybdenum near the grain boundaries/phase boundaries. Long-term exposure tests (up to 850 h) were conducted in simulated acidified water (SAW, pH 3) and simulated concentrated water (SCW, pH 8) at 80°C. Corrosion potential, corrosion current and passive current decay exponent were determined at regular intervals. The specimens aged at 610°C/1 h and 800°C/100 h showed almost identical corrosion behaviors in the SAW environment. The specimen aged at 650°C/100 h showed lower corrosion resistance in the SAW environment indicating the effect of Mo-depletion profile near the grain boundaries. The specimen aged at 800°C for 100 h showed lower corrosion resistance in the SCW environment because of possible dissolution of the Mo-rich precipitates. Compared to the mill annealed condition, the aged specimens showed approximately an order of magnitude higher corrosion current in the SAW environment and almost similar corrosion currents in the SCW environment. Results also indicate that the passivity of Alloy 22, both in mill annealed and in aged conditions was not hampered during dry-out/rewet cycles. Presence of nitrate and other oxyanions in the SAW environment reduced the charge required to form a stable passive film of alloy 22 aged samples as compared to the charge passed in the pure chloride pH 3 environments. The passive film of the aged Alloy 22 specimens exposed to pure chloride solutions showed predominantly n-type semiconducting behavior and the on-set of p-type semiconductivity at higher potentials. The charge carrier density of the passive film of Alloy 22 varied in the range 1.5-9.0 x 10 21/cm3. The predominant charge carriers could be oxygen vacancies. Increase in the charge carrier density was observed in the specimen aged at 800°C/100 h when exposed to pH 3 solution as compared to exposure in pH 8 solution. In Summary, Alloy 22 sustained the heated surface corrosion test without any appreciable surface attack in the simulated repository environments as well as the more corrosive chloride environments.

  1. Comparative effectiveness of plant-based diets for weight loss: a randomized controlled trial of five different diets.

    PubMed

    Turner-McGrievy, Gabrielle M; Davidson, Charis R; Wingard, Ellen E; Wilcox, Sara; Frongillo, Edward A

    2015-02-01

    The aim of this study was to determine the effect of plant-based diets on weight loss. Participants were enrolled in a 6-mo, five-arm, randomized controlled trial in 2013 in South Carolina. Participants attended weekly group meetings, with the exception of the omnivorous group, which served as the control and attended monthly meetings augmented with weekly e-mail lessons. All groups attended monthly meetings for the last 4 mo of the study. Diets did not emphasize caloric restriction. Overweight adults (body mass index 25-49.9 kg/m(2); age 18-65 y, 19% non-white, and 27% men) were randomized to a low-fat, low-glycemic index diet: vegan (n = 12), vegetarian (n = 13), pesco-vegetarian (n = 13), semi-vegetarian (n = 13), or omnivorous (n = 12). Fifty (79%) participants completed the study. In intention-to-treat analysis, the linear trend for weight loss across the five groups was significant at both 2 (P < 0.01) and 6 mo (P < 0.01). At 6 mo, the weight loss in the vegan group (-7.5% ± 4.5%) was significantly different from the omnivorous (-3.1% ± 3.6%; P = 0.03), semi-vegetarian (-3.2% ± 3.8%; P = 0.03), and pesco-vegetarian (-3.2% ± 3.4%; P = 0.03) groups. Vegan participants decreased their fat and saturated fat more than the pesco-vegetarian, semi-vegetarian, and omnivorous groups at both 2 and 6 mo (P < 0.05). Vegan diets may result in greater weight loss than more modest recommendations. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Assembly of a new inorganic-organic frameworks based on [Sb4Mo12(OH)6O48]10- polyanion

    NASA Astrophysics Data System (ADS)

    Thabet, Safa; Ayed, Meriem; Ayed, Brahim; Haddad, Amor

    2014-10-01

    A new organic-inorganic hybrid material, (C4N2H7)8[K(H2O)]2[Sb4Mo12(OH)6O48]ṡ16H2O (1) has been isolated by the conventional solution method and characterized by elemental analysis, single-crystal X-ray diffraction, infrared spectroscopy, UV-visible spectroscopies, cyclic voltammetry and TG-DTA analysis. The compound crystallizes in the triclinic space group P - 1 with a = 13.407(6) Å, b = 13.906(2) Å, c = 14.657(7) Å, α = 77.216(9)°, β = 71.284(6)°, γ = 71.312(3)° and Z = 1. The crystal structure exhibits an infinite 1D inorganic structure built from [Sb4Mo12(OH)6O48]10- clusters and potassium cations; adjacent chains are further joined up hydrogen bonding interactions between protonated 2-methylimidazolim cations, water molecules and polyoxoanions to form a 3D supramolecular architecture.

  3. Relative susceptibility of titanium alloys to hot-salt stress-corrosion

    NASA Technical Reports Server (NTRS)

    Gray, H. R.

    1971-01-01

    Susceptibility of titanium alloys to hot-salt stress-corrosion cracking increased as follows: Ti-2Al-11Sn-5Zr-0.2Si(679), Ti-6Al-2Sn-4Zr-2Mo(6242), Ti-6Al-4V(64), Ti-6Al-4V-3Co(643), Ti-8Al-1Mo-1V(811), and Ti-13V-11Cr-3A1(13-11-3). The Ti-5Al-6Sn-2Zr-1Mo-0.25Si(5621S) alloy was both the least and most susceptible depending on heat treatment. Such rankings can be drastically altered by heat-to-heat and processing variations. Residual compressive stresses and cyclic exposures also reduce susceptibility to stress-corrosion. Simulated turbine-engine compressor environmental variables such as air velocity, pressure, dewpoint, salt concentration, and salt deposition temperature have only minor effects. Detection of substantial concentrations of hydrogen in all corroded alloys confirmed the existence of a hydrogen embrittlement mechanism.

  4. Mono- and binuclear molybdenum and tungsten complexes containing asymmetric bridging ligands: Effects of ligand conjugation and conformation on metal-metal interactions

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

    Das, A.; Jeffery, J.C.; Maher, J.P.

    The authors have prepared the new monodentate ligands 4-(4-methoxyphenyl)pyridine, 1-(4-pyridyl)-2-(4-methoxyphenyl)ethene, 1-(4-pyridyl)-2-(3-methoxyphenyl)ethene, and 1-(3-pyridyl)-2-(4-methoxyphenyl)ethene (L[sup 5]-L[sup 8]); demethylation of the methoxy group in each case afforded the new bridging bidentate ligands HL[sup 1]-HL[sup 4], which contain one pyridyl and one phenolate donor. Attachment of a MoL*(NO)Cl [L* = hydrotris(3,5-dimethylpyrazolyl)borate] moiety to the pyridyl groups of L[sup 5]-L[sup 8] gave the 17-electron complexes [Mo(NO)L*ClL[prime

  5. Maternal serum free-beta-chorionic gonadotrophin, pregnancy-associated plasma protein-A and fetal nuchal translucency thickness at 10-13(+6) weeks in relation to co-variables in pregnant Saudi women.

    PubMed

    Ardawi, Mohammed-Salleh M; Nasrat, Hasan A; Rouzi, Abdulrahim A; Qari, Mohammed H; Al-Qahtani, Mohammed H; Abuzenadah, Adel M

    2007-04-01

    To establish normative values and distribution parameters of first-trimester screening markers, namely, fetal nuchal translucency (NT), maternal serum free beta-human chorionic gonadotrophin (beta-hCG) and pregnancy-associated plasma protein-A (PAPP-A), at 10 to 13(+6) weeks of gestation in Saudi women and to evaluate the effect of co-variables including maternal body weight, gravidity, parity, fetal gender, twin pregnancy, smoking and ethnicity on these markers. A cohort of Saudi women (first cohort n = 1616) with singleton pregnancies prospectively participated in the present study, and fetal NT together with maternal serum free beta-hCG and PAPP-A were determined at 10 to 13(+6) weeks of gestation. The distribution of gestational age-independent multiples of the median (MoM) of the parameters was defined and normative values were established, and correction for maternal body weight was made accordingly. The influence of various co-variables was examined using the data collected from the first and the second (n = 1849) cohorts of women and 62 twin pregnancies, and compared with other studies. All markers exhibited log-normally distributed MoMs. Gestational age-independent normative values were established. Maternal body weight was corrected, particularly for maternal free beta-hCG and PAPP-A using standard methods. Fetal NT showed a negative relationship with increasing gravidity (r = -0.296) or parity (r = -0.311), whereas both free beta-hCG and PAPP-A exhibited a significant positive relationship. There was a significant increase in the MoM of free beta-hCG in female fetuses. Smoking decreased MoM values of free beta-hCG (by 14.6%; P < 0.01) and PAPP-A (by 18.8%; P < 0.001). Twin pregnancy showed significant increases in MoM values of free beta-hCG (by 1.87-fold) and PAPP-A (by 2.24-fold), with no significant changes in fetal NT MoM values. Fetal NT MoM values were lower in Africans and Asians but higher in Orientals, as compared to Saudi women (P < 0.05; in each case). MoM values (body weight-corrected) of free beta-hCG were 25.2% higher in Africans and 19.4% higher in Orientals but 6.8% lower in other Arabian and Asian (by 5.8%) women as compared to Saudi women (P < 0.05; in each case). The normative values and distribution parameters for fetal NT, maternal serum free beta-hCG and PAPP-A were established in Saudi singleton pregnancies, the maternal body weight together with smoking, twin pregnancy and ethnicity being important first-trimester screening co-variables. Gravidity, parity and fetal gender are also considered to influence one or more of the first-trimester markers examined. Copyright (c) 2007 John Wiley & Sons, Ltd.

  6. Materials Data on Mo3H24C8S13N2 (SG:157) by Materials Project

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

    Kristin Persson

    2016-02-11

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  7. Serum Carbon Isotope Values Change in Adults in Response to Changes in Sugar-Sweetened Beverage Intake12

    PubMed Central

    Fakhouri, Tala H. I.; Jahren, A. Hope; Appel, Lawrence J.; Chen, Liwei; Alavi, Reza; Anderson, Cheryl A. M.

    2014-01-01

    Serum carbon isotope values [13C-to-12C serum carbon isotope ratio (δ13C)], which reflect consumption of corn- and cane-based foods, differ between persons consuming high and low amounts of sugar-sweetened beverages (SSBs). In this study, we determined whether serum δ13C changes in response to change in SSB intake during an 18-mo behavioral intervention trial. Data were from a subset of 144 participants from the PREMIER trial, a completed behavioral intervention (Maryland, 1998–2004). SSB intake was assessed using 2 24-h dietary recall interviews. Blinded serum samples were assayed for δ13C by natural abundance stable isotope mass spectroscopy. Multiple linear regression models with generalized estimating equations and robust variance estimation were used. At baseline, mean SSB intake was 13.8 ± 14.2 fl oz/d, and mean δ13C serum value was −19.3 ± 0.6 units per mil (designated ‰). A reduction of 12 oz (355 mL)/d SSB (equivalent to 1 can of soda per day) was associated with 0.17‰ (95% CI: 0.08‰, 0.25‰ P < 0.0001) reduction in serum δ13C values over 18 mo (equivalent to a 1% reduction in δ13C from baseline). After adjusting for potential confounders, a reduction of 12 oz/d SSB (equivalent to 1 can of soda per day), over an 18-mo period, was associated with 0.12‰ (95% CI: 0.01‰, 0.22‰ P = 0.025) reduction in serum δ13C. These findings suggest that serum δ13C can be used as a measure of dietary changes in SSB intake. PMID:24717368

  8. Serum carbon isotope values change in adults in response to changes in sugar-sweetened beverage intake.

    PubMed

    Fakhouri, Tala H I; Jahren, A Hope; Appel, Lawrence J; Chen, Liwei; Alavi, Reza; Anderson, Cheryl A M

    2014-06-01

    Serum carbon isotope values [13C-to-12C serum carbon isotope ratio (δ(13)C)], which reflect consumption of corn- and cane-based foods, differ between persons consuming high and low amounts of sugar-sweetened beverages (SSBs). In this study, we determined whether serum δ(13)C changes in response to change in SSB intake during an 18-mo behavioral intervention trial. Data were from a subset of 144 participants from the PREMIER trial, a completed behavioral intervention (Maryland, 1998-2004). SSB intake was assessed using 2 24-h dietary recall interviews. Blinded serum samples were assayed for δ(13)C by natural abundance stable isotope mass spectroscopy. Multiple linear regression models with generalized estimating equations and robust variance estimation were used. At baseline, mean SSB intake was 13.8 ± 14.2 fl oz/d, and mean δ(13)C serum value was -19.3 ± 0.6 units per mil (designated ‰). A reduction of 12 oz (355 mL)/d SSB (equivalent to 1 can of soda per day) was associated with 0.17‰ (95% CI: 0.08‰, 0.25‰ P < 0.0001) reduction in serum δ(13)C values over 18 mo (equivalent to a 1% reduction in δ(13)C from baseline). After adjusting for potential confounders, a reduction of 12 oz/d SSB (equivalent to 1 can of soda per day), over an 18-mo period, was associated with 0.12‰ (95% CI: 0.01‰, 0.22‰ P = 0.025) reduction in serum δ(13)C. These findings suggest that serum δ(13)C can be used as a measure of dietary changes in SSB intake. © 2014 American Society for Nutrition.

  9. Tunable electronic structure in stained two dimensional van der Waals g-C2N/XSe2 (X = Mo, W) heterostructures

    NASA Astrophysics Data System (ADS)

    Zheng, Z. D.; Wang, X. C.; Mi, W. B.

    2017-10-01

    The electronic structure of the strained g-C2N/XSe2 (X=Mo, W) van der Waals heterostructures are investigated by first-principles calculations. The g-C2N/MoSe2 heterostructure is an indirect band gap semiconductor at a strain from 0% to 8%, where its band gap is 0.66, 0.61, 0.73, 0.60 and 0.33 eV. At K point, the spin splitting is 186, 181, 39, 13 and 9 meV, respectively. For g-C2N/WSe2 heterostructures, the band gap is 0.32, 0.37, 0.42, 0.45 and 0.36 eV, and the conduction band minimum is shifted from Г-M region to K-Г region as the strain increases from 0% to 8%. Its spin splitting monotonically decreases as a strain raises to 8%, which is 445, 424, 261, 111 and 96 meV, respectively. Moreover, at a strain less than 4%, the conduction band mainly comes from g-C2N, but it comes from XSe2 (X=Mo, W) above 6%. Our results show that the g-C2N/XSe2 heterostructures have tunable electronic structures, which makes it a potential candidate for novel electronic devices.

  10. All-fiber Yb-doped fiber laser passively mode-locking by monolayer MoS2 saturable absorber

    NASA Astrophysics Data System (ADS)

    Zhang, Yue; Zhu, Jianqi; Li, Pingxue; Wang, Xiaoxiao; Yu, Hua; Xiao, Kun; Li, Chunyong; Zhang, Guangyu

    2018-04-01

    We report on an all-fiber passively mode-locked ytterbium-doped (Yb-doped) fiber laser with monolayer molybdenum disulfide (ML-MoS2) saturable absorber (SA) by three-temperature zone chemical vapor deposition (CVD) method. The modulation depth, saturation fluence, and non-saturable loss of this ML-MoS2 are measured to be 3.6%, 204.8 μJ/cm2 and 6.3%, respectively. Based on this ML-MoS2SA, a passively mode-locked Yb-doped fiber laser has been achieved at 979 nm with pulse duration of 13 ps and repetition rate of 16.51 MHz. A mode-locked fiber laser at 1037 nm is also realized with a pulse duration of 475 ps and repetition rate of 26.5 MHz. To the best of our knowledge, this is the first report that the ML-MoS2 SA is used in an all-fiber Yb-doped mode-locked fiber laser at 980 nm. Our work further points the excellent saturable absorption ability of ML-MoS2 in ultrafast photonic applications.

  11. Optimizing catalysis conditions to decrease aromatic hydrocarbons and increase alkanes for improving jet biofuel quality.

    PubMed

    Cheng, Jun; Li, Tao; Huang, Rui; Zhou, Junhu; Cen, Kefa

    2014-04-01

    To produce quality jet biofuel with high amount of alkanes and low amount of aromatic hydrocarbons, two zeolites of HY and HZSM-5 supporting Ni and Mo were used as catalysts to convert soybean oil into jet fuel. Zeolite HY exhibited higher jet range alkane selectivity (40.3%) and lower jet range aromatic hydrocarbon selectivity (23.8%) than zeolite HZSM-5 (13.8% and 58.9%). When reaction temperature increased from 330 to 390°C, yield of jet fuel over Ni-Mo/HY catalyst at 4 MPa hydrogen pressure increased from 0% to 49.1% due to the shift of reaction pathway from oligomerization to cracking reaction. Further increase of reaction temperature from 390 to 410°C resulted in increased yield of jet range aromatic hydrocarbons from 18.7% to 30%, which decreased jet fuel quality. A high yield of jet fuel (48.2%) was obtained at 1 MPa low hydrogen pressure over Ni (8 wt.%)-Mo (12 wt.%)/HY catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Red Blood Cell Distribution Width, Hematology, and Serum Biochemistry in Dogs with Echocardiographically Estimated Precapillary and Postcapillary Pulmonary Arterial Hypertension.

    PubMed

    Mazzotta, E; Guglielmini, C; Menciotti, G; Contiero, B; Baron Toaldo, M; Berlanda, M; Poser, H

    2016-11-01

    Red blood cell distribution width (RDW) is a quantitative measurement of anisocytosis. RDW has prognostic value in humans with different cardiovascular and systemic disorders, but few studies have investigated this biomarker in dogs. To compare the RDW in dogs with precapillary and postcapillary pulmonary hypertension (PH) and a control population of dogs and to correlate RDW with demographic, echocardiographic, and laboratory variables. One hundred and twenty-seven client-owned dogs including 19 healthy dogs, 82 dogs with myxomatous mitral valve disease (50 dogs without PH and 32 dogs with postcapillary PH), and 26 dogs with precapillary PH. Prospective study. Dogs were allocated to groups according to clinical and echocardiographic evaluation. RDW and selected laboratory and echocardiographic variables were compared among dog groups. Associations between RDW and demographic, laboratory, and echocardiographic variables were analyzed using correlation and multiple regression analysis. Median RDW in dogs with precapillary PH (13.8%, interquartile range 13.2-14.9%) and postcapillary PH (13.7, 13.2-14.7%) was significantly increased compared to healthy dogs (13.3, 12.3-13.7%; P < .05 for both comparisons), but only dogs with severe PH had significantly increased RDW compared to dogs without PH (P < .05). Peak tricuspid regurgitation pressure gradient was significantly associated with increased RDW (rho = 0.263, P = .007). Serum urea concentration, hematocrit, age, and white blood cell number were significantly associated with RDW in the multivariate analysis. Underlying pathophysiologic processes associated with PH instead of severity of PH are likely responsible for increased RDW in dogs with PH. Copyright © 2016 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

  13. Trilayer TMDC Heterostructures for MOSFETs and Nanobiosensors

    NASA Astrophysics Data System (ADS)

    Datta, Kanak; Shadman, Abir; Rahman, Ehsanur; Khosru, Quazi D. M.

    2017-02-01

    Two dimensional materials such as transition metal dichalcogenides (TMDC) and their bi-layer/tri-layer heterostructures have become the focus of intense research and investigation in recent years due to their promising applications in electronics and optoelectronics. In this work, we have explored device level performance of trilayer TMDC heterostructure (MoS2/MX2/MoS2; M = Mo or, W and X = S or, Se) metal oxide semiconductor field effect transistors (MOSFETs) in the quantum ballistic regime. Our simulation shows that device `on' current can be improved by inserting a WS2 monolayer between two MoS2 monolayers. Application of biaxial tensile strain reveals a reduction in drain current which can be attributed to the lowering of carrier effective mass with increased tensile strain. In addition, it is found that gate underlap geometry improves electrostatic device performance by improving sub-threshold swing. However, increase in channel resistance reduces drain current. Besides exploring the prospect of these materials in device performance, novel trilayer TMDC heterostructure double gate field effect transistors (FETs) are proposed for sensing Nano biomolecules as well as for pH sensing. Bottom gate operation ensures these FETs operating beyond Nernst limit of 59 mV/pH. Simulation results found in this work reveal that scaling of bottom gate oxide results in better sensitivity while top oxide scaling exhibits an opposite trend. It is also found that, for identical operating conditions, proposed TMDC FET pH sensors show super-Nernst sensitivity indicating these materials as potential candidates in implementing such sensor. Besides pH sensing, all these materials show high sensitivity in the sub-threshold region as a channel material in nanobiosensor while MoS2/WS2/MoS2 FET shows the least sensitivity among them.

  14. Preparation of Mo-Re-C samples containing Mo7Re13C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

    NASA Astrophysics Data System (ADS)

    Oh-ishi, Katsuyoshi; Nagumo, Kenta; Tateishi, Kazuya; Takafumi, Ohnishi; Yoshikane, Kenta; Sugiyama, Machiko; Oka, Kengo; Kobayashi, Ryota

    2017-01-01

    Mo-Re-C compounds containing Mo7Re13C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo7Re13C with the β-Mn structure using the solid state method. Almost single-phase Mo7Re13C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with a pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K.

  15. A 21-Week Bone Deposition Promoting Exercise Programme Increases Bone Mass in Young People with Down Syndrome

    ERIC Educational Resources Information Center

    Gonzalez-Aguero, Alejandro; Vicente-Rodriguez, German; Gomez-Cabello, Alba; Ara, Ignacio; Moreno, Luis A.; Casajus, Jose A.

    2012-01-01

    Aim: To determine whether the bone mass of young people with Down syndrome may increase, following a 21-week conditioning training programme including plyometric jumps. Method: Twenty-eight participants with Down syndrome (13 females, 15 males) aged 10 to 19 years were divided into exercise (DS-E; n = 14; eight females, six males mean age 13y 8mo,…

  16. Dual UV irradiation-based metal oxide nanoparticles for enhanced antimicrobial activity in Escherichia coli and M13 bacteriophage

    PubMed Central

    Jin, Su-Eon; Hwang, Woochul; Lee, Hyo Jung; Jin, Hyo-Eon

    2017-01-01

    Metal oxide (MO) nanoparticles have been studied as nano-antibiotics due to their antimicrobial activities even in antibiotic-resistant microorganisms. We hypothesized that a hybrid system of dual UV irradiation and MO nanoparticles would have enhanced antimicrobial activities compared with UV or MO nanoparticles alone. In this study, nanoparticles of ZnO, ZnTiO3, MgO, and CuO were selected as model nanoparticles. A dual UV collimated beam device of UV-A and UV-C was developed depending upon the lamp divided by coating. Physicochemical properties of MO nanoparticles were determined using powder X-ray diffractometry (PXRD), Brunauer-Emmett-Teller analysis, and field emission-scanning electron microscopy with energy-dispersive X-ray spectroscopy. Atomic force microscopy with an electrostatic force microscopy mode was used to confirm the surface topology and electrostatic characteristics after dual UV irradiation. For antimicrobial activity test, MO nanoparticles under dual UV irradiation were applied to Escherichia coli and M13 bacteriophage (phage). The UV-A and UV-C showed differential intensities in the coated and uncoated areas (UV-A, coated = uncoated; UV-C, coated ≪ uncoated). MO nanoparticles showed sharp peaks in PXRD patterns, matched to pure materials. Their primary particle sizes were less than 100 nm with irregular shapes, which had an 8.6~25.6 m2/g of specific surface area with mesopores of 22~262 nm. The electrostatic properties of MO nanoparticles were modulated after UV irradiation. ZnO, MgO, and CuO nanoparticles, except ZnTiO3 nanoparticles, showed antibacterial effects on E. coli. Antimicrobial effects on E. coli and phages were also enhanced after cyclic exposure of dual UV and MO nanoparticle treatment using the uncoated area, except ZnO nanoparticles. Our results demonstrate that dual UV-MO nanoparticle hybrid system has a potential for disinfection. We anticipate that it can be developed as a next-generation disinfection system in pharmaceutical industries and water purification systems. PMID:29138562

  17. Dual UV irradiation-based metal oxide nanoparticles for enhanced antimicrobial activity in Escherichia coli and M13 bacteriophage.

    PubMed

    Jin, Su-Eon; Hwang, Woochul; Lee, Hyo Jung; Jin, Hyo-Eon

    2017-01-01

    Metal oxide (MO) nanoparticles have been studied as nano-antibiotics due to their antimicrobial activities even in antibiotic-resistant microorganisms. We hypothesized that a hybrid system of dual UV irradiation and MO nanoparticles would have enhanced antimicrobial activities compared with UV or MO nanoparticles alone. In this study, nanoparticles of ZnO, ZnTiO 3 , MgO, and CuO were selected as model nanoparticles. A dual UV collimated beam device of UV-A and UV-C was developed depending upon the lamp divided by coating. Physicochemical properties of MO nanoparticles were determined using powder X-ray diffractometry (PXRD), Brunauer-Emmett-Teller analysis, and field emission-scanning electron microscopy with energy-dispersive X-ray spectroscopy. Atomic force microscopy with an electrostatic force microscopy mode was used to confirm the surface topology and electrostatic characteristics after dual UV irradiation. For antimicrobial activity test, MO nanoparticles under dual UV irradiation were applied to Escherichia coli and M13 bacteriophage (phage). The UV-A and UV-C showed differential intensities in the coated and uncoated areas (UV-A, coated = uncoated; UV-C, coated ≪ uncoated). MO nanoparticles showed sharp peaks in PXRD patterns, matched to pure materials. Their primary particle sizes were less than 100 nm with irregular shapes, which had an 8.6~25.6 m 2 /g of specific surface area with mesopores of 22~262 nm. The electrostatic properties of MO nanoparticles were modulated after UV irradiation. ZnO, MgO, and CuO nanoparticles, except ZnTiO 3 nanoparticles, showed antibacterial effects on E. coli . Antimicrobial effects on E. coli and phages were also enhanced after cyclic exposure of dual UV and MO nanoparticle treatment using the uncoated area, except ZnO nanoparticles. Our results demonstrate that dual UV-MO nanoparticle hybrid system has a potential for disinfection. We anticipate that it can be developed as a next-generation disinfection system in pharmaceutical industries and water purification systems.

  18. Assessment of CO2 discharge in a spring using time-variant stable carbon isotope data as a natural analogue study of CO2 leakage

    NASA Astrophysics Data System (ADS)

    Yu, Soonyoung; Chae, Gitak; Jo, Minki; Kim, Jeong-Chan; Yun, Seong-Taek

    2015-04-01

    CO2-rich springs have been studied as a natural analogue of CO2 leakage through shallow subsurface environment, as they provide information on the behaviors of CO2 during the leakage from geologic CO2 storage sites. For this study, we monitored the δ13C values as well as temperature, pH, EC, DO, and alkalinity for a CO2-rich spring for 48 hours. The water samples (N=47) were collected every hour in stopper bottles without headspace to avoid the interaction with air and the CO2 degassing. The δ13C values of total dissolved inorganic carbon (TDIC) in the water samples were analyzed using a cavity ring-down spectroscopy (CRDS) system (Picarro). The values of δ13CTDIC, temperature, pH, EC, DO, and alkalinity were in the range of -9.43 ~ -8.91 o 12.3 ~ 13.2oC, 4.86 ~ 5.02, 186 ~ 189 μS/cm, 1.8 ~ 3.4 mg/L, and 0.74 ~ 0.95 meq/L, respectively. The concentrations of TDIC calculated using pH and alkalinity values were between 22.5 and 34.8 mmol/L. The δ13CTDIC data imply that dissolved carbon in the spring was derived from a deep-seated source (i.e., magmatic) that was slightly intermixed with soil CO2. Careful examination of the time-series variation of measured parameters shows the following characteristics: 1) the δ13CTDIC values are negatively correlated with pH (r = -0.59) and positively correlated with TDIC (r = 0.58), and 2) delay times of the change of pH and alkalinity following the change of δ13CTDIC values are 0 and -3 hours, respectively; the pH change occurs simultaneously with the change of δ13CTDIC, while the alkalinity change happens before 3 hours. Our results indicate that the studied CO2-rich spring is influenced by the intermittent supply of deep-seated CO2. [Acknowledgment] This work was financially supported by the fundamental research project of KIGAM and partially by the "Geo-Advanced Innovative Action (GAIA) Project (2014000530003)" from Korea Ministry of Environment (MOE).

  19. Albumin adsorption on CoCrMo alloy surfaces

    NASA Astrophysics Data System (ADS)

    Yan, Yu; Yang, Hongjuan; Su, Yanjing; Qiao, Lijie

    2015-12-01

    Proteins can adsorb on the surface of artificial joints immediately after being implanted. Although research studying protein adsorption on medical material surfaces has been carried out, the mechanism of the proteins’ adsorption which affects the corrosion behaviour of such materials still lacks in situ observation at the micro level. The adsorption of bovine serum albumin (BSA) on CoCrMo alloy surfaces was studied in situ by AFM and SKPFM as a function of pH and the charge of CoCrMo alloy surfaces. Results showed that when the specimens were uncharged, hydrophobic interaction could govern the process of the adsorption rather than electrostatic interaction, and BSA molecules tended to adsorb on the surfaces forming a monolayer in the side-on model. Results also showed that adsorbed BSA molecules could promote the corrosion process for CoCrMo alloys. When the surface was positively charged, the electrostatic interaction played a leading role in the adsorption process. The maximum adsorption occurred at the isoelectric point (pH 4.7) of BSA.

  20. Survey of practices around pharmaceutical company funding for continuing professional development among medical oncologists and trainees in Australia.

    PubMed

    Lee, Yeh Chen; Kroon, René; Koczwara, Bogda; Haines, Ian; Francis, Kay; Millward, Michael; Kefford, Richard; Olver, Ian; Mileshkin, Linda

    2017-08-01

    The completion of continuing professional development (CPD) is mandatory for medical oncologists and trainees (MO&T). Pharmaceutical companies may fund some CPD activities, but there is increasing debate about the potential for conflicts of interest (COI). To assess current practices around funding to attend CPD activities. An electronic survey was distributed to Australian MO&T. The survey asked questions about current practices, institutional policies and perceptions about attending CPD funded by pharmaceutical companies. The design looked at comparing responses between MO&T as well as their understanding of and training around institutional and ethical process. A total of 157 of 653 (24%) responses was received, the majority from MO (76%). Most CPD activities attended by MO&T were self-funded (53%), followed by funding from institutions (19%), pharmaceutical companies (16%) and salary award (16%). Most institutions allowed MO&T to receive CPD funding from professional organisations (104/157, 66%) or pharmaceutical companies (90/157, 57%). A minority of respondents (13/157, 8%) reported that the process to use pharmaceutical funds had been considered by an ethics committee. Although 103/157 (66%) had received pharmaceutical funding for CPD, most (109/157, 69%) reported never receiving training about potential COI. The lack of education was more noticeable among trainees (odds ratio (OR) 8.61, P = 0.02). MO&T acknowledged the potential bias towards a pharmaceutical product (P = 0.05) but believed there was adequate separation between themselves and pharmaceutical companies (P < 0.01). Majority of CPD attended by MO&T is self-funded. There is lack of clarity in institutional policies regarding external funding support for CPD activities. Formal education about potential COI is lacking. © 2017 Royal Australasian College of Physicians.

  1. Reaction of BH4- with [Mo2Cp2(mu-SMe)n] species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands.

    PubMed

    Cabon, Nolwenn; Petillon, Francois Y; Schollhammer, Philippe; Talarmin, Jean; Muir, Kenneth W

    2004-09-07

    The reaction of mono- or dichloro-dimolybdenum(III) complexes [Mo2Cp2(mu-SMe)2(mu-Cl)(mu-Y)] (Cp=eta5-C5H5; 1, Y=SMe; 2, Y=PPh2; 3, Y=Cl) with NaBH4 at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives and has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the mu-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-PPh2)(mu-N=CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4 with nitrile derivatives, [Mo2Cp2(mu-SMe)4-n(CH3CN)2n]n+(5, n=1; 6 n=2), afforded the tetrahydroborato compound 8, together with a mu-azavinylidene species [Mo2Cp2(mu-SMe)3(mu-N=CHMe)](14), when n=1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-BH4)(mu-N=CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(mu-SMe)2(mu-X)(mu-Y)] (1, X/Y=Cl/SMe; 2, X/Y=Cl/PPh2; 4, X/Y=SMe/PPh2).

  2. Early impairment of somatosensory evoked potentials in very young children with achondroplasia with foramen magnum stenosis.

    PubMed

    Fornarino, Stefania; Rossi, Daniela Paola; Severino, Mariasavina; Pistorio, Angela; Allegri, Anna Elsa Maria; Martelli, Simona; Doria Lamba, Laura; Lanteri, Paola

    2017-02-01

    To evaluate the contribution of somatosensory evoked potentials after median nerve (MN-SEPs) and posterior tibial nerve (PTN-SEPs) stimulation in functional assessment of cervical and lumbar spinal stenosis in children with achondroplasia. We reviewed MN-SEPs, PTN-SEPs, and spinal magnetic resonance imaging (MRI) examinations performed in 58 patients with achondroplasia (25 males, 33 females; age range 21d-16y 10mo; mean age 4y 3mo [SD 4y 1mo]). Patients were subdivided into four age categories: <2 years, between 2 to 4 years, between 4 to 8 years, and ≥8 years. The peak latency of P37 for PTN-SEPs, the peak latencies of N11, N13, P14, and N20, and the N13-N20 interpeak latency (IPL) for MN-SEPs were collected; the diagnostic accuracy measures of these parameters (analysis of receiver operating characteristic [ROC] curves) with respect to the presence of foramen magnum or lumbar spinal stenosis were analysed in each age category. The ROC curve analysis showed that the most sensitive parameter in detecting the presence of foramen magnum stenosis was P37 latency in the first two age categories (<2y and ≥2-4y; sensitivity 0.63, specificity 1.00, and sensitivity 1.00, specificity 0.75 respectively). In the third age category (≥4-8y), the most sensitive parameter in detecting the presence of foramen magnum stenosis was IPLs N13-N20 (sensitivity 0.73, specificity 0.87), whereas in the last age category (≥8y), the most important parameter was N20 latency (sensitivity 0.75, specificity 0.77). In children with achondroplasia, the cortical component of PTN-SEPs is more sensitive than the cortical component and central conduction time of MN-SEPs in detection of cervical spinal cord compression at early ages. © 2016 Mac Keith Press.

  3. 78 FR 55246 - Combined Notice of Filings

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-09-10

    ... that the Commission has received the following Natural Gas Pipeline Rate and Refund Report filings: Filings Instituting Proceedings Docket Numbers: RP13-1290-000. Applicants: MoGas Pipeline LLC. Description: Annual Fuel and Gas Loss Retention Percentage Adjustment Filing to be effective 10/1/2013. Filed Date: 8...

  4. 40 CFR 471.31 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... TSS 6.97 3.32 pH (1) (1) 1 Within the range of 7.5 to 10.0 at all times. (c) Rolling contact cooling... Nickel 7.24 4.79 Fluoride 225 99.6 Oil and grease 75.4 45.3 TSS 155 73.5 pH (1) (1) 1 Within the range of... 0.295 Fluoride 13.8 6.13 Oil and grease 4.64 2.79 TSS 9.51 4.53 pH (1) (1) 1 Within the range of 7.5...

  5. 40 CFR 471.31 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... TSS 6.97 3.32 pH (1) (1) 1 Within the range of 7.5 to 10.0 at all times. (c) Rolling contact cooling... Nickel 7.24 4.79 Fluoride 225 99.6 Oil and grease 75.4 45.3 TSS 155 73.5 pH (1) (1) 1 Within the range of... 0.295 Fluoride 13.8 6.13 Oil and grease 4.64 2.79 TSS 9.51 4.53 pH (1) (1) 1 Within the range of 7.5...

  6. The use of refused tea as litter material for broiler chickens.

    PubMed

    Atapattu, N S B M; Wickramasinghe, K P

    2007-05-01

    A completely randomized design experiment was conducted to determine the suitability of refused tea (RT) as a litter material for broiler chickens. Physiochemical properties of RT were compared with paddy husk (PH). Subsequently, broilers were raised on RT- or PH-based litter to compare the performances and litter qualities. Twenty-day-old broiler chicks (n = 150) were randomly allocated into 6 deep litter pens so that each treatment had 3 replicates. Chicks received 0.8 ft(2) of floor spacing until d 28 and 1.3 ft(2) thereafter. Each cage had a feeder and a drinker. Litter materials and litter samples taken on 28, 35, and 39 d were analyzed for bulk density, moisture, ash, and N. Chick mortality was low (1.3%) and similar on 2 types of litters. Live weights on d 28, 35, 39, and weight gains, feed intakes, dressing percentages, and feed conversion ratios were not affected by the type of litter material. The bulk density, moisture level, and pH of the RT were comparable with PH. Even though the water-holding capacity of PH (213%) was significantly higher (P < 0.01) than RT (70%), the latter material had significantly higher (P < 0.01) water-releasing capacity compared with the former (17.9 vs. 13.6%). Throughout the experiment the RT litter had around 10% units higher moisture level than PH litter. By d 39, the moisture content of the RT litter was (48%) significantly higher (P = 0.05) than PH litter (37%). The N contents of RT litter were higher (P < 0.05) than those of PH on d 28, 35, and 39, being 8.1, 7.8, and 7% and 3.4, 3.6, and 3%, respectively. It was concluded that RT could be successfully used as an alternative litter material for broilers. A higher N content in RT-based spent broiler litter would make it be a better organic fertilizer and ruminant feed compared with PH-based litter.

  7. Changes in activation energy and kinetics of heat-activated persulfate oxidation of phenol in response to changes in pH and temperature.

    PubMed

    Ma, Jie; Li, Haiyan; Chi, Liping; Chen, Hongkun; Chen, Changzhao

    2017-12-01

    Persulfate (peroxydisulfate, S 2 O 8 2- ) is the newest oxidant used for the in situ chemical oxidation (ISCO) remediation of soil and groundwater. The present study investigated impacts of solution pH, temperature, and persulfate concentration on the reaction rate constant (k 1 ), activation energy (E a ), and reaction order of the heat-activated persulfate process. Phenol was chosen as the model organic contaminant. As temperature increased from 30 °C to 70 °C, k 1 exhibited a significant increase from 0.003 h -1 ∼0.962 h -1 (pH 1.3-13.9) to 1.184 h -1 ∼9.91 h -1 (pH 1.3-13.9), which corroborated with the activation of persulfate using heat. As pH increased from 1.3 to 13.9, k 1 exhibited a 4.3-fold increase at 70 °C and a 320-fold increase at 30 °C, thereby suggesting that: 1) the phenol oxidation rate increased under alkaline conditions, and 2) the enhancement of reaction rate due to alkaline activation was more pronounced at a lower temperature. Increasing pH significantly reduced E a from 139.7 ± 1.3 kJ/mol at pH 1.3 to 52.0 ± 3.3 kJ/mol at pH 13.9. In contrast to changing pH, increasing persulfate concentration from 20 to 320 mM significantly increased k 1 but did not affect E a . Changes in E a suggest that persulfate oxidation of phenol experienced different reaction pathways or elementary reaction sequences as the pH changed from 1.3 to 13.9. In addition, the k 1 and E a data also suggest that a minimal pH threshold of ∼11 was required for the effective alkaline activation of persulfate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Hyperpolarized Amino Acid Derivatives as Multivalent Magnetic Resonance pH Sensor Molecules.

    PubMed

    Hundshammer, Christian; Düwel, Stephan; Ruseckas, David; Topping, Geoffrey; Dzien, Piotr; Müller, Christoph; Feuerecker, Benedikt; Hövener, Jan B; Haase, Axel; Schwaiger, Markus; Glaser, Steffen J; Schilling, Franz

    2018-02-15

    pH is a tightly regulated physiological parameter that is often altered in diseased states like cancer. The development of biosensors that can be used to non-invasively image pH with hyperpolarized (HP) magnetic resonance spectroscopic imaging has therefore recently gained tremendous interest. However, most of the known HP-sensors have only individually and not comprehensively been analyzed for their biocompatibility, their pH sensitivity under physiological conditions, and the effects of chemical derivatization on their logarithmic acid dissociation constant (p K a ). Proteinogenic amino acids are biocompatible, can be hyperpolarized and have at least two pH sensitive moieties. However, they do not exhibit a pH sensitivity in the physiologically relevant pH range. Here, we developed a systematic approach to tailor the p K a of molecules using modifications of carbon chain length and derivatization rendering these molecules interesting for pH biosensing. Notably, we identified several derivatives such as [1- 13 C]serine amide and [1- 13 C]-2,3-diaminopropionic acid as novel pH sensors. They bear several spin-1/2 nuclei ( 13 C, 15 N, 31 P) with high sensitivity up to 4.8 ppm/pH and we show that 13 C spins can be hyperpolarized with dissolution dynamic polarization (DNP). Our findings elucidate the molecular mechanisms of chemical shift pH sensors that might help to design tailored probes for specific pH in vivo imaging applications.

  9. Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method.

    PubMed

    Park, Kyung Ho; Mohapatra, D; Reddy, B Ramachandra

    2006-11-16

    The petroleum refining industry makes extensive use of hydroprocessing catalysts. These catalysts contain environmentally critical and economically valuable metals such as Mo, V, Ni and Co. In the present study, a simple hydrometallurgical processing of spent hydrodesulphurization (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixture was investigated. Recovery of molybdenum was largely dependent on the concentrations of Na2CO3 and H2O2 in the reaction medium, which in turn controls the pH of leach liquor and the presence of Al and Ni as impurities. Under the optimum leaching conditions (40 g L(-1) Na2CO3, 6 vol.% H2O2, room temperature, 1h) about 85% recovery of Mo was achieved. The leach liquor was processed by the carbon adsorption method, which selectively adsorbs Mo at pH around 0.75. Desorption of Mo was selective at 15 vol.% NH4OH. With a single stage contact, it was found possible to achieve >99%, adsorption and desorption efficiency. Using this method, recovery of molybdenum as MoO3 product of 99.4% purity was achieved.

  10. Interstrain Differences in CO2-Induced Pulmonary Hemorrhage in Mice.

    PubMed

    Fisher, Suhrim; Burgess, Winona L; Hines, Kenneth D; Mason, Gary L; Owiny, James R

    2016-11-01

    Carbon dioxide is the most commonly used gas for euthanasia of rodents. The current AVMA Guidelines recommend slowly filling the container with CO2 (SF) and now indicate that the practice of placing conscious animals in containers prefilled with CO2 (PF) is unacceptable. An investigator noted pulmonary hemorrhage (PH) in BALB/c mice euthanized by SF that was not observed after PF. Here we evaluated whether the air-displacement rate (SF compared with PF) influenced the development of PH or nasal hemorrhage (NH) in 2 commonly used mouse strains. In addition, we investigated the prevalence of PH and NH in mice euthanized by isoflurane overdose (IO). Male and female (age groups, 6 wk and 6 mo) BALB/c and C57BL/6 mice were euthanized by SF or PF. In addition, 6-mo-old BALB/c male mice were euthanized by IO. Lung, nasal turbinates, brain, and reproductive organs were collected for gross and histologic evaluation and scored for degree of hemorrhage (score, 0 to 3). Severity of hemorrhage did not differ according to mouse age or sex. PH in BALB/c mice was more severe after SF than PF, and SF and PF induced more severe PH in BALB/c than in C57BL/6 mice. PH in 6-mo-old male BALB/c mice was more severe after SF than IO. Neither SF, PF, nor IO influenced the prevalence of NH in any group. This study demonstrates that the method of euthanasia may need to be altered depending on the mouse strain used.

  11. Optimizing Heat Treatment Process of Fe-13Cr-3Mo-3Ni Martensitic Stainless of Steel

    NASA Astrophysics Data System (ADS)

    Anwar, M. S.; Prifiharni, S.; Mabruri, E.

    2017-05-01

    The Fe-13Cr-3Mo-3Ni stainless steels are modified into martensitic stainless steels for steam turbine blades application. The working temperature of steam turbine was around 600 - 700 °C. The improvement properties of turbine blade material is necessary to maintain steam turbine work. The previous research revealed that it has corrosion resistance of Fe-13Cr-3Mo-3Ni which is better than 13Cr stainless steels in the chloride environment. In this work, the effect of heat treatment on microstructure and hardness of Fe-13Cr-3Mo-3Ni stainless steels has been studied. The steel was prepared by induction melting followed by hot forging. The steels were austenitized at 1000, 1050, and 1100 °C for 1 hour and were tempered at 600, 650, and 700 °C for 1 hour. The steels were then subjected to metallographic observation and hardness test of Rockwell C. The optimal heat treatment of Fe-13Cr-3Mo-3Ni was carried out austenitized in 1050 °C and tempered in 600 - 700 °C.

  12. Biosorption of molybdenum and chromium

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

    Pryfogle, P.A.; Maiers, D.T.; Wichlacz, P.L.

    1989-01-01

    The effects of metal solution concentration, biomass density, length of exposure time, and pH were determined for biosorption of molybdenum (Mo) and chromium (Cr) by three organisms. Results indicate that it is possible to sorb Mo and Cr from dilute solutions. Differences were observed in the abilities of an organism to sorb Mo and Cr as well as among respective abilities of the three microorganisms. This suggests an inherent selectivity of the organism which may afford the selectivity of the organism which may afford the means to control a sorption-based process. Results also indicate that the metal sorption abilities ofmore » these microorganisms depend on duration of exposure, biomass density, solution pH, and the metal concentration of the solution. Each of these parameters suggests an additional means of controlling the sorption process. 20 refs., 6 figs., 3 tabs.« less

  13. Terrain Analysis Procedural Guide for Built-Up Areas (Report Number 13 in the ETL (Engineer Topographic Laboratories) Series on Guides for Army Terrain Analysts).

    DTIC Science & Technology

    1984-04-01

    J FRODIGH APR 84 TTL-0354 UNCLASSIFIED F/ 8/2 NLE E EIIEII EEEBhEEBh|hEEE EEEBiEEEEEEEEE LI mo|mommoll mo|mlollsom| so|||lmomllsIEEE|lhEEEE|hEE EEE...DISTRIBUTION STATEMENT (of thie Report) SHDL Approved for Public Release; Distribution Unlimited 18.~~~~- SUPEMNAY OE Thi. dcIumnt sATEMEN bo e ...and Mr. Robert P. Macchia, and Mr. Walter E . Boge, were Technical Directors of the Engineer Topographic Laboratories during this period. DI AoeesUlof

  14. Charge disproportionation in tetragonal La2MoO5, a small band gap semiconductor influenced by direct Mo-Mo bonding.

    PubMed

    Colabello, Diane M; Camino, Fernando E; Huq, Ashfia; Hybertsen, Mark; Khalifah, Peter G

    2015-01-28

    The structure of the novel compound La2MoO5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo2O10) and square prismatic (Mo2O8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo2O10 dimers is 2.684(8) Å, while there are two types of Mo2O8 dimers with Mo-Mo bonds lengths of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La2MoO5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo2O10 dimers contain only Mo(5+) (d(1)), while the prismatic Mo2O8 dimers only contain Mo(3+) (d(3)), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo(4+), a phenomenon which has not previously been observed in solid-state compounds. La2MoO5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La2MoO5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. It is shown that the d-orbital splitting associated with the Mo2O8 and Mo2O10 dimeric units can be rationalized using simple molecular orbital bonding concepts.

  15. Neonatal Acid-Base Status in Fetuses with Abnormal Vertebro- and Cerebro-Placental Ratios.

    PubMed

    Morales-Roselló, José; Khalil, Asma; Ferri-Folch, Blanca; Perales-Marín, Alfredo

    2015-01-01

    A low cerebro-placental ratio (CPR) at term suggests the existence of failure to reach growth potential (FRGP) with a higher risk of poor neonatal acid-base status. This study aimed to evaluate whether similar findings were also seen in the vertebral artery (vertebro-placental ratio, VPR), supplying 30% of the cerebral flow. We studied term fetuses classified into groups according to birth weight (BW), CPR and VPR. BW was expressed in centiles and ratios in multiples of the median (MoM). Subsequently, associations with neonatal pH values were evaluated by means of regression curves and Mann-Whitney tests. VPR MoM correlated with BW centiles (p < 0.0001, R2 = 0.042) and its distribution resembled that of CPR MoM (p < 0.001). When both arteries were compared, adequate-for-gestational-age (AGA) fetuses with either low CPR or low VPR had lower neonatal venous pH values (p < 0.05, p < 0.01, respectively). However, in case of small-for-gestational-age (SGA) fetuses, only those with low VPR had significantly lower neonatal arterial and venous pH values (p < 0.05). Blood flow in the vertebral artery mimics that in the middle cerebral artery supporting the FRGP model. Both CPR and VPR identify AGA fetuses with lower neonatal pH values, but only VPR identifies SGA with lower pH values. Hypoxemia might be reflected as a generalized cerebral vasodilation demonstrated as low CPR and VPR.

  16. The Hardest Superconducting Metal Nitride

    NASA Astrophysics Data System (ADS)

    Wang, Shanmin; Antonio, Daniel; Yu, Xiaohui; Zhang, Jianzhong; Cornelius, Andrew L.; He, Duanwei; Zhao, Yusheng

    2015-09-01

    Transition-metal (TM) nitrides are a class of compounds with a wide range of properties and applications. Hard superconducting nitrides are of particular interest for electronic applications under working conditions such as coating and high stress (e.g., electromechanical systems). However, most of the known TM nitrides crystallize in the rock-salt structure, a structure that is unfavorable to resist shear strain, and they exhibit relatively low indentation hardness, typically in the range of 10-20 GPa. Here, we report high-pressure synthesis of hexagonal δ-MoN and cubic γ-MoN through an ion-exchange reaction at 3.5 GPa. The final products are in the bulk form with crystallite sizes of 50 - 80 μm. Based on indentation testing on single crystals, hexagonal δ-MoN exhibits excellent hardness of ~30 GPa, which is 30% higher than cubic γ-MoN (~23 GPa) and is so far the hardest among the known metal nitrides. The hardness enhancement in hexagonal phase is attributed to extended covalently bonded Mo-N network than that in cubic phase. The measured superconducting transition temperatures for δ-MoN and cubic γ-MoN are 13.8 and 5.5 K, respectively, in good agreement with previous measurements.

  17. Effect of molybdenum additions on the microstructures and corrosion behaviours of 316L stainless steel-based alloys

    DOE PAGES

    Rahman, T.; Ebert, W. L.; Indacochea, J. E.

    2018-02-28

    Alloys were made by alloying 5, 10, 15, 17.5, and 20 wt % Mo with Type 316L stainless steel. Sigma phases containing 21–29 wt % Mo formed along the austenite grain boundaries with the addition of 5 wt % Mo and increased with additions up to 15 wt % Mo, but they decreased with further additions. Laves phases containing 33–40 wt % Mo co-precipitated at additions of 10 wt % Mo which increased with further Mo increases. The corrosion resistance, assessed by potentiodynamic polarisation in a 10 mM NaCl solution adjusted to pH 4, increased relative to Type 316L formore » alloys made with 5 and 10 wt % added Mo, but decreased with further additions due to preferential corrosion of the Laves phase. The alloy made with 10 wt % added Mo had the highest corrosion resistance due primarily to the high Mo content of the austenite.« less

  18. Effect of molybdenum additions on the microstructures and corrosion behaviours of 316L stainless steel-based alloys

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

    Rahman, T.; Ebert, W. L.; Indacochea, J. E.

    Alloys were made by alloying 5, 10, 15, 17.5, and 20 wt % Mo with Type 316L stainless steel. Sigma phases containing 21–29 wt % Mo formed along the austenite grain boundaries with the addition of 5 wt % Mo and increased with additions up to 15 wt % Mo, but they decreased with further additions. Laves phases containing 33–40 wt % Mo co-precipitated at additions of 10 wt % Mo which increased with further Mo increases. The corrosion resistance, assessed by potentiodynamic polarisation in a 10 mM NaCl solution adjusted to pH 4, increased relative to Type 316L formore » alloys made with 5 and 10 wt % added Mo, but decreased with further additions due to preferential corrosion of the Laves phase. The alloy made with 10 wt % added Mo had the highest corrosion resistance due primarily to the high Mo content of the austenite.« less

  19. Ganoderma-Like MoS2 /NiS2 with Single Platinum Atoms Doping as an Efficient and Stable Hydrogen Evolution Reaction Catalyst.

    PubMed

    Guan, Yongxin; Feng, Yangyang; Wan, Jing; Yang, Xiaohui; Fang, Ling; Gu, Xiao; Liu, Ruirui; Huang, Zhengyong; Li, Jian; Luo, Jun; Li, Changming; Wang, Yu

    2018-05-27

    Herein, a unique ganoderma-like MoS 2 /NiS 2 hetero-nanostructure with isolated Pt atoms anchored is reported. This novel ganoderma-like heterostructure can not only efficiently disperse and confine the few-layer MoS 2 nanosheets to fully expose the edge sites of MoS 2 , and provide more opportunity to capture the Pt atoms, but also tune the electronic structure to modify the catalytic activity. Because of the favorable dispersibility and exposed large specific surface area, single Pt atoms can be easily anchored on MoS 2 nanosheets with ultrahigh loading of 1.8 at% (the highest is 1.3 at% to date). Owing to the ganoderma-like structure and platinum atoms doping, this catalyst shows Pt-like catalytic activity for the hydrogen evolution reaction with an ultralow overpotential of 34 mV and excellent durability of only 2% increase in overpotential for 72 h under the constant current density of 10 mA cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Solubility of ammonium acid urate nephroliths from bottlenose dolphins (Tursiops truncatus).

    PubMed

    Argade, Sulabha; Smith, Cynthia R; Shaw, Timothy; Zupkas, Paul; Schmitt, Todd L; Venn-Watson, Stephanie; Sur, Roger L

    2013-12-01

    Nephrolithiasis has been identified in managed populations of bottlenose dolphins (Tursiops truncatus); most of these nephroliths are composed of 100% ammonium acid urate (AAU). Several therapies are being investigated to treat and prevent nephrolithiasis in dolphins including the alkalization of urine for dissolution of nephroliths. This study evaluates the solubility of AAU nephroliths in a phosphate buffer, pH range 6.0-8.0, and in a carbonate-bicarbonate buffer, pH range 9.0-10.8. AAU nephroliths were obtained from six dolphins and solubility studies were conducted using reverse-phase high performance liquid chromatography with ultraviolet detection at 290 nm. AAU nephroliths were much more soluble in a carbonate-bicarbonate buffer, pH range 9.0-10.8 compared to phosphate buffer pH range 6.0-8.0. In the pH range 6.0-8.0, the solubility was 45% lower in potassium phosphate buffer compared to sodium phosphate buffer. When citrate was used along with phosphate in the same pH range, the solubility was improved by 13%. At pH 7 and pH 8, 150 mM ionic strength buffer was optimum for dissolution. In summary, adjustment of urinary pH alone does not appear to be a useful way to treat AAU stones in bottlenose dolphins. Better understanding of the pathophysiology of AAU nephrolithiasis in dolphins is needed to optimize kidney stone prevention and treatment.

  1. Electron-paramagnetic-resonance studies on nitrogenase of Klebsiella pneumoniae. Evidence for acetylene- and ethylene-nitrogenase transient complexes.

    PubMed Central

    Lowe, D J; Eady, R R; Thorneley, N F

    1978-01-01

    Klebsiella pneumoniae nitrogenase exhibited four new electron-paramagnetic-resonance signals during turnover at 10 degrees C, pH7.4, which were assigned to intermediates present in low concentrations in the steady state. 57Fe-substituted Mo--Fe protein showed that they arose from Fe--S clusters in the Mo--Fe protein of nitrogenase. The new signals are designated: Ic, g values at 4.67, 3.37 and approx. 2.0; VI, g values at 2.125, 2.000 and 2.000; VII, g values at 5.7 and 5.4; VIII, g values at 2.092, 1.974 and 1.933. The sharp axial signal VI arises from a Fe4S4 cluster at the --1 oxidation level. This signal was only detected in the presence of ethylene and provides the first evidence of an enzyme--product complex for nitrogenase. [13C]Acetylene and [13C]ethylene provided no evidence for direct binding of this substrate and product to the Fe--S clusters giving rise to these signals. The dependence of signal intensities on acetylene concentration indicated two types of binding site, with apparent dissociation constants K less than 16 micron and K approximately 13mM. A single binding site for ethylene (K=1.5mM) was detected. A scheme is proposed for the mechanism of reduction of acetylene to ethylene and inhibition of this reaction by CO. PMID:210766

  2. Incorporation of Co into MoS2/graphene nanocomposites: One effective way to enhance the cycling stability of Li/Na storage

    NASA Astrophysics Data System (ADS)

    Li, Xiaomin; Feng, Zhenxing; Zai, Jiantao; Ma, Zi-Feng; Qian, Xuefeng

    2018-01-01

    Layered transition metal dichalcogenides are promising as lithium and/or sodium storage materials for lithium and sodium (Li/Na) ion batteries. However they always exhibit limited rate capability and long-term cycling stability, due to the fact that their 2D structures are easily restacking and agglomeration during cycling process and further result poor electrochemical reversibility. Herein, hierarchical Co1/3Mo2/3S2/graphene nanocomposites without CoSx and MoS2 impurities have been synthesized via one-pot solvothermal process. The incorporation of Co into MoS2 at atomic level can not only give rise to thinner and smaller nanosheets in the nanocomposites than MoS2/graphene nanocomposites, but also significantly decrease the size of in-situ formed MoS2/CoSx nanoparticles during electrochemical conversion process, which can greatly promoting the ion diffusion and suppressing the aggregation of active materials. Furthermore, the conductivity of Co1/3Mo2/3S2/graphene nanocomposites can be enhanced from 0.46 S m-1 (MoS2/graphene) to 1.39 S m-1via changing the semiconducting MoS2 to metallic Co1/3Mo2/3S2. The simultaneously optimized electron conductivity and ions diffusion dynamics of Co1/3Mo2/3S2/graphene nanocomposites can effectively improve the reversibility of electrochemical conversion reactions. A capacity of 940 mAh g-1 and 529 mAh g-1 can be maintained at 3200th cycle (2 A g-1) in lithium-ion batteries and 200th cycle (1 A g-1) in sodium-ion batteries, respectively.

  3. Bioaccessibility of micron-sized powder particles of molybdenum metal, iron metal, molybdenum oxides and ferromolybdenum--Importance of surface oxides.

    PubMed

    Mörsdorf, Alexander; Odnevall Wallinder, Inger; Hedberg, Yolanda

    2015-08-01

    The European chemical framework REACH requires that hazards and risks posed by chemicals, including alloys and metals, that are manufactured, imported or used in different products (substances or articles) are identified and proven safe for humans and the environment. Metals and alloys need hence to be investigated on their extent of released metals (bioaccessibility) in biologically relevant environments. Read-across from available studies may be used for similar materials. This study investigates the release of molybdenum and iron from powder particles of molybdenum metal (Mo), a ferromolybdenum alloy (FeMo), an iron metal powder (Fe), MoO2, and MoO3 in different synthetic body fluids of pH ranging from 1.5 to 7.4 and of different composition. Spectroscopic tools and cyclic voltammetry have been employed to characterize surface oxides, microscopy, light scattering and nitrogen absorption for particle characterization, and atomic absorption spectroscopy to quantify released amounts of metals. The release of molybdenum from the Mo powder generally increased with pH and was influenced by the fluid composition. The mixed iron and molybdenum surface oxide of the FeMo powder acted as a barrier both at acidic and weakly alkaline conditions. These findings underline the importance of the surface oxide characteristics for the bioaccessibility of metal alloys. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  4. Atomically Thin-Layered Molybdenum Disulfide (MoS2) for Bulk-Heterojunction Solar Cells.

    PubMed

    Singh, Eric; Kim, Ki Seok; Yeom, Geun Young; Nalwa, Hari Singh

    2017-02-01

    Transition metal dichalcogenides (TMDs) are becoming significant because of their interesting semiconducting and photonic properties. In particular, TMDs such as molybdenum disulfide (MoS 2 ), molybdenum diselenide (MoSe 2 ), tungsten disulfide (WS 2 ), tungsten diselenide (WSe 2 ), titanium disulfide (TiS 2 ), tantalum sulfide (TaS 2 ), and niobium selenide (NbSe 2 ) are increasingly attracting attention for their applications in solar cell devices. In this review, we give a brief introduction to TMDs with a focus on MoS 2 ; and thereafter, emphasize the role of atomically thin MoS 2 layers in fabricating solar cell devices, including bulk-heterojunction, organic, and perovskites-based solar cells. Layered MoS 2 has been used as the hole-transport layer (HTL), electron-transport layer (ETL), interfacial layer, and protective layer in fabricating heterojunction solar cells. The trilayer graphene/MoS 2 /n-Si solar cell devices exhibit a power-conversion efficiency of 11.1%. The effects of plasma and chemical doping on the photovoltaic performance of MoS 2 solar cells have been analyzed. After doping and electrical gating, a power-conversion efficiency (PCE) of 9.03% has been observed for the MoS 2 /h-BN/GaAs heterostructure solar cells. The MoS 2 -containing perovskites-based solar cells show a PCE as high as 13.3%. The PCE of MoS 2 -based organic solar cells exceeds 8.40%. The stability of MoS 2 solar cells measured under ambient conditions and light illumination has been discussed. The MoS 2 -based materials show a great potential for solar cell devices along with high PCE; however, in this connection, their long-term environmental stability is also of equal importance for commercial applications.

  5. Cyclopentadienylniobium and -molybdenum phosphorodithioate complexes. X-ray crystal structures of CpNbCl sub 3 (S sub 2 P(OPr sup i ) sub 2 ), CpNbCl(. mu. -Cl) sub 2 Nb(S sub 2 P(OPr sup i ) sub 2 )Cp, and cis-Cp prime Mo(CO) sub 2 (S sub 2 P(OPr sup i ) sub 2 )

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

    Woodward, S.; Riaz, U.; Curtis, M.D.

    1990-10-01

    Reaction of CpNbCl{sub 4} (Cp = {eta}-C{sub 5}H{sub 5}) with (Pr{sup i}O){sub 2}P(S)(SH) in the presence of NEt{sub 3} yields CpNbCl{sub 3}(S{sub 2}P(S{sub 2}Pr{sup i}){sub 2}) (1). Reduction of 1 with Na/Hg affords the Nb-Nb-bonded complex CpNbCl({mu}-Cl){sub 2}Nb(S{sub 2}P(OR){sub 2})Cp (2). In refluxing toluene, (Pr{sup i}O){sub 2}P(S)(SH) with (Cp{prime}Mo(CO){sub 3}){sub 2} (Cp{prime} = {eta}-C{sub 5}H{sub 4}Me) gives cis-Cp{prime}Mo(CO){sub 2}(S{sub 2}P(OPr{sup i}){sub 2}) (3). Oxidation of 3 with I{sub 2} affords Cp{prime}MoI{sub 2}(CO)(S{sub 2}P(OPr{sup i}){sub 2}) (4). The crystal structures of 1-3 are compared. For 1, triclinic, P{bar 1}, a = 7.122 (3) {angstrom}, b = 11.365 (4) {angstrom}, c =more » 12.532 (4) {angstrom}, {alpha} = 77.38 (3){degree}, {beta} = 89.08 (3){degree}, {gamma} = 72.87 (3){degree}, V = 944.5 (8) {angstrom}{sup 3}. For 2, triclinic, P{bar 1}, a = 7.251 (3) {angstrom}, b = 12.386 (5) {angstrom}, c = 13.988 (5) {angstrom}, {alpha} = 102.66 (3){degree}, {beta} = 103.56 (3){degree}, {gamma} = 94.66 (3){degree}, V = 1180.0 (8) {angstrom}{sup 3}, Z = 2. For 3, orthorhombic, Pbca, a = 12.703 (3) {angstrom}, b = 16.707 (4) {angstrom}, c = 18.398 (4) {angstrom}, V = 3904.4 (17) {angstrom}{sup 3}, Z = 8.« less

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

    Youker, Amanda J.; Krebs, John F.; Quigley, Kevin J.

    With funding from the National Nuclear Security Administrations Material Management and Minimization Office, Argonne National Laboratory (Argonne) is providing technical assistance to help accelerate the U.S. production of Mo-99 using a non-highly enriched uranium (non-HEU) source. A potential Mo-99 production pathway is by accelerator-initiated fissioning in a subcritical uranyl sulfate solution containing low enriched uranium (LEU). As part of the Argonne development effort, we are undertaking the AMORE (Argonne Molybdenum Research Experiment) project, which is essentially a pilot facility for all phases of Mo-99 production, recovery, and purification. Production of Mo-99 and other fission products in the subcritical target solutionmore » is initiated by putting an electron beam on a depleted uranium (DU) target; the fast neutrons produced in the DU target are thermalized and lead to fissioning of U-235. At the end of irradiation, Mo is recovered from the target solution and separated from uranium and most of the fission products by using a titania column. The Mo is stripped from the column with an alkaline solution. After acidification of the Mo product solution from the recovery column, the Mo is concentrated (and further purified) in a second titania column. The strip solution from the concentration column is then purified with the LEU Modified Cintichem process. A full description of the process can be found elsewhere [1–3]. The initial commissioning steps for the AMORE project include performing a Mo-99 spike test with pH 1 sulfuric acid in the target vessel without a beam on the target to demonstrate the initial Mo separation-and-recovery process, followed by the concentration column process. All glovebox operations were tested with cold solutions prior to performing the Mo-99 spike tests. Two Mo-99 spike tests with pH 1 sulfuric acid have been performed to date. Figure 1 shows the flow diagram for the remotely operated Mo-recovery system for the AMORE project. There are two separate pumps and flow paths for the acid and base operations. The system contains three sample ladders with eight sample loops per ladder for target mixing; column loading, including acid and water washes; and column stripping, including the final water wash.« less

  7. Bactericidal efficacy of molybdenum oxide nanoparticles against antimicrobial-resistant pathogens.

    PubMed

    Lopes, E; Piçarra, S; Almeida, P L; de Lencastre, H; Aires-de-Sousa, M

    2018-06-25

    Multidrug-resistant bacteria pose a major threat to effective antibiotics and alternatives to fight multidrug-resistant pathogens are needed. We synthetized molybdenum oxide (MoO3) nanoparticles (NP) and determined their antibacterial activity against 39 isolates: (i) eight Staphylococcus aureus, including representatives of methicillin-resistant S. aureus epidemic clones; (ii) six enterococci, including vancomycin-resistant isolates; and (iii) 25 Gram-negative isolates (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter baumannii, Enterobacter cloacae), including extended spectrum beta-lactamases and carbapenemases producers. All isolates showed a MoO3 NP MIC of 700-800 mg l -1 . MoO3 NP produced a clear inhibition zone for S. aureus and all Gram-negative isolates at concentrations ≥25 mg ml -1 and ≥50 mg ml -1 for enterococci. When the NP solutions were adjusted to pH ~7, the biocidal activity was completely abolished. MoO3 NP create an acidic pH and show a universal antimicrobial activity against susceptible and resistant isolates belonging to the most relevant bacterial species responsible for hospital-acquired infections.

  8. Effects of primary selective laser trabeculoplasty on anterior segment parameters

    PubMed Central

    Guven Yilmaz, Suzan; Palamar, Melis; Yusifov, Emil; Ates, Halil; Egrilmez, Sait; Yagci, Ayse

    2015-01-01

    AIM To investigate the effects of selective laser trabeculoplasty (SLT) on the main numerical parameters of anterior segment with Pentacam rotating Scheimpflug camera in patients with ocular hypertension (OHT) and primary open angle glaucoma (POAG). METHODS Pentacam measurements of 45 eyes of 25 (15 females and 10 males) patients (12 with OHT, 13 with POAG) before and after SLT were obtained. Measurements were taken before and 1 and 3mo after SLT. Pentacam parameters were compared between OHT and POAG patients, and age groups (60y and older, and younger than 60y). RESULTS The mean age of the patients was 57.8±13.9 (range 20-77y). Twelve patients (48%) were younger than 60y, while 13 patients (52%) were 60y and older. Measurements of pre-SLT and post-SLT 1mo were significantly different for the parameters of central corneal thickness (CCT) and anterior chamber volume (ACV) (P<0.05). These parameters returned back to pre-SLT values at post-SLT 3mo. Decrease of ACV at post-SLT 1mo was significantly higher in younger than 60y group than 60y and older group. There was no statistically significant difference in Pentacam parameters between OHT and POAG patients at pre- and post-treatment measurements (P>0.05). CONCLUSION SLT leads to significant increase in CCT and decrease in ACV at the 1st month of the procedure. Effects of SLT on these anterior segment parameters, especially for CCT that interferes IOP measurement, should be considered to ensure accurate clinical interpretation. PMID:26558208

  9. Impact of anaerobic oxidation of methane on the geochemical cycle of redox-sensitive elements at cold-seep sites of the northern South China Sea

    NASA Astrophysics Data System (ADS)

    Hu, Yu; Feng, Dong; Liang, Qianyong; Xia, Zhen; Chen, Linying; Chen, Duofu

    2015-12-01

    Cold hydrocarbon seepage is a frequently observed phenomenon along continental margins worldwide. However, little is known about the impact of seeping fluids on the geochemical cycle of redox-sensitive elements. Pore waters from four gravity cores (D-8, D-5, D-7, and D-F) collected from cold-seep sites of the northern South China Sea were analyzed for SO42-, Mg2+, Ca2+, Sr2+, dissolved inorganic carbon (DIC), δ13CDIC, dissolved Fe, Mn, and trace elements (e.g. Mo, U). The sulfate concentration-depth profiles, δ13CDIC values and (ΔDIC+ΔCa2++ΔMg2+)/ΔSO42- ratios suggest that organoclastic sulfate reduction (OSR) is the dominant process in D-8 core. Besides OSR, anaerobic oxidation of methane (AOM) is partially responsible for depletion of sulfate at D-5 and D-7 cores. The sulfate consumption at D-F core is predominantly caused by AOM. The depth of sulfate-methane interface (SMI) and methane diffusive flux of D-F core are calculated to be ~7 m and 0.035 mol m-2 yr-1, respectively. The relatively shallow SMI and high methane flux at D-F core suggest the activity of gas seepage in this region. The concentrations of dissolved uranium (U) were inferred to decrease significantly within the iron reduction zone. It seems that AOM has limited influence on the U geochemical cycling. In contrast, a good correlation between the consumption of sulfate and the removal of molybdenum (Mo) suggests that AOM has a significantly influence on the geochemical cycle of Mo at cold seeps. Accordingly, cold seep environments may serve as an important potential sink in the marine geochemical cycle of Mo.

  10. EUV multilayer mirrors with enhanced stability

    NASA Astrophysics Data System (ADS)

    Benoit, Nicolas; Yulin, Sergiy; Feigl, Torsten; Kaiser, Norbert

    2006-08-01

    The application of multilayer optics in EUV lithography requires not only the highest possible normal-incidence reflectivity but also a long-term thermal and radiation stability at operating temperatures. This requirement is most important in the case of the collector mirror of the illumination system close to the EUV source where a short-time decrease in reflectivity is most likely. Mo/Si multilayer mirrors, designed for high normal reflectivity at the wavelength of 13.5 nm and deposited by dc magnetron sputtering, were directly exposed to EUV radiation without mitigation system. They presented a loss of reflectivity of more than 18% after only 8 hours of irradiation by a Xe-discharge source. Another problem of Mo/Si multilayers is the instability of reflectivity and peak wavelength under high heat load. It becomes especially critical at temperatures above 200°C, where interdiffusion between the molybdenum and the silicon layers is observed. The development of high-temperature multilayers was focused on two alternative Si-based systems: MoSi II/Si and interface engineered Mo/C/Si/C multilayer mirrors. The multilayer designs as well as the deposition parameters of all systems were optimized in terms of high peak reflectivity (>= 60 %) at a wavelength of 13.5 nm and high thermal stability. Small thermally induced changes of the MoSi II/Si multilayer properties were found but they were independent of the annealing time at all temperatures examined. A wavelength shift of -1.7% and a reflectivity drop of 1.0% have been found after annealing at 500°C for 100 hours. The total degradation of optical properties above 650°C can be explained by a recrystallization process of MoSi II layers.

  11. Handwriting, Visuomotor Integration, and Neurological Condition at School Age

    ERIC Educational Resources Information Center

    Van Hoorn, Jessika F.; Maathuis, Carel G. B.; Peters, Lieke H. J.; Hadders-Algra, Mijna

    2010-01-01

    Aim: The study investigated the relationships between handwriting, visuomotor integration, and neurological condition. We paid particular attention to the presence of minor neurological dysfunction (MND). Method : Participants were 200 children (131 males, 69 females; age range 8-13y) of whom 118 received mainstream education (mean age 10y 5mo, SD…

  12. Effect of electroslag remelting on carbides in 8Cr13MoV martensitic stainless steel

    NASA Astrophysics Data System (ADS)

    Zhu, Qin-tian; Li, Jing; Shi, Cheng-bin; Yu, Wen-tao

    2015-11-01

    The effect of electroslag remelting (ESR) on carbides in 8Cr13MoV martensitic stainless steel was experimentally studied. Phases precipitated from liquid steel during solidification were calculated using the Thermo-Calc software. The carbon segregation was analyzed by original position analysis (OPA), and the carbides were analyzed by optical microscopy (OM), scanning electron microscopy (SEM), energy- dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The results indicated that more uniform carbon distribution and less segregation were obtained in the case of samples subjected to the ESR process. After ESR, the amount of netty carbides decreased significantly, and the chromium and vanadium contents in the grain-boundary carbides was reduced. The total area and average size of carbides were obviously smaller after the ESR process. In the sample subjected to ESR, the morphology of carbides changed from lamellar and angular to globular or lump, whereas the types of carbides did not change; both M23C6 and M7C3 were present before and after the ESR process.

  13. A new oxomolybdate component extracted from the "virtual dynamic library" yielding the macrocyclic anion [(Mo(VI)(8)O(28))(4)(Mo(V)(2)O(2)S(2))(4)](24-).

    PubMed

    Korenev, Vladimir S; Boulay, Antoine G; Dolbecq, Anne; Sokolov, Maxim N; Hijazi, Akram; Floquet, Sébastien; Fedin, Vladimir P; Cadot, Emmanuel

    2010-11-01

    A rare isomer of the {Mo(8)O(28)}(8-) anion has been trapped from an acidified aqueous solution of molybdate by using the {Mo(2)O(2)S(2)}(2+) oxothio cation as the linker and isolated as a part of a unique macrocyclic anion, which consists of four isopolyoxomolybdate fragments {Mo(8)O(28)} bridged by four {Mo(2)O(2)S(2)} units.

  14. n-MoSe2 photoelectrochemical halogen storage cell

    NASA Astrophysics Data System (ADS)

    Ang, P. G. P.; Sammells, A. F.

    1982-01-01

    In the study reported here, single-crystal n-MoSe2 photoanodes are investigated in a variety of halogen redox couples. The photoanode is prepared by allowing the silver epoxy cement to come into contact with the front surface of the crystal before being insulated from the redox electrolyte with paraffin wax. This photoanode is evaluated in bromine redox electrolytes in various pH ranges. In 1M HBr + 1M Br2 (pH, approximately zero), the initial open-circuit potential of the MoSe2 versus a platinum reference electrode in the same electrolyte is -130 mV in the dark and -480 mV under 200 mW/sq cm xenon illumination. It is noted that improved performance could be achieved with such crystals by subjecting them to an anodic polarization of around 1 volt from the initial resting potential, a current of about 5 mA/sq cm flowing in the dark.

  15. a Study of the Synchrotron Laue Method for Quantitative Crystal Structure Analysis.

    NASA Astrophysics Data System (ADS)

    Gomez de Anderez, Dora M.

    1990-01-01

    Available from UMI in association with The British Library. Quantitative crystal structure analyses have been carried out on small molecule crystals using synchrotron radiation and the Laue method. A variety of single crystal structure determinations and associated refinements are used and compared with the monochromatic analyses. The new molecular structure of 7-amino-5-bromo -4-methyl-2-oxo-1,2,3,4-tetrahidro-1, 6 -naphthyridine-8-carbonitrile (C_{10 }H_9ON_4 Br.H_2O) has been determined, first using monochromatic Mo Kalpha radiation and a four-circle diffractometer, then using synchrotron Laue diffraction photography. The structure refinements showed a R-factor of 4.97 and 14.0% for the Mo Kalpha and Laue data respectively. The molecular structure of (S)-2-chloro-2-fluoro-N-((S)-1-phenylethyl) ethanamide, (C_{10}H _{11}ClFNO), has been determined using the same crystal throughout for X-ray monochromatic analyses (Mo Kalpha and Cu K alpha) followed by synchrotron Laue data collection. The Laue and monochromatic data compare favourably. The R -factors (on F) were 6.23, 6.45 and 8.19% for the Mo K alpha, Cu Kalpha and Laue data sets respectively. The molecular structure of 3-(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)-1,3-diphenyl -prop- 2-en-1-one, (C_{25 }H_{20}N _2O_2) has been determined using the synchrotron Laue method. The results compare very well with Mo Kalpha monochromatic data. The R-factors (on F) were 4.60 and 5.29% for Mo Kalpha and Laue analysis respectively. The Laue method is assessed in locating the 20 hydrogen atoms in this structure. The structure analysis of the benzil compound ((C_6H_5 O.CO_2)) is carried out using the synchrotron Laue method firstly at room temperature and secondly at low temperature -114 ^circC. The structure shows an R-factor (on F) of 13.06% and 6.85% for each data set respectively. The synchrotron Laue method was used to collect data for ergocalciferol (Vitamin D_2). The same crystal was also used to record oscillation data with the synchrotron radiation monochromatic beam. A new molecular structure of (Dinitrato-(N,N ^'-dimethylethylene-diamine)copper(II)) has been determined using Mo Kalpha radiation on a four circle diffractometer. The refinement resulted in an R-factor (on F) of 4.06%.

  16. A Study of the Synchrotron Laue Method for Quantitative Crystal Structure Analysis

    NASA Astrophysics Data System (ADS)

    Gomez de Anderez, Dora M.

    1990-01-01

    Quantitative crystal structure analyses have been carried out on small molecule crystals using synchrotron radiation and the Laue method. A variety of single crystal structure determinations and associated refinements are used and compared with the monochromatic analyses. The new molecular structure of 7-amino-5-bromo -4-methyl-2-oxo-1,2,3,4 -tetrahidro-1,6 -naphthyridine-8-carbonitrile (C_{10 }H_9ON_4 BrcdotH_2O) has been determined, first using monochromatic Mo K alpha radiation and a four-circle diffractometer, then using synchrotron Laue diffraction photography. The structure refinements showed an R-factor of 4.97 and 14.0% for the Mo Kalpha and Laue data respectively. The molecular structure of (S)-2-chloro-2-fluoro-N-((S)-1-phenylethyl) ethanamide, (C_{10}H _{11}ClFNO), has been determined using the same crystal throughout for X-ray monochromatic analyses (Mo Kalpha and Cu K alpha) followed by synchrotron Laue data collection. The Laue and monochromatic data compare favourably. The R -factors (on F) were 6.23, 6.45 and 8.19% for the Mo K alpha, Cu Kalpha and Laue data sets respectively. The molecular structure of 3-(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)-1,3-diphenyl -prop-2-en-1-one, (C_{25}H _{20}N_2 O_2) has been determined using the synchrotron Laue method. The results compare very well with Mo Kalpha monochromatic data. The R-factors (on F) were 4.60 and 5.29% for Mo Kalpha and Laue analyses respectively. The Laue method is assessed in locating the 20 hydrogen atoms in this structure. The structure analyses of the benzil compound ((C_6H_5 OcdotCO_2)) is carried out using the synchrotron Laue method firstly at room temperature and secondly at low temperature. The structure shows an R-factor (on F) of 13.06% and 6.85% for each data set respectively. The synchrotron Laue method was used to collect data for ergocalciferol (Vitamin D_2). The same crystal was also used to record oscillation data with the synchrotron radiation monochromatic beam. A new molecular structure of (Dinitrato-(N,N ^'-dimethylethylene-diamine)copper(II)) has been determined using Mo Kalpha radiation on a four circle diffractometer. The refinement resulted in an R-factor (on F) of 4.06%.

  17. Acetylcholinesterase-catalyzed acetate - water oxygen exchange studied by /sup 13/C-NMR

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

    Van Etten, R.L.; Dayton, B.; Cortes, S.

    1986-05-01

    The kinetics of the oxygen exchange reaction between (l-/sup 13/C,/sup 18/O/sub 2/)acetate and H/sub 2//sup 16/O catalyzed by homogeneous acetyl-cholinesterase from the electric eel, Electrophorus electricus, was studied using the /sup 18/O-isotope-induced shift on /sup 13/C-nuclear magnetic resonance spectra. Pseudo-first-order rate constants for the exchange reactions were determined at pH values from 4.5 to 8. The exchange reaction exhibits a maximum at pH 5.8. The apparent catalytic rate constant for the exchange reaction is 10/sup 2/ to 10/sup 4/ times smaller than that for the deacylation of the acetyl-enzyme intermediate over the pH range tested. Oxygen exchange occurs by amore » random sequential pathway rather than by multiple (coupled) exchange. The inhibition of acetylcholinesterase by sodium acetate showed a sigmoidal dependence on pH, with K/sub i/ increasing 2.5 orders of magnitude over the pH range. Protonation of an active site residue having an apparent pKa of 6.8 is associated with an increase in acetate binding. Deacylation also exhibits a sigmoidal dependence on (H/sup +/). The experimental data fits titration curves with inflection points at 5.0 +/- 0.3 and 6.7 +/-0.1. Results support the role of histidine in acetylation of the active site serine, but the conjugate base of another active site residue with a pKa of 5.0 appears necessary for maximal catalytic activity in both the deacylation and exchange reactions.« less

  18. Charge Disproportionation in Tetragonal La 2MoO 5 , a Small Band Gap Semiconductor Influenced by Direct Mo–Mo Bonding

    DOE PAGES

    Colabello, Diane M.; Camino, Fernando E.; Huq, Ashfia; ...

    2014-12-31

    The structure of the novel compound La 2MoO 5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo 2O 10) and square prismatic (Mo 2O 8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo 2O 10dimers is 2.684(8) Å, while there are two types of Mo 2O 8 dimers with Mo-Mo bonds lengthsmore » of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La 2MoO 5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo 2O 10 dimers contain only Mo5+ (d(1)), while the prismatic Mo2O8 dimers only contain Mo 3+ (d 3), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo 4+, a phenomenon which has not previously been observed in solid-state compounds. La 2MoO 5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La 2MoO 5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. Lastly, we show that the d-orbital splitting associated with the Mo 2O 8 and Mo 2O 10 dimeric units can be rationalized using simple molecular orbital bonding concepts.« less

  19. Nanoscale coordination polymers exhibiting luminescence properties and NMR relaxivity

    NASA Astrophysics Data System (ADS)

    Chelebaeva, Elena; Larionova, Joulia; Guari, Yannick; Ferreira, Rute A. S.; Carlos, Luis D.; Trifonov, Alexander A.; Kalaivani, Thangavel; Lascialfari, Alessandro; Guérin, Christian; Molvinger, Karine; Datas, Lucien; Maynadier, Marie; Gary-Bobo, Magali; Garcia, Marcel

    2011-03-01

    This article presents the first example of ultra-small (3-4 nm) magneto-luminescent cyano-bridged coordination polymer nanoparticles Ln0.333+Gdx3+/[Mo(CN)8]3- (Ln = Eu (x = 0.34), Tb (x = 0.35)) enwrapped by a natural biocompatible polymer chitosan. The aqueous colloidal solutions of these nanoparticles present a luminescence characteristic of the corresponding lanthanides (5D0 --> 7F0-4 (Eu3+) or the 5D4 --> 7F6-2 (Tb3+)) under UV excitation and a green luminescence of the chitosan shell under excitation in the visible region. Magnetic Resonance Imaging (MRI) efficiency, i.e. the nuclear relaxivity, measurements performed for Ln0.333+Gdx3+/[Mo(CN)8]3- nanoparticles show r1p and r2p relaxivities slightly higher than or comparable to the ones of the commercial paramagnetic compounds Gd-DTPA® or Omniscan® indicating that our samples may potentially be considered as a positive contrast agent for MRI. The in vitro studies performed on these nanoparticles show that they maybe internalized into human cancer and normal cells and well detected by fluorescence at the single cell level. They present high stability even at low pH and lack of cytotoxicity both in human cancer and normal cells.This article presents the first example of ultra-small (3-4 nm) magneto-luminescent cyano-bridged coordination polymer nanoparticles Ln0.333+Gdx3+/[Mo(CN)8]3- (Ln = Eu (x = 0.34), Tb (x = 0.35)) enwrapped by a natural biocompatible polymer chitosan. The aqueous colloidal solutions of these nanoparticles present a luminescence characteristic of the corresponding lanthanides (5D0 --> 7F0-4 (Eu3+) or the 5D4 --> 7F6-2 (Tb3+)) under UV excitation and a green luminescence of the chitosan shell under excitation in the visible region. Magnetic Resonance Imaging (MRI) efficiency, i.e. the nuclear relaxivity, measurements performed for Ln0.333+Gdx3+/[Mo(CN)8]3- nanoparticles show r1p and r2p relaxivities slightly higher than or comparable to the ones of the commercial paramagnetic compounds Gd-DTPA® or Omniscan® indicating that our samples may potentially be considered as a positive contrast agent for MRI. The in vitro studies performed on these nanoparticles show that they maybe internalized into human cancer and normal cells and well detected by fluorescence at the single cell level. They present high stability even at low pH and lack of cytotoxicity both in human cancer and normal cells. Electronic supplementary information (ESI) available: TEM images and size distribution histograms, IR and emission spectra, diffraction pattern and HRTEM coupled EDX analysis. See DOI: 10.1039/c0nr00709a

  20. 40 CFR 410.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (pounds per 1,000 lb) of product BOD5 1.4 0.7 COD 2.8 1.4 TSS 1.4 0.7 ph (1) (1) 1 Within the range 6.0 to... 8.9 4.6 COD 21.3 13.7 TSS 5.5 2.5 ph (1) (1) 1 Within the range 6.0 to 9.0 at all times. ...

  1. 40 CFR 410.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... (pounds per 1,000 lb) of product BOD5 1.4 0.7 COD 2.8 1.4 TSS 1.4 0.7 ph (1) (1) 1 Within the range 6.0 to... 8.9 4.6 COD 21.3 13.7 TSS 5.5 2.5 ph (1) (1) 1 Within the range 6.0 to 9.0 at all times. ...

  2. 40 CFR 410.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... (pounds per 1,000 lb) of product BOD5 1.4 0.7 COD 2.8 1.4 TSS 1.4 0.7 ph (1) (1) 1 Within the range 6.0 to... 8.9 4.6 COD 21.3 13.7 TSS 5.5 2.5 ph (1) (1) 1 Within the range 6.0 to 9.0 at all times. ...

  3. 40 CFR 410.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... (pounds per 1,000 lb) of product BOD5 1.4 0.7 COD 2.8 1.4 TSS 1.4 0.7 ph (1) (1) 1 Within the range 6.0 to... 8.9 4.6 COD 21.3 13.7 TSS 5.5 2.5 ph (1) (1) 1 Within the range 6.0 to 9.0 at all times. ...

  4. Structural, magnetic and transport properties of Pb{sub 2}Cr{sub 1+x}Mo{sub 1−x}O{sub 6} (−1≤x≤1/3)

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

    Zhao, H.F.; School of Mathematics and Physics, University of Science and Technology, Beijing 100083; Cao, L.P.

    Pb{sub 2}Cr{sub 1+x}Mo{sub 1-x}O{sub 6} (−1≤x≤1/3) samples were synthesized via a high pressure and high temperature route. X-ray diffraction results suggest the samples crystallize in a disordered double perovskite structure (Pm-3m). X-ray photoemission spectroscopy results confirm the presence of Mo{sup 4+} for x=−1 and Mo{sup 6+} for x=1/3. The measured magnetic and electrical properties exhibit systematic change with increasing x. - Highlights: • A series of Pb{sub 2}Cr{sub 1+x}Mo{sub 1−x}O{sub 6} samples were synthesized under high pressure. • Magnetic and electrical properties of the series samples were investigated. • Valence states of Cr and Mo were determined through the analysesmore » of XRD and XPS results. • Ground state of PbMoO{sub 3} were determined through the transport study and first-principles calculations.« less

  5. Tensile Properties of 17-7 PH and 12 MoV Stainless-Steel Sheet under Rapid-Heating and Constant-Temperature Conditions

    NASA Technical Reports Server (NTRS)

    Manning, Charles R., Jr.; Price, Howard L.

    1961-01-01

    Results are presented of rapid-heating tests of 17-7 PH and 12 MoV stainless-steel sheet heated to failure at temperature rates from about 1 F to 170 F per second under constant-load conditions. Yield and rupture strengths obtained from rapid-heating tests are compared with yield and tensile strengths obtained from short-time elevated-temperature tensile tests (30-minute exposure). A rate-temperature parameter was used to construct master curves from which yield and rupture stresses or temperatures can be predicted. A method for measuring strain by optical means is described.

  6. Neutron structure and inelastic-neutron-scattering and theoretical studies of Mo(CO)(H[sub 2])[(C[sub 6]D[sub 5])[sub 2]PC[sub 2]H[sub 4]P(C[sub 6]D[sub 5])[sub 2

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

    Kubas, G.J.; Burns, C.J.; Eckert, J.

    1993-01-27

    The synthesis and characterization of derivatives of Mo(CO)(R[sub 2]PC[sub 2]H[sub 4]PR[sub 2])[sub 2] (R = Et, i-Bu, Ph, Et-Ph) and their reactions with H[sub 2], N[sub 2], and SO[sub 2] are reported. For R = Et and i-Bu, the H[sub 2] oxidatively adds to give dihydrides, but for R = Ph, a [eta][sup 2]-H[sub 2] complex is formed. Single-crystal neutron diffraction of Mo(CO)(H[sub 2])(Ph[sub 2]PC[sub 2]H[sub 4]PPh[sub 2])[sub 2] (as a 4.5-benzene solvate with all Ph groups deuterated) at 12 K showed the H-H bond to be oriented trans to the CO and parallel to a P-Mo-P axis, with amore » length close to that of free H[sub 2] (0.74 [Angstrom]). However, the thermal ellipsoids were very large, and inelastic neutron scattering showed that the barrier to rotation of the H[sub 2] is the lowest yet measured, ca. 0.7 kcal/mol. These observations indicate that librational motion of the H[sub 2] is artificially foreshortening the H-H bond length. Application of a correction procedure gave a distance of 0.80-0.85 [Angstrom] as being more likely. Extended Huckel calculations successfully modeled the H[sub 2] coordination and also showed a low rotational barrier (1.4 kcal/mol). Theoretical considerations suggest that the degree of distortion of the MP[sub 4] skeleton is largely responsible for the ability of the complex to bind molecular hydrogen and controls the amount of back-bonding from the metal d-orbital to H[sub 2] [sigma][sup *]. The lack of an elongated H-H bond length or equilibrium with a dihydride tautomer, despite the apparent nearness of the H[sub 2] to cleavage, leads to the conclusion that the reaction coordinate for oxidative addition of H[sub 2] is rather flat until relatively precipitous cleavage of the H[sub 2]. Mo(CO)(H[sub 2])[(C[sub 6]D[sub 5])[sub 2]PC[sub 2]H[sub 4]P(C[sub 6]D[sub 5])[sub 2

  7. Nature's polyoxometalate chemistry: X-ray structure of the Mo storage protein loaded with discrete polynuclear Mo-O clusters.

    PubMed

    Kowalewski, Björn; Poppe, Juliane; Demmer, Ulrike; Warkentin, Eberhard; Dierks, Thomas; Ermler, Ulrich; Schneider, Klaus

    2012-06-13

    Some N(2)-fixing bacteria prolong the functionality of nitrogenase in molybdenum starvation by a special Mo storage protein (MoSto) that can store more than 100 Mo atoms. The presented 1.6 Å X-ray structure of MoSto from Azotobacter vinelandii reveals various discrete polyoxomolybdate clusters, three covalently and three noncovalently bound Mo(8), three Mo(5-7), and one Mo(3) clusters, and several low occupied, so far undefinable clusters, which are embedded in specific pockets inside a locked cage-shaped (αβ)(3) protein complex. The structurally identical Mo(8) clusters (three layers of two, four, and two MoO(n) octahedra) are distinguishable from the [Mo(8)O(26)](4-) cluster formed in acidic solutions by two displaced MoO(n) octahedra implicating three kinetically labile terminal ligands. Stabilization in the covalent Mo(8) cluster is achieved by Mo bonding to Hisα156-N(ε2) and Gluα129-O(ε1). The absence of covalent protein interactions in the noncovalent Mo(8) cluster is compensated by a more extended hydrogen-bond network involving three pronounced histidines. One displaced MoO(n) octahedron might serve as nucleation site for an inhomogeneous Mo(5-7) cluster largely surrounded by bulk solvent. In the Mo(3) cluster located on the 3-fold axis, the three accurately positioned His140-N(ε2) atoms of the α subunits coordinate to the Mo atoms. The formed polyoxomolybdate clusters of MoSto, not detectable in bulk solvent, are the result of an interplay between self- and protein-driven assembly processes that unite inorganic supramolecular and protein chemistry in a host-guest system. Template, nucleation/protection, and catalyst functions of the polypeptide as well as perspectives for designing new clusters are discussed.

  8. Physical properties of monolithic U8 wt.%-Mo

    NASA Astrophysics Data System (ADS)

    Hengstler, R. M.; Beck, L.; Breitkreutz, H.; Jarousse, C.; Jungwirth, R.; Petry, W.; Schmid, W.; Schneider, J.; Wieschalla, N.

    2010-07-01

    As a possible high density fuel for research reactors, monolithic U8 wt.%-Mo ("U8Mo") was examined with regard to its structural, thermal and electric properties. X-ray diffraction by the Bragg-Brentano method was used to reveal the tetragonal lattice structure of rolled U8Mo. The specific heat capacity of cast U8Mo was determined by differential scanning calorimetry, its thermal diffusivity was measured by the laser flash method and its mass density by Archimedes' principle. From these results, the thermal conductivity of U8Mo in the temperature range from 40 °C to 250 °C was calculated; in the measured temperature range, it is in good accordance with literature data for UMo with 8 and 9 wt.% Mo, is higher than for 10 wt.% Mo and lower than for 5 wt.% Mo. The electric conductivity of rolled and cast U8Mo was measured by a four-wire method and the electron based part of the thermal conductivity calculated by the Wiedemann-Frantz law. Rolled and cast U8Mo was irradiated at about 150 °C with 80 MeV 127I ions to receive the same iodine ion density in the damage peak region as the fission product density in the fuel of a typical high flux reactor after the targeted nuclear burn-up. XRD analysis of irradiated U8Mo showed a change of the lattice parameters as well as the creation of UO 2 in the superficial sample regions; however, a phase change by irradiation was not observed. The determination of the electron based part of the thermal conductivity of the irradiated samples failed due to high measurement errors which are caused by the low thickness of the damage region in the ion irradiated samples.

  9. Tunneling Spectroscopy of Superconducting MoN and NbTiN Grown by Atomic Layer Deposition.

    DOE PAGES

    Groll, Nickolas; Klug, Jeffrey A.; Cao, Chaoyue; ...

    2014-03-03

    A tunneling spectroscopy study is presented of superconducting MoN and Nbo.8Tio.2N thin films grown by atomic layer deposition (ALD). The films exhibited a superconducting gap of 2meV and 2.4meV, respectively, with a corresponding critical temperature of 11.5K and 13.4 K, among the highest reported Tc values achieved by the ALD technique.Tunnel junctions were obtained using a mechanical contact method with a Au tip. While the native oxides of these films provided poor tunnel barriers, high quality tunnel junctions with low zero bias conductance (below rvl0%) were obtained using an artificial tunnel barrier of Ah03 on the film's surface grown exmore » situ by ALD. We find a large critical current density on the order of 4 x 106Ncm2 at T =0.8Tc for a 60 run MoN film and demonstrate conformal coating capabilities of ALD onto high aspect ratio geometries. These results suggest that the ALD technique offers significant promise for thin film superconducting device applications.« less

  10. Tunneling spectroscopy of superconducting MoN and NbTiN grown by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Groll, Nickolas R.; Klug, Jeffrey A.; Cao, Chaoyue; Altin, Serdar; Claus, Helmut; Becker, Nicholas G.; Zasadzinski, John F.; Pellin, Michael J.; Proslier, Thomas

    2014-03-01

    A tunneling spectroscopy study is presented of superconducting MoN and Nb0.8Ti0.2N thin films grown by atomic layer deposition (ALD). The films exhibited a superconducting gap of 2 meV and 2.4 meV, respectively, with a corresponding critical temperature of 11.5 K and 13.4 K, among the highest reported Tc values achieved by the ALD technique. Tunnel junctions were obtained using a mechanical contact method with a Au tip. While the native oxides of these films provided poor tunnel barriers, high quality tunnel junctions with low zero bias conductance (below ˜10%) were obtained using an artificial tunnel barrier of Al2O3 on the film's surface grown ex situ by ALD. We find a large critical current density on the order of 4 × 106 A/cm2 at T = 0.8Tc for a 60 nm MoN film and demonstrate conformal coating capabilities of ALD onto high aspect ratio geometries. These results suggest that the ALD technique offers significant promise for thin film superconducting device applications.

  11. On the Linear Stability of Two-Dimensional Barium Clouds. I. The Inviscid Case.

    DTIC Science & Technology

    1984-04-30

    MECVRDT FKPR--7;PG ON13& TYPE OF REPORT 13R1. TIME 8 CIEDO 1 4 AT OF REOT .Y,. Mo.. Day, 37PAECON Interim FROM 10183 TO17’I April 30, 1984 I37 IS...Note that if we write our perturbation ( 8 ) in terms of arc length ro 0 multiplied by a wavenumber k then cos m6 - cos k r0 and m/ro - k (10) 4 ...38 APR 84 NRL-MR-53i2 UNCLASSIFIED F/G 4 /1 NI I EEEEEEEEE L &, 12 am... ~ a m II) ,uut_ _- 7-_ MICROCOPY RESOLUTION TEST CHART NATIONAL BUREAU OF

  12. Rubber band ligation for 750 cases of symptomatic hemorrhoids out of 2200 cases

    PubMed Central

    Nakeeb, Ayman M El; Fikry, Amir A; Omar, Waleed H; Fouda, Elyamani M; Metwally, Tito A El; Ghazy, Hosam E; Badr, Sabry A; Elkhar, Mohmed Y Abu; Elawady, Salih M; Elmoniam, Hisham H Abd; Khafagy, Waiel W; Morshed, Mosaad M; Lithy, Ramadan E El; Farid, Mohamed E

    2008-01-01

    AIM: To study the results for the treatment of symptomatic hemorrhoids using rubber band ligation (RBL) method. METHODS: A retrospective study for 750 patients who came to the colorectal unit from June, 1998 to September, 2006, data was retrieved from archived files. RBL was performed using the Mc Gown applicator on an outpatient basis. The patients were asked to return to out-patient clinic for follow up at 2 wk, 1 mo, 6 mo and through telephone call every 6 mo for 2 years). RESULTS: After RBL, 696 patients (92.8%) were cured with no difference in outcome for second or third degree hemorrhoids (P = 0.31). Symptomatic recurrence was detected in 11.04% after 2 years. A total of 52 patients (6.93%) had 77 complications from RBL which required no hospitalization. Complications were pain, rectal bleeding and vaso-vagal symptoms (4.13%, 4.13% and 1.33% of patients, respectively). At 1 mo there were a significant improvement in mean SF-36 scores over baseline in five items, while after 2 years there were improvement in all items over baseline, but not significant. No significant manometric changes after band ligation. CONCLUSION: RBL is a simple, safe and effective method for treating symptomatic second and third degree hemorrhoids as an out patient procedure with significant improvement in quality of life. RBL doesn’t alter ano-rectal functions. PMID:19030206

  13. Rubber band ligation for 750 cases of symptomatic hemorrhoids out of 2200 cases.

    PubMed

    El Nakeeb, Ayman-M; Fikry, Amir-A; Omar, Waleed-H; Fouda, Elyamani-M; El Metwally, Tito-A; Ghazy, Hosam-E; Badr, Sabry-A; Abu Elkhar, Mohmed-Y; Elawady, Salih-M; Abd Elmoniam, Hisham-H; Khafagy, Waiel-W; Morshed, Mosaad-M; El Lithy, Ramadan-E; Farid, Mohamed-E

    2008-11-14

    To study the results for the treatment of symptomatic hemorrhoids using rubber band ligation (RBL) method. A retrospective study for 750 patients who came to the colorectal unit from June, 1998 to September, 2006, data was retrieved from archived files. RBL was performed using the Mc Gown applicator on an outpatient basis. The patients were asked to return to out-patient clinic for follow up at 2 wk, 1 mo, 6 mo and through telephone call every 6 mo for 2 years). After RBL, 696 patients (92.8%) were cured with no difference in outcome for second or third degree hemorrhoids (P = 0.31). Symptomatic recurrence was detected in 11.04% after 2 years. A total of 52 patients (6.93%) had 77 complications from RBL which required no hospitalization. Complications were pain, rectal bleeding and vaso-vagal symptoms (4.13%, 4.13% and 1.33% of patients, respectively). At 1 mo there were a significant improvement in mean SF-36 scores over baseline in five items, while after 2 years there were improvement in all items over baseline, but not significant. No significant manometeric changes after band ligation. RBL is a simple, safe and effective method for treating symptomatic second and third degree hemorrhoids as an out patient procedure with significant improvement in quality of life. RBL doesn't alter ano-rectal functions.

  14. The genesis of the Hashitu porphyry molybdenum deposit, Inner Mongolia, NE China: constraints from mineralogical, fluid inclusion, and multiple isotope (H, O, S, Mo, Pb) studies

    NASA Astrophysics Data System (ADS)

    Zhai, Degao; Liu, Jiajun; Tombros, Stylianos; Williams-Jones, Anthony E.

    2018-03-01

    The Hashitu porphyry molybdenum deposit is located in the Great Hinggan Range Cu-Mo-Pb-Zn-Ag polymetallic metallogenic province of NE China, in which the Mo-bearing quartz veins are hosted in approximately coeval granites and porphyries. The deposit contains more than 100 Mt of ore with an average grade of 0.13 wt.% Mo. This well-preserved magmatic-hydrothermal system provides an excellent opportunity to determine the source of the molybdenum, the evolution of the hydrothermal fluids and the controls on molybdenite precipitation in a potentially important but poorly understood metallogenic province. Studies of fluid inclusions hosted in quartz veins demonstrate that the Hashitu hydrothermal system evolved to progressively lower pressure and temperature. Mineralogical and fluid inclusion analyses and physicochemical calculations suggest that molybdenite deposition occurred at a temperature of 285 to 325 °C, a pressure from 80 to 230 bars, a pH from 3.5 to 5.6, and a Δlog fO2 (HM) of -3.0, respectively. Results of multiple isotope (O, H, S, Mo, and Pb) analyses are consistent in indicating a genetic relationship between the ore-forming fluids, metals, and the Mesozoic granitic magmatism (i.e., δ 18OH2O from +1.9 to +9.7‰, δDH2O from -106 to -87‰, δ 34SH2S from +0.3 to +3.9‰, δ 98/95Mo from 0 to +0.37‰, 206Pb/204Pb from 18.2579 to 18.8958, 207Pb/204Pb from 15.5384 to 15.5783, and 208Pb/204Pb from 38.0984 to 42.9744). Molybdenite deposition is interpreted to have occurred from a low-density magmatic-hydrothermal fluid in response to decreases in temperature, pressure, and fO2.

  15. Standard Gibbs energy of formation of Mo 3Te 4 by emf measurements

    NASA Astrophysics Data System (ADS)

    Mallika, C.; Sreedharan, O. M.

    1990-03-01

    The emf of the galvanic cells Pt, Mo, MoO 2¦8 YSZ¦'FeO', Fe, Pt (I) and Pt, Fe,'FeO' ¦8 YSZ¦MoO 2, Mo 3Te 4, MoTe 2(α), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo 3Te 4/MoTe 2(α), Δ ḠMo was found to be Δ ḠMo ± 1.19 ( kJ/mol) = -025.08 + 0.00420T(K) . Using the literature data for the Gibbs energy of formation of MoTe 2(α). the expression ΔG° f( Mo3Te4, s) ± 5.97 (kj/mol) = -253.58 + 0.09214 T( K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of -209 ± 10 kJ/mol for ΔH° f.298o of Mo 3Te 4(s).

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

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopicmore » and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(OxMe2)2ImMes}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (14) or {PhB(OxMe2)2ImMes}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(OxMe2)2ImMes}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.« less

  17. Synthesis of amphiphilic alternating polyesters with oligo(ethylene glycol) side chains and potential use for sustained release drug delivery.

    PubMed

    Wang, Wei; Ding, Jianxun; Xiao, Chunsheng; Tang, Zhaohui; Li, Di; Chen, Jie; Zhuang, Xiuli; Chen, Xuesi

    2011-07-11

    Novel amphiphilic alternating polyesters, poly((N-phthaloyl-l-glutamic anhydride)-co-(2-(2-(2-methoxyethoxy)ethoxy)methyl)oxirane) (P(PGA-co-ME(2)MO)), were synthesized by alternating copolymerization of PGA and ME(2)MO. The structures of the synthesized polyesters were characterized by (1)H NMR, (13)C NMR, FT-IR, and GPC analyses. Because of the presence of oligo(ethylene glycol) (OEG) side chains, the polyesters could self-assemble into thermosensitive micelles. Dynamic light scattering (DLS) showed that these micelles underwent thermoinduced size decrease without intermicellar aggregation. In vitro methyl thiazolyl tetrazolium (MTT) assay demonstrated that the polyesters were biocompatible to Henrietta Lacks (HeLa) cells, rendering their potential for drug delivery applications. Two hydrophobic drugs, rifampin and doxorubicin (DOX), were loaded into the polyester micelles and observed to be released in a zero-order sustained manner. The sustained release could be accelerated in lower pH or in the presence of proteinase K, due to the degradation of the polyester under these conditions. Remarkably, in vitro cell experiments showed that the polyester micelles accomplished fast release of DOX inside cells and higher anticancer efficacy as compared with the free DOX. With enhanced stability during circulation condition and accelerated drug release at the target sites (e.g., low pH or enzyme presence), these novel polyesters with amphiphilic structures are promising to be used in sustained release drug delivery systems.

  18. A study of the formation, purification and application as a SWNT growth catalyst of the nanocluster [HxPMo12O40[subset]H4Mo72Fe30(O2CMe)15O254(H2O)98].

    PubMed

    Anderson, Robin E; Colorado, Ramon; Crouse, Christopher; Ogrin, Douglas; Maruyama, Benji; Pender, Mark J; Edwards, Christopher L; Whitsitt, Elizabeth; Moore, Valerie C; Koveal, Dorothy; Lupu, Corina; Stewart, Michael P; Smalley, Richard E; Tour, James M; Barron, Andrew R

    2006-07-07

    The synthetic conditions for the isolation of the iron-molybdenum nanocluster FeMoC [HxPMo12O40 [subset]H4Mo72Fe30(O2CMe)15O254(H2O)98], along with its application as a catalyst precursor for VLS growth of SWNTs have been studied. As-prepared FeMoC is contaminated with the Keplerate cage [H4Mo72Fe30(O2CMe)15O254(H2O)98] without the Keggin [HxPMo12O40]n- template, however, isolation of pure FeMoC may be accomplished by Soxhlet extraction with EtOH. The resulting EtOH solvate is consistent with the replacement of the water ligands coordinated to Fe being substituted by EtOH. FeMoC-EtOH has been characterized by IR, UV-vis spectroscopy, MS, XPS and 31P NMR. The solid-state 31P NMR spectrum for FeMoC-EtOH (delta-5.3 ppm) suggests little effect of the paramagnetic Fe3+ centers in the Keplerate cage on the Keggin ion's phosphorous. The high chemical shift anisotropy, and calculated T1 (35 ms) and T2 (8 ms) values are consistent with a weak magnetic interaction between the Keggin ion's phosphorus symmetrically located within the Keplerate cage. Increasing the FeCl2 concentration and decreasing the pH of the reaction mixture optimizes the yield of FeMoC. The solubility and stability of FeMoC in H2O and MeOH-H2O is investigated. The TGA of FeMoC-EtOH under air, Ar and H2 (in combination with XPS) shows that upon thermolysis the resulting Fe : Mo ratio is highly dependent on the reaction atmosphere: thermolysis in air results in significant loss of volatile molybdenum components. Pure FeMoC-EtOH is found to be essentially inactive as a pre-catalyst for the VLS growth of single-walled carbon nanotubes (SWNTs) irrespective of the substrate or reaction conditions. However, reaction of FeMoC with pyrazine (pyz) results in the formation of aggregates that are found to be active catalysts for the growth of SWNTs. Activation of FeMoC may also be accomplished by the addition of excess iron. The observation of prior work's reported growth of SWNTs from FeMoC is discussed with respect to these results.

  19. Development of the Mini-Assisting Hand Assessment: evidence for content and internal scale validity.

    PubMed

    Greaves, Susan; Imms, Christine; Dodd, Karen; Krumlinde-Sundholm, Lena

    2013-11-01

    To describe the development of the Mini-Assisting Hand Assessment (Mini-AHA) for children with signs of unilateral cerebral palsy (CP) aged 8 to 18 months, and evaluate aspects of content and internal scale validity. The ability of the video-recorded Mini-AHA play session to provoke bimanual performance in children with unilateral CP and typical development was evaluated. Original AHA test items were examined for their suitability for younger children and possible new items were generated. Data from 108 assessments of children with unilateral CP (86 children, 53 males, 33 females; mean age 13 mo, SD 3 mo, range 8-18 mo) were entered into a Rasch measurement model analysis to evaluate internal scale validity. A Spearman's correlation analysis explored the relationship between age and ability measures for children with unilateral CP. The frequency of maximum scores in 40 children with typical development (22 males, 18 females; mean age 12 mo, SD 3 mo) was examined. The Mini-AHA play session provoked bimanual responses in typically developing children 99% of the time. Person and item fit criteria established 20 items for the scale. The resultant unidimensional scale also demonstrated excellent discriminative features through high separation reliability. The item calibration values covered the range of person ability measures well. Age was not related to the ability measures for children with unilateral CP (rs =0.178). All children with typical development achieved maximum scores. Accumulated evidence shows that the Mini-AHA validly measures use of the affected hand during bimanual performance for children with unilateral CP aged 8 to 18 months. The Mini-AHA has the potential to be a useful assessment to evaluate functional hand use and the effects of intervention in an age group when potential for change is high. © 2013 Mac Keith Press.

  20. Internal Magnetic Field on the Two-Dimensional Triangular Lattice Formed by Mo3O8 Trimers

    NASA Astrophysics Data System (ADS)

    Sugiyama, Jun; Nozaki, Hiroshi; Umegaki, Izumi; Haraguchi, Yuya; Michioka, Chishiro; Ueda, Hiroaki; Yoshimura, Kazuyoshi; Sassa, Yasmine; Forslund, Ola Kenji; Andreica, Daniel; Goko, Tatsuo; Amato, Alex; Månsson, Martin

    In order to elucidate the magnetic ground state of the cluster magnets with a half filled triangular lattice, we have recorded zero field (ZF-) and weak transverse field (wTF-) μ+SR spectra using powder samples of Li2InMo3O8 and Li2ScMo3O8 down to 1.9 K. The ZF measurements at 1.9 K demonstrated the presence of static magnetic order in Li2InMo3O8, whereas paramagnetic nature in Li2ScMo3O8. The wTF measurements clarified that the magnetic transition occurs at around 11 K (= TN) in Li2InMo3O8. However, for Li2ScMo3O8, there is no detectable change in the ZF- and wTF-μ+SR fit-parameters in the temperature range between 60 and 1.9 K.

  1. Preparation of Mo-Re-C samples containing Mo{sub 7}Re{sub 13}C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

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

    Oh-ishi, Katsuyoshi, E-mail: oh-ishi@kc.chuo-u.ac.jp; Nagumo, Kenta; Tateishi, Kazuya

    Mo-Re-C compounds containing Mo{sub 7}Re{sub 13}C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo{sub 7}Re{sub 13}C with the β-Mn structure using the solid state method. Almost single-phase Mo{sub 7}Re{sub 13}C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with amore » pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K. - Graphical abstract: Temperature dependence of the magnetic susceptibility measured under 10 Oe for the superconducting PBM-T samples without Fe element and non-superconducting PBM-S with Fe element. The inset is the enlarged view of the data for the PBM-S sample.« less

  2. Efficacy and safety of new complementary feeding guidelines with an emphasis on red meat consumption: a randomized trial in Bogota, Colombia.

    PubMed

    Olaya, Gilma A; Lawson, Margaret; Fewtrell, Mary S

    2013-10-01

    Iron deficiency and poor linear growth are common in infants from deprived socioeconomic backgrounds and may be associated with inadequate complementary feeding (CF) practices. We tested the hypothesis that new CF guidelines emphasizing meat as a source of iron and zinc would improve linear growth, iron, and zinc status in infants living in poor socioeconomic circumstances in Bogota, Colombia. A total of 85 term infants who were exclusively breastfed for ≥4 mo were randomly assigned at 6 mo of age to a control group [CG (n = 43); current advice] or intervention group (new guidelines group [NGG (n = 42); with counseling to 1) continue breastfeeding, 2) offer red meat ≥3 d/wk, and 3) offer fruit and vegetables daily]). Main outcomes were 1) linear growth from 6 to 12 mo of age; 2) hemoglobin, hematocrit, iron [serum ferritin (SF)], and zinc status at 12 mo of age; and 3) meat intake at 12 mo of age (by using a food-frequency questionnaire). A total of 38 infants/group provided data at 12 mo of age. NGG infants had significantly higher red meat intake [mean ± SD: 5.4 ± 1.8 compared with 3.5 ± 1.7 d/wk at 12 mo of age; P < 0.001), higher hemoglobin and hematocrit at 12 mo of age, and a significantly greater increase in hemoglobin (mean ± SD change: 0.41 ± 0.8 compared with -0.13 ± 1.0; P = 0.01) and hematocrit (1.04 ± 2.2 compared with -0.15 ± 2.4; P = 0.03) from 6 to 12 mo of age than those in CG infants. There were no significant differences in linear growth from 6 to 12 mo of age or in SF or zinc. The new guidelines showed efficacy with higher red meat intake and positive effects on hemoglobin and hematocrit. The intervention was acceptable and affordable for most mothers. These preliminary results suggest that the intervention merits investigation in a larger cohort with longer-term follow-up. This trial was registered at http://isrctn.org as ISRCTN57733004.

  3. Dedifferentiated liposarcoma of the spermatic cord: a series of 42 cases.

    PubMed

    Kryvenko, Oleksandr N; Rosenberg, Andrew E; Jorda, Merce; Epstein, Jonathan I

    2015-09-01

    Dedifferentiated liposarcoma (DDL) of the spermatic cord is rare, with limited data regarding morphology and prognosis. We analyzed the morphologic spectrum of DDL of the spermatic cord and its clinical significance in 42 patients from 1990 to 2014. The median age of the patients was 70.5 years (range: 43 to 90 y). The median tumor size was 10.9 cm (range: 3 to 30 cm). Six cases were low-grade DDL, 28 were high-grade DDL, and in 8 cases both coexisted. Five cases had osteosarcoma, and 2 had leiomyosarcoma differentiation. Low-grade DDL had a fibrosarcoma-like (n=11), myxofibrosarcoma-like (n=2), and fibrosarcoma and inflammatory-like (n=1) pattern. High-grade DDL had a fibrosarcoma-like (n=22), undifferentiated pleomorphic sarcoma-like (n=7), myxofibrosarcoma and undifferentiated pleomorphic sarcoma-like (n=4), fibrosarcoma and undifferentiated pleomorphic sarcoma-like (n=2), and myxofibrosarcoma-like (n=1) pattern. Resection margins were positive in 22, negative in 13, and unknown in 7 cases. MDM2 was positive in 24/24 cases. Two patients received neoadjuvant radiotherapy (1 with chemotherapy). Patients received postoperative radiation (n=13), reexcision (n=5) with radiation (n=3), chemotherapy (n=2), chemotherapy and radiation (n=1), no therapy (n=11), and unknown (n=6). Follow-up information was available in 31 patients (mean: 54.2 mo; median: 38.5 mo; range: 2 to 180 mo). Seven patients developed local recurrence. Two patients had systemic metastases and succumbed to disease. Recurrence developed at an average of 40.9 months (median: 24 mo; range: 12 to 100 mo) after resection. Average follow-up in patients without recurrence was 45.2 months (median: 25 mo; range: 2 to 180 mo) (P=0.87). Margin status, size, and grade did not correlate with recurrence (P>0.05). Thus, DDL of the spermatic cord includes a spectrum of morphologic patterns. Complete excision is difficult at first attempt. Local recurrence is common, and relatively few patients develop systemic disease.

  4. A combined theoretical and experimental approach of a new ternary metal oxide in molybdate composite for hybrid energy storage capacitors

    NASA Astrophysics Data System (ADS)

    Minakshi, M.; Watcharatharapong, T.; Chakraborty, S.; Ahuja, R.

    2018-04-01

    Sustainable energy sources require an efficient energy storage system possessing excellent electrochemical properties. The better understanding of possible crystal configurations and the development of a new ternary metal oxide in molybdate composite as an electrode for hybrid capacitors can lead to an efficient energy storage system. Here, we reported a new ternary metal oxide in molybdate composite [(Mn1/3Co1/3Ni1/3)MoO4] prepared by simple combustion synthesis with an extended voltage window (1.8 V vs. Carbon) resulting in excellent specific capacity 35 C g-1 (58 F g-1) and energy density (50 Wh kg-1 at 500 W kg-1) for a two electrode system in an aqueous NaOH electrolyte. The binding energies measured for Mn, Co, and Ni 2p are consistent with the literature, and with the metal ions being present as M(II), implying that the oxidation states of the transition metals are unchanged. The experimental findings are correlated well through density functional theory based electronic structure calculations. Our reported work on the ternary metal oxide studies (Mn1/3Co1/3Ni1/3)MoO4 suggests that will be an added value to the materials for energy storage.

  5. Pregnancy-Associated Plasma Protein A Levels in Late First Trimester Pregnancies with Small-for-Gestational Age Neonates: A Prospective Case-Control Study.

    PubMed

    Agarwal, Rachna; Kumari, Radhika; Mehndiratta, Mohit; Radhakrishnan, Gita; Faridi, M M A; Chandra, Nilesh

    2017-08-01

    We aimed to investigate the association of pregnancy associated plasma protein A (PAPP-A) levels in late first trimester with small for gestational age (SGA) neonates and adverse pregnancy outcomes in a low-income setting. The inclusion criteria were late first trimester (11-13 + 6 weeks) women with singleton and non-anomalous pregnancy. Enrolled participants were sampled for PAPP-A and prospectively followed up for delivery outcome and antenatal complications. A multiple of median (MoM) was calculated and statistically compared between groups. Out of total 284 subjects, 14.54% delivered SGA babies and formed cases (Group A), 66.5% delivered appropriate for gestational age (AGA) neonates with uneventful antenatal period (controls, Group B), and 19.3% were AGA group with adverse pregnancy complications (Group C). The late first trimester median PAPP-A MoM was significantly lower (0.61) in Group A compared to Group B (1.47). Using receiver operating characteristic (ROC) curve for PAPP-A MoM, optimal cutoff value was found at 0.45 MoM, with positive predictive value of 56.2%, specificity of 92.6% and sensitivity of 45%. The median interquartile range (IQR) of PAPP-A MoM value in Group C in comparison with Group B was significantly lower except for abruption. At PAPP-A MoM cutoff value <1, <0.8, <0.6 and <0.4, the odds ratio for adverse pregnancy outcome was 8.30, 7.29, 10.97 and 10.60, respectively, indicating an inverse relationship. With 0.45 MoM cutoff of PAPP-A, the detection rate, specificity and positive predictive value for SGA were 45, 92.6 and 56.2%, respectively. As PAPP-A MoM values decreased, the odds ratio of having adverse pregnancy outcomes increased.

  6. Modulation of immune response to Lol p I by pretreatment with anti-idiotypic antibody is not restricted to the idiotypic expression.

    PubMed Central

    Boutin, Y; Hébert, J

    1994-01-01

    To study the role of anti-idiotypic antibodies in the regulation of the immune response to Lol p I (the major allergenic component of rye grass pollen), we have recently generated a panel of three MoAbs directed against distinct epitopes of Lolp I and an anti-idiotypic MoAb directed against the idiotype borne by one of the anti-Lol p I MoAbs (290A-167). The effects of pretreatment with this anti-idiotypic MoAb in BALB/c mice before immunization with the antigen have been examined. The anti-idiotypic MoAb or unrelated MoAb were given weekly for 8 weeks intraperitoneally. Mice then received the antigen (2 micrograms) adsorbed with alum (2 mg) at weeks 9, 11 and 13. Serum anti-Lol p I antibodies (IgG or IgE) and specific idiotypic responses were measured. Anti-Lol p I IgG antibodies could be detected before immunization with Lol p I only in mice pretreated with anti-idiotypic MoAb. Immunization with Lol p I induced an anti-Lol p I IgG response in both groups, but this response was higher in mice that received anti-idiotypic MoAb. Similar profiles were seen for specific IgE antibodies and idiotypic responses. Surprisingly, idiotypes borne by other anti-Lol p I MoAbs (539A-6 and 348A-6) had also been enhanced after pretreatment with the anti-290A-167 MoAb. These observations suggested that the pretreatment with this anti-idiotypic MoAb modulates not only the expression of the respective idiotype, but also affects other idiotype responses. PMID:7514517

  7. Value of a new multiparametric score for prediction of microvascular obstruction lesions in ST-segment elevation myocardial infarction revascularized by percutaneous coronary intervention.

    PubMed

    Amabile, Nicolas; Jacquier, Alexis; Gaudart, Jean; Sarran, Anthony; Shuaib, Anes; Panuel, Michel; Moulin, Guy; Bartoli, Jean-Michel; Paganelli, Franck

    2010-10-01

    Despite improvement in revascularization strategies, microvascular obstruction (MO) lesions remain associated with poor outcome after ST-segment elevation myocardial infarction (STEMI). To establish a bedside-available score for predicting MO lesions in STEMI, with cardiac magnetic resonance imaging (CMR) as the reference standard, and to test its prognostic value for clinical outcome. Patients with STEMI of<12 hours' evolution treated by percutaneous coronary intervention (PCI) were included. CMR was performed 4-8 days later, to measure myocardial infarction (MI) extent, left ventricular ejection fraction (LVEF) and volumes, and to identify MO lesions. An MO score was built from multivariable logistic regression results and included clinical, angiographic and electrocardiographic criteria. Adverse cardiovascular events were recorded prospectively after STEMI. We analysed data from 112 patients. MO lesions were found in 63 (56%) patients and were associated with larger MI as assessed by higher peak creatine phosphokinase (3755 ± 351 vs 1467 ± 220 IU, p<0.001), lower LVEF (46.7 ± 1.5 vs 53.4 ± 1.6%, p<0.01) and larger MI extent (18.7 ± 1.2 vs 9.0 ± 1.3% LV, p<0.001) on CMR. MO score>4 accurately identified microcirculatory injuries (sensitivity 84%; specificity 82%) and independently predicted the presence of MO lesions on CMR. MO score>4 predicted adverse cardiovascular events during the first year after STEMI (relative risk 2.60 [1.10-6.60], p=0.03). MO lesions are frequent in PCI-treated STEMI and are associated with larger MIs. MO score accurately predicted MO lesions and identified patients with poor outcome post-STEMI. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

  8. A Mo-95 and C-13 Solid-state NMR and Relativistic DFT Investigation of Mesitylenetricarbonylmolybdenum(0) -a Typical Transition Metal Piano-stool Complex

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

    Bryce, David L.; Wasylishen, Roderick E.

    2002-06-21

    The chemical shift (CS) and electric field gradient (EFG) tensors in the piano-stool compound mesitylenetricarbonylmolybdenum(0), 1, have been investigated via {sup 95}Mo and {sup 13}C solid-state magic-angle spinning (MAS) NMR as well as relativistic zeroth-order regular approximation density functional theory (ZORA-DFT) calculations. Molybdenum-95 (I = 5/2) MAS NMR spectra acquired at 18.8 T are dominated by the anisotropic chemical shift interaction ({Omega} = 775 {+-} 30 ppm) rather than the 2nd-order quadrupolar interaction (C{sub Q} = -0.96 {+-} 0.15 MHz), an unusual situation for a quadrupolar nucleus. ZORA-DFT calculations of the {sup 95}Mo EFG and CS tensors are in agreementmore » with the experimental data. Mixing of appropriate occupied and virtual d-orbital dominated MOs in the region of the HOMO-LUMO gap are shown to be responsible for the large chemical shift anisotropy. The small, but non-negligible, {sup 95}Mo quadrupolar interaction is discussed in terms of the geometry about Mo. Carbon-13 CPMAS spectra acquired at 4.7 T demonstrate the crystallographic and magnetic nonequivalence of the twelve {sup 13}C nuclei in 1, despite the chemical equivalence of some of these nuclei in isotropic solutions. The principal components of the carbon CS tensors are determined via a Herzfeld-Berger analysis, and indicate that motion of the mesitylene ring is slow compared to a rate which would influence the carbon CS tensors (i.e. tens of {micro}s). ZORA-DFT calculations reproduce the experimental carbon CS tensors accurately. Oxygen-17 EFG and CS tensors for 1 are also calculated and discussed in terms of existing experimental data for related molybdenum carbonyl compounds. This work provides an example of the information available from combined multi-field solid-state multinuclear magnetic resonance and computational investigations of transition metal compounds, in particular the direct study of quadrupolar transition metal nuclei with relatively small magnetic moments.« less

  9. Bio-dissolution of Ni, V and Mo from spent petroleum catalyst using iron oxidizing bacteria.

    PubMed

    Pradhan, Debabrata; Kim, Dong J; Roychaudhury, Gautam; Lee, Seoung W

    2010-01-01

    Bioleaching studies of spent petroleum catalyst containing Ni, V and Mo were carried out using iron oxidizing bacteria. Various leaching parameters such as Fe(II) concentration, pulp density, pH, temperature and particle size were studied to evaluate their effects on the leaching efficiency as well as the kinetics of dissolution. The percentage of leaching of Ni and V were higher than Mo. The leaching process followed a diffusion controlled model and the product layer was observed to be impervious due to formation of ammonium jarosite (NH(4))Fe(3)(SO(4))(2)(OH)(6). Apart from this, the lower leaching efficiency of Mo was due to a hydrophobic coating of elemental sulfur over Mo matrix in the spent catalyst. The diffusivities of the attacking species for Ni, V and Mo were also calculated.

  10. Preparation of Zr(Mo,W)2O8 with a larger negative thermal expansion by controlling the thermal decomposition of Zr(Mo,W)2(OH,Cl)2∙2H2O.

    PubMed

    Petrushina, Mariya Yu; Dedova, Elena S; Filatov, Eugeny Yu; Plyusnin, Pavel E; Korenev, Sergei V; Kulkov, Sergei N; Derevyannikova, Elizaveta A; Sharafutdinov, Marat R; Gubanov, Alexander I

    2018-03-28

    Solid solutions of Zr(Mo,W) 2 O 7 (OH,Cl) 2 ∙2H 2 O with a preset ratio of components were prepared by a hydrothermal method. The chemical composition of the solutions was determined by energy dispersive X-ray spectroscopy (EDX). For all the samples of ZrMo x W 2-x O 7 (OH,Cl) 2 ∙2H 2 O (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, and 2.0), TGA and in situ powder X-ray diffraction (PXRD) studies (300-1100 K) were conducted. For each case, the boundaries of the transformations were determined: Zr(Mo,W) 2 O 7 (OH,Cl) 2 ∙2H 2 O → orthorhombic-ZrMo x W 2-x O 8 (425-525 K), orthorhombic-ZrMo x W 2-x O 8  → cubic-ZrMo x W 2-x O 8 (700-850 K), cubic-ZrMo x W 2-x O 8  → trigonal-ZrMo x W 2-x O 8 (800-1050 K for x > 1) and cubic-ZrMo x W 2-x O 8  → oxides (1000-1075 K for x ≤ 1). The cell parameters of the disordered cubic-ZrMo x W 2-x O 8 (space group Pa-3) were measured within 300-900 K, and the thermal expansion coefficients were calculated: -3.5∙10 -6  - -4.5∙10 -6  K -1 . For the ordered ZrMo 1.8 W 0.2 O 8 (space group P2 1 3), a negative thermal expansion (NTE) coefficient -9.6∙10 -6  K -1 (300-400 K) was calculated. Orthorhombic-ZrW2O 8 is formed upon the decomposition of ZrW 2 O 7 (OH,Cl) 2 ∙2H 2 O within 500-800 K.

  11. Adsorption and photocatalysis for methyl orange and Cd removal from wastewater using TiO2/sewage sludge-based activated carbon nanocomposites

    PubMed Central

    Eltaher, M. A.; Abdou, A. N. A.

    2017-01-01

    Nanocomposite TiO2/ASS (TiO2 nanoparticle coated sewage sludge-based activated carbon) was synthesized by the sol-gel method. The changes in surface properties of the TiO2/ASS nanocomposite were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray fluorescence. The prepared TiO2/ASS nanocomposite was applied for simultaneous removal of methyl orange dye (MO) and Cd2+ from bi-pollutant solution. The factors influencing photocatalysis (TiO2 : ASS ratios, initial pollutant concentrations, solution pH, nanocomposite dosage and UV irradiation time) were investigated. The results revealed that high removal efficiency of methyl orange dye (MO) and Cd2+ from bi-pollutant solution was achieved with TiO2/ASS at a ratio (1 : 2). The obtained results revealed that degradation of MO dye on the TiO2/ASS nanocomposite was facilitated by surface adsorption and photocatalytic processes. The coupled photocatalysis and adsorption shown by TiO2/ASS nanocomposite resulted in faster and higher degradation of MO as compared to MO removal by ASS adsorbent. The removal efficiency of MO by ASS adsorbent and TiO2/ASS (1 : 2) nanocomposite at optimum pH value 7 were 74.14 and 94.28%, respectively, while for Cd2+ it was more than 90%. The experimental results fitted well with the second-order kinetic reaction. PMID:29308227

  12. Adsorption and photocatalysis for methyl orange and Cd removal from wastewater using TiO2/sewage sludge-based activated carbon nanocomposites.

    PubMed

    Rashed, M Nageeb; Eltaher, M A; Abdou, A N A

    2017-12-01

    Nanocomposite TiO 2 /ASS (TiO 2 nanoparticle coated sewage sludge-based activated carbon) was synthesized by the sol-gel method. The changes in surface properties of the TiO 2 /ASS nanocomposite were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray fluorescence. The prepared TiO 2 /ASS nanocomposite was applied for simultaneous removal of methyl orange dye (MO) and Cd 2+ from bi-pollutant solution. The factors influencing photocatalysis (TiO 2  : ASS ratios, initial pollutant concentrations, solution pH, nanocomposite dosage and UV irradiation time) were investigated. The results revealed that high removal efficiency of methyl orange dye (MO) and Cd 2+ from bi-pollutant solution was achieved with TiO 2 /ASS at a ratio (1 : 2). The obtained results revealed that degradation of MO dye on the TiO 2 /ASS nanocomposite was facilitated by surface adsorption and photocatalytic processes. The coupled photocatalysis and adsorption shown by TiO 2 /ASS nanocomposite resulted in faster and higher degradation of MO as compared to MO removal by ASS adsorbent. The removal efficiency of MO by ASS adsorbent and TiO 2 /ASS (1 : 2) nanocomposite at optimum pH value 7 were 74.14 and 94.28%, respectively, while for Cd 2+ it was more than 90%. The experimental results fitted well with the second-order kinetic reaction.

  13. Adsorption and photocatalysis for methyl orange and Cd removal from wastewater using TiO2/sewage sludge-based activated carbon nanocomposites

    NASA Astrophysics Data System (ADS)

    Rashed, M. Nageeb; Eltaher, M. A.; Abdou, A. N. A.

    2017-12-01

    Nanocomposite TiO2/ASS (TiO2 nanoparticle coated sewage sludge-based activated carbon) was synthesized by the sol-gel method. The changes in surface properties of the TiO2/ASS nanocomposite were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray fluorescence. The prepared TiO2/ASS nanocomposite was applied for simultaneous removal of methyl orange dye (MO) and Cd2+ from bi-pollutant solution. The factors influencing photocatalysis (TiO2 : ASS ratios, initial pollutant concentrations, solution pH, nanocomposite dosage and UV irradiation time) were investigated. The results revealed that high removal efficiency of methyl orange dye (MO) and Cd2+ from bi-pollutant solution was achieved with TiO2/ASS at a ratio (1 : 2). The obtained results revealed that degradation of MO dye on the TiO2/ASS nanocomposite was facilitated by surface adsorption and photocatalytic processes. The coupled photocatalysis and adsorption shown by TiO2/ASS nanocomposite resulted in faster and higher degradation of MO as compared to MO removal by ASS adsorbent. The removal efficiency of MO by ASS adsorbent and TiO2/ASS (1 : 2) nanocomposite at optimum pH value 7 were 74.14 and 94.28%, respectively, while for Cd2+ it was more than 90%. The experimental results fitted well with the second-order kinetic reaction.

  14. Modelling the local atomic structure of molybdenum in nuclear waste glasses with ab initio molecular dynamics simulations.

    PubMed

    Konstantinou, Konstantinos; Sushko, Peter V; Duffy, Dorothy M

    2016-09-21

    The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO 2 ) 57.5 -(B 2 O 3 ) 10 -(Na 2 O) 15 -(CaO) 15 -(MoO 3 ) 2.5 and (SiO 2 ) 57.3 -(B 2 O 3 ) 20 -(Na 2 O) 6.8 -(Li 2 O) 13.4 -(MoO 3 ) 2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na 2 MoO 4 and CaMoO 4 ). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations.

  15. Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations.

    PubMed

    Aarnts, Maxim P.; Wilms, Maikel P.; Peelen, Karin; Fraanje, Jan; Goubitz, Kees; Hartl, Frantisek; Stufkens, Derk J.; Baerends, Evert Jan; Vlcek, Antonín

    1996-09-11

    Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) Å, b = 13.902(3) Å, c = 19.643(2) Å, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) Å(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.

  16. The Hardest Superconducting Metal Nitride

    DOE PAGES

    Wang, Shanmin; Antonio, Daniel; Yu, Xiaohui; ...

    2015-09-03

    Transition–metal (TM) nitrides are a class of compounds with a wide range of properties and applications. Hard superconducting nitrides are of particular interest for electronic applications under working conditions such as coating and high stress (e.g., electromechanical systems). However, most of the known TM nitrides crystallize in the rock–salt structure, a structure that is unfavorable to resist shear strain, and they exhibit relatively low indentation hardness, typically in the range of 10–20 GPa. Here, we report high–pressure synthesis of hexagonal δ–MoN and cubic γ–MoN through an ion–exchange reaction at 3.5 GPa. The final products are in the bulk form withmore » crystallite sizes of 50 – 80 μm. Based on indentation testing on single crystals, hexagonal δ–MoN exhibits excellent hardness of ~30 GPa, which is 30% higher than cubic γ–MoN (~23 GPa) and is so far the hardest among the known metal nitrides. The hardness enhancement in hexagonal phase is attributed to extended covalently bonded Mo–N network than that in cubic phase. The measured superconducting transition temperatures for δ–MoN and cubic γ–MoN are 13.8 and 5.5 K, respectively, in good agreement with previous measurements.« less

  17. Synthesis, Structural, Thermal, and Electronic Properties of Palmierite-Related Double Molybdate α-Cs2Pb(MoO4)2.

    PubMed

    Solodovnikov, Sergey F; Atuchin, Victor V; Solodovnikova, Zoya A; Khyzhun, Oleg Y; Danylenko, Mykola I; Pishchur, Denis P; Plyusnin, Pavel E; Pugachev, Alexey M; Gavrilova, Tatiana A; Yelisseyev, Alexander P; Reshak, Ali H; Alahmed, Zeyad A; Habubi, Nadir F

    2017-03-20

    Cs 2 Pb(MoO 4 ) 2 crystals were prepared by crystallization from their own melt, and the crystal structure has been studied in detail. At 296 K, the molybdate crystallizes in the low-temperature α-form and has a monoclinic palmierite-related superstructure (space group C2/m, a = 2.13755(13) nm, b = 1.23123(8) nm, c = 1.68024(10) nm, β = 115.037(2)°, Z = 16) possessing the largest unit cell volume, 4.0066(4) nm 3 , among lead-containing palmierites. The compound undergoes a distortive phase transition at 635 K and incongruently melts at 943 K. The electronic structure of α-Cs 2 Pb(MoO 4 ) 2 was explored by using X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy methods. For α-Cs 2 Pb(MoO 4 ) 2 , the photoelectron core-level and valence-band spectra and the XES band representing the energy distribution of Mo 4d and O 2p states were recorded. Our results allow one to conclude that the Mo 4d and O 2p states contribute mainly to the central part and at the top of the valence band, respectively, with also significant contributions throughout the whole valence-band region of the molybdate under consideration.

  18. Magnetism of the spin-1 tetramer compound A2Ni2Mo3O12(A =Rb or K)

    NASA Astrophysics Data System (ADS)

    Hase, Masashi; Matsuo, Akira; Kindo, Koichi; Matsumoto, Masashige

    2017-12-01

    We measured the temperature dependence of the magnetic susceptibility χ (T ) and the specific heat C (T ) and the magnetic-field dependence of the magnetization M (H ) of A2Ni2Mo3O12 (A = Rb or K) powder. We consider that the probable spin model is an interacting spin-1 antiferromagnetic tetramer model. We evaluated values of the intratetramer interactions as J1=9 K and J2=18 K, and the effective intertetramer interaction as Jeff=4 K for Rb2Ni2Mo3O12 . The susceptibility and magnetization at 1.3 K of K2Ni2Mo3O12 are very close to those of Rb2Ni2Mo3O12 . We observed a phase transition to a magnetically ordered state in C (T )/T in magnetic fields above 3 T. The transition temperature increases with magnetic field. Probably, the ordered state appears around 1.8 K even in 0 T. The ordered state in 0 T, however, is not stable enough like an order in the vicinity of a quantum critical point. Longitudinal-mode magnetic excitations may be observable in single crystalline A2Ni2Mo3O12 (A = Rb or K).

  19. 40 CFR 471.51 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Molybdenum 7.87 4.07 Oil and grease 23.8 14.3 TSS 48.8 23.2 pH (1) (1) 1 Within the range of 7.5 to 10.0 at... Fluoride 7,200 3,200 Molybdenum 800 414 Oil and grease 2,420 1,450 TSS 4,960 2,360 pH (1) (1) 1 Within the... Molybdenum 2.21 1.14 Oil and grease 6.68 4.01 TSS 13.7 6.51 pH (1) (1) 1 Within the range of 7.5 to 10.0 at...

  20. 40 CFR 471.51 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Molybdenum 7.87 4.07 Oil and grease 23.8 14.3 TSS 48.8 23.2 pH (1) (1) 1 Within the range of 7.5 to 10.0 at... Fluoride 7,200 3,200 Molybdenum 800 414 Oil and grease 2,420 1,450 TSS 4,960 2,360 pH (1) (1) 1 Within the... Molybdenum 2.21 1.14 Oil and grease 6.68 4.01 TSS 13.7 6.51 pH (1) (1) 1 Within the range of 7.5 to 10.0 at...

  1. Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine and Pyrazines to M(PR3)2(CO)3 (M=Mo, W; R=Me, iPr)

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

    Hoff, C.D.; Muckerman, J.; Achord, P.

    2009-08-17

    The enthalpies of binding of a number of N-donor ligands to the complex Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3} in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of {approx}10 kcal mol{sup -1}: {Delta}H{sub binding} = -8.8 {+-} 1.2 (N{sub 2}-Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}); -10.3 {+-} 0.8 (N{sub 2}); -11.2 {+-} 0.4 (AdN{sub 3} (Ad = 1-adamantyl)); -13.8 {+-} 0.5 (N{sub 2}CHSiMe{sub 3}); -14.9 {+-} 0.9 (pyrazine = pz); -14.8 {+-} 0.6 (2,6-Me{sub 2}pz); -15.5 {+-} 1.8 (Me{sub 2}NCN); -16.6 {+-} 0.4 (CH{sub 3}CN); -17.0 {+-} 0.4 (pyridine); -17.5 {+-} 0.8more » ([4-CH{sub 3}pz][PF{sub 6}] (in tetrahydrofuran)); -17.6 {+-} 0.4 (C{sub 6}H{sub 5}CN); -18.6 {+-} 1.8 (N{sub 2}CHC(=O)OEt); and -19.3 {+-} 2.5 kcal mol{sup -1} (pz)Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}). The value for the isonitrile AdNC (-29.0 {+-} 0.3) is 12.3 kcal mol{sup -1} more exothermic than that of the nitrile AdCN (-16.7 {+-} 0.6 kcal mol{sup -1}). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol{sup -1} range despite dramatic color changes and variation of v{sub CN}. Computed structural and spectroscopic parameters for the complexes Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L are in good agreement with experimental data. Computed binding enthalpies for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe{sub 3}){sub 2}(CO){sub 3}L show a better fit to experimental data than that for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L using a smaller basis set. Crystal structures of Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(Me{sub 2}NCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-F{sub 2}C{sub 6}H{sub 3}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,4,6-Me{sub 3}C{sub 6}H{sub 2}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-Me{sub 2}pz), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC), and W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC) are reported.« less

  2. Radionuclide sorption in Yucca Mountain tuffs with J-13 well water: Neptunium, uranium, and plutonium. Yucca Mountain site characterization program milestone 3338

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

    Triay, I.R.; Cotter, C.R.; Kraus, S.M.

    1996-08-01

    We studied the retardation of actinides (neptunium, uranium, and plutonium) by sorption as a function of radionuclide concentration in water from Well J-13 and of tuffs from Yucca Mountain. Three major tuff types were examined: devitrified, vitric, and zeolitic. To identify the sorbing minerals in the tuffs, we conducted batch sorption experiments with pure mineral separates. These experiments were performed with water from Well J-13 (a sodium bicarbonate groundwater) under oxidizing conditions in the pH range from 7 to 8.5. The results indicate that all actinides studied sorb strongly to synthetic hematite and also that Np(V) and U(VI) do notmore » sorb appreciably to devitrified or vitric tuffs, albite, or quartz. The sorption of neptunium onto clinoptilolite-rich tuffs and pure clinoptilolite can be fitted with a sorption distribution coefficient in the concentration range from 1 X 10{sup -7} to 3 X 10{sup -5} M. The sorption of uranium onto clinoptilolite-rich tuffs and pure clinoptilolite is not linear in the concentration range from 8 X 10{sup -8} to 1 X 10{sup -4} M, and it can be fitted with nonlinear isotherm models (such as the Langmuir or the Freundlich Isotherms). The sorption of neptunium and uranium onto clinoptilolite in J-13 well water increases with decreasing pH in the range from 7 to 8.5. The sorption of plutonium (initially in the Pu(V) oxidation state) onto tuffs and pure mineral separates in J-13 well water at pH 7 is significant. Plutonium sorption decreases as a function of tuff type in the order: zeolitic > vitric > devitrified; and as a function of mineralogy in the order: hematite > clinoptilolite > albite > quartz.« less

  3. Electronic Structure and Multisite Basicity of the Pyramidal Phosphinidene-Bridged Dimolybdenum Complex [Mo2(η(5)-C5H5)(μ-κ(1):κ(1),η(5)-PC5H4)(η(6)-C6H3(t)Bu3)(CO)2(PMe3)].

    PubMed

    Albuerne, Isabel G; Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Ruiz, Miguel A

    2015-10-19

    The title phosphinidene complex could be sequentially protonated with HBF4·OEt2 or [H(OEt2)2](BAr'4) to give the phosphido-bridged derivatives [Mo2Cp(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X and then the hydrides [Mo2Cp(H)(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X2 (X = BF4, BAr'4; Ar' = 3,5-C6H3(CF3)2; Mes* = 2,4,6-C6H2(t)Bu3). Density functional theory (DFT) calculations revealed that the most favored site for initial electrophilic attack is the metallocene Mo atom, but attachment of the electrophile to the phosphinidene P atom gives more stable products. This was in agreement with all other reactions investigated, which invariably involved the attachment of the added electrophile at the P site. Thus, the title compound reacted with S8 at 223 K to give the thiophosphinidene-bridged complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(S)C5H4}(η(6)-HMes*)(CO)2(PMe3)], a poorly stable molecule which reacted with MeI at room temperature to give the corresponding thiolatophosphido derivative, isolated as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(SMe)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4) (P-S = 2.128(4) Å) after anion exchange with Na(BAr'4). Reaction of the title compound with MeI proceeded smoothly to give the corresponding methylphosphido derivative, isolated analogously as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4). The related complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe2Ph)](BAr'4) (P-C(Me) = 1.841(5) Å) could be prepared analogously from the neutral precursor [Mo2Cp{μ-κ(1):κ(1),η(5)-PC5H4}(η(6)-HMes*)(CO)2(PMe2Ph)]. In contrast, reaction of the title complex with ethylene sulfide involved opening of the C2S ring and formation of new P-C and Mo-S bonds (1.886(7) and 2.493(2) Å, respectively), with displacement of the PMe3 ligand, to give the phosphido-thiolato complex [Mo2Cp{μ-κ(2)(P,S):κ(1)P,η(5)-P(C2H4S)C5H4}(η(6)-HMes*)(CO)2]. All these derivatives of the title complex displayed an unusual trigonal pyramidal-like environment around the bridging P atom, with the added electrophile placed in the Mo2P plane as a result of the directionality of the relevant frontier orbital of the phosphinidene complex, according to DFT calculations.

  4. Characteristics of HY-180 and Ti-100 for Welded High Strength Structures

    DTIC Science & Technology

    1974-12-01

    materials in welded structures are reported. The 10Ni-8Co-2Cr-lMo steel arid the Ti- 6Al -2Cb-lTa-0. 8Mo titanium alloy were selected as candidate...only li- 6Al -iCb-na-0.»Mo (Ti-6-2-1-1) and’Ii- 6Al - 4V are competitive with 10Ni-8Co-2Cr-lMo steel on a strength-weight basis, while possessing ade...Ti- 6Al -2Cb-lTa-0. 8Mo has better toughness in plate form, based upon dynamic tear properties. There- fore the Ti- 6Al -2Cb-lTa-0.8Mo titanium alloy

  5. In situ changes of tropical crustose coralline algae along carbon dioxide gradients

    NASA Astrophysics Data System (ADS)

    Fabricius, K. E.; Kluibenschedl, A.; Harrington, L.; Noonan, S.; de'Ath, G.

    2015-04-01

    Crustose coralline algae (CCA) fulfill important ecosystem functions in coral reefs, including reef framework stabilization and induction of larval settlement. To investigate in situ the effects of high carbon dioxide on CCA communities, we deployed settlement tiles at three tropical volcanic CO2 seeps in Papua New Guinea along gradients spanning from 8.1 to 7.4 pH. After 5 and 13 months deployment, there was a steep transition from CCA presence to absence around pH 7.8 (660 μatm pCO2): 98% of tiles had CCA at pH > 7.8, whereas only 20% of tiles had CCA at pH <= 7.8. As pH declined from 8.0 to 7.8, the least and most sensitive CCA species lost 43% and 85% of cover, respectively. Communities on upward facing surfaces exposed to high light and high grazing pressure showed less steep losses than those on shaded surfaces with low grazing. Direct CO2 effects on early life stages were the main mechanisms determining CCA cover, rather than competitive interactions with other benthic groups. Importantly, declines were steepest at near-ambient pH, suggesting that CCA may have already declined in abundance due to the recent seawater pH decline of 0.1 units, and that future severe losses are likely with increasing ocean acidification.

  6. Statistical Optimization of 1,3-Propanediol (1,3-PD) Production from Crude Glycerol by Considering Four Objectives: 1,3-PD Concentration, Yield, Selectivity, and Productivity.

    PubMed

    Supaporn, Pansuwan; Yeom, Sung Ho

    2018-04-30

    This study investigated the biological conversion of crude glycerol generated from a commercial biodiesel production plant as a by-product to 1,3-propanediol (1,3-PD). Statistical analysis was employed to derive a statistical model for the individual and interactive effects of glycerol, (NH 4 ) 2 SO 4 , trace elements, pH, and cultivation time on the four objectives: 1,3-PD concentration, yield, selectivity, and productivity. Optimum conditions for each objective with its maximum value were predicted by statistical optimization, and experiments under the optimum conditions verified the predictions. In addition, by systematic analysis of the values of four objectives, optimum conditions for 1,3-PD concentration (49.8 g/L initial glycerol, 4.0 g/L of (NH 4 ) 2 SO 4 , 2.0 mL/L of trace element, pH 7.5, and 11.2 h of cultivation time) were determined to be the global optimum culture conditions for 1,3-PD production. Under these conditions, we could achieve high 1,3-PD yield (47.4%), 1,3-PD selectivity (88.8%), and 1,3-PD productivity (2.1/g/L/h) as well as high 1,3-PD concentration (23.6 g/L).

  7. A study on the complexes between human erythrocyte enzymes participating in the conversions of 1,3-diphosphoglycerate.

    PubMed

    Fokina, K V; Dainyak, M B; Nagradova, N K; Muronetz, V I

    1997-09-15

    The ability of D-glyceraldehyde-3-phosphate dehydrogenase (GAPDH) catalyzing the reaction of 1,3-diphosphoglycerate synthesis in human erythrocytes to form complexes with enzymes which use this metabolite as substrate (3-phosphoglycerate kinase (3-PGK) or 2,3-diphosphoglycerate mutase (2,3-DPGM)) was studied. It was found that highly active 2,3-DPGM can be extracted from human erythrocyte hemolysates in a complex with GAPDH adsorbed on Sepharose-bound anti-GAPDH antibodies at pH 6.5, the molar ratio being one 2,3-GPGM subunit per subunit of GAPDH. No complexation was, however, detected at pH 8.0. The opposite was true for the interaction between GAPDH and 3-PGK, which could be observed at pH 8.0. In experiments carried out at pH 7.4, both GAPDH x 2,3-DPGM and GAPGH x 3-PGK complexes were detected. The Kd values of the complexes determined with purified enzyme preparations were in the range 2.40-2.48 microM for both the GAPDH x 2,3-DPGM and GAPGH x 3-PGK enzyme pairs, when titrations of GAPDH covalently bound to CNBr-activated Sepharose were performed by the soluble 2,3-DPGM or 3-PGK. If, however, GAPDH adsorbed on the specific antibodies covalently bound to Sepharose was used in the titration experiments, the Kd for the GAPDH x 2,3-DPGM complex was found to be 0.54 microM, and the Kd for the GAPDH x 3-PGK complex was 0.49 microM. The concentration of 2,3-diphosphoglycerate determined after 1 h of incubation of erythrocytes in the presence of glucose was found to increase 1.5-fold if the incubation was carried out at pH 6.5, but did not change upon incubation at pH 8.0. On the other hand, the concentration of 3-phosphoglycerate after incubation at pH 8.0 was twice as large as that found after incubation at pH 6.5. The results are interpreted on the hypothesis that specific protein-protein interactions between GAPDH and 2,3-DPGM or between GAPDH and 3-PGK may play a role in determining the fate of 1,3-diphosphoglycerate produced in the GAPDH-catalyzed reaction.

  8. High radioactive concentration of 99mTc from a zirconium [99Mo]molybdate gel generator using an acidic alumina column for purification and concentration.

    PubMed

    Sarkar, S K; Saraswathy, P; Arjun, G; Ramamoorthy, N

    2004-06-01

    Newer applications of radiopharmaceuticals in nuclear medicine require pertechnetate of moderate to high radioactive concentration. Hence there is a need to develop simple procedures for the concentration of pertechnetate, and such a procedure is given in this paper. Ten to 20 ml of sodium [Tc]pertechnetate eluted in de-ionized water from a zirconium [Mo]molybdate (ZrMo) gel column generator was passed through 2 g of an acidic alumina bed (35 x 8 mm) in order to remove the co-eluted traces of Mo and to retain the pertechnetate. The retained pertechnetate was then re-eluted, quantitatively, in 3 ml of normal saline, from the alumina column. About a 4-fold increase in radioactive concentration of Tc was obtained (cf. approximately 10-12 ml normal saline is required for the elution of Tc from the gel column). Generators containing up to 22.2 GBq (600 mCi) Mo in 6-7 g ZrMo gel column (35 x 13 mm) were prepared and a radioactive concentration of Tc up to 4 GBq x ml (110 mCi x ml) was obtained on the first day of use. The overall recovery of Tc was >90%, Mo breakthrough was 10 to 10% and the duration of concentration was 3-5 min. The chemical impurity in terms of Al, Mo and Zr was <10 ppm each. The same procedure for the concentration of pertechnetate was applied to generators with 12-15 g ZrMo gel beds to obtain a higher capacity Tc gel generator, with similar findings.

  9. Neurodevelopmental and mental health comorbidities in children and adolescents with epilepsy and migraine: a response to identified research gaps.

    PubMed

    Wagner, Janelle L; Wilson, Dulaney A; Smith, Gigi; Malek, Angela; Selassie, Anbesaw W

    2015-01-01

    To determine the distribution and risk characteristics of comorbid neurodevelopmental and mental health comorbidities among children and adolescents (6-18y) with epilepsy or migraine (i.e. a neurological condition with shared features and potential etiology) compared with lower extremity fracture (LEF). This case-control study involved a subset analysis of surveillance data in South Carolina, USA. Hospital admission, outpatient, and emergency department visits for individuals with an International Classification of Disease, 9th revision Clinical Modification diagnosis of epilepsy (n=6730; 54.5% females, 45.5% males; mean age [SD] 14y 2mo [4y 5mo]); migraine (n=10 495; 74.5% females, 25.5% males; 15y 6mo [2y 6mo]), or LEF (n=15 305; 40.3% females, 59.7% males; 13y 11mo [2y 11mo]) from January 1 2000 to December 31 2011 were identified. The association of epilepsy, migraine, or LEF with any mental health comorbidity was evaluated with univariate and multivariate polytomous logistic regression. Comorbidities were highly prevalent in children and adolescents, with epilepsy with a rate of 29.7% (95% confidence interval [CI]: 28.6-30.8) for mental health comorbidities and 30.8% (95% CI: 29.7-31.9) for neurodevelopmental comorbidities. The odds of mental health comorbidity was 2.20 (95% CI: 2.02-2.39) for children and adolescents with epilepsy and 1.60 (95% CI: 1.48-1.73) for migraine, in reference to children and adolescents with LEF after adjusting for potential confounders. Prevalence and risk for specific comorbidities are presented. Neuropathophysiological and psychosocial factors specific to epilepsy may provide more risk for adolescents with epilepsy compared to migraine. © 2014 Mac Keith Press.

  10. Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

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

    Zhang, Shaoguang; Bullock, R. Morris

    2015-07-06

    CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)Hmore » with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. We thank Monte Helm, Elliott Hulley and Deanna Miller for help on the crystallography, and Ming Fang for assistance on the electrochemical experiments.« less

  11. Adsorption of methyl orange from aqueous solution using chitosan/diatomite composite.

    PubMed

    Zhao, Peng; Zhang, Runhu; Wang, Jianglin

    2017-04-01

    A novel chitosan/diatomite composite was prepared by a simple mixture in the mass ratio to remove methyl orange (MO) from aqueous media in this study. The composite adsorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy analysis. The parameters to influence the adsorption of MO were studied under such conditions as kinetics, adsorption isotherm, pH effect, and thermodynamics. The results revealed that adsorption of MO was initially rapid and the equilibrium time was reached after 40 min. The optimal value of the pH was 5.0 for better adsorption. The equilibrium data were well fitted to the Langmuir isotherm compared to the Freundlich isotherm, and exhibited the highest capacity and a removal rate of 88.37% under an initial dye concentration of 50 mg/L. The kinetic data were well described by the pseudo-second order model. The thermodynamic calculations revealed that the sorption was viable, spontaneous, and exothermic under the conditions studied. In addition, the chitosan/diatomite composite had good adsorption and desorption performance with respect to reusability after six cycles. These results showed that the chitosan/diatomite could be considered as a potential adsorbent for the removal of MO in aqueous solution.

  12. [Sexual maturation of children and adolescents in Germany. Results of the German Health Interview and Examination Survey for Children and Adolescents (KiGGS)].

    PubMed

    Kahl, H; Schaffrath Rosario, A; Schlaud, M

    2007-01-01

    Following the standstill in maturity acceleration in the eighties of the twentieth century, now a further shift in maturity development towards younger ages is the issue of an international and also German discussion. The collection of sexual maturity data in boys and girls as part of the nationwide German Health Interview and Examination Survey for Children and Adolescents (KiGGS) is intended to pro vide population-representative information on sexual maturation and to evaluate associations between maturity status and selected health and social data. Girls were interviewed regarding their first menstrual period (menarche) and boys regarding voice change (status-quo method). Pubic hair was self-assessed by children and adolescents from 10 to 17 years of age, based on drawings of Tanner's defined developmental stages. The median age for menarche, for voice change and pubic hair stages were calculated using a logit model. At an age of 10 years, 42.4 % of girls and 35.7 % of boys report the development of pubic hair. At 17 years of age, the majority of girls and boys have reached the stages PH5 (girls 57.5 %, boys 47.8 %) and PH6 (girls 23.6 %, boys 46.5 %) according to Tanner. The average age for each pubic hair stage is lower in girls (PH2 10.8; PH3 11.7; PH4 12.3; PH5 13.4 years) than in boys (PH2 10.9; PH3 12.6; PH4 13.4; PH5 14.1). The median age at menarche is 12.8 years, the median for voice change (voice low) 15.1 years. Significant differences in age at menarche are found in girls depending on socioeconomic status (12.7/12.9/13.0 years for low/middle/high status) and between girls with and without migration background (12.5/12.9 years). No differences in age at menarche can be seen between East and West Germany or cities and rural areas. The association between maturity status and BMI is more pronounced in girls than in boys. Overall, the onset of maturity development in German children and adolescents is not significantly earlier than in other European studies.

  13. Magnetic Resonance Imaging-Guided Transurethral Ultrasound Ablation of Prostate Tissue in Patients with Localized Prostate Cancer: A Prospective Phase 1 Clinical Trial.

    PubMed

    Chin, Joseph L; Billia, Michele; Relle, James; Roethke, Matthias C; Popeneciu, Ionel V; Kuru, Timur H; Hatiboglu, Gencay; Mueller-Wolf, Maya B; Motsch, Johann; Romagnoli, Cesare; Kassam, Zahra; Harle, Christopher C; Hafron, Jason; Nandalur, Kiran R; Chronik, Blaine A; Burtnyk, Mathieu; Schlemmer, Heinz-Peter; Pahernik, Sascha

    2016-09-01

    Magnetic resonance imaging-guided transurethral ultrasound ablation (MRI-TULSA) is a novel minimally invasive technology for ablating prostate tissue, potentially offering good disease control of localized cancer and low morbidity. To determine the clinical safety and feasibility of MRI-TULSA for whole-gland prostate ablation in a primary treatment setting of localized prostate cancer (PCa). A single-arm prospective phase 1 study was performed at three tertiary referral centers in Canada, Germany, and the United States. Thirty patients (median age: 69 yr; interquartile range [IQR]: 67-71 yr) with biopsy-proven low-risk (80%) and intermediate-risk (20%) PCa were treated and followed for 12 mo. MRI-TULSA treatment was delivered with the therapeutic intent of conservative whole-gland ablation including 3-mm safety margins and 10% residual viable prostate expected around the capsule. Primary end points were safety (adverse events) and feasibility (technical accuracy and precision of conformal thermal ablation). Exploratory outcomes included quality of life, prostate-specific antigen (PSA), and biopsy at 12 mo. Median treatment time was 36min (IQR: 26-44) and prostate volume was 44ml (IQR: 38-48). Spatial control of thermal ablation was ±1.3mm on MRI thermometry. Common Terminology Criteria for Adverse Events included hematuria (43% grade [G] 1; 6.7% G2), urinary tract infections (33% G2), acute urinary retention (10% G1; 17% G2), and epididymitis (3.3% G3). There were no rectal injuries. Median pretreatment International Prostate Symptom Score 8 (IQR: 5-13) returned to 6 (IQR: 4-10) at 3 mo (mean change: -2; 95% confidence interval [CI], -4 to 1). Median pretreatment International Index of Erectile Function 13 (IQR: 6-28) recovered to 13 (IQR: 5-25) at 12 mo (mean change: -1; 95% CI, -5 to 3). Median PSA decreased 87% at 1 mo and was stable at 0.8 ng/ml (IQR: 0.6-1.1) to 12 mo. Positive biopsies showed 61% reduction in total cancer length, clinically significant disease in 9 of 29 patients (31%; 95% CI, 15-51), and any disease in 16 of 29 patients (55%; 95% CI, 36-74). MRI-TULSA was feasible, safe, and technically precise for whole-gland prostate ablation in patients with localized PCa. Phase 1 data are sufficiently compelling to study MRI-TULSA further in a larger prospective trial with reduced safety margins. We used magnetic resonance imaging-guided transurethral ultrasound to heat and ablate the prostate in men with prostate cancer. We showed that the treatment can be targeted within a narrow range (1mm) and has a well-tolerated side effect profile. A larger study is under way. NCT01686958, DRKS00005311. Copyright © 2016. Published by Elsevier B.V.

  14. Multiples of Median-Transformed, Normalized Reference Ranges of Steroid Profiling Data Independent of Age, Sex, and Units.

    PubMed

    Zalas, Dominika; Reinehr, Thomas; Niedziela, Marek; Borzikowsky, Christoph; Flader, Maciej; Simic-Schleicher, Gunter; Akkurt, Halit Ilker; Heger, Sabine; Hornig, Nadine; Holterhus, Paul-Martin; Kulle, Alexandra E

    2018-01-01

    The high complexity of pediatric reference ranges across age, sex, and units impairs clinical application and comparability of steroid hormone data, e.g., in congenital adrenal hyperplasia (CAH). We developed a multiples-of-median (MoM) normalization tool to overcome this major drawback in pediatric endocrinology. Liquid chromatography tandem mass spectrometry data comprising 10 steroid hormones representing 905 controls (555 males, 350 females, 0 to > 16 years) from 2 previous datasets were MoM transformed across age and sex. Twenty-three genetically proven CAH patients were included (21-hydroxylase deficiency [21OHD], n = 19; 11β-hydroxylase deficiency [11OHD], n = 4). MoM cutoffs for single steroids predicting 21OHD and 11OHD were computed and validated through new, independent patients (21OHD, n = 8; adrenal cortical carcinoma, n = 6; obesity, n = 40). 21OHD and 11OHD patients showed disease-typical, easily recognizable MoM patterns independent of age, sex, and concentration units. Two single-steroid cutoffs indicated 21OHD: 3.87 MoM for 17-hydroxyprogesterone (100% sensitivity and 98.83% specificity) and 12.28 MoM for 21-deoxycortisol (94.74% sensitivity and 100% specificity). A cutoff of 13.18 MoM for 11-deoxycortisol indicated 11OHD (100% sensitivity and 100% specificity). Age- and sex-independent MoMs are straightforward for a clinically relevant display of multi-steroid patterns. In addition, defined single-steroid MoMs can serve alone as predictors of 21OHD and 11OHD. Finally, MoM transformation offers substantial enhancement of routine and scientific steroid hormone data exchange due to improved comparability. © 2018 S. Karger AG, Basel.

  15. Formic acid enhanced effective degradation of methyl orange dye in aqueous solutions under UV-Vis irradiation.

    PubMed

    Wang, Jingjing; Bai, Renbi

    2016-09-15

    Developing efficient technologies to treat recalcitrant organic dye wastewater has long been of great research and practical interest. In this study, a small molecule, formic acid (FA), was applied as a process enhancer for the degradation of methyl orange (MO) dye as a model recalcitrant organic pollutant in aqueous solutions under the condition of UV-Vis light irradiation and air aeration at the ambient temperature of 25 °C. It was found that the decolouration of the dye solutions can be rapidly achieved, reducing the time, for example, from around 17.6 h without FA to mostly about less than 2 h with the presence of FA. The mineralization rate of MO dye reached as high as 81.8% in 1.5 h in the case of initial MO dye concentration at 25 mg L(-1), which is in contrast to nearly no mineralization of the MO dye for a similar system without the FA added. The study revealed that the generation of the H2O2 species in the system was enhanced and the produced OH radicals effectively contributed to the degradation of the MO dye. Process parameters such as the initial concentration of MO dye, FA dosage and solution pH were all found to have some effect on the degradation efficiency under the same condition of UV-Vis light irradiation and air aeration. The MO dye degradation performance was found to follow a first-order reaction rate to the MO dye concentration in most cases and there existed a positive correlation between the reaction rate constant and the initial FA concentration. Compared to the traditional H2O2/UV-Vis oxidation system, the use of FA as a process-enhancing agent can have the advantages of low cost, easy availability, and safe to use. The study hence demonstrates a promising approach to use a readily available small molecule of FA to enhance the degradation of recalcitrant organic pollutants, such as MO dye, especially for their pre-treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions.

    PubMed

    Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping

    2017-08-08

    It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.

  17. A study on the swelling behavior of poly(acrylic acid) hydrogels obtained by electron beam crosslinking

    NASA Astrophysics Data System (ADS)

    Sheikh, N.; Jalili, L.; Anvari, F.

    2010-06-01

    Poly(acrylic acid) (PAA) hydrogels were prepared by using electron beam (EB) crosslinking of PAA homopolymer from its aqueous solutions. The swelling behavior of the hydrogels was studied as a function of the concentration of PAA solution, radiation dose, pH of the swelling medium and swelling time. Also the environmental pH effect on the water diffusion mode into hydrogels was investigated. These hydrogels clearly showed pH-sensitive swelling behavior with Fickian type of diffusion in the stomach-like pH medium (pH 1.3) and non-Fickian type in the intestine-like pH medium (pH 6.8).

  18. Effects of rabeprazole, lansoprazole and omeprazole on intragastric pH in CYP2C19 extensive metabolizers.

    PubMed

    Saitoh, T; Fukushima, Y; Otsuka, H; Hirakawa, J; Mori, H; Asano, T; Ishikawa, T; Katsube, T; Ogawa, K; Ohkawa, S

    2002-10-01

    To investigate the inhibitory effects on gastric acid secretion of three proton pump inhibitors, omeprazole, lansoprazole and rabeprazole, using a three-way crossover design in healthy Helicobacter pylori-negative,S-mephenytoin 4'-hydroxylase (CYP2C19) homo- and hetero-extensive metabolizers. Eight healthy Japanese male volunteers were enrolled. After the administration of rabeprazole (10 mg/day), lansoprazole (30 mg/day) or omeprazole (20 mg/day), intragastric pH monitoring was commenced from 24 h before the first proton pump inhibitor dose, and continued for days 1-3 after proton pump inhibitor administration. The pH electrode was used for 48 h and changed just before pH monitoring on day 2. For the administration of 10 mg/day rabeprazole, the mean ratios of the 24-h pH > or = 3 holding time were 5.7 +/- 1.1%,13.6 +/- 2.2%, 35.3 +/- 2.7% and 62.8 +/- 3.1% for the pre-treatment day and days 1, 2 and 3, respectively. The same ratios for lansoprazole (30 mg/day) were 5.7 +/- 0.7%, 7.4 +/- 1.5%, 13.6 +/- 3.4% and 26.6 +/- 4.9%; the same ratios for 20 mg/day omeprazole were 5.9 +/- 0.9%, 6.1 +/- 1.2%, 11.4 +/- 2.8% and 16.4 +/- 4.6%. The mean ratio of the 24-h pH > or = 3 holding time of days 1-3 increased significantly compared to the pre-treatment day (P < 0.01) with the administration of rabeprazole and lansoprazole. The magnitude of inhibition of gastric acid secretion after rabeprazole administration was stronger than that after lansoprazole. A significant elevation of the mean ratio of the 24-h pH > or = 3 holding time was demonstrated on days 2 and 3 with omeprazole (P < 0.01). In H. pylori-negative CYP2C19 extensive metabolizers, rabeprazole (10 mg/day) shows a faster onset of rising intragastric pH and a stronger inhibition of gastric acid secretion than do lansoprazole (30 mg/day) or omeprazole (20 mg/day).

  19. Molecular Dynamics Simulation of the Titration of Polyoxocations in Aqueous Solution

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

    Rustad, James R.

    The aqueous complex ion Al30O8(OH)56(H2O)26 18+(Al30) has a variety of bridging and terminal amphoteric surface functional groups which deprotonate over a pH range of 4–7. Their relative degree of protonation is calculated here from a series of molecular dynamics simulations in what appear to be the first molecular dynamics simulations of an acidometric titration. In these simulations, a model M30O8(OH)56(H2O)26 18+ ion is embedded in aqueous solution and titrated with hydroxide ions in the presence of a charge-compensating background of perchlorate ions. Comparison with titration of a model M13O4(OH)24(H2O)12 7+ reveals that the M30 ion is more acidic than themore » M13 ion due to the presence of acidic nH2O functional groups. The higher acidities of the functional groups on the M30 ion appear to result from enhanced hydration. Metal–oxygen bond lengths are calculated for the ion in solution, an isolated ion in the gas phase, and in its crystalline hydrate sulfate salt. Gas-phase and crystalline bond lengths do not correlate well with those calculated in solution. The acidities do not relate in any simple way to the number of metals coordinating the surface functional group or the M-O bond length. Moreover, the calculated acidity in solution does not correlate with proton affinities calculated for the isolated ion in the absence of solvent. It is concluded that the search for simple indicators of structure–reactivity relationships at the level of individual reactive sites faces major limitations, unless specific information on the hydration states of the functional groups is available.« less

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

    Murgia, Fabrizio; Antitomaso, Philippe; Stievano, Lorenzo

    The ternary Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} was successfully synthetized using a simple and cost-effective solid-state microwave-assisted reaction. While solid-state routes require days of high-temperature treatment under inert atmosphere, highly pure and crystalline Cu{sub 2}Mo{sub 6}S{sub 8} could be obtained in only 400 s from this precursor, the Chevrel binary phase Mo{sub 6}S{sub 8} was then obtained by copper removal through acidic leaching, and was evaluated as a positive electrode material for Mg-battery. The electrochemical performance in half-cell configuration shows reversible capacity exceeding 80 mAh/g, which is comparable to previous works carried out with materials synthesized by conventional high-temperaturemore » solid-state routes. - Graphical abstract: Ultrafast micro-wave synthesis of Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} towards Mo{sub 6}S{sub 8} as positive electrode of Mg-battery. - Highlights: • Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} is synthesized by fast microwave-assisted solid-state reaction. • Highly-pure and well-crystalline Cu{sub 2}Mo{sub 6}S{sub 8} is obtained. • Mo{sub 6}S{sub 8} obtained from leaching is tested as a positive electrode for Mg batteries.« less

  1. Stunting at 24 Months Is Not Related to Incidence of Overweight through Young Adulthood in an Urban South African Birth Cohort.

    PubMed

    Hanson, Sara K; Munthali, Richard J; Lundeen, Elizabeth A; Richter, Linda M; Norris, Shane A; Stein, Aryeh D

    2018-05-15

    The role that childhood stunting plays in the development of overweight and obesity later in life is not well understood, particularly in adolescence and young adulthood, because most studies have only followed up through midchildhood. The objective of this study was to examine the relation between stunting and age-specific patterns of overweight and obesity incidence from early childhood to young adulthood in the context of a country in the process of the nutrition transition while these children were growing up. We analyzed data from 895 participants in the Birth-to-Twenty Plus Cohort (Bt20+), an urban South African birth cohort initiated in 1990. Anthropometric data were collected at multiple ages and participants were included if they provided height at age 24 mo and ≥1 measure of body mass index [BMI; weight (kg)/height (m)2] in each of the following time periods: 4-8 y, 11-12 y, 13-15 y, 16-18 y, and 22-24 y. We defined stunting at age 24 mo as height-for-age z score <2 and overweight as BMI z score (BMIZ) >1 in childhood (4-8 y) and adolescence (11-12 y, 13-15 y, and 16-18 y) and BMI ≥25 in young adulthood (22-24 y). We compared BMI, BMIZ, and the prevalence of overweight by stunting status, stratified by sex. Our sample was 93% black and 51% female. The prevalence of stunting at 24 mo was 26% in males and 19% in females. In young adulthood, the prevalence of overweight and obesity was 15.5% (males) and 47.5% (females). Among both males and females, neither mean BMI nor a combined measure of overweight and obesity in any subsequent period differed by stunting status at 24 mo (P ≥ 0.05). Stunting at 24 mo was not related to the risk of overweight or obesity in this cohort. Stunting may not be an important contributor to the increasing obesity rates in urban South Africa.

  2. Effect of pH on the rheological properties of borate crosslinked hydroxypropyl guar gum hydrogel and hydroxypropyl guar gum.

    PubMed

    Wang, Shibin; Tang, Hongbiao; Guo, Jianchun; Wang, Kunjie

    2016-08-20

    pH is an important factor affecting the performance of polymer fluid. The rheological properties of hydroxypropyl guar gum (HPG) base fluid and the structural strength, rheological properties, viscoelastic properties and thixotropy properties of HPG gel depend largely on the pH values. For the base fluid, an apparent viscosity-increasing effect was observed over the pH range from 7 to 11, and the apparent viscosity gradually decreased at pH 11.5-14, exhibiting electrostatic repulsion behavior and steric effects. For the HPG gel, at pH 7-12.5, the gel possessed higher apparent viscosity, higher elastic modulus (G'), lower tanδ (the ratio of the viscous modulus to the elastic modulus) and an "8"-shaped hysteresis loop, indicating stronger gel structure strength and the elastic dominant property. At pH 13-13.5, the gel samples exhibited the transition from a pseudoplastic fluid to a Newtonian fluid, and their viscosity, elastic modulus decreased but tanδ increased with the increase in pH values, exhibiting gradually weakened elastic properties. When the pH was 14, the gel mainly exhibited viscous characteristics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Daytime Changes of Skin Biophysical Characteristics: A Study of Hydration, Transepidermal Water Loss, pH, Sebum, Elasticity, Erythema, and Color Index on Middle Eastern Skin.

    PubMed

    Firooz, Alireza; Zartab, Hamed; Sadr, Bardia; Bagherpour, Leili Naraghi; Masoudi, Aidin; Fanian, Ferial; Dowlati, Yahya; Ehsani, Amir Hooshang; Samadi, Aniseh

    2016-01-01

    The exposure of skin to ultraviolet radiation and temperature differs significantly during the day. It is reasonable that biophysical parameters of human skin have periodic daily fluctuation. The objective of this study was to study the fluctuations of various biophysical characteristics of Middle Eastern skin in standardized experimental conditions. Seven biophysical parameters of skin including stratum corneum hydration, transepidermal water loss, pH, sebum, elasticity, skin color, and erythema index were measured at three time points (8 a.m., 12 p.m. and 4 p.m.) on the forearm of 12 healthy participants (mean age of 28.4 years) without any ongoing skin disease using the CK MPA 580 device in standard temperature and humidity conditions. A significant difference was observed between means of skin color index at 8 a.m. (175.42 ± 13.92) and 4 p.m. (164.44 ± 13.72, P = 0.025), between the pH at 8 a.m. (5.72 ± 0.48) and 4 p.m. (5.33 ± 0.55, P = 0.001) and pH at 12 p.m. (5.60 ± 0.48) and 4 p.m. (5.33 ± 0.55, P = 0.001). Other comparisons between the means of these parameters at different time points resulted in nonsignificant P values. There are daytime changes in skin color index and pH. Skin color index might be higher and cutaneous pH more basic in the early morning compared to later of the day.

  4. Predicting cattle age from eye lens weight and nitrogen content, dentition, and United States Department of Agriculture maturity score.

    PubMed

    Raines, C R; Dikeman, M E; Unruh, J A; Hunt, M C; Knock, R C

    2008-12-01

    This research explores the relationship between generally accepted and alternative cattle age-prediction methods and chronological age. Cattle (n = 386) of documented ages ranging from 370 to 1,115 d of age were used. Dentition (DEN), USDA maturity score (MS), lens weight (LW), and lens total N (LN) content were used as possible predictors of age. Correlations with age were determined: LW (r = 0.77); DEN (r = 0.74); LN (r = 0.71); and MS (r = 0.64). Stepwise backward regression was used to generate an age prediction equation: Age (mo) = -21.79 + 17.23(LW, g) + 0.038(DEN). By this equation, 38% of cattle

  5. A comparison of the fatigue behavior of cast Ti-7.5Mo with c.p. titanium, Ti-6Al-4V and Ti-13Nb-13Zr alloys.

    PubMed

    Lin, Chia-Wei; Ju, Chien-Ping; Chern Lin, Jiin-Huey

    2005-06-01

    The purpose of the present study is to compare the high-cycle fatigue behavior of newly developed Ti-7.5Mo alloy with that of c.p. Ti, Ti-13Nb-13Zr and Ti-6Al-4V alloys in their as-cast state. Experimental results indicate that Ti-6Al-4V and c.p. Ti have higher stress-controlled fatigue resistance but lower strain-controlled fatigue resistance than Ti-7.5Mo and Ti-13Nb-13Zr. Among four materials Ti-7.5Mo demonstrates the best strain-controlled fatigue performance. The fracture surfaces of the present materials are comprised of three morphologically distinct zones: crack initiation zone, crack propagation zone, and the final-stage overload zone. The fatigue cracks almost always initiate from casting-induced surface/subsurface pores. A river pattern is observed in the propagation zone. In the overload zone dimples are typically observed. Three factors most significantly affecting the fatigue performance of the present materials are the presence of the casting-induced surface/subsurface pores; the location of the pores; and the inherent mechanical properties of the materials.

  6. Scintigraphy in laryngopharyngeal and gastroesophageal reflux disease: a definitive diagnostic test?

    PubMed

    Falk, Gregory L; Beattie, John; Ing, Alvin; Falk, S E; Magee, Michael; Burton, Leticia; Van der Wall, Hans

    2015-03-28

    To investigate the utility of scintigraphic studies in predicting response to laparoscopic fundoplication (LF) for chronic laryngopharyngeal reflux symptoms. Patients with upper aero-digestive symptoms that remained undiagnosed after a period of 2 mo were studied with conventional pH and manometric studies. Patients mainly complained of cough, sore throat, dysphonia and globus. These patients were imaged after ingestion of 99m-technetium diethylene triamine pentaacetic acid. Studies were quantified with time activity curves over the pharynx, upper and lower oesophagus and background. Late studies of the lungs were obtained for aspiration. Patients underwent LF with post-operative review at 3 mo after surgery. Thirty four patients (20 F, 14 M) with an average age of 57 years and average duration of symptoms of 4.8 years were studied. Twenty four hour pH and manometry studies were abnormal in all patients. On scintigraphy, 27/34 patients demonstrated pharyngeal contamination and a rising or flat pharyngeal curve. Lung aspiration was evident in 50% of patients. There was evidence of pulmonary aspiration in 17 of 34 patients in the delayed study (50%). Pharyngeal contamination was found in 27 patients. All patients with aspiration showed pharyngeal contamination. In the 17 patients with aspiration, graphical time activity curve showed rising activity in the pharynx in 9 patients and a flat curve in 8 patients. In those 17 patients without pulmonary aspiration, 29% (5 patients) had either a rising or flat pharyngeal graph. A rising or flat curve predicted aspiration with a positive predictive value of 77% and a negative predictive value of 100%. Over 90% of patients reported a satisfactory symptomatic response to LF with an acceptable side-effect profile. Scintigraphic reflux studies offer a good screening tool for pharyngeal contamination and aspiration in patients with gastroesophageal reflux disease.

  7. Polymeric nanoparticle PET/MR imaging allows macrophage detection in atherosclerotic plaques

    PubMed Central

    Majmudar, Maulik D.; Yoo, Jeongsoo; Keliher, Edmund J.; Truelove, Jessica; Iwamoto, Yoshiko; Sena, Brena; Dutta, Partha; Borodovsky, Anna; Fitzgerald, Kevin; Di Carli, Marcelo; Libby, Peter; Anderson, Daniel G.; Swirski, Filip K.; Weissleder, Ralph; Nahrendorf, Matthias

    2013-01-01

    Rationale Myeloid cell content in atherosclerotic plaques associates with rupture and thrombosis. Thus, imaging of lesional monocyte and macrophages (Mo/Mϕ) could serve as a biomarker of disease progression and therapeutic intervention. Objective To noninvasively assess plaque inflammation with dextran nanoparticle-facilitated hybrid PET/MR imaging. Methods and Results Using clinically approved building blocks, we systematically developed 13nm polymeric nanoparticles consisting of crosslinked short chain dextrans which were modified with desferoxamine for zirconium-89 radiolabeling (89Zr-DNP) and a near infrared fluorochrome (VT680) for microscopic and cellular validation. Flow cytometry of cells isolated from excised aortas showed DNP uptake predominantly in Mo/Mϕ (76.7%) and lower signal originating from other leukocytes such as neutrophils and lymphocytes (11.8% and 0.7%, p<0.05 versus Mo/Mϕ). DNP colocalized with the myeloid cell marker CD11b on immunohistochemistry. PET/MRI revealed high uptake of 89Zr-DNP in the aortic root of ApoE−/− mice (standard uptake value, ApoE−/− mice versus wild type controls, 1.9±0.28 versus 1.3±0.03, p<0.05), corroborated by ex vivo scintillation counting and autoradiography. Therapeutic silencing of the monocyte-recruiting receptor CCR2 with siRNA decreased 89Zr-DNP plaque signal (p<0.05) and inflammatory gene expression (p<0.05). Conclusions Hybrid PET/MR imaging with a 13nm DNP enables noninvasive assessment of inflammation in experimental atherosclerotic plaques and reports on therapeutic efficacy of anti-inflammatory therapy. PMID:23300273

  8. Unprecedented {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} polymeric chains and four novel organic-inorganic hybrids based on Mo-POMs and azaheterocycles templates

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

    Du Haijuan; Zunzhe Shu; Niu Yunyin, E-mail: niuyy@zzu.edu.cn

    2012-06-15

    Abstrct: Four novel organic-inorganic hybrid materials based on Mo-POMs and organic templates, namely [DEB] [{beta}-Mo{sub 8}O{sub 26}] [NH{sub 4}]{sub 2} (1), [BMIM] [{beta}-Mo{sub 8}O{sub 26}]{sub 0.5}{center_dot}H{sub 2}O (2), [BMIM] [1D-Mo{sub 8}O{sub 26}]{sub 0.5} (3) and {l_brace}3D-[Cu(DIE){sub 2}] [1D-Mo{sub 8}O{sub 26}]{sub 0.5}{r_brace}{sub {infinity}} (4) [DEB= 1,1 Prime -diethyl-4,4 Prime -bipyridinium, BMIM=1,1 Prime -bis(1-methylimidazolium)methylene, DIE=1,2-diimidazoloethane] have been hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, thermal gravimetric analysis(TGA) and single-crystal X-ray diffraction. Both compounds 1 and 2 are POMs-based supramolecular compounds consisted of independent [{beta}-Mo{sub 8}O{sub 26}]{sup 4-} anions and [DEB]{sup 2+} or [BMIM]{sup 2+} organic cations. Compound 3 is themore » first external template example of Mo-POMs-based supramolecular network incorporated with novel {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} polymeric chains. Compound 4 is a rare supramolecular structure that contains octamolybdate {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} polymeric chains interconnected via DIE ligands to form a 3D net. Moreover, it was indicated that these polyacid compounds had definite catalytic activities on the probe reaction of acetaldehyde oxidation to acetic acid with H{sub 2}O{sub 2}. - Graphical abstract: Four novel organic templated polyoxometalates comprising of 0D, 1D and 3D supramolecular frameworks together with the catalytic activities on the acetaldehyde oxidation to acetic acid were reported. Highlights: Using cation templated self-assembly four novel polyoxometalates were prepared. Compounds 1 and 2 consisted of independent [{beta}-Mo{sub 8}O{sub 26}]{sup 4-} anions and organic cations. Compound 3 is the first external template-assisted POMs with {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} chain. Compound 4 is a rare 3D net containing {sup 1}/{sub {infinity}}[{beta}-Mo{sub 8}O{sub 26}]{sup 4-} 1D chain and DIE ligands. These compounds had definite catalytic activities on the acetaldehyde oxidation.« less

  9. 78 FR 73749 - Proposed Amendment of Class D Airspace; St. Joseph, MO

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-09

    ...-0917; Airspace Docket No. 13-ACE-16] Proposed Amendment of Class D Airspace; St. Joseph, MO AGENCY... action proposes to amend Class D airspace at St. Joseph, MO. Additional controlled airspace is necessary... Rosecrans Municipal Airport, St. Joseph, MO. Accordingly, additional segments would extend from the 4.3-mile...

  10. The late Variscan ferroan granite magmatism of southern Sardinia: inferences from Mo metallogenesis

    NASA Astrophysics Data System (ADS)

    Naitza, Stefano; Conte, Aida Maria; Cuccuru, Stefano; Fadda, Sandro; Fiori, Maddalena; Oggiano, Giacomo; Secchi, Francesco

    2017-04-01

    Metallogeny is a powerful tool to investigate crustal evolution; a good example is offered by the Variscan basement of Sardinia and its Mo deposits. Mo ores are poorly represented in Variscan metallogenic provinces of Europe: however, in Sardinia, numerous small Mo deposits, often associated to Sn, W and F ores, are present, invariably related to an early Permian intrusive peak bracketed at about 290 Ma (Fadda et al., 2015; Naitza et al., 2017). In Sardinia, two main magmatic peaks have been schematized at pre-300 and 290 Ma. In southern Sardinia, the 290 magmatic peak is made up of several intrusive F-bearing rock-suites (Conte et al., 2016), belonging to ilmenite series, showing a slight peraluminous character and mostly classifiable as ferroan granites (sensu Frost and Frost, 2011). Mo-bearing granites form a distinct suite of relatively small plutons, emplaced at very shallow depth (about 1kb) in an exhumed Variscan low-grade basement. Peculiar characters of Mo-bearing granites are the occurrence of greisenized microgranite and granophyre cupolas, with fayalite-bearing pegmatites, and ilmenite, xenotime-(Y), monazite, fluorite, and local topaz as accessory phases. Recently, Conte et al. (2016) interpreted these granites as originated by partial melting of low crustal felsic metaigneous photoliths enriched in granophiles (Mo, Sn, W). Mo ores occur as: a) endo- and exo- quartz-muscovite greisens with molybdenite±Fe-Cu sulphides, and b) quartz-molybdenite±wolframite±Fe-Cu-Zn sulphides±fluorite±topaz hydrothermal veins and stockworks, hosted in granites or in country rocks. Redox state of magmas exerts a strong control on Mo metallogeny, as in Mo districts worldwide ores are usually hosted by high-fO2 magnetite series intrusions (Ishihara, 1981). The close field association of Sardinian Mo mineralization with ferroan, low-fO2 ilmenite-series granites may be explained in terms of Mo-enriched crustal sources of magmas, and very efficient geochemical concentration processes. Mo concentration occurred during latest intrusive phases in granitic cupolas, as local subsolidus reactions. They involve: 1) leaching of Mo5+ and Mo6+ from their primary hosts (e.g., biotites) by Cl- and F-rich fluids under decreasing pH and increasing fH2O and fO2, and 2) transport of Mo cations towards intrusive contacts, where they quickly reacted with Sulphur from country rocks to be reduced as MoS2. Overall, the late Variscan Mo metallogenic peak in Sardinia is a single event located in a short timespan at around 290 Ma. In the early Permian extensional setting of Corsica-Sardinia batholith, a distinct HT/LP event related to melting of mantle lithosphere (Rossi et al., 2015), triggered partial melting of Mo-bearing deep crustal sources, producing the F-bearing ferroan magmas. The singular concentration of Mo-bearing granites could indicate a peculiar compositional character of the Sardinian lower crust. References: Conte A.M. et al. (2016). Proc. 2nd European Mineralogical Conference, Rimini, Italy, 154. Fadda et al. (2015). Proc. 13th Biennial SGA Meeting, Nancy, France, Vol. 2, 721-724. Frost, C. D. and Frost R. B. (2011). J. Petrol. 52, 39-53. Ishihara S. (1981). Econ. Geol., 75th Anniversary Volume, 458-484. Naitza S. et al. (2017). Ore Geol. Rev. 80, 1259-1278. Rossi et al. (2015). Bull. Soc. Géol. France 186, 171-192.

  11. Hydrogen Doping into MoO3 Supports toward Modulated Metal-Support Interactions and Efficient Furfural Hydrogenation on Iridium Nanocatalysts.

    PubMed

    Xie, Lifang; Chen, Ting; Chan, Hang Cheong; Shu, Yijin; Gao, Qingsheng

    2018-03-16

    As promising supports, reducible metal oxides afford strong metal-support interactions to achieve efficient catalysis, which relies on their band states and surface stoichiometry. In this study, in situ and controlled hydrogen doping (H doping) by means of H 2 spillover was employed to engineer the metal-support interactions in hydrogenated MoO x -supported Ir (Ir/H-MoO x ) catalysts and thus promote furfural hydrogenation to furfuryl alcohol. By easily varying the reduction temperature, the resulting H doping in a controlled manner tailors low-valence Mo species (Mo 5+ and Mo 4+ ) on H-MoO x supports, thereby promoting charge redistribution on Ir and H-MoO x interfaces. This further leads to clear differences in H 2 chemisorption on Ir, which illustrates its potential for catalytic hydrogenation. As expected, the optimal Ir/H-MoO x with controlled H doping afforded high activity (turnover frequency: 4.62 min -1 ) and selectivity (>99 %) in furfural hydrogenation under mild conditions (T=30 °C, PH2 =2 MPa), which means it performs among the best of current catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

    DOEpatents

    Hilsenbeck, S.J.; McCarley, R.E.; Schrader, G.L.; Xie, X.B.

    1999-02-16

    New amorphous molybdenum/tungsten sulfides with the general formula M{sup n+}{sub 2x/n}(L{sub 6}S{sub 8})S{sub x}, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M{sub 6}S{sub 8}){sup 0} cluster units are present. Vacuum thermolysis of the amorphous Na{sub 2x}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH first produces poorly crystalline NaMo{sub 6}S{sub 8} by disproportionation at 800 C and well-crystallized NaMo{sub 6}S{sub 8} at {>=} 900 C. Ion-exchange of the sodium material in methanol with soluble M{sup 2+} and M{sup 3+} salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M{sup n+}{sub 2x/n}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M{sup n+}{sub 2x/n}Mo{sub 6}S{sub 8+x}(MeOH){sub y}[MMOS] (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as ``Chevrel phase-like`` in that both contain Mo{sub 6}S{sub 8} cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst is shown to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS{sub 2} catalysts. 9 figs.

  13. Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

    DOEpatents

    Hilsenbeck, Shane J.; McCarley, Robert E.; Schrader, Glenn L.; Xie, Xiaobing

    1999-02-16

    New amorphous molybdenum/tungsten sulfides with the general formula M.sup.n+.sub.2x/n (L.sub.6 S.sub.8)S.sub.x, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M.sub.6 S.sub.8).sup.0 cluster units are present. Vacuum thermolysis of the amorphous Na.sub.2x (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH first produces poorly crystalline NaMo.sub.6 S.sub.8 by disproportionation at 800.degree. C. and well-crystallized NaMo.sub.6 S.sub.8 at .gtoreq. 900.degree. C. Ion-exchange of the sodium material in methanol with soluble M.sup.2+ and M.sup.3+ salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M.sup.n+.sub.2x/n (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M.sup.n+.sub.2x/n Mo.sub.6 S.sub.8+x (MeOH).sub.y ›MMOS! (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as "Chevrel phase-like" in that both contain Mo.sub.6 S.sub.8 cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst showed to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS.sub.2 catalysts.

  14. Chevrel-phase solid solution Mo 6Se 8- xTe x. Study of its superconducting, magnetic and NMR properties

    NASA Astrophysics Data System (ADS)

    Hamard1a, C.; Auffret, V.; Peña, O.; Le Floch, M.; Nowak, B.; Wojakowski, A.

    2000-09-01

    The Chevrel-phase solid solution Mo 6Se 8-Mo 6Te 8 was studied by X-ray diffraction, AC and DC magnetic susceptibility and 77Se and 125Te NMR spectroscopy. From the smooth evolution of the lattice parameters and superconducting critical temperatures, a progressive substitution of selenium atoms by tellurium is shown, on the whole range of composition 0⩽ x⩽8, in the formulation Mo 6Se 8- xTe x: the unit-cell volume increases linearly because of the larger ionic size of tellurium, while Tc decreases rapidly (from 6.45 down to 0 K) because of the different formal oxidation states of the anions and a probable evolution of the Fermi level in the density of states. Results of magnetic susceptibility support this model and suggest the inhibition of the intrinsic metallic behavior with increasing x. The NMR spectra of the binaries Mo 6Se 8 and Mo 6Te 8 reveal two significant features, attributed to two different chalcogen positions in the R 3¯ symmetry. At low Se contents in Mo 6Se 8- xTe x ( x=7.5, 7 and 6), selenium first fills the two X(2) sites along the three-fold axis (2c positions), and then it becomes statistically distributed over the general 6f positions, leading to broad 77Se NMR lines. On the other hand, substitution of Te atoms in Mo 6Se 8 seems to occur in a random way, creating large perturbations on the 125Te NMR spectra, over the whole range of x. Theoretical analysis based on the presence of two anisotropic lines (of axial and non-axial symmetries, respectively) allowed us to estimate their anisotropy factors and to perfectly simulate the frequency response of both Mo 6Se 8 and Mo 6Te 8 binaries. Analysis of the Knight shift anisotropy leads us to conclude about the importance of the molybdenum z 2 molecular orbital contribution which controls the Mo-X dipolar interactions.

  15. Nearly amorphous Mo-N gratings for ultimate resolution in extreme ultraviolet interference lithography

    NASA Astrophysics Data System (ADS)

    Wang, L.; Kirk, E.; Wäckerlin, C.; Schneider, C. W.; Hojeij, M.; Gobrecht, J.; Ekinci, Y.

    2014-06-01

    We present fabrication and characterization of high-resolution and nearly amorphous Mo1 - xNx transmission gratings and their use as masks for extreme ultraviolet (EUV) interference lithography. During sputter deposition of Mo, nitrogen is incorporated into the film by addition of N2 to the Ar sputter gas, leading to suppression of Mo grain growth and resulting in smooth and homogeneous thin films with a negligible grain size. The obtained Mo0.8N0.2 thin films, as determined by x-ray photoelectron spectroscopy, are characterized to be nearly amorphous using x-ray diffraction. We demonstrate a greatly reduced Mo0.8N0.2 grating line edge roughness compared with pure Mo grating structures after e-beam lithography and plasma dry etching. The amorphous Mo0.8N0.2 thin films retain, to a large extent, the benefits of Mo as a phase grating material for EUV wavelengths, providing great advantages for fabrication of highly efficient diffraction gratings with extremely low roughness. Using these grating masks, well-resolved dense lines down to 8 nm half-pitch are fabricated with EUV interference lithography.

  16. Rates of proton transfer to Fe-S-based clusters: comparison of clusters containing {MFe(mu(2)-S)(2)}n+ and {MFe(3)(mu(3)-S)(4)}n+ (M = Fe, Mo, or W) cores.

    PubMed

    Bates, Katie; Garrett, Brendan; Henderson, Richard A

    2007-12-24

    The rates of proton transfer from [pyrH]+ (pyr = pyrrolidine) to the binuclear complexes [Fe2S2Cl4]2- and [S2MS2FeCl2]2- (M = Mo or W) are reported. The reactions were studied using stopped-flow spectrophotometry, and the rate constants for proton transfer were determined from analysis of the kinetics of the substitution reactions of these clusters with the nucleophiles Br- or PhS- in the presence of [pyrH]+. In general, Br- is a poor nucleophile for these clusters, and proton transfer occurs before Br- binds, allowing direct measure of the rate of proton transfer from [pyrH]+ to the cluster. In contrast, PhS- is a better nucleophile, and a pathway in which PhS- binds preferentially to the cluster prior to proton transfer from [pyrH]+ usually operates. For the reaction of [Fe2S2Cl4]2- with PhS- in the presence of [pyrH]+ both pathways are observed. Comparison of the results presented in this paper with analogous studies reported earlier on cuboidal Fe-S-based clusters allows discussion of the factors which affect the rates of proton transfer in synthetic clusters including the nuclearity of the cluster core, the metal composition, and the nature of the terminal ligands. The possible relevance of these findings to the protonation sites of natural Fe-S-based clusters, including FeMo-cofactor from nitrogenase, are presented.

  17. Comparative study on cubic and tetragonal CexZr1-xO2 supported MoO3-catalysts for sulfur-resistant methanation

    NASA Astrophysics Data System (ADS)

    Liu, Zhaopeng; Xu, Yan; Cheng, Jiaming; Wang, Weihan; Wang, Baowei; Li, Zhenhua; Ma, Xinbin

    2018-03-01

    In this paper, two kinds of CexZr1-xO2 solid solution carriers with different Ce/Zr ratio were prepared by one-step co-precipitation method: the cubic Ce0.8Zr0.2O2 and the tetragonal Ce0.2Zr0.8O2 support. The MoO3/Ce0.8Zr0.2O2 and MoO3/Ce0.2Zr0.8O2 catalysts were prepared by incipient wetness impregnation method for comparative study on sulfur-resistant methanation reaction. The N2 adsorption/desorption, X-ray diffraction (XRD), Raman spectroscopy (RS), X-ray photoelectron (XPS), transmission electron microscopy (TEM), temperature-programmed reduction by hydrogen (H2-TPR) were undertaken to characterize the physico-chemical properties of the samples. The results indicated that the prepared MoO3/CexZr1-xO2 catalysts have a mesoporous structure with high surface area and uniform pore size distribution, achieving good MoO3 dispersion on CexZr1-xO2 supports. As for the catalytic performance of sulfur-resistant methanation, the cubic MoO3/Ce0.8Zr0.2O2 exhibited better than the tetragonal MoO3/Ce0.2Zr0.8O2 catalyst at reaction temperature 400 °C and 450 °C. CO conversion on the cubic MoO3/Ce0.8Zr0.2O2 catalyst was 50.1% at 400 °C and 75.5% at 450 °C, which is respectively 7% and 20% higher than that on the tetragonal MoO3/Ce0.2Zr0.8O2 catalyst. These were mainly attributed to higher content of active MoS2 on the surface of catalyst, the enhanced oxygen mobility, increased Mo-species dispersion as well as the excellent reducibility resulted from the increased amount of the reducible Ce3+ on the cubic MoO3/Ce0.8Zr0.2O2 catalyst.

  18. Brooker's merocyanine: Comparison of single crystal structures

    NASA Astrophysics Data System (ADS)

    Hayes, Kathleen L.; Lasher, Emily M.; Choczynski, Jack M.; Crisci, Ralph R.; Wong, Calvin Y.; Dragonette, Joseph; Deschner, Joshua; Cardenas, Allan Jay P.

    2018-06-01

    Brooker's merocyanine and its derivatives are well-studied molecules due to their very interesting optical properties. Merocyanine dyes exhibit different colors in solution depending on the solvent's polarity, pH, aggregation and intermolecular interactions. The synthesis of 1-methyl-4-[(oxocyclohexadienylidene)ethylidene]-1,4-dihydropyridine (MOED) dye yielded a particularly interesting solid state structure where in one crystal lattice, MOED and its protonated form are bound by hydrogen bonding interactions.

  19. Infant growth and health outcomes associated with 3 compared with 6 mo of exclusive breastfeeding.

    PubMed

    Kramer, Michael S; Guo, Tong; Platt, Robert W; Sevkovskaya, Zinaida; Dzikovich, Irina; Collet, Jean-Paul; Shapiro, Stanley; Chalmers, Beverley; Hodnett, Ellen; Vanilovich, Irina; Mezen, Irina; Ducruet, Thierry; Shishko, George; Bogdanovich, Natalia

    2003-08-01

    Opinions and recommendations about the optimal duration of exclusive breastfeeding have been strongly divided, but few published studies have provided direct evidence on the relative risks and benefits of different breastfeeding durations in recipient infants. We examined the effects on infant growth and health of 3 compared with 6 mo of exclusive breastfeeding. We conducted an observational cohort study nested within a large randomized trial in Belarus by comparing 2862 infants exclusively breastfed for 3 mo (with continued mixed breastfeeding through >/= 6 mo) with 621 infants who were exclusively breastfed for >/= 6 mo. Regression to the mean, within-cluster correlation, and cluster- and individual-level confounding variables were accounted for by using multilevel regression analyses. From 3 to 6 mo, weight gain was slightly greater in the 3-mo group [difference: 29 g/mo (95% CI: 13, 45 g/mo)], as was length gain [difference: 1.1 mm (0.5, 1.6 mm)], but the 6-mo group had a faster length gain from 9 to 12 mo [difference: 0.9 mm/mo (0.3, 1.5 mm/mo)] and a larger head circumference at 12 mo [difference: 0.19 cm (0.07, 0.31 cm)]. A significant reduction in the incidence density of gastrointestinal infection was observed during the period from 3 to 6 mo in the 6-mo group [adjusted incidence density ratio: 0.35 (0.13, 0.96)], but no significant differences in risk of respiratory infectious outcomes or atopic eczema were apparent. Exclusive breastfeeding for 6 mo is associated with a lower risk of gastrointestinal infection and no demonstrable adverse health effects in the first year of life.

  20. Topical Hazard Evaluation Program of Candidate Insect Repellent AI3- 39053a

    DTIC Science & Technology

    1987-05-01

    StudyNo. 75-51-O 71-R7 Mnay 19R71 12 PERSONAL AUTHOR(S) William T. Huebsam, SGT, U.S.A.; Maurice H. Weeks 1I8. TYPE Of REPORT 13b TIME COVERED 114...ARMY u.S. AUT ENVIVIf[NNIAL HYGINE AMIdT ASCROELN PROVING GROUND. MARYLAND M1蚉 HSHB-MO-T TOPICAL HAZARD EVALUATION PROGRAM OF CANDIDATE INSECT

  1. Nano-composite stainless steel

    DOEpatents

    Dehoff, Ryan R.; Blue, Craig A.; Peter, William H.; Chen, Wei; Aprigliano, Louis F.

    2015-07-14

    A composite stainless steel composition is composed essentially of, in terms of wt. % ranges: 25 to 28 Cr; 11 to 13 Ni; 7 to 8 W; 3.5 to 4 Mo; 3 to 3.5 B; 2 to 2.5 Mn; 1 to 1.5 Si; 0.3 to 1.7 C; up to 2 O; balance Fe. The composition has an austenitic matrix phase and a particulate, crystalline dispersed phase.

  2. The crystal structure of the monohydrate R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O (R=Pr, Nd, Sm, and Eu): a layer structure containing disordered [Mo{sub 2}O{sub 7}]{sup 2-} groups

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

    Naruke, Haruo; Yamase, Toshihiro

    2005-03-15

    Although R{sub 2}O{sub 3}:MoO{sub 3}=1:6 (R=rare earth) compounds are known in the R{sub 2}O{sub 3}-MoO{sub 3} phase diagrams since a long time, no structural characterization has been achieved because a conventional solid-state reaction yields powder samples. We obtained single crystals of R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O (R=Pr, Nd, Sm, and Eu) by thermal decomposition of [R{sub 2}(H{sub 2}O){sub 12}Mo{sub 8}O{sub 27}].nH{sub 2}O at around 685-715{sup o}C for 2h, and determined their crystal structures. The simulated XRD patterns of R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O were consistent with those of previously reported R{sub 2}O{sub 3}:MoO{sub 3}=1:6 compounds. All R{sub 2}Mo{sub 6}O{sub 21}.H{submore » 2}O compounds crystallize isostructurally in tetragonal, P4/ncc (No. 130), a=8.9962(5), 8.9689(6), 8.9207(4), and 8.875(2)A; c=26.521(2), 26.519(2), 26.304(2), and 26.15(1)A; Z=4; R{sub 1}=0.026, 0.024, 0.024, and 0.021, for R=Pr, Nd, Sm, and Eu, respectively. The crystal structure of R{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O consists of two [Mo{sub 2}O{sub 7}]{sup 2-}-containing layers (A and B layers) and two interstitial R(1){sup 3+} and R(2){sup 3+} cations. Each [Mo{sub 2}O{sub 7}]{sup 2-} group is composed of two corner-sharing [MoO{sub 4}] tetrahedra. The [Mo{sub 2}O{sub 7}]{sup 2-} in the B layer exhibits a disorder to form a pseudo-[Mo{sub 4}O{sub 9}] group, in which four Mo and four O sites are half occupied. R(1){sup 3+} achieves 8-fold coordination by O{sup 2-} to form a [R(1)O{sub 8}] square antiprism, while R(2){sup 3+} achieves 9-fold coordination by O{sup 2-} and H{sub 2}O to form a [R(2)(H{sub 2}O)O{sub 8}] monocapped square antiprism. The disorder of the [Mo{sub 2}O{sub 7}]{sup 2-} group in the B layer induces a large displacement of the O atoms in another [Mo{sub 2}O{sub 7}]{sup 2-} group (in the A layer) and in the [R(1)O{sub 8}] and [R(2)(H{sub 2}O)O{sub 8}] polyhedra. A remarkable broadening of the photoluminescence spectrum of Eu{sub 2}Mo{sub 6}O{sub 21}.H{sub 2}O supported the large displacement of O ligands coordinating Eu(1) and Eu(2)« less

  3. Grissom AFB, Indiana. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

    DTIC Science & Technology

    1983-07-01

    8.8i 15.51 1b.3 27.1 7%39 USAFETAC 0 TOS N. OL. ), O~ Poyaw 0mo IMS rOR Omm V~ Jm- - - - - -- - - -- - - - - - - U A 2AL CLIMATOLOY B’ANCH 2 Z .Ac...2Z812.o3410.911 S. 945 ,.137 6.561 6.607 8.977 9.95612.15813.1I5 19.923 6~ 3 .46 927. 920 --U 9 R. Z 9Z5. 3 U. 9CC 93 Q 900 927. 1 C9 4. 13. 11.7 3j

  4. Isolation and structural analysis of antihypertensive peptides that exist naturally in Gouda cheese.

    PubMed

    Saito, T; Nakamura, T; Kitazawa, H; Kawai, Y; Itoh, T

    2000-07-01

    Seven kinds of ripened cheeses (8-mo-aged and 24-mo-aged Gouda, Emmental, Blue, Camembert, Edam, and Havarti) were homogenized with distilled water, and water-soluble peptides were prepared by C-18 hydrophobic chromatography. The inhibitory activity to angiotensin I-converting enzyme and decrease in the systolic blood pressure in spontaneously hypertensive rats were measured before and after oral administration of each peptide sample. The strongest depressive effect in the systolic blood pressure (-24.7 mm Hg) and intensive inhibitory activity to angiotensin I-converting enzyme (75.7%) were detected in the peptides from 8-mo-aged Gouda cheese. Four peptides were isolated by HPLC with reverse-phase and gel filtration modes. Their chemical structures and origins, clarified by combination analyses of protein sequencing, amino acid composition, and mass spectrometry, were as follows: peptide A, Arg-Pro-Lys-His-Pro-Ile-Lys-His-Gln [alpha(s1)-casein (CN), B-8P; f 1-9]; peptide B, Arg-Pro-Lys-His-Pro-Ile-Lys-His-Gln-Gly-Leu-Pro-Gln (alpha(s1)-CN, B-8P; f 1-13); peptide F, Tyr-Pro-Phe-Pro-Gly-Pro-Ile-Pro-Asn (beta-CN, A2-5P; f 60-68); and peptide G, Met-Pro-Phe-Pro-Lys-Tyr-Pro-Val-Gln-Pro-Phe (beta-CN, A2-5P; f 109-119). Peptides A and F, which were chemically synthesized, showed potent angiotensin I-converting enzyme inhibitory activity with little antihypertensive effects.

  5. New electrochemiluminescent biosensors combining polyluminol and an enzymatic matrix.

    PubMed

    Sassolas, Audrey; Blum, Loïc J; Leca-Bouvier, Béatrice D

    2009-06-01

    Performant reagentless electrochemiluminescent (ECL) (bio)sensors have been developed using polymeric luminol as the luminophore. The polyluminol film is obtained by cyclic voltammetry (CV) on a screen-printed electrode either in a commonly used H(2)SO(4) medium or under more original near-neutral buffered conditions. ECL responses obtained after performing polymerization either at acidic pH or at pH 6 have been compared. It appears that polyluminol formed in near-neutral medium gives the best responses for hydrogen peroxide detection. Polymerization at pH 6 by cyclic voltammetry gives a linear range extending from 8 x 10(-8) to 1.3 x 10(-4) M H(2)O(2) concentrations. Based on this performant sensor for hydrogen peroxide detection, an enzymatic biosensor has been developed by associating the polyluminol film with an H(2)O(2)-producing oxidase. Here, choline oxidase (ChOD) has been chosen as a model enzyme. To develop the biosensor, luminol has been polymerized at pH 6 by CV, and then an enzyme-entrapping matrix has been formed on the above modified working electrode. Different biological (chitosan, agarose, and alginate) and chemical (silica gels, photopolymers, or reticulated matrices) gels have been tested. Best performances have been obtained by associating a ChOD-immobilizing photopolymer with the polyluminol film. In this case, choline can be detected with a linear range extending from 8 x 10(-8) to 1.3 x 10(-4) M.

  6. Activation Energy of the Low-pH-Induced Lamellar to Bicontinuous Cubic Phase Transition in Dioleoylphosphatidylserine/Monoolein.

    PubMed

    Oka, Toshihiko; Saiki, Takahiro; Alam, Jahangir Md; Yamazaki, Masahito

    2016-02-09

    Electrostatic interaction is an important factor for phase transitions between lamellar liquid-crystalline (Lα) and inverse bicontinuous cubic (QII) phases. We investigated the effect of temperature on the low-pH-induced Lα to double-diamond cubic (QII(D)) phase transition in dioleoylphosphatidylserine (DOPS)/monoolein (MO) using time-resolved small-angle X-ray scattering with a stopped-flow apparatus. Under all conditions of temperature and pH, the Lα phase was directly transformed into an intermediate inverse hexagonal (HII) phase, and subsequently the HII phase slowly converted to the QII(D) phase. We obtained the rate constants of the initial step (i.e., the Lα to HII phase transition) and of the second step (i.e., the HII to QII(D) phase transition) using the non-negative matrix factorization method. The rate constant of the initial step increased with temperature. By analyzing this result, we obtained the values of its apparent activation energy, Ea (Lα → HII), which did not change with temperature but increased with an increase in pH. In contrast, the rate constant of the second step decreased with temperature at pH 2.6, although it increased with temperature at pH 2.7 and 2.8. These results indicate that the value of Ea (HII → QII(D)) at pH 2.6 increased with temperature, but the values of Ea (HII → QII(D)) at pH 2.7 and 2.8 were constant with temperature. The values of Ea (HII → QII(D)) were smaller than those of Ea (Lα → HII) at the same pH. We analyzed these results using a modified quantitative theory on the activation energy of phase transitions of lipid membranes proposed initially by Squires et al. (Squires, A. M.; Conn, C. E.; Seddon, J. M.; Templer, R. H. Soft Matter 2009, 5, 4773). On the basis of these results, we discuss the mechanism of this phase transition.

  7. Rapid Photodegradation of Methyl Orange (MO) Assisted with Cu(II) and Tartaric Acid

    PubMed Central

    Guo, Jing; Chen, Xue; Shi, Ying; Lan, Yeqing; Qin, Chao

    2015-01-01

    Cu(II) and organic carboxylic acids, existing extensively in soil and aquatic environments, can form complexes that may play an important role in the photodegradation of organic contaminants. In this paper, the catalytic role of Cu(II) in the removal of methyl orange (MO) in the presence of tartaric acid with light was investigated through batch experiments. The results demonstrate that the introduction of Cu(II) could markedly enhance the photodegradation of MO. In addition, high initial concentrations of Cu(II) and tartaric acid benefited the decomposition of MO. The most rapid removal of MO assisted by Cu(II) was achieved at pH 3. The formation of Cu(II)-tartaric acid complexes was assumed to be the key factor, generating hydroxyl radicals (•OH) and other oxidizing free radicals under irradiation through a ligand-to-metal charge-transfer pathway that was responsible for the efficient degradation of MO. Some intermediates in the reaction system were also detected to support this reaction mechanism. PMID:26241043

  8. Dual element (CCl) isotope approach to distinguish abiotic reactions of chlorinated methanes by Fe(0) and by Fe(II) on iron minerals at neutral and alkaline pH.

    PubMed

    Rodríguez-Fernández, Diana; Heckel, Benjamin; Torrentó, Clara; Meyer, Armin; Elsner, Martin; Hunkeler, Daniel; Soler, Albert; Rosell, Mònica; Domènech, Cristina

    2018-05-07

    A dual element CCl isotopic study was performed for assessing chlorinated methanes (CMs) abiotic transformation reactions mediated by iron minerals and Fe(0) to further distinguish them in natural attenuation monitoring or when applying remediation strategies in polluted sites. Isotope fractionation was investigated during carbon tetrachloride (CT) and chloroform (CF) degradation in anoxic batch experiments with Fe(0), with FeCl 2 (aq), and with Fe-bearing minerals (magnetite, Mag and pyrite, Py) amended with FeCl 2 (aq), at two different pH values (7 and 12) representative of field and remediation conditions. At pH 7, only CT batches with Fe(0) and Py underwent degradation and CF accumulation evidenced hydrogenolysis. With Py, thiolytic reduction was revealed by CS 2 yield and is a likely reason for different Λ value (Δδ 13 C/Δδ 37 Cl) comparing with Fe(0) experiments at pH 7 (2.9 ± 0.5 and 6.1 ± 0.5, respectively). At pH 12, all CT experiments showed degradation to CF, again with significant differences in Λ values between Fe(0) (5.8 ± 0.4) and Fe-bearing minerals (Mag, 2 ± 1, and Py, 3.7 ± 0.9), probably evidencing other parallel pathways (hydrolytic and thiolytic reduction). Variation of pH did not significantly affect the Λ values of CT degradation by Fe(0) nor Py. CF degradation by Fe(0) at pH 12 showed a Λ (8 ± 1) similar to that reported at pH 7 (8 ± 2), suggesting CF hydrogenolysis as the main reaction and that CF alkaline hydrolysis (13.0 ± 0.8) was negligible. Our data establish a base for discerning the predominant or combined pathways of CMs natural attenuation or for assessing the effectiveness of remediation strategies using recycled minerals or Fe(0). Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. Serotonin and Dopamine Transporter Binding in Children with Autism Determined by SPECT

    ERIC Educational Resources Information Center

    Makkonen, Ismo; Riikonen, Raili; Kokki, Hannu; Airaksinen, Mauno M.; Kuikka, Jyrki T.

    2008-01-01

    Disturbances in the serotonergic system have been recognized in autism. To investigate the association between serotonin and dopamine transporters and autism, we studied 15 children (14 males, one female; mean age 8y 8mo [SD 3y 10mo]) with autism and 10 non-autistic comparison children (five males, five females; mean age 9y 10mo [SD 2y 8mo]) using…

  10. Defect structure in electrodeposited nanocrystalline Ni layers with different Mo concentrations

    NASA Astrophysics Data System (ADS)

    Kapoor, Garima; Péter, László; Fekete, Éva; Gubicza, Jenő

    2018-05-01

    The effect of molybdenum (Mo) alloying on the lattice defect structure in electrodeposited nanocrystalline nickel (Ni) films was studied. The electrodeposited layers were prepared on copper substrate at room temperature, with a constant current density and pH value. The chemical composition of these layers was determined by EDS. In addition, X-ray diffraction line profile analysis was carried out to study the microstructural parameters such as the crystallite size, the dislocation density and the stacking fault probability. It was found that the higher Mo content yielded more than one order of magnitude larger dislocation density while the crystallite size was only slightly smaller. In addition, the twin boundary formation activity during deposition increased with increasing Mo concentration. The results obtained on electrodeposited layers were compared with previous research carried out on bulk nanocrystalline Ni-Mo materials with similar compositions but processed by severe plastic deformation.

  11. Biomarkers of airway acidity and oxidative stress in exhaled breath condensate from grain workers.

    PubMed

    Do, Ron; Bartlett, Karen H; Dimich-Ward, Helen; Chu, Winnie; Kennedy, Susan M

    2008-11-15

    Grain workers report adverse respiratory symptoms due to exposures to grain dust and endotoxin. Studies have shown that biomarkers in exhaled breath condensate (EBC) vary with the severity of airway inflammation. The purpose of the study was to evaluate biomarkers of airway acidity (pH and ammonium [NH(4)(+)]) and oxidative stress (8-isoprostane) in the EBC of grain workers. A total of 75 workers from 5 terminal elevators participated. In addition to EBC sampling, exposure monitoring for inhalable grain dust and endotoxin was performed; spirometry, allergy testing, and a respiratory questionnaire derived from that of the American Thoracic Society were administered. Dust and endotoxin levels ranged from 0.010 to 13 mg/m(3) (median, 1.0) and 8.1 to 11,000 endotoxin units/m(3) (median, 610) respectively. EBC pH values varied from 4.3 to 8.2 (median, 7.9); NH(4)(+) values from 22 to 2,400 microM (median, 420); and 8-isoprostane values from 1.3 to 45 pg/ml (median, 11). Univariate and multivariable analyses revealed a consistent effect of cumulative smoking and obesity with decreased pH and NH(4)(+), and intensity of grain dust and endotoxin with increased 8-isoprostane. Duration of work on the test day was associated with decreased pH and NH(4)(+), whereas duration of employment in the industry was associated with decreased 8-isoprostane. Chronic exposures are associated with airway acidity, whereas acute exposures are more closely associated with oxidative stress. These results suggest that the collection of EBC may contribute to predicting the pathological state of the airways of workers exposed to acute and chronic factors.

  12. Are risk factors associated with invasive pneumococcal disease according to different serotypes?

    PubMed Central

    Ciruela, Pilar; Soldevila, Núria; Selva, Laura; Hernández, Sergi; Garcia-Garcia, Juan Jose; Moraga, Fernando; de Sevilla, Mariona F.; Codina, Gemma; Planes, Ana Maria; Esteva, Cristina; Coll, Francis; Cardeñosa, Neus; Jordan, Iolanda; Batalla, Joan; Salleras, Luis; Muñoz-Almagro, Carmen; Domínguez, Angela

    2013-01-01

    The aim of this study was to investigate risk factors for the most common serotypes of invasive pneumococcal disease (IPD). A total of 293 IPD cases were analyzed in children aged 3–59 mo in a community with intermediate vaccination coverage with the 7-valent pneumococcal vaccine (PCV7). IPD cases were reviewed during 2007–2009 in two pediatric hospitals in Catalonia (Spain). A multivariate analysis using unconditional logistic regression was performed to estimate the adjusted odds ratio. PCV7 coverage was 45.4%. Pneumonia with empyema (64.5%) was the most frequent clinical manifestation. The most common serotypes were: serotype 1 (21.2%), 19A (16.0%), 3 (12.6%) and 7F/A (6.8%). 70.0% of serotypes found were included in the 13-valent conjugate vaccine (PCV13), 39.2% in the 10-valent conjugate vaccine and 8.1% in the PCV7. PCV7 was protective in IPD cases due to PCV7-serotypes (aOR: 0.15, 95% CI:0.04–0.55). Serotype 1 was positively associated with attending day care or school (aOR: 3.55, 95% CI: 1.21–10.38) and age 24–59 mo (aOR: 7.70, 95% CI:2.70–21.98). Serotype 19A was positively associated with respiratory infection in the previous month (aOR: 2.26, 95% CI: 1.03–4.94), non-penicillin susceptible IPD (aOR: 1.89, 95% CI:1.13–3.16) and negatively associated with age 24–59 mo (aOR: 0.19, 95% CI:0.09–0.41). Serotype 3 was positively associated with vaccination (aOR: 4.87, 95% CI:2.05–11.59). No factors were associated with serotype 7F/A. Vaccination with pneumococcal vaccines including more serotypes may reduce the risk of disease in our setting. PMID:23295982

  13. Are risk factors associated with invasive pneumococcal disease according to different serotypes?

    PubMed

    Ciruela, Pilar; Soldevila, Núria; Selva, Laura; Hernández, Sergi; Garcia-Garcia, Juan Jose; Moraga, Fernando; de Sevilla, Mariona F; Codina, Gemma; Planes, Ana Maria; Esteva, Cristina; Coll, Francis; Cardeñosa, Neus; Jordan, Iolanda; Batalla, Joan; Salleras, Luis; Muñoz-Almagro, Carmen; Domínguez, Angela

    2013-03-01

    The aim of this study was to investigate risk factors for the most common serotypes of invasive pneumococcal disease (IPD). A total of 293 IPD cases were analyzed in children aged 3-59 mo in a community with intermediate vaccination coverage with the 7-valent pneumococcal vaccine (PCV7). IPD cases were reviewed during 2007-2009 in two pediatric hospitals in Catalonia (Spain). A multivariate analysis using unconditional logistic regression was performed to estimate the adjusted odds ratio. PCV7 coverage was 45.4%. Pneumonia with empyema (64.5%) was the most frequent clinical manifestation. The most common serotypes were: serotype 1 (21.2%), 19A (16.0%), 3 (12.6%) and 7F/A (6.8%). 70.0% of serotypes found were included in the 13-valent conjugate vaccine (PCV13), 39.2% in the 10-valent conjugate vaccine and 8.1% in the PCV7. PCV7 was protective in IPD cases due to PCV7-serotypes (aOR: 0.15, 95% CI:0.04-0.55). Serotype 1 was positively associated with attending day care or school (aOR: 3.55, 95% CI: 1.21-10.38) and age 24-59 mo (aOR: 7.70, 95% CI:2.70-21.98). Serotype 19A was positively associated with respiratory infection in the previous month (aOR: 2.26, 95% CI: 1.03-4.94), non-penicillin susceptible IPD (aOR: 1.89, 95% CI:1.13-3.16) and negatively associated with age 24-59 mo (aOR: 0.19, 95% CI:0.09-0.41). Serotype 3 was positively associated with vaccination (aOR: 4.87, 95% CI:2.05-11.59). No factors were associated with serotype 7F/A. Vaccination with pneumococcal vaccines including more serotypes may reduce the risk of disease in our setting.

  14. Ecological distribution of Spirillum lipoferum Beijerinck.

    PubMed

    Dobereiner, J; Marriel, I E; Nery, M

    1976-10-01

    A survey in various countries revealed that the N2-fixing Spirillum lipoferum Beijerinck is a very common root and soil inhabitant in the tropics. More than half of the grass root and soil samples collected in tropical countries (four African countries and Brazil) contained abundant S. lipoferum populations, while less than 10% of the samples collected in temperate South Brazil, Kenya, and the U.S.A. contained the organism. There is a pronounced vegetation effect. Panicum maximum seems the most favorable among the forage grasses, while few positive samples were found under virgin tropical forest. Legume roots contained less S. lipoferum than adjacent soils. More than 80% of the samples from cereal roots (maize, sorghum, wheat, and rye) grown in fields fertilized with PK and Mo, in Rio de Janeiro State, were positive. Maize and sorghum grown under similar conditions in Wisconsin contained less than 10% of positive samples, but when maize fields were inoculated 90% of the root samples contained S. lipoferum. Alluvial soils were more favorable than eroded hill soils. Occurrence in soil was strongly pH-dependent with a pH around 7, being optimal (correlation coefficient r = 0.90). Sporadic occurrence was observed even in soils with pH 4.8. Surface-sterilized P. maximum roots collected from soils with pH ranging from 4.8 to 7.2 contained high S. lipoferum numbers which did not correlate with soil pH (r = 0.41). Amendment with malate of acid soils was not very effective in increasing nitrogenase (N2-ase) activity, but in two soils with pH above 6.4, high N2-ase activity was obtained after 16 to 48 h of incubation. In two soils from a temperate climate region, inoculation with S. lipoferum increased N2-ase activity produced through malate amendment.

  15. pH homeostasis during coral calcification in a free ocean CO2 enrichment (FOCE) experiment, Heron Island reef flat, Great Barrier Reef

    PubMed Central

    Georgiou, Lucy; Falter, James; Trotter, Julie; Kline, David I.; Holcomb, Michael; Dove, Sophie G.; Hoegh-Guldberg, Ove; McCulloch, Malcolm

    2015-01-01

    Geochemical analyses (δ11B and Sr/Ca) are reported for the coral Porites cylindrica grown within a free ocean carbon enrichment (FOCE) experiment, conducted on the Heron Island reef flat (Great Barrier Reef) for a 6-mo period from June to early December 2010. The FOCE experiment was designed to simulate the effects of CO2-driven acidification predicted to occur by the end of this century (scenario RCP4.5) while simultaneously maintaining the exposure of corals to natural variations in their environment under in situ conditions. Analyses of skeletal growth (measured from extension rates and skeletal density) showed no systematic differences between low-pH FOCE treatments (ΔpH = ∼−0.05 to −0.25 units below ambient) and present day controls (ΔpH = 0) for calcification rates or the pH of the calcifying fluid (pHcf); the latter was derived from boron isotopic compositions (δ11B) of the coral skeleton. Furthermore, individual nubbins exhibited near constant δ11B compositions along their primary apical growth axes (±0.02 pHcf units) regardless of the season or treatment. Thus, under the highly dynamic conditions of the Heron Island reef flat, P. cylindrica up-regulated the pH of its calcifying fluid (pHcf ∼8.4–8.6), with each nubbin having near-constant pHcf values independent of the large natural seasonal fluctuations of the reef flat waters (pH ∼7.7 to ∼8.3) or the superimposed FOCE treatments. This newly discovered phenomenon of pH homeostasis during calcification indicates that coral living in highly dynamic environments exert strong physiological controls on the carbonate chemistry of their calcifying fluid, implying a high degree of resilience to ocean acidification within the investigated ranges. PMID:26438833

  16. pH homeostasis during coral calcification in a free ocean CO2 enrichment (FOCE) experiment, Heron Island reef flat, Great Barrier Reef.

    PubMed

    Georgiou, Lucy; Falter, James; Trotter, Julie; Kline, David I; Holcomb, Michael; Dove, Sophie G; Hoegh-Guldberg, Ove; McCulloch, Malcolm

    2015-10-27

    Geochemical analyses (δ(11)B and Sr/Ca) are reported for the coral Porites cylindrica grown within a free ocean carbon enrichment (FOCE) experiment, conducted on the Heron Island reef flat (Great Barrier Reef) for a 6-mo period from June to early December 2010. The FOCE experiment was designed to simulate the effects of CO2-driven acidification predicted to occur by the end of this century (scenario RCP4.5) while simultaneously maintaining the exposure of corals to natural variations in their environment under in situ conditions. Analyses of skeletal growth (measured from extension rates and skeletal density) showed no systematic differences between low-pH FOCE treatments (ΔpH = ∼-0.05 to -0.25 units below ambient) and present day controls (ΔpH = 0) for calcification rates or the pH of the calcifying fluid (pHcf); the latter was derived from boron isotopic compositions (δ(11)B) of the coral skeleton. Furthermore, individual nubbins exhibited near constant δ(11)B compositions along their primary apical growth axes (±0.02 pHcf units) regardless of the season or treatment. Thus, under the highly dynamic conditions of the Heron Island reef flat, P. cylindrica up-regulated the pH of its calcifying fluid (pHcf ∼8.4-8.6), with each nubbin having near-constant pHcf values independent of the large natural seasonal fluctuations of the reef flat waters (pH ∼7.7 to ∼8.3) or the superimposed FOCE treatments. This newly discovered phenomenon of pH homeostasis during calcification indicates that coral living in highly dynamic environments exert strong physiological controls on the carbonate chemistry of their calcifying fluid, implying a high degree of resilience to ocean acidification within the investigated ranges.

  17. Undetected Severe Fetal Myelosuppression following Administration of High-Dose Cytarabine for Acute Myeloid Leukemia: Is More Frequent Surveillance Necessary?

    PubMed Central

    Holland, Marium

    2017-01-01

    Background Cytarabine use during pregnancy carries a 5–7% risk of neonatal cytopenia. We report two cases of fetal myelosuppression following high-dose cytarabine administration for acute myeloid leukemia (AML). Case 1 A 36-year-old G9P6 diagnosed with AML at 21 weeks was monitored for fetal anemia weekly and growth monthly. At 33 weeks (after 2 cycles), BPP was 2/10 and MCA PSV was elevated at 1.51 MoM. Urgent cesarean section was performed. The infant had an initial pH of 6.78 and pancytopenia (hematocrit 13.3%, platelets 3 K/UL, and white blood cell count 2.0 K/UL). Initially transfusion dependent, the neonate had count recovery by 3 weeks. Case 2 A 30-year-old G4P3 with AML at 26 weeks was monitored for fetal anemia twice weekly and growth monthly. At 34 weeks (after cycle 1), she was admitted with neutropenic fever. The fetal MCA PSV was borderline at 1.48 MoM. It improved to 1.38 MoM at 35 weeks but the fetal tracing worsened. At delivery the fetus was found to have a hematocrit of 30%, but with normal platelet and WBC. The fetus did not require any transfusions. Conclusion Cytarabine use during pregnancy may cause neonatal myelosuppression. We recommend monitoring for fetal anemia with MCA Dopplers twice weekly. PMID:29075543

  18. 3D ordered porous MoxC (x = 1 or 2) for advanced hydrogen evolution and Li storage.

    PubMed

    Yu, Hong; Fan, Haosen; Wang, Jiong; Zheng, Yun; Dai, Zhengfei; Lu, Yizhong; Kong, Junhua; Wang, Xin; Kim, Young Jin; Yan, Qingyu; Lee, Jong-Min

    2017-06-01

    3D ordered porous structures of Mo x C are prepared with different Mo to C ratios and tested for two possible promising applications: hydrogen evolution reaction (HER) through water splitting and lithium ion batteries (LIBs). Mo 2 C and MoC with 3D periodic ordered structures are prepared with a similar process but different precursors. The 3D ordered porous MoC exhibits excellent cycling stability and rate performance as an anode material for LIBs. A discharge capacity of 450.9 mA h g -1 is maintained up to 3000 cycles at 10.0 A g -1 . The Mo 2 C with a similar ordered porous structure shows impressive electrocatalytic activity for the HER in neutral, alkaline and acidic pH solutions. In particular, Mo 2 C shows an onset potential of only 33 mV versus a reversible hydrogen electrode (RHE) and a Tafel slope of 42.5 mV dec -1 in a neutral aqueous solution (1.0 M phosphate buffer solution), which is approaching that of the commercial Pt/C catalyst.

  19. Effect of pH on Semiconducting Property of Passive Film Formed on Ultra-High-Strength Corrosion-Resistant Steel in Sulfuric Acid Solution

    NASA Astrophysics Data System (ADS)

    Sun, Min; Xiao, Kui; Dong, Chaofang; Li, Xiaogang; Zhong, Ping

    2013-10-01

    Because Cr9Ni5MoCo14 is a new ultra-high-strength corrosion-resistant steel, it is important to study its corrosion behavior in sulfuric acid solution, which is used to simulate the aggressive environment. The effect of pH on the electrochemical and semiconducting properties of passive films formed on ultra-high-strength corrosion-resistant steel in sulfuric acid solution was investigated by means of the potentiodynamic polarization technique, electrochemical impedance spectroscopy (EIS), Mott-Schottky analysis, and X-ray photoelectron spectroscopy (XPS). The results indicated that Cr9Ni5MoCo14 steel showed a passive state in acid solutions. The corrosion behavior of this Cr9Ni5MoCo14 alloy was influenced by the passive film formed on the surface, including thickness, stability, and partitioning of elements of the passive film. The passive current density decreases with increasing pH, and the corrosion resistance was enhanced by the increasing thickness and depletion of the defects within the passive film. Moreover, an enrichment of chromium (primarily the oxides of Cr) and depletion of iron in the passive film led to improved corrosion resistance. These results can provide a theoretical basis for use of this alloy and further development of ultra-high-strength corrosion-resistant steel in today's society.

  20. Daytime Changes of Skin Biophysical Characteristics: A Study of Hydration, Transepidermal Water Loss, pH, Sebum, Elasticity, Erythema, and Color Index on Middle Eastern Skin

    PubMed Central

    Firooz, Alireza; Zartab, Hamed; Sadr, Bardia; Bagherpour, Leili Naraghi; Masoudi, Aidin; Fanian, Ferial; Dowlati, Yahya; Ehsani, Amir Hooshang; Samadi, Aniseh

    2016-01-01

    Background: The exposure of skin to ultraviolet radiation and temperature differs significantly during the day. It is reasonable that biophysical parameters of human skin have periodic daily fluctuation. The objective of this study was to study the fluctuations of various biophysical characteristics of Middle Eastern skin in standardized experimental conditions. Materials and Methods: Seven biophysical parameters of skin including stratum corneum hydration, transepidermal water loss, pH, sebum, elasticity, skin color, and erythema index were measured at three time points (8 a.m., 12 p.m. and 4 p.m.) on the forearm of 12 healthy participants (mean age of 28.4 years) without any ongoing skin disease using the CK MPA 580 device in standard temperature and humidity conditions. Results: A significant difference was observed between means of skin color index at 8 a.m. (175.42 ± 13.92) and 4 p.m. (164.44 ± 13.72, P = 0.025), between the pH at 8 a.m. (5.72 ± 0.48) and 4 p.m. (5.33 ± 0.55, P = 0.001) and pH at 12 p.m. (5.60 ± 0.48) and 4 p.m. (5.33 ± 0.55, P = 0.001). Other comparisons between the means of these parameters at different time points resulted in nonsignificant P values. Conclusion: There are daytime changes in skin color index and pH. Skin color index might be higher and cutaneous pH more basic in the early morning compared to later of the day. PMID:27904203

  1. The conformations of 13-vertex ML2C2B10 metallacarboranes: experimental and computational studies.

    PubMed

    Dalby, Kelly J; Ellis, David; Erhardt, Stefan; McIntosh, Ruaraidh D; Macgregor, Stuart A; Rae, Karen; Rosair, Georgina M; Settels, Volker; Welch, Alan J; Hodson, Bruce E; McGrath, Thomas D; Stone, F Gordon A

    2007-03-21

    The docosahedral metallacarboranes 4,4-(PMe(2)Ph)2-4,1,6-closo-PtC(2)B(10)H(12), 4,4-(PMe(2)Ph)2-4,1,10-closo-PtC(2)B(10)H(12), and [N(PPh(3))2][4,4-cod-4,1,10-closo-RhC(2)B(10)H(12)] were prepared by reduction/metalation of either 1,2-closo-C(2)B(10)H(12) or 1,12-closo-C(2)B(10)H(12). All three species were fully characterized, with a particular point of interest of the latter being the conformation of the {ML2} fragment relative to the carborane ligand face. Comparison with conformations previously established for six other ML(2)C(2)B(10) species of varying heteroatom patterns (4,1,2-MC(2)B(10), 4,1,6-MC(2)B(10), 4,1,10-MC(2)B(10), and 4,1,12-MC(2)B(10)) reveals clear preferences. In all cases a qualitative understanding of these was afforded by simple MO arguments applied to the model heteroarene complexes [(PH3)2PtC(2)B(4)H(6)]2- and [(PH3)2PtCB(5)H(6)]3-. Moreover, DFT calculations on [(PH3)2PtC(2)B(4)H(6)]2- in its various isomeric forms approximately reproduced the observed conformations in the 4,1,2-, 4,1,6-, and 4,1,10-MC(2)B(10) species, although analogous calculations on [(PH3)2PtCB(5)H(6)]3- did not reproduce the conformation observed in the 4,1,12-MC(2)B(10) metallacarborane. DFT calculations on (PH3)2PtC(2)B(10)H(12) yielded good agreement with experimental conformations in all four isomeric cases. Apparent discrepancies between observed and computed Pt-C distances were probed by further refinement of the 4,1,2- model to 1,2-(CH2)3-4,4-(PMe3)2-4,1,2-closo-PtC(2)B(10)H(10). This still has a more distorted structure than measured experimentally for 1,2-(CH2)3-4,4-(PMe(2)Ph)2-4,1,2-closo-PtC(2)B(10)H(10), but the structural differences lie on a very shallow potential energy surface. For the model compound a henicosahedral transition state was located 8.3 kcal mol(-1) above the ground-state structure, consistent with the fluxionality of 1,2-(CH2)3-4,4-(PMe(2)Ph)2-4,1,2-closo-PtC(2)B(10)H(10) in solution.

  2. Stereochemical and electronic control of M-SO/sub 2/ bonding geometry in d/sup 6/ molybdenum and tungsten SO/sub 2/ complexes: novel n/sup 1/reverse arrown/sup 2/ SO/sub 2/ linkage isomerization in Mo(CO)/sub 2/(PPh/sub 3/)/sub 2/(CNR)(SO/sub 2/) and structures of Mo(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/(SO/sub 2/) and (Mo(CO)/sub 2/(py)(PPh/sub 3/)(. mu. -SO/sub 2/))/sub 2/

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

    Kubas, G.J.; Jarvinen, G.D.; Ryan, R.R.

    1983-04-06

    New complexes, mer,trans,M(CO)/sub 3/(PR/sub 3/)/sub 2/(SO/sub 2/) (M = Mo,W; R = Ph,Cy,i-Pr) (I), cis,trans-Mo(CO)/sub 2/-(PPh/sub 3/)/sub 2/(SO/sub 2/)(L) (L = NCMe,py,CNCy,CN-t-Bu and CN(p-tolyl))(II), and (Mo(CO)/sub 2/(py)(PPh/sub 3/)(..mu..-SO/sub 2/))/sub 2/, have been prepared and characterized by infrared spectroscopy, /sup 17/O and /sup 31/P NMR spectroscopy, and X-ray crystallography. Syntheses for fac-Mo(CO)/sub 3/(n/sup 2/-SO/sub 2/)(LL) (LL = dppe,bpy,phen,2 py) have also been developed. Depending upon L, II has been found to coordinate SO/sub 2/ either in the S-bonded (n/sup 1/ planar) or O,S-bonded (n/sup 2/) geometries. Remarkably, for L = CNCy or CN-t-Bu, II has been found to contain, in themore » solid state, an apparent equimixture of both coordination types. Isomerization of fac-M(CO)/sub 3/(dppe)(n/sup 2/-SO/sub 2/) (M=Mo,w; dppe = 1,2-bis(diphenylphosphino)ethane) to an n/sup 1/-planar SO/sub 2/ form, mer-M(CO)/sub 3/(dppe)(SO/sub 2/), has also been found to occur. Thus, control of the SO/sub 2/ coordination geometry has been achieved by varying either the electronic properties of the ancillary ligands or their disposition with respect to the SO/sub 2/. The X-ray crystal structure of mer,trans-Mo(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/(SO/sub 2/) revealed n/sup 1/-planar SO/sub 2/ binding, the first example of this geometry for group 6 metals. The M-S distance, 2.239 (3) angstrom, is the longest such distance for this geometry recorded to date. Crystal data: Pbca, Z=8, a=24.712(8) angstrom, b=16.033(6) angstrom, c=14.058(5) angstrom, R=0.079 for 2934 reflections with Igreater than or equal to2sigma(I). The structure of (Mo(CO)/sub 2/(py)(PPh/sub 3/)(..mu..-SO/sub 2/))/sub 2/ showed a novel SO/sub 2/ bridging geometry in which all three atoms of SO/sub 2/ are metal coordinated. Crystal data: P1, Z=1, a=14.883(4) angstrom, b=9.264(2) angstrom, c=10.808(2) angstrom, R=0.039 for 3282 reflections with Igreater than or equal to2sigma(I).« less

  3. Maternal serum analytes as predictors of IUGR with different degrees of placental vascular dysfunction.

    PubMed

    Roman, Amanda; Desai, Neeraj; Krantz, David; Liu, Hsiao-Pin; Rosner, Jonathan; Vohra, Nidhi; Rochelson, Burton

    2014-07-01

    Our primary objective was to determine the association of maternal serum analytes in pregnancies complicated by intrauterine growth restriction (IUGR) stratified by umbilical artery (UA) Doppler versus pregnancies with appropriately grown for gestational age (AGA) and its potential use as screening model. Retrospective cohort evaluating first and second trimester maternal serum aneuploidy screening markers in women complicated with IUGR [90 with absent or reversed end diastolic velocity (AREDV), 46 with UA systolic/diastolic ratio ≥95th percentile and 215 with normal UA Doppler] versus 2590 women with AGA fetuses (control). Extreme levels of each analyte were significantly more common in the IUGR/AREDV group than in AGA group: inhibin A >97th percentile [≥2.27 multiples of the median (MoM)], OR: 41 (95% CI: 21-80); unconjugated estriol <3rd percentile (≤0.6 MoM), OR: 17.2 (95% CI: 8.1-42); AFP >97th percentile (≥1.88 MoM), OR: 15 (95% CI: 8.2-27); PAPP-A <3rd percentile (≤0.33 MoM), OR: 13 (95% CI: 6.6-25.5); and free-beta human chorionic gonadotrophin second trimester >97th percentile (≥3.24 MoM), OR: 11.6 (95% CI: 4.2-32). In a subgroup of pregnancies in which all markers were evaluated on each patient, a combination of abnormal markers detected 73% (95% CI: 54-87%) of IUGR/AREDV fetuses. When maternal risk factors were included into the risk calculation, it increased to 91% (95% CI: 76-98%). Abnormal maternal serum aneuploidy markers preferentially identify those pregnancies at greatest risk of IUGR with AREDV in the UA. © 2014 John Wiley & Sons, Ltd.

  4. Synthesis and characterization of Cadmium selenide nanoparticles loaded on activated carbon and its efficient application for removal of Muroxide from aqueous solution

    NASA Astrophysics Data System (ADS)

    Ghaedi, M.; Amirabad, S. Zamani; Marahel, F.; Nasiri Kokhdan, S.; Sahraei, R.; Nosrati, M.; Daneshfar, A.

    2011-12-01

    In the first, Cadmium selenide Nanoparticle loaded on activated carbon (CdSe-NP-AC) has been synthesized and characterized by different techniques including XRD and SEM. Then, this new adsorbent successfully has been applied for the removal of muroxide (MO) from aqueous solution in batch studies, while the effect of various experimental parameters like initial pH (pH 0), contact time, amount of (CdSe-NP-AC) and initial MO concentration ( C0) on its removal percentage was examined by one at a time optimization method. It was found following optimization of variable, the adsorption of MO onto (CdSe-NP-AC) followed pseudo-second-order kinetics and show Tempkin and Langmuir models for interpretation of experimental data. It was observed that by increasing the temperature the removal percentage was improved and the positive change in entropy (Δ S°) and heat of adsorption (Δ H°) show the endothermic nature of process, while the high negative value in Gibbs free energy change (Δ G°) indicates the feasible nature of adsorption process.

  5. Nearly amorphous Mo-N gratings for ultimate resolution in extreme ultraviolet interference lithography.

    PubMed

    Wang, L; Kirk, E; Wäckerlin, C; Schneider, C W; Hojeij, M; Gobrecht, J; Ekinci, Y

    2014-06-13

    We present fabrication and characterization of high-resolution and nearly amorphous Mo1 - xNx transmission gratings and their use as masks for extreme ultraviolet (EUV) interference lithography. During sputter deposition of Mo, nitrogen is incorporated into the film by addition of N2 to the Ar sputter gas, leading to suppression of Mo grain growth and resulting in smooth and homogeneous thin films with a negligible grain size. The obtained Mo0.8N0.2 thin films, as determined by x-ray photoelectron spectroscopy, are characterized to be nearly amorphous using x-ray diffraction. We demonstrate a greatly reduced Mo0.8N0.2 grating line edge roughness compared with pure Mo grating structures after e-beam lithography and plasma dry etching. The amorphous Mo0.8N0.2 thin films retain, to a large extent, the benefits of Mo as a phase grating material for EUV wavelengths, providing great advantages for fabrication of highly efficient diffraction gratings with extremely low roughness. Using these grating masks, well-resolved dense lines down to 8 nm half-pitch are fabricated with EUV interference lithography.

  6. Psychological well-being and independent living of young adults with childhood-onset craniopharyngioma.

    PubMed

    Memmesheimer, Rodica Mia; Lange, Karin; Dölle, Michael; Heger, Sabine; Mueller, Iris

    2017-08-01

    To assess the psychological well-being and social integration of adults with craniopharyngioma diagnosed in childhood. A cross-sectional study of a nationwide cohort of young adults with craniopharyngioma in Germany was performed. A structured questionnaire covered the sociodemographic, clinical data, and subjective effects of the condition on social integration. Psychological well-being was assessed using the Hospital Anxiety and Depression Scale (HADS). Results were compared to young adults with type 1 diabetes mellitus (T1DM). The study included 59 participants (29 females, 30 males; mean age 25y 2mo [SD 5y 10mo]), mean age at first surgery 10y 2mo [SD 3y 7mo]. Compared to the T1DM group, significantly more young people with craniopharyngioma aged 25 to 35 years lived at their parents' homes (craniopharyngioma 43.34%; T1DM 13.7%; χ 2 =4.14, p=0.049), and fewer lived in a relationship (craniopharyngioma 8.69%; T1DM 54.7%; χ 2 =15.74, p<0.001). The HADS revealed a score for depression above the cut-off in 20.69 per cent of young adults with craniopharyngioma and in 6 per cent of young adults with T1DM (χ 2 =13.42, p<0.001). Young adults with craniopharyngioma reported subjective disadvantages in professional and social integration. Further, they presented with reduced well-being and increased depression rates. Better psychosocial support and self-management education might reduce the long-term burden of the disease. © 2017 Mac Keith Press.

  7. Molybdate adsorption from steel slag eluates by subsoils.

    PubMed

    Matern, K; Rennert, T; Mansfeldt, T

    2013-11-01

    Steel slags are industrial by-products which are generated in large amounts worldwide, e.g. 150-230×10(6) Mg in 2012, and which are partly used for construction. Molybdenum (Mo) can be added during steel processing in order to harden the steel. The objective of this study was to evaluate the adsorption behaviour of molybdate (MoO4(2-)) from slag eluates in subsoils. Molybdate batch adsorption experiments were carried out with eluates obtained from two different kinds of steel slags (i) LD slag (Linz-Donawitz operation, LDS) and (ii) electric arc furnace slag (EAF) to assess the risk that may arise from the contamination of groundwater by the leaching of molybdate. Six different subsoils were chosen in order to provide a wide range of chemical properties (pH 4.0-7.6; dithionite-extractable Fe 0.73-14.7 g kg(-1)). Molybdate adsorption experiments were carried out at the pH of the steel slag eluates (pH 11-12) as well as at pH values adjusted to the soil pH. The data were evaluated with the Freundlich equation. Molybdate adsorption exhibited a maximum near pH 4 for steel slag eluates adjusted to the soil pH, and decreased rapidly with increasing pH until adsorption was virtually zero at pH>11. Adsorption was greater for soils with high amounts of dithionite-extractable Fe oxides. The extent and behaviour of molybdate adsorption from both eluates was similar. After a reaction time of 24h, the pH of the EAF slag eluate was lower than that of the LD steel slag eluate, which was caused by different acid buffer capacities. Some soils were able to decrease the pH of the EAF slag eluates by about 4 pH units, enhancing the adsorption of molybdate. Transport simulations indicated that molybdate discharge is low in acidic soils. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Chemotherapy and Your Mouth

    MedlinePlus

    ... their contributions. Scientific Committee Gerry Barker, RDH, MA University of Missouri-Kansas City Kansas City, MO Susan L. Beck, PhD, APRN, FAAN University of Utah Salt Lake City, UT Marylin J. ...

  9. Re-assessing the surface cycling of molybdenum and rhenium

    NASA Astrophysics Data System (ADS)

    Miller, Christian A.; Peucker-Ehrenbrink, Bernhard; Walker, Brett D.; Marcantonio, Franco

    2011-11-01

    We re-evaluate the cycling of molybdenum (Mo) and rhenium (Re) in the near-surface environment. World river average Mo and Re concentrations, initially based on a handful of rivers, are calculated using 38 rivers representing five continents, and 11 of 19 large-scale drainage regions. Our new river concentration estimates are 8.0 nmol kg -1 (Mo), and 16.5 pmol kg -1 (Re, natural + anthropogenic). The linear relationship of dissolved Re and SO42- in global rivers ( R2 = 0.76) indicates labile continental Re is predominantly hosted within sulfide minerals and reduced sediments; it also provides a means of correcting for the anthropogenic contribution of Re to world rivers using independent estimates of anthropogenic sulfate. Approximately 30% of Re in global rivers is anthropogenic, yielding a pre-anthropogenic world river average of 11.2 pmol Re kg -1. The potential for anthropogenic contribution is also seen in the non-negligible Re concentrations in precipitation (0.03-5.9 pmol kg -1), and the nmol kg -1 level Re concentrations of mine waters. The linear Mo- SO42- relationship ( R2 = 0.69) indicates that the predominant source of Mo to rivers is the weathering of pyrite. An anthropogenic Mo correction was not done as anthropogenically-influenced samples do not display the unambiguous metal enrichment observed for Re. Metal concentrations in high temperature hydrothermal fluids from the Manus Basin indicate that calculated end-member fluids (i.e. Mg-free) yield negative Mo and Re concentrations, showing that Mo and Re can be removed more quickly than Mg during recharge. High temperature hydrothermal fluids are unimportant sinks relative to their river sources 0.4% (Mo), and 0.1% (pre-anthropogenic Re). We calculate new seawater response times of 4.4 × 10 5 yr ( τMo) and 1.3 × 10 5 yr ( τRe, pre-anthropogenic).

  10. The effect of pH on solubilization of organic matter and microbial community structures in sludge fermentation.

    PubMed

    Maspolim, Yogananda; Zhou, Yan; Guo, Chenghong; Xiao, Keke; Ng, Wun Jern

    2015-08-01

    Sludge fermentation between pH 4 and 11 was investigated to generate volatile fatty acids (VFA). Despite the highest sludge solubilization of 25.9% at pH 11, VFA accumulation was optimized at pH 8 (12.5% out of 13.1% sludge solubilization). 454 pyrosequencing identified wide diversity of acidogens in bioreactors operated at the various pHs, with Tissierella, Petrimonas, Proteiniphilum, Levilinea, Proteiniborus and Sedimentibacter enriched and contributing to the enhanced fermentation at pH 8. Hydrolytic enzymatic assays determined abiotic effect to be the leading cause for improved solubilization under high alkaline condition but the environmental stress at pH 9 and above might lead to disrupt biological activities and eventually VFA production. Furthermore, molecular weight (MW) characterization of the soluble fractions found large MW aromatic substances at pH 9 and above, that is normally associated with poor biodegradability, making them disadvantageous for subsequent bioprocesses. The findings provided information to better understand and control sludge fermentation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Conductive Hybrid Crystal Composed from Polyoxomolybdate and Deprotonatable Ionic-Liquid Surfactant

    PubMed Central

    Kobayashi, Jun; Kawahara, Ryosuke; Uchida, Sayaka; Koguchi, Shinichi; Ito, Takeru

    2016-01-01

    A polyoxomolybdate inorganic-organic hybrid crystal was synthesized with deprotonatable ionic-liquid surfactant. 1-dodecylimidazolium cation was employed for its synthesis. The hybrid crystal contained δ-type octamolybdate (Mo8) isomer, and possessed alternate stacking of Mo8 monolayers and interdigitated surfactant bilayers. The crystal structure was compared with polyoxomolybdate hybrid crystals comprising 1-dodecyl-3-methylimidazolium surfactant, which preferred β-type Mo8 isomer. The less bulky hydrophilic moiety of the 1-dodecylimidazolium interacted with the δ-Mo8 anion by N–H···O hydrogen bonds, which presumably induced the formation of the δ-Mo8 anion. Anhydrous conductivity of the hybrid crystal was estimated to be 5.5 × 10−6 S·cm−1 at 443 K by alternating current (AC) impedance spectroscopy. PMID:27347926

  12. Fat distribution in children and adolescents with myelomeningocele.

    PubMed

    Mueske, Nicole M; Ryan, Deirdre D; Van Speybroeck, Alexander L; Chan, Linda S; Wren, Tishya A L

    2015-03-01

    To evaluate fat distribution in children and adolescents with myelomeningocele using dual-energy X-ray absorptiometry (DXA). Cross-sectional DXA measurements of the percentage of fat in the trunk, arms, legs, and whole body were compared between 82 children with myelomeningocele (45 males, 37 females; mean age 9y 8mo, SD 2y 7mo; 22 sacral, 13 low lumbar, 47 mid lumbar and above) and 119 comparison children (65 males, 54 females; mean age 10y 4mo, SD 2y 4mo). Differences in fat distribution between groups were evaluated using univariate and multivariate analyses. Children with myelomeningocele had higher total body fat (34% vs 31%, p=0.02) and leg fat (42% vs 35%, p<0.001) than comparison children, but no differences in trunk or arm fat after adjustment for anthropometric measures. Children with myelomeningocele have higher than normal total body and leg fat, but only children with higher level lesions have increased trunk fat, which may be caused by greater obesity in this group. Quantifying segmental fat distribution may aid in better assessment of excess weight and, potentially, the associated health risks. © 2014 Mac Keith Press.

  13. Fat distribution in children and adolescents with myelomeningocele

    PubMed Central

    Mueske, Nicole M; Ryan, Deirdre D; Van Speybroeck, Alexander L; Chan, Linda S; Al Wren, Tishya

    2014-01-01

    AIM To evaluate quantitatively fat distribution in children and adolescents with myelomeningocele using dual-energy X-ray absorptiometry (DXA). METHOD Cross-sectional DXA measurements of the percentage of fat in the trunk, arms, legs, and whole body were compared between 82 children with myelomeningocele (45 males, 37 females; mean age 9y 8mo, SD 2y 7mo; 22 sacral, 13 low lumbar, 47 mid lumbar and above) and 119 comparison children (65 males, 54 females; mean age 10y 4mo, SD 2y 4mo). Differences in fat distribution between groups were evaluated using univariate and multivariate analyses. RESULTS Children with myelomeningocele had higher total body fat (34% vs 31%, p=0.02) and leg fat (42% vs 35%, p<0.001than comparison children, but no differences in trunk or arm fat after adjustment for anthropometric measures. INTERPRETATION Children with myelomeningocele have higher than normal total body and leg fat, but only children with higher level lesions have increased trunk fat, which may be caused by greater obesity in this group. Quantifying segmental fat distribution may aid in better assessment of excess weight and, potentially, the associated health risks. PMID:25251828

  14. Mo-CBP3, an Antifungal Chitin-Binding Protein from Moringa oleifera Seeds, Is a Member of the 2S Albumin Family

    PubMed Central

    Freire, José E. C.; Vasconcelos, Ilka M.; Moreno, Frederico B. M. B.; Batista, Adelina B.; Lobo, Marina D. P.; Pereira, Mirella L.; Lima, João P. M. S.; Almeida, Ricardo V. M.; Sousa, Antônio J. S.; Monteiro-Moreira, Ana C. O.; Oliveira, José T. A.; Grangeiro, Thalles B.

    2015-01-01

    Mo-CBP3 is a chitin-binding protein from M. oleifera seeds that inhibits the germination and mycelial growth of phytopathogenic fungi. This protein is highly thermostable and resistant to pH changes, and therefore may be useful in the development of new antifungal drugs. However, the relationship of MoCBP3 with the known families of carbohydrate-binding domains has not been established. In the present study, full-length cDNAs encoding 4 isoforms of Mo-CBP3 (Mo-CBP3-1, Mo-CBP3-2, Mo-CBP3-3 and Mo-CBP3-4) were cloned from developing seeds. The polypeptides encoded by the Mo-CBP3 cDNAs were predicted to contain 160 (Mo-CBP3-3) and 163 amino acid residues (Mo-CBP3-1, Mo-CBP3-2 and Mo-CBP3-4) with a signal peptide of 20-residues at the N-terminal region. A comparative analysis of the deduced amino acid sequences revealed that Mo-CBP3 is a typical member of the 2S albumin family, as shown by the presence of an eight-cysteine motif, which is a characteristic feature of the prolamin superfamily. Furthermore, mass spectrometry analysis demonstrated that Mo-CBP3 is a mixture of isoforms that correspond to different mRNA products. The identification of Mo-CBP3 as a genuine member of the 2S albumin family reinforces the hypothesis that these seed storage proteins are involved in plant defense. Moreover, the chitin-binding ability of Mo-CBP3 reveals a novel functionality for a typical 2S albumin. PMID:25789746

  15. Molar absorptivity (ε) and spectral characteristics of cyanidin-based anthocyanins from red cabbage.

    PubMed

    Ahmadiani, Neda; Robbins, Rebecca J; Collins, Thomas M; Giusti, M Monica

    2016-04-15

    Red cabbage extract contains mono and di-acylated cyanidin (Cy) anthocyanins and is often used as food colorants. Our objectives were to determine the molar absorptivity (ε) of different red cabbage Cy-derivatives and to evaluate their spectral behaviors in acidified methanol (MeOH) and buffers pH 1-9. Major red cabbage anthocyanins were isolated using a semi-preparatory HPLC, dried and weighed. Pigments were dissolved in MeOH and diluted with either MeOH (0.1% HCl) or buffers to obtain final concentrations between 5×10(-5) and 1×10(-3) mol/L. Spectra were recorded and ε calculated using Lambert-Beer's law. The ε in acidified MeOH and buffer pH 1 ranged between ~16,000-30,000 and ~13,000-26,000 L/mol cm, respectively. Most pigments showed higher ε in pH 8 than pH 2, and lowest ε between pH 4 and 6. There were bathochromic shifts (81-105 nm) from pH 1 to 8 and hypsochromic shifts from pH 8 to 9 (2-19 nm). Anthocyanins molecular structures and the media were important variables which greatly influenced their ε and spectral behaviors. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Mycolytic enzymes produced by Streptomyces violaceusniger and their role in antagonism towards wood-rotting fungi.

    PubMed

    Nagpure, Anand; Choudhary, Bharti; Gupta, Rajinder K

    2014-05-01

    Extracellular mycolytic enzymes produced under submerged fermentation by the fungal antagonist Streptomyces violaceusniger MTCC 3959 were characterized. This streptomycete produced higher amounts of extracellular chitinase and protease during late exponential phase, whereas β-1,3-glucanase production was at peak in mid-stationary phase. Cell-free culture filtrate (CCF) exhibited a broad range of antifungal activity against both white rot and brown rot fungi. The inhibitory activity was completely lost after treatment with proteinase K and heat, indicating that extracellular antifungal metabolites are heat labile and proteinaceous in nature. Optimum pH and temperature for enzyme activity were: 9.0 and 60 °C for chitinase; 6.0 and 60 °C for β-1,3-glucanase; and 9.0 and 70 °C for protease. Mycolytic enzymes were moderately thermostable, and had a wide pH stability range extending from pH 5.0 to 10.0. The zymogram analysis of CCF revealed five chitinase isoenzymes with an apparent molecular weight of 20.8, 33.3, 45.6, 67.4, and 114.8 kDa, one β-1,3-glucanase appeared as a single band of ∼131.8 kDa and four protease isoenzymes with approximate molecular weights of 22.8, 62.52, 74.64, and 120.5 kDa. S. violaceusniger MTCC 3959 produced mycolytic enzymes that can be effectively used for suppression of phytopathogenic basidiomycetes. It has the potential to be an effective biofungicide. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Radiation resistance of endohedral metallofullerenols under neutron irradiation

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

    Szhogina, A. A.; Shilin, V. A., E-mail: allin-ok2@mail.ru; Sedov, V. P.

    2016-07-15

    The endohedral metallofullerenols Me@C{sub 2n}(OH){sub 38–40} + C{sub 2n}(OH){sub 38–40} (Me = Tb, Sc, Gd, Fe, Pr, Mo) have been obtained and their radiation resistance under irradiation by a neutron flux of 8 × 10{sup 13} cm{sup –2} s{sup –1} has been studied. The factors affecting the radiation resistance of endohedral metallofullerenols are discussed.

  18. Effect of sodium, potassium, magnesium, and calcium salt cations on pH, proteolysis, organic acids, and microbial populations during storage of full-fat Cheddar cheese.

    PubMed

    McMahon, D J; Oberg, C J; Drake, M A; Farkye, N; Moyes, L V; Arnold, M R; Ganesan, B; Steele, J; Broadbent, J R

    2014-01-01

    Sodium reduction in cheese can assist in reducing overall dietary Na intake, yet saltiness is an important aspect of cheese flavor. Our objective was to evaluate the effect of partial substitution of Na with K on survival of lactic acid bacteria (LAB) and nonstarter LAB (NSLAB), pH, organic acid production, and extent of proteolysis as water-soluble nitrogen (WSN) and protein profiles using urea-PAGE, in Cheddar cheese during 9mo of storage. Seven Cheddar cheeses with molar salt contents equivalent to 1.7% salt but with different ratios of Na, K, Ca, and Mg cations were manufactured as well as a low-salt cheese with 0.7% salt. The 1.7% salt cheeses had a mean composition of 352g of moisture/kg, 259g of protein/kg and 50% fat-on-dry-basis, and 17.5g of salt/kg (measured as Cl(-)). After salting, a faster initial decrease in cheese pH occurred with low salt or K substitution and it remained lower throughout storage. No difference in intact casein levels or percentage WSN levels between the various cheeses was observed, with the percentage WSN increasing from 5% at d 1 to 25% at 9mo. A greater decrease in intact αs1-casein than β-casein was detected, and the ratio of αs1-casein (f121-199) to αs1-casein could be used as an index of ripening. Typical changes in bacteria microflora occurred during storage, with lactococci decreasing gradually and NSLAB increasing. Lowering the Na content, even with K replacement, extended the crossover time when NSLAB became dominant. The crossover time was 4.5mo for the control cheese and was delayed to 5.2, 6.0, 6.1, and 6.2mo for cheeses with 10, 25, 50, and 75% K substitution. Including 10% Mg or Ca, along with 40% K, further increased crossover time, whereas the longest crossover time (7.3mo) was for low-salt cheese. By 9mo, NSLAB levels in all cheeses had increased from initial levels of ≤10(2) to approximately 10(6)cfu/g. Lactococci remained at 10(6) cfu/g in the low-salt cheese even after 9mo of storage. The propionic acid concentration in the cheese increased when NSLAB numbers were high. Few other trends in organic acid concentration were observed as a function of Na content. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  19. Isolation and characterization of Chinese standard fulvic acid sub-fractions separated from forest soil by stepwise elution with pyrophosphate buffer.

    PubMed

    Bai, Yingchen; Wu, Fengchang; Xing, Baoshan; Meng, Wei; Shi, Guolan; Ma, Yan; Giesy, John P

    2015-03-04

    XAD-8 adsorption technique coupled with stepwise elution using pyrophosphate buffers with initial pH values of 3, 5, 7, 9, and 13 was developed to isolate Chinese standard fulvic acid (FA) and then separated the FA into five sub-fractions: FApH3, FApH5, FApH7, FApH9 and FApH13, respectively. Mass percentages of FApH3-FApH13 decreased from 42% to 2.5%, and the recovery ratios ranged from 99.0% to 99.5%. Earlier eluting sub-fractions contained greater proportions of carboxylic groups with greater polarity and molecular mass, and later eluting sub-fractions had greater phenolic and aliphatic content. Protein-like components, as well as amorphous and crystalline poly(methylene)-containing components were enriched using neutral and basic buffers. Three main mechanisms likely affect stepwise elution of humic components from XAD-8 resin with pyrophosphate buffers including: 1) the carboxylic-rich sub-fractions are deprotonated at lower pH values and eluted earlier, while phenolic-rich sub-fractions are deprotonated at greater pH values and eluted later. 2) protein or protein-like components can be desorbed and eluted by use of stepwise elution as progressively greater pH values exceed their isoelectric points. 3) size exclusion affects elution of FA sub-fractions. Successful isolation of FA sub-fractions will benefit exploration of the origin, structure, evolution and the investigation of interactions with environmental contaminants.

  20. Isolation and Characterization of Chinese Standard Fulvic Acid Sub-fractions Separated from Forest Soil by Stepwise Elution with Pyrophosphate Buffer

    PubMed Central

    Bai, Yingchen; Wu, Fengchang; Xing, Baoshan; Meng, Wei; Shi, Guolan; Ma, Yan; Giesy, John P.

    2015-01-01

    XAD-8 adsorption technique coupled with stepwise elution using pyrophosphate buffers with initial pH values of 3, 5, 7, 9, and 13 was developed to isolate Chinese standard fulvic acid (FA) and then separated the FA into five sub-fractions: FApH3, FApH5, FApH7, FApH9 and FApH13, respectively. Mass percentages of FApH3-FApH13 decreased from 42% to 2.5%, and the recovery ratios ranged from 99.0% to 99.5%. Earlier eluting sub-fractions contained greater proportions of carboxylic groups with greater polarity and molecular mass, and later eluting sub-fractions had greater phenolic and aliphatic content. Protein-like components, as well as amorphous and crystalline poly(methylene)-containing components were enriched using neutral and basic buffers. Three main mechanisms likely affect stepwise elution of humic components from XAD-8 resin with pyrophosphate buffers including: 1) the carboxylic-rich sub-fractions are deprotonated at lower pH values and eluted earlier, while phenolic-rich sub-fractions are deprotonated at greater pH values and eluted later. 2) protein or protein-like components can be desorbed and eluted by use of stepwise elution as progressively greater pH values exceed their isoelectric points. 3) size exclusion affects elution of FA sub-fractions. Successful isolation of FA sub-fractions will benefit exploration of the origin, structure, evolution and the investigation of interactions with environmental contaminants. PMID:25735451

  1. As You Get Older

    MedlinePlus

    ... to the Second Edition: Kathleen Kapp-Simon, PhD, Psychology David J. Reisberg, DDS, Prosthodontics James Sidman, MD, ... Speech ...........................................................................................................................8 Your Ears, Nose and Throat .......................................................................................10 Social Relationships ..........................................................................................................11 Looking Toward the Future ........................................................................................13 Stories ...

  2. The potential leaching and mobilization of trace elements from FGD-gypsum of a coal-fired power plant under water re-circulation conditions.

    PubMed

    Córdoba, Patricia; Castro, Iria; Maroto-Valer, Mercedes; Querol, Xavier

    2015-06-01

    Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO2SO4, H2Se, and HAsO2 are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO4(2) in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe2 and MoSe2, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples. Copyright © 2015. Published by Elsevier B.V.

  3. Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cl2 in solid para-hydrogen.

    PubMed

    Bahou, Mohammed; Wu, Jen-Yu; Tanaka, Keiichi; Lee, Yuan-Pern

    2012-08-28

    The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H(2)) were investigated with infrared (IR) absorption spectra. When a p-H(2) matrix containing Cl(2) and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm(-1), and several weaker ones due to the trans-1-chloromethylallyl radical, ●(CH(2)CHCH)CH(2)Cl, appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the Cl atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of Cl + propene in solid p-H(2) [J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)] in which the addition of Cl to the central C atom is favored, likely through steric effects in a p-H(2) matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm(-1), were observed when the UV-irradiated Cl(2)/trans-1,3-butadiene/p-H(2) matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, ●(CH(2)CHCH)CH(3), produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of Cl atoms with solid p-H(2) exposed to IR radiation.

  4. Maternal "junk-food" feeding of rat dams alters food choices and development of the mesolimbic reward pathway in the offspring.

    PubMed

    Ong, Z Y; Muhlhausler, B S

    2011-07-01

    Individuals exposed to high-fat, high-sugar diets before birth have an increased risk of obesity in later life. Recent studies have shown that these offspring exhibit increased preference for fat, leading to suggestions that perinatal exposure to high-fat, high-sugar foods results in permanent changes within the central reward system that increase the subsequent drive to overconsume palatable foods. The present study has determined the effect of a maternal "junk-food" diet on the expression of key components of the mesolimbic reward pathway in the offspring of rat dams at 6 wk and 3 mo of age. We show that offspring of junk-food-fed (JF) dams exhibit higher fat intake from weaning until at least 3 mo of age (males: 16 ± 0.6 vs. 11 ± 0.8 g/kg/d; females: 19 ± 1.3 vs. 13 ± 0.4 g/kg/d; P<0.01). mRNA expression of μ-opioid receptor (Mu) was 1.6-fold higher (P<0.01) and dopamine active transporter (DAT) was 2-fold lower (P<0.05) in JF offspring at 6 wk of age. By 3 mo, these differences were reversed, and Mu mRNA expression was 2.8-fold lower (P<0.01) and DAT mRNA expression was 1.9-fold higher (P<0.01) in the JF offspring. These findings suggest that perinatal exposure to high-fat, high-sugar diets results in altered development of the central reward system, resulting in increased fat intake and altered response of the reward system to excessive junk-food intake in postnatal life.

  5. 1,2-Dibenzyltetradimethylamido-Dimolybdenum and -Ditungsten (M=M) Compounds and Their Reactions with Carbon Dioxide and 1,3-Diaryltriazines. A Radical Difference.

    DTIC Science & Technology

    1982-07-07

    solution of a mixture of these Mo2- and MoW-containing compounds selectively precipitated the heterobimetallic single elec- tron oxidation product MoW...3.5 and reduction, using 0$ powdered zinc in acetonitrile at 25°C, yielded the heterobimetallic quadruply bonded compound MoW(O2CBu t )4. Katovic, V

  6. Efficient Synthesis of Molecular Precursors for Para-Hydrogen-Induced Polarization of Ethyl Acetate-1-(13) C and Beyond.

    PubMed

    Shchepin, Roman V; Barskiy, Danila A; Coffey, Aaron M; Manzanera Esteve, Isaac V; Chekmenev, Eduard Y

    2016-05-10

    A scalable and versatile methodology for production of vinylated carboxylic compounds with (13) C isotopic label in C1 position is described. It allowed synthesis of vinyl acetate-1-(13) C, which is a precursor for preparation of (13) C hyperpolarized ethyl acetate-1-(13) C, which provides a convenient vehicle for potential in vivo delivery of hyperpolarized acetate to probe metabolism in living organisms. Kinetics of vinyl acetate molecular hydrogenation and polarization transfer from para-hydrogen to (13) C via magnetic field cycling were investigated. Nascent proton nuclear spin polarization (%PH ) of ca. 3.3 % and carbon-13 polarization (%P13C ) of ca. 1.8 % were achieved in ethyl acetate utilizing 50 % para-hydrogen corresponding to ca. 50 % polarization transfer efficiency. The use of nearly 100% para-hydrogen and the improvements of %PH of para-hydrogen-nascent protons may enable production of (13) C hyperpolarized contrast agents with %P13C of 20-50 % in seconds using this chemistry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Reactions of monodithiolene tungsten(VI) sulfido complexes with copper(I) in relation to the structure of the active site of carbon monoxide dehydrogenase.

    PubMed

    Groysman, Stanislav; Majumdar, Amit; Zheng, Shao-Liang; Holm, R H

    2010-02-01

    Reactions directed at the synthesis of structural analogues of the active site of molybdenum-containing carbon monoxide dehydrogenase have been investigated utilizing [WO(2)S(bdt)](2-) (1) and [WOS(2)(bdt)](2-) (2) and sterically hindered [Cu(R)L] or [Cu(SSiR'(3))(2)](-) as reactants. All successful reactions of 2 afford the binuclear W(VI)/Cu(I) products [WO(bdt)(mu(2)-S)(2)Cu(L)](2-/-) with L = carbene (3), Ar*S (4), Ar* (7), SSiR(3) (R = Ph (5), Pr(i) (6)). Similarly, [W(bdt)(OSiPh(3))S(2)](-) leads to [W(bdt)(OSiPh(3))(mu(2)-S)(2)Cu(SAr*)](-) (8). These complexes, with apical oxo and basal dithiolato and sulfido coordination (excluding 8), terminal thiolate ligation at Cu(I) (4-6, 8), and W-(mu(2)-S)-Cu bridging, bear a structural resemblance to the enzyme site. Differences include two bridges instead of one and the absence of basal oxo/hydroxo ligation. Complex 8 differs from the others by utilizing apical and basal sulfido ligands in bridge formation. Related reaction systems based on 1 gave 4 in small yield or product mixtures in which the desired monobridged complex [WO(2)(bdt)(mu(2)-S)Cu(R)](2-) was not detected. Mass spectrometric analysis of the reaction system with L = carbene suggests that any monobridged species forms may converted to the dibridged form by disproportionation. In these experiments, the use of W(VI) preserves the structural integrity of Mo(VI), whose analogues of 1 and 2 have not been isolated. (Ar* = 2,6-bis(2,4,6-triisopropylphenyl)phenyl, bdt = benzene-1,2-dithiolate(2-)).

  8. Characterization of callase (β-1,3-D-glucanase) activity during microsporogenesis in the sterile anthers of Allium sativum L. and the fertile anthers of A. atropurpureum.

    PubMed

    Winiarczyk, Krystyna; Jaroszuk-Ściseł, Jolanta; Kupisz, Kamila

    2012-06-01

    We examined callase activity in anthers of sterile Allium sativum (garlic) and fertile Allium atropurpureum. In A. sativum, a species that produces sterile pollen and propagates only vegetatively, callase was extracted from the thick walls of A. sativum microspore tetrads exhibited maximum activity at pH 4.8, and the corresponding in vivo values ranged from 4.5 to 5.0. Once microspores were released, in vitro callase activity peaked at three distinct pH values, reflecting the presence of three callase isoforms. One isoform, which was previously identified in the tetrad stage, displayed maximum activity at pH 4.8, and the remaining two isoforms, which were novel, were most active at pH 6.0 and 7.3. The corresponding in vivo values ranged from pH 4.75 to 6.0. In contrast, in A. atropurpureum, a sexually propagating species, three callase isoforms, active at pH 4.8-5.2, 6.1, and 7.3, were identified in samples of microsporangia that had released their microspores. The corresponding in vivo value for this plant was 5.9. The callose wall persists around A. sativum meiotic cells, whereas only one callase isoform, with an optimum activity of pH 4.8, is active in the acidic environment of the microsporangium. However, this isoform is degraded when the pH rises to 6.0 and two other callase isoforms, maximally active at pH 6.0 and 7.3, appear. Thus, factors that alter the pH of the microsporangium may indirectly affect the male gametophyte development by modulating the activity of callase and thereby regulating the degradation of the callose wall.

  9. Detection of Supernova Neutrinos on the Earth for Large θ13

    NASA Astrophysics Data System (ADS)

    Xu, Jing; Huang, Ming-Yang; Hu, Li-Jun; Guo, Xin-Heng; Young, Bing-Lin

    2014-02-01

    Supernova (SN) neutrinos detected on the Earth are subject to the shock wave effects, the Mikheyev—Smirnov—Wolfenstein (MSW) effects, the neutrino collective effects and the Earth matter effects. Considering the recent experimental result about the large mixing angle θ13 (≃ 8.8°) provided by the Daya Bay Collaboration and applying the available knowledge for the neutrino conversion probability in the high resonance region of SN, PH, which is in the form of hypergeometric function in the case of large θ13, we deduce the expression of PH taking into account the shock wave effects. It is found that PH is not zero in a certain range of time due to the shock wave effects. After considering all the four physical effects and scanning relevant parameters, we calculate the event numbers of SN neutrinos for the “Garching” distribution of neutrino energy spectrum. From the numerical results, it is found that the behaviors of neutrino event numbers detected on the Earth depend on the neutrino mass hierarchy and neutrino spectrum parameters including the dimensionless pinching parameter βα (where α refers to neutrino flavor), the average energy , and the SN neutrino luminosities Lα. Finally, we give the ranges of SN neutrino event numbers that will be detected at the Daya Bay experiment.

  10. Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

    PubMed

    Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

    2017-12-06

    Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 < MoF 3 < MoF 6 before sharply decreasing for MoF 9 , with a similar effect for the supported systems (MoF 0 ≈ MoF 9 < MoF 6 < MoF 3 ). This is consistent with the different kinetic behavior (zeroth order in alkyne for MoF 9 derivatives instead of first order for the others) and the isolation of stable metallacyclobutadiene intermediates of MoF 9 for both molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

  11. Pelolinea submarina gen. nov., sp. nov., an anaerobic, filamentous bacterium of the phylum Chloroflexi isolated from subseafloor sediment.

    PubMed

    Imachi, Hiroyuki; Sakai, Sanae; Lipp, Julius S; Miyazaki, Masayuki; Saito, Yumi; Yamanaka, Yuko; Hinrichs, Kai-Uwe; Inagaki, Fumio; Takai, Ken

    2014-03-01

    A novel, anaerobic filamentous bacterium, strain MO-CFX1(T), was isolated from a methanogenic community, which was originally established from subseafloor sediments collected from off the Shimokita Peninsula, Japan. Cells were non-spore-forming, non-motile, Gram-stain-negative and filamentous. The filaments were longer than 10 µm and 130-150 nm in width. Growth of the strain was observed at 10-37 °C (optimum 25-30 °C), at pH 5.5-8.5 (optimum pH 7.0) and in 0-50 g NaCl l(-1) (optimum 15 g NaCl l(-1)). The strain was able to grow with a number of carbohydrates in the presence of yeast extract. The major cellular fatty acids were monounsaturated C18 : 1ω9, C16 : 1ω7 and saturated C18 : 0 and C16 : 0. The intact polar lipids of the strain were dominated by diacylglyceride and sphingolipid core lipid structures with monoglycosidic, mixed phosphomonoglycosidic and fatty-acid-modified monoglycosidic polar head groups. The G+C content of the genomic DNA was 52.4 mol%. Based on the comparative 16S rRNA gene sequence analysis, strain MO-CFX1(T) was affiliated with the class Anaerolineae within the phylum Chloroflexi and was most closely related to Leptolinea tardivitalis YMTK-2(T) (sequence identity of 91.0 %). Based on phenotypic and genetic properties of the novel isolate, we propose a novel species representing a new genus Pelolinea submarina gen. nov., sp. nov., for strain MO-CFX1(T) ( = JCM 17238(T), = KCTC 5975(T)). This is the first formal description, to our knowledge, of an isolate of the phylum Chloroflexi from the deep-sea sedimentary environment.

  12. Improved deoxyribozymes for synthesis of covalently branched DNA and RNA.

    PubMed

    Lee, Christine S; Mui, Timothy P; Silverman, Scott K

    2011-01-01

    A covalently branched nucleic acid can be synthesized by joining the 2'-hydroxyl of the branch-site ribonucleotide of a DNA or RNA strand to the activated 5'-phosphorus of a separate DNA or RNA strand. We have previously used deoxyribozymes to synthesize several types of branched nucleic acids for experiments in biotechnology and biochemistry. Here, we report in vitro selection experiments to identify improved deoxyribozymes for synthesis of branched DNA and RNA. Each of the new deoxyribozymes requires Mn²(+) as a cofactor, rather than Mg²(+) as used by our previous branch-forming deoxyribozymes, and each has an initially random region of 40 rather than 22 or fewer combined nucleotides. The deoxyribozymes all function by forming a three-helix-junction (3HJ) complex with their two oligonucleotide substrates. For synthesis of branched DNA, the best new deoxyribozyme, 8LV13, has k(obs) on the order of 0.1 min⁻¹, which is about two orders of magnitude faster than our previously identified 15HA9 deoxyribozyme. 8LV13 also functions at closer-to-neutral pH than does 15HA9 (pH 7.5 versus 9.0) and has useful tolerance for many DNA substrate sequences. For synthesis of branched RNA, two new deoxyribozymes, 8LX1 and 8LX6, were identified with broad sequence tolerances and substantial activity at pH 7.5, versus pH 9.0 for many of our previous deoxyribozymes that form branched RNA. These experiments provide new, and in key aspects improved, practical catalysts for preparation of synthetic branched DNA and RNA.

  13. A Mixed-Valent Molybdenum Monophosphate with a Layer Structure: KMo 3P 2O 14

    NASA Astrophysics Data System (ADS)

    Guesdon, A.; Borel, M. M.; Leclaire, A.; Grandin, A.; Raveau, B.

    1994-03-01

    A new mixed-valent molybdenum monophosphate with a layer structure KMo 3P 2O 14 has been isolated. It crystallizes in the space group P2 1/ m with a = 8.599(2) Å, b = 6.392(2) Å, c = 10.602(1) Å, and β = 111.65(2)°. The layers [Mo 3P 2O 14] ∞ are parallel to (100) and consist of [MoPO 8] ∞ chains running along limitb→ , in which one MoO 6 octahedron alternates with one PO 4 tetrahedron. In fact, four [MoPO 8] ∞ chains share the corners of their polyhedra and the edges of their octahedra, forming [Mo 4P 4O 24] ∞ columns which are linked through MoO 5 bipyramids along limitc→. The K + ions interleaved between these layers are surrounded by eight oxygens, forming bicapped trigonal prisms KO 8. Besides the unusual trigonal bipyramids MoO 5, this structure is also characterized by a tendency to the localization of the electrons, since one octahedral site is occupied by Mo(V), whereas the other octahedral site and the trigonal bipyramid are occupied by Mo(VI). The similarity of this structure with pure octahedral layer structures suggests the possibility of generating various derivatives, and of ion exchange properties.

  14. Replacement of Chromium Electroplating on Gas Turbine Engine Components Using Thermal Spray Coatings

    DTIC Science & Technology

    2005-07-20

    Composition, Wgt % Powder Composition, Wgt % Powder WC/17Co Diamalloy 2005 WC/17Co Metco 73F-NS-1 Cr3C2-20 (Ni,Cr) Amdry 5260/Diam 3007 Co-28 Mo - 8 Cr-2...Si** Metco 66F-NS Co-28 Mo -17 Cr-3 Si* Diamalloy 3001 Co-28 Mo - 8 Cr-2 Si** Diamalloy 3002 * Tribaloy 800 ** Tribaloy 400 20 4.4. Coating...Work WC/17Co Diamalloy 2005 Yes -- Cr3C2-20 (Ni,Cr) Amdry 5260/Diam 3007 -- Yes Co-28 Mo -17 Cr-3 Si* Diamalloy 3001 -- Yes Co-28 Mo - 8 Cr-2 Si

  15. Small-quantity, lipid-based nutrient supplements provided to women during pregnancy and 6 mo postpartum and to their infants from 6 mo of age increase the mean attained length of 18-mo-old children in semi-urban Ghana: a randomized controlled trial12

    PubMed Central

    Arimond, Mary; Vosti, Stephen; Dewey, Kathryn G

    2016-01-01

    Background: Childhood stunting usually begins in utero and continues after birth; therefore, its reduction must involve actions across different stages of early life. Objective: We evaluated the efficacy of small-quantity, lipid-based nutrient supplements (SQ-LNSs) provided during pregnancy, lactation, and infancy on attained size by 18 mo of age. Design: In this partially double-blind, individually randomized trial, 1320 women at ≤20 wk of gestation received standard iron and folic acid (IFA group), multiple micronutrients (MMN group), or SQ-LNS (LNS group) daily until delivery, and then placebo, MMNs, or SQ-LNS, respectively, for 6 mo postpartum; infants in the LNS group received SQ-LNS formulated for infants from 6 to 18 mo of age (endline). The primary outcome was child length by 18 mo of age. Results: At endline, data were available for 85% of 1228 infants enrolled; overall mean length and length-for-age z score (LAZ) were 79.3 cm and −0.83, respectively, and 12% of the children were stunted (LAZ <−2). In analysis based on the intended treatment, mean ± SD length and LAZ for the LNS group (79.7 ± 2.9 cm and −0.69 ± 1.01, respectively) were significantly greater than for the IFA (79.1 ± 2.9 cm and −0.87 ± 0.99) and MMN (79.1 ± 2.9 cm and −0.91 ± 1.01) groups (P = 0.006 and P = 0.009, respectively). Differences were also significant for weight and weight-for-age z score but not head or midupper arm circumference, and the prevalence of stunting in the LNS group was 8.9%, compared with 13.7% in the IFA group and 12.9% in the MMN group (P = 0.12). In analysis based on actual supplement provided at enrollment, stunting prevalences were 8.9% compared with 15.1% and 11.5%, respectively (P = 0.045). Conclusion: Provision of SQ-LNSs to women from pregnancy to 6 mo postpartum and to their infants from 6 to 18 mo of age may increase the child’s attained length by age 18 mo in similar settings. This trial was registered at clinicaltrials.gov as NCT00970866. PMID:27534634

  16. In situ grown Ni9S8 nanorod/O-MoS2 nanosheet nanocomposite on carbon cloth as a free binder supercapacitor electrode and hydrogen evolution catalyst

    NASA Astrophysics Data System (ADS)

    Li, Songzhan; Chen, Tian; Wen, Jian; Gui, Pengbin; Fang, Guojia

    2017-11-01

    Transition metal sulfide nanostructure composites have received significant attention as energy conversion and storage devices. In this work, we report a three-dimension (3D) nanostructure with the Ni9S8 nanorods embedded in oxygen-incorporated MoS2 (O-MoS2) nanosheets for supercapacitors and hydrogen evolution catalysts. The in situ grown Ni9S8/O-MoS2 nanocomposite on carbon cloth can be used as a free binder supercapacitor electrode and hydrogen evolution catalyst. The Ni9S8/O-MoS2 nanocomposite exhibits electrochemical behaviors with a specific capacitance of 907 F g-1 (at 2 A g-1) and good cycle stability after 1200 cycles due to its unique mutual embedding 3D nanostructure. Furthermore, the Ni9S8/O-MoS2 nanocomposite also shows highly electrocatalytic features for hydrogen production with an onset overpotential of ˜150 mV and a low Tafel slope of ˜81 mV dec-1. The oxygen incorporation of MoS2 provides more active sites to participate in the catalytic process for the hydrogen evolution reaction.

  17. Phase behaviour, thermal expansion and compressibility of SnMo2O8

    NASA Astrophysics Data System (ADS)

    Araujo, Luiza R.; Gallington, Leighanne C.; Wilkinson, Angus P.; Evans, John S. O.

    2018-02-01

    The phase behaviour and thermoelastic properties of SnMo2O8, derived from variable temperature and pressure synchrotron powder diffraction data, are reported. SnMo2O8 is a member of the AM2O8 family of negative thermal expansion (NTE) materials, but unexpectedly, has positive thermal expansion. Over the P-T space explored (298-513 K, ambient to 310 MPa) four different forms of SnMo2O8 are observed: α, β, γ and γ‧. The γ to β transition is temperature-, pressure-, and time-dependent. SnMo2O8 is a much softer material (α and γ form have BT = 29 and 26 GPa at 298 K) than other members of the AM2O8 family. Counter-intuitively, its high temperature β phase becomes stiffer with increasing temperature (BT ∼36 GPa at 490 K). The pressure dependence of the thermal expansion for each phase is reported.

  18. Phase behaviour, thermal expansion and compressibility of SnMo 2 O 8

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

    Araujo, Luiza R.; Gallington, Leighanne C.; Wilkinson, Angus P.

    The phase behaviour and thermoelastic properties of SnMo2O8, derived from variable temperature and pressure synchrotron powder diffraction data, are reported. SnMo2O8 is a member of the AM2O8 family of negative thermal expansion (NTE) materials, but unexpectedly, has positive thermal expansion. Over the P-T space explored (298–513 K, ambient to 310 MPa) four different forms of SnMo2O8 are observed: α, β, γ and γ'. The γ to β transition is temperature-, pressure-, and time-dependent. SnMo2O8 is a much softer material (α and γ form have BT = 29 and 26 GPa at 298 K) than other members of the AM2O8 family.more » Counter-intuitively, its high temperature β phase becomes stiffer with increasing temperature (BT ~36 GPa at 490 K). The pressure dependence of the thermal expansion for each phase is reported.« less

  19. Temperature dependent elastic properties of γ-phase U – 8 wt% Mo

    DOE PAGES

    Steiner, M. A.; Garlea, E.; Creasy, J.; ...

    2017-12-28

    Polycrystalline elastic moduli and stiffness tensor components of γ-phase U – 8 wt% Mo have been determined by resonant ultrasound spectroscopy in the temperature range of 25-650°C. The ambient temperature elastic properties are compared to results measured via other experimental methods and show reasonable agreement, though there is considerable variation of these properties within the literature at both the U – 8 wt% Mo composition and as a function of Mo concentration. The Young’s modulus of U – 8 wt% Mo measured in this study decreases steadily with temperature at a rate that is slower than trends previously observed atmore » similar Mo concentrations, though the difference is not statistically significant. This first measurement of the temperature dependent elastic stiffness tensor of a polycrystalline U-Mo alloy clarifies that the behavior of the Young’s modulus is due to a strongly weakening C 11 polycrystalline stiffness tensor component, along with milder decreases in C 12 and C 44. The unique partially auxetic properties recently predicted for singlecrystalline U-Mo are discussed in regard to their possible impact on the polycrystalline behavior of the alloy.« less

  20. Temperature dependent elastic properties of γ-phase U – 8 wt% Mo

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

    Steiner, M. A.; Garlea, E.; Creasy, J.

    Polycrystalline elastic moduli and stiffness tensor components of γ-phase U – 8 wt% Mo have been determined by resonant ultrasound spectroscopy in the temperature range of 25-650°C. The ambient temperature elastic properties are compared to results measured via other experimental methods and show reasonable agreement, though there is considerable variation of these properties within the literature at both the U – 8 wt% Mo composition and as a function of Mo concentration. The Young’s modulus of U – 8 wt% Mo measured in this study decreases steadily with temperature at a rate that is slower than trends previously observed atmore » similar Mo concentrations, though the difference is not statistically significant. This first measurement of the temperature dependent elastic stiffness tensor of a polycrystalline U-Mo alloy clarifies that the behavior of the Young’s modulus is due to a strongly weakening C 11 polycrystalline stiffness tensor component, along with milder decreases in C 12 and C 44. The unique partially auxetic properties recently predicted for singlecrystalline U-Mo are discussed in regard to their possible impact on the polycrystalline behavior of the alloy.« less

  1. Kinetics of Molybdenum Adsorption and Desorption in Soils.

    PubMed

    Sun, Wenguang; Selim, H Magdi

    2018-05-01

    Much uncertainty exists in mechanisms and kinetics controlling the adsorption and desorption of molybdenum (Mo) in the soil environment. To investigate the characteristics of Mo adsorption and desorption and predict Mo behavior in the vadose zone, kinetic batch experiments were performed using three soils: Webster loam, Windsor sand and Mahan sand. Adsorption isotherms for Mo were strongly nonlinear for all three soils. Strong kinetic adsorption of Mo by all soils was also observed, where the rate of retention was rapid initially and was followed by slow retention behavior with time. The time-dependent Mo sorption rate was not influenced when constant pH was maintained. Desorption or release results indicated that there were significant fractions of Mo that appeared to be irreversible or slowly reversibly sorbed by Windsor and Mahan. X-ray absorption near edge structure (XANES) analysis for Windsor and Mahan soils indicated that most of Mo had been bound to kaolinite, whereas Webster had similar XANES features to those of Mo sorbed to montmorillonite. A sequential extraction procedure provided evidence that a significant amount of Mo was irreversibly sorbed. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption parameters was used to describe the adsorption-desorption kinetics of Mo on soils. Our results demonstrated that a formulation of MRM with two sorption sites (equilibrium and reversible) successfully described Mo adsorption-desorption data for Webster loam, and an additional irreversible reaction phase was recommended to describe Mo desorption or release with time for Windsor and Mahan soils. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  2. Core sequence of PAPf39 amyloid fibrils and mechanism of pH-dependent fibril formation: the role of monomer conformation.

    PubMed

    French, Kinsley C; Makhatadze, George I

    2012-12-21

    PAPf39, a 39-residue peptide fragment from human prostatic acidic phosphatase, has been shown to form amyloid fibrils in semen (SEVI), which increase HIV infectivity by up to 5 orders of magnitude. The sequence of the PAPf39 fibrillar core was identified using hydrogen-deuterium exchange (HDX) mass spectrometry and protease protection assays. The central and C-terminal regions are highly protected from HDX and proteolytic cleavage and, thus, are part of the fibrillar core. Conversely, the N-terminal region is unprotected from HDX and proteolytic cleavage, suggesting that it is exposed and not part of the fibrillar core. This finding was tested using two N-terminal truncated variants, PAPf39Δ1-8 and PAPf39Δ1-13. Both variants formed amyloid fibrils at neutral pH. However, these variants showed a markedly different pH dependence of fibril formation versus that of PAPf39. PAPf39 fibrils can form at pH 7.7, but not at pH 5.5 or 2.5, while both N-terminally truncated variants can form fibrils at these pH values. Thus, the N-terminal region is not necessary for fibril formation but modulates the pH dependence of PAPf39 fibril formation. PAPf39Δ1-8 and PAPf39Δ1-13 are capable of seeding PAPf39 fibril formation at neutral pH, suggesting that these variants are structurally compatible with PAPf39, yet no mixed fibril formation occurs between the truncated variants and PAPf39 at low pH. This suggests that pH affects the PAPf39 monomer conformational ensemble, which is supported by far-UV circular dichroism spectroscopy. A conceptual model describing the pH dependence of PAPf39 aggregation is proposed and provides potential biological implications.

  3. Fate and Transport of Molybdenum Disulfide Nanomaterials in Sand Columns

    PubMed Central

    Lanphere, Jacob D.; Luth, Corey J.; Guiney, Linda M.; Mansukhani, Nikhita D.; Hersam, Mark C.; Walker, Sharon L.

    2015-01-01

    Abstract Research and development of two-dimensional transition metal dichalcogenides (TMDC) (e.g., molybdenum disulfide [MoS2]) in electronic, optical, and catalytic applications has been growing rapidly. However, there is little known regarding the behavior of these particles once released into aquatic environments. Therefore, an in-depth study regarding the fate and transport of two popular types of MoS2 nanomaterials, lithiated (MoS2-Li) and Pluronic PF-87 dispersed (MoS2-PL), was conducted in saturated porous media (quartz sand) to identify which form would be least mobile in aquatic environments. The electrokinetic properties and hydrodynamic diameters of MoS2 as a function of ionic strength and pH were determined using a zeta potential analyzer and dynamic light scattering techniques. Results suggest that the stability is significantly decreased beginning at 10 and 31.6 mM KCl, for MoS2-PL and MoS2-Li, respectively. Transport study results from breakthrough curves, column dissections, and release experiments suggest that MoS2-PL exhibits a greater affinity to be irreversibly bound to quartz surfaces as compared with the MoS2-Li at a similar ionic strength. Derjaguin–Landau–Verwey–Overbeek theory was used to help explain the unique interactions between the MoS2-PL and MoS2-Li surfaces between particles and with the quartz collectors. Overall, the results suggest that the fate and transport of MoS2 is dependent on the type of MoS2 that enters the environment, where MoS2-PL will be least mobile and more likely be deposited in porous media from pluronic–quartz interactions, whereas MoS2-Li will travel greater distances and have a greater tendency to be remobilized in sand columns. PMID:25741176

  4. Dependence of Relative Expression of NTR1 and EGFR on Cell Density and Extracellular pH in Human Pancreatic Cancer Cell Lines

    PubMed Central

    Olszewski-Hamilton, Ulrike; Hamilton, Gerhard

    2011-01-01

    Pancreatic adenocarcinoma is a devastating disease characterized by early dissemination and poor prognosis. These solid tumors express receptors for neuropeptides like neurotensin (NT) or epidermal growth factor (EGF) and exhibit acidic regions when grown beyond a certain size. We previously demonstrated increases in intracellular Ca2+ levels, intracellular pH and interleukin-8 (IL-8) secretion in BxPC-3 and PANC-1 pancreatic cancer cells in response to a stable NT analog. The present study aimed at investigation of the dependence of the relative expression of NT receptor 1 (NTR1) and EGFR in BxPC-3 and MIA PaCa-2 cells on cell density and extracellular pH (pHe). MTT assays revealed the NTR1 inhibitor SR 142948-sensitive Lys8-ψ-Lys9NT (8–13)-induced proliferation in BxPC-3 and PANC-1 cells. Confluent cultures of BxPC3 and HT-29 lines exhibited highest expression of NTR1 and lowest of EGFR and expression of NTR1 was maximal at slightly acidic pHe. IL-8 production was stimulated by Lys8-ψ-Lys9NT (8–13) and even enhanced at both acidic and alkaline pHe in BxPC-3 and PANC-1 cells. In conclusion, our in vitro study suggests that one contributing factor to the minor responses obtained with EGFR-directed therapy may be downregulation of this receptor in tumor cell aggregates, possibly resulting in acquisition of a more aggressive phenotype via other growth factor receptors like NTR1. PMID:24212612

  5. Hierarchical Ni-Mo-S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte.

    PubMed

    Miao, Jianwei; Xiao, Fang-Xing; Yang, Hong Bin; Khoo, Si Yun; Chen, Jiazang; Fan, Zhanxi; Hsu, Ying-Ya; Chen, Hao Ming; Zhang, Hua; Liu, Bin

    2015-08-01

    A unique functional electrode made of hierarchal Ni-Mo-S nanosheets with abundant exposed edges anchored on conductive and flexible carbon fiber cloth, referred to as Ni-Mo-S/C, has been developed through a facile biomolecule-assisted hydrothermal method. The incorporation of Ni atoms in Mo-S plays a crucial role in tuning its intrinsic catalytic property by creating substantial defect sites as well as modifying the morphology of Ni-Mo-S network at atomic scale, resulting in an impressive enhancement in the catalytic activity. The Ni-Mo-S/C electrode exhibits a large cathodic current and a low onset potential for hydrogen evolution reaction in neutral electrolyte (pH ~7), for example, current density of 10 mA/cm(2) at a very small overpotential of 200 mV. Furthermore, the Ni-Mo-S/C electrode has excellent electrocatalytic stability over an extended period, much better than those of MoS2/C and Pt plate electrodes. Scanning and transmission electron microscopy, Raman spectroscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy were used to understand the formation process and electrocatalytic properties of Ni-Mo-S/C. The intuitive comparison test was designed to reveal the superior gas-evolving profile of Ni-Mo-S/C over that of MoS2/C, and a laboratory-scale hydrogen generator was further assembled to demonstrate its potential application in practical appliances.

  6. Carbon buffer layers for smoothing superpolished glass surfaces as substrates for molybdenum /silicon multilayer soft-x-ray mirrors.

    PubMed

    Stock, H J; Hamelmann, F; Kleineberg, U; Menke, D; Schmiedeskamp, B; Osterried, K; Heidemann, K F; Heinzmann, U

    1997-03-01

    Zerodur and BK7 glass substrates (developed by Fa. Glaswerke Schott, D-55014 Mainz, Germany) from Carl Zeiss Oberkochen polished to a standard surface roughness of varsigma = 0.8 nm rms were coated with a C layer by electron-beam evaporation in the UHV. The roughness of the C-layer surfaces is reduced to 0.6 nm rms. A normal-incidence reflectance of 50% at a wavelength of 13 nm was measured for a Mo/Si multilayer soft-x-ray mirror with 30 double layers (N = 30) deposited onto the BK7/C substrate, whereas a similar Mo/Si multilayer (N = 30) evaporated directly onto the bare BK7 surface turned out to show a reflectance of only 42%.

  7. Calculation of correlation times for the. gamma. -alumina-supported molybdenum subcarbonyl, Mo(CO) sub 3 (ads)

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

    Wagner, G.W.; Hanson, B.E.

    1989-07-05

    The theory of carbon-13 NMR line widths in the solid state for molecules with large chemical shift anisotropies is applied to the adsorbed molybdenum subcarbonyls Mo(CO){sub 3}(ads) and Mo(CO){sub 5}(ads). Correlation times for the rotation of the molybdenum subcarbonyl groups Mo(CO){sub 3}(ads) and Mo(CO){sub 5}(ads) on partially dehydroxylated alumina are calculated. Good agreement is obtained between data reported at observation frequencies of 15 to 75.5 MHz for carbon-13 for Mo(CO){sub 3}(ads). The correlation time for this adsorbed species is calculated to have a lower limit of 4.6 {plus minus} 0.5 ms. The presence of broad lines in the room temperaturemore » spectra for Mo(CO){sub 3}(ads) is thus explained by a slow molecular motion. Data for Mo(CO){sub 5}(ads) are available at observation frequencies of 15 to 90.5 MHz. A good fit to the experimental data is obtained assuming either long or short correlation times for this species. Thus literature estimates of <10{sup {minus}6}s for the correlation time for this species cannot be confirmed with certainty from the analysis presented here.« less

  8. Electronic and steric influences of pendant amine groups on the protonation of molybdenum bis (dinitrogen) complexes

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

    Labios, Liezel A.; Heiden, Zachariah M.; Mock, Michael T.

    2015-05-04

    The synthesis of a series of P EtP NRR' (P EtP NRR' = Et₂PCH₂CH₂P(CH₂NRR')₂, R = H, R' = Ph or 2,4-difluorophenyl; R = R' = Ph or iPr) diphosphine ligands containing mono- and disubstituted pendant amine groups, and the preparation of their corresponding molybdenum bis(dinitrogen) complexes trans-Mo(N₂)₂(PMePh₂)₂(P EtP NRR') is described. In situ IR and multinuclear NMR spectroscopic studies monitoring the stepwise addition of (HOTf) to trans-Mo(N₂)₂(PMePh₂)₂(P EtP NRR') complexes in THF at -40 °C show that the electronic and steric properties of the R and R' groups of the pendant amines influence whether the complexes are protonated atmore » Mo, a pendant amine, a coordinated N2 ligand, or a combination of these sites. For example, complexes containing mono-aryl substituted pendant amines are protonated at Mo and pendant amine to generate mono- and dicationic Mo–H species. Protonation of the complex containing less basic diphenyl-substituted pendant amines exclusively generates a monocationic hydrazido (Mo(NNH₂)) product, indicating preferential protonation of an N₂ ligand. Addition of HOTf to the complex featuring more basic diisopropyl amines primarily produces a monocationic product protonated at a pendant amine site, as well as a trace amount of dicationic Mo(NNH₂) product that contain protonated pendant amines. In addition, trans-Mo(N₂)₂(PMePh₂)₂(depe) (depe = Et₂PCH₂CH₂PEt₂) without a pendant amine was synthesized and treated with HOTf, generating a monocationic Mo(NNH₂) product. Protonolysis experiments conducted on select complexes in the series afforded trace amounts of NH₄⁺. Computational analysis of the series of trans-Mo(N₂)₂(PMePh₂)₂(P EtP NRR') complexes provides further insight into the proton affinity values of the metal center, N₂ ligand, and pendant amine sites to rationalize the differing reactivity profiles. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Computational resources provided by the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

  9. A General Approach to Access Morphologies of Polyoxometalates in Solution by Using SAXS: An Ab Initio Modeling Protocol.

    PubMed

    Li, Mu; Wang, Weiyu; Yin, Panchao

    2018-05-02

    Herein, we reported a general protocol for an ab initio modeling approach to deduce structure information of polyoxometalates (POMs) in solutions from scattering data collected by the small-angle X-ray scattering (SAXS) technique. To validate the protocol, the morphologies of a serious of known POMs in either aqueous or organic solvents were analyzed. The obtained particle morphologies were compared and confirmed with previous reported crystal structures. To extend the feasibility of the protocol to an unknown system of aqueous solutions of Na 2 MoO 4 with the pH ranging from -1 to 8.35, the formation of {Mo 36 } clusters was probed, identified, and confirmed by SAXS. The approach was further optimized with a multi-processing capability to achieve fast analysis of experimental data, thereby, facilitating in situ studies of formations of POMs in solutions. The advantage of this approach is to generate intuitive 3D models of POMs in solutions without confining information such as symmetries and possible sizes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Toward low friction in water for Mo2N/Ag coatings by tailoring the wettability

    NASA Astrophysics Data System (ADS)

    Dai, Xuan; Wen, Mao; Huang, Keke; Wang, Xin; Yang, Lina; Wang, Jia; Zhang, Kan

    2018-07-01

    Increasing demands for robust surfaces in harsh conditions, such as erosion, abrasion and sea-water, has stimulated the development of self-lubricated protective coatings. Meanwhile, due to the oil crisis, research in water lubrication again attracts much attention from both academics and practical engineers. Here, a higher hydrophilicity accompanying with a remarkable drop of friction coefficient in water environment was achieved successfully in Mo2N/Ag coatings by increasing Ag content. To do these, the Mo2N/Ag coatings with different Ag content were deposited by co-sputtering, which exhibit a nanocomposite structure consisting of precipitate Ag embedded in the Mo2N matrix. The high hydrophilicity can be ascribed to the combined contributions of the partial oxidation of Mo2N and high polarity of Ag precipitates. The decrease of friction coefficient is illustrated by the colloidal friction products and a mode with electric double layer. In which, enhanced hydrophilicity will result in forming a thin "water film" layer between the interface of counterpart and the coatings. And the MoOx/Ag2Mo4O13 derived from the hydrolysis action of Mo2N/Ag sliding in water could function as lubricant phase. Meanwhile, these negative charged MoOx/Ag2Mo4O13 colloidal particles induce the rearrangement of positive ions in the "water film" and form an electric double layer, which also contributes to the decrease of friction coefficient.

  11. Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

    NASA Astrophysics Data System (ADS)

    Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

    2015-03-01

    We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

  12. Whole-genome scan to detect quantitative trait loci associated with milk protein composition in 3 French dairy cattle breeds.

    PubMed

    Sanchez, M P; Govignon-Gion, A; Ferrand, M; Gelé, M; Pourchet, D; Amigues, Y; Fritz, S; Boussaha, M; Capitan, A; Rocha, D; Miranda, G; Martin, P; Brochard, M; Boichard, D

    2016-10-01

    In the context of the PhénoFinLait project, a genome-wide analysis was performed to detect quantitative trait loci (QTL) that affect milk protein composition estimated using mid-infrared spectrometry in the Montbéliarde (MO), Normande (NO), and Holstein (HO) French dairy cattle breeds. The 6 main milk proteins (α-lactalbumin, β-lactoglobulin, and αS1-, αS2-, β-, and κ-caseins) expressed as grams per 100g of milk (% of milk) or as grams per 100g of protein (% of protein) were estimated in 848,068 test-day milk samples from 156,660 cows. Genotyping was performed for 2,773 MO, 2,673 NO, and 2,208 HO cows using the Illumina BovineSNP50 BeadChip (Illumina Inc., San Diego, CA). Individual test-day records were adjusted for environmental effects and then averaged per cow to define the phenotypes analyzed. Quantitative trait loci detection was performed within each breed using a linkage disequilibrium and linkage analysis approach. A total of 39 genomic regions distributed on 20 of the 29 Bos taurus autosomes (BTA) were significantly associated with milk protein composition at a genome-wide level of significance in at least 1 of the 3 breeds. The 9 most significant QTL were located on BTA2 (133 Mbp), BTA6 (38, 47, and 87 Mbp), BTA11 (103 Mbp), BTA14 (1.8 Mbp), BTA20 (32 and 58 Mbp), and BTA29 (8 Mbp). The BTA6 (87 Mbp), BTA11, and BTA20 (58 Mbp) QTL were found in all 3 breeds, and they had highly significant effects on κ-casein, β-lactoglobulin, and α-lactalbumin, expressed as a percentage of protein, respectively. Each of these QTL explained between 13% (BTA14) and 51% (BTA11) of the genetic variance of the trait. Many other QTL regions were also identified in at least one breed. They were located on 14 additional chromosomes (1, 3, 4, 5, 7, 15, 17, 19, 21, 22, 24, 25, 26, and 27), and they explained 2 to 8% of the genetic variance of 1 or more protein composition traits. Concordance analyses, performed between QTL status and sequence-derived polymorphisms from 13 bulls, revealed previously known causal polymorphisms in LGB (BTA11) and GHR (BTA20 at 32 Mbp) and excluded some other previously described mutations. These results constitute a first step in identifying causal mutations and using routinely collected mid-infrared predictions in future genomic selection programs to improve bovine milk protein composition. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  13. Micronutrients (B, Co, Cu, Fe, Mn, Mo, and Zn) content in made tea (Camellia sinensis L.) and tea infusion with health prospect: A critical review.

    PubMed

    Karak, Tanmoy; Kutu, Funso Raphael; Nath, Jyoti Rani; Sonar, Indira; Paul, Ranjit Kumar; Boruah, Romesh Kumar; Sanyal, Sandip; Sabhapondit, Santanu; Dutta, Amrit Kumar

    2017-09-22

    Tea (Camellia sinensis L.) is a perennial acidophilic crop, and known to be a nonalcoholic stimulating beverage that is most widely consumed after water. The aim of this review paper is to provide a detailed documentation of selected micronutrient contents, viz. boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), and zinc (Zn) in made tea and tea infusion. Available data from the literature were used to calculate human health aspect associated with the consumption of tea infusion. A wide range of micronutrients reported in both made tea and tea infusion could be the major sources of micronutrients for human. The content of B, Co, Cu, Fe, Mn, Mo, and Zn in made tea are ranged from 3.04 to 58.44 μg g -1 , below detectable limit (BDL) to 122.4 μg g -1 , BDL to 602 μg g -1 , 0.275 to 13,040 μg g -1 , 0.004 to 15,866 μg g -1 , 0.04 to 570.80 μg g -1 and 0.01 to 1120 μg g -1 , respectively. Only 3.2 μg L -1 to 7.25 mg L -1 , 0.01 μg L -1 to 7 mg L -1 , 3.80 μg L -1 to 6.13 mg L -1 , 135.59 μg L -1 -11.05 mg L -1 , 0.05 μg L -1 to 1980.34 mg L -1 , 0.012 to 3.78 μg L -1 , and 1.12 μg L -1 to 2.32 μg L -1 of B, Co, Cu, Fe, Mn, Mo, and Zn, respectively, are found in tea infusion which are lower than the prescribed limit of micronutrients in drinking water by World Health Organization. Furthermore, micronutrient contents in tea infusion depend on infusion procedure as well as on the instrument used for analysis. The proportion of micronutrients found in different tea types are 1.0-88.9% for B, 10-60% for Co, 2.0-97.8% for Cu, 67.8-89.9% for Fe, 71.0-87.4% for Mn, 13.3-34% for Mo, and 34.9-83% for Zn. From the results, it can also be concluded that consumption of three cups of tea infusion per day does not have any adverse effect on human health with respect to the referred micronutrients rather got beneficial effects to human.

  14. New Composites LnBDC@AC and CB[6]@AC: From Design toward Selective Adsorption of Methylene Blue or Methyl Orange

    PubMed Central

    Santos, Guilherme de C.; Barros, Amanda L.; de Oliveira, Carlos A. F.; da Luz, Leonis L.; da Silva, Fausthon F.; Demets, Grégoire J.-F.; Alves Júnior, Severino

    2017-01-01

    New porous composites LnBDC@AC (AC = Activated carbon, Ln = Eu and Gd and BDC = 1,4-benzenedicaboxylate) and CB[6]@AC (CB[6] = Cucurbit[6]uril) were obtained using hydrothermal route. The LnBDC and CB[B] are located inside the pore of the carbon materials as was observed in SEM-EDS, XRPD and FT-IR analysis. Porosimetry analysis showed values typically between AC and LnBDC material, with pore size and surface area, respectively, 29,56 Å and 353.98 m2g-1 for LnBDC@AC and 35,53 Å and 353.98 m2g-1 for CB[6]@AC. Both materials showed good absorptive capacity of metil orange (MO) and methylene blue (MB) with selectivity as a function of pH. For acid pH, both materials present selectivity by MB and alkaline pH for MO, with notable performance for CB[6]@AC. Additionally, europium luminescence was used as structural probe to investigate the coordination environment of Eu3+ ions in the EuBDC@AC composite after adsorption experiment. PMID:28107440

  15. Effects of chloride ion concentration and pH values on the corrosion behavior of Cr12Ni3Co12Mo4W ultra-high-strength martensitic stainless steel

    NASA Astrophysics Data System (ADS)

    Li, Hui-yan; Dong, Chao-fang; Xiao, Kui; Li, Xiao-gang; Zhong, Ping

    2016-11-01

    The effects of Cl- ion concentration and pH values on the corrosion behavior of Cr12Ni3Co12Mo4W ultra-high-strength martensitic stainless steel (UHSMSS) were investigated by a series of electrochemical tests combined with observations by stereology microscopy and scanning electron microscopy. A critical Cl- ion concentration was found to exist (approximately 0.1wt%), above which pitting occurred. The pitting potential decreased with increasing Cl- ion concentration. A UHSMSS specimen tempered at 600°C exhibited a better pitting corrosion resistance than the one tempered at 400°C. The corrosion current density and passive current density of the UHSMSS tempered at 600°C decreased with increasing pH values of the corrosion solution. The pits developed a shallower dish geometry with increasing polarization potential. A lacy cover on the pits of the UHSMSS tempered at 400°C accelerated pitting, whereas corrosion products deposited in the pits of the UHSMSS tempered at 600°C hindered pitting.

  16. Scientific Basis for Paint Stripping Mechanism for Methylene Chloride Based Paint Removers

    DTIC Science & Technology

    2011-09-01

    2011 Young Han, Ph.D NAVAIR Materials Engineering Division Report Documentation Page Form ApprovedOMB No. 0704-0188 Public reporting burden...11. SPONSOR/MONITOR’S REPORT NUMBER(S) 12. DISTRIBUTION/AVAILABILITY STATEMENT Approved for public release, distribution unlimited 13...8-1 8.1 List of Scientific/Technical Publications

  17. Pulmonary hypertension in idiopathic pulmonary fibrosis does not influence six-minute walk distance: results from a retrospective study.

    PubMed

    Harari, Sergio; Caminati, Antonella; Cassandro, Roberto; Conti, Sara; Madotto, Fabiana; Luisi, Francesca; Cesana, Giancarlo

    2015-01-05

    The characteristics of the six-minute walk test (6MWT) in patients with idiopathic pulmonary fibrosis (IPF) and pulmonary hypertension (PH) have not yet been described; nevertheless, this test has already been used as a "surrogate end point" in some clinical trials. Goal of this retrospective study was to assess whether the presence of PH in patients with IPF might influence 6MWT performances. We retrospectively reviewed the data of patients with IPF who were referred to our hospital. The study population was divided in two groups according to the presence or absence of PH at right heart catheterization; then, the six-minute walking distance (6MWD) and pulmonary function tests (PFTs) were compared between groups. Study population included 30 IPF patients with a mean age of 59.0 years (± 8.3), most of whom (76.7%) were males. A total of 43.3% of patients had PH. PFTs data were similar in IPF patients of the two groups; the only exception was FVC, which was significantly higher in IPF patients with PH (63.8% ± 16.0 vs. 51.6% ± 13.8 in patients without PH, p<0.05). No difference was detected between groups in 6MWD (222.3m ± 118.5 in PH group and 222.1m ± 118.5 in non-PH group, p>0.05). Our data suggested that 6MWD does not differ between IPF patients with or without PH. Thus, 6MWD should not be used as a surrogate endpoint in clinical study in patients affected by IPF and PH.

  18. 76 FR 22166 - Manufacturers Railway Company-Discontinuance Exemption-in St. Louis County, MO

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-20

    ... DEPARTMENT OF TRANSPORTATION Surface Transportation Board [Docket No. AB-1075X] Manufacturers Railway Company--Discontinuance Exemption--in St. Louis County, MO AGENCY: Surface Transportation Board... Mississippi River flood wall on the east to U.S. Interstate 55 on the west, in St. Louis, MO. On April 13...

  19. Eight RGS and RGS-like Proteins Orchestrate Growth, Differentiation, and Pathogenicity of Magnaporthe oryzae

    PubMed Central

    Zhang, Haifeng; Tang, Wei; Liu, Kaiyue; Huang, Qian; Zhang, Xin; Yan, Xia; Chen, Yue; Wang, Jiansheng; Qi, Zhongqiang; Wang, Zhengyi; Zheng, Xiaobo; Wang, Ping; Zhang, Zhengguang

    2011-01-01

    A previous study identified MoRgs1 as an RGS protein that negative regulates G-protein signaling to control developmental processes such as conidiation and appressorium formation in Magnaporthe oryzae. Here, we characterized additional seven RGS and RGS-like proteins (MoRgs2 through MoRgs8). We found that MoRgs1 and MoRgs4 positively regulate surface hydrophobicity, conidiation, and mating. Indifference to MoRgs1, MoRgs4 has a role in regulating laccase and peroxidase activities. MoRgs1, MoRgs2, MoRgs3, MoRgs4, MoRgs6, and MoRgs7 are important for germ tube growth and appressorium formation. Interestingly, MoRgs7 and MoRgs8 exhibit a unique domain structure in which the RGS domain is linked to a seven-transmembrane motif, a hallmark of G-protein coupled receptors (GPCRs). We have also shown that MoRgs1 regulates mating through negative regulation of Gα MoMagB and is involved in the maintenance of cell wall integrity. While all proteins appear to be involved in the control of intracellular cAMP levels, only MoRgs1, MoRgs3, MoRgs4, and MoRgs7 are required for full virulence. Taking together, in addition to MoRgs1 functions as a prominent RGS protein in M. oryzae, MoRgs4 and other RGS and RGS-like proteins are also involved in a complex process governing asexual/sexual development, appressorium formation, and pathogenicity. PMID:22241981

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

    Mabruri, Efendi, E-mail: effe004@lipi.go.id; Anwar, Moch Syaiful, E-mail: moch.syaiful.anwar@lipi.go.id; Prifiharni, Siska, E-mail: siska.prifiharni@lipi.go.id

    This paper reports the influence of Mo and Ni on the tensile properties of the modified 13Cr martensitic stainless steels in tempered condition. Four steels with different content of Mo and Ni were prepared by induction melting followed by hot forging, quenching and tempering. The experimental results showed that the addition of about 1% and 3% Mo has a beneficial effect to increase both the tensile strength and the elongation of the steels. On the contrary, the addition of about 3% Ni into the martensitic stainless steel results in decreasing of both the tensile strength and the elongation. Among themore » alloys investigated the 13Cr3Mo type steel exhibited largest tensile strength of 1348 MPa and largest elongation of 12%. The observation on the tensile fractured surfaces by using scanning electron microscope supported these findings.« less

  1. Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

    PubMed

    Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

    2001-10-22

    The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

  2. Decreased first trimester PAPP-A is a predictor of adverse pregnancy outcome.

    PubMed

    Yaron, Yuval; Heifetz, Sigal; Ochshorn, Yifat; Lehavi, Ofer; Orr-Urtreger, Avi

    2002-09-01

    Low levels of maternal serum pregnancy associated plasma protein-A (PAPP-A) have been linked to chromosome anomalies such as trisomy 21, 13 and 18, triploidy and sex chromosome aneuploidy. Low levels of PAPP-A have also been implicated in spontaneous miscarriage. The purpose of this study was to evaluate whether low levels of first trimester PAPP-A are predictive of other adverse pregnancy outcomes. The study included patients with singleton pregnancies who underwent combined first trimester screening using nuchal translucency (NT) and maternal serum free beta-human chorionic gonadotrophin (free beta-hCG) and PAPP-A at 10-13 weeks' gestation. Patients with chromosome aberrations or fetal anomalies were excluded. Serum marker levels were expressed as gestational age-specific multiples of the median (MoMs). The incidences of various adverse pregnancy outcomes (spontaneous preterm labor, fetal growth restriction (FGR), proteinuric and non-proteinuric pregnancy induced hypertension (PIH), intrauterine fetal demise, oligohydramnios, spontaneous miscarriage and placental abruption) were evaluated, according to maternal PAPP-A MoM levels. Of the 1622 patients in the study, pregnancy complications were observed in 184 (11.3%). Patients with PAPP-A < or =0.25 MoM had significantly higher rates of FGR (RR = 3.12), proteinuric PIH (RR = 6.09), spontaneous miscarriage (RR = 8.76). No statistically significant differences were noted for other adverse outcomes evaluated Women with PAPP-A < or =0.50 MoM also had significantly higher rates of FGR (RR = 3.30) and spontaneous miscarriage (RR = 3.78). We conclude that decreased levels of first trimester maternal serum PAPP-A are predictive not only of chromosome anomalies but also of adverse pregnancy outcome. Copyright 2002 John Wiley & Sons, Ltd.

  3. Grouping Parturients by Parity, Previous-Cesarean, and Mode of Delivery (P-C-MoD Classification) Better Identifies Groups at Risk for Postpartum Hemorrhage.

    PubMed

    Reichman, Orna; Gal, Micahel; Sela, Hen Y; Khayyat, Izzat; Emanuel, Michael; Samueloff, Arnon

    2016-10-01

    Objective We aimed to create a clinical classification to better identify parturients at risk for postpartum hemorrhage (PPH). Method A retrospective cohort, including all women who delivered at a single tertiary care medical center, between 2006 and 2014. Parturients were grouped by parity and history of cesarean delivery (CD): primiparas, multipara, and multipara with previous CD. Each were further subgrouped by mode of delivery (spontaneous vaginal delivery [SVD], operative vaginal delivery [OVD], emergency or elective CD). In all, 12 subgroups, based on parity, previous cesarean, and mode of delivery, formed the P-C-MoD classification. PPH was defined as a decrease of ≥3 gram% hemoglobin from admission and/or transfusion of blood products. Univariate analysis followed by multivariate analysis was performed to assess risk for PPH, controlling for confounders. Results The crude rate of PPH among 126,693 parturients was 7%. The prevalence differed significantly among independent risk factors: primiparity, 14%; multiparity, 4%; OVD, 22%; and CD, 15%. The P-C-MoD classification, segregated better between parturients at risk for PPH. The prevalence of PPH was highest for primiparous undergoing OVD (27%) compared with multiparous with SVD (3%), odds ratio [OR] = 12.8 (95% confidence interval [CI],11.9-13.9). These finding were consistent in the multivariate analysis OR = 13.1 (95% CI,12.1-14.3). Conclusion Employing the P-C-MoD classification more readily identifies parturients at risk for PPH and is superior to estimations based on single risk factors. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

  4. Orbital metastases in Italy

    PubMed Central

    Magliozzi, Patrizio; Strianese, Diego; Bonavolontà, Paola; Ferrara, Mariantonia; Ruggiero, Pasquale; Carandente, Raffaella; Bonavolontà, Giulio; Tranfa, Fausto

    2015-01-01

    AIM To describe a series of Italian patients with orbital metastasis focusing on the outcomes in relation to the different primary site of malignancy. METHODS Retrospective chart review of 93 patients with orbital metastasis collected in a tertiary referral centre in a period of 38y and review of literature. RESULTS Out of 93 patients, 52 were females and 41 were males. Median age at diagnosis was 51y (range 1 to 88y). The patients have been divided into four groups on the basis of the year of diagnosis. The frequency of recorded cases had decreased significantly (P<0.05) during the last 9.5y. Primary tumor site was breast in 36 cases (39%), kidney in 10 (11%), lung in 8 (9%), skin in 6 (6%); other sites were less frequent. In 16 case (17%) the primary tumor remained unknown. The most frequent clinical findings were proptosis (73%), limited ocular motility (55%), blepharoptosis (46%) and blurred vision (43%). The diagnosis were established by history, ocular and systemic evaluation, orbital imaging studies and open biopsy or fine needle aspiration biopsy (FNAB). Treatment included surgical excision, irradiation, chemotherapy, hormone therapy, or observation. Ninety-one percent of patients died of metastasis with an overall mean survival time (OMST) after the orbital diagnosis of 13.5mo. CONCLUSION Breast, kidney and lung are the most frequent primary sites of cancer leading to an orbital metastasis. When the primary site is unknown, gastrointestinal tract should be carefully investigated. In the last decade a decrease in the frequency of orbital metastasis has been observed. Surgery provides a local palliation. Prognosis remains poor with a OMST of 13.5mo ranging from the 3mo in the lung cancer to 24mo in the kidney tumor. PMID:26558220

  5. Fish consumption during pregnancy, prenatal mercury exposure, and anthropometric measures at birth in a prospective mother-infant cohort study in Spain.

    PubMed

    Ramón, Rosa; Ballester, Ferran; Aguinagalde, Xabier; Amurrio, Ascensión; Vioque, Jesús; Lacasaña, Marina; Rebagliato, Marisa; Murcia, Mario; Iñiguez, Carmen

    2009-10-01

    Birth size has been shown to be related to maternal fish intake, although the results are inconsistent. The objective was to assess the association of consumption of different types of fish and prenatal mercury exposure with birth weight, birth length, and classification as small for gestational age (SGA) in newborns. Cord blood total mercury was measured in 554 newborns in a population-based cohort born from 2004 to 2006. Fish consumption was classified in 4 frequency categories (<1 portion/mo, 1-3 portions/mo, 1 portion/wk, and > or =2 portions/wk). When multivariate models were adjusted, newborns in the higher quartile of total mercury weighed 143.7 g less (95% CI: -251.8, -35.6; P for trend = 0.02) and had higher odds of being SGA for length (odds ratio: 5.3; 95% CI: 1.2, 23.9; P from likelihood ratio test = 0.03) without a linear relation (P for trend = 0.13) compared with those in the lowest quartile. Mothers consuming >/=2 portions/wk of canned tuna had newborns who weighed more than those who consumed <1 portion/mo (P for trend = 0.03) and a lower risk of having infants who were SGA for weight (P for trend = 0.01). Consumption of > or =2 portions/wk of large oily fish was associated with a higher risk of being SGA for weight and consumption of lean fish with a lower risk of being SGA for length compared with the consumption of <1 portion/mo, but in neither case was there a linear relation (P for trend >0.05). The role of fish in fetal growth depends on the amount and type of fish consumed. The findings for mercury warrant further investigation in other settings.

  6. A Solution-Based Approach for Mo-99 Production: Considerations for Nitrate versus Sulfate Media

    DOE PAGES

    Youker, Amanda J.; Chemerisov, Sergey D.; Kalensky, Michael; ...

    2013-01-01

    Molybdenum-99 is the parent of Technetium-99m, which is used in nearly 80% of all nuclear medicine procedures. The medical community has been plagued by Mo-99 shortages due to aging reactors, such as the NRU (National Research Universal) reactor in Canada. There are currently no US producers of Mo-99, and NRU is scheduled for shutdown in 2016, which means that another Mo-99 shortage is imminent unless a potential domestic Mo-99 producer fills the void. Argonne National Laboratory is assisting two potential domestic suppliers of Mo-99 by examining the effects of a uranyl nitrate versus a uranyl sulfate target solution configuration onmore » Mo-99 production. Uranyl nitrate solutions are easier to prepare and do not generate detectable amounts of peroxide upon irradiation, but a high radiation field can lead to a large increase in pH, which can lead to the precipitation of fission products and uranyl hydroxides. Uranyl sulfate solutions are more difficult to prepare, and enough peroxide is generated during irradiation to cause precipitation of uranyl peroxide, but this can be prevented by adding a catalyst to the solution. A titania sorbent can be used to recover Mo-99 from a highly concentrated uranyl nitrate or uranyl sulfate solution; however, different approaches must be taken to prevent precipitation during Mo-99 production.« less

  7. Tellurite‐Squarate Driven Assembly of a New Family of Nanoscale Clusters Based on (Mo2O2S2)2+

    PubMed Central

    Purcell, Jamie W.; Miras, Haralampos N.; Long, De‐Liang; Markopoulou, Panagiota

    2017-01-01

    Abstract The preparation and characterization of a new family of four polyoxothiometalate (POTM) clusters are reported, with varying size and complexity, based upon the dimeric [Mo2O2S2(H2O)6]2+ cation with the general formula (NMe4)aKb[(Mo2O2S2)c(TeO4)d(C4O4)e(OH)f] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo28Te2}; {2,26,36,12,10,48}=2, {Mo72Te12}; {0,11,15,3,3,21}=3, {Mo30Te3}; {2,6,12,2,4,16}=4, {Mo24Te2}. The incorporation of tellurite anions allowed the fine tuning of the templating and bridging of the available building blocks, leading to new topologies of increased complexity. The structural diversity of this family of compounds ranges from the highly symmetrical cross‐shaped {Mo24Te2} to the stacked ring structure of {Mo72Te12}, which is the largest tellurium‐containing POTM cluster reported so far. Also a detailed experimental analysis revealed that the pH isolation window extends from acidic to basic values. ESI‐MS analyses not only confirmed the stability of this family in solution but also revealed the stability of the observed virtual building blocks. PMID:28548217

  8. Interpreting the role of pH on stable isotopes in large benthic foraminifera

    USGS Publications Warehouse

    Robbins, Lisa L.; Knorr, P.O.; Wynn, J.G.; Hallock, P.; Harries, P.

    2016-01-01

    Large benthic foraminifera (LBF) are prolific producers of calcium carbonate sediments in shallow, tropical environments that are being influenced by ocean acidification (OA). Two LBF species, Amphistegina gibbosa (Order Rotaliida) with low-Mg calcite tests and Archaias angulatus (Order Miliolida) with high-Mg calcite tests, were studied to assess the effects of pH 7.6 on oxygen and carbon isotopic fractionation between test calcite and ambient seawater. The δ18O and δ13C values of terminal chambers and of whole adult tests of both species after 6 weeks were not significantly different between pH treatments of 8.0 and 7.6. However, tests of juveniles produced during the 6-week treatments showed significant differences between δ18O and δ13C values from control (pH 8.0) when compared with the treatment (pH 7.6) for both species. Although each individual's growth was photographed and measured, difficulty in distinguishing and manually extracting newly precipitated calcite from adult specimens likely confounded any differences in isotopic signals. However, juvenile specimens that resulted from asexual reproduction that occurred during the experiments did not contain old carbonate that could confound the new isotopic signals. These data reveal a potential bias in the design of OA experiments if only adults are used to investigate changes in test chemistries. Furthermore, the results reaffirm that different calcification mechanisms in these two foraminiferal orders control the fractionation of stable isotopes in the tests and will reflect decreasing pH in seawater somewhat differently. .

  9. High magnetic field magnetization of a new triangular lattice antiferromagnet

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

    Zhou, H. D.; Stritzinger, Laurel Elaine Winter; Harrison, Neil

    2017-03-23

    In CsV(MoO 4) 2, the magnetic V 3+ ions with octahedral oxygen-coordination form a geometrically frustrated triangular lattice. So fare, there is no magnetic properties reported on it. Recently, we successfully grew single crystals of CsV(MoO 4) 2 by using flux method. The susceptibility shows a sharp drop around 24 K, representing a long range magnetic ordering. To understand the physical properties of this new triangular lattice antiferromagnet (TLAF), we pursued high field magnetization measurements to answer two questions: (i) what is the saturation field, which will be very useful to calculate the exchange interaction of the system? (ii) Willmore » it exhibit spin state transition, such as the up up down phase with 1/3-saturation moment as other TLAFs? Recently, we performed VSM measurements in Cell 8, Tallahassee, NHMFL, the results show that the magnetization reaches 0.38 MuB at 34 T, which is just 19% of the full moment of 2 MuB for V 3+ (3d 2) ions. Apparently we need higher field to reach 1/3 value or full moment.« less

  10. The Mesozoic Caosiyao giant porphyry Mo deposit in Inner Mongolia, North China and Paleo-Pacific subduction-related magmatism in the northern North China Craton

    NASA Astrophysics Data System (ADS)

    Wu, Huaying; Zhang, Lianchang; Pirajno, Franco; Shu, Qihai; Zhang, Min; Zhu, Mingtian; Xiang, Peng

    2016-09-01

    The Caosiyao giant porphyry Mo deposit is located in the Wulanchabu area of Inner Mongolia, within the northern North China Craton (NCC). It contains more than 2385 Mt of ore with an average grade of 0.075% Mo. In the Caosiyao mining district, Mo mineralization occurs mainly in a Mesozoic granite porphyry as disseminations and stockworks, with some Mo distributed in Archean metamorphic rocks and diabase as stockworks and veins. The host granite porphyry is composed of two different phases that can be distinguished based on mineral assemblages and textures: one phase contains large and abundant phenocrysts (coarse-grained), while the other phase is characterized by fewer and smaller phenocrysts (medium-grained). Zircon U-Pb-Hf analyses of the former phase yielded a concordant 206Pb/238U age of 149.8 ± 2.4 Ma with a 206Pb/238U weighted mean age of 149.9 ± 2.4 Ma and εHf(t) values ranging from -12.2 to 18.3, while the latter phase gave a concordant 206Pb/238U age of 149.0 ± 2.2 Ma with a 206Pb/238U weighted mean age of 149.0 ± 2.1 Ma and εHf(t) values ranging from -13.1 to 17.7. Five samples of disseminated molybdenite have a 187Re-187Os isochron age of 149.5 ± 5.3 Ma with a weighted average age of 149.0 ± 1.8 Ma, whereas six veinlet-type molybdenite samples have a well-constrained 187Re-187Os isochron age of 146.9 ± 3.1 Ma and a weighted average age of 146.5 ± 0.8 Ma. Thus, it is suggested that the Mo mineralization of the Caosiyao deposit occurred during the Late Jurassic (ca. 147-149 Ma), almost coeval with the emplacement of the host granite porphyry (ca. 149-150 Ma). The host granite porphyry is characterized by high silica (SiO2 = 71.52-74.10 wt%), relatively high levels of oxidation (Fe2O3/FeO = 0.32-0.94 wt%) and high alkali element concentrations (Na2O + K2O = 8.21-8.76 wt%). The host granite porphyry also shows enrichments in U and K, and depletion in Ba, Sr, P, Eu, and Ti, suggesting strong fractional crystallization of plagioclase, biotite, and accessory minerals. These observations, together with high SiO2 contents and a high differentiation index (DI = 89.04-92.44), indicate a strong differentiation of the granite magma. Based on geological, geochronological, isotope systematics, and geochemical studies, we propose, for the first time, a genetic model for the Caosiyao porphyry Mo deposit. Under a regional extensional setting caused by far-field tectonics related to the Paleo-Pacific subduction during the Late Jurassic, a series of geodynamic, magmatic, and ore-forming processes took place, including formation of multi-directional and multi-phase faults, emplacement of the granitic host rocks, and Mo mineralization. Highly silicic, highly oxidized, and alkali-rich granitic magma, derived from partial melting of old lower crust, intruded into the country rocks. This highly differentiated granitic magma and the exsolved ore-forming fluids, enriched in Mo, migrated upward and interacted with the wall rocks. Eventually, ore minerals precipitated in fractures, resulting in the extensive deposition of molybdenite.

  11. Reactivity of lanthanocene hydroxides toward ketene, isocyanate, lanthanocene alkyl, and triscyclopentadienyllanthanide complexes.

    PubMed

    Zhang, Chunmei; Liu, Ruiting; Zhang, Jie; Chen, Zhenxia; Zhou, Xigeng

    2006-07-24

    The reactivity of [Cp(2)Ln(mu-OH)(THF)]2 (Ln = Y (1), Er (2), Yb (3)) toward PhEtCCO, PhNCO, Cp3Ln, [Cp2Ln(mu-CH3)]2, and the LiCl adduct of Cp2Ln(n)Bu(THF)x was examined. In all cases, OH-centered reactivity is observed: complexes 1-3 react with PhEtCCO to form the O-H addition products [Cp2Ln(mu-eta1:eta2-O2CCHEtPh)]2 (Ln = Yb (5), Er (6), Y (7), respectively, for 1-3), whereas treatment of 1 with PhNCO affords the addition/CpH-elimination/rearrangement product [{Cp2Y(THF)}2(mu-eta2:eta2-O2CNPh)] (8), which contains an unusual PhNCO(2) dianionic ligand. Analogous compound [Cp2Ln(THF)]2(mu-eta2:eta2-O2CNPh) (Ln = Yb (9), Er (10)) and 8 can be obtained in a higher yield by treatment of [Cp2Ln(mu-OH)(THF)]2 with PhNCO followed by reaction with the corresponding Cp3Ln. However, attempts to prepare the corresponding heterobimetallic complex by reacting stoichiometric amounts of [Cp2Y(mu-OH)(THF)]2 with PhNCO followed by treating it with Cp3Yb are unsuccessful. Instead, only rearrangement products 8 and 9 are obtained. Furthermore, the reaction of 3 with [Cp2Yb(mu-CH3)]2 or Cp3Yb forms oxo-bridged compound [Cp2Yb(THF)]2(mu-O) (11), whereas the reaction of [Cp2ErCl]2 with Li(n)Bu followed by treatment with 2 affords unexpected mu-oxo lanthanocene cluster (Cp2Er)3(mu-OH)(mu3-O)(mu-Cl)Li(THF)4 (12). In contrast to 1 and 2, 3 shows a strong tendency to undergo the intermolecular elimination of CpH at room temperature, giving trinuclear species [Cp2Yb(mu-OH)]2[CpYb(THF)](mu3-O) (4). The single-crystal X-ray diffraction structures of 1, 2, and 4-12 are described. All the results offer an interesting contrast to transition- and main-metal hydroxide complexes.

  12. Wood ash to treat sewage sludge for agricultural use

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

    White, R.K.

    About 90% of the three million tons of wood ash generated in the United States from wood burning facilities is being landfilled. Many landfills are initiated tipping fees and/or restrictions on the disposal of special wastes such as ash. The purpose of this work was to evaluate (1) the feasibility of using wood ash to stabilize sewage sludge and (2) the fertilizer and liming value of the sludge/ash mixture on plant response and soil pH. Research showed that wood ash, when mixed with sludge, will produce a pH above 12.0, which meets US EPA criteria for pathogen reduction for landmore » application on non-direct food chain crops. Different ratios of wood ash to sludge mixtures were tested and the 1:1 ratio (by weight) was found to be optimal. Five replications of wood ash from four sources were tested for moisture content, pH and fertilizer nutrients. The pH of the ash/sludge mixture (1:1) on day one ranged from 12.4 to 13.2. In most cases the pH remained the same over a 21 day test or only dropped 0.1 to 0.3 units. Analyses of the mixtures showed that heavy metal concentrations (As, B, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, S, Se, Zn) were low. The 1:1 ash/sludge mixture had a calcium carbonate equivalency of 17%. Green house pot studies using tall fescue grass were loadings of 300 to 750 pounds per acre of TKN-N than for 500 lb/acre of 10-10-10 commercial fertilizer. Plant tissue analysis showed N, P, K, Ca, and Mg levels to be within the sufficiency range for tall fescue.« less

  13. Analysis and physiological implications of renal 2-oxoglutaramate metabolism.

    PubMed Central

    Nissim, I; Wehrli, S; States, B; Nissim, I; Yudkoff, M

    1991-01-01

    The relative significance of the flux through the glutamine aminotransferase (glutaminase II) pathway to renal ammoniagenesis is poorly understood. A basic and unresolved question is whether 2-oxoglutaramate (2-OGM), a product of the glutaminase II reaction, is deamidated to yield 2-oxoglutarate and NH3, or whether 2-OGM accumulates as an unreactive lactam, depending on the environmental pH. In the current studies we utilized 13C n.m.r. as well as 15N n.m.r. as well as 15N n.m.r. to demonstrate that 2-OGM occurs as a lactam, i.e. 5-hydroxypyroglutamate, regardless of the environmental pH. Our additional aims were to determine whether human kidney cells (HK cells) in culture can produce 2-OGM and to ascertain a pH-dependent relationship between NH3 and 2-OGM production from glutamine. We therefore developed an isotope dilution assay for 2-OGM utilizing 5-hydroxy[4-13C,1-15N]pyroglutamate as the labelled species. Incubations of HK cells in minimal essential medium supplemented with 1 mM-[2-15N]glutamine demonstrated significantly higher production of 2-OGM at pH 6.8 and lower production at pH 7.6 compared with pH 7.4. Similarly both 15NH3 and [15N]alanine formation were significantly higher in acute acidosis (pH 6.8) and lower in acute alkalosis (pH 7.6) compared with that at physiological pH. Addition of 1 mM-amino-oxyacetate to the incubation medium at pH 7.4 significantly diminished [15N]alanine and 2-OGM production, but the production of 15NH3 via the glutamate dehydrogenase pathway was significantly stimulated. The current observations indicate that the glutaminase II pathway plays a minor role and that flux through glutamate dehydrogenase is the predominant site for regulation of ammoniagenesis in human kidney. PMID:1854345

  14. Analysis and physiological implications of renal 2-oxoglutaramate metabolism.

    PubMed

    Nissim, I; Wehrli, S; States, B; Nissim, I; Yudkoff, M

    1991-07-01

    The relative significance of the flux through the glutamine aminotransferase (glutaminase II) pathway to renal ammoniagenesis is poorly understood. A basic and unresolved question is whether 2-oxoglutaramate (2-OGM), a product of the glutaminase II reaction, is deamidated to yield 2-oxoglutarate and NH3, or whether 2-OGM accumulates as an unreactive lactam, depending on the environmental pH. In the current studies we utilized 13C n.m.r. as well as 15N n.m.r. as well as 15N n.m.r. to demonstrate that 2-OGM occurs as a lactam, i.e. 5-hydroxypyroglutamate, regardless of the environmental pH. Our additional aims were to determine whether human kidney cells (HK cells) in culture can produce 2-OGM and to ascertain a pH-dependent relationship between NH3 and 2-OGM production from glutamine. We therefore developed an isotope dilution assay for 2-OGM utilizing 5-hydroxy[4-13C,1-15N]pyroglutamate as the labelled species. Incubations of HK cells in minimal essential medium supplemented with 1 mM-[2-15N]glutamine demonstrated significantly higher production of 2-OGM at pH 6.8 and lower production at pH 7.6 compared with pH 7.4. Similarly both 15NH3 and [15N]alanine formation were significantly higher in acute acidosis (pH 6.8) and lower in acute alkalosis (pH 7.6) compared with that at physiological pH. Addition of 1 mM-amino-oxyacetate to the incubation medium at pH 7.4 significantly diminished [15N]alanine and 2-OGM production, but the production of 15NH3 via the glutamate dehydrogenase pathway was significantly stimulated. The current observations indicate that the glutaminase II pathway plays a minor role and that flux through glutamate dehydrogenase is the predominant site for regulation of ammoniagenesis in human kidney.

  15. Impairment Severity Selectively Affects the Control of Proximal and Distal Components of Reaching Movements in Children with Hemiplegic Cerebral Palsy

    ERIC Educational Resources Information Center

    Domellof, Erik; Rosblad, Birgit; Ronnqvist, Louise

    2009-01-01

    This study explored proximal-to-distal components during goal-directed reaching movements in children with mild or moderate hemiplegic cerebral palsy (HCP); [seven females, four males; mean age 8y 6mo; SD 27mo], compared with age-matched, typically developing children (seven females, five males; mean age 8y 3mo [SD 25mo]. Severity of HCP was…

  16. Metal complexes of fluorophosphines. 13. Reaction of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with (methylamino)bis(difluorophosphine). X-ray crystal structure analysis of a novel binuclear molybdenum fluorophosphine carbonyl complex with a bridging chlorine atom: (CO)/sub 2/Mo(/sup +/-CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/(. mu. -PF/sub 2/)(. mu. -Cl)Mo(CO)(PF/sub 2/NHCH/sub 3/)

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

    King, R.B.; Shimura, M.; Brown, G.M.

    1984-01-01

    Reaction of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with CH/sub 3/N(PF/sub 2/)/sub 2/ in acetonitrile solution at room temperature gives white, volatile, crystalline fac-(CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/Mo(CO)/sub 3/, containing one monodentate and one bidentate CH/sub 3/N(PF/sub 2/)/sub 2/ ligand. The same reactants in boiling acetonitrile give yellow (CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 4/Mo/sub 2/(CO)/sub 3/ in considerably better yield than the previously reported preparation of this binuclear complex from the cycloheptatriene complex C/sub 7/H/sub 8/Mo(CO)/sub 3/ and CH/sub 3/N(PF/sub 2/)/sub 2/ in boiling methylcyclohexane. Reaction in acetonitrile solution of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with CH/sub 3/N(PF/sub 2/)/sub 2/ containing about 0.2% HClmore » gives brown-red, volatile (CO)/sub 2/Mo(/sup +/-CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/(..mu..-PF/sub 2/)(..mu..-Cl)-Mo(CO)(PF/sub 2/NHCH/sub 3/), whose composition and structure were established by single-crystal X-ray structure analysis. This novel quadruply bridged binuclear complex is obtained in considerably better yield from the reaction of (CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 3/Mo/sub 2/(CO)/sub 5/ with ((C/sub 2/H/sub 5/)/sub 3/NH)Cl in acetonitirle solution. The complex has a Mo-Mo bond 2.975 A in length. Crystal data: monoclinic, space group P2/sub 1//c, a = 17.546 (4) A, b = 9.725 (2) A, c = 14.558 (3), ..beta.. = 107.20 (2)/sup 0/, Z = 4. 30 references, 2 figures, 3 tables.« less

  17. Phase stability and mechanical properties of Mo1-xNx with 0 ≤ x ≤ 1

    NASA Astrophysics Data System (ADS)

    Balasubramanian, Karthik; Huang, Liping; Gall, Daniel

    2017-11-01

    First-principle density-functional calculations coupled with the USPEX evolutionary phase-search algorithm are employed to calculate the convex hull of the Mo-N binary system. Eight molybdenum nitride compound phases are found to be thermodynamically stable: tetragonal β-Mo3N, hexagonal δ-Mo3N2, cubic γ-Mo11N8, orthorhombic ɛ-Mo4N3, cubic γ-Mo14N11, monoclinic σ-MoN and σ-Mo2N3, and hexagonal δ-MoN2. The convex hull is a straight line for 0 ≤ x ≤ 0.44 such that bcc Mo and the five listed compound phases with x ≤ 0.44 are predicted to co-exist in thermodynamic equilibrium. Comparing the convex hulls of cubic and hexagonal Mo1-xNx indicates that cubic structures are preferred for molybdenum rich (x < 0.3) compounds, and hexagonal phases are favored for nitrogen rich (x > 0.5) compositions, while similar formation enthalpies for cubic and hexagonal phases at intermediate x = 0.3-0.5 imply that kinetic factors play a crucial role in the phase formation. The volume per atom Vo of the thermodynamically stable Mo1-xNx phases decreases from 13.17 to 9.56 Å3 as x increases from 0.25 to 0.67, with plateaus at Vo = 11.59 Å3 for hexagonal and cubic phases and Vo = 10.95 Å3 for orthorhombic and monoclinic phases. The plateaus are attributed to the changes in the average coordination numbers of molybdenum and nitrogen atoms, which increase from 2 to 6 and decrease from 6 to 4, respectively, indicating an increasing covalent bonding character with increasing x. The change in bonding character and the associated phase change from hexagonal to cubic/orthorhombic to monoclinic cause steep increases in the isotropic elastic modulus E = 387-487 GPa, the shear modulus G = 150-196 GPa, and the hardness H = 14-24 GPa in the relatively narrow composition range x = 0.4-0.5. This also causes a drop in Poisson's ratio from 0.29 to 0.24 and an increase in Pugh's ratio from 0.49 to 0.64, indicating a ductile-to-brittle transition between x = 0.44 and 0.5.

  18. Does Low PAPP-A Predict Adverse Placenta-Mediated Outcomes in a Low-Risk Nulliparous Population? the Great Obstetrical Syndromes (GOS) Study.

    PubMed

    Boutin, Amélie; Gasse, Cédric; Demers, Suzanne; Blanchet, Geneviève; Giguère, Yves; Bujold, Emmanuel

    2018-06-01

    First-trimester low concentration of pregnancy-associated plasma protein A (PAPP-A) has been associated with adverse perinatal outcomes in high-risk populations. This study aimed to estimate the ability of PAPP-A to identify adverse outcomes in a low-risk population. The study investigators recruited nulliparous women with singleton pregnancy at their 11-13-week ultrasound scan. Serum samples were collected, and maternal PAPP-A concentration was measured using the B⋅R⋅A⋅H⋅M⋅S PAPP-A KRYPTOR (ThermoFisher Scientific, Hennigsdorf, Germany) automated assay. PAPP-A was reported in multiple of median (MoM) adjusted for GA. Participants were followed until delivery for pregnancy outcomes including preeclampsia (PE), SGA <3rd percentile, and fetal death. Receiver operating characteristic curves with the area under the curve (AUC) were used to evaluate the predictive value of PAPP-A. The investigators calculated the detection rates (DRs) and positive predictive values (PPVs) of a PAPP-A < 0.4 MoM. The study investigators recruited 4739 eligible participants at a mean GA of 13 ± 6 weeks. The investigators observed 232 (4.9%) cases of PE, 84 (1.8%) cases of SGA, and 14 (0.3%) fetal deaths. PAPP-A was moderately associated with PE (AUC 0.57; 95% CI 0.53-0.61) and SGA (AUC 0.62; 95% CI 0.56-0.69), but not with fetal death (AUC 0.43; 95% CI 0.23-0.63). PAPP-A < 0.4 MoM was observed in 364 (7.7%) participants and had poor predictive values for PE (DR 9.8%; PPV 6.3%), SGA (DR 18.1%; PPV 4.4%), and fetal death (DR 21.4%; PPV 0.9%). Isolated first trimester PAPP-A has a limited predictive value for adverse pregnancy outcomes (other than trisomies). Low PAPP-A (<0.4 MoM) should be used in combination with other markers for the prediction of PE, SGA, or fetal death, and it does not constitute an indication for low-dose aspirin. Copyright © 2018 Society of Obstetricians and Gynaecologists of Canada. Published by Elsevier Inc. All rights reserved.

  19. High-dose vitamin D in Addison's disease regulates T-cells and monocytes: A pilot trial.

    PubMed

    Penna-Martinez, Marissa; Filmann, Natalie; Bogdanou, Dimitra; Shoghi, Firouzeh; Huenecke, Sabine; Schubert, Ralf; Herrmann, Eva; Koehl, Ulrike; Husebye, Eystein S; Badenhoop, Klaus

    2018-05-01

    On the basis of the immunomodulatory actions of vitamin D (VD), we investigated the effects of high-dose VD therapy over a 3 mo period on the immune response in patients with Addison's disease (AD). This randomized, controlled, crossover trial included 13 patients with AD who received either cholecalciferol (4000 IU/d) for 3 mo followed by 3 mo placebo oil or the sequential alternative placebo followed by verum. Glucocorticoid replacement doses remained stable. The primary outcome measures were changes in 25-hydroxyvitamin D3 (25(OH)D 3 ) levels and immune cells including T helper cells (Th; CD3 + CD4 + ), late-activated Th cells (CD3 + CD4 + HLA-DR + ), regulatory T cells (CD3 + CD4 + CD25 bright CD127 dim/neg ), cytotoxic T cells (Tc; CD3 + CD8 + ), late-activated Tc cells (CD3 + CD8 + HLA-DR + ), and monocytes. The explorative analysis included the correlation of changes with VD-related gene polymorphisms and 21-hydroxylase antibody titers. Ten of 13 patients (77%) were VD deficient. Median 25(OH)D 3 concentrations increased significantly to 41.5 ng/ml (median changes: 19.95 ng/ml; P = 0.0005) after 3 mo of cholecalciferol treatment. Within the T-cells, only the late-activated Th (median changes: 1.6%; P = 0.02) and late-activated Tc cells (median changes: 4.05%; P = 0.03) decreased, whereas monocytes (median changes: 1.05%; P = 0.008) increased after VD therapy. T-cell changes were associated with two polymorphisms (CYP27B1-rs108770012 and VDR-rs10735810), but no changes in the 21-hydroxylase antibody titers were observed. Three months of treatment with cholecalciferol achieved sufficient 25(OH)D 3 levels and can regulate late-activated T-cells and monocytes in patients with AD. Explorative analysis revealed potential genetic contributions. This pilot trial provides novel insights about immunomodulation in AD. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Endosomal recognition of Lactococcus lactis G121 and its RNA by dendritic cells is key to its allergy-protective effects.

    PubMed

    Stein, Karina; Brand, Stephanie; Jenckel, André; Sigmund, Anna; Chen, Zhijian James; Kirschning, Carsten J; Kauth, Marion; Heine, Holger

    2017-02-01

    Bacterial cowshed isolates are allergy protective in mice; however, the underlying mechanisms are largely unknown. We examined the ability of Lactococcus lactis G121 to prevent allergic inflammatory reactions. We sought to identify the ligands and pattern recognition receptors through which L lactis G121 confers allergy protection. L lactis G121-induced cytokine release and surface expression of costimulatory molecules by untreated or inhibitor-treated (bafilomycin and cytochalasin D) human monocyte-derived dendritic cells (moDCs), bone marrow-derived mouse dendritic cells (BMDCs), and moDC/naive CD4 + T-cell cocultures were analyzed by using ELISA and flow cytometry. The pathology of ovalbumin-induced acute allergic airway inflammation after adoptive transfer of BMDCs was examined by means of microscopy. L lactis G121-treated murine BMDCs and human moDCs released T H 1-polarizing cytokines and induced T H 1 T cells. Inhibiting phagocytosis and endosomal acidification in BMDCs or moDCs impaired the release of T H 1-polarizing cytokines, costimulatory molecule expression, and T-cell activation on L lactis G121 challenge. In vivo allergy protection mediated by L lactis G121 was dependent on endosomal acidification in dendritic cells (DCs). Toll-like receptor (Tlr) 13 -/- BMDCs showed a weak response to L lactis G121 and were unresponsive to its RNA. The T H 1-polarizing activity of L lactis G121-treated human DCs was blocked by TLR8-specific inhibitors, mediated by L lactis G121 RNA, and synergistically enhanced by activation of nucleotide-binding oligomerization domain-containing protein (NOD) 2. Bacterial RNA is the main driver of L lactis G121-mediated protection against experimentally induced allergy and requires both bacterial uptake by DCs and endosomal acidification. In mice L lactis G121 RNA signals through TLR13; however, the most likely intracellular receptor in human subjects is TLR8. Copyright © 2016 American Academy of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

  1. Maternal serum pregnancy-associated plasma protein A and fetal nuchal translucency thickness for the prediction of fetal trisomies in early pregnancy.

    PubMed

    Brizot, M L; Snijders, R J; Bersinger, N A; Kuhn, P; Nicolaides, K H

    1994-12-01

    To determine if the risk for fetal trisomies during the first trimester of pregnancy can be derived by combining data from maternal serum pregnancy-associated plasma protein A (PAPP-A) and fetal nuchal translucency thickness. Pregnancy-associated plasma protein A was measured in samples from 87 singleton pregnancies with fetal chromosomal abnormalities (45 trisomy 21, 19 trisomy 18, eight trisomy 13, 11 sex chromosome aneuploidies, four triploidies) and 348 chromosomally normal controls at 10-13 weeks' gestation. Likelihood ratios for trisomies 21, 18, and 13 in relation to PAPP-A, in multiples of the normal median (MoM) for crown-rump length, were derived from the overlapping gaussian frequency distribution curves for normal and abnormal pregnancies. In the chromosomally normal group, maternal serum PAPP-A correlated significantly with fetal crown-rump length (r = 0.421, P < .0001). In the chromosomally abnormal group, the median PAPP-A was significantly lower than in the normal controls. The respective median values expressed in MoM for trisomies 21, 18, and 13 and other aneuploidies were 0.5 MoM (90% confidence interval [CI] 0.09-1.67, z = 6.0, P < .001), 0.17 MoM (90% CI 0.06-1.45, z = 6.6, P < .001), 0.25 MoM (90% CI 0.10-0.62, z = 4.5, P < .001), and 0.72 MoM (90% CI 0.09-2.48, z = 2.2, P < .05), respectively. There was no significant linear association between PAPP-A and fetal nuchal translucency thickness in either the chromosomally normal (r = -0.01, P = .89) or abnormal groups (r = -0.19, P = .08). The risks for fetal trisomies at 10-13 weeks' gestation can be derived by combining data on maternal age, maternal serum PAPP-A, and fetal nuchal translucency thickness.

  2. Effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13

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

    John E. Aston; William A. Apel; Brady D. Lee

    2010-12-01

    This study describes the effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13 with a Langmuir model. Copper exhibited the highest loading capacity, 4.76 ± 0.28 mmol g-1, to viable cells at pH 5.5. The highest kL (binding-site affinity) observed was 61.2 ± 3.0 L mmol-1 to dehydrated cells at pH 4.0. The pHs that maximized loading capacities and binding-site affinities were generally between 4.0 and 5.5, where the sum of free-proton and complexed-metal concentrations was near a minimum. Of additional importance, lead, zinc, and copper sorbed to viable cells atmore » pH values as low as 1.5. Previous studies with other acidithiobacilli did not measure viable-cell sorption below pH 4.0. In separate experiments, desorption studies showed that far less copper was recovered from viable cells than any other metal or cell condition, suggesting that uptake may play an important role in copper sorption by At. caldus strain BC13. To reflect an applied system, the sorption of metal mixtures was also studied. In these experiments, lead, zinc, and copper sorption from a tertiary mixture were 40.2 ± 4.3%, 28.7 ± 3.8%, and 91.3 ± 3.0%, respectively, of that sorbed in single-metal systems.« less

  3. Preconcentration and determination of vanadium and molybdenum in milk, vegetables and foodstuffs by ultrasonic-thermostatic-assisted cloud point extraction coupled to flame atomic absorption spectrometry.

    PubMed

    Gürkan, Ramazan; Korkmaz, Sema; Altunay, Nail

    2016-08-01

    A new ultrasonic-thermostatic-assisted cloud point extraction procedure (UTA-CPE) was developed for preconcentration at the trace levels of vanadium (V) and molybdenum (Mo) in milk, vegetables and foodstuffs prior to determination via flame atomic absorption spectrometry (FAAS). The method is based on the ion-association of stable anionic oxalate complexes of V(V) and Mo(VI) with [9-(diethylamino)benzo[a]phenoxazin-5-ylidene]azanium; sulfate (Nile blue A) at pH 4.5, and then extraction of the formed ion-association complexes into micellar phase of polyoxyethylene(7.5)nonylphenyl ether (PONPE 7.5). The UTA-CPE is greatly simplified and accelerated compared to traditional cloud point extraction (CPE). The analytical parameters optimized are solution pH, the concentrations of complexing reagents (oxalate and Nile blue A), the PONPE 7.5 concentration, electrolyte concentration, sample volume, temperature and ultrasonic power. Under the optimum conditions, the calibration curves for Mo(VI) and V(V) are obtained in the concentration range of 3-340µgL(-1) and 5-250µgL(-1) with high sensitivity enhancement factors (EFs) of 145 and 115, respectively. The limits of detection (LODs) for Mo(VI) and V(V) are 0.86 and 1.55µgL(-1), respectively. The proposed method demonstrated good performances such as relative standard deviations (as RSD %) (≤3.5%) and spiked recoveries (95.7-102.3%). The accuracy of the method was assessed by analysis of two standard reference materials (SRMs) and recoveries of spiked solutions. The method was successfully applied into the determination of trace amounts of Mo(VI) and V(V) in milk, vegetables and foodstuffs with satisfactory results. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Partially Unfolded Forms of the Prion Protein Populated under Misfolding-promoting Conditions

    PubMed Central

    Moulick, Roumita; Das, Ranabir; Udgaonkar, Jayant B.

    2015-01-01

    The susceptibility of the cellular prion protein (PrPC) to convert to an alternative misfolded conformation (PrPSc), which is the key event in the pathogenesis of prion diseases, is indicative of a conformationally flexible native (N) state. In the present study, hydrogen-deuterium exchange (HDX) in conjunction with mass spectrometry and nuclear magnetic resonance spectroscopy were used for the structural and energetic characterization of the N state of the full-length mouse prion protein, moPrP(23–231), under conditions that favor misfolding. The kinetics of HDX of 34 backbone amide hydrogens in the N state were determined at pH 4. In contrast to the results of previous HDX studies on the human and Syrian hamster prion proteins at a higher pH, various segments of moPrP were found to undergo different extents of subglobal unfolding events at pH 4, a pH at which the protein is known to be primed to misfold to a β-rich conformation. No residual structure around the disulfide bond was observed for the unfolded state at pH 4. The N state of the prion protein was observed to be at equilibrium with at least two partially unfolded forms (PUFs). These PUFs, which are accessed by stochastic fluctuations of the N state, have altered surface area exposure relative to the N state. One of these PUFs resembles a conformation previously implicated to be an initial intermediate in the conversion of monomeric protein into misfolded oligomer at pH 4. PMID:26306043

  5. Characterization of a Bacteriophage-Induced, Host-Specific Lytic Enzyme from Lysates of Bacillus stearothermophilus Infected with Bacteriophage TP-8

    PubMed Central

    Brehm, Sylvia P.; Welker, N. E.

    1974-01-01

    Phage TP-8 lysates of Bacillus stearothermophilus 4S or 4S(8) contain lytic activity exhibiting two pH optima, one at pH 6.5 and the other at pH 7.5. Using a variety of fractionation procedures, the two lytic activities could not be separated. At pH 7.5 the lytic enzyme is an endopeptidase which hydrolyzes the l-alanyl-d-glutamyl linkage in the peptide subunits of the cell wall peptidoglycan and at pH 6.5 it exhibits N-acetylmuramidase activity. Endopeptidase activity is inhibited by NaCl and neither lytic activity was significantly affected by divalent cations or ethylenediaminetetraacetic acid. Crude lysates contain 2.5 to 3.0 times more endopeptidase activity than N-acetylmuramidase activity. The ratio of the two lytic activities (endopeptidase/N-acetylmuramidase) changes to 1.3 to 1.7 during the course of purification, to 1.0 after isoelectric focusing, and 3.9 and 6.00 after exposure for 2 h at 60 and 65 C, respectively. We conclude that the two lytic activities may be associated with a single protein or a lytic enzyme complex composed of two enzymes. Lytic activity at pH 7.5 is more effective in solubilizing cells or cell walls than the lytic activity at pH 6.5. LiCl extracts of 4S and 4S(8) cells contain lytic activity exhibiting endopeptidase activity at pH 7.5 and N-acetylmuramidase activity at pH 6.5. Lytic activity in these LiCl extracts also has a number of other properties in common with those in lysates of phage TP-8. We proposed that the lytic enzyme(s) are not coded for by the phage genome but are part of the host autolytic system. PMID:4218232

  6. Effect of laser absorption on picosecond laser ablation of Cr12MoV mold steel, 9Cr18 stainless steel and H13A cemented carbide

    NASA Astrophysics Data System (ADS)

    Wu, Baoye; Liu, Peng; Wang, Xizhao; Zhang, Fei; Deng, Leimin; Duan, Jun; Zeng, Xiaoyan

    2018-05-01

    Due to excellent properties, Cr12MoV mold steel, 9Cr18 stainless steel and H13A cemented carbide are widely used in industry. In this paper, the effect of absorption of laser light on ablation efficiency and roughness have been studied using a picosecond pulse Nd:YVO4 laser. The experimental results reveal that laser wavelength, original surface roughness and chemical composition play an important role in controlling ablation efficiency and roughness. Firstly, higher ablation efficiency with lower surface roughness is achieved on the ablation of 9Cr18 at 532, comparing with 1064 nm. Secondly, the ablation efficiency increases while the Ra of the ablated region decreases with the decrease of original surface roughness on ablation of Cr12MoV mold steel at 532 nm. Thirdly, the ablation efficiency of H13A cemented carbide is much higher than 9Cr18 stainless steel and Cr12MoV mold steel at 1064 nm. Scanning electron microscopy images reveals the formation of pores on the surface of 9Cr18 stainless steel and Cr12MoV mold steel at 532 nm while no pores are formed at 1064 nm. As to H13A cemented carbide, worm-like structure is formed at 1064 nm. The synergetic effects of the heat accumulation, plasma shielding and ablation threshold on laser ablation efficiency and machining quality were analyzed and discussed systematically in this paper.

  7. Negative thermal expansion materials related to cubic zirconium tungstate

    NASA Astrophysics Data System (ADS)

    Lind, Cora

    2001-12-01

    A non-hydrolytic sol-gel method for the preparation of ZrW2O 8 was developed. A new trigonal polymorph was discovered, which is structurally related to trigonal ZrMO2O8 and MnRe2O 8 as evidenced by powder x-ray diffraction and EXAFS studies. Seeding of the starting mixtures with cubic ZrW2O8 promoted crystallization of the cubic phase instead of trigonal material. Dehydration of ZrW2O7(OH)2·2H 2O gave cubic ZrW2O8 at 650°C, and a modification of this route led to the discovery of the new NTE materials cubic ZrMo 2O8 and HfMo2O8. These compounds crystallize in the same temperature range as the more stable trigonal AMo2O 8 polymorphs. To facilitate preparation of phase pure cubic molybdates, the influence of precursor chemistry on the crystallization behavior was investigated. The synthesis was extended to the solid solution system ZrxHf 1-xMoyW2-yO8 (0 ≤ x ≤ 1, 0 ≤ y ≤ 2). All compounds showed negative thermal expansion between 77 and 573 K. High-pressure in situ diffraction experiments were conducted on several AM2O8 polymorphs. With the exception of monoclinic ZrMo2O8, all materials underwent at least one pressure induced phase transition. Quasi-hydrostatic experiments on cubic AMo 2O8 led to a reversible transition to a new high-pressure structure, while low-pressure amorphization was observed under non-hydrostatic conditions. Isothermal kinetic studies of the cubic to trigonal transformation for ZrMo2O8 were carried out on four samples. Apparent activation energies of 170--290 kJ/mol were obtained using an Avrami model in combination with an Arrhenius analysis. This corresponds to 5% conversion levels after one year at temperatures between 220 and 315°C. Ex situ studies showed that the conversion at lower temperatures was considerably slower than what would be expected from extrapolation of the kinetic data. Drop solution calorimetry was carried out on several polymorphs of ZrMo 2O8, HfMo2O8 and ZrW2O 8. Only monoclinic ZrMo2O8 was enthalpically stabilized with respect to the binary oxides. For all other polymorphs, the differences in enthalpies of formation from the binary oxides for each AM2O 8 system (A = Zr, Hf; M = Mo, W) were small. Attempts to synthesize new materials MIIRe2O 8 (M = Mg, Zn, Mn, Co) with the cubic ZrW2O8 structure from a hydrate precursor were not successful.

  8. Effect of thermal acclimation on locomotor energetics and locomotor performance in a lungless salamander, Desmognathus ochrophaeus.

    PubMed

    Feder, M E

    1986-03-01

    To determine the effects of thermal acclimation upon locomotor performance and the rate of oxygen consumption (MO2) during activity, small (less than 3 g), lungless salamanders, Desmognathus ochrophaeus Cope, were acclimated to three temperatures (5, 13 and 21 degrees C) and exercised at various controlled speeds within an exercise wheel while their MO2 was measured. MO2 increased with speed at low speeds (less than 14 cm min-1). Although animals could sustain greater speeds, MO2 did not increase further. These small, exclusively skin-breathing salamanders could increase their MO2 9-11 times during exercise and could sustain nearly half of the oxygen flux expected across a similar surface area of the mammalian lung. However, their maximum aerobic speed was remarkably slow (14 cm min-1) and their net cost of transport remarkably large (15-17 ml O2 g-1 km-1). Thermal acclimation affected MO2 during activity, the maximum sustainable speed and locomotor stamina in different ways. During exercise at 13 degrees C, cold-acclimated animals had a significantly greater MO2 than warm-acclimated animals, but did not differ in stamina or the maximum sustainable speed. During exercise at 21 degrees C, cold acclimation did not affect the MO2 significantly, but it decreased the stamina and increased the rate of lactate accumulation. Thus, these results suggest that thermal acclimation of the MO2 is not tightly coupled to thermal acclimation of locomotor performance in salamanders.

  9. Do patients with a failed metal-on-metal hip implant with a pseudotumor present differences in their peripheral blood lymphocyte subpopulations?

    PubMed

    Catelas, Isabelle; Lehoux, Eric A; Hurda, Ian; Baskey, Stephen J; Gala, Luca; Foster, Ryan; Kim, Paul R; Beaulé, Paul E

    2015-12-01

    Early adverse tissue reactions around metal-on-metal (MoM) hip replacements, especially pseudotumors, are a major concern. Because the causes and pathomechanisms of these pseudotumors remain largely unknown, clinical monitoring of patients with MoM bearings is challenging. The purpose of this study was to compare the lymphocyte subpopulations in peripheral blood from patients with a failed MoM hip implant with and without a pseudotumor and patients with a well-functioning MoM hip implant without a pseudotumor. Potential differences in the systemic immune response are expected to reflect local differences in the periprosthetic tissues. Consenting patients who underwent a revision of a failed MoM hip implant at The Ottawa Hospital (TOH) from 2011 to 2014, or presented with a well-functioning MoM hip implant for a postoperative clinical followup at TOH from 2012 to 2013, were recruited for this study, unless they met any of the exclusion criteria (including diagnosed conditions that can affect peripheral blood lymphocyte subpopulations). Patients with a failed implant were divided into two groups: those with a pseudotumor (two hip resurfacings and five total hip arthroplasties [THAs]) and those without a pseudotumor (10 hip resurfacings and two THAs). Patients with a well-functioning MoM hip implant (nine resurfacings and three THAs) at 5 or more years postimplantation and who did not have a pseudotumor as demonstrated sonographically served as the control group. Peripheral blood subpopulations of T cells (specifically T helper [Th] and cytotoxic T [Tc]), B cells, natural killer (NK) cells, memory T and B cells as well as type 1 (expressing interferon-γ) and type 2 (expressing interleukin-4) Th and Tc cells were analyzed by flow cytometry after immunostaining. Serum concentrations of cobalt and chromium were measured by inductively coupled plasma-mass spectrometry. The mean percentages of total memory T cells and, specifically, memory Th and memory Tc cells were lower in patients with a failed MoM hip implant with a pseudotumor than in both patients with a failed implant without a pseudotumor and patients with a well-functioning implant without a pseudotumor (memory Th cells: 29% ± 5% [means ± SD] versus 55% ± 17%, d = 1.8, 95% confidence interval [CI] [1.2, 2.5] and versus 48% ± 14%, d = 1.6, 95% CI [1.0, 2.2], respectively; memory Tc cells: 18% ± 5% versus 45% ± 14%, d = 2.3, 95% CI [1.5, 3.1] and versus 41% ± 12%, d = 2.3, 95% CI [1.5, 3.1], respectively; p < 0.001 in all cases). The mean percentage of memory B cells was also lower in patients with a failed MoM hip implant with a pseudotumor than in patients with a well-functioning implant without a pseudotumor (12% ± 8% versus 29% ± 16%, d = 1.3, 95% CI [0.7, 1.8], p = 0.025). In addition, patients with a failed MoM hip implant with a pseudotumor had overall lower percentages of type 1 Th cells than both patients with a failed implant without a pseudotumor and patients with a well-functioning implant without a pseudotumor (5.5% [4.9%-5.8%] [median with interquartile range] versus 8.7% [6.5%-10.2%], d = 1.4, 95% CI [0.8, 2.0] and versus 9.6% [6.4%-11.1%], d = 1.6, 95% CI [1.0, 2.2], respectively; p ≤ 0.010 in both cases). Finally, serum cobalt concentrations in patients with a failed MoM hip implant with a pseudotumor were overall higher than those in patients with a well-functioning implant without a pseudotumor (5.8 µg/L [2.9-17.0 µg/L] versus 0.9 µg/L [0.6-1.3 µg/L], d = 2.2, 95% CI [1.4, 2.9], p < 0.001). Overall, results suggest the presence of a type IV hypersensitivity reaction, with a predominance of type 1 Th cells, in patients with a failed MoM hip implant with a pseudotumor. The lower percentages of memory T cells (specifically Th and Tc) as well as type 1 Th cells in peripheral blood of patients with a failed MoM hip implant with a pseudotumor could potentially become diagnostic biomarkers for the detection of pseudotumors. Although implant design (hip resurfacing or THA) did not seem to affect the results, as suggested by the scatter of the data with respect to this parameter, future studies with additional patients could include the analysis of implant design in addition to correlations with histological analyses of specific Th subsets in periprosthetic tissues.

  10. Monoanionic molybdenum and tungsten tris(dithiolene) complexes: a multifrequency EPR study.

    PubMed

    Sproules, Stephen; Banerjee, Priyabrata; Weyhermüller, Thomas; Yan, Yong; Donahue, James P; Wieghardt, Karl

    2011-08-01

    Numerous Mo and W tris(dithiolene) complexes in varying redox states have been prepared and representative examples characterized crystallographically: [M(S(2)C(2)R(2))(3)](z) [M = Mo, R = Ph, z = 0 (1) or 1- (2); M = W, R = Ph, z = 0 (4) or 1- (5); R = CN, z = 2-, M = Mo (3) or W (6)]. Changes in dithiolene C-S and C-C bond lengths for 1 versus 2 and 4 versus 5 are indicative of ligand reduction. Trigonal twist angles (Θ) and dithiolene fold angles (α) increase and decrease, respectively, for 2 versus 1, 5 versus 4. Cyclic voltammetry reveals generally two reversible couples corresponding to 0/1- and 1-/2- reductions. The electronic structures of monoanionic molybdenum tris(dithiolene) complexes have been analyzed by multifrequency (S-, X-, Q-band) EPR spectroscopy. Spin-Hamiltonian parameters afforded by spectral simulation for each complex demonstrate the existence of two distinctive electronic structure types. The first is [Mo(IV)((A)L(3)(5-•))](1-) ((A)L = olefinic dithiolene, type A), which has the unpaired electron restricted to the tris(dithiolene) unit and is characterized by isotropic g-values and small molybdenum superhyperfine coupling. The second is formulated as [Mo(V)((B)L(3)(6-))](1-) ((B)L = aromatic dithiolene, type B) with spectra distinguished by a prominent g-anisotropy and hyperfine coupling consistent with the (d(z(2)))(1) paramagnet. The electronic structure disparity is also manifested in their electronic absorption spectra. The compound [W(bdt)(3)](1-) exhibits spin-Hamiltonian parameters similar to those of [Mo(bdt)(3)](1-) and thus is formulated as [W(V)((B)L(3)(6-))](1-). The EPR spectra of [W((A)L(3))](1-) display spin-Hamiltonian parameters that suggest their electronic structure is best represented by two resonance forms {[W(IV)((A)L(3)(5-•))](1-) ↔ [W(V)((A)L(3)(6-))](1-)}. The contrast with the corresponding [Mo(IV)((A)L(3)(5-•))](1-) complexes highlights tungsten's preference for higher oxidation states. © 2011 American Chemical Society

  11. Children at Risk for Developmental Coordination Disorder: Judgement of Changes in Action Capabilities

    ERIC Educational Resources Information Center

    Johnson, Daniel C.; Wade, Michael G.

    2009-01-01

    In three separate manipulations, a group of children at risk for developmental coordination disorder (DCD; five males, seven females; mean age 11y 6mo [SD 6.8mo] who were at or below the 15th percentile on the Movement ABC) and a group of typically developing children (TDC; seven males, five females; mean age 11y 3mo [SD 6.8mo]) judged the limit…

  12. The Characteristics and Generating Mechanism of Large Precipitates in Ti-Containing H13 Tool Steel

    NASA Astrophysics Data System (ADS)

    Xie, You; Cheng, Guoguang; Chen, Lie; Zhang, Yandong; Yan, Qingzhong

    2017-02-01

    The characteristics of large precipitates in H13 tool steel with 0.015wt% Ti were studied. The result shows that three types of phases larger than 1 μm exist in the as-cast ingot, that is, (Ti, V) (C, N) type phase, (V, Mo, Cr)C type phase and sulfide. (Ti, V) (C, N) type phase could be further classified as the homogeneous Ti-rich one and the Ti-V-rich one in which Ti/V ratio gradually changes. (V, Mo, Cr)C type phase contains the V-rich one and the Mo-Cr-rich one. The compositional characteristics in all of them have little relation with the cutting position or cooling rate. The precipitating process could be well described through calculation by Thermo-Calc software. During solidification, the primary phase (Ti, V)(C, N) first starts to precipitate in the form of Ti-rich carbonitride. With the development of solidification, the ratio of Ti decreases and that of V increases. Then the primary phase Ti-V-rich (Ti, V)(C, N) and V-rich (V, Mo, Cr)C appears successively. Mo-Cr-rich (V, Mo, Cr)C phase does not precipitate until the solidification process reaches to the end. Sulfide precipitates before (V, Mo, Cr)C type phase and it could act as the nucleus of (V, Mo, Cr)C.

  13. Effects of Various Passivation Layers on Electrical Properties of Multilayer MoS₂ Transistors.

    PubMed

    Ma, Jiyeon; Yoo, Geonwook

    2018-09-01

    So far many of research on transition metal dichalcogenides (TMDCs) are based on a bottomgate device structure due to difficulty with depositing a dielectric film on top of TMDs channel layer. In this work, we study different effects of various passivation layers on electrical properties of multilayer MoS2 transistors: spin-coated CYTOP, SU-8, and thermal evaporated MoOX. The SU-8 passivation layer alters device performance least significantly, and MoOX induces positive threshold voltage shift of ~8.0 V due to charge depletion at the interface, and the device with CYTOP layer exhibits decreased field-effect mobility by ~50% due to electric dipole field effect of C-F bonds in the end groups. Our results imply that electrical properties of the multilayer MoS2 transistors can be modulated using a passivation layer, and therefore a proper passivation layer should be considered for MoS2 device structures.

  14. Community structure and soil pH determine chemoautotrophic carbon dioxide fixation in drained paddy soils.

    PubMed

    Long, Xi-En; Yao, Huaiying; Wang, Juan; Huang, Ying; Singh, Brajesh K; Zhu, Yong-Guan

    2015-06-16

    Previous studies suggested that microbial photosynthesis plays a potential role in paddy fields, but little is known about chemoautotrophic carbon fixers in drained paddy soils. We conducted a microcosm study using soil samples from five paddy fields to determine the environmental factors and quantify key functional microbial taxa involved in chemoautotrophic carbon fixation. We used stable isotope probing in combination with phospholipid fatty acid (PLFA) and molecular approaches. The amount of microbial (13)CO2 fixation was determined by quantification of (13)C-enriched fatty acid methyl esters and ranged from 21.28 to 72.48 ng of (13)C (g of dry soil)(-1), and the corresponding ratio (labeled PLFA-C:total PLFA-C) ranged from 0.06 to 0.49%. The amount of incorporationof (13)CO2 into PLFAs significantly increased with soil pH except at pH 7.8. PLFA and high-throughput sequencing results indicated a dominant role of Gram-negative bacteria or proteobacteria in (13)CO2 fixation. Correlation analysis indicated a significant association between microbial community structure and carbon fixation. We provide direct evidence of chemoautotrophic C fixation in soils with statistical evidence of microbial community structure regulation of inorganic carbon fixation in the paddy soil ecosystem.

  15. Metal leaching in mine tailings: short-term impact of biochar and wood ash amendments.

    PubMed

    Beauchemin, Suzanne; Clemente, Joyce S; MacKinnon, Ted; Tisch, Bryan; Lastra, Rolando; Smith, Derek; Kwong, John

    2015-01-01

    Biochar is perceived as a promising amendment to reclaim degraded, metal-contaminated lands. The objective of this study was to compare the potential of biochar and wood ash amendments to reduce metal(loid) leaching in mine tailings. A 2-mo leaching experiment was conducted in duplicate on acidic and alkaline tailings, each mixed with 5 wt.% of one of the following amendments: three wood-derived, fast-pyrolysis biochars (OC > 57 wt.%) and two wood ash materials (organic carbon [OC] ≤ 16 wt.%); a control test with no carbon input was also added. The columns were leached with water after 1, 2, 4, 8, 16, 32, and 64 d, and the leachates were monitored for dissolved metals, OC, and pH. For the acidic and alkaline tailings, the most significant impact on metal mobility was observed with wood ash materials due to their greater neutralization potential (>15% CaCO eq.) compared with biochar (≤3.3% CaCO eq.). An increase of 1 pH unit in the wood ash-treated alkaline tailings led to an undesirable mobilization of As and Se. The addition of biochar did not significantly reduce the leaching of the main contaminants (Cu and Ni in the acidic tailings and As in the alkaline tailings) over 2 mo. The Se attenuation noted in some biochar-treated acid tailings may be mainly due to a slight alkaline effect rather than Se removal by biochar, given the low capacity for the fresh biochars to retain Se under acidic conditions (pH 4.5). The increased loss of dissolved OC in the biochar-amended systems was of short duration and was not associated with metal(loid) mobilization. Copyright © Her Majesty the Queen in Right of Canada, as represented by the Minister of Agriculture and Agri-Food Canada.

  16. Assessment of the use of Moringa oleifera seed husks for removal of pesticide diuron from contaminated water.

    PubMed

    Bezerra, Charleston de O; Cusioli, Luís F; Quesada, Heloise B; Nishi, Letícia; Mantovani, Daniel; Vieira, Marcelo F; Bergamasco, Rosangela

    2018-06-22

    Considering the need of new technologies for the removal of pesticides from the aqueous environment, the Moringa oleifera seed husks (h-MO) was investigated for the diuron adsorption from contaminated water at different temperatures and solute concentrations. The biosorbent used in this study was characterized by chemical, structural and textural analyzes. The best experimental condition for the biosorption was determined by evaluating the mass of the biosorbent and the pH solution. It was found a good adsorption capacity for the herbicide where the maximum adsorption capacity was 14.74 mg/g at pH 5 and 45°C. In addition, the adsorption process of diuron by the h-MO occurred spontaneously, in which, ΔG° values increased as the temperature increased meaning that the process tends to a more energetically favorable process at higher temperatures. Both Langmuir and Sips isotherm models presented satisfactory adjustment at all temperatures and the pseudo-second-order model presented the best fit for the experimental results. The application of the intra-particle diffusion model showed that the adsorption process started instantaneously through the boundary layer of the adsorbent and that the pore diffusion step was a limiting step in the process. Finally, the capacity of the h-MO was compared with others adsorbents that had been used to diuron removal from contaminated where it was found that the adsorption capacity of the h-MO is much higher than other natural adsorbents.

  17. Macronutrients and micronutrients of soybean oil bodies extracted at different pH.

    PubMed

    Chen, Yeming; Cao, Yanyun; Zhao, Luping; Kong, Xiangzhen; Hua, Yufei

    2014-07-01

    In this study, the macronutrients and micronutrients of pH 6.8, 8.0, 9.5, and 11.0 extracted soybean oil bodies (OBs) were examined, revealing that soybean OBs might be used as a natural carrier for bioactive components (unsaturated fatty acids, phospholipid, tocopherol, and phytosterol). pH 6.8 extracted OBs (dry basis) contained 85.88% neutral lipid, 8.18% protein, and 5.85% polar lipid (mainly phospholipid) by gravimetric analysis. The percentage of neutral lipid was increased, while those of protein and polar lipid were decreased with increasing pH. Tocopherol (about 75 mg/100 g neutral lipid of OBs) was not affected, while phytosterol was decreased (136 to 110 mg/100 g neutral lipid of OBs) with increasing pH. The detectable total monosaccaride (galactosamine, glucosamine, and glucose) content of extracted OBs was low and also decreased (35.80 to 6.13 mg/100 g neutral lipid of OBs) with increasing pH. The protein of extracted OBs had higher percentage of essential amino acids than soybean protein isolate with tryptophan and methionine as limited amino acids. The fatty acid composition of extracted OBs was rich in linoleic acid (about 59%), oleic acid (about 20%), and α-linolenic acid (about 7%). Oil bodies (OBs) from soybean and other plant seeds are greatly examined owing to their potential utilizations in food ingredients. The determination of its macronutrients and micronutrients would be very meaningful for its efficient utilization in the future. © 2014 Institute of Food Technologists®

  18. Protein-targeted corona phase molecular recognition

    PubMed Central

    Bisker, Gili; Dong, Juyao; Park, Hoyoung D.; Iverson, Nicole M.; Ahn, Jiyoung; Nelson, Justin T.; Landry, Markita P.; Kruss, Sebastian; Strano, Michael S.

    2016-01-01

    Corona phase molecular recognition (CoPhMoRe) uses a heteropolymer adsorbed onto and templated by a nanoparticle surface to recognize a specific target analyte. This method has not yet been extended to macromolecular analytes, including proteins. Herein we develop a variant of a CoPhMoRe screening procedure of single-walled carbon nanotubes (SWCNT) and use it against a panel of human blood proteins, revealing a specific corona phase that recognizes fibrinogen with high selectivity. In response to fibrinogen binding, SWCNT fluorescence decreases by >80% at saturation. Sequential binding of the three fibrinogen nodules is suggested by selective fluorescence quenching by isolated sub-domains and validated by the quenching kinetics. The fibrinogen recognition also occurs in serum environment, at the clinically relevant fibrinogen concentrations in the human blood. These results open new avenues for synthetic, non-biological antibody analogues that recognize biological macromolecules, and hold great promise for medical and clinical applications. PMID:26742890

  19. In-situ determination of austenite and martensite formation in 13Cr6Ni2Mo supermartensitic stainless steel

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

    Bojack, A., E-mail: a.bojack@tudelft.nl; Delft University of Technology, Department of Materials Science and Engineering, Mekelweg 2, 2628 CD Delft; Zhao, L.

    2012-09-15

    In-situ analysis of the phase transformations in a 13Cr6Ni2Mo supermartensitic stainless steel (X2CrNiMoV13-5-2) was carried out using a thermo-magnetic technique, dilatometry and high temperature X-ray diffractometry (HT-XRD). A combination of the results obtained by the three applied techniques gives a valuable insight in the phase transformations during the austenitization treatment, including subsequent cooling, of the 13Cr6Ni2Mo supermartensitic stainless steel, where the magnetic technique offers a high accuracy in monitoring the austenite fraction. It was found by dilatometry that the austenite formation during heating takes place in two stages, most likely caused by partitioning of Ni into austenite. The in-situ evolutionmore » of the austenite fraction is monitored by high-temperature XRD and dilatometry. The progress of martensite formation during cooling was described with a Koistinen-Marburger relation for the results obtained from the magnetic and dilatometer experiments. Enhanced martensite formation at the sample surface was detected by X-ray diffraction, which is assumed to be due to relaxation of transformation stresses at the sample surface. Due to the high alloy content and high thermodynamic stability of austenite at room temperature, 4 vol.% of austenite was found to be stable at room temperature after the austenitization treatment. - Highlights: Black-Right-Pointing-Pointer We in-situ analyzed phase transformations and fractions of a 13Cr6Ni2Mo SMSS. Black-Right-Pointing-Pointer Higher accuracy of the austenite fraction was obtained from magnetic technique. Black-Right-Pointing-Pointer Austenite formation during heating takes place in two stages. Black-Right-Pointing-Pointer Enhanced martensite formation at the sample surface detected by X-ray diffraction.« less

  20. Carbonic Anhydrase Activity Monitored In Vivo by Hyperpolarized 13C-Magnetic Resonance Spectroscopy Demonstrates Its Importance for pH Regulation in Tumors.

    PubMed

    Gallagher, Ferdia A; Sladen, Helen; Kettunen, Mikko I; Serrao, Eva M; Rodrigues, Tiago B; Wright, Alan; Gill, Andrew B; McGuire, Sarah; Booth, Thomas C; Boren, Joan; McIntyre, Alan; Miller, Jodi L; Lee, Shen-Han; Honess, Davina; Day, Sam E; Hu, De-En; Howat, William J; Harris, Adrian L; Brindle, Kevin M

    2015-10-01

    Carbonic anhydrase buffers tissue pH by catalyzing the rapid interconversion of carbon dioxide (CO2) and bicarbonate (HCO3 (-)). We assessed the functional activity of CAIX in two colorectal tumor models, expressing different levels of the enzyme, by measuring the rate of exchange of hyperpolarized (13)C label between bicarbonate (H(13)CO3(-)) and carbon dioxide ((13)CO2), following injection of hyperpolarized H(13)CO3(-), using (13)C-magnetic resonance spectroscopy ((13)C-MRS) magnetization transfer measurements. (31)P-MRS measurements of the chemical shift of the pH probe, 3-aminopropylphosphonate, and (13)C-MRS measurements of the H(13)CO3(-)/(13)CO2 peak intensity ratio showed that CAIX overexpression lowered extracellular pH in these tumors. However, the (13)C measurements overestimated pH due to incomplete equilibration of the hyperpolarized (13)C label between the H(13)CO3(-) and (13)CO2 pools. Paradoxically, tumors overexpressing CAIX showed lower enzyme activity using magnetization transfer measurements, which can be explained by the more acidic extracellular pH in these tumors and the decreased activity of the enzyme at low pH. This explanation was confirmed by administration of bicarbonate in the drinking water, which elevated tumor extracellular pH and restored enzyme activity to control levels. These results suggest that CAIX expression is increased in hypoxia to compensate for the decrease in its activity produced by a low extracellular pH and supports the hypothesis that a major function of CAIX is to lower the extracellular pH. ©2015 American Association for Cancer Research.

  1. Percutaneous cecostomy in the management of organic fecal incontinence in children

    PubMed Central

    Donkol, Ragab Hani; Al-Nammi, Ahmed

    2010-01-01

    AIM: To assess the effectiveness and safety of imaging-guided percutaneous cecostomy in the management of pediatric patients with organic fecal incontinence. METHODS: Twenty three cecostomies were performed on 21 children with organic fecal incontinence (13 males, 8 females), aged from 5 to 16 years (mean 9.5 years). Thirteen patients had neurogenic fecal incontinence and 8 patients had anorectal anomalies. Procedures were performed under general anesthesia and fluoroscopic guidance. Effectiveness and complication data were obtained for at least 1 year after the procedure. RESULTS: Cecostomy was successful in 20 patients (primary technical success rate 95%). Cecostomy failed in one patient due to tube breakage (secondary technical success rate 100%). The tubes were in situ for an average of 18 mo (range 12-23 mo). Eighteen patients (87%) expressed satisfaction with the procedures. Resolution of soiling was achieved in all patients with neurogenic fecal incontinence (100%) and in 5 of 8 patients with anorectal anomalies (62.5%). Eleven patients (52%) experienced minor problems. No major complications were noted. CONCLUSION: Percutaneous cecostomy improves the quality of life in children with organic fecal incontinence. A satisfactory outcome is more prevalent in patients with neurogenic fecal incontinence than anorectal anomalies. PMID:21225001

  2. "Hexagonal molybdenum trioxide"--known for 100 years and still a fount of new discoveries.

    PubMed

    Lunk, Hans-Joachim; Hartl, Hans; Hartl, Monika A; Fait, Martin J G; Shenderovich, Ilya G; Feist, Michael; Frisk, Timothy A; Daemen, Luke L; Mauder, Daniel; Eckelt, Reinhard; Gurinov, Andrey A

    2010-10-18

    In 1906, the preparation of “molybdic acid hydrate” was published by Arthur Rosenheim. Over the past 40 years, a multitude of isostructural compounds, which exist within a wide phase range of the system MoO3−NH3−H2O, have been published. The reported molecular formulas of “hexagonal molybdenum oxide” varied from MoO3 to MoO3·0.33NH3 to MoO3·nH2O (0.09 ≤ n ≤ 0.69) to MoO3·mNH3·nH2O (0.09 ≤ m ≤ 0.20; 0.18 ≤ n ≤ 0.60). Samples, prepared by the acidification route were investigated using thermal analysis coupled online to a mass spectrometer for evolved gas analysis, X-ray powder diffraction, Fourier transform infrared, Raman, magic-angle-spinning 1H- and 15N NMR spectroscopy, and incoherent inelastic neutron scattering. A comprehensive characterization of these samples will lead to a better understanding of their structure and physical properties as well as uncover the underlying relationship between the various compositions. The synthesized polymeric parent samples can be represented by the structural formula (NH4)(x∞)(3)[Mo(y square 1−y)O(3y)(OH)(x)(H2O)(m−n)]·nH2O with 0.10 ≤ x ≤ 0.14, 0.84 ≤ y ≤ 0.88, and m + n ≥ 3 − x − 3y. The X-ray study of a selected monocrystal confirmed the presence of the well-known 3D framework of edge- and corner-sharing MoO6 octahedra. The colorless monocrystal crystallizes in the hexagonal system with space group P6(3)/m, Z = 6, and unit cell parameters of a = 10.527(1) Å, c = 3.7245(7) Å, V = 357.44(8) Å3, and ρ = 3.73 g·cm(−3). The structure of the prepared monocrystal can best be described by the structural formula (NH4)(0.13∞)(3)[Mo(0.86 square 0.14)O2.58(OH)0.13(H2O)(0.29−n)]·nH2O, which is consistent with the existence of one vacancy (square) for six molybdenum sites. The sample MoO3·0.326NH3·0.343H2O, prepared by the ammoniation of a partially dehydrated MoO3·0.170NH3·0.153H2O with dry gaseous ammonia, accommodates NH3 in the hexagonal tunnels, in addition to [NH4]+ cations and H2O. The “chimie douce” reaction of MoO3·0.155NH3·0.440H2O with a 1:1 mixture of NO/NO2 at 100 °C resulted in the synthesis of MoO3·0.539H2O. This material is of great interest as a host of various molecules and cations.

  3. Improved photoelectrochemical performance of BiVO4/MoO3 heterostructure thin films

    NASA Astrophysics Data System (ADS)

    Kodan, Nisha; Mehta, B. R.

    2018-05-01

    Bismuth vanadate (BiVO4) and Molybdenum trioxide (MoO3) thin films have been prepared by RF sputtering technique. BiVO4 thin films were deposited on indium doped tin oxide (In: SnO2; ITO) substrates at room temperature and 80W applied rf power. The prepared BiVO4 thin films were further annealed at 450°C for 2 hours in air to obtain crystalline monoclinic phase and successively coated with MoO3 thin films deposited at 150W rf power and 400°C for 30 minutes. The effect of coupling BiVO4 and MoO3 on the structural, optical and photoelectrochemical (PEC) properties have been studied. Optical studies reveal that coupling of BiVO4 and MoO3 results in improvement of optical absorption in visible region of solar spectrum. PEC study shows approximate 3-fold and 38-fold increment in photocurrent values of BiVO4/MoO3 (0.38 mA/cm2) heterostructure thin film as compared to MoO3 (0.15 mA/cm2) and BiVO4 (10 µA/cm2) thin films at applied bias of 1 V vs Ag/AgCl in 0.5 M Na2SO4 (pH=7) electrolyte.

  4. Infrared spectroscopic characterization of molybdenum carbonyl species formed by ultraviolet photoreduction of silica-supported Mo(VI) in carbon monoxide

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

    Williams, C.C.; Ekerdt, J.G.

    1993-07-01

    The molybdenum carbonyl species formed by ultraviolet photoreduction of Mo[sup 6+]SiO[sub 2] in CO were characterized with Fourier transform infrared spectroscopy and temperature-programmed decomposition (TPDE). Mo[sup 6+]SiO[sub 2] samples containing 0.07-6.4% Mo were prepared from MoCl[sub 5], Mo[sub 2]([eta][sup 3]-C[sub 3]H[sub 5])[sub 4], and (NH[sub 4])[sub 6]Mo[sub 7]O[sub 24][center dot]4H[sub 2]O. Four molybdenum carbonyl species have been identified: mer-Mo[sup 4+](CO)[sub 3], cis-Mo[sup 4+](CO)[sub 2], linear Mo[sup 4+](CO), and Mo(CO)[sub 6]. The stoichiometry of photoreduction, decomposition, and reoxidation supports the +4 oxidation state for the mono-, di-, and tricarbonyls. The C[sub 2v] symmetry of mer-Mo(CO)[sub 3] resulted in an IR spectrummore » consisting of a weak (A[sub 1])[sub 1] symmetric trans C-O stretch at 2181 cm[sup [minus]1], a strong B[sub 2] antisymmetric trans C-O stretch at 2141 cm[sup [minus]1], and a strong (A[sub 1])[sub 2] cis C-O stretch at 2108 cm[sup [minus]1]. The mer-Mo(CO)[sub 3] structure successfully predicted the observed frequencies and intensities of partially substituted Mo([sup 12]C[sup 16]O)[sub x]([sup 13]C[sup 16]O)[sub 3[minus]x] and Mo([sup 12]C[sup 16]O)[sub x]([sup 13]C[sup 18]O)[sub 3[minus]x] (x = 1, 2). Mo(CO)[sub 3] was stable at 300 K with CO partial pressures above 60 Torr. At 193 K, this species was stable under vacuum. Evacuation of mer-Mo(CO)[sub 3] at 300 K led to CO ligand loss, resulting in the sequential formation of cis-Mo(CO)[sub 2], linear Mo(CO), and finally, CO-free Mo[sup 4+]. The tricarbonyl assignment is supported by the TPDE pattern, in which two CO ligands were released near 350 K, followed by desorption of the final CO group near 440 K. The stable species are photoformed in the sequence mer-Mo[sup 4+](CO)[sub 3], cis-Mo[sup 4+](CO)[sub 2], and Mo(CO)[sub 6]. 31 refs., 9 figs., 4 tabs.« less

  5. Self-assembled 3D sphere-like SrMoO4 and SrMoO4:Ln3+ (Ln=Eu, Sm, Tb, Dy) microarchitectures: facile sonochemical synthesis and optical properties.

    PubMed

    Zhang, Junjun; Li, Ruiqing; Liu, Lu; Li, Linlin; Zou, Lianchun; Gan, Shucai; Ji, Guijuan

    2014-09-01

    Three-dimensional (3D) well-defined SrMoO4 and SrMoO4:Ln(3+) (Ln=Eu, Sm, Tb, Dy) hierarchical structures of obvious sphere-like shape have been successfully synthesized using a large-scale and facile sonochemical route without using any catalysts or templates. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), and photoluminescence (PL) spectra were used to characterize the samples. The intrinsic structural feature of SrMoO4 and external factor, namely the ultrasonic time and the pH value, are responsible for the ultimate shape evolutions of the product. The possible formation mechanism for the product is presented. Additionally, the PL properties of SrMoO4 and SrMoO4:Ln(3+) (Ln=Eu, Sm, Tb, Dy) hierarchical structures were investigated in detail. The Ln(3+) ions doped SrMoO4 samples exhibit respective bright red-orange, yellow, green and white light of Eu(3+), Sm(3+), Tb(3+) and Dy(3+) under ultraviolet excitation, and have potential application in the field of color display. Simultaneously, this novel and efficient pathway could open new opportunities for further investigating about the properties of molybdate materials. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Covalent heterogenization of discrete bis(8-quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes by a metal-template/metal-exchange method: Cyclooctene epoxidation catalysts with enhanced performances

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

    Yang, Ying; Chattopadhyay, Soma; Shibata, Tomohiro

    A metal-template/metal-exchange method was used to imprint covalently attached bis(8- quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes onto large surface-area, mesoporous SBA-15 silica to obtain discrete MoO2 VIT and WO2 VIT catalysts bearing different metal loadings, respectively. Homogeneous counterparts, MoO2 VIN and WO2 VIN, as well as randomly ligandgrafted heterogeneous analogues, MoO2 VIG and WO2 VIG, were also prepared for comparison. X-ray absorption fine structure (XAFS), pair distribution function (PDF) and UV–vis data demonstrate that MoO2 VIT and WO2 VIT adopt a more solution-like bis(8-quinolinol) coordination environment than MoO2 VIG and WO2 VIG, respectively. Correspondingly, the templated MoVI and WVI catalysts show superiormore » performances to their randomly grafted counterparts and neat analogues in the epoxidation of cyclooctene. It is found that the representative MoO2 VIT-10% catalyst can be recycled up to five times without significant loss of reactivity, and heterogeneity test confirms the high stability of MoO2 VIT-10% catalyst against leaching of active species into solution. The homogeneity of the discrete bis(8-quinolinol) metal spheres templated on SBA-15 should be responsible for the superior performances.« less

  7. Mobilization of arsenic and other naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers.

    PubMed

    Rango, Tewodros; Vengosh, Avner; Dwyer, Gary; Bianchini, Gianluca

    2013-10-01

    This study investigates the mechanisms of arsenic (As) and other naturally occurring contaminants (F(-), U, V, B, and Mo) mobilization from Quaternary sedimentary aquifers of the Main Ethiopian Rift (MER) and their enrichment in the local groundwater. The study is based on systematic measurements of major and trace elements as well as stable oxygen and hydrogen isotopes in groundwater, coupled with geochemical and mineralogical analyses of the aquifer rocks. The Rift Valley aquifer is composed of rhyolitic volcanics and Quaternary lacustrine sediments. X-ray fluorescence (XRF) results revealed that MER rhyolites (ash, tuff, pumice and ignimbrite) and sediments contain on average 72 wt. % and 65 wt. % SiO2, respectively. Petrographic studies of the rhyolites indicate predominance of volcanic glass, sanidine, pyroxene, Fe-oxides and plagioclase. The As content in the lacustrine sediments (mean = 6.6 mg/kg) was higher than that of the rhyolites (mean: 2.5 mg/kg). The lacustrine aquifers of the Ziway-Shala basin in the northern part of MER were identified as high As risk zones, where mean As concentration in groundwater was 22.4 ± 33.5 (range of 0.60-190 μg/L) and 54% of samples had As above the WHO drinking water guideline value of 10 μg/L. Field As speciation measurements showed that most of the groundwater samples contain predominantly (~80%) arsenate-As(V) over arsenite-As(III) species. The As speciation together with field data of redox potential (mean Eh = +73 ± 65 mV) and dissolved-O2 (6.6 ± 2.2 mg/L) suggest that the aquifer is predominantly oxidative. Water-rock interactions, including the dissolution of volcanic glass produces groundwater with near-neutral to alkaline pH (range 6.9-8.9), predominance of Na-HCO3 ions, and high concentration of SiO2 (mean: 85.8 ± 11.3 mg/L). The groundwater data show high positive correlation of As with Na, HCO3, U, B, V, and Mo (R(2) > 0.5; p < 0.001). Chemical modeling of the groundwater indicates that Fe-oxides and oxyhydroxides minerals were saturated in the groundwater, suggesting that the As reactivity is controlled by adsorption/desorption processes with these minerals. The data show that As and other oxyanion-forming elements such as U, B, Mo, and V had typically higher concentrations at pH > ~8, reflecting the pH-dependence of their mobilization. Based on the geochemical and stable isotope variations we have established a conceptual model for the occurrence of naturally occurring contaminants in MER groundwater: 1) regional groundwater recharge from the Highland, along the Rift margins, followed by lateral flow and water-rock interactions with the aquifer rocks resulted in a gradual increase of the salinity and naturally occurring contaminants towards the center of the valley; and (2) local δ(18)O-rich lake water recharge into adjacent shallow aquifers, followed by additional mobilization of As and other oxyanion-forming elements from the aquifer rocks. We posit that the combined physical-chemical conditions of the aquifers such as oxidizing state, Na-HCO3 composition, and pH>~8 lead to enhanced mobilization of oxyanion-forming elements from Fe-oxides and consequently contamination of local groundwater. These geochemical conditions characterize groundwater resources along the Eastern African Rift and thus constitute a potential threat to the quality of groundwater in larger areas of Eastern Africa. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Y{sub 2}MoSe{sub 3}O{sub 12} and Y{sub 2}MoTe{sub 3}O{sub 12}: Solid-state synthesis, structure determination, and characterization of two new quaternary mixed metal oxides containing asymmetric coordination environment

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

    Bang, Seong-eun; Pan, Zhi; Kim, Yeong Hun

    Two new quaternary yttrium molybdenum selenium/tellurium oxides, Y{sub 2}MoSe{sub 3}O{sub 12} and Y{sub 2}MoTe{sub 3}O{sub 12} have been prepared by standard solid-state reactions using Y{sub 2}O{sub 3}, MoO{sub 3}, and SeO{sub 2} (or TeO{sub 2}) as reagents. Single-crystal X-ray diffraction was used to determine the crystal structures of the reported materials. Although both of the materials contain second-order Jahn–Teller (SOJT) distortive cations and are stoichiometrically similar, they reveal different structural features: while Y{sub 2}MoSe{sub 3}O{sub 12} shows a three-dimensional framework consisting of YO{sub 8}, MoO{sub 6}, and SeO{sub 3} groups, Y{sub 2}MoTe{sub 3}O{sub 12} exhibits a layered structure composed ofmore » YO{sub 8}, MoO{sub 4}, TeO{sub 3}, and TeO{sub 4} polyhedra. With the Mo{sup 6+} cations in Y{sub 2}MoSe{sub 3}O{sub 12}, a C{sub 3}-type intraoctahedral distortion toward a face is observed, in which the direction of the out-of-center distortion for Mo{sup 6+} is away from the oxide ligand linked to a Se{sup 4+} cation. The Se{sup 4+} and Te{sup 4+} cations in both materials are in asymmetric coordination environment attributed to the lone pairs. Elemental analyses, infrared spectroscopy, thermal analyses, intraoctahedral distortions, and dipole moment calculations for the compounds are also presented. - Graphical abstract: Y{sub 2}MoSe{sub 3}O{sub 12} reveals a three-dimensional framework consisting of YO{sub 8}, MoO{sub 6}, and SeO{sub 3} polyhedra, whereas Y{sub 2}MoTe{sub 3}O{sub 12} exhibits a layered structure composed of YO{sub 8}, MoO{sub 4}, TeO{sub 3}, and TeO{sub 4} groups. - Highlights: • Two new selenite and tellurite (Y{sub 2}MoQ{sub 3}O{sub 12}; Q=Se and Te) are synthesized. • Y{sub 2}MoQ{sub 3}O{sub 12} contain second-order Jahn–Teller distortive cations in asymmetric environments. • The intra-octahedral distortion of the Mo{sup 6+} is influenced by the Se{sup 4+}.« less

  9. Two-gap superconductivity in Mo8Ga41 and its evolution upon vanadium substitution

    NASA Astrophysics Data System (ADS)

    Verchenko, V. Yu.; Khasanov, R.; Guguchia, Z.; Tsirlin, A. A.; Shevelkov, A. V.

    2017-10-01

    Zero-field and transverse-field muon spin rotation/relaxation (μ SR ) experiments were undertaken in order to elucidate the microscopic properties of a strongly coupled superconductor Mo8Ga41 with Tc=9.8 K. The upper critical field extracted from the transverse-field μ SR data exhibits significant reduction with respect to the data from thermodynamic measurements indicating the coexistence of two independent length scales in the superconducting state. Accordingly, the temperature-dependent magnetic penetration depth of Mo8Ga41 is described using a model in which two s wave superconducting gaps are assumed. A V for Mo substitution in the parent compound leads to the complete suppression of one superconducting gap, and Mo7VGa41 is well described within the single s wave gap scenario. The reduction in the superfluid density and the evolution of the low-temperature resistivity upon V substitution indicate the emergence of a competing state in Mo7VGa41 that may be responsible for the closure of one of the superconducting gaps.

  10. Pressure-Temperature Studies and Structural Setting of Amphibolite-Grade Rocks Within the Easternmost Indus-Ysangpo Suture Zone and Forearc Complex (Tidding Formation), N. Indo-Burma Ranges of N.E. India

    NASA Astrophysics Data System (ADS)

    Braza, M.; Haproff, P. J.

    2016-12-01

    The easternmost extension of the Indus-Ysangpo suture (IYS) and Xigaze forearc complex, the Tidding Formation of northeastern India, remains the least-studied sequence representing closure of the Neotethys ocean and syn-tectonic sedimentation. In this study, we present P-T determinations coupled with detrital zircon U-Pb geochronology and detailed geologic mapping to uncover the depositional and metamorphic history of Tidding suture and forearc rocks during Himalayan orogenesis. Four mica schists were sampled from successive NW-SE-striking thrust sheets within the Dibang Valley of Arunachal Pradesh (N.E. India), southwest of the easternmost L. Cretaceous Gangdese batholith. Use of the garnet-muscovite-biotite-plagioclase (GMBP) thermobarometer and Ti-in-biotite thermometer on schist sample PH-1-8-13-26 yield peak conditions of 627 ± 28°C and 10.4 ± 1.1 kbar. Similarly, use of the garnet-biotite Fe-Mg exchange thermometer and garnet-aluminosilicate-silica-plagioclase (GASP) barometer yield 644 ± 50°C and 12 ± 1 kbar for schist sample PH-11-14-15-24 within the same thrust sheet. Both samples contain recrystallized quartz along grain boundaries and garnets contain no significant compositional zoning. At structurally lower levels, garnet chlorite schist (PH-1-8-13-8) sampled from the Mayodia klippe records peak temperatures below 650°C. Garnets display growth zoning, with increasing Mn and decreasing Fe and Mg from rim to core. Application of the Ti-in-biotite thermometer to a mafic schist (PH-1-3-13-1B) within the Mayodia klippe near a southwestward-directed thrust yields a peak temperature of 679 ± 24°C. Our study reveals metamorphism of IYS rocks occurred at deep crustal levels (>30 km) during northward Neotethys subduction. Suture rocks were subsequently exhumed by orogen-scale N-dipping thrusts during growth of the easternmost Himalayan orogen.

  11. Photoemission and Auger-electron spectroscopic study of the Chevrel-phase compound FexMo6S8

    NASA Astrophysics Data System (ADS)

    Fujimori, A.; Sekita, M.; Wada, H.

    1986-05-01

    The electronic structure of the Chevrel-phase compound FexMo6S8 has been studied by photoemission and Auger-electron spectroscopy. Core-level shifts suggest a large charge transfer from the Fe atoms to the Mo6S8 clusters and a small Mo-to-S charge transfer within the cluster. Line-shape asymmetry in the core levels indicates that the density of states (DOS) at the Fermi level has a finite S 3p component as well as the dominant Mo 3d character. Satellite structure and exchange splitting in the Fe core levels point to weak Fe 3d-S 3p hybridization in spite of the short Fe-S distances comparable to that in FeS. The x-ray and ultraviolet valence-band photoemission spectra and the Mo 4d partial DOS obtained by deconvoluting the Mo M4,5VV Auger spectrum are compared with existing band-structure calculations, and the Mo 4d-S 3p bonding character, the structure of the Mo 4d-derived conduction band etc., are discussed. In particular, it is shown that the conduction-band structure is sensitive to the noncubic distortion of the crystal through changes in the intercluster Mo 4d-S 3p hybridization. A pronounced final-state effect is found in the Mo M4,5N2,3V Auger spectrum and is attributed to strong 4p-4d intershell coupling.

  12. Photocatalytic wastewater purification with simultaneous hydrogen production using MoS2 QD-decorated hierarchical assembly of ZnIn2S4 on reduced graphene oxide photocatalyst.

    PubMed

    Zhang, Shuqu; Wang, Longlu; Liu, Chengbin; Luo, Jinming; Crittenden, John; Liu, Xia; Cai, Tao; Yuan, Jili; Pei, Yong; Liu, Yutang

    2017-09-15

    It is attractive to photocatalytically purify wastewater and simultaneously convert solar energy into clean hydrogen energy. However, it is still a challenge owing to the relatively low photocatalytic efficiency of photocatalysts. In this study, we synthesized a molybdenum disulfide (MoS 2 ) quantum dot-decorated 3D nanoarchitecture (MoS 2 QDs) of indium zinc sulfide (ZnIn 2 S 4 ) and reduced grapheme oxide (MoS 2 QDs@ZnIn 2 S 4 @RGO) photocatalyst using a simple solvothermal method. The RGO promotes the electron transfer, and the highly dispersed MoS 2 QDs provides numerous catalytic sites. The photocatalytic purification of rhodamine B (RhB), eosin Y (EY), fulvic acid (FA), methylene blue (MB) and p-nitrophenol (PNP) in simulated wastewaters were further tested. The degradation efficiencies and TOC removal were 91% and 75% for PNP, 92.2% and 72% for FA, 98.5% and 80% for MB, 98.6% and 84% for EY, and 98.8% and 88% for RhB, respectively (C organics  = 20 mg/L, C catalyst  = 1.25 g/L, t = 12 h, I light  = 3.36 × 10 -5  E L -1  s -1 ). Among these tests, the highest hydrogen production was achieved (45 μmol) during RhB degradation. Both experimental and calculational results prove that lower LUMO (lowest unoccupied molecular orbit) level of organic molecules was available for transferring electrons to catalysts, resulting in more efficient hydrogen production. Significantly, the removal efficiencies of natural organic substances in actual river water reached 76.3-98.4%, and COD reduced from 32 to 16 mg/L with 13.8 μmol H 2 production after 12 h. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Exploration of a Variety of Copper Molybdate Coordination Hybrids Based on a Flexible Bis(1,2,4-triazole) Ligand: A Look through the Composition-Space Diagram.

    PubMed

    Senchyk, Ganna A; Lysenko, Andrey B; Domasevitch, Konstantin V; Erhart, Oliver; Henfling, Stefan; Krautscheid, Harald; Rusanov, Eduard B; Krämer, Karl W; Decurtins, Silvio; Liu, Shi-Xia

    2017-11-06

    We investigated the coordination ability of the bis(1,2,4-triazolyl) module, tr 2 pr = 1,3-bis(1,2,4-triazol-4-yl)propane, toward the engineering of solid-state structures of copper polyoxomolybdates utilizing a composition space diagram approach. Different binding modes of the ligand including [N-N]-bridging and N-terminal coordination and the existence of favorable conformation forms (anti/anti, gauche/anti, and gauche/gauche) resulted in varieties of mixed metal Cu I /Mo VI and Cu II /Mo VI coordination polymers prepared under hydrothermal conditions. The composition space analysis employed was aimed at both the development of new coordination solids and their crystallization fields through systematic changes of the reagent ratios [copper(II) and molybdenum(VI) oxide precursors and the tr 2 pr ligand]. Nine coordination compounds were synthesized and structurally characterized. The diverse coordination architectures of the compounds are composed of cationic fragments such as [Cu II 3 (μ 2 -OH) 2 (μ 2 -tr) 2 ] 4+ , [Cu II 3 (μ 2 -tr) 6 ] 6+ , [Cu II 2 (μ 2 -tr) 3 ] 4+ , etc., connected to polymeric arrays by anionic species (molybdate MoO 4 2- , isomeric α-, δ-, and β-octamolybdates {Mo 8 O 26 } 4- or {Mo 8 O 28 H 2 } 6- ). The inorganic copper(I,II)/molybdenum(VI) oxide matrix itself forms discrete or low-dimensional subtopological motifs (0D, 1D, or 2D), while the organic spacers interconnect them into higher-dimensional networks. The 3D coordination hybrids show moderate thermal stability up to 230-250 °C, while for the 2D compounds, the stability of the framework is distinctly lower (∼190 °C). The magnetic properties of the most representative samples were investigated. The magnetic interactions were rationalized in terms of analyzing the planes of the magnetic orbitals.

  14. Comparative Effectiveness of Tacrolimus-Based Steroid Sparing versus Steroid Maintenance Regimens in Kidney Transplantation: Results from Discrete Event Simulation.

    PubMed

    Desai, Vibha C A; Ferrand, Yann; Cavanaugh, Teresa M; Kelton, Christina M L; Caro, J Jaime; Goebel, Jens; Heaton, Pamela C

    2017-10-01

    Corticosteroids used as immunosuppressants to prevent acute rejection (AR) and graft loss (GL) following kidney transplantation are associated with serious cardiovascular and other adverse events. Evidence from short-term randomized controlled trials suggests that many patients on a tacrolimus-based immunosuppressant regimen can withdraw from steroids without increased AR or GL risk. To measure the long-term tradeoff between GL and adverse events for a heterogeneous-risk population and determine the optimal timing of steroid withdrawal. A discrete event simulation was developed including, as events, AR, GL, myocardial infarction (MI), stroke, cytomegalovirus, and new onset diabetes mellitus (NODM), among others. Data from the United States Renal Data System were used to estimate event-specific parametric regressions, which accounted for steroid-sparing regimen (avoidance, early 7-d withdrawal, 6-mo withdrawal, 12-mo withdrawal, and maintenance) as well as patients' demographics, immunologic risks, and comorbidities. Regression-equation results were used to derive individual time-to-event Weibull distributions, used, in turn, to simulate the course of patients over 20 y. Patients on steroid avoidance or an early-withdrawal regimen were more likely to experience AR (45.9% to 55.0% v. 33.6%, P < 0.05) and GL (51.5% to 68.8% v. 37.8%, P < 0.05) compared to patients on steroid maintenance. Patients in 6-mo and 12-mo steroid withdrawal groups were less likely to experience MI (11.1% v. 13.3%, P < 0.05), NODM (30.7% to 34.4% v. 37.7%, P < 0.05), and cardiac death (29.9% to 30.5% v. 32.4%, P < 0.05), compared to steroid maintenance. Strategies of 6- and 12-mo steroid withdrawal post-kidney transplantation are expected to reduce the rates of adverse cardiovascular events and other outcomes with no worsening of AR or GL rates compared with steroid maintenance.

  15. Psychroflexus saliphilus sp. nov., isolated from a marine solar saltern

    USDA-ARS?s Scientific Manuscript database

    A Gram-stain-negative, non-motile, rod-shaped, orange pigmented strain, WDS4A13**T, was isolated from a marine solar saltern in Weihai, China. WDS4A13**T grows optimally at pH at 7.0-8.0, 33°C, with 6% (w/v) NaCl. The polar lipid profile of the novel isolate consisted of two unidentified phospholipi...

  16. Effects of chronic copper exposure during early life in rhesus monkeys.

    PubMed

    Araya, Magdalena; Kelleher, Shannon L; Arredondo, Miguel A; Sierralta, Walter; Vial, María Teresa; Uauy, Ricardo; Lönnerdal, Bo

    2005-05-01

    Whether infants regulate copper absorption and the potential effects of excess copper in early life remain poorly defined. The objective of the study was to assess copper retention, liver copper content, and liver function in infant rhesus monkeys fed infant formula containing 6.6 mg Cu/L. From birth to 5 mo of age, infant rhesus monkeys were fed formula that was supplemented with copper (0.6 mg Cu/L; n = 5) or not supplemented (n = 4). In all animals, weight and crown-rump length (by anthropometry), hemoglobin, hematocrit, plasma ceruloplasmin activity, and zinc and copper concentrations were measured monthly (birth to 6 mo) and at 8 and 12 mo. When the animals were 1, 5, and 8 mo old, liver copper and metallothionein concentrations, liver histology (by light and electron microscopy), and the number of Kupffer cells were assessed, and 67Cu retention was measured. Liver function was assessed by measurement of plasma alanine aminotransferase, aspartate aminotransferase, gamma-glutamyl transferase, and alkaline phosphatase activities and protein, albumin, bilirubin, and blood urea nitrogen concentrations. 67Cu retention was 19.2% and 10.9% after 1 and 5 mo of copper treatment, respectively, compared with approximately 75% in controls at age 2 mo. At age 8 mo, 67Cu retention was 22.9% in copper-treated animals and 31.5% in controls. Liver histology remained normal by light microscopy, with mild ultrastructural signs of cell damage at 5 mo. Liver copper concentration was 4711, 1139, and 498 microg/g dry tissue at 1, 5, and 8 mo, respectively, in copper-treated animals and 250 microg/g at 2 mo in controls. Measurements could not be completed in all animals. No clinical evidence of copper toxicity was observed. Copper absorption was down-regulated; increases in liver copper content at ages 1 and 5 mo did not result in histologic damage. Ultrastructural changes at age 5 mo could signal early cellular damage.

  17. Nutritional significance of the Cu:Mo interrelationship to ruminants and non-ruminants

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

    Suttle, N.F.

    1973-01-01

    Mo has been shown to interfere with the Cu metabolism of several species but the interrelationship is thought to be of practical significance only to ruminants when herbage Mo concentrations exceed 5 ppM. Evidence has been obtained that Mo interferes with Cu metabolism in both ruminants and non-ruminants at concentrations below 5 ppM and within a range encountered in foods for human consumption. Groups of hypocupraemic ewes were repleted with a semi-purified diet containing 8 mgCu/kg and one of four levels of dietary Mo, 0.5, 2.5, 4.5 and 8.5 mg/kg. Rate of recovery in plasma Cu was used as amore » measure of the efficiency of Cu utilization and successive increments in dietary Mo were found to decrease that efficiency by 40, 80 and 40%, respectively. The results suggest that differences of 1 mg/kg in dietary Mo are of biological significance to ruminants. When groups of Cu-depleted guinea pigs were subjected to repletion with diets containing 8 mg Cu/kg and 0.6, 4.1, 26 or 104 mg Mo/kg the lowest increment in Mo, 3.5 mg/kg, decreased the response in liver Cu as much as the highest, 75 mg/kg, a reduction fo 23% being recorded. The industrial uses of Mo make it a potential contaminant of man's environment and Mo concentrations > 4 mg/kg have been reported in vegetables and meats. The possibility that the Cu:Mo interrelationship influences Cu metabolism in man should therefore be re-examined. 20 references, 3 tables.« less

  18. Double salt crystal structure of hexa-sodium hemiundeca-hydrogen α-hexa-molybdoplatinate(IV) heminona-hydrogen α-hexa-molybdoplatinate(IV) nona-cosa-hydrate: di-hydrogen disordered-mixture double salt.

    PubMed

    Joo, Hea-Chung; Park, Ki-Min; Lee, Uk

    2015-10-01

    The title double salt containing two distinct, differently protonated hexa-molybdoplatinate(IV) polyanions, Na6[H5.5 α-PtMo6O24][H4.5 α-PtMo6O24]·29H2O, has been synthesized by a hydro-thermal reaction at ca pH 1.80. The positions of the H atoms in the polyanions were established from difference Fourier maps and confirmed by the inter-polyanion hydrogen bonds, bond-distance elongation, and bond-valence sum (BVS) calculations. The fractional numbers of H atoms in each polyanion are required for charge balance and in order to avoid unrealistically short H⋯H distances in the inter-polyanion hydrogen bonds. Considering the disorder, the refined formula of the title polyanion, {[H5.5 α-PtMo6O24]; polyanion (A) and [H4.5 α-PtMo6O24]; polyanion (B)}(6-), can be rewritten as a set of real formula, viz. {[H6 α-PtMo6O24]; polyanion (A). [H4 α-PtMo6O24]; polyanion (B)}(6-) and {[H5 α-PtMo6O24]; polyanion (A). [H5 α-PtMo6O24]; polyanion (B)}(6-). The polyanion pairs both form dimers of the same formula, viz. {[H10 α-Pt2Mo12O48]}(6-) connected by seven inter-polyanion O-H⋯O hydrogen bonds.

  19. Petrogenesis of the Yaochong granite and Mo deposit, Western Dabie orogen, eastern-central China: Constraints from zircon U-Pb and molybdenite Re-Os ages, whole-rock geochemistry and Sr-Nd-Pb-Hf isotopes

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Xu, Zhaowen; Qiu, Wenhong; Li, Chao; Yu, Yang; Wang, Hao; Su, Yang

    2015-05-01

    The Dabie orogen is among the most famous continent-continent collisional orogenic belts in the world, and is characterized by intensive post-collisional extension, magmatism and Mo mineralization. However, the genetic links between the mineralization and the geodynamic evolution of the orogen remain unresolved. In this paper, the Yaochong Mo deposit and its associated granitic stocks were investigated to elucidate this issue. Our new zircon U-Pb ages yielded an Early Cretaceous age (133.3 ± 1.3 Ma) for the Yaochong granite, and our molybdenite Re-Os dating gave a similar age (135 ± 1 Ma) for the Mo deposit. The Yaochong stock is characterized by high silica and alkali but low Mg, Fe and Ca. It is enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs: Rb, K, Th and U), but strongly depleted in heavy REEs, and high field strength elements (HFSEs: Nb, Ta, Ti and Y). The Yaochong granite has initial 87Sr/86Sr ratios of 0.7087-0.7096, and Pb isotopic ratios of (206Pb/204Pb)i = 16.599-16.704, (207Pb/204Pb)i = 15.170-15.618 and (208Pb/204Pb)i = 36.376-38.248. The granite has εNd(t) of -18.0 to -16.3 and εHf(t) values of -26.5 to -20.0. All these data indicate that the Yaochong granite is a high-K calc-alkaline fractionated I-type granite, and may have originated from partial melting of the thickened Yangtze continental crust. The Mo ores also show low radiogenic Pb isotopes similar to the Yaochong stock. Medium Re content in molybdenite (21.8-74.8 ppm) also suggests that the ore-forming materials were derived from the thickened lower crust with possibly minor mixing with the mantle. Similar to the Eastern Dabie orogen, the thickened crust beneath the Western Dabie orogen may also have experienced tectonic collapse, which may have exerted fundamental geodynamic controls on the two-stage Mo mineralization in the region.

  20. Investigation of the thermal annealing effect on electrical properties of Ni/Au, Ni/Mo/Au and Mo/Au Schottky barriers on AlGaN/GaN heterostructures

    NASA Astrophysics Data System (ADS)

    Sleptsov, E. V.; Chernykh, A. V.; Chernykh, S. V.; Dorofeev, A. A.; Gladysheva, N. B.; Kondakov, M. N.; Sleptsova, A. A.; Panichkin, A. V.; Konovalov, M. P.; Didenko, S. I.

    2017-03-01

    Investigation of the thermal annealing effect on Schottky barrier parameters and the leakage current of Ni/Au, Ni/Mo/Au and Mo/Au Schottky barriers on AlGaN/GaN heterostructures has been performed. Improvement of Schottky barrier parameters after annealing of the investigated metallization schemes was observed. Ni/Au and Mo/Au contacts drastically degrade after annealing at the temperatures higher than 400 °C, whereas the Ni/Mo/Au contact exhibits excellent parameters after 500 °C annealing (qϕb = 1.00 eV, n = 1.13 и Ileak = 5 μA).

  1. The impact of highly concentrated Mo and Cu dietary supplements, fed as a bolus, on the efficacy of chelated versus inorganic Cu in cattle on a low-Cu diet.

    PubMed

    Grace, N D; West, D M; Smith, S L; Knowles, S O

    2013-11-01

    To compare the efficacy of chelated versus inorganic forms of dietary Cu supplements, fed as a bolus, when challenged by a daily bolus of dietary Mo in cattle on a low-Cu diet. Forty non-lactating, Friesian dairy cows of adequate Cu status were assigned to four groups and fed a basal diet of baled silage containing 5.3 mg Cu and 0.4 mg Mo/kg DM. The experimental design was a factorial of two chemical forms of supplemental Cu and two levels of Mo intake, provided as pelleted grain supplements made from crushed barley/molasses plus Cu and Mo. The supplements contained 140 mg Cu/kg as Cu sulphate pentahydrate (CS), 140 mg Cu/kg as Cu glycinate (CG), CS plus 38 mg Mo/kg as sodium molybdate (CS+Mo), or CG plus 38 mg Mo/kg (CG+Mo). Commencing on Day 0, supplements were fed once daily (offered 1-1.2 kg/cow) and were completely consumed within 5-10 minutes, which constitutes a bolus type of administration. Liver samples were collected by biopsy at Days -24, 13, 41 or 47, and 69 for Cu determinations. The diets fed to the Cu+Mo groups were roughly equivalent to 25 mg Cu and 5.7 mg Mo/kg DM. Mean initial concentration of Cu in liver for all groups was 516 (SE 54) μmol Cu/kg fresh tissue. In cows supplemented with CS and CG, the final (Day 69) concentrations increased (p<0.01) to 939 (SE 166) and 853 (SE 163) μmol Cu/kg, respectively. These values were not different (p=0.72). For groups CS+Mo and CG+Mo, the final concentrations of 535 (SE 122) and 453 (SE 102) μmol Cu/kg were not different from initial values or from each other (p>0.25). The rate of accumulation of Cu in liver following bolus Cu and Mo intake was highly variable but was not affected by initial concentration of Cu in liver (p>0.9) or by the form of Cu (p>0.6). Mean rates of accumulation of Cu in liver were 4.0 (SD 3.8) and 0.65 (SD 2.0) μmol Cu/kg fresh tissue/day for the Cu-only treatments and the Cu+Mo treatments, respectively. When fed together as a bolus, high Mo intake negated the effect of supplemental Cu but it did not reduce liver Cu stores. There was no difference in the reaction of dietary Mo with chelated Cu (as glycinate) versus inorganic Cu (as sulphate) dietary supplements.

  2. Applications of ZVMo NMR spectroscopy. 17. ZVMo and UN relaxation time measurements confirming that (Mo(CN)8)U is dodecahedral in aqueous solution

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

    Brownlee, R.T.; Shehan, B.P.; Wedd, A.G.

    1987-07-01

    Variable-temperature NMR line width measurements of ZVMo and UN in aqueous solutions of K4(Mo(CN)8) x 2H2O indicate that the stereochemistry of the (Mo(CN)8)U ion in solution is dodecahedral. A value for the ZVMo quadrupole coupling constant of 3.61 MHz is obtained. 27 references, 1 figure, 1 table.

  3. Highly Reversible Zinc-ion Intercalation with Chevrel Phase Mo6S8 Nanocubes and Applications for Advanced Zinc-ion Batteries

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

    Cheng, Yingwen; Luo, Langli; Zhong, Li

    We demonstrate the application of the Chevrel phase Mo6S8 nanocubes as the anode material for rechargeable Zn-ion batteries. Mo6S8 can host Zn2+ ions reversibility both in aqueous and nonaqueous electrolytes with specific capacities around 90 mAh/g and exhibited remarkable intercalation kinetics as well as stability. Furthermore, we assembled full cells by integrating Mo6S8 anode with zinc-polyiodide (I-/I3-) based catholytes, and demonstrated that such fuel cells was also able to deliver outstanding rate performance and cyclic stability. This first demonstration of zinc intercalating anode could inspire the design of advanced Zn ion batteries.

  4. CDC Kerala 3: At-risk baby clinic service using different screening tools--outcome at 12 months using Developmental Assessment Scale for Indian Infants.

    PubMed

    Nair, M K C; Krishnan, Rajee; Harikumaran Nair, G S; George, Babu; Bhaskaran, Deepa; Leena, M L; Russell, Paul Swamidhas Sudhakar

    2014-12-01

    To describe CDC Kerala experience of establishing an at-risk baby clinic and the comparison of different developmental screening tools at 12 mo against the gold standard Developmental Assessment Scale for Indian Infants (DASII). At risk baby clinic of CDC, Kerala was established as a facility for follow up of NICU graduates from Sree Avittam Thirunal Hospital at 2, 4, 6, 8 and 12 mo corrected age and during each visit the mother is taught the CDC model early stimulation by developmental therapists and encouraged to continue to do the same at home. At 12 mo, assessment results of four simple developmental tools were compared with the gold standard DASII administered by a senior developmental therapist. Out of a total of 800 babies, outcome measurements at 12 mo were available for 604 infants. The prevalence of developmental delay using the screening tools, CDC grading for standing, Amiel Tison angles and DDST II (Denver II) gross motor were 24.8, 24 and 24.3% respectively and using DASII, a diagnostic tool (13.3%). Also the combination of Amiel Tison angles, CDC standing grading and DDST gross motor against DASII motor DQ had high specificity (94.15%) and negative predictive value (NPV) (70.18%) but with a very low sensitivity of 14.58% and low positive predictive value (PPV) of 53.85%. It was observed that a significant odds ratio for DASII mental deviation quotient (DQ) was seen for neonatal seizures (2.34) and low birth weight (1.49). The prevalence of developmental delay using the screening tools, CDC grading for standing, Amiel Tison angles and DDST II (Denver II) gross motor were 24.8, 24 and 24.3% respectively and together they had a high specificity, NPV and accuracy against DASII motor DQ as gold standard at one year assessment.

  5. Verbal and memory skills in males with Duchenne muscular dystrophy

    PubMed Central

    Hinton, V J; BA, R J Fee; Goldstein, E M; De Vivo, D C

    2007-01-01

    Duchenne muscular dystrophy (DMD) is a progressive pediatric disorder that affects both muscle and brain. Children with DMD have mean IQ scores that are about one standard deviation lower than population means, with lower Verbal IQ than Performance IQ scores. For the present study, verbal skills and verbal memory skills were examined in males with DMD with the Clinical Evaluation of Language Fundamentals, 3rd edition, and the California Verbal Learning Test for Children. Performance of 50 males with DMD (age range 6–14y, mean 9y 4mo [SD 2y 1mo]) was compared to normative values. Two subsets of the probands were also compared with two comparison groups: unaffected siblings (n=24; DMD group age range 6–12y, mean 9y 1mo [SD 1y 8mo]; sibling age range 6–15y, mean 9y 11mo [SD 2y 4mo]) and males with cerebral palsy (CP); (n=23; DMD group age range 6–9y, mean 7y 8mo [SD 1y 2mo]; CP age range 6–8y, mean 6y 8mo [SD 0y 8mo]). Results demonstrated that although males with DMD performed slightly more poorly than normative values, they performed comparably to the controls on most measures. Consistent deficits were observed only on tests requiring immediate repetition for verbal material (Recalling Sentences, and Concepts and Directions). On other language tasks, including tests of understanding and use of grammar, and understanding of semantic relationships, the males with DMD performed well. Moreover, the males with DMD performed well on multiple indices of verbal recall, and there was no evidence of declarative memory deficits. DMD is a single-gene disorder that is selectively associated with decreased verbal span capacity, but not impaired recall. PMID:17254000

  6. Template-free synthesis of ZnWO{sub 4} powders via hydrothermal process in a wide pH range

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

    Hojamberdiev, Mirabbos, E-mail: mirabbos_uz@yahoo.com; Zhu, Gangqiang; Xu, Yunhua

    ZnWO{sub 4} powders with different morphologies were fabricated through a template-free hydrothermal method at 180 {sup o}C for 8 h in a wide pH range. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible and luminescence spectrophotometers were applied to study the effects of pH values on crystallinity, morphology, optical and luminescence properties. The XRD results showed that the WO{sub 3} + ZnWO{sub 4}, ZnWO{sub 4}, and ZnO phases could form after hydrothermal processing at 180 {sup o}C for 8 h with the pH values of 1, 3-11, and 13, respectively. The SEM and TEM observation revealedmore » that the morphological transformation of ZnWO{sub 4} powders occurred with an increase in pH values as follows: star anise-, peony-, and desert rose-like microstructures and soya bean- and rod-like nanostructures. The highest luminescence intensity was found to be in sample consisting of star anise-like crystallites among all the samples due to the presence of larger particles with high crystallinity resulted from the favorable pH under the current hydrothermal conditions.« less

  7. Inorganic Carbon Source for Photosynthesis in the Seagrass Thalassia hemprichii (Ehrenb.) Aschers.

    PubMed

    Abel, K M

    1984-11-01

    Photosynthetic carbon uptake of the tropical seagrass Thalassia hemprichii (Ehrenb.) Aschers was studied by several methods. Photosynthesis in buffered seawater in media in the range of pH 6 to pH 9 showed an exponentially increasing rate with decreasing pH, thus indicating that free CO(2) was a photosynthetic substrate. However, these experiments were unable to determine whether photosynthesis at alkaline pH also contained some component due to HCO(3) (-) uptake. This aspect was further investigated by studying photosynthetic rates in a number of media of varying pH (7.8-8.61) and total inorganic carbon (0.75-13.17 millimolar). In these media, photosynthetic rate was correlated with free CO(2) concentration and was independent of the HCO(3) (-) concentration in the medium. Short time-course experiments were conducted during equilibration of free CO(2) and HCO(3) (-) after injection of (14)C labeled solution at acid or alkaline pH. High initial photosynthetic rates were observed when acidic solutions (largely free CO(2)) were used but not with alkaline solutions. The concentration of free CO(2) was found to be a limiting factor for photosynthesis in this plant.

  8. Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to-allene rearrangement, and the electronic transition relevant to the back-bonding interaction.

    PubMed

    Pinkas, Jiří; Gyepes, Róbert; Císařová, Ivana; Kubišta, Jiří; Horáček, Michal; Mach, Karel

    2015-04-28

    The titanocene-ethene complex [Ti(II)(η(2)-C2H4)(η(5)-C5Me5)2] (1) with simple internal alkynes R(1)C≡CR(2) gives complexes [Ti(II)(η(2)-R(1)C≡CR(2))(η(5)-C5Me5)2] {R(1), R(2): Ph, Ph (3), Ph, Me (4), Me, SiMe3 (5), Ph, SiMe3 (6), t-Bu, SiMe3 (7), and SiMe3, SiMe3 (8). In contrast, alkynes with R(1) = Me and R(2) = t-Bu or i-Pr afford allene complexes [Ti(II)(η(2)-CH2=C=CHR(2))(η(5)-C5Me5)2] (11) and (12), whereas for R(2) = Et a mixture of alkyne complex (13A) and minor allene (13) is obtained. Crystal structures of 4, 6, 7 and 11 have been determined; the latter structure proved the back-bonding interaction of the allene terminal double bond. Only the synthesis of 8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiC≡CSiMe3] ⇌ [8] + [C2H4] approached 1. Compound 9 (R(1), R(2): Me), not obtainable from 1, together with compounds 3–6 and 10 (R(1), R(2): Et) were also prepared by alkyne exchange with 8, however this reaction did not take place in attempts to obtain 7. Compounds 1 and 3–9 display the longest-wavelength electronic absorption band in the range 670-940 nm due to the HOMO → LUMO transition. The assignment of the first excitation to be of predominantly a b2 → a1 transition was confirmed by DFT calculations. The calculated first excitation energies for 3–9 followed the order of hypsochromic shifts of the absorption band relative to 8 that were induced by acetylene substituents: Me > Ph ≫ SiMe3. Computational results have also affirmed the back-bonding nature in the alkyne-to-metal coordination.

  9. DoD Priorities for Autonomy Research and Development

    DTIC Science & Technology

    2011-10-21

    Research and Development MORLEY O. STONE, ST, PhD Autonomy PSC Lead 21 October 2011 NDIA Disruptive Technologies Conference November 8-9, 2011...AVAILABILITY STATEMENT Approved for public release; distribution unlimited 13. SUPPLEMENTARY NOTES Presented at the NDIA Disruptive Technologies Conference

  10. Batch sorption results for neptunium transport through Yucca Mountain tuffs. Yucca Mountain Site Characterization Program milestone 3349

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

    Triay, I.R.; Cotter, C.R.; Huddleston, M.H.

    1996-09-01

    We studied the sorption of neptunium onto tuffs characteristic of the proposed nuclear waste repository at Yucca Mountain, Nevada. The neptunium was in the Np(V) oxidation state under oxidizing conditions in groundwaters from two wells located close to the repository site (J-13 and UE-25 p No.1). We used devitrified, vitric, zeolitic (with emphasis on clinoptilolite-rich samples), and calcite-rich tuffs characteristic of the geology of the site. Neptunium sorbed well onto calcite and calcite-rich tuffs, indicating that a significant amount of neptunium retardation can be expected under fractured-flow scenarios because of calcite coating of the fractures. Neptunium sorption onto clinoptilolite-rich zeoliticmore » tuffs in J-13 well water (pH from 7 to 8.5) was moderate, increased with decreasing pH, and correlated to surface area and amount of clinoptilolite. Neptunium sorbed poorly onto zeolitic tuffs from UE-25 p No.1 groundwater (pH from 7 to 9) and onto devitrified and vitric tuffs from J-13 and UE-25 p No.1 waters (pH from 7 to 9). Iron oxides appeared to be passivated in tuffs, not seeming to contribute to the observed neptunium sorption, even though neptunium sorption onto synthetic iron oxide is significant.« less

  11. Outcomes of different bearings in total hip arthroplasty - implant survival, revision causes, and patient-reported outcome.

    PubMed

    Varnum, Claus

    2017-03-01

    Total hip arthroplasty (THA) is a common and successful treatment of patients suffering from severe osteoarthritis that significantly reduces pain and improves hip function and quality of life. Traditionally, the outcome of THA has been evaluated by orthopaedic surgeons and assessed in morbidity and mortality rates, and implant survival. As patients and surgeons may assess outcome after THA differently, patient-reported outcomes (PROMs) have gained much more interest and are today recognized as very important tools for evaluating the outcome and satisfaction after THA. One of the prognostic factors for the outcome of THA is the type of bearings. This PhD thesis focuses on the influence of different types of bearings on implant survival, revision causes, PROMs, and noises from THA. The aims of the thesis were: Study I: To examine the revision risk and to investigate the causes of revision of cementless ceramic-on-ceramic (CoC) THAs comparing them to those of "standard" metal-on-polyethylene (MoP) THAs. Study II: To compare the six-year revision risk for metal-on-metal (MoM) with that for MoP bearings in cementless stemmed THA, and further to study the revision risk for different designs of stemmed MoM THAs and the causes of revision. Study III: To examine the association between CoC, MoM, and MoP bearings and both generic and disease-specific PROMs, and furthermore to examine the incidence and types of noises from the three types of bearings and identify the effect of noises on PROM scores. In study I and III, we used data from the Danish Hip Arthroplasty Registry combined with data from the Civil Registration System and the Danish National Patient Registry. In study II, data from the Nordic Arthroplasty Register Association, containing data from hip arthroplasty registries in Denmark, Norway, Sweden, and Finland, was used. In study I, 11,096 patients operated from 2002 through 2009 with cementless THA were included. Of these, 16% had CoC THA and 84% had MoP THA. At 8.7-year follow-up, no difference in RR of revision for any cause was found for CoC compared to MoP THA. One cause of revision related only to CoC THA is ceramic fracture. Medical records were reviewed for patients who had revision surgery due to component failure, and six patients (0,34%) had been revised due to ceramic fracture. No other difference in prevalence of causes of revision was found when comparing CoC to MoP THA. Study II included 32,678 patients who were operated from 2002 through 2010 with cementless stemmed THA with either MoM bearings (11,567 patients, 35%) or MoP bearings (21,111 patients, 65%). At six-year follow-up, the RR of revision for any cause was significantly higher for MoM compared to MoP THA. When comparing different combinations of cup/stem with MoM to MoP bearings, there was an increased RR of revision for any cause for the ASR/Summit, ASR/Corail, and "other" combinations. There was a higher prevalence of revision due to aseptic loosening for MoM compared to MoP THA. In contrast, the prevalence of revision due to dislocation was lower for MoM THA. In study III, a set of questionnaires including HOOS, EQ-5D, UCLA activity score, and a questionnaire about noises from the THA was sendt to patients having THA with CoC, MoM, or MoP bearings. The response rate was 85% and among the 3,089 patients responding, 45% received CoC, 17% MoM, and 38% MoP THA. No differences in mean subscale scores were found for CoC and MoM compared to MoP THA, except for CoC THA that had a lower mean HOOS symptoms score than MoP THA. 27% of patients with CoC, 29% of patients with MoM, and 12% of patients with MoP bearings had experienced noises from the THA. For the three types of bearings, PROM scores from patients with noisy THA were significantly lower when compared to silent MoP THA, except for noisy CoC and MoM THA that had the same mean UCLA activity score as silent MoP THA.

  12. Transfer of Oleic Acid between Albumin and Phospholipid Vesicles

    NASA Astrophysics Data System (ADS)

    Hamilton, James A.; Cistola, David P.

    1986-01-01

    The net transfer of oleic acid between egg phosphatidylcholine unilamellar vesicles and bovine serum albumin has been monitored by 13C NMR spectroscopy and 90% isotopically substituted [1-13C]oleic acid. The carboxyl chemical shifts of oleic acid bound to albumin were different from those for oleic acid in phospholipid vesicles. Therefore, in mixtures of donor particles (vesicles or albumin with oleic acid) and acceptor particles (fatty acid-free albumin or vesicles), the equilibrium distribution of oleic acid was determined from chemical shift and peak intensity data without separation of donor and acceptor particles. In a system containing equal masses of albumin and phospholipid and a stoichiometry of 4-5 mol of oleic acid per mol of albumin, the oleic acid distribution was pH dependent, with >= 80% of the oleic acid associated with albumin at pH 7.4; association was >= 90% at pH 8.0. Decreasing the pH below 7.4 markedly decreased the proportion of fatty acid bound to albumin; at pH 5.4, <= 10% of the oleic acid was bound to albumin and >90% was associated with vesicles. The distribution was reversible with pH and was independent of whether vesicles or albumin acted as a donor. These data suggest that pH may strongly influence the partitioning of fatty acid between cellular membranes and albumin. The 13C NMR method is also advantageous because it provides information about the structural environments of oleic acid bound to albumin or phospholipid, the ionization state of oleic acid in each environment, and the structural integrity of the vesicles. In addition, minimum and maximum limits for the exchange rates of oleic acid among different environments were obtained from the NMR data.

  13. Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

    PubMed

    Norkus, E; Vaskelis, A; Zakaite, I

    1996-03-01

    D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

  14. Vitamin D status and functional health outcomes in children aged 2-8 y: a 6-mo vitamin D randomized controlled trial.

    PubMed

    Brett, Neil R; Parks, Colleen A; Lavery, Paula; Agellon, Sherry; Vanstone, Catherine A; Kaufmann, Martin; Jones, Glenville; Maguire, Jonathon L; Rauch, Frank; Weiler, Hope A

    2018-03-01

    Most Canadian children do not meet the recommended dietary intake for vitamin D. The aims were to test how much vitamin D from food is needed to maintain a healthy serum 25-hydroxyvitamin D3 [25(OH)D3] status from fall to spring in young children and to examine musculoskeletal outcomes. Healthy children aged 2-8 y (n = 51) living in Montreal, Canada, were randomly assigned to 1 of 2 dietary vitamin D groups (control or intervention to reach 400 IU/d by using vitamin D-fortified foods) for 6 mo, starting October 2014. At baseline and at 3 and 6 mo, anthropometric characteristics, vitamin D metabolites (liquid chromatography-tandem mass spectrometry), and bone biomarkers (IDS-iSYS, Immunodiagnositc Systems; Liaison; Diasorin) were measured and physical activity and food intakes surveyed. At baseline and at 6 mo, bone outcomes and body composition (dual-energy X-ray absorptiometry) were measured. Cross-sectional images of distal tibia geometry and muscle density were conducted with the use of peripheral quantitative computed tomography scans at 6 mo. At baseline, participants were aged 5.2 ± 1.9 (mean ± SD) y and had a body mass index z score of 0.65 ± 0.12; 53% of participants were boys. There were no differences between groups in baseline serum 25(OH)D3 (66.4 ± 13.6 nmol/L) or vitamin D intake (225 ± 74 IU/d). Median (IQR) compliance was 96% (89-99%) for yogurt and 84% (71-97%) for cheese. At 3 mo, serum 25(OH)D3 was higher in the intervention group (P < 0.05) but was not different between groups by 6 mo. Although lean mass accretion was higher in the intervention group (P < 0.05), no differences in muscle density or bone outcomes were observed. The consumption of 400 IU vitamin D/d from fall to spring did not maintain serum 25(OH)D3 concentration or improve bone outcomes. Further work with lean mass accretion as the primary outcome is needed to confirm if vitamin D enhances lean accretion in healthy young children. This trial was registered at www.clinicaltrials.gov as NCT02387892.

  15. A vacuum (10(exp -9) Torr) friction apparatus for determining friction and endurance life of MoSx films

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Honecy, Frank S.; Abel, Phillip B.; Pepper, Stephen V.; Spalvins, Talivaldis; Wheeler, Donald R.

    1992-01-01

    The first part of this paper describes an ultrahigh vacuum friction apparatus (tribometer). The tribometer can be used in a ball-on-disk configuration and is specifically designed to measure the friction and endurance life of solid lubricating films such as MoS(x) in vacuum at a pressure of 10 exp -7 Pa. The sliding mode is typically unidirectional at a constant rotating speed. The second part of this paper presents some representative friction and endurance life data for magnetron sputtered MoS(x) films (110 nm thick) deposited on sputter-cleaned 440 C stainless-steel disk substrates, which were slid against a 6-mm-diameter 440 C stainless-steel bearing ball. All experiments were conducted with loads of 0.49 to 3.6 N (average Hertzian contact pressure, 0.33 to 0.69 GPa), at a constant rotating speed of 120 rpm (sliding velocity ranging from 31 to 107 mm/s due to the range of wear track radii involved in the experiments), in a vacuum of 7 x 10 exp -7 Pa and at room temperature. The results indicate that there are similarities in friction behavior of MoS(x) films overs their life cycles regardless of load applied. The coefficient of friction (mu) decreases as load W increases according to mu = kW exp -1/3. The endurance life E of MoS(x) films decreases as the load W increases according to E = KW exp -1.4 for the load range. The load- (or contract-pressure-) dependent endurance life allows us to reduce the time for wear experiments and to accelerate endurance life testing of MoS(x) films. For the magnetron-sputtered MoS(x) films deposited on 440 C stainless-steel disks: the specific wear rate normalized to the load and the number of revolutions was 3 x 10 exp -8 mm exp 3/N-revolution; the specific wear rate normalized to the load and the total sliding distance was 8 x 10 exp -7 mm exp 3/N-m; and the nondimensional wear coefficient of was approximately 5 x 10 exp -6. The values are almost independent of load in the range 0.49 to 3.6 N (average Hertzian contact pressures of 0.33 to 0.69 GPa).

  16. Hydrodesulfurization reactions of atmospheric gas oil over CoMo/alumina-aluminum borate catalysts

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

    Chiuping Li; Jungchung Wu; Yuwen Chen

    1993-08-01

    A precipitation technique at constant pH value was used to prepare a series of alumina-aluminum borates (AABs) with various Al/B atomic ratios. These materials were used as the supports of Co-Mo catalysts. Hydrodesulfurization (HDS) of Kuwait atmospheric gas (AGO) oil was carried out over these presulfided catalysts in a bench-scale trickle bed reactor at 400 psi and 340 C. All CoMo/AAB catalysts are much more active than the conventional CoMo/Al[sub 2]O[sub 3] catalyst on HDS reactions. A correlation exists between the acidity and the HDS activity of the catalysts. The high activities of the CoMo/AAB catalysts can be rationalized onmore » the presence of boron. On one hand, it can increase the metal dispersions and hydrogenation capabilities. On the other hand, it can enhance the acidities and cracking abilities of the catalysts. The desulfurization data can be fitted with a pseudo-second-order rate equation. The activation energy for desulfurization is found to be 26 kcal/mol.« less

  17. Synthesis, characterization and cytotoxic studies of water soluble [(η5-C5H5)2Mo(thionucleobase/thionucleoside)]Cl complexes in breast and colon cancer cell lines

    PubMed Central

    Acevedo-Acevedo, Débora; Matta, Jaime; Meléndez, Enrique

    2010-01-01

    Four new water soluble molybdenocene complexes were synthesized in aqueous solution at pH 7.0. The new species, [(η5-C5H5)2Mo(L)]Cl (L= 6-mercaptopurine, 2-amino-6-mercaptopurine, (-)-2-amino-6-mercaptopurine ribose and 6-mercaptopurine ribose), were characterized by spectroscopic methods. NMR spectroscopic data showed the presence of two coordination isomers, S(6), N(7) and S(6), N(1), in aqueous solution, being S(6), N(7) the most stable. The antiproliferative activities of the new species were investigated in HT-29 colon and MCF-7 breast cancer cell lines. The incorporation of molybdenocene (Cp2Mo2+) into the thionucleobases/thionucleosides decreases their cytotoxic activities in HT-29 colon cancer cell line. In contrast, in the MCF-7 cell line, [Cp2Mo(2-amino-6-mercaptopurine)]Cl showed a high cytotoxic activity. This is most likely a consequence of the enhanced lipophilic character on the thionucleobase combined with synergism between Cp2Mo2+ and the thionucleobase ligand. PMID:21399723

  18. A pure inorganic 1D chain based on {Mo8O28} clusters and Mn(II) ions: [Mn(H2O)2Mo8O28 ] n 6 n -

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaofen; Yan, Yonghong; Wu, Lizhou; Yu, Chengxin; Dong, Xinbo; Hu, Huaiming; Xue, Ganglin

    2016-01-01

    A new pure inorganic polymer, (NH4)6n[Mn(H2O)2Mo8O28)]n(H2O)2n(1), has been synthesized and characterized by elemental analyses, IR spectrum, UV-vis absorption spectra, TG-DSC and electrochemical studies. In 1, [Mo8O28]8- anions act as tetradentate ligands and are alternately linked by Mn(H2O)2 2 + ions into a one-dimensional chain structure. It is interesting that 1 represents the first example of pure inorganic-inorganic hybrid based on octamolybdate and transition metal ions. Moreover, it was indicated that 1 had definite catalytic activities on the probe reaction of benzyl alcohol oxidation to benzaldehyde with H2O2.

  19. Safety and effectiveness of the INVATEC MO.MA proximal cerebral protection device during carotid artery stenting: results from the ARMOUR pivotal trial.

    PubMed

    Ansel, Gary M; Hopkins, L Nelson; Jaff, Michael R; Rubino, Paolo; Bacharach, J Michael; Scheinert, Dierk; Myla, Subbarao; Das, Tony; Cremonesi, Alberto

    2010-07-01

    The multicenter ARMOUR (ProximAl PRotection with the MO.MA Device DUring CaRotid Stenting) trial evaluated the 30-day safety and effectiveness of the MO.MA Proximal Cerebral Protection Device (Invatec, Roncadelle, Italy) utilized to treat high surgical risk patients undergoing carotid artery stenting (CAS). Distal embolic protection devices (EPD) have been traditionally utilized during CAS. The MO.MA device acts as a balloon occlusion "endovascular clamping" system to achieve cerebral protection prior to crossing the carotid stenosis. This prospective registry enrolled 262 subjects, 37 roll-in and 225 pivotal subjects evaluated with intention to treat (ITT) from September 2007 to February 2009. Subjects underwent CAS using the MO.MA device. The primary endpoint, myocardial infarction, stroke, or death through 30 days (30-day major adverse cardiac and cerebrovascular events [MACCE]) was compared to a performance goal of 13% derived from trials utilizing distal EPD. For the ITT population, the mean age was 74.7 years with 66.7% of the cohort being male. Symptomatic patients comprised 15.1% and 28.9% were octogenarians. Device success was 98.2% and procedural success was 93.2%. The 30-day MACCE rate was 2.7% [95% CI (1.0-5.8%)] with a 30-day major stroke rate of 0.9%. No symptomatic patient suffered a stroke during this trial. The ARMOUR trial demonstrated that the MO.MA(R) Proximal Cerebral Protection Device is safe and effective for high surgical risk patients undergoing CAS. The absence of stroke in symptomatic patients is the lowest rate reported in any independently adjudicated prospective multicenter registry trial to date. (c) 2010 Wiley-Liss, Inc.

  20. Laser-assisted development of titanium alloys: the search for new biomedical materials

    NASA Astrophysics Data System (ADS)

    Almeida, Amelia; Gupta, Dheeraj; Vilar, Rui

    2011-02-01

    Ti-alloys used in prosthetic applications are mostly alloys initially developed for aeronautical applications, so their behavior was not optimized for medical use. A need remains to design new alloys for biomedical applications, where requirements such as biocompatibility, in-body durability, specific manufacturing ability, and cost effectiveness are considered. Materials for this application must present excellent biocompatibility, ductility, toughness and wear and corrosion resistance, a large laser processing window and low sensitivity to changes in the processing parameters. Laser deposition has been investigated in order to access its applicability to laser based manufactured implants. In this study, variable powder feed rate laser cladding has been used as a method for the combinatorial investigation of new alloy systems that offers a unique possibility for the rapid and exhaustive preparation of a whole range of alloys with compositions variable along a single clad track. This method was used as to produce composition gradient Ti-Mo alloys. Mo has been used since it is among the few elements biocompatible, non-toxic β-Ti phase stabilizers. Alloy tracks with compositions in the range 0-19 wt.%Mo were produced and characterized in detail as a function of composition using microscale testing procedures for screening of compositions with promising properties. Microstructural analysis showed that alloys with Mo content above 8% are fully formed of β phase grains. However, these β grains present a cellular substructure that is associated to a Ti and Mo segregation pattern that occurs during solidification. Ultramicroindentation tests carried out to evaluate the alloys' hardness and Young's modulus showed that Ti-13%Mo alloys presented the lowest hardness and Young's modulus (70 GPa) closer to that of bone than common Ti alloys, thus showing great potential for implant applications.

  1. Comparison of the risk of revision in cementless total hip arthroplasty with ceramic-on-ceramic and metal-on-polyethylene bearings

    PubMed Central

    Varnum, Claus; Pedersen, Alma B; Kjærsgaard-Andersen, Per; Overgaard, Søren

    2015-01-01

    Background and purpose Ceramic-on-ceramic (CoC) bearings were introduced in total hip arthroplasty (THA) to reduce problems related to polyethylene wear. We compared the 9-year revision risk for cementless CoC THA and for cementless metal-on-polyethylene (MoP) THA. Patients and methods In this prospective, population-based study from the Danish Hip Arthroplasty Registry, we identified all the primary cementless THAs that had been performed from 2002 through 2009 (n = 25,656). Of these, 1,773 THAs with CoC bearings and 9,323 THAs with MoP bearings were included in the study. To estimate the relative risk (RR) of revision, we used regression with the pseudo-value approach and treated death as a competing risk. Results 444 revisions were identified: 4.0% for CoC THA (71 of 1,773) and 4.0% for MoP THA (373 of 9,323). No statistically significant difference in the risk of revision for any reason was found for CoC and MoP bearings after 9 years of follow-up (adjusted RR = 1.3, 95% CI: 0.72–2.4). Revision rates due to component failure were 0.5% (n = 8) for CoC bearings and 0.1% (n = 6) for MoP bearings (p < 0.001). 6 patients with CoC bearings (0.34%) underwent revision due to ceramic fracture. Interpretation When compared to the “standard” MoP bearings, CoC THA had a 33% higher (though not statistically significantly higher) risk of revision for any reason at 9 years. PMID:25637339

  2. Reversible intercalation of ammonia molecules into a layered double hydroxide structure without exchanging nitrate counter-ions

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

    Carbajal Arizaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.m; Wypych, Fernando; Castillon Barraza, Felipe

    2010-10-15

    A zinc/aluminum LDH was precipitated with recycled ammonia from a chemical vapor deposition reaction. The LDH presented a crystalline phase with basal distance of 8.9 A, typical for nitrate-containing LDHs, and another phase with a basal distance of 13.9 A. Thermal treatment at 150 {sup o}C eliminated the phase with the bigger basal distance leaving only the anhydrous nitrate-intercalated LDH structure with 8.9 A. Intense N-H stretching modes in the FTIR spectra suggested that the expansion was due to intercalation of ammonia in the form of [NH{sub 4}(NH{sub 3}){sub n}]{sup +} species. When additional samples were precipitated with pure ammonia,more » the conventional LDH nitrate structure was obtained (8.9 A basal distance) at pH=7, as well as a pure crystalline phase with 13.9 A basal distance at pH=10 due to ammonia intercalation that can be removed by heating at 150 {sup o}C or by stirring in acetone, confirming a unusual sensu stricto intercalation process into a LDH without exchanging nitrate ions. - Graphical abstract: LDH-nitrate precipitated with ammonia expands the interlayer space if ammonia is bubbled up to pH 10. The basal distance decreased when the compound was heated at 150 {sup o}C or stirred in acetone. Nitrate ions are not exchanged.« less

  3. Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution.

    PubMed

    Kistler, Melissa L; Liu, Tianbo; Gouzerh, Pierre; Todea, Ana Maria; Müller, Achim

    2009-07-14

    We report the self-assembly processes in solution of three Keplerate-type molybdenum-oxide based clusters {Mo72V30}, {Mo72Cr30} and {Mo72Fe30} (all with diameters of approximately 2.5 nm). These clusters behave as unique weak polyprotic acids owing to the external water ligands attached to the non-Mo metal centers. Whereas the Cr and Fe clusters have 30 water ligands attached at the 30 M3+ centers pointing outside, {Mo72V30} has 20 water ligands coordinated to vanadium atoms, of which only 10 are pointing outside. The self-assembly processes of the Keplerates leading to supramolecular blackberry-type structures are influenced by the effective charge densities on the cluster surfaces, which can be tuned by the pH values and solvent properties. As expected, {Mo72Cr30} and {Mo72Fe30} behave similarly in aqueous solution due to their analogous structures and in both cases the self-assembly follows the partial deprotonation of the external water ligands attached to the non-Mo metal centers. However, the M-OH2 functionalities differ not only in acidity but also lability, i.e. in different residence times of the H2O ligands. In contrast to {Mo72Cr30} and {Mo72Fe30}, the {Mo72V30} clusters carry a rather large number of negative charges so that their solution properties are different. They exist as discrete macroions in dilute aqueous solution, and form only in mixed water/organic solvent (like acetone) blackberry-type structures whose size increases with acetone content. The comparison of the properties of the clusters allows more general information about the interesting self-assembly phenomenon to be unveiled.

  4. Four-wave-mixing and nonlinear cavity dumping of 280 picosecond 2nd Stokes pulse at 1.3 μm from Nd:SrMoO4 self-Raman laser

    NASA Astrophysics Data System (ADS)

    Smetanin, S. N.; Jelínek, M., Jr.; Kubeček, V.; Jelínková, H.; Ivleva, L. I.; Shurygin, A. S.

    2016-01-01

    The 280 picosecond 2nd Stokes Raman pulses at 1.3 μm were generated directly from the miniature diode-pumped Nd:SrMoO4 self-Raman laser. Using the 90° phase matching insensitive to the angular mismatch, the self-Raman laser allowed for the achievement of the four-wave-mixing generation of the 2nd Stokes Raman pulse directly in the active Nd:SrMoO4 crystal at stimulated Raman scattering (SRS) self-conversion of the laser radiation. The passive Cr:YAG Q-switching and nonlinear cavity dumping was used without any phase locking device.

  5. PP13, Maternal ABO Blood Groups and the Risk Assessment of Pregnancy Complications

    PubMed Central

    Than, Nandor Gabor; Romero, Roberto; Meiri, Hamutal; Erez, Offer; Xu, Yi; Tarquini, Federica; Barna, Laszlo; Szilagyi, Andras; Ackerman, Ron; Sammar, Marei; Fule, Tibor; Karaszi, Katalin; Kovalszky, Ilona; Dong, Zhong; Kim, Chong Jai; Zavodszky, Peter; Papp, Zoltan; Gonen, Ron

    2011-01-01

    Background Placental Protein 13 (PP13), an early biomarker of preeclampsia, is a placenta-specific galectin that binds beta-galactosides, building-blocks of ABO blood-group antigens, possibly affecting its bioavailability in blood. Methods and Findings We studied PP13-binding to erythrocytes, maternal blood-group effect on serum PP13 and its performance as a predictor of preeclampsia and intrauterine growth restriction (IUGR). Datasets of maternal serum PP13 in Caucasian (n = 1078) and Hispanic (n = 242) women were analyzed according to blood groups. In vivo, in vitro and in silico PP13-binding to ABO blood-group antigens and erythrocytes were studied by PP13-immunostainings of placental tissue-microarrays, flow-cytometry of erythrocyte-bound PP13, and model-building of PP13 - blood-group H antigen complex, respectively. Women with blood group AB had the lowest serum PP13 in the first trimester, while those with blood group B had the highest PP13 throughout pregnancy. In accordance, PP13-binding was the strongest to blood-group AB erythrocytes and weakest to blood-group B erythrocytes. PP13-staining of maternal and fetal erythrocytes was revealed, and a plausible molecular model of PP13 complexed with blood-group H antigen was built. Adjustment of PP13 MoMs to maternal ABO blood group improved the prediction accuracy of first trimester maternal serum PP13 MoMs for preeclampsia and IUGR. Conclusions ABO blood group can alter PP13-bioavailability in blood, and it may also be a key determinant for other lectins' bioavailability in the circulation. The adjustment of PP13 MoMs to ABO blood group improves the predictive accuracy of this test. PMID:21799738

  6. Preparation of single-crystal spherical γ-Mo2N by temperature-programmed reaction between β-MoO3 and NH3

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Zhang, Guo-Hua; Chou, Kuo-Chih

    2017-10-01

    In the present wok, single-crystalline spherical γ-Mo2N powders was successfully prepared by the temperature-programmed reaction of single-crystal spherical β-MoO3 with NH3 in the temperature ranges of 1013-1073 K. Herein, the Mo source used was monoclinic system, β-MoO3, a metastable phase of MoO3. It is found that the characterizations of the as-prepared γ-Mo2N powders are strongly depended on the selection of the MoO3 precursor. In other words, the as-prepared γ-Mo2N powders inherited the shape, size and structure of the used β-MoO3 precursors upon reaction with NH3. In order to make a comparison, β-MoO3 was also reduced by the mixed gases of N2 and H2 with the flow rate ratio of 1:3 at the identical conditions. It was found that pure β-Mo2N polycrystalline can be obtained when the temperature was 1013 K; while further increasing the reaction temperature, metal Mo powder will be turned up.

  7. National Dam Safety Program. Lipps Lake Dam (MO 30214). Mississippi - Kaskaskia - St. Louis Basin, Cape Girardeau County, Missouri. Phase I Inspection Report.

    DTIC Science & Technology

    1980-10-01

    AD-A105 988 HOSKINSEWESTERN-SONOER EGGER INC LINCOLN NEM F/S 13/13 NATIONAL DA -M SAFETY PROGRAM. LI PS LAKE DAM (MO 3021 ). MISS! SS7 - TC(U...COMPLETING FORM i. REPORT NUMBER 12. GOVT ACCESSION NO. 3. RECIPIENT’S CATALOG NIOMBER 4. TITLE (and Subtitle) 5. TYPE OF REPORT & PERIOD COVERED Phase I Dam

  8. Improvement of Tribological Performance of AISI H13 Steel by Means of a Self-Lubricated Oxide-Containing Tribo-layer

    NASA Astrophysics Data System (ADS)

    Cui, Xianghong; Jin, Yunxue; Chen, Wei; Zhang, Qiuyang; Wang, Shuqi

    2018-03-01

    A self-lubricated oxide-containing tribo-layer was induced to form by continuously adding particles of MoS2, Fe2O3 or their mixtures onto sliding interfaces of AISI H13 and 52100 steels. The artificial tribo-layer was always noticed to form continuously and cover the worn surface (termed as cover-type), whereas the original tribo-layer spontaneously formed with no additive was usually discontinuous and inserted into the substrate (termed as insert-type). Clearly, the cover-type and insert-type tribo-layers exactly corresponded to low and high wear rates, respectively. For the mixed additives of Fe2O3 + MoS2, the protective tribo-layers presented a load-carrying capability and lubricative function, which are attributed to the existence of Fe2O3 and MoS2. Hence, the wear rates and friction coefficients of H13 steel were markedly reduced.

  9. EFFECT OF PH, DIC, ORTHOPHOSPHATE AND SULFATE ON DRINKING WATER CUPROSOLVENCY

    EPA Science Inventory

    Field data from various copper monitoring studies and Lead and Copper Rule compliance data are often inappropriate and misleading for reliably determining fundamental chemical relationships behind copper corrosion control. To address this deficiency, a comprehensive solubility mo...

  10. Assembly of three organic-inorganic hybrid supramolecular materials based on reduced molybdenum(V) phosphates

    NASA Astrophysics Data System (ADS)

    Zhang, He; Yu, Kai; Lv, Jing-Hua; Wang, Chun-Mei; Wang, Chun-Xiao; Zhou, Bai-Bin

    2014-09-01

    Three supramolecular materials based on {P4Mo6} polyoxoanions, (Hbbi)2(H2bbi)[Cu3Mo12VO24(OH)6(H2O)6(HPO4)4(H2PO4)2(PO4)2]·3H2O (1), (Hbbi)2(H2bbi)[Ni3Mo12VO24(OH)6(H2O)2(HPO4)4(H2PO4)2(PO4)2]·9H2O (2), (Hbpy)(bpy)3[Ni2(H2O)10Na(PCA)2][NiMo12VO24(OH)6(H2PO4)6(PO4)2]·6H2O (3) (bbi=1,1‧-(1,4-butanediyl)bis(imidazole), bpy=4,4‧-bipyridine, PCA=pyridine-4-carboxylic acid), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV-vis, PXRD and the single-crystal X-ray diffraction. Compounds 1 and 2 exhibit covalent 1-D chains constructed from M[P4Mo6]2 dimeric cluster and {M(H2O)n} (M=Cu, n=3 for 1 and M=Ni, n=1 for 2) linker. Compound 3 possesses an unusual POMMOF supramolecular layers based on [Ni(P4Mo6)]2 dimeric units and 1-D metal-organic strings [Ni(H2O)5Na(PCA)]n, in which an in situ ligand of PCA from 1,3-bis(4-pyridyl)propane (bpp) precursor was observed. Furthermore, the electrochemical behavior of 1-3-CPE and magnetic properties of 1-3 have been investigated in detail.

  11. Pulmonary hypertension registry of Kerala, India (PRO-KERALA) - Clinical characteristics and practice patterns.

    PubMed

    Harikrishnan, S; Sanjay, G; Ashishkumar, M; Menon, Jaideep; Rajesh, Gopalan Nair; Kumar, Raman Krishna; George Koshy, A; Attacheril, Thankachan V; George, Raju; Punnoose, Eapen; Ashraf, S M; Arun, S R; Cholakkal, Mohammed; Jeemon, Panniyammakal

    2018-08-15

    Epidemiological data on pulmonary hypertension (PH) are scarce from developing countries including India. We established a multi-center registry of PH, the PRO-KERALA registry, in Kerala, India. Fifty hospitals enrolled consecutive adult (>18 years) patients for one year. Echocardiographic criteria (right ventricular systolic pressure - RVSP > 50 mmHg) or invasively obtained mean pulmonary artery pressure > 25 mmHg was the criteria for entry. There were 2003 patients (52% Women, mean age 56 ± 16.1 years) enrolled. The mean RVSP was 68.2 (SD = 17.9) mmHg. Majority of the study participants (59%) belonged to group 2 of the WHO Nice Classification 2013 (PH secondary to left heart disease). One-fifth (21.2%) belonged to group 1, while 13.3%, 3.8% and 2.4% of the study population belonged to groups 3, 4 and 5 respectively. More than a quarter (27%) reported PH due to left heart disease with valvular disease etiology; while 20.7% had coronary artery disease. The other common etiological factors were chronic obstructive pulmonary disease (10.6%), congenital heart disease (14.6%), idiopathic pulmonary hypertension (5.8%), and chronic thromboembolic pulmonary hypertension (3.8%). Only one of two patients with pulmonary artery hypertension was receiving PH specific therapies. The use of combination therapy was negligible and PH-specific therapies were prescribed off-label to a small proportion of patients too. PRO-KERALA is the first PH registry from South Asia and the second largest globally. Left heart diseases attribute to three fifths of patients with PH. Utilization rates of PH specific drug therapies are remarkably lower than the Western population. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. Syntheses and crystal structures of two topologically related modifications of Cs(2)[(UO(2))(2)(MoO(4))(3)].

    PubMed

    Krivovichev, S V; Cahill, C L; Burns, P C

    2002-01-14

    Two polymorphs of Cs(2)(UO(2))(2)(MoO(4))(3) have been synthesized by hydrothermal (alpha-phase) and high-temperature (beta-phase) routes. Both were characterized by single-crystal X-ray diffraction: alpha-Cs(2)(UO(2))(2)(MoO(4))(3), orthorhombic, Pna2(1), a = 20.4302(15) A, b = 8.5552(7) A, c = 9.8549(7) A, Z = 4; beta-Cs(2)(UO(2))(2)(MoO(4))(3), tetragonal, P4(2)/n, a = 10.1367(8) A, c = 16.2831(17) A, Z = 4. The structures of both phases consist of linked UO(7) pentagonal bipyramids and MoO(4) tetrahedra: alpha-Cs(2)(UO(2))(2)(MoO(4))(3) is a framework compound with large channels parallel to the c axis. Two cesium sites are located in these channels and are coordinated by 8 and 10 oxygen atoms. The structure of beta-Cs(2)(UO(2))(2)(MoO(4))(3) contains corrugated [(UO(2))(2)(MoO(4))(3)] sheets that are parallel to (001). The cesium cations are located between the sheets and are coordinated by eight oxygen atoms. The structures are topologically related; both can be described in terms of chains of 5-connected UO(7) pentagonal bipyramids and 3- and 4-connected MoO(4) tetrahedra.

  13. High incidence of biallelic point mutations in the Runt domain of the AML1/PEBP2 alpha B gene in Mo acute myeloid leukemia and in myeloid malignancies with acquired trisomy 21.

    PubMed

    Preudhomme, C; Warot-Loze, D; Roumier, C; Grardel-Duflos, N; Garand, R; Lai, J L; Dastugue, N; Macintyre, E; Denis, C; Bauters, F; Kerckaert, J P; Cosson, A; Fenaux, P

    2000-10-15

    The AML1 gene, situated in 21q22, is often rearranged in acute leukemias through t(8;21) translocation, t(12;21) translocation, or less often t(3;21) translocation. Recently, point mutations in the Runt domain of the AML1 gene have also been reported in leukemia patients. Observations for mutations of the Runt domain of the AML1 gene in bone marrow cells were made in 300 patients, including 131 with acute myeloid leukemia (AML), 94 with myelodysplastic syndrome (MDS), 28 with blast crisis chronic myeloid leukemia (CML), 3 with atypical CML, 41 with acute lymphoblastic leukemia (ALL), and 3 with essential thrombocythemia (ET). Forty-one of the patients had chromosome 21 abnormalities, including t(8;21) in 6 of the patients with AML, t(12;21) in 8 patients with ALL, acquired trisomy 21 in 17 patients, tetrasomy 21 in 7 patients, and constitutional trisomy 21 (Down syndrome) in 3 patients. A point mutation was found in 14 cases (4.7%), including 9 (22%) of the 41 patients with AML of the Mo type (MoAML) (none of them had detectable chromosome 21 rearrangement) and 5 (38%) of the 13 myeloid malignancies with acquired trisomy 21 (1 M1AML, 2 M2AML, 1 ET, and 1 atypical CML). In at least 8 of 9 mutated cases of MoAML, both AML alleles were mutated: 3 patients had different stop codon mutations of the 2 AML1 alleles, and 5 patients had the same missense or stop codon mutation in both AML1 alleles, which resulted in at least 3 of the patients having duplication of the mutated allele and deletion of the normal residual allele, as shown by FISH analysis and by comparing microsatellite analyses of several chromosome 21 markers on diagnosis and remission samples. In the remaining mutated cases, with acquired trisomy 21, a missense mutation of AML1, which involved 2 of the 3 copies of the AML1 gene, was found. Four of the 7 mutated cases could be reanalyzed in complete remission, and no AML1 mutation was found, showing that mutations were acquired in the leukemic clone. In conclusion, these findings confirm the possibility of mutations of the Runt domain of the AML1 gene in leukemias, mainly in MoAML and in myeloid malignancies with acquired trisomy 21. AML1 mutations, in MoAML, involved both alleles and probably lead to nonfunctional AML1 protein. As AML1 protein regulates the expression of the myeloperoxidase gene, the relationship between AML1 mutations and Mo phenotype in AML will have to be further explored. (Blood. 2000;96:2862-2869)

  14. Application of Quantum 1/F Noise Theory to Hg(1-x)Cd(x)Te Infrared Detectors

    DTIC Science & Technology

    1988-06-25

    Hooge parameter. 2. 1 / f Noise of the Recombination Current Generated in the Depletion Region The quantum I...Correction of the Hooge Parameter for Umklaop 1 / f Noise ", Ph,,’sia 1412, 145-147 (1906). 13. P.H. Handel: "Bolts from the Blue"("Has the Mystery of...Continue on revrerse s de if tecseear and Identify by block nutber) Infrared Detectors, Quantum 1 / f Noise , HgCdTe, Electronic Noise 2CL A8SRACT

  15. Identification of Bacillus anthracis by Using Monoclonal Antibody to Cell Wall Galactose-N-Acetylglucosamine Polysaccharide

    DTIC Science & Technology

    1990-02-01

    which appear to be directed to an epitope associated with the galactose-N-acetyl-D- glucosamine polysaccharide. Both demonstrated specificity in their...liquid composed primarily of D-galactose and N-acetyl-D-glu - R medium (28) buffered with 50 mM Tris hydrochloride , pH cosamine (12, 13) (Gal-NAG...Ascites fluid (5 ml) was dialyzed (Cel-Line Associates, Inc., Newfield, N.J.). Suspensions against 20 mM Tris hydrochloride (pH 8.0) for 18 to 20 h, were

  16. The effect of pH and concentration upon aggregation transitions in aqueous solutions of poloxamine T701.

    PubMed

    Armstrong, J K; Chowdhry, B Z; Snowden, M J; Dong, J; Leharne, S A

    2001-10-23

    Thermally induced aggregation transitions have been investigated for aqueous solutions of the poloxamine block copolymer T701-(OE(4)OP(13))(2)NCH(2)CH(2)N(OP(13)OE(4))(2)-using differential scanning calorimetry. The calorimetric signals obtained were fitted to a mass action model description of aggregation using a previously reported analytical procedure (Patterson et al., Langmuir 13 (1997) 2219). The presence of a central ethylene diamine moiety in the molecular structure renders the T701 molecule basic; this was confirmed and measured by acid/base titration. Basicity is shown to have an important impact upon aggregation. At low pH (2.5), the poloxamine exists in its protonated form and the bulk solution proton concentration is sufficient to suppress de-protonation, aggregation-as a consequence-is shifted to a higher temperature range. Any increase in pH reduces the temperature range over which aggregation occurs. The derived experimental calorimetric parameters, obtained from model fitting procedures, can be used to compute the fraction of poloxamine existing in an aggregated form, at any particular temperature. The data sets obtained were interpolated to show that at human body temperature (310.6 K) the fraction of poloxamine found in its aggregated form is zero at a pH of 2.5. However at a pH of 6.8, the percentage aggregation increases to about 85%. These aggregation characteristics of T701 have important implications for the design of drug delivery systems, which incorporate poloxamines.

  17. Stretchable wireless system for sweat pH monitoring.

    PubMed

    Dang, Wenting; Manjakkal, Libu; Navaraj, William Taube; Lorenzelli, Leandro; Vinciguerra, Vincenzo; Dahiya, Ravinder

    2018-06-01

    Sensor-laden wearable systems that are capable of providing continuous measurement of key physiological parameters coupled with data storage, drug delivery and feedback therapy have attracted huge interest. Here we report a stretchable wireless system for sweat pH monitoring, which is able to withstand up to 53% uniaxial strain and more than 500 cycles to 30% strain. The stretchability of the pH sensor patch is provided by a pair of serpentine-shaped stretchable interconnects. The pH sensing electrode is made of graphite-polyurethane composite, which is suitable for biosensor application. The sensing patch validated through in-depth electrochemical studies, exhibits a pH sensitivity of 11.13 ± 5.8 mV/pH with a maximum response time of 8 s. Interference study of ions and analyte (Na + , K + and glucose) in test solutions shows negligible influence on the pH sensor performance. The pH data can be wirelessly and continuously transmitted to smartphone through a stretchable radio-frequency-identification antenna, of which the radiating performance is stable under 20% strain, as proved by vector network analyzer measurement. To evaluate the full system, the pH value of a human sweat equivalent solution has been measured and wirelessly transmitted to a custom-developed smart phone App. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Removing Molybdenum with the Microalgae Extracted from the Wastewater in Semiconductor Plants

    NASA Astrophysics Data System (ADS)

    Chiu, Yi-Chuan

    2017-04-01

    It has been well recognized that algae biomass can treat highly contaminated water in an effective way. Algae can grows in the natural environment without any care and can be efficiently cultivated. Both of living algae and dry algae biomass have been tested to absorb many kinds of toxic pollutants, because there are multiple functional groups on the algae surface capable of binding molybdenum. Therefore, algae become a good choice for the treatment of molybdenum in contaminated waters. In addition, in Taiwan, semiconductor industry is highly developed in the recent three decades. Subsequently, it is believed that some pollutants, such as molybdenum in this study, have become a threat to the surface water, groundwater and even the whole environment. In the previous studies, molybdenum is a well-known essential nutrient for the algae; therefore, the potential to remove molybdenum with algae from the wastewater is worth to be evaluated. The algae species, Chloroidium saccharophilum, was extracted from the wastewater in semiconductor plants for the study of removing molybdenum. A few sorption experiments have been conducted for evaluating the efficiency of removing molybdenum under different values of pH and molybdenum concentration. The absorption of Chloroidium saccharophilum can reach equilibrium in short times, which are 60 and 120 mins for molybdenum concentrations of 600 and 1200 ppb, respectively. The sorption experiments would accept the duration of 120 mins as the contact time and were performed at pH values of 6, 4 and 2 with different concentrations of molybdenum diluted by deionized water. The experiment data confirms that the isotherm has an excellent agreement on Langmuir adsorption model with the correlation coefficients (r2) of > 0.97. It demonstrates that the adsorption capacity (qmax) has an inverse relationship with pH value, which are 826, 2564 and 4761 mgkg-1 for pH 6, 4 and 2, respectively, while those of net enthalpy of adsorption (KL) are 3.98, 2.98 and 1.5 × 10-5 mgkg-1. In addition, a similar experiment was also conducted with domestic sewage instead of deionized water under pH=6 and obtained a much higher value of qmax (1923 mgkg-1) than that with deionized water. It is believed that the cations in the domestic sewage, such as Ca2+, Mg2+, Na+ and K+, are capable of replacing H+ from the algae surface, which can decrease the pH value of water and subsequently promote the absorption of MoO42- as the aforementioned. FTIR was utilized for determining the functional groups on algae surface in this study. There are five major absorption bands, which are corresponding to -O-H, -COO- , C-O-C, Mo-O and Mo-N. However, the responsible functional group to absorb MoO42- is still uncertain and the comparison of absorption behaviour of molybdenum among different algae species should be also evaluated. More researches will be studied in the future.

  19. The dynamics of methane emissions in Alaskan peatlands at different trophic levels

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Liu, X.; Langford, L.; Chanton, J.; Hines, M. E.

    2016-12-01

    One major uncertainty in estimating methane (CH4) emission from wetlands is extrapolating from highly heterogeneous and inadequately studied local sites to larger scales. The heterogeneity of peatlands comes from contrasting surface vegetation compositions within short distances that are usually associated with different nutrient sources and trophic status. Different microbial communities and metabolic pathways occur at different trophic levels. Stable isotope C ratios (δ13C) have been used as a robust tool to distinguish methanogenic pathways, but different sources of parent compounds (acetate and CO2) with unique δ13C signatures, and unresolved fractionation factors associated with different methanogens, add complexity. To better understand the relationships between trophic status, surface vegetation compositions and methanogenic pathways, 28 peatland sites were studied in Fairbanks and Anchorage, Alaska in the summer of 2015. These sites were ordinated using multiple factor analysis into 3 clusters based on pH, temp, CH4 and volatile fatty acids production rates, δ13C values, and surface vegetation composition. In the low-pH trophic cluster (pH 4.2), Sphagnum fuscum was the dominant species with specific sedges (Ledum decumbens), and primary fermentation rates was slow with no CH4 detected. In the intermediate trophic level (pH 5.3), in which Sphagnum magellanicum was largely present, both hydrogenotrophic (HM) and acetoclastic methanogenesis (AM) were very active. Syntrophy was present at certain sites, which may provide CO2 and acetate with unique δ13C for CH4 production. At the highest pH trophic cluster examined in this study (pH 5.8), Carex tenuiflora, Carex aquatilis, and Sphagnum Squarrosum dominated. CH4 production rates were higher than those in the intermediate cluster and the apparent fractionation factor a was lower.

  20. Round-bale feeder design affects hay waste and economics during horse feeding.

    PubMed

    Martinson, K; Wilson, J; Cleary, K; Lazarus, W; Thomas, W; Hathaway, M

    2012-03-01

    Many horse owners find round bales convenient, less labor intensive, and more affordable than other hay types, but report an inability to control horse BW gain and excessive hay waste. The objectives were to compare hay waste, hay intake, and payback of 9 round-bale feeders and a no-feeder control when used during horse feeding. Nine round-bale feeders were tested: Cinch Net, Cone, Covered Cradle, Hayhut, Hay Sleigh, Ring, Tombstone, Tombstone Saver, and Waste Less. Each feeder design was placed on the ground in a dirt paddock. Five groups of 5 horses were fed in rotation for a 4-d period with each feeder. Every fourth day, groups were rotated among paddocks and a new round bale was placed in each feeder. In the 5 paddocks used, 5 feeders were installed for d 1 through 20, and the remaining 4 feeders and no-feeder control were installed for d 21 through 40. Groups of horses were sequentially assigned to feeders using two 5 × 5 Latin squares, the first for d 1 through 20, the second for d 21 through 40. Horse groups of similar age, BW, breed, and sex were formed from 25 Quarter Horse and Thoroughbred geldings and open mares (means: 11 yr; 541 kg of BW). Hay on the ground surrounding the feeder was collected daily, dried, and weighed. The total amount of hay removed around each feeder for a 4-d period was considered waste. Dry matter intake was estimated as the difference between hay disappearance and waste. Number of months for the reduction in waste to repay feeder cost (payback) were calculated using hay valued at $110/t, and improved feeder efficiency over the control. Feeder design did not affect hay intake (P > 0.05); all feeders resulted in an estimated hay intake of 2.0 to 2.4% BW; the no-feeder control resulted in a reduced intake of 1.3% BW (P = 0.001). Mean percentage of hay waste differed among feeders (P < 0.001): Waste Less, 5%; Cinch Net, 6%; Hayhut, 9%; Covered Cradle, 11%; Tombstone Saver, 13%; Tombstone, Cone, and Ring, 19%; Hay Sleigh, 33%; and no-feeder control, 57%. Feeder design also affected payback (P < 0.01). The Cinch Net paid for itself in less than 1 mo; Tombstone and Ring, 2 mo; Hayhut and Tombstone Saver, 4 mo; Hay Sleigh, 5 mo; Waste Less, 8 mo; Cone, 9 mo; and Covered Cradle, 20 mo. Round-bale feeder design affected hay waste and payback, but not estimated hay intake or BW change during horse feeding.

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