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Sample records for molybdenum disulphide particles

  1. Superlubricity of molybdenum disulphide

    NASA Astrophysics Data System (ADS)

    Martin, J. M.; Donnet, C.; Le Mogne, Th.; Epicier, Th.

    1993-10-01

    We have studied the atomistic origins of the ultralow friction coefficient of a molybdenum disulphide (MoS2) coating in ultrahigh vacuum conditions. A friction coefficient in the 10-3 range is associated with friction-induced orientation of ``easy shear'' basal planes of the MoS2 crystal structure parallel to the sliding direction. In addition to this basal plane orientation, an orientation disorder around the c axis is observed, indicating that frictional anisotropy during intercrystallite slip could be at the origin of the vanishing of the friction force. Experimental HRTEM lattice fringe imaging of MoS2 wear particles clearly show the existence of characteristic Moiré patterns. We have simulated TEM lattice fringe images of a [0001] MoS2 crystal and produced rotational Moiré patterns by superimposing two such images. A qualitative agreement between experimental and simulated Moiré patterns is demonstrated, which gives credence that ultralow friction of MoS2 in high vacuum can be attributed to a superlubric situation, by frictional anisotropy of sulphur-rich basal planes during intercrystallite slip.

  2. Exploring atomic defects in molybdenum disulphide monolayers

    NASA Astrophysics Data System (ADS)

    Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

    2015-02-01

    Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 1013 cm-2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

  3. Exploring atomic defects in molybdenum disulphide monolayers

    PubMed Central

    Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

    2015-01-01

    Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment–theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 1013 cm−2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices. PMID:25695374

  4. Nanomechanical cleavage of molybdenum disulphide atomic layers.

    PubMed

    Tang, Dai-Ming; Kvashnin, Dmitry G; Najmaei, Sina; Bando, Yoshio; Kimoto, Koji; Koskinen, Pekka; Ajayan, Pulickel M; Yakobson, Boris I; Sorokin, Pavel B; Lou, Jun; Golberg, Dmitri

    2014-04-03

    The discovery of two-dimensional materials became possible due to the mechanical cleavage technique. Despite its simplicity, the as-cleaved materials demonstrated surprising macro-continuity, high crystalline quality and extraordinary mechanical and electrical properties that triggered global research interest. Here such cleavage processes and associated mechanical behaviours are investigated by a direct in situ transmission electron microscopy probing technique, using atomically thin molybdenum disulphide layers as a model material. Our technique demonstrates layer number selective cleavage, from a monolayer to double layer and up to 23 atomic layers. In situ observations combined with molecular dynamics simulations reveal unique layer-dependent bending behaviours, from spontaneous rippling (<5 atomic layers) to homogeneous curving (~ 10 layers) and finally to kinking (20 or more layers), depending on the competition of strain energy and interfacial energy.

  5. Nanomechanical cleavage of molybdenum disulphide atomic layers

    NASA Astrophysics Data System (ADS)

    Tang, Dai-Ming; Kvashnin, Dmitry G.; Najmaei, Sina; Bando, Yoshio; Kimoto, Koji; Koskinen, Pekka; Ajayan, Pulickel M.; Yakobson, Boris I.; Sorokin, Pavel B.; Lou, Jun; Golberg, Dmitri

    2014-04-01

    The discovery of two-dimensional materials became possible due to the mechanical cleavage technique. Despite its simplicity, the as-cleaved materials demonstrated surprising macro-continuity, high crystalline quality and extraordinary mechanical and electrical properties that triggered global research interest. Here such cleavage processes and associated mechanical behaviours are investigated by a direct in situ transmission electron microscopy probing technique, using atomically thin molybdenum disulphide layers as a model material. Our technique demonstrates layer number selective cleavage, from a monolayer to double layer and up to 23 atomic layers. In situ observations combined with molecular dynamics simulations reveal unique layer-dependent bending behaviours, from spontaneous rippling (<5 atomic layers) to homogeneous curving (~ 10 layers) and finally to kinking (20 or more layers), depending on the competition of strain energy and interfacial energy.

  6. Dichroic spin–valley photocurrent in monolayer molybdenum disulphide

    PubMed Central

    Eginligil, Mustafa; Cao, Bingchen; Wang, Zilong; Shen, Xiaonan; Cong, Chunxiao; Shang, Jingzhi; Soci, Cesare; Yu, Ting

    2015-01-01

    The aim of valleytronics is to exploit confinement of charge carriers in local valleys of the energy bands of semiconductors as an additional degree of freedom in optoelectronic devices. Thanks to strong direct excitonic transitions in spin-coupled K valleys, monolayer molybdenum disulphide is a rapidly emerging valleytronic material, with high valley polarization in photoluminescence. Here we elucidate the excitonic physics of this material by light helicity-dependent photocurrent studies of phototransistors. We demonstrate that large photocurrent dichroism (up to 60%) can also be achieved in high-quality molybdenum disulphide monolayers grown by chemical vapour deposition, due to the circular photogalvanic effect on resonant excitations. This opens up new opportunities for valleytonic applications in which selective control of spin–valley-coupled photocurrents can be used to implement polarization-sensitive light-detection schemes or integrated spintronic devices, as well as biochemical sensors operating at visible frequencies. PMID:26134143

  7. Modified chemical route for deposition of molybdenum disulphide thin films

    SciTech Connect

    Vyas, Akshay N. Sartale, S. D.

    2014-04-24

    Molybdenum disulphide (MoS{sub 2}) thin films were deposited on quartz substrates using a modified chemical route. Sodium molybdate and sodium sulphide were used as precursors for molybdenum and sulphur respectively. The route involves formation of tetrathiomolybdate ions (MoS{sub 4}{sup 2−}) and further reduction by sodium borohydride to form MoS{sub 2}. The deposition was performed at room temperature. The deposited films were annealed in argon atmosphere at 1073 K for 1 hour to improve its crystallinity. The deposited films were characterized using scanning electron microscopy (SEM) for morphology, UV-Vis absorption spectroscopy for optical studies and X-ray diffraction (XRD) for structure determination.

  8. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide.

    PubMed

    van der Zande, Arend M; Huang, Pinshane Y; Chenet, Daniel A; Berkelbach, Timothy C; You, YuMeng; Lee, Gwan-Hyoung; Heinz, Tony F; Reichman, David R; Muller, David A; Hone, James C

    2013-06-01

    Recent progress in large-area synthesis of monolayer molybdenum disulphide, a new two-dimensional direct-bandgap semiconductor, is paving the way for applications in atomically thin electronics. Little is known, however, about the microstructure of this material. Here we have refined chemical vapour deposition synthesis to grow highly crystalline islands of monolayer molybdenum disulphide up to 120 μm in size with optical and electrical properties comparable or superior to exfoliated samples. Using transmission electron microscopy, we correlate lattice orientation, edge morphology and crystallinity with island shape to demonstrate that triangular islands are single crystals. The crystals merge to form faceted tilt and mirror twin boundaries that are stitched together by lines of 8- and 4-membered rings. Density functional theory reveals localized mid-gap states arising from these 8-4 defects. We find that mirror twin boundaries cause strong photoluminescence quenching whereas tilt boundaries cause strong enhancement. Meanwhile, mirror twin boundaries slightly increase the measured in-plane electrical conductivity, whereas tilt boundaries slightly decrease the conductivity.

  9. Superconductivity in the alkali metal intercalates of molybdenum disulphide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1972-01-01

    The complete series of alkali metals, lithium through cesium, have been intercalated into molybdenum disulphide, using both the liquid ammonia and vapor techniques. All the intercalates with the exception of lithium yielded full superconducting transitions with onset temperatures of 6 K for AxMoS2(Ax=K,Rb,Cs) and 4 K for BxMoS2(Bx=Li,Na). The superconducting transition for lithium was incomplete down to 1.5 K. Stoichiometries and unit cell parameters have been determined for the intercalation compounds. Both rhombohedral and hexagonal polymorphs of MoS2 have been intercalated and found to exhibit the same superconductivity behavior. The nature of the extraneous superconducting transition of some intercalated samples on exposure to air was elucidated.

  10. Superconductivity in the alkali metal intercalates of molybdenum disulphide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1972-01-01

    The complete series of alkali metals, lithium through cesium, have been intercalated into molybdenum disulphide, using both the liquid ammonia and vapor techniques. All the intercalates with the exception of lithium yielded full superconducting transitions with onset temperatures of 6 K for AxMoS2(Ax=K,Rb,Cs) and 4 K for BxMoS2(Bx=Li,Na). The superconducting transition for lithium was incomplete down to 1.5 K. Stoichiometries and unit cell parameters have been determined for the intercalation compounds. Both rhombohedral and hexagonal polymorphs of MoS2 have been intercalated and found to exhibit the same superconductivity behavior. The nature of the extraneous superconducting transition of some intercalated samples on exposure to air was elucidated.

  11. Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers.

    PubMed

    Najmaei, Sina; Liu, Zheng; Zhou, Wu; Zou, Xiaolong; Shi, Gang; Lei, Sidong; Yakobson, Boris I; Idrobo, Juan-Carlos; Ajayan, Pulickel M; Lou, Jun

    2013-08-01

    Single-layered molybdenum disulphide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for the next generation of nanoelectronics. Here, we report the controlled vapour phase synthesis of molybdenum disulphide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area, single- and few-layered films. Using high-resolution electron microscopy imaging, the atomic structure and morphology of the grains and their boundaries in the polycrystalline molybdenum disulphide atomic layers are examined, and the primary mechanisms for grain boundary formation are evaluated. Grain boundaries consisting of 5- and 7- member rings are directly observed with atomic resolution, and their energy landscape is investigated via first-principles calculations. The uniformity in thickness, large grain sizes, and excellent electrical performance signify the high quality and scalable synthesis of the molybdenum disulphide atomic layers.

  12. Onset of superconductivity in sodium and potassium intercalated molybdenum disulphide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Rembaum, A.

    1971-01-01

    Molybdenum disulfide in the form of natural crystals or powder has been intercalated at -65 to -70 C with sodium and potassium using the liquid ammonia technique. All intercalated samples were found to show a superconducting transition. A plot of the percent of diamagnetic throw versus temperature indicates the possible existence of two phases in the potassium intercalated molybdenum disulfide. The onset of superconductivity in potassium and sodium intercalated molybdenite powder was found to be approximately 6.2 and approximately 4.5 K, respectively. The observed superconductivity is believed to be due to an increase in electron density as a result of intercalation.

  13. Optoelectronic crystal of artificial atoms in strain-textured molybdenum disulphide

    PubMed Central

    Li, Hong; Contryman, Alex W.; Qian, Xiaofeng; Ardakani, Sina Moeini; Gong, Yongji; Wang, Xingli; Weisse, Jeffery M.; Lee, Chi Hwan; Zhao, Jiheng; Ajayan, Pulickel M.; Li, Ju; Manoharan, Hari C.; Zheng, Xiaolin

    2015-01-01

    The isolation of the two-dimensional semiconductor molybdenum disulphide introduced a new optically active material possessing a band gap that can be facilely tuned via elastic strain. As an atomically thin membrane with exceptional strength, monolayer molybdenum disulphide subjected to biaxial strain can embed wide band gap variations overlapping the visible light spectrum, with calculations showing the modified electronic potential emanating from point-induced tensile strain perturbations mimics the Coulomb potential in a mesoscopic atom. Here we realize and confirm this ‘artificial atom' concept via capillary-pressure-induced nanoindentation of monolayer molybdenum disulphide from a tailored nanopattern, and demonstrate that a synthetic superlattice of these building blocks forms an optoelectronic crystal capable of broadband light absorption and efficient funnelling of photogenerated excitons to points of maximum strain at the artificial-atom nuclei. Such two-dimensional semiconductors with spatially textured band gaps represent a new class of materials, which may find applications in next-generation optoelectronics or photovoltaics. PMID:26088550

  14. Low-temperature growth of layered molybdenum disulphide with controlled clusters

    PubMed Central

    Mun, Jihun; Kim, Yeongseok; Kang, Il-Suk; Lim, Sung Kyu; Lee, Sang Jun; Kim, Jeong Won; Park, Hyun Min; Kim, Taesung; Kang, Sang-Woo

    2016-01-01

    Layered molybdenum disulphide was grown at a low-temperature of 350 °C using chemical vapour deposition by elaborately controlling the cluster size. The molybdenum disulphide grown under various sulphur-reaction-gas to molybdenum-precursor partial-pressure ratios were examined. Using spectroscopy and microscopy, the effect of the cluster size on the layered growth was investigated in terms of the morphology, grain size, and impurity incorporation. Triangular single-crystal domains were grown at an optimized sulphur-reaction-gas to molybdenum-precursor partial-pressure ratio. Furthermore, it is proved that the nucleation sites on the silicon-dioxide substrate were related with the grain size. A polycrystalline monolayer with the 100-nm grain size was grown on a nucleation site confined substrate by high-vacuum annealing. In addition, a field-effect transistor was fabricated with a MoS2 monolayer and exhibited a mobility and on/off ratio of 0.15 cm2 V−1 s−1 and 105, respectively. PMID:26902316

  15. Temperature-dependent mechanical properties of single-layer molybdenum disulphide: Molecular dynamics nanoindentation simulations

    NASA Astrophysics Data System (ADS)

    Zhao, Junhua; Jiang, Jin-Wu; Rabczuk, Timon

    2013-12-01

    The temperature-dependent mechanical properties of single-layer molybdenum disulphide (MoS2) are obtained using molecular dynamics (MD) nanoindentation simulations. The Young's moduli, maximum load stress, and maximum loading strain decrease with increasing temperature from 4.2 K to 500 K. The obtained Young's moduli are in good agreement with those using our MD uniaxial tension simulations and the available experimental results. The tendency of maximum loading strain with different temperature is opposite with that of metal materials due to the short range Stillinger-Weber potentials in MoS2. Furthermore, the indenter tip radius and fitting strain effect on the mechanical properties are also discussed.

  16. Computational study of electronic and thermal properties of single-layer molybdenum disulphide folded nanostructure

    NASA Astrophysics Data System (ADS)

    Peng, Jie; Chung, Peter

    Single-layer Molybdenum disulphide (SLMoS2), a two-dimensional transition-metal dichalcogenide with a large band gap and high mobility, is considered to be a next generation material for transistors and optoelectronic devices. We present recent results on the electronic and thermal behavior of SLMoS2 folded nanostructures. Through an approach that uses both molecular dynamics (MD) and density functional theory (DFT), we estimate the stable equilibrium structure of folded sheets as well as the related phonon and electronic band structures. The MD simulations are based on a Stillinger-Weber potential and the DFT simulations employ projector augmented wave (PAW) pseudopotentials using generalized gradient approximation (GGA) and local density approximation (LDA). The structure is examined as a function of folding orientation, layer number and system size. Mechanisms of the phonon transport and electronic band gap properties in such a mechanically distorted atomic-layer nanostructure will be discussed.

  17. The energy-band alignment at molybdenum disulphide and high-k dielectrics interfaces

    SciTech Connect

    Tao, Junguang; Chai, J. W.; Zhang, Z.; Pan, J. S.; Wang, S. J.

    2014-06-09

    Energy-band alignments for molybdenum disulphide (MoS{sub 2}) films on high-k dielectric oxides have been studied using photoemission spectroscopy. The valence band offset (VBO) at monolayer MoS{sub 2}/Al{sub 2}O{sub 3} (ZrO{sub 2}) interface was measured to be 3.31 eV (2.76 eV), while the conduction-band offset (CBO) was 3.56 eV (1.22 eV). For bulk MoS{sub 2}/Al{sub 2}O{sub 3} interface, both VBO and CBO increase by ∼0.3 eV, due to the upwards shift of Mo 4d{sub z{sup 2}} band. The symmetric change of VBO and CBO implies Fermi level pinning by interfacial states. Our finding ensures the practical application of both p-type and n-type MoS{sub 2} based complementary metal-oxide semiconductor and other transistor devices using Al{sub 2}O{sub 3} and ZrO{sub 2} as gate materials.

  18. High performance asymmetric supercapacitor based on molybdenum disulphide/graphene foam and activated carbon from expanded graphite.

    PubMed

    Masikhwa, Tshifhiwa M; Madito, Moshawe J; Bello, Abdulhakeem; Dangbegnon, Julien K; Manyala, Ncholu

    2017-02-15

    Molybdenum disulphide which has a graphene-like single layer structure has excellent mechanical and electrical properties and unique morphology, which might be used with graphene foam as composite in supercapacitor applications. In this work, Molybdenum disulphide (MoS2)/graphene foam (GF) composites with different graphene foam loading were synthesized by the hydrothermal process to improve on specific capacitance of the composites. Asymmetric supercapacitor device was fabricated using the best performing MoS2/GF composite and activated carbon derived from expanded graphite (AEG) as positive and negative electrodes, respectively, in 6M KOH electrolyte. The asymmetric MoS2/GF//AEG device exhibited a maximum specific capacitance of 59Fg(-1) at a current density of 1Ag(-1) with maximum energy and power densities of 16Whkg(-1) and 758Wkg(-1), respectively. The supercapacitor also exhibited a good cyclic stability with 95% capacitance retention over 2000 constant charge-discharge cycles. The results obtained demonstrate the potential of MoS2/GF//AEG as a promising material for electrochemical energy storage application. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Tension-induced phase transition of single-layer molybdenum disulphide (MoS2) at low temperatures.

    PubMed

    Zhao, Junhua; Kou, Liangzhi; Jiang, Jin-Wu; Rabczuk, Timon

    2014-07-25

    We show that the hexagonal structure of single-layer molybdenum disulphide (MoS2), under uniaxial tension along a zigzag direction for large deformations, can transfer to a new quadrilateral structure by molecular dynamics (MD) simulations when the temperature is below 40 K. The new phase remains stable after unloading, even at room temperature. The Young's modulus of the new phase along the zigzag direction is about 2.5 times higher than that of normal MoS2. Checking against density functional theory calculations shows that the new phase is preserved and displays excellent electrical conductivity. Our results provide physical insights into the origins of the new phase transition of MoS2 at low temperatures.

  20. Impact of high energy ball milling on the nanostructure of magnetite–graphite and magnetite–graphite–molybdenum disulphide blends

    SciTech Connect

    Österle, W.; Orts-Gil, G.; Gross, T.; Deutsch, C.; Hinrichs, R.; Vasconcellos, M.A.Z.; Zoz, H.; Yigit, D.; Sun, X.

    2013-12-15

    Different, partly complementary and partly redundant characterization methods were applied to study the transition of magnetite, graphite and MoS{sub 2} powders to mechanically alloyed nanostructures. The applied methods were: Transmission electron microscopy (TEM), Mössbauer spectroscopy (MS), Raman spectroscopy (RS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The main objective was to prepare a model material providing the essential features of a typical tribofilm forming during automotive braking, and to assess the impact of different constituents on sliding behaviour and friction level. Irrespective of the initial grain size, the raw materials were transferred to a nanocrystalline structure and mixed on a nanoscopic scale during high energy ball milling. Whereas magnetite remained almost unchanged, graphite and molybdenum disulphide were transformed to a nanocrystalline and highly disordered structure. The observed increase of the coefficient of friction was attributed to a loss of lubricity of the latter ingredient due to this transformation and subsequent oxidation. - Highlights: • Characterization of microstructural changes induced by high energy ball milling • Assessment of the potential of different characterization methods • Impact of mechanical alloying on tribological performance revealed by tests • Preparation of an artificial third body resembling the one formed during braking.

  1. Large area molybdenum disulphide- epitaxial graphene vertical Van der Waals heterostructures

    PubMed Central

    Pierucci, Debora; Henck, Hugo; Naylor, Carl H.; Sediri, Haikel; Lhuillier, Emmanuel; Balan, Adrian; Rault, Julien E.; Dappe, Yannick J.; Bertran, François; Fèvre, Patrick Le; Johnson, A. T. Charlie; Ouerghi, Abdelkarim

    2016-01-01

    Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design. PMID:27246929

  2. Unusual isotope effect on thermal transport of single layer molybdenum disulphide

    SciTech Connect

    Wu, Xufei; Yang, Nuo; Luo, Tengfei

    2015-11-09

    Thermal transport in single layer molybdenum disulfide (MoS{sub 2}) is critical to advancing its applications. In this paper, we use molecular dynamics simulations with first-principles force constants to study the isotope effect on the thermal transport of single layer MoS{sub 2}. Through phonon modal analysis, we found that isotopes can strongly scatter phonons with intermediate frequencies, and the scattering behavior can be radically different from that predicted by conventional scattering model based on perturbation theory, where Tamura's formula is combined with Matthiessen's rule to include isotope effects. Such a discrepancy becomes smaller for low isotope concentrations. Natural isotopes can lead to a 30% reduction in thermal conductivity for large size samples. However, for small samples where boundary scattering becomes significant, the isotope effect can be greatly suppressed. It was also found that the Mo isotopes, which contribute more to the phonon eigenvectors in the intermediate frequency range, have stronger impact on thermal conductivity than S isotopes.

  3. Large area molybdenum disulphide- epitaxial graphene vertical Van der Waals heterostructures.

    PubMed

    Pierucci, Debora; Henck, Hugo; Naylor, Carl H; Sediri, Haikel; Lhuillier, Emmanuel; Balan, Adrian; Rault, Julien E; Dappe, Yannick J; Bertran, François; Fèvre, Patrick Le; Johnson, A T Charlie; Ouerghi, Abdelkarim

    2016-06-01

    Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design.

  4. Molybdenum disulphide/titanium dioxide nanocomposite-poly 3-hexylthiophene bulk heterojunction solar cell

    NASA Astrophysics Data System (ADS)

    Shanmugam, Mariyappan; Bansal, Tanesh; Durcan, Chris A.; Yu, Bin

    2012-04-01

    Demonstration of hybrid bulk heterojunction (BHJ) solar photovoltaic cell employing molybdenum disulfide (MoS2)/titanium dioxide (TiO2) nanocomposite (˜15 μm thick) and poly 3-hexylthiophene (P3HT) active layers is presented in this letter. The dominant Raman peak at 146 cm-1 confirmed TiO2, while two other peaks observed at 383 cm-1 and 407 cm-1 asserted MoS2 in the nanocomposite film. The demonstrated BHJ solar cell, having a stacked structure of indium tin oxide/TiO2/MoS2/P3HT/gold, exhibits a short circuit current density of 4.7 mA/cm2, open circuit voltage of 560 mV, and photoconversion efficiency of 1.3% under standard AM1.5 illumination condition. We observe that the quality of TiO2/MoS2/P3HT interfaces, as reflected in the dark saturation current in low- and medium-forward-bias region, plays a key role in impacting solar cell performance due to interfacial recombination effect.

  5. 2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction.

    PubMed

    Rowley-Neale, Samuel J; Fearn, Jamie M; Brownson, Dale A C; Smith, Graham C; Ji, Xiaobo; Banks, Craig E

    2016-08-21

    Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm(-2) modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.

  6. 2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

    2016-08-01

    Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets

  7. Two-dimensional molybdenum disulphide nanosheet-covered metal nanoparticle array as a floating gate in multi-functional flash memories

    NASA Astrophysics Data System (ADS)

    Han, Su-Ting; Zhou, Ye; Chen, Bo; Zhou, Li; Yan, Yan; Zhang, Hua; Roy, V. A. L.

    2015-10-01

    Semiconducting two-dimensional materials appear to be excellent candidates for non-volatile memory applications. However, the limited controllability of charge trapping behaviors and the lack of multi-bit storage studies in two-dimensional based memory devices require further improvement for realistic applications. Here, we report a flash memory consisting of metal NPs-molybdenum disulphide (MoS2) as a floating gate by introducing a metal nanoparticle (NP) (Ag, Au, Pt) monolayer underneath the MoS2 nanosheets. Controlled charge trapping and long data retention have been achieved in a metal (Ag, Au, Pt) NPs-MoS2 floating gate flash memory. This controlled charge trapping is hypothesized to be attributed to band bending and a built-in electric field ξbi between the interface of the metal NPs and MoS2. The metal NPs-MoS2 floating gate flash memories were further proven to be multi-bit memory storage devices possessing a 3-bit storage capability and a good retention capability up to 104 s. We anticipate that these findings would provide scientific insight for the development of novel memory devices utilizing an atomically thin two-dimensional lattice structure.Semiconducting two-dimensional materials appear to be excellent candidates for non-volatile memory applications. However, the limited controllability of charge trapping behaviors and the lack of multi-bit storage studies in two-dimensional based memory devices require further improvement for realistic applications. Here, we report a flash memory consisting of metal NPs-molybdenum disulphide (MoS2) as a floating gate by introducing a metal nanoparticle (NP) (Ag, Au, Pt) monolayer underneath the MoS2 nanosheets. Controlled charge trapping and long data retention have been achieved in a metal (Ag, Au, Pt) NPs-MoS2 floating gate flash memory. This controlled charge trapping is hypothesized to be attributed to band bending and a built-in electric field ξbi between the interface of the metal NPs and MoS2. The metal

  8. Industrial grade 2D molybdenum disulphide (MoS2): an in vitro exploration of the impact on cellular uptake, cytotoxicity, and inflammation

    NASA Astrophysics Data System (ADS)

    Moore, Caroline; Movia, Dania; Smith, Ronan J.; Hanlon, Damien; Lebre, Filipa; Lavelle, Ed C.; Byrne, Hugh J.; Coleman, Jonathan N.; Volkov, Yuri; McIntyre, Jennifer

    2017-06-01

    The recent surge in graphene research, since its liquid phase monolayer isolation and characterization in 2004, has led to advancements which are accelerating the exploration of alternative 2D materials such as molybdenum disulphide (MoS2), whose unique physico-chemical properties can be exploited in applications ranging from cutting edge electronic devices to nanomedicine. However, to assess any potential impact on human health and the environment, the need to understand the bio-interaction of MoS2 at a cellular and sub-cellular level is critical. Notably, it is important to assess such potential impacts of materials which are produced by large scale production techniques, rather than research grade materials. The aim of this study was to explore cytotoxicity, cellular uptake and inflammatory responses in established cell-lines that mimic different potential exposure routes (inhalation, A549; ingestion, AGS; monocyte, THP-1) following incubation with MoS2 flakes of varying sizes (50 nm, 117 nm and 177 nm), produced by liquid phase exfoliation. Using high content screening (HCS) and Live/Dead assays, it was established that 1 µg ml-1 (for the three different MoS2 sizes) did not induce toxic effects on any of the cell-lines. Confocal microscopy images revealed a normal cellular morphology in all cases. Transmission electron microscopy (TEM) confirmed the uptake of all MoS2 nanomaterials in all the cell-lines, the MoS2 ultimately locating in single membrane vesicles. At such sub-lethal doses, inflammatory responses are observed, however, associated, at least partially, with the presence of lipopolysaccharide endotoxin in nanomaterial suspensions and surfactant samples. Therefore, the inflammatory response of the cells to the MoS2 or endotoxin contamination was interrogated using a 10-plex ELISA which illustrates cytokine production. The experiments carried out using wild-type and endotoxin hyporesponsive bone marrow derived dendritic cells confirmed that the

  9. Molybdenum

    Integrated Risk Information System (IRIS)

    Molybdenum ; CASRN 7439 - 98 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

  10. Cellulose acetate-based composites with antimicrobial properties from embedded molybdenum trioxide particles.

    PubMed

    Shafaei, S; Dörrstein, J; Guggenbichler, J P; Zollfrank, C

    2017-01-01

    The objective of this research was to develop novel cellulose acetate (biopolymer) composite materials with an excellent antimicrobial activity by embedding molybdenum trioxide particles with unique high specific surface area. High surface area molybdenum trioxide particles were prepared from freshly precipitated molybdenum trioxide dihydrate (MoO3 ·2H2 O) and subsequent calcination at 340°C under H2 /N2 gas. Microbiological evaluation against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed applying a roll-on test and excellent antimicrobial activities were determined for composites with embedded anhydrous molybdenum trioxide with a high specific surface area. Cellulose acetate composites comprising MoO3 particles can eliminate three harmful bacteria as a result of the release of protons from the material and surface enlargement of the molybdenum trioxide particles. The findings support a proposed antimicrobial mechanism based on local acidity increase due to large specific surface areas.

  11. Neutron single-particle structure of molybdenum isotopes within the dispersive optical model

    SciTech Connect

    Bespalova, O. V. Klimochkina, A. A.; Spasskaya, T. I.

    2016-07-15

    The evolution of neutron single-particle spectra in molybdenum isotopes was calculated on the basis of the dispersive optical model over the region extending from stable isotopes to the neutron drip line. The question of how the dependence of surface absorption on the neutron–proton asymmetry and the weakening of spin–orbit interaction affect the single-particle spectra in question is studied. The results agree with the concept according to which the shell effect becomes weaker near the neutron drip line.

  12. 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.

  13. Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

    PubMed Central

    Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard III, William A.; Chen, Shuo; Ren, Zhifeng

    2016-01-01

    With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity. PMID:27633712

  14. Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam.

    PubMed

    Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J; He, Ran; Bao, Jiming; Goddard Iii, William A; Chen, Shuo; Ren, Zhifeng

    2016-09-16

    With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

  15. Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

    NASA Astrophysics Data System (ADS)

    Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard, William A., III; Chen, Shuo; Ren, Zhifeng

    2016-09-01

    With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

  16. Process R&D for Particle Size Control of Molybdenum Oxide

    SciTech Connect

    Sen, Sujat; Dzwiniel, Trevor; Pupek, Krzysztof; Krumdick, Gregory; Tkac, Peter; Vandegrift, George F.

    2016-12-01

    The primary goal of this study was to produce MoO3 powder with a particle size range of 50 to 200 μm for use in targets for production of the medical isotope 99Mo. Molybdenum metal powder is commercially produced by thermal reduction of oxides in a hydrogen atmosphere. The most common source material is MoO3, which is derived by the thermal decomposition of ammonium heptamolybdate (AHM). However, the particle size of the currently produced MoO3 is too small, resulting in Mo powder that is too fine to properly sinter and press into the desired target. In this study, effects of heating rate, heating temperature, gas type, gas flow rate, and isothermal heating were investigated for the decomposition of AHM. The main conclusions were as follows: lower heating rate (2-10°C/min) minimizes breakdown of aggregates, recrystallized samples with millimeter-sized aggregates are resistant to various heat treatments, extended isothermal heating at >600°C leads to significant sintering, and inert gas and high gas flow rate (up to 2000 ml/min) did not significantly affect particle size distribution or composition. In addition, attempts to recover AHM from an aqueous solution by several methods (spray drying, precipitation, and low temperature crystallization) failed to achieve the desired particle size range of 50 to 200 μm. Further studies are planned.

  17. In-situ molybdenum nano-attached particle synthesis from spent Mo scrap.

    PubMed

    Han, Chulwoong; Kim, Byungmoon; Choi, Hanshin

    2014-10-01

    Radio frequency thermal plasma is a versatile process for engineering powder preparation owing to its high energy density and reactivity. Molybdenum powders were prepared from molybdenum sheet scrap by RF thermal plasma in association with powder comminution process. Molybdenum scrap which was used in high temperature environment was friable enough to be broken into micropowders by hammer milling. Spherical molybdenum micro-powder was obtained from the hammer milled powders were treated via thermal plasma. On the other hand, vaporization and condensation pathway for nanoparticle synthesis is largely dependent on both thermo-physical properties and thermal plasma properties. In this regard, molybdenum trioxide was chosen for the feedstock of nanoparticle synthesis. Additional reactivity of argon-hydrogen thermal plasma, oxide feedstock was fully reduced to bcc molybdenum. Considering different reaction pathway of each feedstock, molybdenum nanoparticle attached molybdenum spherical micro-powder could be effectively synthesized by feeding a blended feedstock of molybdenum micro-powder and molybdenum trioxide micro-powder into argon-hydrogen thermal plasma.

  18. Cell damage in vitro following direct contact with fine particles of titanium, titanium alloy and cobalt-chrome-molybdenum alloy.

    PubMed

    Evans, E J

    1994-07-01

    Fibroblastic cells in vitro were exposed to powders of titanium, titanium-aluminium-vanadium alloy and cobalt-chrome-molybdenum (Co-Cr-Mo) alloy, either in direct contact with the cells or separated from the cells by a microporous membrane. Fine particles of all the materials reduced cell growth when in direct contact with cells, but only the finest particles of Co-Cr-Mo alloy caused cell damage through the microporous membrane. This provides further evidence that there is a mechanism of cell damage in vitro which depends on a direct interaction between cells and particles and is largely independent of the chemical nature of the particle.

  19. Investigation of the α-particle induced nuclear reactions on natural molybdenum

    NASA Astrophysics Data System (ADS)

    Ditrói, F.; Hermanne, A.; Tárkányi, F.; Takács, S.; Ignatyuk, A. V.

    2012-08-01

    Cross-sections of alpha particle induced nuclear reactions on natural molybdenum have been studied in the frame of a systematic investigation of charged particle induced nuclear reactions on metals for different applications. The excitation functions of 93mTc, 93gTc(m+), 94mTc, 94gTc, 95mTc, 95gTc, 96gTc(m+), 99mTc, 93mMo, 99Mo(cum), 90Nb(m+), 94Ru, 95Ru,97Ru, 103Ru and 88Zr were measured up to 40 MeV alpha energy by using a stacked foil technique and activation method. The main goals of this work were to get experimental data for accelerator technology, for monitoring of alpha beam, for thin layer activation technique and for testing nuclear reaction theories. The experimental data were compared with critically analyzed published data and with the results of model calculations, obtained by using the ALICE-IPPE, EMPIRE and TALYS codes (TENDL-2011).

  20. Targeting allosteric disulphide bonds in cancer.

    PubMed

    Hogg, Philip J

    2013-06-01

    Protein action in nature is generally controlled by the amount of protein produced and by chemical modification of the protein, and both are often perturbed in cancer. The amino acid side chains and the peptide and disulphide bonds that bind the polypeptide backbone can be post-translationally modified. Post-translational cleavage or the formation of disulphide bonds are now being identified in cancer-related proteins and it is timely to consider how these allosteric bonds could be targeted for new therapies.

  1. Colloidal synthesis of biocompatible iron disulphide nanocrystals.

    PubMed

    Santos-Cruz, J; Nuñez-Anita, R E; Mayén-Hernández, S A; Martínez-Alvarez, O; Acosta-Torres, L S; de la Fuente-Hernández, J; Campos-González, E; Vega-González, M; Arenas-Arrocena, M C

    2017-08-06

    The aim of this research was to synthesis biocompatible iron disulphide nanocrystals at different reaction temperatures using the colloidal synthesis methodology. Synthesis was conducted at the 220-240 °C range of reaction temperatures at intervals of 5 °C in an inert argon atmosphere. The toxicity of iron disulphide nanocrystals was evaluated in vitro using mouse fibroblast cell line. Two complementary assays were conducted: the first to evaluate cell viability of the fibroblast via an MTT assay and the second to determine the preservation of fibroblast nuclei integrity through DAPI staining, which labels nuclear DNA in fluorescence microscopes. Through TEM and HRTEM, we observed a cubic morphology of pyrite iron disulphide nanocrystals ranging in sizes 25-50 nm (225 °C), 50-70 nm (230 °C) and >70 nm (235 °C). Through X-ray diffraction, we observed a mixture of pyrite and pyrrohotite in the samples synthesized at 225 °C and 240 °C, showing the best photocatalytic activity at 80% and 65%, respectively, for the degradation of methylene blue after 120 minutes. In all experimental groups, iron disulphide nanocrystals were biocompatible, i.e. no statistically significant differences were observed between experimental groups as shown in a one-way ANOVA and Tukey's test. Based on all of these results, we recommend non-cytotoxic semiconductor iron sulphide nanocrystals for biomedical applications.

  2. The effect of disulphides on mitochondrial oxidations

    PubMed Central

    Skrede, S.; Bremer, J.; Eldjarn, L.

    1965-01-01

    1. Nicotinamide nucleotide-linked mitochondrial oxidations were inhibited by the disulphides NNN′N′-tetraethylcystamine, cystamine and cystine diethyl ester, whereas l-homocystine, oxidized mercaptoethanol, oxidized glutathione, NN′-diacetylcystamine and tetrathionate were only slightly inhibitory. Mitochondrial oxidations were not blocked by the thiol cysteamine. 2. NAD-independent oxidations were not inhibited by cystamine. The oxidation of choline was initially stimulated. 3. The inactivation of isocitrate, malate and β-hydroxybutyrate oxidation of intact mitochondria could be partially reversed by external NAD. For the reactivation of α-oxoglutarate oxidation a thiol was also required. 4. A leakage of nicotinamide nucleotides from the mitochondria is suggested as the main cause of the inhibition. In addition, a strong inhibition of α-oxoglutarate dehydrogenase by cystamine was observed. A mixed disulphide formation with CoA and possibly also lipoic acid and lipoyl dehydrogenase is suggested to explain this inhibition. PMID:14342523

  3. Radiolysis of solutions containing organo-disulphides

    NASA Astrophysics Data System (ADS)

    Elliot, Allen John; Simsons, Anita Sandra; Sopchyshyn, Frederick Charles

    When oxidized dithiothreitol (DTT- ox), oxidized gluthathione (GSSG), or dithiodiproprionic acid is radiolysed in N 2O-saturated sodium formate solutions, a chain reduction of the disulphide to the corresponding thiol occurs. The chain propagating step is the abstraction of the hydrogen atom in the formate ion by the thiyl radical. For the dithiothreitol thiyl radical, the rate constant for the abstraction is ≥ 3.6 × 10 4 mol -1 dm 3 s -1. The more sterically hindered penicillamine disulphide does not undergo this chain reaction. While the (CH 3) 2ĊOH radical does not reduce DTT- ox, it reduces GSSG to glutathione. At pH 9, the acetone radical anion, (CH 3) 2ĊO -, reduces both DTT- ox and GSSG.

  4. Synthesis and characterization of molybdenum/phenolic resin composites binding with aluminum nitride particles for diamond cutters

    NASA Astrophysics Data System (ADS)

    Lin, Chun-Te; Lee, Hsun-Tsing; Chen, Jem-Kun

    2013-11-01

    Novolac-type bisphenol-F based molybdenum-phenolic resins/silane-modified aluminum nitride (Mo-BPF/m-AlN) composites were successfully prepared. In the preparation process, molybdate reacted with bisphenol-F based phenolic resins (BPF) to form a low cross-linked Mo-BPF with new Mosbnd O bonds which were confirmed by the FTIR and XPS spectra. Simultaneously, a special silane-modified aluminum nitride (m-AlN) was prepared with 3-aminopropyltriethoxysilane (APTES) modifier. Then, this m-AlN was fully mixed with Mo-BPF to form Mo-BPF/m-AlN which can be further cured with hexamethylenetetramine at 200 °C. The structure and characterization of BPF, Mo-BPF and Mo-BPF/m-AlN were determined by using FTIR, DSC, DMA, TGA, SEM, mechanical properties and contact angle measurements. SEM photographs show that m-AlN particles are uniformly distributed in the Mo-BPF/m-AlN composites. Also there are no gaps or void between m-AlN and Mo-BPF phases, which implies a strong physical bonding between the two phases. The glass transition temperature, thermal resistance, flexural strength, and hardness of Mo-BPF are respectively higher than those of BPF. This is due to the presence of Mosbnd O cross-linking bonds in Mo-BPF. When the m-AlN was additionally incorporated into Mo-BPF, the well-dispersed and well-adhered m-AlN can further promote all the above-mentioned properties of the composites. Typically, the glass transition temperature, decomposition temperature at 5% weight loss and flexural strength of Mo-BPF/m-AlN are 245 °C, 428 °C and 82.7 MPa respectively, which are much higher than the corresponding values of 184 °C, 358 °C and 58.2 MPa for BPF. In addition, the hygroscopic nature of BPF can be inhibited by treating with molybdate or incorporating with m-AlN. This is due to that the m-AlN is hydrophobic and Mosbnd O groups in Mo-BPF are more hydrophobic than OH groups in BPF. Furthermore, Mo-BPF/m-AlN was compared with BPF in the performance as a binder for diamond cutting

  5. Evaluation of Dynamic Disulphide/Thiol Homeostasis in Silica Exposed Workers

    PubMed Central

    Gündüzöz, Meşide; Bal, Ceylan; Büyükşekerci, Murat; Neşelioğlu, Salim; Nadir Öziş, Türkan; İritaş, Servet; Kara, Halil; Erel, Özcan

    2017-01-01

    Background: Oxidative stress is implicated as one of the main molecular mechanism underlying silicosis. Aims: In this study, our aim was to asses the redox status in occupationally silica-exposed workers, by evaluating the dynamic thiol-disulphide homeostasis. Study Design: Case-control study. Methods: Thirty-six male workers occupationally exposed to silica particles and 30 healthy volunteers, working as office workers were included to the study. Posteroanterior chest radiographs and pulmonary function tests of both groups were evaluated. Also serum thiol disulphide levels were measured using the spectrophotometric method described by Erel and Neşelioğlu. Results: Among the 36 workers that underwent pulmonary function tests 6 (17%) had obstructive, 7 (19%) had restrictive, 6 (17%) had obstructive and restrictive signs whereas 17 (47%) had no signs. The mean PFTs results of silica-exposed workers were significantly lower than control subjects. The serum disulphide levels of silica-exposed workers were significantly higher than control subjects (23.84±5.89 μmol/L and 21.18±3.44 μmol/L, respectively p=0.02). Conclusion: The serum disulphide levels, a biomarker of oxidative stress, are found to be higher in silica-exposed workers. PMID:28418335

  6. Gel Fabrication of Molybdenum “Beads”

    SciTech Connect

    Lowden, Richard Andrew; Armstrong, Beth L.; Cooley, Kevin M.

    2016-11-01

    Spherical molybdenum particles or “beads” of various diameters are of interest as feedstock materials for the additive manufacture of targets and assemblies used in the production of 99Mo medical isotopes using accelerator technology. Small metallic beads or ball bearings are typically fabricated from wire; however, small molybdenum spheres cannot readily be produced in this manner. Sol-gel processes are often employed to produce small dense microspheres of metal oxides across a broad diameter range that in the case of molybdenum could be reduced and sintered to produce metallic spheres. These Sol-gel type processes were examined for forming molybdenum oxide beads; however, the molybdenum trioxide was chemically incompatible with commonly used gelation materials. As an alternative, an aqueous alginate process being assessed for the fabrication of oxide spheres for catalyst applications was employed to form molybdenum trioxide beads that were successfully reduced and sintered to produce small molybdenum spheres.

  7. Kinetics of interaction of hydroperoxides with some disulphides

    SciTech Connect

    Aslanov, A.D.; Zolotova, N.V.; Denisov, E.T.; Kuliyev, F.A.

    1982-01-01

    Disulphides catalytically break down tert-butyl and cumyl hydroperoxides. In chlorobenzene breakdown takes place by a bimolecular mechanism at a rate which is directly proportional to the concentration of hydroperoxide and disulphide; the rate constant of this reaction varies from 0.4 to 1.2 1./mole.sec at 373/sup 0/K for disulphides and tert-butyl hydroperoxide, respectively. No radicals are formed by the reaction of tert-butyl hydroperoxide with disulphide. 3 references, 2 figures, 2 tables.

  8. Low temperature photoresponse of monolayer tungsten disulphide

    SciTech Connect

    Cao, Bingchen; Shen, Xiaonan; Shang, Jingzhi; Cong, Chunxiao; Yang, Weihuang; Eginligil, Mustafa E-mail: meginligil@ntu.edu.sg; Yu, Ting E-mail: meginligil@ntu.edu.sg

    2014-11-01

    High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD) method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup), while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

  9. Several N-Glycans on the HIV Envelope Glycoprotein gp120 Preferentially Locate Near Disulphide Bridges and Are Required for Efficient Infectivity and Virus Transmission.

    PubMed

    Mathys, Leen; Balzarini, Jan

    2015-01-01

    The HIV envelope glycoprotein gp120 contains nine disulphide bridges and is highly glycosylated, carrying on average 24 N-linked glycans. Using a probability calculation, we here demonstrate that there is a co-localization of disulphide bridges and N-linked glycans in HIV-1 gp120, with a predominance of N-linked glycans in close proximity to disulphide bridges, at the C-terminal side of the involved cysteines. Also, N-glycans are frequently found immediately adjacent to disulphide bridges in gp120 at the N-terminal side of the involved cysteines. In contrast, N-glycans at positions close to, but not immediately neighboring disulphide bridges seem to be disfavored at the N-terminal side of the involved cysteines. Such a pronounced co-localization of disulphide bridges and N-glycans was also found for the N-glycans on glycoprotein E1 of the hepatitis C virus (HCV) but not for other heavily glycosylated proteins such as E2 from HCV and the surface GP from Ebola virus. The potential functional role of the presence of N-glycans near disulphide bridges in HIV-1 gp120 was studied using site-directed mutagenesis, either by deleting conserved N-glycans or by inserting new N-glycosylation sites near disulphide bridges. The generated HIV-1NL4.3 mutants were subjected to an array of assays, determining the envelope glycoprotein levels in mutant viral particles, their infectivity and the capture and transmission efficiencies of mutant virus particles by DC-SIGN. Three N-glycans located nearby disulphide bridges were found to be crucial for the preservation of several of these functions of gp120. In addition, introduction of new N-glycans upstream of several disulphide bridges, at locations where there was a significant absence of N-glycans in a broad variety of virus strains, was found to result in a complete loss of viral infectivity. It was shown that the N-glycan environment around well-defined disulphide bridges of gp120 is highly critical to allow efficient viral infection

  10. Magneto photoluminescence measurements of tungsten disulphide monolayers

    NASA Astrophysics Data System (ADS)

    Kuhnert, Jan; Rahimi-Iman, Arash; Heimbrodt, Wolfram

    2017-03-01

    Layered transition-metal dichalcogenides have attracted great interest in the last few years. Thinned down to the monolayer limit they change from an indirect band structure to a direct band gap in the visible region. Due to the monolayer thickness the inversion symmetry of the crystal is broken and spin and valley are coupled to each other. The degeneracy between the two equivalent valleys, K and K‧, respectively, can be lifted by applying an external magnetic field. Here, we present photoluminescence measurements of CVD-grown tungsten disulphide (WS2) monolayers at temperatures of 2 K. By applying magnetic fields up to 7 T in Faraday geometry, a splitting of the photoluminescence peaks can be observed. The magnetic field dependence of the A-exciton, the trion and three bound exciton states is discussed and the corresponding g-factors are determined.

  11. Diallyl disulphide depletes glutathione in Candida albicans

    PubMed Central

    Lemar, Katey M.; Aon, Miguel A.; Cortassa, Sonia; O’Rourke, Brian; T. Müller, Carsten; Lloyd, David

    2008-01-01

    Using two-photon scanning laser microscopy, we investigated the effect of an Allium sativum (garlic) constituent, diallyl disulphide (DADS), on key physiological functions of the opportunistic pathogen Candida albicans. A short 30 min exposure to 0.5 mm DADS followed by removal induced 70% cell death (50% necrotic, 20% apoptotic) within 2 h, increasing to 75% after 4 h. The early intracellular events associated with DADS-induced cell death were monitored with two-photon fluorescence microscopy to track mitochondrial membrane potential (ΔΨm), reactive oxygen species (ROS) and NADH or reduced glutathione (GSH) under aerobic conditions. DADS treatment decreased intracellular GSH and elevated intracellular ROS levels. Additionally, DADS induced a marked decrease of ΔΨm and lowered respiration in cell suspensions and isolated mitochondria. In vitro kinetic experiments in cell-free extracts suggest that glutathione-S-transferase (GST) is one of the intracellular targets of DADS. Additional targets were also identified, including inhibition of a site or sites between complexes II-IV in the electron transport chain, as well as the mitochondrial ATP-synthase. The results indicate that DADS is an effective antifungal agent able to trigger cell death in Candida, most probably by eliciting oxidative stress as a consequence of thiol depletion and impaired mitochondrial function. PMID:17534841

  12. Weldable ductile molybdenum alloy development

    NASA Astrophysics Data System (ADS)

    Cockeram, B. V.; Ohriner, E. K.; Byun, T. S.; Miller, M. K.; Snead, L. L.

    2008-12-01

    Molybdenum and its alloys are attractive structural materials for high-temperature applications. However, various practical issues have limited its use. One concern relates to the loss of ductility occurring in the heat-affected weld zone caused by segregation of oxygen to grain boundaries. In this study, a series of arc melted molybdenum alloys have been produced containing controlled additions of B, C, Zr, and Al. These alloys were characterized with respect to their tensile properties, smooth bend properties, and impact energy for both the base metal and welds. These alloys were compared with a very high purity low carbon arc cast molybdenum reference. For discussion purposes the alloys produced are separated into two categories: Mo-Al-B alloys, and Mo-Zr-B alloys. The properties of Mo-Zr-B alloy welds containing higher carbon levels exhibited slight improvement over unalloyed molybdenum, though the base-metal properties for all Mo-Zr-B alloys were somewhat inconsistent with properties better, or worse, than unalloyed molybdenum. A Mo-Al-B alloy exhibited the best DBTT values for welds, and the base metal properties were comparable to or slightly better than unalloyed molybdenum. The Mo-Al-B alloy contained a low volume fraction of second-phase particles, with segregation of boron and carbon to grain boundaries believed to displace oxygen resulting in improved weld properties. The volume fractions of second-phase particles are higher for the Mo-Zr-B alloys, and these alloys were prone to brittle fracture. It is also noted that these Mo-Zr-B alloys exhibited segregation of zirconium, boron and carbon to the grain boundaries.

  13. Isolation and characterization of lost copper and molybdenum particles in the flotation tailings of Kennecott copper porphyry ores

    NASA Astrophysics Data System (ADS)

    Tserendavga, Tsend-Ayush

    The importance of flotation separation has long been, and continues to be, an important technology for the mining industry, especially to metallurgical engineers. However, the flotation process is quite complex and expensive, in addition to being influenced by many variables. Understanding the variables affecting flotation efficiency and how valuable minerals are lost to the tailings gives metallurgists an advantage in their attempts to increase efficiency by designing operations to target the areas of greatest potential value. A successful, accurate evaluation of lost minerals in the tailings and appropriate solutions to improve flotation efficiency can save millions of dollars in the effective utilization of our mineral resources. In this dissertation research, an attempt has been made to understand the reasons for the loss of valuable mineral particles in the tailings from Kennecott Utah Copper ores. Possibilities include liberation, particle aggregation (slime coating) and surface chemistry issues associated with the flotation separation. This research generally consisted of three main aspects. The first part involved laboratory flotation experiments and factors, which affect the flotation efficiency. Results of flotation testing are reported that several factors such as mineral exposure/liberation and slime coating and surface oxidation strongly affect the flotation efficiency. The second part of this dissertation research was to develop a rapid scan dual energy (DE) methodology using 2D radiography to identify, isolate, and prepare lost sulfide mineral particles with the advantages of simple sample preparation, short analysis time, statistically reliable accuracy and confident identification. The third part of this dissertation research was concerned with detailed characterization of lost particles including such factors as liberation, slime coating, and surface chemistry characteristics using advanced analytical techniques and instruments. Based on the

  14. Facile and novel synthetic method to prepare nano molybdenum and its catalytic activity.

    PubMed

    Sam Jaikumar, Sugumaran; Yuvakkumar, Rathinam; Suriya Prabha, Rangaraj; Karunakaran, Gopalu; Rajendran, Venkatachalam; Hong, Sun Ig

    2015-08-01

    This study reports on a facile and economical synthetic method to prepare nano molybdenum by solid-state reaction technique. Metallic nano molybdenum was synthesised from molybdenum trioxide, molybdenum IV oxide and molybdenum VI oxide through thermal decomposition technique. Metallic nano molybdenum prepared from molybdenum IV oxide was used to study the catalytic effect of molybdenum nanoparticles on the growth of Anabaena sp. The increase in concentration of nano molybdenum from 0.1 to 100% in BG11 (N⁻ Mo⁻ + nano Mo) medium increases heterocyst frequency. The chlorophyll and protein content in Anabaena sp. was found to improve when compared with bulk molybdenum particles and showed a positive influence to be used as a nano nutrient for Anabaena sp.

  15. Disulphide bond formation in food protein aggregation and gelation.

    PubMed

    Visschers, Ronald W; de Jongh, Harmen H J

    2005-01-01

    In this short review we discuss the role of cysteine residues and cystine bridges for the functional aggregation of food proteins. We evaluate how formation and cleavage of disulphide bonds proceeds at a molecular level, and how inter- and intramolecular disulfide bonds can be detected and modified. The differences between heat-, high-pressure-, and denaturant-induced unfolding and aggregation are discussed. The effect of disulphide bonding between aggregates of proteins and protein mixtures on the functional macroscopic properties of space filling networks in protein gels is briefly presented.

  16. Investigation of thiol-disulphide balance in patients with acute urticaria and chronic spontaneous urticaria.

    PubMed

    Akbas, Ayse; Kilinc, Fadime; Sener, Sertac; Aktaş, Akın; Baran, Pervin; Ergin, Merve

    2017-09-01

    Thiol-disulphide balance plays a major role in health and diseases. This balance may be disrupted by various diseases. We aimed to determine status of the effect of thiol-disulphide balance in urticaria. We aimed to investigate the thiol-disulphide balance in patients with acute urticaria (AUP) and chronic spontaneous urticaria (CSU). Study included 53 AUP and 47 healthy controls plus 57 patients with chronic spontaneous urticaria (CSUP) and 57 healthy controls. Levels of native thiols, disulphides and total thiols were evaluated in plasma using a new and automated spectrophotometric method. Ratios of disulphides/total thiols, disulphides/native thiols and native thiols/total thiols were calculated. For AU, there was no statistical difference compared to control group in levels of native thiols, disulphides and total thiols. For CSU, however, there was an increase in levels of native thiols, disulphides and total thiols and the ratio of thiol/disulphide in favour of disulphide. Thiol-disulphide balance was not affected by AU but shifted towards to disulphide in CSU indicating the presence of oxidative stress (OS).

  17. The Molybdenum Cofactor*

    PubMed Central

    Mendel, Ralf R.

    2013-01-01

    The transition element molybdenum needs to be complexed by a special cofactor to gain catalytic activity. Molybdenum is bound to a unique pterin, thus forming the molybdenum cofactor (Moco), which, in different variants, is the active compound at the catalytic site of all molybdenum-containing enzymes in nature, except bacterial molybdenum nitrogenase. The biosynthesis of Moco involves the complex interaction of six proteins and is a process of four steps, which also require iron, ATP, and copper. After its synthesis, Moco is distributed, involving Moco-binding proteins. A deficiency in the biosynthesis of Moco has lethal consequences for the respective organisms. PMID:23539623

  18. The molybdenum cofactor.

    PubMed

    Mendel, Ralf R

    2013-05-10

    The transition element molybdenum needs to be complexed by a special cofactor to gain catalytic activity. Molybdenum is bound to a unique pterin, thus forming the molybdenum cofactor (Moco), which, in different variants, is the active compound at the catalytic site of all molybdenum-containing enzymes in nature, except bacterial molybdenum nitrogenase. The biosynthesis of Moco involves the complex interaction of six proteins and is a process of four steps, which also require iron, ATP, and copper. After its synthesis, Moco is distributed, involving Moco-binding proteins. A deficiency in the biosynthesis of Moco has lethal consequences for the respective organisms.

  19. A Novel Oxidative Stress Mediator in Acute Appendicitis: Thiol/Disulphide Homeostasis

    PubMed Central

    Turan, Umit; Kuvvetli, Adnan; Kilavuz, Huseyin; Karakaya, Burak; Ozaltun, Pınar; Alısık, Murat; Erel, Ozcan

    2016-01-01

    Aim. To investigate the role of a novel oxidative stress marker, thiol/disulphide homeostasis, in patients diagnosed with acute appendicitis (AA). Methods. In this study, seventy-one (43 male and 28 female) patients diagnosed with AA and 71 (30 male and 41 female) healthy volunteers were included. Age, gender, body mass index (BMI), haemoglobin (Hb), white blood cell (WBC), c-reactive protein (CRP), and thiol/disulphide homeostasis parameters (native thiol, total thiol, disulphide, disulphide/native thiol, native thiol/total thiol, and disulphide/total thiol ratios) were compared between the groups. Thiol/disulphide homeostasis was determined by a newly developed method by Erel and Neselioglu. Results. The native thiol, total thiol, and the native thiol/total thiol ratio levels were statistically significantly decreased in the AA compared with the control group (p < 0.001). Disulphide level and the ratios of disulphide/native thiol and disulphide/total thiol were higher in the AA group than in the control group (p < 0.001). There was a negative correlation of CRP with native thiol, total thiol, and native thiol/total thiol ratio while there was a positive correlation of CRP with disulphide/native thiol and disulphide/total thiol in the AA group. In the stepwise regression model, risk factors as disulphide/native thiol (OR = 1.368; p = 0.018) and CRP (OR = 1.635; p = 0.003) were determined as predictors of perforated appendicitis compared to the nonperforated group. Conclusion. This is the first study examining the thiol/disulphide homeostasis as a diagnostic aid in AA and establishing thiol/disulphide homeostatis balance shifted towards the disulphide formation due to thiol oxidation. Further studies are needed to optimize the use of this novel oxidative stress marker in AA. PMID:27642237

  20. High-throughput production of two disulphide-bridge toxins.

    PubMed

    Upert, Grégory; Mourier, Gilles; Pastor, Alexandra; Verdenaud, Marion; Alili, Doria; Servent, Denis; Gilles, Nicolas

    2014-08-07

    A quick and efficient production method compatible with high-throughput screening was developed using 36 toxins belonging to four different families of two disulphide-bridge toxins. Final toxins were characterized using HPLC co-elution, CD and pharmacological studies.

  1. Molybdenum, molybdenum oxides, and their electrochemistry.

    PubMed

    Saji, Viswanathan S; Lee, Chi-Woo

    2012-07-01

    The electrochemical behaviors of molybdenum and its oxides, both in bulk and thin film dimensions, are critical because of their widespread applications in steels, electrocatalysts, electrochromic materials, batteries, sensors, and solar cells. An important area of current interest is electrodeposited CIGS-based solar cells where a molybdenum/glass electrode forms the back contact. Surprisingly, the basic electrochemistry of molybdenum and its oxides has not been reviewed with due attention. In this Review, we assess the scattered information. The potential and pH dependent active, passive, and transpassive behaviors of molybdenum in aqueous media are explained. The major surface oxide species observed, reversible redox transitions of the surface oxides, pseudocapacitance and catalytic reduction are discussed along with carefully conducted experimental results on a typical molybdenum glass back contact employed in CIGS-based solar cells. The applications of molybdenum oxides and the electrodeposition of molybdenum are briefly reviewed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Laser Light Induced Transformation of Molybdenum Disulphide-Based Nanoplatelet Arrays

    PubMed Central

    Jagminas, Arūnas; Niaura, Gediminas; Žalnėravičius, Rokas; Trusovas, Romualdas; Račiukaitis, Gediminas; Jasulaitiene, Vitalija

    2016-01-01

    One-pot hydrothermal synthesis of MoS2 nanoplatelet arrays on various substrates is perhaps the most promising approach to fabricate efficient electrocatalysts for hydrogen evolution reaction. However, the main challenges in this synthesis remain the purity and crystallinity of MoS2. In this study, we show for the first time that irradiation of amorphous, defect-rich MoS2 nanoplatelets with a green nanosecond laser at a proper irradiation dose, ca ≤0.35 J cm−2, can significantly improve the crystallinity and purity of MoS2 nanoplatelets. The effect was confirmed by Raman spectroscopy investigations demonstrating a surprising intensity increase of the A1g and modes after the laser irradiation. Further increase of irradiation energy, however, resulted in the photocorrosion and destruction of MoS2 nanoplatelets. The variation of A1g and Raman mode intensities ratio depending on the green light irradiation dose was also presented and is discussed below. PMID:27892489

  3. First-principles study of electronic structures and phase transitions of lithiated molybdenum disulphide

    NASA Astrophysics Data System (ADS)

    Li, Jun; Chen, Xiaobo

    2012-02-01

    By first-principles calculations, electronic structures of MoS2, intercalation-induced 2H to 1T phase transition and reversibility are investigated. It is revealed that change of interlayer stacking from 2H to 3R imposes negligible influence on the band structure and stability of MoS2. In contrast, the change of intralayer stacking from 2H to 1T changes the character of p-d repulsion, resulting in a semiconductor-to-metal transition. We demonstrate that the Kohn-Sham band energy, rather than the coulomb repulsion energy, plays dominant roles in both the phase stabilization and transition during Li intercalation. It is found that the evolution of 1T phase is crucially determined by chemical hardness, which underlies the cycle irreversibility. Due to the charge-density-wave (CDW) phase, Li extraction is impeded by the enhancement of Li-host binding. It is indicated that the cycle reversibility can be improved by electron-donor doping in MoS2, because the resultant pre-reduction of Mo and S eliminates the electron transfer from Li to host.

  4. High density decoration of noble metal nanoparticles on polydopamine-functionalized molybdenum disulphide.

    PubMed

    Hussain, Muhammad Asif; Yang, MinHo; Lee, Tae Jae; Kim, Jung Won; Choi, Bong Gill

    2015-08-01

    Here, we report a highly stable colloidal suspension of nanoparticles (i.e., Pt and Au)-deposited MoS2 sheets, in which polydopamine (PD) serves as surface functional groups. The adoption of polydopamine coating onto the MoS2 surface enables homogeneous deposition of nanoparticles in an aqueous solution. As-synthesized nanohybrids are thoroughly characterized by transmission electron microscopy (TEM), Raman spectroscopy, and X-ray diffraction (XRD) measurement. These intensive investigations reveal that noble metal nanocrystals are uniformly distributed on the surface of ultrathin MoS2 sheets (∼4 layers). Moreover, as-prepared Au/PD/MoS2 nanohybrids can be applied as a heterogeneous catalyst for reduction of 4-nitrophenol to 4-aminophenol, and they exhibit an excellent catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Laser Light Induced Transformation of Molybdenum Disulphide-Based Nanoplatelet Arrays

    NASA Astrophysics Data System (ADS)

    Jagminas, Arūnas; Niaura, Gediminas; Žalnėravičius, Rokas; Trusovas, Romualdas; Račiukaitis, Gediminas; Jasulaitiene, Vitalija

    2016-11-01

    One-pot hydrothermal synthesis of MoS2 nanoplatelet arrays on various substrates is perhaps the most promising approach to fabricate efficient electrocatalysts for hydrogen evolution reaction. However, the main challenges in this synthesis remain the purity and crystallinity of MoS2. In this study, we show for the first time that irradiation of amorphous, defect-rich MoS2 nanoplatelets with a green nanosecond laser at a proper irradiation dose, ca ≤0.35 J cm‑2, can significantly improve the crystallinity and purity of MoS2 nanoplatelets. The effect was confirmed by Raman spectroscopy investigations demonstrating a surprising intensity increase of the A1g and modes after the laser irradiation. Further increase of irradiation energy, however, resulted in the photocorrosion and destruction of MoS2 nanoplatelets. The variation of A1g and Raman mode intensities ratio depending on the green light irradiation dose was also presented and is discussed below.

  6. Transfer of molybdenum disulfide to various metals

    NASA Technical Reports Server (NTRS)

    Barton, G. C.; Pepper, S. V.

    1977-01-01

    Sliding friction experiments were conducted with molybdenum disulfide single crystals in contact with sputter cleaned surfaces of copper, nickel, gold, and 304 stainless steel. Transfer of the molybdenum disulfide to the metals was monitored with Auger electron spectroscopy. Results of the investigation indicate molybdenum disulfide transfers to all clean metal surfaces after a single pass over the metal surface with film thickness observed to increase with repeated passes over the same surfaces. Large particle transfer occurs when the orientation of the crystallites is other than basal. This is frequently accompanied by abrasion of the metal. Adhesion of molybdenum disulfide films occurred readily to copper and nickel, less readily to 304 stainless steel, and even less effectively to the gold, which indicates a chemical effect.

  7. Molybdenum disilicide composites

    DOEpatents

    Rodriguez, Robert P.; Petrovic, John J.

    2001-01-01

    Molybdenum disilicide/.beta.'-Si.sub.6-z Al.sub.z O.sub.z N.sub.8-z, wherein z=a number from greater than 0 to about 5, composites are made by use of in situ reactions among .alpha.-silicon nitride, molybdenum disilicide, and aluminum. Molybdenum disilicide within a molybdenum disilicide/.beta.'-Si.sub.6-z Al.sub.z O.sub.z N.sub.8-z eutectoid matrix is the resulting microstructure when the invention method is employed.

  8. Molybdenum: biological activity and metabolism.

    PubMed

    Mendel, Ralf R

    2005-11-07

    Molybdenum and tungsten are available to all organisms, with molybdenum having the far greater abundance and availability. Molybdenum occurs in a wide range of metalloenzymes in bacteria, fungi, algae, plants and animals, while tungsten was found to be essential only for a limited range of bacteria. In order to gain biological activity, molybdenum has to be complexed by a pterin compound, thus forming a molybdenum cofactor. In this article I will review the way that molybdenum takes from uptake into the cell, via formation of the molybdenum cofactor and its storage, to the final modification of molybdenum cofactor and its insertion into apo-metalloenzymes.

  9. Molecular dynamics simulation of carbon disulphide with a Gaussian correction

    NASA Astrophysics Data System (ADS)

    Trumpakaj, Zygmunt; Linde, Bogumił B. J.

    2017-02-01

    Molecular Dynamics (MD) simulations of liquid carbon disulphide (CS2) in the temperature range 164-318 K under normal pressure and at experimental density were performed using an expa-6 potential with a Gaussian correction plus electrostatic interactions. This correction allowed to modify the curvature of the potential. The results of the MD simulation are compared with available experimental data. The agreement is good.

  10. Phosphoglycerate kinase acts in tumour angiogenesis as a disulphide reductase

    NASA Astrophysics Data System (ADS)

    Lay, Angelina J.; Jiang, Xing-Mai; Kisker, Oliver; Flynn, Evelyn; Underwood, Anne; Condron, Rosemary; Hogg, Philip J.

    2000-12-01

    Disulphide bonds in secreted proteins are considered to be inert because of the oxidizing nature of the extracellular milieu. An exception to this rule is a reductase secreted by tumour cells that reduces disulphide bonds in the serine proteinase plasmin. Reduction of plasmin initiates proteolytic cleavage in the kringle 5 domain and release of the tumour blood vessel inhibitor angiostatin. New blood vessel formation or angiogenesis is critical for tumour expansion and metastasis. Here we show that the plasmin reductase isolated from conditioned medium of fibrosarcoma cells is the glycolytic enzyme phosphoglycerate kinase. Recombinant phosphoglycerate kinase had the same specific activity as the fibrosarcoma-derived protein. Plasma of mice bearing fibrosarcoma tumours contained several-fold more phosphoglycerate kinase, as compared with mice without tumours. Administration of phosphoglycerate kinase to tumour-bearing mice caused an increase in plasma levels of angiostatin, and a decrease in tumour vascularity and rate of tumour growth. Our findings indicate that phosphoglycerate kinase not only functions in glycolysis but is secreted by tumour cells and participates in the angiogenic process as a disulphide reductase.

  11. Molybdenum disilicide matrix composite

    DOEpatents

    Petrovic, John J.; Carter, David H.; Gac, Frank D.

    1990-01-01

    A composition consisting of an intermetallic compound, molybdenum disilicide, which is reinforced with VS silicon carbide whiskers dispersed throughout it and a method of making the reinforced composition. Use of the reinforcing material increases fracture toughness at low temperatures and strength at high temperatures, as compared to pure molybdenum disilicide.

  12. Molybdenum disilicide matrix composite

    DOEpatents

    Petrovic, John J.; Carter, David H.; Gac, Frank D.

    1991-01-01

    A composition consisting of an intermetallic compound, molybdenum disilicide, which is reinforced with VS silicon carbide whiskers dispersed throughout it and a method of making the reinforced composition. Use of the reinforcing material increases fracture toughness at low temperatures and strength at high temperatures, as compared to pure molybdenum disilicide.

  13. Molybdenum nutriture in humans

    USDA-ARS?s Scientific Manuscript database

    Molybdenum is a trace element that functions as a cofactor for at least four enzymes: sulfite oxidase, xanthine oxidase, aldehyde oxidase, and mitochondrial amidoxime reducing component. In each case, molybdenum is bound to a complex, multi-ring organic component called molybdopterin, forming the e...

  14. Biology of the molybdenum cofactor.

    PubMed

    Mendel, Ralf R

    2007-01-01

    The transition element molybdenum (Mo) is an essential micronutrient for plants where it is needed as a catalytically active metal during enzyme catalysis. Four plant enzymes depend on molybdenum: nitrate reductase, sulphite oxidase, xanthine dehydrogenase, and aldehyde oxidase. However, in order to gain biological activity and fulfil its function in enzymes, molybdenum has to be complexed by a pterin compound thus forming the molybdenum cofactor. In this article, the path of molybdenum from its uptake into the cell, via formation of the molybdenum cofactor and its storage, to the final modification of the molybdenum cofactor and its insertion into apo-metalloenzymes will be reviewed.

  15. Cell biology of molybdenum.

    PubMed

    Mendel, Ralf R

    2009-01-01

    The transition element molybdenum (Mo) is an essential micronutrient that is needed as catalytically active metal during enzyme catalysis. In humans four enzymes depend on Mo: sulfite oxidase, xanthine oxidoreductase, aldehyde oxidase, and mitochondrial amidoxime reductase. In addition to these enzymes, plants harbor a fifth Mo-enzyme namely nitrate reductase. To gain biological activity and fulfill its function in enzymes, Mo has to be complexed by a pterin compound thus forming the molybdenum cofactor. This article will review the way that Mo takes from uptake into the cell, via formation of the molybdenum cofactor and its storage, up to the final insertion of the molybdenum cofactor into apometalloenzymes. Copyright 2009 International Union of Biochemistry and Molecular Biology, Inc.

  16. Organometallic Chemistry of Molybdenum.

    ERIC Educational Resources Information Center

    Lucas, C. Robert; Walsh, Kelly A.

    1987-01-01

    Suggests ways to avoid some of the problems students have learning the principles of organometallic chemistry. Provides a description of an experiment used in a third-year college chemistry laboratory on molybdenum. (TW)

  17. Organometallic Chemistry of Molybdenum.

    ERIC Educational Resources Information Center

    Lucas, C. Robert; Walsh, Kelly A.

    1987-01-01

    Suggests ways to avoid some of the problems students have learning the principles of organometallic chemistry. Provides a description of an experiment used in a third-year college chemistry laboratory on molybdenum. (TW)

  18. Biomonitoring Equivalents for molybdenum.

    PubMed

    Hays, Sean M; Macey, Kristin; Poddalgoda, Devika; Lu, Ming; Nong, Andy; Aylward, Lesa L

    2016-06-01

    Molybdenum is an essential trace element for mammalian, plant, and other animal systems. The Institute of Medicine (IOM) has established an Estimated Average Requirement (EAR) to assure sufficient molybdenum intakes for human populations; however excessive exposures can cause toxicity. As a result, several agencies have established exposure guidance values to protect against molybdenum toxicity, including a Reference Dose (RfD), Tolerable Daily Intake (TDI) and a Tolerable Upper Intake Level (UL). Biomonitoring for molybdenum in blood or urine in the general population is being conducted by the Canadian Health Measures Survey (CHMS) and the U.S. National Health and Nutrition Examination Survey (NHANES). Using pharmacokinetic data from controlled human dosing studies, Biomonitoring Equivalents (BEs) were calculated for molybdenum in plasma, whole blood, and urine associated with exposure guidance values set to protect against both nutritional deficits and toxicity. The BEEAR values in plasma, whole blood and urine are 0.5, 0.45 and 22 μg/L, respectively. The BEs associated with toxicity range from 0.9 to 31 μg/L in plasma, 0.8-28 μg/L in whole blood and 200-7500 μg/L in urine. These values can be used to interpret molybdenum biomonitoring data from a nutritional and toxicity perspective. Copyright © 2016. Published by Elsevier Inc.

  19. Evaluation of thiol-disulphide homeostasis in radiation workers.

    PubMed

    Koc, Ural; Tan, Sinan; Ertem, Ahmet Goktug; Gumus, Mehmet; Ozbek, Betul; Erel, Ozcan

    2017-07-01

    To evaluate thiol-disulphide homeostasis - a novel, easily calculated, readily available, and relatively cheap oxidative stress marker - in radiation workers and compare the results with healthy controls. A total of 108 participants were enrolled in the study including 63 hospital workers occupationally exposed to ionizing radiation in the units of interventional radiology, interventional cardiology and nuclear medicine. A control group consisted of 45 individuals staff in the same hospital. Serum thiol-disulphide homeostasis measurement was investigated via the spectrophotometric method newly described by Erel and Neşelioğlu. The mean serum native thiol levels of radiation workers (528.96 ± 86.42 μmol/l) was significantly lower than control subjects (561.05 ± 104.83 μmol/l) (p = .045). The mean serum total thiol levels of radiation workers (547.70 ± 91.50 μmol/l) was lower than control subjects (580.36 ± 112.24 μmol/l). Nevertheless, there was no significant difference between total thiol of exposed workers and controls. The results show that long-term low dose ionizing radiation may lead to oxidative stress and have side-effects in antioxidant thiol groups. We may suggest supporting radiation workers by safe antioxidant nutritional formulations and following up via both physical dosimetry and biodosimetric methods.

  20. Preparation of thick molybdenum targets

    NASA Technical Reports Server (NTRS)

    Singh, J. J.

    1974-01-01

    Thick natural molybdenum deposits on nickel plated copper substrates were prepared by thermal decomposition of molybdenum hexacarbonyl vapors on a heated surface in an inert gas atmosphere. The molybdenum metal atoms are firmly bonded to the substrate atoms, thus providing an excellent thermal contact across the junction. Molybdenum targets thus prepared should be useful for internal bombardment in a cyclotron where thermal energy inputs can exceed 10 kW.

  1. Reactive sulphur species: an in vitro investigation of the oxidation properties of disulphide S-oxides.

    PubMed Central

    Giles, Gregory I; Tasker, Karen M; Collins, Catriona; Giles, Niroshini M; O'rourke, Elizabeth; Jacob, Claus

    2002-01-01

    We have recently proposed that disulphide S-monoxides (thiosulphinates) and disulphide S-dioxides (thiosulphonates) are formed from their parent disulphides and 'reactive oxygen species' during oxidative stress. These 'reactive sulphur species' are themselves strong oxidizing agents that preferably attack the thiol functionality. We now show that under conditions where disulphides show little effect, disulphide S-oxides rapidly modify metallothionein, alcohol and glyceraldehyde 3-phosphate dehydrogenases and a zinc finger-protein fragment in vitro. The known antioxidants ascorbate, NADH, trolox and melatonin are unable to inhibit this oxidation pathway and only an excess of the cellular redox-buffer glutathione quenches the disulphide S-oxide activity. These results suggest that, under conditions of oxidative stress, despite the presence of high concentrations of antioxidants, reactive sulphur species formation may occur and inhibit the function of thiol-dependent proteins. Such a characterization of the disulphide S-oxide-oxidation pathway might also account for some previously observed anomalies in protein oxidation. PMID:12023902

  2. Method of producing molybdenum-99

    SciTech Connect

    Pitcher, Eric John

    2013-05-28

    Method of producing molybdenum-99, comprising accelerating ions by means of an accelerator; directing the ions onto a metal target so as to generate neutrons having an energy of greater than 10 MeV; directing the neutrons through a converter material comprising techentium-99 to produce a mixture comprising molybdenum-99; and, chemically extracting the molybdenum-99 from the mixture.

  3. Degradation of protein disulphide bonds in dilute alkali.

    PubMed Central

    Florence, T M

    1980-01-01

    The degradation of S--S bonds in 0.2 M-NaOH at 25 degrees C was studied for a series of proteins and simple aliphatic disulphide compounds, by using cathodic stripping voltammetry, ion-selective-electrode potentiometry, spectrophotometry and ultrafiltration. The disulphide bonds that dissociated in 0.2 M-NaOH were usually those that are solvent accessible and that can be reduced by mild chemical reductants. Some unexpected differences were found between similar proteins, both in the number of S--S bonds dissociated and in their rates of decomposition. Chymotrypsin has one S--S bond attacked, whereas chymotrypsinogen and trypsinogen have two. Ribonuclease A has two S--S bonds dissociated, but ribonuclease S and S-protein have three. Denaturation in 6 M-guanidine hydrochloride before alkaline digestion caused the loss of an additional S--S bond in ribonuclease A and insulin, and increased the rate of dissociation of the S--S bonds of some other proteins. The initial product of S--S bond dissociation in dilute alkali is believed to be a persulphide intermediate formed by a beta-elimination reaction. This intermediate is in mobile equilibrium with bisulphide ion, HS-, and decomposes at a mercury electrode or in acid solution to yield a stoichiometric amount of sulphide. Rate constants and equilibrium constants were measured for the equilibria between HS- and the intermediates involved in the alkaline dissociation of several proteins. Elemental sulphur was not detected in any of the protein digests. It is suggested that formation of HS- from a persulphide intermediate involves a hydrolysis reaction to yield a sulphenic acid derivative. The small polypeptides glutathione and oxytocin gave only a low yield of persulphide, and their alkaline decomposition must proceed by a mechanism different from that of the proteins. PMID:7213343

  4. Incorporation of molybdenum in rubredoxin: models for mononuclear molybdenum enzymes.

    PubMed

    Maiti, Biplab K; Maia, Luisa B; Silveira, Célia M; Todorovic, Smilja; Carreira, Cintia; Carepo, Marta S P; Grazina, Raquel; Moura, Isabel; Pauleta, Sofia R; Moura, José J G

    2015-07-01

    Molybdenum is found in the active site of enzymes usually coordinated by one or two pyranopterin molecules. Here, we mimic an enzyme with a mononuclear molybdenum-bis pyranopterin center by incorporating molybdenum in rubredoxin. In the molybdenum-substituted rubredoxin, the metal ion is coordinated by four sulfurs from conserved cysteine residues of the apo-rubredoxin and two other exogenous ligands, oxygen and thiol, forming a Mo((VI))-(S-Cys)4(O)(X) complex, where X represents -OH or -SR. The rubredoxin molybdenum center is stabilized in a Mo(VI) oxidation state, but can be reduced to Mo(IV) via Mo(V) by dithionite, being a suitable model for the spectroscopic properties of resting and reduced forms of molybdenum-bis pyranopterin-containing enzymes. Preliminary experiments indicate that the molybdenum site built in rubredoxin can promote oxo transfer reactions, as exemplified with the oxidation of arsenite to arsenate.

  5. Molybdenum Trafficking for Nitrogen Fixation†

    PubMed Central

    Hernandez, Jose A.; George, Simon J.; Rubio, Luis M.

    2009-01-01

    The molybdenum nitrogenase is responsible for most biological nitrogen fixation, a prokaryotic metabolic process that determines the global biogeochemical cycles of nitrogen and carbon. Here we describe the trafficking of molybdenum for nitrogen fixation in the model diazotrophic bacterium Azotobacter vinelandii. The genes and proteins involved in molybdenum uptake, homeostasis, storage, regulation, and nitrogenase cofactor biosynthesis are reviewed. Molybdenum biochemistry in A. vinelandii reveals unexpected mechanisms and a new role for iron-sulfur clusters in the sequestration and delivery of molybdenum. PMID:19772354

  6. Disulphide linkage in mouse ST6Gal-I: determination of linkage positions and mutant analysis.

    PubMed

    Hirano, Yuichi; Suzuki, Takehiro; Matsumoto, Takumi; Ishihara, Yoshimi; Takaki, Yoshie; Kono, Mari; Dohmae, Naoshi; Tsuji, Shuichi

    2012-02-01

    All cloned sialyltransferases from vertebrates are classified into four subfamilies and are characterized as having type II transmembrane topology. The catalytic domain has highly conserved motifs known as sialylmotifs. Besides sialylmotifs, each family has several unique conserved cysteine (Cys) residues mainly in the catalytic domain. The number and loci of conserved amino acids, however, differ with each subfamily, suggesting that the conserved Cys-residues and/or disulphide linkages they make may contribute to linkage specificity. Using Matrix Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF)-mass spectrometry, the present study performed disulphide linkage analysis on soluble mouse ST6Gal-I, which has six Cys-residues. Results confirmed that there were no free Cys-residues, and all six residues contributed to disulphide linkage formation, C(139)-C(403), C(181)-C(332) and C(350)-C(361). Study of single amino acid-substituted mutants revealed that the disulphide linkage C(181)-C(332) was necessary for molecular expression of the enzyme, and that the disulphide linkage C(350)-C(361) was necessary for enzyme activity. The remaining disulphide linkage C(139)-C(403) was not necessary for enzyme expression or for activity, including substrate specificity. Crystallographic study of pig ST3Gal I has recently been reported. Interestingly, the loci of disulphide linkages in ST6Gal-I differ from those in ST3Gal I, suggesting that the linkage specificity of sialyltransferase may results from significant structural differences, including the loci of disulphide linkages.

  7. Disulphide linkage in mouse ST6Gal-I: determination of linkage positions and mutant analysis

    PubMed Central

    Hirano, Yuichi; Suzuki, Takehiro; Matsumoto, Takumi; Ishihara, Yoshimi; Takaki, Yoshie; Kono, Mari; Dohmae, Naoshi; Tsuji, Shuichi

    2012-01-01

    All cloned sialyltransferases from vertebrates are classified into four subfamilies and are characterized as having type II transmembrane topology. The catalytic domain has highly conserved motifs known as sialylmotifs. Besides sialylmotifs, each family has several unique conserved cysteine (Cys) residues mainly in the catalytic domain. The number and loci of conserved amino acids, however, differ with each subfamily, suggesting that the conserved Cys-residues and/or disulphide linkages they make may contribute to linkage specificity. Using Matrix Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF)-mass spectrometry, the present study performed disulphide linkage analysis on soluble mouse ST6Gal-I, which has six Cys-residues. Results confirmed that there were no free Cys-residues, and all six residues contributed to disulphide linkage formation, C139–C403, C181–C332 and C350–C361. Study of single amino acid-substituted mutants revealed that the disulphide linkage C181–C332 was necessary for molecular expression of the enzyme, and that the disulphide linkage C350–C361 was necessary for enzyme activity. The remaining disulphide linkage C139–C403 was not necessary for enzyme expression or for activity, including substrate specificity. Crystallographic study of pig ST3Gal I has recently been reported. Interestingly, the loci of disulphide linkages in ST6Gal-I differ from those in ST3Gal I, suggesting that the linkage specificity of sialyltransferase may results from significant structural differences, including the loci of disulphide linkages. PMID:22039275

  8. Cardiovascular effects of occupational exposure to carbon disulphide.

    PubMed

    Kotseva, K P; De Bacquer, D

    2000-01-01

    The objective of this study was to investigate the effect of occupational exposure to carbon disulphide (CS2) on the total cholesterol, blood pressure and prevalence of coronary heart disease (CHD). A cross-sectional study involving 252 viscose rayon workers and 252 age and sex matched controls was carried out. Depending on the job and specific work place, the CS2 concentrations were between 10 and 64 mg/m3. A cumulative exposure index (CS2 index) was calculated for each worker by multiplying the number of years he had held a particular job with the CS2 concentrations in that job. CHD prevalence among the exposed was higher than among the controls; the difference reaching significance only for highly exposed workers. Cholesterol levels were significantly higher in both highly and moderately exposed groups. In conclusion, the results demonstrated that occupational exposure to CS2 increases total cholesterol and the risk for CHD. While the risk for CHD is increased in workers exposed to high CS2 concentration for many years (CS2 index > or = 300), even the relatively modest exposure (CS2 < 300) may increase the serum cholesterol.

  9. Control of Coherently Coupled Exciton Polaritons in Monolayer Tungsten Disulphide

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoze; Bao, Wei; Li, Quanwei; Ropp, Chad; Wang, Yuan; Zhang, Xiang

    2017-07-01

    Monolayer transition metal dichalcogenides (TMD) with confined 2D Wannier-Mott excitons are intriguing for the fundamental study of strong light-matter interactions and the exploration of exciton polaritons at high temperatures. However, the research of 2D exciton polaritons has been hindered because the polaritons in these atomically thin semiconductors discovered so far can hardly support strong nonlinear interactions and quantum coherence due to uncontrollable polariton dynamics and weakened coherent coupling. In this work, we demonstrate, for the first time, a precisely controlled hybrid composition with angular dependence and dispersion-correlated polariton emission by tuning the polariton dispersion in TMD over a broad temperature range of 110-230 K in a single cavity. This tamed polariton emission is achieved by the realization of robust coherent exciton-photon coupling in monolayer tungsten disulphide (WS2 ) with large splitting-to-linewidth ratios (>3.3 ). The unprecedented ability to manipulate the dispersion and correlated properties of TMD exciton polaritons at will offers new possibilities to explore important quantum phenomena such as inversionless lasing, Bose-Einstein condensation, and superfluidity.

  10. Metabolism of molybdenum.

    PubMed

    Mendel, Ralf R

    2013-01-01

    The transition element molybdenum is of essential importance for (nearly) all biological systems. It needs to be complexed by a special cofactor in order to gain catalytic activity. With the exception of bacterial Mo-nitrogenase, where Mo is a constituent of the FeMo-cofactor, Mo is bound to a pterin, thus forming the molybdenum cofactor Moco, which in different versions is the active compound at the catalytic site of all other Mo-containing enzymes. In eukaryotes, the most prominent Mo enzymes are nitrate reductase, sulfite oxidase, xanthine dehydrogenase, aldehyde oxidase, and the mitochondrial amidoxime reductase. The biosynthesis of Moco involves the complex interaction of six proteins and is a process of four steps, which also requires iron, ATP, and copper. After its synthesis, Moco is distributed to the apoproteins of Mo enzymes by Moco-carrier/binding proteins. A deficiency in the biosynthesis of Moco has lethal consequences for the respective organisms. In humans, Moco deficiency is a severe inherited inborn error in metabolism resulting in severe neurodegeneration in newborns and causing early childhood death. Eubacteria possess different versions of the pteridin cofactor as reflected by a large number of enzymes such as nitrate reductase, formate dehydrogenase, and dimethyl sulfoxide reductase, while in archaea a tungsten atom replaced molybdenum as catalytic metal in the active center.

  11. Molybdenum in icelandic geothermal waters

    NASA Astrophysics Data System (ADS)

    Arnórsson, Stefán; Ívarsson, Gretar

    1985-07-01

    Molybdenum concentrations in Icelandic geothermal waters lie in the range 1 70 ppb. Warm waters and dilute high-temperature waters which contain high concentrations of sulphide are lowest in molybdenum. No correlation is otherwise observed between molybdenum concentrations and temperature. Surface waters and cold ground waters do not contain detectable molybdenum (<1 ppb). It seems likely that leaching rate is the prime factor in limiting molybdenum levels in these waters. Within individual geothermal fields molybdenum concentrations are either approximately constant or they vary regularly across the field. This regular variation may often be correlated with variations in other solute concentrations and subsurface temperatures and is taken to indicate a control of molybdenum mobility by a temperature dependent equilibrium. The evidence suggests that the solubility of molybdenite is responsible. Molybdenite has not been found in active geothermal systems in Iceland but is known to occur in some New Zealand geothermal systems and it has been identified in hydrothermally altered Tertiary basalt formations at Reydarártindur in southeast Iceland. Boiling and mixing with cold water leads to molybdenite undersaturation and thus these processes favour leaching of molybdenum from the rock. On the other hand, conductive cooling leads to supersaturation which favours removal of molybdenum from solution.

  12. Effect of the amount of nickel sulphide, molybdenum disulphide and carbon nanosupport towards Tafel Slope and overpotential optimization.

    PubMed

    Sarno, Maria; Ponticorvo, Eleonora

    2017-04-06

    A Tafel slope of 40 mV/dec and a very small overpotential were measured for our NiSMoS2G nanocatalyst prepared by a scalable approach and consisting of: NiS nanoparticles covered by a stabilizing coating of MoS2 nanosheets on unsophisticated and easy to be obtained physical exfoliated graphite (PHG). A careful study proves that it is possible to improve the Tafel Slope and the overpotential through the optimization of the amounts of the different components. The conductive nanocarbons network, the highly active to charge accumulation NiS nanoparticles and the coupling with MoS2 nanosheets exposing a large number of edges, result in a very high hydrogen production rate of 1.63 mL cm-2 h-1 at -0.12 V, measured by means of an on-line mass spectrometry analysis.

  13. 2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Rowley-Neale, Samuel J.; Brownson, Dale A. C.; Smith, Graham C.; Sawtell, David A. G.; Kelly, Peter J.; Banks, Craig E.

    2015-10-01

    We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05164a|ART

  14. 2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction.

    PubMed

    Rowley-Neale, Samuel J; Brownson, Dale A C; Smith, Graham C; Sawtell, David A G; Kelly, Peter J; Banks, Craig E

    2015-11-21

    We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.

  15. Engineering chemically exfoliated dispersions of two-dimensional graphite and molybdenum disulphide for ink-jet printing

    NASA Astrophysics Data System (ADS)

    Michel, Monica; Desai, Jay A.; Biswas, Chandan; Kaul, Anupama B.

    2016-12-01

    Stable ink dispersions of two-dimensional-layered-materials (2DLMs) MoS2 and graphite are successfully obtained in organic solvents exhibiting a wide range of polarities and surface energies. The role of sonication time, ink viscosity and surface tension is explored in the context of dispersion stability using these solvents, which include N-methyl-2-pyrrolidone (NMP), N,N-Dimethylacetamide (DMA), dimethylformamide (DMF), Cyclohexanone (C), as well as less-toxic and more environmentally friendly Isopropanol (IPA) and Terpineol (T). The ink viscosity is engineered through the addition of Ethyl-Cellulose (EC) which has been shown to optimize the jettability of the dispersions. In contrast to prior work, the addition of EC after sonication—instead of prior to it—is noted to be effective in generating a high-density dispersion, yielding a uniform film morphology. High-quality inks are obtained using C/T and NMP as solvents for MoS2 and graphite, respectively, as gauged through optical absorption spectroscopy. Electronic transport data on the solution-cast inks is gathered at room temperature. Arrays of 2D graphite-rod based inks are printed on rigid Si, as well as flexible and transparent polyethylene terephthalate (PET) substrates. The results clearly show the promise of ink-jet printing for casting 2DLMs into hierarchically assembled structures over a range of substrates for flexible and printed-electronics applications.

  16. Thiol/disulphide homeostasis in Bell's palsy as a novel pathogenetic marker.

    PubMed

    Babademez, M A; Gul, F; Kale, H; Muderris, T; Bayazit, Y; Ergin, M; Erel, O; Kiris, M

    2017-04-01

    The aim of this study was to investigate the relationship between Bell's palsy and a novel oxidative stress parameter, thiol/disulphide homeostasis. A prospective study evaluating oxidative stress in Bell's palsy. This research took place in the department of Otorhinolaryngology, Ataturk Training and Research Hospital. Totally, 77 patients with Bell's palsy and 38 healthy controls were included in this study. The blood levels of total and native thiol and disulphide activity were assessed, and their levels were compared in the patients and controls. There were statistically significant differences between the patients and controls regarding thiol/disulphide parameters. The mean native thiol and total thiol were significantly lower and disulphide levels were higher in the Bell's palsy than controls. On binary logistic regression analysis, the created model showed 45.3% variation. The cut-off value was 18.95 for disulphides. Native and total thiol levels were low in the Bell's palsy. This metabolic disturbance may have a role in the pathogenesis of Bell's palsy. © 2016 John Wiley & Sons Ltd.

  17. Assisted refolding of recombinant prochymosin with the aid of protein disulphide isomerase.

    PubMed Central

    Tang, B; Zhang, S; Yang, K

    1994-01-01

    Protein disulphide isomerase (PDI) was shown to be able to accelerate the refolding of unfolded recombinant prochymosin and to enhance the overall yield of active protein. Unlike previous reports in this study PDI was found to be active at pH values as high as 11. The coincidence of the similar apparent optimum pH values of uncatalysed and PDI-catalysed reactions suggests that conditions favourable to spontaneous refolding of proteins may help PDI to catalyse thiol/disulphide interchange. Under the conditions described here no exogenously added dithiothreitol was required for PDI-catalysed renaturation, implying that the disulphide form of PDI was reduced to its active form by the free thiol groups in prochymosin molecules. PMID:8037666

  18. Oral treatment of polioencephalomalacia and subclinical thiamine deficiency with thiamine propyl disulphide and thiamine hydrochloride.

    PubMed

    Thomas, K W

    1986-12-01

    Thiaminase type I production by Bacillus thiaminolyticus and activity in vitro were repressed by the primary substate thiamine and by thiamine monophosphate and thiamine propyl disulphide. At thiamine concentrations of 300-3000 mumol/l production of active enzyme by B. thiaminolyticus, and activity of purified enzyme, were totally repressed. Growth of B. thiaminolyticus was inhibited by thiamine propyl disulphide at 3000 mumol/l. Activity of purified thiaminase was lost when incubated with ruminal fluid from healthy thiaminase free sheep. Enzyme activity was also lost when exposed to mildly alkaline conditions but was stimulated and stabilized against heat denaturation if treated with dithiothreitol. Thiaminase activities in the ruminal fluids of cases of ovine polioencephalomalacia were repressed within 2 h of oral administration of thiamine propyl disulphide. Blood pyruvate levels and transketolase activities were restored to normal following treatment. Treated animals recovered clinically and were returned to pasture.

  19. Mineral resource of the month: molybdenum

    USGS Publications Warehouse

    Polyak, Désire E.

    2011-01-01

    The article offers information about the mineral molybdenum. Sources includes byproduct or coproduct copper-molybdenum deposits in the Western Cordillera of North and South America. Among the uses of molybdenum are stainless steel applications, as an alloy material for manufacturing vessels and as lubricants, pigments or chemicals. Also noted is the role played by molybdenum in renewable energy technology.

  20. The mononuclear molybdenum enzymes

    SciTech Connect

    Hille, R.

    1996-11-01

    Molybdenum is widely available to biological systems due to the solubility of its high-valent oxides in water and is found in two basic forms: as an integral component of the multinuclear M center of nitrogenases and as the mononuclear active sites of a much more diverse group of enzymes that in general function catalytically to transfer an oxygen atom either to or from a physiological acceptor/donor molecule. It is on the basis of this commonly encountered aspect of catalysis that these enzymes are frequently referred to as oxotransferases, although no mechanistic connotation is intended in using the term. Similarly, the vast majority of these enzymes possess a Mo{double_bond}O unit in their active sites and are often referred to as oxomolybdenum enzymes. Neither of these terms is strictly applicable to the entire class of enzymes, however, as some (polysulfide reductase, for example, and possibly formate dehydrogenase) do not possess a Mo{double_bond}O unit. Here the term mononuclear molybdenum enzymes will be used in order to be as generic as possible. 431 refs.

  1. Selective Loss of Cysteine Residues and Disulphide Bonds in a Potato Proteinase Inhibitor II Family

    PubMed Central

    Li, Xiu-Qing; Zhang, Tieling; Donnelly, Danielle

    2011-01-01

    Disulphide bonds between cysteine residues in proteins play a key role in protein folding, stability, and function. Loss of a disulphide bond is often associated with functional differentiation of the protein. The evolution of disulphide bonds is still actively debated; analysis of naturally occurring variants can promote understanding of the protein evolutionary process. One of the disulphide bond-containing protein families is the potato proteinase inhibitor II (PI-II, or Pin2, for short) superfamily, which is found in most solanaceous plants and participates in plant development, stress response, and defence. Each PI-II domain contains eight cysteine residues (8C), and two similar PI-II domains form a functional protein that has eight disulphide bonds and two non-identical reaction centres. It is still unclear which patterns and processes affect cysteine residue loss in PI-II. Through cDNA sequencing and data mining, we found six natural variants missing cysteine residues involved in one or two disulphide bonds at the first reaction centre. We named these variants Pi7C and Pi6C for the proteins missing one or two pairs of cysteine residues, respectively. This PI-II-7C/6C family was found exclusively in potato. The missing cysteine residues were in bonding pairs but distant from one another at the nucleotide/protein sequence level. The non-synonymous/synonymous substitution (Ka/Ks) ratio analysis suggested a positive evolutionary gene selection for Pi6C and various Pi7C. The selective deletion of the first reaction centre cysteine residues that are structure-level-paired but sequence-level-distant in PI-II illustrates the flexibility of PI-II domains and suggests the functionality of their transient gene versions during evolution. PMID:21494600

  2. Change in membrane permeability induced by protegrin 1: implication of disulphide bridges for pore formation.

    PubMed

    Mangoni, M E; Aumelas, A; Charnet, P; Roumestand, C; Chiche, L; Despaux, E; Grassy, G; Calas, B; Chavanieu, A

    1996-03-25

    Protegrin 1 (PG-1) is a naturally occurring cationic antimicrobial peptide that is 18 residues long, has an aminated carboxy terminus and contains two disulphide bridges. Here, we investigated the antimicrobial activity of PG-1 and three linear analogues. Then, the membrane permeabilisation induced by these peptides was studied upon Xenopus laevis oocytes by electrophysiological methods. From the results obtained, we concluded that protegrin is able to form anion channels. Moreover, it seems clear that the presence of disulphide bridges is a prerequisite for the pore formation at the membrane level and not for the antimicrobial activity.

  3. Molybdenum enzymes in higher organisms

    PubMed Central

    Hille, Russ; Nishino, Takeshi; Bittner, Florian

    2010-01-01

    Recent progress in our understanding of the structural and catalytic properties of molybdenum-containing enzymes in eukaryotes is reviewed, along with aspects of the biosynthesis of the cofactor and its insertion into apoprotein. PMID:21516203

  4. A direct, continuous, sensitive assay for protein disulphide-isomerase based on fluorescence self-quenching.

    PubMed

    Raturi, Arun; Vacratsis, Panayiotis O; Seslija, Dana; Lee, Lana; Mutus, Bulent

    2005-10-15

    PDI (protein disulphide-isomerase) activity is generally monitored by insulin turbidity assay or scrambled RNase assay, both of which are performed by UV-visible spectroscopy. In this paper, we present a sensitive fluorimetric assay for continuous determination of disulphide reduction activity of PDI. This assay utilizes the pseudo-substrate diabz-GSSG [where diabz stands for di-(o-aminobenzoyl)], which is formed by the reaction of isatoic anhydride with the two free N-terminal amino groups of GSSG. The proximity of two benzoyl groups leads to quenching of the diabz-GSSG fluorescence by approx. 50% in comparison with its non-disulphide-linked form, abz-GSH (where abz stands for o-aminobenzoyl). Therefore the PDI-dependent disulphide reduction can be monitored by the increase in fluorescence accompanying the loss of proximity-quenching upon conversion of diabz-GSSG into abz-GSH. The apparent K(m) of PDI for diabz-GSSG was estimated to be approx. 15 muM. Unlike the insulin turbidity assay and scrambled RNase assay, the diabz-GSSG-based assay was shown to be effective in determining a single turnover of enzyme in the absence of reducing agents with no appreciable blank rates. The assay is simple to perform and very sensitive, with an estimated detection limit of approx. 2.5 nM PDI, enabling its use for the determination of platelet surface PDI activity in crude sample preparations.

  5. Thiol/disulphide homeostasis as a novel indicator of oxidative stress in sudden sensorineural hearing loss.

    PubMed

    Dinc, M E; Ulusoy, S; Is, A; Ayan, N N; Avincsal, M O; Bicer, C; Erel, O

    2016-05-01

    To investigate a novel oxidative stress marker, thiol/disulphide literature homeostasis, in patients with idiopathic sudden sensorineural hearing loss, and to compare the results with healthy controls for the first time. Thirty-two patients with idiopathic sudden sensorineural hearing loss and 30 healthy individuals were included in the study. Serum native thiol, total thiol and disulphide levels were measured, and disulphide/native thiol and disulphide/total thiol ratios were determined in all subjects. Serum native thiol and total thiol levels were significantly lower in patients with sudden sensorineural hearing loss compared with controls (p < 0.05). Of the 32 patients, 25 had lower native thiol levels than controls (333.2 ± 73.9 vs 381.8 ± 35.6 μmol/l, p = 0.002) and 24 had lower total thiol levels (375.1 ± 74.3 vs 426.1 ± 39.3 μmol/l, p = 0.002). The changes in oxidative markers evident in a significant number of patients may be associated with oxidative stress, which may, in turn, have caused sudden sensorineural hearing loss in those patients.

  6. Oxide strengthened molybdenum-rhenium alloy

    DOEpatents

    Bianco, Robert; Buckman, Jr., R. William

    2000-01-01

    Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (a) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (b) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (c) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (d) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (e) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (f) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method. A preferred Mo--Re-ODS alloy contains 7-14 weight % rhenium and 2-4 volume % lanthanum oxide.

  7. Oxide strengthened molybdenum-rhenium alloy

    SciTech Connect

    Bianco, Robert; Buckman, William R. Jr.

    1998-12-01

    Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (1) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (2) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (3) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (4) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (5) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (6) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method.

  8. Large-scale prediction of disulphide bridges using kernel methods, two-dimensional recursive neural networks, and weighted graph matching.

    PubMed

    Cheng, Jianlin; Saigo, Hiroto; Baldi, Pierre

    2006-03-15

    The formation of disulphide bridges between cysteines plays an important role in protein folding, structure, function, and evolution. Here, we develop new methods for predicting disulphide bridges in proteins. We first build a large curated data set of proteins containing disulphide bridges to extract relevant statistics. We then use kernel methods to predict whether a given protein chain contains intrachain disulphide bridges or not, and recursive neural networks to predict the bonding probabilities of each pair of cysteines in the chain. These probabilities in turn lead to an accurate estimation of the total number of disulphide bridges and to a weighted graph matching problem that can be addressed efficiently to infer the global disulphide bridge connectivity pattern. This approach can be applied both in situations where the bonded state of each cysteine is known, or in ab initio mode where the state is unknown. Furthermore, it can easily cope with chains containing an arbitrary number of disulphide bridges, overcoming one of the major limitations of previous approaches. It can classify individual cysteine residues as bonded or nonbonded with 87% specificity and 89% sensitivity. The estimate for the total number of bridges in each chain is correct 71% of the times, and within one from the true value over 94% of the times. The prediction of the overall disulphide connectivity pattern is exact in about 51% of the chains. In addition to using profiles in the input to leverage evolutionary information, including true (but not predicted) secondary structure and solvent accessibility information yields small but noticeable improvements. Finally, once the system is trained, predictions can be computed rapidly on a proteomic or protein-engineering scale. The disulphide bridge prediction server (DIpro), software, and datasets are available through www.igb.uci.edu/servers/psss.html. (c) 2005 Wiley-Liss, Inc.

  9. Silicon nitride reinforced with molybdenum disilicide

    DOEpatents

    Petrovic, John J.; Honnell, Richard E.

    1991-01-01

    Compositions of matter comprised of silicon nitride and molybdenum disilicide and methods of making the compositions, where the molybdenum disilicide is present in amounts ranging from about 5 to about 50 vol. %.

  10. Silicon nitride reinforced with molybdenum disilicide

    SciTech Connect

    Petrovic, J.J.; Honnell, R.E.

    1990-12-31

    Compositions of matter comprised of silicon nitride and molybdenum disilicide and methods of making the compositions, where the molybdenum disilicide is present in amounts ranging from about 5 to about 50 vol%.

  11. Nitrogen reduction: Molybdenum does it again

    NASA Astrophysics Data System (ADS)

    Schrock, Richard R.

    2011-02-01

    Nature reduces dinitrogen under mild conditions using nitrogenases, the most active of which contains molybdenum and iron. The only abiological dinitrogen reduction catalyst that avoids the harsh conditions of the Haber-Bosch process contains just molybdenum.

  12. Molybdenum compounds in organic synthesis

    NASA Astrophysics Data System (ADS)

    Khusnutdinov, R. I.; Oshnyakova, T. M.; Dzhemilev, U. M.

    2017-02-01

    The review presents the first analysis and systematic discussion of data published in the last 35–40 years on the use of molybdenum compounds and complexes in organic synthesis and catalysis of various ion coordination and radical reactions. Detailed account is given of the key trends in the use of molybdenum complexes as catalysts of alkene epoxidation and oxyketonation, oxidation of sulfur, nitrogen and phosphorus compounds, hydrosilylation of 1,3-dienes, ketones and aldehydes, hydrostannylation of acetylenes and hydrogermylation of norbornadienes. Considerable attention is paid to the description of new reactions and in situ generation of highly reactive hypohalites, ROX and HOX, induced by molybdenum complexes and the use of hypohalites in oxidative transformations. Data on the application of molybdenum complexes in well-known reactions are discussed, including Kharasch and Pauson–Khand reactions, allylic alkylation of C-nucleophiles, aminocarbonylation of halo derivatives and oligomerization of cyclic dienes, trienes, alkynes and 1,3-dienes. The last Section of the review considers 'unusual' organic reactions involving molybdenum compounds and complexes. The bibliography includes 257 references.

  13. Determination of small amounts of molybdenum in tungsten and molybdenum ores

    USGS Publications Warehouse

    Grimaldi, F.S.; Wells, R.C.

    1943-01-01

    A rapid method has been developed for the determination of small amounts of molybdenum in tungsten and molybdenum ores. After removing iron and other major constituents the molybdenum thiocyanate color is developed in water-acetone solutions, using ammonium citrate to eliminate the interference of tungsten. Comparison is made by titrating a blank with a standard molybdenum solution. Aliquots are adjusted to deal with amounts of molybdenum ranging from 0.01 to 1.30 mg.

  14. Investigation of dynamic thiol-disulphide homoeostasis in age-related cataract patients with a novel and automated assay.

    PubMed

    Sagdik, Haci Murat; Ucar, Fatma; Tetikoglu, Mehmet; Aktas, Serdar; Ozcura, Fatih; Kocak, Havva; Neselioglu, Salim; Eren, Funda

    2017-04-10

    The aim of this study was to determine plasma thiol-disulphide homoeostasis in patients with age-related cataract (ARC) and compare the results of the patients with healthy subjects. Plasma malondialdehyde (MDA) levels and catalase (CAT) activity were also investigated. The study included 53 cataract patients and 52 healthy volunteers. Native thiol-disulphide exchanges were determined using a novel and automated method. CAT activity was determined using the method described by Aebi, and MDA levels were calculated using the thiobarbituric acid method. Native thiol and total thiol levels were significantly lower in the cataract patients compared with the controls (p < 0.001, p = 0.002, respectively). The disulphide levels of the cataract patients were significantly higher than the controls (p = 0.002). The ratios of disulphide/native thiol and disulphide/total thiol were statistically higher in the cataract patients compared with the control group (p < 0.001, p < 0.001, respectively). Furthermore, CAT activity was significantly lower in the cataract patient group compared with the control group (p < 0.001), and MDA levels were insignificantly higher in the patient group (p = 0.581). Our study showed that dynamic thiol-disulphide homoeostasis has shifted towards disulphide formation, as a result of thiol oxidation in ARC patients. The present study is the first to measure thiol-disulphide homoeostasis in ARC patients with a novel automated assay. This study supports the hypothesis that cataract is an oxidative disorder. Further studies are required in order to examine the relationship between oxidative stress and the development of cataract formation.

  15. A structural homologue of colipase in black mamba venom revealed by NMR floating disulphide bridge analysis.

    PubMed

    Boisbouvier, J; Albrand, J P; Blackledge, M; Jaquinod, M; Schweitz, H; Lazdunski, M; Marion, D

    1998-01-01

    The solution structure of mamba intestinal toxin 1 (MIT1), isolated from Dendroaspis polylepis polylepis venom, has been determined. This molecule is a cysteine-rich polypeptide exhibiting no recognised family membership. Resistance to MIT1 to classical specific endoproteases produced contradictory NMR and biochemical information concerning disulphide-bridge topology. We have used distance restraints allowing ambiguous partners between S atoms in combination with NMR-derived structural information, to correctly determine the disulphide-bridge topology. The resultant solution structure of MIT1, determined to a resolution of 0.5 A, reveals an unexpectedly similar global fold with respect to colipase, a protein involved in fatty acid digestion. Colipase exhibits an analogous resistance to endoprotease activity, indicating for the first time the possible topological origins of this biochemical property. The biochemical and structural homology permitted us to propose a mechanically related digestive function for MIT1 and provides novel information concerning snake venom protein evolution. Copyright 1998 Academic Press.

  16. Molybdenum sulfide/carbide catalysts

    DOEpatents

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda

    2007-05-29

    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

  17. Engineering and introduction of de novo disulphide bridges in organophosphorus hydrolase enzyme for thermostability improvement.

    PubMed

    Farnoosh, Gholamreza; Khajeh, Khosro; Latifi, Ali Mohammad; Aghamollaei, Hossein

    2016-12-01

    The organophosphorus hydrolase (OPH) has been used to degrade organophosphorus chemicals, as one of the most frequently used decontamination methods. Under chemical and thermal denaturing conditions, the enzyme has been shown to unfold. To utilize this enzyme in various applications, the thermal stability is of importance. The engineering of de novo disulphide bridges has been explored as a means to increase the thermal stability of enzymes in the rational method of protein engineering. In this study, Disulphide by Design software, homology modelling and molecular dynamics simulations were used to select appropriate amino acid pairs for the introduction of disulphide bridge to improve protein thermostability. The thermostability of the wild-type and three selected mutant enzymes were evaluated by half-life, delta G inactivation (ΔGi) and structural studies (fluorescence and far-UV CD analysis). Data analysis showed that half-life of A204C/T234C and T128C/E153C mutants were increased up to 4 and 24 min, respectively; however, for the G74C/A78C mutant, the half-life was decreased up to 9 min. For the T128C/E124C mutant, both thermal stability and Catalytic efficiency (kcat) were also increased. The half-life and ΔGi results were correlated to the obtained information from structural studies by circular dichroism (CD) spectrometry and extrinsic fluorescence experiments; as rigidity increased in A204C/T2234C and T128C/E153C mutants, half-life and ΔGi also increased. For G74C/A78C mutant, these parameters decreased due to its higher flexibility. The results were submitted a strong evidence for the possibility to improve the thermostability of OPH enzyme by introducing a disulphide bridge after bioinformatics design, even though this design would not be always successful.

  18. Aberrant disulphide bonding contributes to the ER retention of alpha1-antitrypsin deficiency variants.

    PubMed

    Ronzoni, Riccardo; Berardelli, Romina; Medicina, Daniela; Sitia, Roberto; Gooptu, Bibek; Fra, Anna Maria

    2016-02-15

    Mutations in alpha1-antitrypsin (AAT) can cause the protein to polymerise and be retained in the endoplasmic reticulum (ER) of hepatocytes. The ensuing systemic AAT deficiency leads to pulmonary emphysema, while intracellular polymers are toxic and cause chronic liver disease. The severity of this process varies considerably between individuals, suggesting the involvement of mechanistic co-factors and potential for therapeutically beneficial interventions. We show in Hepa1.6 cells that the mildly polymerogenic I (Arg39Cys) AAT mutant forms aberrant inter- and intra-molecular disulphide bonds involving the acquired Cys39 and the only cysteine residue in the wild-type (M) sequence (Cys232). Substitution of Cys39 to serine partially restores secretion, showing that disulphide bonding contributes to the intracellular retention of I AAT. Covalent homodimers mediated by inter-Cys232 bonding alone are also observed in cells expressing the common Z and other polymerising AAT variants where conformational behaviour is abnormal, but not in those expressing M AAT. Prevention of such disulphide linkage through the introduction of the Cys232Ser mutation or by treatment of cells with reducing agents increases Z AAT secretion. Our results reveal that disulphide interactions enhance intracellular accumulation of AAT mutants and implicate the oxidative ER state as a pathogenic co-factor. Redox modulation, e.g. by anti-oxidant strategies, may therefore be beneficial in AAT deficiency-associated liver disease. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  19. Disulphide bridge formation of proinsulin fusion proteins during secretion in Streptomyces.

    PubMed

    Vértesy, L; Tripier, D; Koller, K P; Riess, G

    1991-03-01

    To study disulphide bridge formation by Streptomyces lividans TK 24 in secreted single chain precursors of insulin a fusion protein (PTF 1) was investigated consisting of monkey proinsulin and the aminoterminal sequence Asp1 to Gly43 of the alpha-amylase inhibitor tendamistat from Streptomyces tendae. The purified soluble protein PTF 1 has a molecular mass of 14.4 kDa. The primary structure was elucidated after digestion with lysyl endopeptidase and fragment analysis. In this system, disulphide bond formation occurs in a way that the first cysteine in proinsulin is linked to the next following cysteine in the amino-acid chain resulting in a non-natural folding of the insulin part of the fusion protein. Re-folding of PTF 1 by reduction and re-oxidation followed by proteolytic digestions led to insulins which are identical to authentic material. The ease of correct disulphide bond formation in solution and incorrect processing during secretion suggests involvement of yet unknown factors leading to an unfavourable folding of proinsulin.

  20. Molybdenum recycling in the United States in 1998

    USGS Publications Warehouse

    Blossom, John W.

    2002-01-01

    This report describes the flow of molybdenum in the United States in 1998 with emphasis on the extent to which molybdenum was recycled. Molybdenum was mostly recycled from products of molybdenum-bearing steels and superalloys, with some molybdenum products recovered specifically for their high molybdenum content. In 1998, 8,000 metric tons (t) of molybdenum was estimated to have been recycled, and the recycling rate was calculated to be 33 percent, with recycling efficiency at about 30 percent.

  1. High-performance MoS{sub 2} transistors with low-resistance molybdenum contacts

    SciTech Connect

    Kang, Jiahao; Liu, Wei; Banerjee, Kaustav

    2014-03-03

    In this Letter, molybdenum (Mo) is introduced and evaluated as an alternative contact metal to atomically-thin molybdenum disulphide (MoS{sub 2}), and high-performance field-effect transistors are experimentally demonstrated. In order to understand the physical nature of the interface and highlight the role of the various factors contributing to the Mo-MoS{sub 2} contacts, density functional theory (DFT) simulations are employed, which reveal that Mo can form high quality contact interface with monolayer MoS{sub 2} with zero tunnel barrier and zero Schottky barrier under source/drain contact, as well as an ultra-low Schottky barrier (0.1 eV) at source/drain-channel junction due to strong Fermi level pinning. In agreement with the DFT simulations, high mobility, high ON-current, and low contact resistance are experimentally demonstrated on both monolayer and multilayer MoS{sub 2} transistors using Mo contacts. The results obtained not only reveal the advantages of using Mo as a contact metal for MoS{sub 2} but also highlight the fact that the properties of contacts with 2-dimensional materials cannot be intuitively predicted by solely considering work function values and Schottky theory.

  2. Amorphous molybdenum sulfides as hydrogen evolution catalysts.

    PubMed

    Morales-Guio, Carlos G; Hu, Xile

    2014-08-19

    Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

  3. SURFACE TREATMENT OF MOLYBDENUM METAL

    DOEpatents

    Coffer, C.O.

    1961-12-01

    A process of descaling molybdenum articles comprises first immersing them in an aqueous sodium hydroxide-potassium permanganate solution of between 60 and 85 deg C, rinsing, and then immersing them in an aqueous solution containing a mixture of sulfuric, hydrochloric, and chromic acids.

  4. Enhanced molybdenum uptake in rice

    USDA-ARS?s Scientific Manuscript database

    Molybdenum (Mo) is a cofactor for nitrate reductase. When nitrate reductase activity is limited by Mo deficiency, crop yields are also potentially limited. Plant deficiencies in Mo often occur in acidic soil due to mineral fixation. The long-term goal is to identify genes that can be used to develop...

  5. Parameters affecting in vitro oxidation/folding of maurotoxin, a four-disulphide-bridged scorpion toxin.

    PubMed Central

    di Luccio, E; Azulay, D O; Regaya, I; Fajloun, Z; Sandoz, G; Mansuelle, P; Kharrat, R; Fathallah, M; Carrega, L; Estève, E; Rochat, H; De Waard, M; Sabatier, J M

    2001-01-01

    Maurotoxin (MTX) is a 34-mer scorpion toxin cross-linked by four disulphide bridges that acts on various K(+) channel subtypes. MTX adopts a disulphide bridge organization of the type C1-C5, C2-C6, C3-C4 and C7-C8, and folds according to the common alpha/beta scaffold reported for other known scorpion toxins. Here we have investigated the process and kinetics of the in vitro oxidation/folding of reduced synthetic L-MTX (L-sMTX, where L-MTX contains only L-amino acid residues). During the oxidation/folding of reduced L-sMTX, the oxidation intermediates were blocked by iodoacetamide alkylation of free cysteine residues, and analysed by MS. The L-sMTX intermediates appeared sequentially over time from the least (intermediates with one disulphide bridge) to the most oxidized species (native-like, four-disulphide-bridged L-sMTX). The mathematical formulation of the diffusion-collision model being inadequate to accurately describe the kinetics of oxidation/folding of L-sMTX, we have formulated a derived mathematical description that better fits the experimental data. Using this mathematical description, we have compared for the first time the oxidation/folding of L-sMTX with that of D-sMTX, its stereoisomer that contains only D-amino acid residues. Several experimental parameters, likely to affect the oxidation/folding process, were studied further; these included temperature, pH, ionic strength, redox potential and concentration of reduced toxin. We also assessed the effects of some cellular enzymes, peptidylprolyl cis-trans isomerase (PPIase) and protein disulphide isomerase (PDI), on the folding pathways of reduced L-sMTX and D-sMTX. All the parameters tested affect the oxidative folding of sMTX, and the kinetics of this process were indistinguishable for L-sMTX and D-sMTX, except when stereospecific enzymes were used. The most efficient conditions were found to be: 50 mM Tris/HCl/1.4 mM EDTA, pH 7.5, supplemented by 0.5 mM PPIase and 50 units/ml PDI for 0.1 m

  6. Transmission electron microscopy of oxide dispersion strengthened (ODS) molybdenum: effects of irradiation on material microstructure

    SciTech Connect

    Baranwal, R. and Burke, M.G.

    2003-03-03

    Oxide dispersion strengthened (ODS) molybdenum has been characterized using transmission electron microscopy (TEM) to determine the effects of irradiation on material microstructure. This work describes the results-to-date from TEM characterization of unirradiated and irradiated ODS molybdenum. The general microstructure of the unirradiated material consists of fine molybdenum grains (< 5 {micro}m average grain size) with numerous low angle boundaries and isolated dislocation networks. 'Ribbon'-like lanthanum oxides are aligned along the working direction of the product form and are frequently associated with grain boundaries, serving to inhibit grain boundary and dislocation movement. In addition to the 'ribbons', discrete lanthanum oxide particles have also been detected. After irradiation, the material is characterized by the presence of nonuniformly distributed large ({approx} 20 to 100 nm in diameter), multi-faceted voids, while the molybdenum grain size and oxide morphology appear to be unaffected by irradiation.

  7. Mechanical properties of electron-beam-melted molybdenum and dilute molybdenum-rhenium alloys

    NASA Technical Reports Server (NTRS)

    Klopp, W. D.; Witzke, W. R.

    1972-01-01

    A study of molybdenum and three dilute molybdenum-rhenium alloys was undertaken to determine the effects of rhenium on the low temperature ductility and other mechanical properties of molybdenum. Alloys containing 3.9, 5.9, and 7.7 atomic percent rhenium exhibited lower ductile-brittle transition temperatures than did the unalloyed molybdenum. The maximum improvement in the annealed condition was observed for molybdenum - 7.7 rhenium, which had a ductile-brittle transition temperature approximately 200 C (360 F) lower than that for unalloyed molybdenum. Rhenium additions also increased the low and high temperature tensile strengths and the high temperature creep strength of molybdenum. The mechanical behavior of dilute molybdenum-rhenium alloys is similar to that observed for dilute tungsten-rhenium alloys.

  8. Engineering the thermostability of Trichoderma reesei endo-1,4-beta-xylanase II by combination of disulphide bridges.

    PubMed

    Xiong, Hairong; Fenel, Fred; Leisola, Matti; Turunen, Ossi

    2004-10-01

    Disulphide bridges were introduced in different combinations into the N-terminal region and the single alpha-helix of mesophilic Trichoderma reesei xylanase II (TRX II). We used earlier disulphide-bridge data and designed new disulphide bridges for the combination mutants. The most stable mutant contained two disulphide bridges (between positions 2 and 28 and between positions 110 and 154, respectively) and the mutations N11D, N38E, and Q162H. With a half-life of approximately 56 h at 65 degrees C, the thermostability of this sevenfold mutant was approximately 5,000 times higher than that of TRX II, and the half-life was 25 min even at 75 degrees C. The thermostability of this mutant was approximately 30 times higher than that of the corresponding mutant missing the bridge between positions 2 and 28. The extensive stabilization at two protein regions did not alter the kinetic properties of the sevenfold mutant from that of the wild-type TRX II. The combination of disulphide bridges enhanced significantly the pH-dependent stability in a wide pH range.

  9. Different redox sensitivity of endoplasmic reticulum associated degradation clients suggests a novel role for disulphide bonds in secretory proteins.

    PubMed

    Medraño-Fernandez, Iria; Fagioli, Claudio; Mezghrani, Alexandre; Otsu, Mieko; Sitia, Roberto

    2014-04-01

    To maintain proteostasis in the endoplasmic reticulum (ER), terminally misfolded secretory proteins must be recognized, partially unfolded, and dislocated to the cytosol for proteasomal destruction, in a complex process called ER-associated degradation (ERAD). Dislocation implies reduction of inter-chain disulphide bonds. When in its reduced form, protein disulphide isomerase (PDI) can act not only as a reductase but also as an unfoldase, preparing substrates for dislocation. PDI oxidation by Ero1 favours substrate release and transport across the ER membrane. Here we addressed the redox dependency of ERAD and found that DTT stimulates the dislocation of proteins with DTT-resistant disulphide bonds (i.e., orphan Ig-μ chains) but stabilizes a ribophorin mutant (Ri332) devoid of them. DTT promotes the association of Ri332, but not of Ig-µ, with PDI. This discrepancy may suggest that disulphide bonds in cargo proteins can be utilized to oxidize PDI, hence facilitating substrate detachment and degradation also in the absence of Ero1. Accordingly, Ero1 silencing retards Ri332 degradation, but has little if any effect on Ig-µ. Thus, some disulphides can increase the stability and simultaneously favour quality control of secretory proteins.

  10. Mechanical Properties of Iron Alumininides Intermetallic Alloy with Molybdenum Addition

    SciTech Connect

    Zuhailawati, H.; Fauzi, M. N. A.

    2010-03-11

    In this work, FeAl-based alloys with and without molybdenum addition were fabricated by sintering of mechanically alloyed powders in order to investigate the effect of molybdenum on iron aluminide mechanical properties. Bulk samples were prepared by mechanical alloying for 4 hours, pressing at 360 MPa and sintering at 1000 deg. C for 2 hours. The specimens were tested in compression at room temperature using Instron machine. The phase identification and microstructure of the consolidated material was examined by x-ray diffraction and scanning electron microscope correspondingly. Results show that 2.5 wt%Mo addition significantly increased the ultimate stress and ultimate strain in compressive mode due to solid solution hardening. However, the addition of Mo more than 2.5 wt% was accompanied by a reduction in both properties caused by the presence of Mo-rich precipitate particles.

  11. The involvement of molybdenum in life.

    PubMed

    Williams, R J P; Fraústo da Silva, J J R

    2002-03-29

    Quite extraordinarily molybdenum is an essential element in life for the uptake of nitrogen from both nitrogen gas and nitrate, yet it is a relatively rare heavy trace element. It also functions in a few extremely important oxygen-atom transfer reactions at low redox potential. This review poses the question "Why does life depend upon molybdenum?" The answer has to be based upon the availability of the element and on chemical superiority in carrying out the essential tasks. We illustrate here the peculiarities of molybdenum chemistry and how they have become part of certain enzymes. The uptake and incorporation of molybdenum are dependent on its availability, selective pumps, and carriers (chaperones), but 4.5 x 10(9) years ago molybdenum was not available when both tungsten and vanadium or even iron were possibly used in its place. While these possibilities are explored, they leave many unanswered questions concerning the selection today of molybdenum. (c)2002 Elsevier Science (USA).

  12. Neutron scattering and models : molybdenum.

    SciTech Connect

    Smith, A.B.

    1999-05-26

    A comprehensive interpretation of the fast-neutron interaction with elemental and isotopic molybdenum at energies of {le} 30 MeV is given. New experimental elemental-scattering information over the incident energy range 4.5 {r_arrow} 10 MeV is presented. Spherical, vibrational and dispersive models are deduced and discussed, including isospin, energy-dependent and mass effects. The vibrational models are consistent with the ''Lane potential''. The importance of dispersion effects is noted. Dichotomies that exist in the literature are removed. The models are vehicles for fundamental physical investigations and for the provision of data for applied purposes. A ''regional'' molybdenum model is proposed. Finally, recommendations for future work are made.

  13. Molybdenum cofactor and human disease.

    PubMed

    Schwarz, Guenter

    2016-04-01

    Four molybdenum-dependent enzymes are known in humans, each harboring a pterin-based molybdenum cofactor (Moco) in the active site. They catalyze redox reactions using water as oxygen acceptor or donator. Moco is synthesized by a conserved biosynthetic pathway. Moco deficiency results in a severe inborn error of metabolism causing often early childhood death. Disease-causing symptoms mainly go back to the lack of sulfite oxidase (SO) activity, an enzyme in cysteine catabolism. Besides their name-giving functions, Mo-enzymes have been recognized to catalyze novel reactions, including the reduction of nitrite to nitric oxide. In this review we cover the biosynthesis of Moco, key features of Moco-enzymes and focus on their deficiency. Underlying disease mechanisms as well as treatment options will be discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Molybdenum disilicide alloy matrix composite

    DOEpatents

    Petrovic, John J.; Honnell, Richard E.; Gibbs, W. Scott

    1990-01-01

    Compositions of matter consisting of matrix matrials having silicon carbide dispersed throughout them and methods of making the compositions. A matrix material is an alloy of an intermetallic compound, molybdenum disilicide, and at least one secondary component which is a refractory silicide. The silicon carbide dispersant may be in the form of VLS whiskers, VS whiskers, or submicron powder or a mixture of these forms.

  15. Zirconia-molybdenum disilicide composites

    DOEpatents

    Petrovic, John J.; Honnell, Richard E.

    1991-01-01

    Compositions of matter comprised of molybdenum disilicide and zirconium oxide in one of three forms: pure, partially stabilized, or fully stabilized and methods of making the compositions. The stabilized zirconia is crystallographically stabilized by mixing it with yttrium oxide, calcium oxide, cerium oxide, or magnesium oxide and it may be partially stabilized or fully stabilized depending on the amount of stabilizing agent in the mixture.

  16. Molybdenum disilicide alloy matrix composite

    DOEpatents

    Petrovic, J.J.; Honnell, R.E.; Gibbs, W.S.

    1991-12-03

    Compositions of matter consisting of matrix materials having silicon carbide dispersed throughout them and methods of making the compositions are disclosed. A matrix material is an alloy of an intermetallic compound, molybdenum disilicide, and at least one secondary component which is a refractory silicide. The silicon carbide dispersant may be in the form of VLS whiskers, VS whiskers, or submicron powder or a mixture of these forms. 3 figures.

  17. Molybdenum disilicide alloy matrix composite

    DOEpatents

    Petrovic, John J.; Honnell, Richard E.; Gibbs, W. Scott

    1991-01-01

    Compositions of matter consisting of matrix materials having silicon carbide dispersed throughout them and methods of making the compositions. A matrix material is an alloy of an intermetallic compound, molybdenum disilicide, and at least one secondary component which is a refractory silicide. The silicon carbide dispersant may be in the form of VLS whiskers, VS whiskers, or submicron powder or a mixture of these forms.

  18. Annealed CVD molybdenum thin film surface

    DOEpatents

    Carver, Gary E.; Seraphin, Bernhard O.

    1984-01-01

    Molybdenum thin films deposited by pyrolytic decomposition of Mo(CO).sub.6 attain, after anneal in a reducing atmosphere at temperatures greater than 700.degree. C., infrared reflectance values greater than reflectance of supersmooth bulk molybdenum. Black molybdenum films deposited under oxidizing conditions and annealed, when covered with an anti-reflecting coating, approach the ideal solar collector characteristic of visible light absorber and infrared energy reflector.

  19. Mineral resource of the month: molybdenum

    USGS Publications Warehouse

    Magyar, Michael J.

    2004-01-01

    Molybdenum is a metallic element that is most frequently used in alloy and stainless steels, which together represent the single largest market for molybdenum. Molybdenum has also proven invaluable in carbon steel, cast iron and superalloys. Its alloying versatility is unmatched because its addition enhances material performance under high-stress conditions in expanded temperature ranges and in highly corrosive environments. The metal is also used in catalysts, other chemicals, lubricants and many other applications.

  20. Thiol/disulphide homeostasis in pregnant women with Familial Mediterranean fever.

    PubMed

    Yucel, Aykan; Sanhal, Cem Yasar; Daglar, Korkut; Kara, Ozgur; Uygur, Dilek; Erel, Ozcan

    2016-11-01

    To investigate the presence of oxidative stress (OS) in pregnant women with Familial Mediterranean fever (FMF) in the first trimester by evaluating thiol/disulphide homeostasis. A total of 31 pregnant women with a diagnosis of FMF, between 11(0) and 13(6) weeks of gestation, were compared with 51 healthy pregnant controls at the same gestational weeks. A recently defined method was used to measure plasma native thiol, total thiol and disulphide levels. There were no differences between groups in terms of maternal age, body mass index and numbers of gravida and parity. Antenatal complications (45.2% vs. 9.8%, P = 0.001) and primary caesarean section (22.6% vs. 5.9%, P = 0.037) were higher in the FMF group. Pregnant women with FMF had significantly lower first trimester serum levels of native thiol (297.5 μmol/l (153.2-441.8) vs. 366.1 μmol/l (288.7-432.4), P = 0.000), total thiol (327.2 μmol/l (171.0-471.0) vs. 389.9 μmol/l (317.1-449.8), P = 0.000) and higher levels of disulphide (14.2 ± 4.5 μmol/l vs. 12.4 ± 3.4 μmol/l, P = 0.045). No differences were found in these parameters among FMF patients with and without antenatal complications. The main outcome demonstrates a relation between OS and pregnant women with FMF in the first trimester of gestation. OS in the first trimester may be a major aetiological factor of unfavourable pregancy outcomes in this group of patients.

  1. Exposure to carbon disulphide and ischaemic heart disease in a viscose rayon factory.

    PubMed Central

    Sweetnam, P M; Taylor, S W; Elwood, P C

    1987-01-01

    The cohort of viscose rayon workers previously described by Tiller et al has been reconstructed and followed up to the end of 1982. The pattern of mortality at ages 45 to 64 for the extended period 1950-82 is similar to that described by Tiller et al for 1950-64. The spinners, the workers most heavily exposed to carbon disulphide, have a significantly higher mortality from all causes than the least exposed group. The excess mortality is largely accounted for by ischaemic heart disease (IHD) for which the spinners have an SMR of 172. When mortality is related to an exposure score in the same group, both all cause (p less than 0.01) and IHD (p less than 0.001) mortality increase with increasing exposure level. When this analysis is repeated covering all ages these trends become much less strong and only that for IHD remains significant (p less than 0.05). Over the age of 65 there is a tendency for mortality to decline with increasing exposure. This is contrary to expectation under the usual hypothesis that carbon disulphide promotes atherosclerosis. Instead it suggests that carbon disulphide has some type of reversible, direct cardiotoxic or thrombotic effect. This is supported by the findings that there is a strong trend (p less than 0.01) for IHD mortality to increase with increasing exposure in the previous two years. Further, both IHD (p less than 0.001) and total (p less than 0.01) mortality show highly significant trends with exposure among current workers but no such trends among workers who have left the industry. PMID:3567096

  2. Selective molybdenum deposition by LPCVD

    SciTech Connect

    Lifshitz, N.; Williams, D.S.; Capio, C.D.; Brown, J.M.

    1987-08-01

    Molybdenum films have been deposited by low pressure chemical vapor deposition (LPCVD) on silicon substrates by the reduction of molybdenum hexafluoride in hydrogen and argon atmospheres. The deposition is extremely selective, with no Mo observed on silicon dioxide surfaces over the temperature range of 200/sup 0/-400/sup 0/C. Reduction by both hydrogen and silicon contribute to the deposition, with approximately equal, extremely high deposition rates; no self-limiting thickness was observed. Extensive TEM and SEM studies were conducted in order to characterize the microstructure of the deposited films. The main feature of the films is their extreme porosity - about 30%, which can explain many unusual properties of the process and the films. On the basis of experiments the authors propose a model to explain the origin of the porosity in the films. Comparative studies of tungsten and molybdenum LPCVD reveal that the difference between the two processes lie in the self-limiting mechanism occurring during the silicon reduction of tungsten hexafluoride.

  3. Molybdenum-base cermet fuel development

    NASA Astrophysics Data System (ADS)

    Pilger, James P.; Gurwell, William E.; Moss, Ronald W.; White, George D.; Seifert, David A.

    Development of a multimegawatt (MMW) space nuclear power system requires identification and resolution of several technical feasibility issues before selecting one or more promising system concepts. Demonstration of reactor fuel fabrication technology is required for cermet-fueled reactor concepts. The MMW reactor fuel development activity at Pacific Northwest Laboratory (PNL) is focused on producing a molybdenum-matrix uranium-nitride (UN) fueled cermte. This cermet is to have a high matrix density (greater than or equal to 95 percent) for high strength and high thermal conductance coupled with a high particle (UN) porosity (approximately 25 percent) for retention of released fission gas at high burnup. Fabrication process development involves the use of porous TiN microspheres as surrogate fuel material until porous Un microspheres become available. Process development was conducted in the areas of microsphere synthesis, particle sealing/coating, and high-energy-rate forming (HERF) and the vacuum hot press consolidation techniques. This paper summarizes the status of these activities.

  4. Activation of the p75 neurotrophin receptor through conformational rearrangement of disulphide-linked receptor dimers

    PubMed Central

    Vilar, Marçal; Charalampopoulos, Ioannis; Kenchappa, Rajappa S.; Simi, Anastasia; Karaca, Esra; Reversi, Alessandra; Choi, Soyoung; Bothwell, Mark; Mingarro, Ismael; Friedman, Wilma J.; Schiavo, Giampietro; Bastiaens, Philippe I. H.; Verveer, Peter J.; Carter, Bruce D.; Ibáñez, Carlos F.

    2010-01-01

    SUMMARY Ligand-mediated dimerization has emerged as a universal mechanism of growth factor receptor activation. Recent structural studies have shown that neurotrophins interact with dimers of the p75 neurotrophin receptor (p75NTR), but the actual mechanism of receptor activation has remained elusive. Here we show that p75NTR forms disulphide-linked dimers independently of neurotrophin binding through the highly conserved Cys257 in its transmembrane domain. Mutation of Cys257 abolished neurotrophin-dependent receptor activity but did not affect downstream signaling by the p75NTR/NgR/Lingo-1 complex in response to MAG, indicating the existence of distinct, ligand-specific activation mechanisms for p75NTR. FRET experiments revealed a close association of p75NTR intracellular domains that was transiently disrupted by conformational changes induced upon NGF binding. Although mutation of Cys257 did not alter the oligomeric state of p75NTR, the mutant receptor was no longer able to propagate conformational changes to the cytoplasmic domain upon ligand binding. We propose that neurotrophins activate p75NTR by a novel mechanism involving rearrangement of disulphide-linked receptor subunits. PMID:19376068

  5. SS-Stabilizing Proteins Rationally: Intrinsic Disorder-Based Design of Stabilizing Disulphide Bridges in GFP.

    PubMed

    Melnik, Bogdan S; Povarnitsyna, Tatiana V; Glukhov, Anatoly S; Melnik, Tatyana N; Uversky, Vladimir N; Sarma, Ramaswamy H

    2012-01-01

    Abstract The most attractive and methodologically convenient way to enhance protein stability is via the introduction of disulphide bond(s). However, the effect of the artificially introduced SS-bond on protein stability is often quite unpredictable. This raises the question of how to choose the protein sites in an intelligent manner, so that the 'fastening' of these sites by the SS-bond(s) would provide maximal protein stability. We hypothesize that the successful design of a stabilizing SS-bond requires finding highly mobile protein regions. Using GFP as an illustrative example, we demonstrate that the knowledge of the peculiarities of the intramolecular hydrophobic interactions, combined with the understanding of the local intrinsic disorder propensities (that can be evaluated by various disorder predictors, e.g., PONDRFIT), is sufficient to find the candidate sites for the introduction of stabilizing SS-bridge(s). In fact, our analysis revealed that the insertion of the engineered SS-bridge between two highly flexible regions of GFP noticeably increased the conformational stability of this protein toward the thermal and chemical unfolding. Therefore, our study represents a novel approach for the rational design of stabilizing disulphide bridges in proteins.

  6. Male exposure mediated adverse reproductive outcomes in carbon disulphide exposed rayon workers.

    PubMed

    Patel, K G; Yadav, P C; Pandya, C B; Saiyed, H N

    2004-10-01

    The authors examined 100 carbon disulphide (CS2) exposed male workers who had been employed ten years prior to study were selected for the study. They were virtually obliged to participate in the study by the Medical Labor Inspector and all of them participated voluntary. The aim was to assess the effects of occupational exposure to carbon disulphide concentrations below the threshold limit value (31 mg/m3) on the reproductive functions with special emphasis on miscarriages. Specially, workers history records were build up on number of children, miscarriages and general weakness, mental fatigue etc. It was found that the incidences of number of miscarriages against number of living children correlated well with environmental concentration of CS2. Where the average CS2 levels were 1.695 ppm, the incidences of miscarriages was 5.71% (group 1). Where as in group 2 environmental concentrations were 12.28 ppm and the incidences of miscarriages were 18.91%. It was also found that in the spinning department the exposure exceeds many times the Threshold Limit Values (TL V).

  7. Formation of alumina-nickel-molybdenum catalysts

    SciTech Connect

    Erofeev, V.I.; Basov, V.G.; Vagin, A.I.; Kalechits, I.V.

    1982-06-01

    On the basis of the results obtained in physical and chemical studies of alumina-nickel-molybdenum oxide catalysts as well as binary system and the individual oxides, the conclusions show that the commercial catalyst consists mainly of nickel and aluminium molybdates, aluminium molybdates, molybdenum oxide, and the alumina support. 4 figures.

  8. Molybdenum sealing glass-ceramic composition

    DOEpatents

    Eagan, Robert J.

    1976-01-01

    The invention relates to a glass-ceramic composition having low hydrogen and helium permeability properties, along with high fracture strength, a thermal coefficient of expansion similar to that of molybdenum, and adaptable for hermetically sealing to molybdenum at temperatures of between about 900.degree. and about 950.degree.C. to form a hermatically sealed insulator body.

  9. Molybdenum Enzymes, Cofactors, and Model Systems.

    ERIC Educational Resources Information Center

    Burgmayer, S. J. N; Stiefel, E. I.

    1985-01-01

    Discusses: (l) molybdoenzymes (examining their distribution and metabolic role, composition and redox strategy, cofactors, substrate reactions, and mechanistic possibilities); (2) structural information on molybdenum (Mo) centers; (3) modeling studies (Mo-co models, nitrogenase models, and the MO-S duo); and (4) the copper-molybdenum antagonism.…

  10. Molybdenum as a Micronutrient for Nitrobacter

    PubMed Central

    Finstein, M. S.; Delwiche, C. C.

    1965-01-01

    Finstein, M. S. (University of California, Davis), and C. C. Delwiche. Molybdenum as a micronutrient for Nitrobacter. J. Bacteriol. 89:123–128. 1965.—The requirement of Nitrobacter for molybdenum was investigated by use of a medium purified by chemical means, as well as by depletion by the prior growth of this autotrophic bacterium. During 5 days of growth, added molybdenum induced an approximately 11-fold increase in both nitrite utilization and cell-mass development. In short-term studies, maximal response was obtained with concentrations as low as 10−9m. No other metal tested substituted for molybdenum. It is estimated that a minimum of 2,000 atoms of molybdenum is required for the synthesis of one Nitrobacter cell. Molybdenum did not directly influence the thermodynamic efficiency of Nitrobacter. The efficiency of molybdenum-deficient cultures and of cultures supplied with the micronutrient declined equally during the early stage of development, despite large differences in the amount of nitrite consumed. After the utilization of about 100 μmoles of nitrite per ml, cultures supplied with molybdenum became relatively less efficient. A procedure is described whereby large masses of Nitrobacter cells can be obtained with relative ease. PMID:14255651

  11. Molybdenum Enzymes, Cofactors, and Model Systems.

    ERIC Educational Resources Information Center

    Burgmayer, S. J. N; Stiefel, E. I.

    1985-01-01

    Discusses: (l) molybdoenzymes (examining their distribution and metabolic role, composition and redox strategy, cofactors, substrate reactions, and mechanistic possibilities); (2) structural information on molybdenum (Mo) centers; (3) modeling studies (Mo-co models, nitrogenase models, and the MO-S duo); and (4) the copper-molybdenum antagonism.…

  12. Molybdenum Oxides - From Fundamentals to Functionality.

    PubMed

    de Castro, Isabela Alves; Datta, Robi Shankar; Ou, Jian Zhen; Castellanos-Gomez, Andres; Sriram, Sharath; Daeneke, Torben; Kalantar-Zadeh, Kourosh

    2017-08-16

    The properties and applications of molybdenum oxides are reviewed in depth. Molybdenum is found in various oxide stoichiometries, which have been employed for different high-value research and commercial applications. The great chemical and physical characteristics of molybdenum oxides make them versatile and highly tunable for incorporation in optical, electronic, catalytic, bio, and energy systems. Variations in the oxidation states allow manipulation of the crystal structure, morphology, oxygen vacancies, and dopants, to control and engineer electronic states. Despite this overwhelming functionality and potential, a definitive resource on molybdenum oxide is still unavailable. The aim here is to provide such a resource, while presenting an insightful outlook into future prospective applications for molybdenum oxides. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Vapor deposition of molybdenum oxide using bis(ethylbenzene) molybdenum and water

    SciTech Connect

    Drake, Tasha L.; Stair, Peter C.

    2016-09-15

    Three molybdenum precursors—bis(acetylacetonate) dioxomolybdenum, molybdenum isopropoxide, and bis(ethylbenzene) molybdenum—were tested for molybdenum oxide vapor deposition. Quartz crystal microbalance studies were performed to monitor growth. Molybdenum isopropoxide and bis(ethylbenzene) molybdenum achieved linear growth rates 0.01 and 0.08 Å/cycle, respectively, using atomic layer deposition techniques. Negligible MoO{sub x} growth was observed on alumina powder using molybdenum isopropoxide, as determined by inductively coupled plasma optical emission spectroscopy. Bis(ethylbenzene) molybdenum achieved loadings of 0.5, 1.1, and 1.9 Mo/nm{sup 2} on alumina powder after one, two, and five cycles, respectively, using atomic layer deposition techniques. The growth window for bis(ethylbenzene) molybdenum is 135–150 °C. An alternative pulsing strategy was also developed for bis(ethylbenzene) molybdenum that results in higher growth rates in less time compared to atomic layer deposition techniques. The outlined process serves as a methodology for depositing molybdenum oxide for catalytic applications. All as-deposited materials undergo further calcination prior to characterization and testing.

  14. Reptilian transferrins: evolution of disulphide bridges and conservation of iron-binding center.

    PubMed

    Ciuraszkiewicz, Justyna; Biczycki, Marian; Maluta, Aleksandra; Martin, Samuel; Watorek, Wiesław; Olczak, Mariusz

    2007-07-01

    Transferrins, found in invertebrates and vertebrates, form a physiologically important family of proteins playing a major role in iron acquisition and transport, defense against microbial pathogens, growth and differentiation. These proteins are bilobal in structure and each lobe is composed of two domains divided by a cleft harboring an iron atom. Vertebrate transferrins comprise of serotransferrins, lactoferrins and ovotransferrins. In mammals serotransferrins transport iron in physiological fluids and deliver it to cells, while lactoferrins scavenge iron, limiting its availability to invading microbes. In oviparous vertebrates there is only one transferrin gene, expressed either in the liver to be delivered to physiological fluids as serotransferrin, or in the oviduct with a final localization in egg white as ovotransferrin. Being products of one gene sero- and ovotransferrin are identical at the amino-acid sequence level but with different, cell specific glycosylation patterns. Our knowledge of the mechanisms of transferrin iron binding and release is based on sequence and structural data obtained for human serotransferrin and hen and duck ovotransferrins. No sequence information about other ovotransferrins was available until our recent publication of turkey, ostrich, and red-eared turtle (TtrF) ovotransferrin mRNA sequences [Ciuraszkiewicz, J., Olczak, M., Watorek, W., 2006. Isolation, cloning and sequencing of transferrins from red-eared turtle, African ostrich and turkey. Comp. Biochem. Physiol. 143 B, 301-310]. In the present paper, ten new reptilian mRNA transferrin sequences obtained from the Nile crocodile (NtrF), bearded dragon (BtrF), Cuban brown anole (AtrF), veiled and Mediterranean chameleons (VtrF and KtrF), sand lizard (StrF), leopard gecko (LtrF), Burmese python (PtrF), African house snake (HtrF), and grass snake (GtrF) are presented and analyzed. Nile crocodile and red-eared turtle transferrins have a disulphide bridge pattern identical to

  15. Understanding the contribution of disulphide bridges to the folding and misfolding of an anti-Aβ scFv.

    PubMed

    Montoliu-Gaya, Laia; Martínez, Jose C; Villegas, Sandra

    2017-03-24

    ScFv-h3D6 is a single chain variable fragment that precludes Aβ peptide-induced cytotoxicity by withdrawing Aβ oligomers from the amyloid pathway to the worm-like pathway. Production of scFv molecules is not a straightforward procedure because of the occurrence of disulphide scrambled conformations generated in the refolding process. Here, we separately removed the disulphide bond of each domain and solved the scrambling problem; and then, we intended to compensate the loss of thermodynamic stability by adding three C-terminal elongation mutations previously described to stabilize the native fold of scFv-h3D6. Such stabilization occurred through stabilization of the intermediate state in the folding pathway and destabilization of a different, β-rich, intermediate state driving to worm-like fibrils. Elimination of the disulphide bridge of the less stable domain, VL , deeply compromised the yield and increased the aggregation tendency, but elimination of the disulphide bridge of the more stable domain, VH , solved the scrambling problem and doubled the production yield. Notably, it also changed the aggregation pathway from the protective worm-like morphology to an amyloid one. This was so because a partially unfolded intermediate driving to amyloid aggregation was present, instead of the β-rich intermediate driving to worm-like fibrils. When combining with the elongation mutants, stabilization of the partially unfolded intermediate driving to amyloid fibrils was the only effect observed. Therefore, the same mutations drove to completely different scenarios depending on the presence of disulphide bridges and this illustrates the relevance of such linkages in the stability of different intermediate states for folding and misfolding. This article is protected by copyright. All rights reserved.

  16. Effects of Diaceto-Dipropyl-Disulphide on Plasma Sialic Acid and Renal Tissue Thiol Levels in Alloxan Diabetic Rats.

    PubMed

    Venkataiah, Vijay; Vickram; Thirumalarao, Kashinath Rattihalli; Raiker, Veena Gajana; Puttaswamy, Sandhya Hanumanthappa

    2016-06-01

    Plasma sialic acid levels are elevated in Diabetes Mellitus (DM) patients with proteinuria. Renal damage is mainly caused by free radicals that are excessively generated in DM. Thiols play an important role in the cellular antioxidative defence mechanisms mainly through thiol-disulphide exchange reaction. Diallyl disulphide, a garlic oil principle component, is known for its anti-diabetic properties. Its structural analogue, Diaceto-Dipropyl Disulphide (DADPDS), is a less toxic and more palatable disulphide and possesses similar anti-diabetic actions. This study was undertaken to assess the usefulness of DADPDS in prevention of de-sialation of Glomerular Basement Membrane (GBM) in alloxan diabetic rats and to assess effect of DADPDS on renal tissue thiol levels. Rats were divided into Normal, Diabetic and DADPDS treated diabetic groups. Diabetes was induced by intraperitoneal injection (IP) of alloxan. DADPDS was fed by gastric intubation. Plasma Sialic acid was determined by Ehrlich's method and renal tissue thiol levels by Nitroprusside reaction method. This study showed a significant decrease (p<0.001) in plasma sialic acid, plasma glucose and renal tissue TBARS levels along with significant increase (p<0.001) in renal tissue thiol levels in DADPDS treated alloxan diabetic rats when compared to diabetic control rats. Hence it may be concluded that DADPDS helps in preventing de-sialation of GBM in alloxan diabetic rats and improves renal tissue antioxidant defence mechanisms, may be through thiol-disulphide exchange reaction and thereby exhibits a possible clinical use in prevention of renal complications like diabetic nephropathy.

  17. Effects of Diaceto-Dipropyl-Disulphide on Plasma Sialic Acid and Renal Tissue Thiol Levels in Alloxan Diabetic Rats

    PubMed Central

    Vickram; Thirumalarao, Kashinath Rattihalli; Raiker, Veena Gajana; Puttaswamy, Sandhya Hanumanthappa

    2016-01-01

    Introduction Plasma sialic acid levels are elevated in Diabetes Mellitus (DM) patients with proteinuria. Renal damage is mainly caused by free radicals that are excessively generated in DM. Thiols play an important role in the cellular antioxidative defence mechanisms mainly through thiol-disulphide exchange reaction. Diallyl disulphide, a garlic oil principle component, is known for its anti-diabetic properties. Its structural analogue, Diaceto-Dipropyl Disulphide (DADPDS), is a less toxic and more palatable disulphide and possesses similar anti-diabetic actions. Aim This study was undertaken to assess the usefulness of DADPDS in prevention of de-sialation of Glomerular Basement Membrane (GBM) in alloxan diabetic rats and to assess effect of DADPDS on renal tissue thiol levels. Materials and Methods Rats were divided into Normal, Diabetic and DADPDS treated diabetic groups. Diabetes was induced by intraperitoneal injection (IP) of alloxan. DADPDS was fed by gastric intubation. Plasma Sialic acid was determined by Ehrlich’s method and renal tissue thiol levels by Nitroprusside reaction method. Results This study showed a significant decrease (p<0.001) in plasma sialic acid, plasma glucose and renal tissue TBARS levels along with significant increase (p<0.001) in renal tissue thiol levels in DADPDS treated alloxan diabetic rats when compared to diabetic control rats. Conclusion Hence it may be concluded that DADPDS helps in preventing de-sialation of GBM in alloxan diabetic rats and improves renal tissue antioxidant defence mechanisms, may be through thiol-disulphide exchange reaction and thereby exhibits a possible clinical use in prevention of renal complications like diabetic nephropathy. PMID:27504279

  18. Direct rate constant measurement of radical disulphide anion formation for cysteine and cysteamine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Mezyk, Stephen P.

    1995-03-01

    The techniques of pulse radiolysis, laser photolysis and absorption spectroscopy have been used to directly determine rate constants for radical disulphide anion formation for cysteine and cysteamine in aqueous solution. The measured values for cysteine, over the pH range 7-12, allowed calculation of individual rate constants for the constituent reactions RS . + RSH → RSSR -. + H + and RS . + RS - → RSSR -. as (3.39 ± 0.31) × 10 8 and (1.21 ± 0.04) × 10 9 dm 3 mol -1 s -1, respectively. Analogous values for cysteamine were also determined by this technique as (3.06 ± 0.16) × 10 8 and (3.65 ± 0.07) × 10 9 dm 3 mol -1 s -1.

  19. Tungsten disulphide based all fiber Q-switching cylindrical-vector beam generation

    SciTech Connect

    Lin, J.; Yan, K.; Zhou, Y.; Xu, L. X. Gu, C.; Zhan, Q. W.

    2015-11-09

    We proposed and demonstrated an all fiber passively Q-switching laser to generate cylindrical-vector beam, a two dimensional material, tungsten disulphide (WS{sub 2}), was adopted as a saturable absorber inside the laser cavity, while a few-mode fiber Bragg grating was used as a transverse mode-selective output coupler. The repetition rate of the Q-switching output pulses can be varied from 80 kHz to 120 kHz with a shortest duration of 958 ns. Attributed to the high damage threshold and polarization insensitivity of the WS{sub 2} based saturable absorber, the radially polarized beam and azimuthally polarized beam can be easily generated in the Q-switching fiber laser.

  20. Konjac glucomannan-induced changes in thiol/disulphide exchange and gluten conformation upon dough mixing.

    PubMed

    Zhou, Yun; Zhao, Dan; Foster, Tim J; Liu, Yixin; Wang, Yu; Nirasawa, Satoru; Tatsumi, Eizo; Cheng, Yongqiang

    2014-01-15

    Effects of konjac glucomannan (KGM) on the changes in gluten upon dough mixing were investigated in this study. Wheat flour was blended with KGM and processed into dough. Farinographic analysis showed that KGM caused a significant increase in water absorption and dough development time to reach maximum consistency. Comparison of electrophoretic protein profile from control dough and KGM-dough revealed that protein fractions were similar in molecular size distribution, but the lability of glutenin aggregates slightly differed. Addition of KGM to gluten induced negative effects on exchange between sulfhydryl groups and disulphide bonds. Fourier transform-Raman spectroscopy indicated that secondary structure of gluten proteins was differentially modified related with water absorption of flours before dough formation. This study reveals that when KGM is added to the dough, conformational behaviours of gluten proteins are changed and the hydroxyl groups of KGM might be involved in the interaction by forming strong intermolecular hydrogen bonding system.

  1. Distribution of sulphydryl groups and disulphide linkages in tissue proteins of quail uropygial glands.

    PubMed

    Suzuki, T; Maruyama, T; Morohashi, M

    1994-07-01

    1. The distribution of sulphydryl (-SH) groups and disulphide (S-S) linkages in the tissue proteins of quail uropygial glands was histochemically observed by a staining method using N-[7-dimethylamino-4-methyl-3-coumarinyl]maleimide. 2. In the uropygial gland, the -SH groups of the tissue proteins of glandular cells displayed a progressive change to S-S linkages concomitant with the shift from the transitional cell layer to the degenerating cell layer, suggesting that cell destruction was occurring with the products being released as secretions. This phenomenon was apparently more pronounced in the deep compared with the shallow portion of secretory tubules. 3. The above results indicated that a mechanism similar to epidermal differentiation operates in the process of holocrine secretion in the uropygial gland.

  2. particles

    NASA Astrophysics Data System (ADS)

    Xia, Yu; Chen, Zhihong; Zhang, Zhengguo; Fang, Xiaoming; Liang, Guozheng

    2014-05-01

    We explore a facile and nontoxic hydrothermal route for synthesis of a Cu2ZnSnS4 nanocrystalline material by using l-cysteine as the sulfur source and ethylenediaminetetraacetic acid (EDTA) as the complexing agent. The effects of the amount of EDTA, the mole ratio of the three metal ions, and the hydrothermal temperature and time on the phase composition of the obtained product have been systematically investigated. The addition of EDTA and an excessive dose of ZnCl2 in the hydrothermal reaction system favor the generation of kesterite Cu2ZnSnS4. Pure kesterite Cu2ZnSnS4 has been synthesized at 180°C for 12 h from the reaction system containing 2 mmol of EDTA at 2:2:1 of Cu/Zn/Sn. It is confirmed by Raman spectroscopy that those binary and ternary phases are absent in the kesterite Cu2ZnSnS4 product. The kesterite Cu2ZnSnS4 material synthesized by the hydrothermal process consists of flower-like particles with 250 to 400 nm in size. It is revealed that the flower-like particles are assembled from single-crystal Cu2ZnSnS4 nanoflakes with ca. 20 nm in size. The band gap of the Cu2ZnSnS4 nanocrystalline material is estimated to be 1.55 eV. The films fabricated from the hierarchical Cu2ZnSnS4 particles exhibit fast photocurrent responses under intermittent visible-light irradiation, implying that they show potentials for use in solar cells and photocatalysis.

  3. Identification of disulphide stress-responsive extracytoplasmic function sigma factors in Rothia mucilaginosa.

    PubMed

    Nambu, Takayuki; Yamane, Kazuyoshi; Yamanaka, Takeshi; Mashimo, Chiho; Maruyama, Hugo; Yoshida, Masahiro; Hayashi, Hiroyuki; Leung, Kai-Poon; Fukushima, Hisanori

    2013-06-01

    Rothia mucilaginosa is known as a member of commensal bacterial flora in the oral cavity and has received attention as a potential opportunistic pathogen. We previously determined the genomic sequence of R. mucilaginosa DY-18, a clinical strain with biofilm-like structures isolated from an infected root canal of a tooth with persistent apical periodontitis. We found that the DY-18 genome had only two sigma factor genes that encoded the primary and extracytoplasmic function (ECF) sigma factors. Genomic analysis on the available database of R. mucilaginosa ATCC 25296 (a type strain for R. mucilaginosa) revealed that ATCC 25296 has three sigma factors: one primary sigma factor and two ECF sigma factors, one of which was highly homologous to that of DY-18. ECF sigma factors play an important role in the response to environmental stress and to the production of virulence factors. Therefore, we first examined gene-encoding sigma factors on R. mucilaginosa genome in silico. The homologous ECF sigma factors found in strains DY-18 and ATCC 25296 formed a distinct SigH (SigR) clade in a phylogenetic tree and their cognate anti-sigma factor has a HXXXCXXC motif known to respond against disulphide stress. Quantitative reverse transcription polymerase chain reaction (PCR) and microarray analysis showed that the transcriptional levels of sigH were markedly up-regulated under disulphide stress in both strains. Microarray data also demonstrated that several oxidative-stress-related genes (thioredoxin, mycothione reductase, reductase and oxidoreductase) were significantly up-regulated under the diamide stress. On the basis of these results, we conclude that the alternative sigma factor SigH of R. mucilaginosa is a candidate regulator in the redox state. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Effect of Diallyl Disulphide on Diabetes Induced Dyslipidemia in Male Albino Rats

    PubMed Central

    Kashinath, R.T.; Ambekar, J.G.

    2015-01-01

    Background Diabetes Mellitus is a chronic metabolic disorder which may lead to various complications, the important being dyslipidemia leading to Coronary Heart Disorders (CHD), the major cause for morbidity and mortality in diabetic patients. Diabetes Mellitus could be treated by nutritional therapy/drug therapy and others. But the drug therapy would have its own limitations and side effects. To overcome from this an herbal extract is recommended, such as Diallyl Disulphide (DADS) a principle compound of Garlic oil. Aim To assess the hypolipidemic effect of Diallyl Disulphide (DADS) in alloxan induced diabetic rats. Materials and Methods Healthy adult wistar strain male albino rats weighing around 100-150 grams were randomly selected from the animal house at BLDE University’s Shri B.M.Patil Medical College, Hospital and Research Centre, Bijapur, India. Diabetes was induced using alloxan and was treated with DADS. After a stipulated time the rats were anesthetised and sacrificed to collect the blood and liver tissue. Various Lipid parameters, HMG CoA Reductase, Fecal bile acids were estimated in the blood, feces and homogenised liver tissue using standard procedures. Statiscal Analysis One-way ANOVA followed by post-hoc t-test is done. Result There was significant decrease in the blood and liver tissue lipid parameters of DADS treated alloxan induced diabetic rats when compared to the alloxan induced diabetic rats. Conclusion From this study it can be concluded that the DADS a principle compound of garlic, definitely has the hypolipidemic effect in diabetic rats, which is reducing the morbidity in diabetic cases due to dyslipidemia without the adverse effects. PMID:26023549

  5. Separation of molybdenum and technetium

    NASA Astrophysics Data System (ADS)

    Andersson, J. D.; Gagnon, K.; Wilson, J. S.; Romaniuk, J.; Abrams, D. N.; McQuarrie, S. A.

    2012-12-01

    After the production of 99mTc via the 100Mo(p,2n)99mTc reaction, there is a requirement for separating 99mTc from bulk 100Mo. Although a number of separation methods have been demonstrated, the possibility of using a cartridge-based system is particularly attractive for routine use in a good manufacturing practice (GMP) regulatory environment. This study confirmed that hydrophobic interaction chromatography (HIC) solid phase extraction (SPE) with PEG as stationary phase is an efficient and easily automated method for separating molybdate and pertechnetate, and that PEG degradation in the conditions used does not affect the performance of the resin. In addition, reversed phase SPE using Waters Oasis® HLB shows promise for successful separation of molybdenum and technetium and work continues to extend this technology to readily available commercial SPE cartridges.

  6. Upper critical field of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Woollam, J. A.

    1978-01-01

    The upper critical field of sintered and sputtered copper molybdenum sulfide Cu(x)Mo6S8 was measured and found to exceed the Werthamer, Helfand, and Hohenberg (1966) value for a type II superconductor characterized by dirty limit, weak isotropic electron phonon coupling, and no paramagnetic limiting. It is suggested that the enhancement results from anisotropy or clean limit or both. Other ternary molybdenum sulfides appear to show similar anomalies.

  7. Upper critical field of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Woollam, J. A.

    1978-01-01

    The upper critical field of sintered and sputtered copper molybdenum sulfide Cu(x)Mo6S8 was measured and found to exceed the Werthamer, Helfand, and Hohenberg (1966) value for a type II superconductor characterized by dirty limit, weak isotropic electron phonon coupling, and no paramagnetic limiting. It is suggested that the enhancement results from anisotropy or clean limit or both. Other ternary molybdenum sulfides appear to show similar anomalies.

  8. Effects of copper sulfate supplement on growth, tissue concentration, and ruminal solubilities of molybdenum and copper in sheep fed low and high molybdenum diets

    SciTech Connect

    Ivan, M.; Veira, D.M.

    1985-01-01

    Each of four groups of six wethers were fed one of a low molybdenum, high molybdenum, high molybdenum plus copper sulfate, or high molybdenum plus copper sulfate corn silage-based diet for ad libitum intake for 221 days. Average daily gains and ratios of feed/gain were depressed for the high molybdenum diet as compared with the low molybdenum diet suggesting molybdenum toxicity in sheep fed the high molybdenum diet. This was alleviated partly by the copper sulfate supplement. The supplement also decreased solubility of both copper and molybdenum in the rumen but had no effect on copper concentration in blood plasma. Concentration of molybdenum was higher in both liver and kidney in sheep fed high-molybdenum diets as compared with low-molybdenum diets. Copper concentration was higher in kidneys of sheep fed high-molybdenum diets, but no difference was significant in liver copper between sheep fed diets high or low in molybdenum.

  9. The Densification of Molybdenum and Molybdenum Alloy Powders Using Hot Isostatic Pressing.

    DTIC Science & Technology

    1985-08-01

    TECHNICAL REPORT ARLCB-TR-85025 00 THE DENSIFICATION OF MOLYBDENUM (n AND MOLYBDENUM ALLOY POWDERS USING HOT ISOSTATIC PRESSING J. BARRANCO I. AHMAD S...ISOSTATIC PRESSING Final 6. PERFORMING ORG. REPORT NUMBER 7. AUTHOR(o) . CONTRACT OR GRANT NUMBER(e) J. Barranco , I. Ahmad, S. Isserow, and R. Warenchak

  10. Evaluation of Oxide Dispersion Strengthened (ODS) molybdenum alloys

    SciTech Connect

    Bianco, R.; Buckman, R.W. Jr.

    1995-12-31

    A series of fourteen (14) novel high-strength molybdenum alloy compositions containing a dispersion of very fine (< 1 {mu}m diameter) oxide particles were consolidated using two proprietary powder metallurgy techniques. The developmental compositions were evaluated to determine the microstructural stability and mechanical properties from cryogenic (-148{degrees}F) to elevated temperatures (4000{degrees}F) for material in the as-swaged (>98% cold work) condition and for as-swaged material in the heat treated condition. Extremely fine oxide particle sizes (<1000 {Angstrom}) were observed by Transmission Electron Microscopy (TEM) for a number of the experimental compositions in the as-swaged condition. A one hour recrystallization temperature as high as 3990{degrees}F was measured and a ductile-to-brittle transition temperature as low as {approximately}58{degrees}F for material in the recrystallized condition was determined. The preliminary results support the alloy design concept feasibility.

  11. Molybdenum Isotopes and Soil Processes

    NASA Astrophysics Data System (ADS)

    Siebert, C.; Pett-Ridge, J. C.; Halliday, A. N.; Burton, K. W.

    2011-12-01

    The oxygenation state of Earth's oceans is a driver of evolution and extinction events as well as climate change. In recent years stable isotope fractionation of redox sensitive elements such as molybdenum (Mo) have been used as quantitative tracers of past redox-conditions in a number of marine environments. However, little is known about the processes controlling the Mo isotope compositions of the riverine inputs to the oceans and their short- and long-term variations. Several recent studies [Archer & Vance, 2008; Pearce et al., 2010] have shown that many river waters have heavy Mo isotope compositions. In some terrestrial weathering environments dissolved Mo isotope compositions in rivers are controlled by the catchment lithology [Neubert et al., 2011]. However, many rivers show fractionation of Mo isotopes relative to their catchment lithology. Possible mechanisms causing this fractionation are chemical weathering and pedogenic processes. This study has investigated the behavior of Mo isotopes during weathering of basalt under different conditions. Results from oxic to reducing soil profiles in Hawaii show that redox conditions during soil formation can control Mo isotope compositions in soils. Reducing soil profiles have light isotope compositions whereas oxidizing profiles are heavy. This general isotope behavior is confirmed by results from soil profiles from Iceland. Here reducing layers within the profiles show marked negative isotope excursions. In oxic profiles a surprisingly strong interaction of Mo with organic matter can be observed producing significant Mo isotope fractionation. This behavior might explain long term retention of Mo in soils besides its high mobility in molybdate form. Mo associated with organic matter is bioavailable and essential for processes like nitrogen fixation. In addition, we observe that fractionation relative to the source rock is dependent on the degree of weathering, i.e. relatively un-weathered profiles do not show

  12. Heptacoordinated molybdenum(VI) complexes of phenylenediamine bis(phenolate): a stable molybdenum amidophenoxide radical.

    PubMed

    Hänninen, Mikko M; Paturi, Petriina; Tuononen, Heikki M; Sillanpää, Reijo; Lehtonen, Ari

    2013-05-20

    The syntheses, crystallographic structures, magnetic properties, and theoretical studies of two heptacoordinated molybdenum complexes with N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine (H4N2O2) are reported. A formally molybdenum(VI) complex [Mo(N2O2)Cl2(dmf)] (1) was synthesized by the reaction between [MoO2Cl2(dmf)2] and H4N2O2, whereas the other molybdenum(VI) complex [Mo(N2O2)(HN2O2)] (2) was formed when [MoO2(acac)2] was used as a molybdenum source. Both complexes represent a rare case of the Mo(VI) ion without any multiply bonded terminal ligands. In addition, molecular structures, magnetic measurements, ESR spectroscopy, and density functional theory calculations indicate that complex 2 is the first stable molybdenum(VI) amidophenoxide radical.

  13. Tungsten-molybdenum fractionation in estuarine environments

    NASA Astrophysics Data System (ADS)

    Mohajerin, T. Jade; Helz, George R.; Johannesson, Karen H.

    2016-03-01

    Dissolved tungsten (W) and molybdenum (Mo) concentrations were measured in surface waters and sediment pore waters of Terrebonne Bay, a shallow estuary in the Mississippi River delta, to investigate the biogeochemical processes that fractionate these Group 6 elements relative to one another during transit from weathering to sedimentary environments. Although many of the chemical properties of W and Mo are similar, the two elements behave autonomously, and the fractionation mechanisms are only partly understood. In sulfidic pore waters, dissolved Mo is depleted relative to river water-seawater mixtures, whereas dissolved W is >10-fold enriched. Reductive dissolution of poorly crystalline phases like ferrihydrite, which is a preferential host of W relative to Mo in grain coatings on river-borne particles, can explain the dissolved W enrichment. Dissolved W becomes increasingly enriched as H2S(aq) rises above about 60 μM due to transformation of WO42- to thiotungstates as well as to additional reductive dissolution of phases that host W. In contrast, as rising sulfide transforms MoO42- to thiomolybdates in pore waters, dissolved Mo is suppressed, probably owing to equilibration with an Fe-Mo-S phase. This putative phase appears to control the aqueous ion product, Q = [Fe2+][MoS42-]0.6 [H2S0]0.4/[H+]0.8, at a value of 10-7.78. Concentrations of dissolved W and Mo in pore waters bear no relation to concentrations in surface waters of the same salinity. In surface waters, dissolved Mo is nearly conserved in the estuarine mixing zone. Dissolved W appears also to be conserved except for several cases where W may have been enhanced by exchange with underlying, W-rich pore waters. With increasing salinity, the molar Mo/W ratio rises from about 10 to about 1000 in surface waters whereas it is mostly <10 in underlying pore waters and in highly sulfidic pore waters is mostly near 1. Differences in two chemical properties may account for this fractionation of Mo with respect to

  14. Co-expression of sulphydryl oxidase and protein disulphide isomerase in Escherichia coli allows for production of soluble CRM197.

    PubMed

    Roth, R; van Zyl, P; Tsekoa, T; Stoychev, S; Mamputha, S; Buthelezi, S; Crampton, M

    2017-05-01

    To investigate the production of soluble cross-reacting material 197 (CRM197 ) in Escherichia coli, a safe and effective T-cell-dependent protein carrier for polysaccharides used in the manufacture and application of multivalent conjugate vaccines. The use of co-expression of a sulphydryl oxidase (SOX) and protein disulphide isomerase for the production of soluble CRM197 in E. coli is described. CRM197 contains two disulphide bonds, which are normally unable to form in the reducing environment of the E. coli cytoplasm. It was found that co-expression yielded soluble CRM197 , at a production rate ~10% of the production of insoluble CRM197 , in equivalent small-scale cultures. Structural analysis of the purified CRM197 compared to CRM197 commercially produced in cultures of recombinant Pseudomonas fluorescens indicated that the E. coli soluble protein compares favourably on all structural levels. SOX and protein disulphide isomerase are enzymes involved in the formation of intra-protein disulphide bonds, and can influence the tertiary structure of the protein being produced, resulting in increased solubility due to the correct folding of the protein. Their use enabled the production of soluble untagged CRM197 in E. coli, which was previously unachievable. Previous literature reports have shown that CRM197 can be expressed in E. coli, though only in an insoluble form, or in soluble form as a fusion protein. It is currently commercially produced in cultures of recombinant P. fluorescens. The use of a widely used, well-characterized expression host such as E. coli, rather than P. fluorescens broadens the applicability of the production technology, and the production system described here is worthy of further investigation for scaled up manufacture of CRM197 . © 2017 The Society for Applied Microbiology.

  15. Molybdenum reduction to molybdenum blue in Serratia sp. Strain DRY5 is catalyzed by a novel molybdenum-reducing enzyme.

    PubMed

    Shukor, M Y; Halmi, M I E; Rahman, M F A; Shamaan, N A; Syed, M A

    2014-01-01

    The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction.

  16. Molybdenum Reduction to Molybdenum Blue in Serratia sp. Strain DRY5 Is Catalyzed by a Novel Molybdenum-Reducing Enzyme

    PubMed Central

    Shukor, M. Y.; Halmi, M. I. E.; Rahman, M. F. A.; Shamaan, N. A.; Syed, M. A.

    2014-01-01

    The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m) of the Mo-reducing enzyme was 5.47 M−1 s−1. The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction. PMID:24724104

  17. Submicrodeterminations of thiols, disulphides and thiol esters in serum by using o-hydroxymercuribenzoic acid and dithiofluorescein

    PubMed Central

    Wroński, Mieczysław

    1967-01-01

    1. Methods are described for selective estimation of thiols, disulphides and thiol esters in standard solutions and in serum. The methods are based on the reaction with the excess of o-hydroxymercuribenzoic acid (HMB) in alkaline solution with subsequent addition of dithiofluorescein in excess and determination of the extinction at 588mμ. The sensitivity of the methods amounts to 1·5×10−9g.equiv. in 5ml. of final solution. Of results obtained on standard solutions 80% have the errors within the range ±4%. 2. It has been found that serum contains an unidentified substance (substance X) producing green complexes with dithiofluorescein which undergo decomposition on addition of formaldehyde. The correction for substance X must be estimated in a separate sample and taken into account. The concentration of substance X can be calculated from extinctions measured at 588mμ and 635mμ in the presence of dithiofluorescein in excess. 3. The selective determination of thiols and disulphides is based on different reaction rates with formaldehyde. The complexes between HMB and cysteine can be selectively decomposed by formaldehyde, and free glutathione can be selectively removed by formaldehyde in the presence of protein thiols. 4. Thiols are determined in the presence of triethylamine, thiols plus disulphides in the presence of triethylamine and sulphite, and thiols plus thiol esters in the presence of dimethylamine, with subsequent addition of ammonium sulphate. PMID:6049936

  18. Disulphide bond restrains the C-terminal region of thermostable direct hemolysin during folding to promote oligomerization.

    PubMed

    Kundu, Nidhi; Tichkule, Swapnil; Pandit, Shashi Bhushan; Chattopadhyay, Kausik

    2017-01-15

    Pore-forming toxins (PFTs) are typically produced as water-soluble monomers, which upon interacting with target cells assemble into transmembrane oligomeric pores. Vibrio parahaemolyticus thermostable direct hemolysin (TDH) is an atypical PFT that exists as a tetramer in solution, prior to membrane binding. The TDH structure highlights a core β-sandwich domain similar to those found in the eukaryotic actinoporin family of PFTs. However, the TDH structure harbors an extended C-terminal region (CTR) that is not documented in the actinoporins. This CTR remains tethered to the β-sandwich domain through an intra-molecular disulphide bond. Part of the CTR is positioned at the inter-protomer interface in the TDH tetramer. Here we show that the truncation, as well as mutation, of the CTR compromise tetrameric assembly, and the membrane-damaging activity of TDH. Our study also reveals that intra-protomer disulphide bond formation during the folding/assembly process of TDH restrains the CTR to mediate its participation in the formation of inter-protomer contact, thus facilitating TDH oligomerization. However, once tetramerization is achieved, disruption of the disulphide bond does not affect oligomeric assembly. Our study provides critical insights regarding the regulation of the oligomerization mechanism of TDH, which has not been previously documented in the PFT family.

  19. Molybdenum Metallopharmaceuticals Candidate Compounds - The "Renaissance" of Molybdenum Metallodrugs?

    PubMed

    Jurowska, Anna; Jurowski, Kamil; Szklarzewicz, Janusz; Buszewski, Boguslaw; Kalenik, Tatiana; Piekoszewski, Wojciech

    2016-01-01

    Metal-based drugs, also called "metallopharmaceuticals" or "metallodrugs", are examples of sophisticated compounds that have been used in inorganic medicinal chemistry as therapeutic agents for a long time. Few of them have shown substantially promising results and many of them have been used in different phases of clinical trials. The Mo-based metallodrugs were successfully applied in the past for treating conditions such as anemia or Wilson's disease. Moreover, Mo complexes are supposed to exert their effect by intercalation/ cleavage of DNA/RNA, arrest of the cell cycle, and alteration of cell membrane functions. However, in the current literature, there are no reliable and in-depth reviews about the hypothetical therapeutic applications of all of the known molybdenum complexes as metallopharmaceuticals/ metallodrugs. The main emphasis was on the in-depth review of the potential applications of Mo-based complexes in medicinal chemistry as metallopharmaceuticals in treating diseases such as cancer and tumors, Wilson's disease, diabetes mellitus, Huntington's disease, atherosclerosis, and anemia. It must be emphasized that today the development of innovative and new Mo-based metalo-pharmaceuticals is not rapid, and hence the aim of this paper was also to inspire colleagues working in the field of Mo compounds who are trying to find "signpost" for research. The authors hope that this article will increase interest and initiate the Renaissance of Mo-compounds among medicinal inorganic chemists. This paper is the first review article in the literature that refers to and emphasizes many different and complex aspects of possible applications and capabilities of Mo-based metallodrugs.

  20. Zinc deficiency in molybdenum poisoned cattle

    SciTech Connect

    Parada, R.

    1981-02-01

    Clinical signs ascribable to zinc deficiency were noted in a group of Friesian cows industrially poisoned with molybdenum. Zinc, copper, and molybdenum were determined in blood serum and black hair, and in the contaminated alfalfa pasture the group grazed on. Hematological parameters, and serum calcium and alkaline phosphatase activity, were also determined. Pooled samples of alfalfa from 2 uncontaminated pastures, and of blood, serum and black hair of clinically normal Friesian cattle grazing on these were used as controls. A mixed contamination of the polluted pasture with molybdenum and copper was found, both metals being inversely correlated with he distance to the polluting chimney. Zinc concentrations were normal and not significantly correlated with the distance to the chimney very high molybdenum was found in serum and hair of the poisoned animals; copper was normal in serum and hair. Low calcium and Alkaline phosphatase activity were found in serum, both variables being significantly correlated with serum zinc. Reduced red blood cell number, packed cell volumes and hemoglobin concentrations were also found, but no significant correlation of these parameters with any of the trace metals in serum or hair was found. Signs ascribed to zinc deficiency were consistent with the reduction of zinc in serum and hair and decreased alkaline phosphatase activity in serum. A zinc deficiency conditioned by a simultaneous increased intake of molybdenum and copper is proposed.

  1. A novel function of tissue-type transglutaminase: protein disulphide isomerase.

    PubMed Central

    Hasegawa, Go; Suwa, Motoi; Ichikawa, Yasuo; Ohtsuka, Tetsuro; Kumagai, Satoru; Kikuchi, Masashi; Sato, Yoshitaka; Saito, Yuji

    2003-01-01

    We have found that tissue-type transglutaminase (tTG), also called TGc, TGase2 and Galpha(h), has the activity of protein disulphide isomerase (PDI). We have shown that tTG converts completely reduced/denatured inactive RNase A molecule to the native active enzyme. The PDI activity of tTG was strongly inhibited by bacitracin, which is a frequently used inhibitor of conventional PDI activity. It was substantially inhibited by the simultaneous presence of other potential substrate proteins such as completely reduced BSA, but not by native BSA. This activity was especially high in the presence of GSSG, but not GSH. The addition of GSH to the reaction mixture in the presence of GSSG at a fixed concentration up to at least 200-fold excess did not very substantially inhibit the PDI activity. It is possible that tTG can exert PDI activity in a fairly reducing environment like cytosol, where most of tTG is found. It is quite obvious from the following observations that PDI activity of tTG is catalysed by a domain different from that used for the transglutaminase reaction. Although the alkylation of Cys residues in tTG completely abolished the transglutaminase activity, as was expected, it did not affect the PDI activity at all. This PDI activity did not require the presence of Ca(2+). It was not inhibited by nucleotides including GTP at all, unlike the other activity of tTG. PMID:12737632

  2. Snake venom disintegrins: novel dimeric disintegrins and structural diversification by disulphide bond engineering.

    PubMed Central

    Calvete, Juan J; Moreno-Murciano, M Paz; Theakston, R David G; Kisiel, Dariusz G; Marcinkiewicz, Cezary

    2003-01-01

    We report the isolation and amino acid sequences of six novel dimeric disintegrins from the venoms of Vipera lebetina obtusa (VLO), V. berus (VB), V. ammodytes (VA), Echis ocellatus (EO) and Echis multisquamatus (EMS). Disintegrins VLO4, VB7, VA6 and EO4 displayed the RGD motif and inhibited the adhesion of K562 cells, expressing the integrin alpha5beta1 to immobilized fibronectin. A second group of dimeric disintegrins (VLO5 and EO5) had MLD and VGD motifs in their subunits and blocked the adhesion of the alpha4beta1 integrin to vascular cell adhesion molecule 1 with high selectivity. On the other hand, disintegrin EMS11 inhibited both alpha5beta1 and alpha4beta1 integrins with almost the same degree of specificity. Comparison of the amino acid sequences of the dimeric disintegrins with those of other disintegrins by multiple-sequence alignment and phylogenetic analysis, in conjunction with current biochemical and genetic data, supports the view that the different disintegrin subfamilies evolved from a common ADAM (a disintegrin and metalloproteinase-like) scaffold and that structural diversification occurred through disulphide bond engineering. PMID:12667142

  3. Comprehensive structural characterization of the cyclic disulphide-bridged nonapeptides, Arg- and Lys-conopressins.

    PubMed

    Janzsó, Gábor; Rákhely, Gábor; Leitgeb, Balázs

    2009-01-01

    Arg-conopressin-S and Lys-conopressin-G are cyclic disulphide-bridged nonapeptides isolated from the venom of cone snails. We performed a comprehensive conformational analysis for the cis and trans isomers of these conopeptides, in order to identify their characteristic structural and conformational features. In the course of our theoretical study, the Phi-Psi and chi(1) conformational spaces were explored in detail and the conformational distributions were compared to each other. For both cis and trans isomers of conopressins, the characteristic secondary structural elements and intramolecular H-bonds were identified. Our results pointed out that various turn structures stabilized by typical intramolecular H-bonds could be observed in the conformers of these conopeptides. Comparing the different conformational features of the cis and trans isomers of conopressins disclosed that several of them could be found for both isomers, however, structural properties characteristic for only the cis or trans isomer were also identified. Altogether, our comprehensive conformational study provided a detailed description of the three-dimensional (3D) structure of both conopressins.

  4. Protein disulphide isomerase as a target for nanoparticle-mediated sensitisation of cancer cells to radiation

    NASA Astrophysics Data System (ADS)

    Taggart, L. E.; McMahon, S. J.; Butterworth, K. T.; Currell, F. J.; Schettino, G.; Prise, K. M.

    2016-05-01

    Radiation resistance and toxicity in normal tissues are limiting factors in the efficacy of radiotherapy. Gold nanoparticles (GNPs) have been shown to be effective at enhancing radiation-induced cell death, and were initially proposed to physically enhance the radiation dose deposited. However, biological responses of GNP radiosensitization based on physical assumptions alone are not predictive of radiosensitisation and therefore there is a fundamental research need to determine biological mechanisms of response to GNPs alone and in combination with ionising radiation. This study aimed to identify novel mechanisms of cancer cell radiosensitisation through the use of GNPs, focusing on their ability to induce cellular oxidative stress and disrupt mitochondrial function. Using N-acetyl-cysteine, we found mitochondrial oxidation to be a key event prior to radiation for the radiosensitisation of cancer cells and suggests the overall cellular effects of GNP radiosensitisation are a result of their interaction with protein disulphide isomerase (PDI). This investigation identifies PDI and mitochondrial oxidation as novel targets for radiosensitisation.

  5. An effective approach to synthesize monolayer tungsten disulphide crystals using tungsten halide precursor

    SciTech Connect

    Thangaraja, Amutha; Shinde, Sachin M.; Kalita, Golap Tanemura, Masaki

    2016-02-01

    The synthesis of large-area monolayer tungsten disulphide (WS{sub 2}) single crystal is critical for realistic application in electronic and optical devices. Here, we demonstrate an effective approach to synthesize monolayer WS{sub 2} crystals using tungsten hexachloride (WCl{sub 6}) as a solid precursor in atmospheric chemical vapor deposition process. In this technique, 0.05M solution of WCl{sub 6} in ethanol was drop-casted on SiO{sub 2}/Si substrate to create an even distribution of the precursor, which was reduced and sulfurized at 750 °C in Ar atmosphere. We observed growth of triangular, star-shaped, as well as dendritic WS{sub 2} crystals on the substrate. The crystal geometry evolves with the shape and size of the nuclei as observed from the dendritic structures. These results show that controlling the initial nucleation and growth process, large WS{sub 2} single crystalline monolayer can be grown using the WCl{sub 6} precursor. Our finding shows an easier and effective approach to grow WS{sub 2} monolayer using tungsten halide solution-casting, rather than evaporating the precursor for gas phase reaction.

  6. Revealing the nature of excitons in liquid exfoliated monolayer tungsten disulphide

    NASA Astrophysics Data System (ADS)

    Kłopotowski, Ł.; Backes, C.; Mitioglu, A. A.; Vega-Mayoral, V.; Hanlon, D.; Coleman, J. N.; Ivanov, V. Y.; Maude, D. K.; Plochocka, P.

    2016-10-01

    Transition metal dichalcogenides (TMD) hold promise for applications in novel optoelectronic devices. There is therefore a need for materials that can be obtained in large quantities and with well understood optical properties. In this report, we present thorough photoluminescence (PL) investigations of monolayer tungsten disulphide obtained via liquid phase exfoliation. As shown by microscopy studies, the exfoliated nanosheets have dimensions of tens of nanometers and thickness of 2.5 monolayers on average. The monolayer content is about 20%. Our studies show that at low temperature the PL is dominated by excitons localized on nanosheet edges. As a consequence, the PL is strongly sensitive to the environment and exhibits an enhanced splitting in magnetic field. As the temperature is increased, the excitons are thermally excited out of the defect states and the dominant transition is that of the negatively charged exciton. Furthermore, upon excitation with a circularly polarized light, the PL retains a degree of polarization reaching 50% and inherited from the valley polarized photoexcited excitons. The studies of PL dynamics reveal that the PL lifetime is on the order of 10 ps, which is probably limited by non-radiative processes. Our results underline the potential of liquid exfoliated TMD monolayers in large scale optoelectronic devices.

  7. Structure of a novel class II phospholipase D: catalytic cleft is modified by a disulphide bridge.

    PubMed

    de Giuseppe, Priscila Oliveira; Ullah, Anwar; Silva, Dilza Trevisan; Gremski, Luiza Helena; Wille, Ana Carolina Martins; Chaves Moreira, Daniele; Ribeiro, Andrea Senff; Chaim, Olga Meiri; Murakami, Mario Tyago; Veiga, Silvio Sanches; Arni, Raghuvir Krishnaswamy

    2011-06-17

    Phospholipases D (PLDs) are principally responsible for the local and systemic effects of Loxosceles envenomation including dermonecrosis and hemolysis. Despite their clinical relevance in loxoscelism, to date, only the SMase I from Loxosceles laeta, a class I member, has been structurally characterized. The crystal structure of a class II member from Loxosceles intermedia venom has been determined at 1.7Å resolution. Structural comparison to the class I member showed that the presence of an additional disulphide bridge which links the catalytic loop to the flexible loop significantly changes the volume and shape of the catalytic cleft. An examination of the crystal structures of PLD homologues in the presence of low molecular weight compounds at their active sites suggests the existence of a ligand-dependent rotamer conformation of the highly conserved residue Trp230 (equivalent to Trp192 in the glycerophosphodiester phosphodiesterase from Thermus thermophofilus, PDB code: 1VD6) indicating its role in substrate binding in both enzymes. Sequence and structural analyses suggest that the reduced sphingomyelinase activity observed in some class IIb PLDs is probably due to point mutations which lead to a different substrate preference. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Synthesis, structure and bonding of actinide disulphide dications in the gas phase.

    PubMed

    Lucena, Ana F; Bandeira, Nuno A G; Pereira, Cláudia C L; Gibson, John K; Marçalo, Joaquim

    2017-04-11

    Actinide disulphide dications, AnS2(2+), were produced in the gas phase for An = Th and Np by reaction of An(2+) cations with the sulfur-atom donor COS, in a sequential abstraction process of two sulfur atoms, as examined by FTICR mass spectrometry. For An = Pu and Am, An(2+) ions were unreactive with COS and did not yield any sulphide species. High level multiconfigurational (CASPT2) calculations were performed to assess the structures and bonding of the new AnS2(2+) species obtained for An = Th, Np, as well as for An = Pu to examine trends along the An series, and for An = U to compare with a previous experimental study and DFT computational scrutiny of US2(2+). The CASPT2 results showed that, like in the case of uranium, the new AnS2(2+) ions have ground states with triangular geometries, corresponding to the presence of a persulphide in the case of thorium that formally leads to a stable Th(IV)S2(2+) species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a An(III)S2(2+) species. The computations also revealed that linear thioactinyl structures are higher in energy, with a difference that increases fourfold upon moving from U to Pu, apparently indicating that it will be even more pronounced for Am.

  9. Stress and Activity of Molybdenum-Containing Complex (Molybdenum Cofactor) in Winter Wheat Seeds

    PubMed Central

    Vunkova-Radeva, Reneta; Schiemann, Johan; Mendel, Ralf-Reiner; Salcheva, Galitona; Georgieva, Damyana

    1988-01-01

    Molybdenum, applied in vivo, restored the damage from low temperature with winter wheat (Triticum aestivum, var “Sadovo 1”) grown on acid soil and, in addition, sharply increased productivity (G Salcheva, D Georgieva, 1982; G Salcheva et al., 1977, 1979). Two fractions with molybdenum-cofactor activity in seeds were detected. One of them has a molecular weight of about 230 kilodaltons corresponding to xanthine oxidase activity and leaf nitrate reductase activity. The other has a molecular weight of about 60 kilodaltons. The ratio between the molybdenum-cofactor activity of these fractions was different in `mother' seeds used in the experiment, in seeds obtained from the damaged plants, and in seeds obtained from the damaged plants restored by in vivo molybdenum addition. Every one of these fractions consisted of several components in which molybdenum-cofactor activity and stability in vitro was different. We suggest that plants store molybdenum as molybdenum carriers in these low molecular weight fractions. Images Fig. 2 PMID:16666178

  10. Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

    SciTech Connect

    Afanasiev, Pavel

    2014-05-01

    Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow at 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.

  11. Effect of molybdenum treatment on molybdenum concentration and nitrate reduction in maize seedlings.

    PubMed

    Kovács, Béla; Puskás-Preszner, Anita; Huzsvai, László; Lévai, László; Bódi, Éva

    2015-11-01

    Since 1940 molybdenum has been known as an essential trace element in plant nutrition and physiology. It has a central role in nitrogen metabolism, and its deficiency leads to nitrate accumulation in plants. In this study, we cultivated maize seedlings (Zea mays L. cv. Norma SC) in nutrient solution and soil (rhizoboxes) to investigate the effect of molybdenum treatment on the absorption of molybdenum, sulfur and iron. These elements have been previously shown to play important roles in nitrate reduction, because they are necessary for the function of the nitrate reductase enzyme. We also investigated the relationship between molybdenum treatments and different nitrogen forms in maize. Molybdenum treatments were 0, 0.96, 9.6 and 96 μg kg(-1) in the nutrition solution experiments, and 0, 30, 90, 270 mg kg(-1) in the rhizobox experiments. On the basis of our results, the increased Mo level produced higher plant available Mo concentration in nutrient solution and in soil, which resulted increased concentration of Mo in shoots and roots of maize seedlings. In addition it was observed that maize seedlings accumulated more molybdenum in their roots than in their shoots at all treatments. In contrast, molybdenum treatments did not affect significantly either iron or sulfur concentrations in the plant, even if these elements (Mo, S and Fe) play alike important roles in nitrogen metabolism. Furthermore, the physiological molybdenum level (1× Mo = 0.01 μM) reduced NO3-N and enhanced the NH4-N concentrations in seedlings, suggesting that nitrate reduction was more intense under a well-balanced molybdenum supply.

  12. Mullite-whisker reinforced molybdenum disilicide composites

    NASA Astrophysics Data System (ADS)

    McFayden, Andre Anthony

    Molybdenum disilicide (MoSisb2) is a potential high temperature structural material. The use of such materials may raise the operating temperatures of heat engines and therefore their efficiencies, leading to fuel savings. Molybdenum disilicide has good oxidation resistance to 1650sp°C and high temperature strength to about 1000sp°C. This work was an attempt to improve the poor room temperature toughness and high temperature creep resistance of this material. Mullite was used as a reinforcement in the form of whiskers. Whiskers may increase the toughness of a matrix by extrinsic mechanisms, while mullite has intrinsically high creep resistance. Mechanical property predictions were made for the proposed composite material. The toughening mechanisms examined were crack bridging, pullout, crack deflection and microcracking. For the bridging model alone, a doubling of the fracture toughness was expected for a 40 percent mullite whisker volume. The creep models examined were the isostress, isostrain, shear-lag and self-consistent scheme. The shear-lag model predicted a factor of five decrease in the creep rate compared to pure MoSisb2. Composites of MoSisb2 containing 0, 20 and 40 volume percent of mullite were fabricated by means of a powder processing route. This involved mixing powders of the component materials, followed by hot-pressing and hot isostatic pressing to form a composite body. Both equi-axed particles and elongated whiskers of mullite were used. The mullite whisker size, powder mixing time, and glass content of the initial MoSisb2 powder were also varied. The resulting materials were subjected to mechanical testing. At room temperature, indentation testing was used to determine the toughness and modulus of the composites. Indented beams were subjected to four-point bending until failure to determine the toughness. The maximum fracture toughness measured was 1.7 MPasurdm, compared to 1.6 MPasurdm for the matrix, with very little variation with

  13. Molybdenum Valence in Basaltic Silicate Melts

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

    2010-01-01

    The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

  14. Pre-treatment for molybdenum or molybdenum-rich alloy articles to be plated

    DOEpatents

    Wright, Ralph R.

    1980-01-01

    This invention is a method for etching a molybdenum or molybdenum-rich alloy surface to promote the formation of an adherent bond with a subsequently deposited metallic plating. In a typical application, the method is used as a pre-treatment for surfaces to be electrolessly plated with nickel. The pre-treatment comprises exposing the crystal boundaries of the surface by (a) anodizing the surface in acidic solution to form a continuous film of gray molybdenum oxide thereon and (b) removing the film.

  15. High-throughput expression of animal venom toxins in Escherichia coli to generate a large library of oxidized disulphide-reticulated peptides for drug discovery.

    PubMed

    Turchetto, Jeremy; Sequeira, Ana Filipa; Ramond, Laurie; Peysson, Fanny; Brás, Joana L A; Saez, Natalie J; Duhoo, Yoan; Blémont, Marilyne; Guerreiro, Catarina I P D; Quinton, Loic; De Pauw, Edwin; Gilles, Nicolas; Darbon, Hervé; Fontes, Carlos M G A; Vincentelli, Renaud

    2017-01-17

    Animal venoms are complex molecular cocktails containing a wide range of biologically active disulphide-reticulated peptides that target, with high selectivity and efficacy, a variety of membrane receptors. Disulphide-reticulated peptides have evolved to display improved specificity, low immunogenicity and to show much higher resistance to degradation than linear peptides. These properties make venom peptides attractive candidates for drug development. However, recombinant expression of reticulated peptides containing disulphide bonds is challenging, especially when associated with the production of large libraries of bioactive molecules for drug screening. To date, as an alternative to artificial synthetic chemical libraries, no comprehensive recombinant libraries of natural venom peptides are accessible for high-throughput screening to identify novel therapeutics. In the accompanying paper an efficient system for the expression and purification of oxidized disulphide-reticulated venom peptides in Escherichia coli is described. Here we report the development of a high-throughput automated platform, that could be adapted to the production of other families, to generate the largest ever library of recombinant venom peptides. The peptides were produced in the periplasm of E. coli using redox-active DsbC as a fusion tag, thus allowing the efficient formation of correctly folded disulphide bridges. TEV protease was used to remove fusion tags and recover the animal venom peptides in the native state. Globally, within nine months, out of a total of 4992 synthetic genes encoding a representative diversity of venom peptides, a library containing 2736 recombinant disulphide-reticulated peptides was generated. The data revealed that the animal venom peptides produced in the bacterial host were natively folded and, thus, are putatively biologically active. Overall this study reveals that high-throughput expression of animal venom peptides in E. coli can generate large

  16. The cytotoxicity of garlic-related disulphides and thiosulfonates in WHCO1 oesophageal cancer cells is dependent on S-thiolation and not production of ROS.

    PubMed

    Smith, Muneerah; Hunter, Roger; Stellenboom, Nashia; Kusza, Daniel A; Parker, M Iqbal; Hammouda, Ahmed N H; Jackson, Graham; Kaschula, Catherine H

    2016-07-01

    Garlic has been used for centuries in folk medicine for its health promoting and cancer preventative properties. The bioactive principles in crushed garlic are allyl sulphur compounds which are proposed to chemically react through (i) protein S-thiolation and (ii) production of ROS. A collection of R-propyl disulphide and R-thiosulfonate compounds were synthesised to probe the importance of thiolysis and ROS generation in the cytotoxicity of garlic-related compounds in WHCO1 oesophageal cancer cells. A significant correlation (R(2)=0.78, Fcrit (7,1) α=0.005) was found between the cytotoxicity IC(50) and the leaving group pK(a) of the R-propyl disulphides and thiosulfonates, supporting a mechanism that relies on the thermodynamics of a mixed disulphide exchange reaction. Disulphide (1) and thiosulfonate (11) were further evaluated mechanistically and found to induce G(2)/M cell-cycle arrest and apoptosis, inhibit cell proliferation, and generate ROS. When the ROS produced by 1 and 11 were quenched with Trolox, ascorbic acid or N-acetyl cysteine (NAC), only NAC was found to counter the cytotoxicity of both compounds. However, NAC was found to chemically react with 11 through mixed disulphide formation, providing an explanation for this apparent inhibitory result. Cellular S-thiolation by garlic related disulphides appears to be the cause of cytotoxicity in WHCO1 cells. Generation of ROS appears to only play a secondary role. Our findings do not support ROS production causing the cytotoxicity of garlic-related disulphides in WHCO1 cells. Importantly, it was found that the popular ROS inhibitor NAC interferes with the assay. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Comparison of radiation shielding ratios of nano-sized bismuth trioxide and molybdenum

    NASA Astrophysics Data System (ADS)

    Cho, J. H.; Kim, M. S.; Rhim, J. D.

    2015-07-01

    In this study, radiation shielding fibers using non-hazardous nano-sized bismuth trioxide and molybdenum instead of lead were developed and evaluated. Among the elements with high densities and atomic numbers, non-hazardous elements such as bismuth trioxide and molybdenum were chosen as a shielding element. Then, bismuth trioxide (Bi2O3) with average particle size 1-500 µm was ball milled for 10 min to produce a powdered form of nanoparticles with average particle size of 10-100 nm. Bismuth trioxide nanoparticles were dispersed to make a colloidal suspension, followed by spreading and hardening onto one or two sides of fabric, to create the radiation shielding fabric. The thicknesses of the shielding sheets using nano-sized bismuth and molybdenum were 0.4 and 0.7 mm. According to the lead equivalent test of X-ray shielding products suggested by KS, the equivalent dose was measured, followed by calculation of the shielding rate. The shielding rate of bismuth with 0.4 mm thickness and at 50 kVp was 90.5%, which is comparable to lead of 0.082 mm thickness. The shielding rate of molybdenum was 51.89%%, which is comparable to lead of 0.034 mm. At a thickness of 0.7 mm, the shielding rate of bismuth was 98.73%, equivalent to 0.101 mm Pb, whereas the shielding rate of molybdenum was 74.68%, equivalent to 0.045 mm Pb. In conclusion, the radiation shielding fibers using nano-sized bismuth developed in this study are capable of reducing radiation exposure by X-ray and its low-dose scatter ray.

  18. Investigation of activation cross section data of alpha particle induced nuclear reaction on molybdenum up to 40 MeV: Review of production routes of medically relevant 97,103Ru

    NASA Astrophysics Data System (ADS)

    Tárkányi, F.; Hermanne, A.; Ditrói, F.; Takács, S.; Ignatyuk, A.

    2017-05-01

    The main goals of this investigations were to expand and consolidate reliable activation cross-section data for the natMo(α,x) reactions in connection with production of medically relevant 97,103Ru and the use of the natMo(α,x)97Ru reaction for monitoring beam parameters. The excitation functions for formation of the gamma-emitting radionuclides 94Ru, 95Ru, 97Ru, 103Ru, 93mTc, 93gTc(m+), 94mTc, 94gTc, 95mTc, 95gTc, 96gTc(m+), 99mTc, 93mMo, 99Mo(cum), 90Nb(m+) and 88Zr were measured up to 40 MeV alpha-particle energy by using the stacked foil technique and activation method. Data of our earlier similar experiments were re-evaluated and resulted in corrections on the reported results. Our experimental data were compared with critically analyzed literature data and with the results of model calculations, obtained by using the ALICE-IPPE, EMPIRE 3.1 (Rivoli) and TALYS codes (TENDL-2011 and TENDL-2015 on-line libraries). Nuclear data for different production routes of 97Ru and 103Ru are compiled and reviewed.

  19. Evaluation of molybdenum and its alloys. [Reactor core heat pipes

    SciTech Connect

    Lundberg, L.B.

    1981-01-01

    The choice of pure molybdenum as the prime candidate material for space reactor core heat pipes is critically examined. Pure molybdenum's high ductile-brittle transition temperature appears to be its major disadvantage. The candidate materials examined in detail for this application include low carbon arc-cast molybdenum, TZM-molybdenum alloy, and molybdenum-rhenium alloys. Published engineering properties are collected and compared, and it appears that Mo-Re alloys with 10 to 15% rhenium offer the best combination. Hardware is presently being made from electron beam melted Mo-13Re to test this conclusion.

  20. Evolution of a new enzyme for carbon disulphide conversion by an acidothermophilic archaeon.

    PubMed

    Smeulders, Marjan J; Barends, Thomas R M; Pol, Arjan; Scherer, Anna; Zandvoort, Marcel H; Udvarhelyi, Anikó; Khadem, Ahmad F; Menzel, Andreas; Hermans, John; Shoeman, Robert L; Wessels, Hans J C T; van den Heuvel, Lambert P; Russ, Lina; Schlichting, Ilme; Jetten, Mike S M; Op den Camp, Huub J M

    2011-10-19

    Extremophilic organisms require specialized enzymes for their exotic metabolisms. Acid-loving thermophilic Archaea that live in the mudpots of volcanic solfataras obtain their energy from reduced sulphur compounds such as hydrogen sulphide (H(2)S) and carbon disulphide (CS(2)). The oxidation of these compounds into sulphuric acid creates the extremely acidic environment that characterizes solfataras. The hyperthermophilic Acidianus strain A1-3, which was isolated from the fumarolic, ancient sauna building at the Solfatara volcano (Naples, Italy), was shown to rapidly convert CS(2) into H(2)S and carbon dioxide (CO(2)), but nothing has been known about the modes of action and the evolution of the enzyme(s) involved. Here we describe the structure, the proposed mechanism and evolution of a CS(2) hydrolase from Acidianus A1-3. The enzyme monomer displays a typical β-carbonic anhydrase fold and active site, yet CO(2) is not one of its substrates. Owing to large carboxy- and amino-terminal arms, an unusual hexadecameric catenane oligomer has evolved. This structure results in the blocking of the entrance to the active site that is found in canonical β-carbonic anhydrases and the formation of a single 15-Å-long, highly hydrophobic tunnel that functions as a specificity filter. The tunnel determines the enzyme's substrate specificity for CS(2), which is hydrophobic. The transposon sequences that surround the gene encoding this CS(2) hydrolase point to horizontal gene transfer as a mechanism for its acquisition during evolution. Our results show how the ancient β-carbonic anhydrase, which is central to global carbon metabolism, was transformed by divergent evolution into a crucial enzyme in CS(2) metabolism.

  1. Effects of exposure to carbon disulphide on low density lipoprotein cholesterol concentration and diastolic blood pressure.

    PubMed Central

    Egeland, G M; Burkhart, G A; Schnorr, T M; Hornung, R W; Fajen, J M; Lee, S T

    1992-01-01

    The relation of carbon disulphide (CS2) exposure to risk factors for ischaemic heart disease was recently examined using data from a 1979 cross sectional study of 410 male textile workers, of whom 165 were exposed and 245 were unexposed to CS2. Average eight hour CS2 exposure concentrations ranged from 0.6 to 11.8 ppm by job title category among the exposed workers. A significant and positive linear trend in low density lipoprotein cholesterol concentration (LDLc) and diastolic blood pressure with increasing CS2 exposure was found after adjustment for potential confounders. When exposure was examined as a categorical variable (none, low, moderate, and high), the high exposure group had an adjusted mean LDLc that was 0.32 mmol/l greater than the non-exposed group (p = 0.02), and an adjusted mean diastolic blood pressure that was 3.16 mm Hg greater than the non-exposed group (p = 0.09). The effect of CS2 on diastolic blood pressure was strengthened in analyses limited to exposed workers: the high exposure group had an adjusted mean diastolic blood pressure that was 5 mm Hg greater than that of the low exposed group (p = 0.03). Triglyceride, high density lipoprotein cholesterol, and fasting glucose concentration, and systolic blood pressure were not affected by exposure. Blood lead concentration was positively associated with systolic and diastolic blood pressure. The results indicate that relatively modest exposure to CS2 may raise LDLc concentration and diastolic blood pressure and suggest mechanisms by which exposure to CS2 may influence risk of ischaemic heart disease. Also the results provide further support for the hypothesis of a possible association between blood lead concentration and blood pressure. PMID:1571299

  2. Haematopoietic, Antioxidant and Membrane Stabilizing Property of Diallyl Disulphide in Irradiated Mice

    PubMed Central

    Tenkanidiyoor, Yogish Somayaji; Vasudeva, Vidya; Rao, Shama; Gowda, Damodara; Rao, Chandrika; Sanjeev, Ganesh

    2016-01-01

    Introduction Diallyl disulphide is an organo-sulphur compound which is present in garlic and responsible for the characteristic odor of garlic. It is known for its anticancer and invitro membrane stabilizing properties. Aim The main aim was to evaluate the haematopoietic, antioxidant and membrane stabilizing property of diallyl disulfide in irradiated mice. Materials and Methods Mice were grouped into 6 groups as control, drug control, radiation control and drug pre-treatment groups (i.e. drug administration + radiation group) The mice were fed orally for 15 consecutive days and on the 15th day, one hour after drug administration, the mice were irradiated with 6Gy electron beam radiation. The changes in blood cell count, total antioxidant levels, malondialdehyde and reduced glutathione levels were determined. The immunomodulatory response of DADS to the radiological effects was determined by the estimation of IL-6 levels. Results A significant improvement in pre-drug treatment group when compared to control groups in the haemoglobin, red blood cell count, white blood cell count, haematocrit and platelet counts was observed. There is an increased level of interleukin-6 in the drug treated groups compared to the radiation control. An increase in the malondialdehyde levels and decrease in the glutathione levels in the irradiated group indicate increased lipid peroxidation and oxidative stress, whereas, there is a significant reduction in the malondialdehyde levels and increased glutathione levels in the drug pre-treatment groups showing membrane stabilization. Conclusion Thus DADS proves to be an effective haematopoietic and antioxidative agent to counter radiation induced haematopoietic suppression and oxidative stress. PMID:27042448

  3. Separation and identification by gel filtration and high-performance liquid chromatography with UV or electrochemical detection of the disulphides produced from cysteine and glutathione oxidation.

    PubMed

    Vignaud, Caroline; Rakotozafy, Lalatiana; Falguières, Annie; Potus, Jacques; Nicolas, Jacques

    2004-03-26

    Methods for quantification of oxidised and reduced forms of glutathione (GSSG and GSH) and cysteine (CSSC and CSH) and the disulphide glutathione-cysteine (GSSC) resulting from the oxidation of the mixture of CSH and GSH are performed by RP-HPLC with coulometric and UV detection after separation of these compounds by size-exclusion fast protein liquid chromatography. The fractionation of the disulphides (GSSG, GSSC and CSSC) was achieved by size exclusion using a Superdex peptide column coupled with an UV detection at 254 nm. The conditions of separation of these compounds by RP-HPLC were optimised using the response surface methodology. Optimal peak resolution and retention times were obtained on a C18 YMC ODS AQ column with 20 mM of ammonium phosphate at pH 2.5 and 2% of acetonitrile in the elution phase. In these experimental conditions, CSH, CSSC, GSH and GSSG were eluted within 20 min. Coulometric detection enabled a sensitivity 100 times higher for the disulphides than the UV detection at 220 nm. These methods were applied to follow the consumption of thiols and the disulphide formation by three oxidising systems, sulphydryl oxidase, glutathione dehydroascorbate oxidoreductase and potassium bromate. This study revealed that the relative proportions of the disulphides formed were similar for the three oxidising systems when the reactions are in their state of equilibrium.

  4. The effects of ozone on bacterial growth and thiol-disulphide homeostasis in vascular graft infection caused by MRSA in rats.

    PubMed

    Ozturk, Barcin; Kurtoglu, Tunay; Durmaz, Selim; Kozaci, Leyla Didem; Abacigil, Filiz; Ertugrul, Bulent; Erel, Ozcan

    2017-03-01

    To investigate the microbiological, inflammatory and oxidant effects of adjuvant ozone administration in experimental rat vascular graft infection model which has not been previously investigated. Forty adult Wistar rats were divided into Sham, Control, Vancomycin, Ozone, Vancomycin+Ozone groups. Grafts were inoculated with Methicillin-resistant Staphylococcus aureus (MRSA) strain and implanted subcutaneously. Rats were treated intraperitoneally with ozone and /or intramuscularly with vancomycin for 10 days. Grafts were evaluated by quantitative bacterial cultures. Blood samples were harvested for determination of thiol-disulphide and cytokine profiles. There was no significant difference in bacterial counts between Control and Ozone Groups. In the Ozone Group median colony count was significantly higher than the Vancomycin and Vancomycin+Ozone Groups. Total thiol and disulphide levels increased and disulphide/native thiol and disulphide/total thiol ratios decreased in Ozone Group significantly. Albumin levels decreased significantly in Vancomycin and Vancomycin+Ozone Groups compared to the Sham Group. IL-1 and TNF-alpha levels significantly increased in infected rats. Decreased levels of VEGF due to infection reversed by ozone therapy in control and vancomycin groups. We didn't observe any benefit of the agent on MRSA elimination in our model. Likewise, effects of ozone on thiol-disulphide homeostasis and inflammatory cytokines were contradictory.

  5. Piezoelectric resonator assembly with thin molybdenum mounting clips

    DOEpatents

    Peters, R. Donald

    1981-01-01

    A resonator mounting assembly wherein the resonator blank is mounted agai an essentially planar surface presented by a plurality of peripherally disposed mounting clips and bonded to this surface to provide substantially all the mechanical support for the blank in a direction normal to the major faces of the resonator blank, while being flexible in the directions parallel to said major faces so as to minimize radial stresses on the resonator blank, particularly during thermal cycling of the resonator assembly. The clips are fabricated of a low thermal expansion material, such as molybdenum, which also has considerable yield strength after exposure to processing temperatures; the bonding of the clips to the edges of the resonator blank can be achieved by a polyimide containing electrically conductive particles.

  6. Molybdenum oxide electrodes for thermoelectric generators

    DOEpatents

    Schmatz, Duane J.

    1989-01-01

    The invention is directed to a composite article suitable for use in thermoelectric generators. The article comprises a thin film comprising molybdenum oxide as an electrode deposited by physical deposition techniques onto solid electrolyte. The invention is also directed to the method of making same.

  7. The biosynthesis of the molybdenum cofactors.

    PubMed

    Mendel, Ralf R; Leimkühler, Silke

    2015-03-01

    The biosynthesis of the molybdenum cofactors (Moco) is an ancient, ubiquitous, and highly conserved pathway leading to the biochemical activation of molybdenum. Moco is the essential component of a group of redox enzymes, which are diverse in terms of their phylogenetic distribution and their architectures, both at the overall level and in their catalytic geometry. A wide variety of transformations are catalyzed by these enzymes at carbon, sulfur and nitrogen atoms, which include the transfer of an oxo group or two electrons to or from the substrate. More than 50 molybdoenzymes were identified to date. In all molybdoenzymes except nitrogenase, molybdenum is coordinated to a dithiolene group on the 6-alkyl side chain of a pterin called molybdopterin (MPT). The biosynthesis of Moco can be divided into three general steps, with a fourth one present only in bacteria and archaea: (1) formation of the cyclic pyranopterin monophosphate, (2) formation of MPT, (3) insertion of molybdenum into molybdopterin to form Moco, and (4) additional modification of Moco in bacteria with the attachment of a nucleotide to the phosphate group of MPT, forming the dinucleotide variant of Moco. This review will focus on the biosynthesis of Moco in bacteria, humans and plants.

  8. Method for welding chromium molybdenum steels

    DOEpatents

    Sikka, Vinod K.

    1986-01-01

    Chromium-molybdenum steels exhibit a weakening after welding in an area adjacent to the weld. This invention is an improved method for welding to eliminate the weakness by subjecting normalized steel to a partial temper prior to welding and subsequently fully tempering the welded article for optimum strength and ductility.

  9. Minerals yearbook, 1991: Molybdenum. Annual report

    SciTech Connect

    Blossom, J.W.

    1993-01-01

    Mr. Blossom, a physical scientist/engineer with 44 years' industry and Government experience, has been the commodity specialist for molybdenum since 1982. Survey and trade data were prepared by Sherwood C. Jordan, mineral data assistant; and the world production tables were prepared by Harold D. Willis, international data coordinator.

  10. Post-Irradiation Fracture Toughness of Unalloyed Molybdenum, ODS molybdenum, and TZM molybdenum following irradiation at 244C to 507C

    SciTech Connect

    Cockeram, Brian V; Byun, Thak Sang; Leonard, Keith J; Snead, Lance Lewis

    2013-01-01

    Commercially available unalloyed molybdenum (Low Carbon Arc Cast (LCAC)), Oxide Dispersion Strengthened (ODS) molybdenum, and TZM molybdenum were neutron irradiated at temperatures of nominally 244 C, 407 C, and 509 C to neutron fluences between 1.0 to 4.6x1025 n/m2 (E>0.1 MeV). Post-irradiation fracture toughness testing was performed. All alloys exhibited a Ductile to Brittle Transition Temperature that was defined to occur at 30 4 MPa-m1/2. The highest post-irradiated fracture toughness values (26-107 MPa-m1/2) and lowest DBTT (100-150 C) was observed for ODS molybdenum in the L-T orientation. The finer grain size for ODS molybdenum results in fine laminates that improve the ductile laminate toughening. The results for ODS molybdenum are anisotropic with lower post-irradiated toughness values (20-30 MPa-m1/2) and higher DBTT (450-600 C) in the T-L orientation. The results for T-L ODS molybdenum are consistent or slightly better than those for LCAC molybdenum (21-71 MPa-m1/2 and 450-800 C DBTT). The fracture toughness values measured for LCAC and T-L ODS molybdenum at temperatures below the DBTT were determined to be 8-18 MPa-m1/2. Lower non-irradiated fracture toughness values were measured for TZM molybdenum that are attributed to the large carbide precipitates serving as preferential fracture initiation sites. The role of microstructure and grain size on post-irradiated fracture toughness was evaluated by comparing the results for LCAC molybdenum and ODS molybdenum.

  11. Electronic properties of reduced molybdenum oxides.

    PubMed

    Inzani, K; Nematollahi, M; Vullum-Bruer, F; Grande, T; Reenaas, T W; Selbach, S M

    2017-03-29

    The electronic properties of MoO3 and reduced molybdenum oxide phases are studied by density functional theory (DFT) alongside characterization of mixed phase MoOx films. Molybdenum oxide is utilized in compositions ranging from MoO3 to MoO2 with several intermediary phases. With increasing degree of reduction, the lattice collapses and the layered MoO3 structure is lost. This affects the electronic and optical properties, which range from the wide band gap semiconductor MoO3 to metallic MoO2. DFT is used to determine the stability of the most relevant molybdenum oxide phases, in comparison to oxygen vacancies in the layered MoO3 lattice. The non-layered phases are more stable than the layered MoO3 structure for all oxygen stoichiometries of MoOx studied where 2 ≤ x < 3. Reduction and lattice collapse leads to strong changes in the electronic density of states, especially the filling of the Mo 4d states. The DFT predictions are compared to experimental studies of molybdenum oxide films within the same range of oxygen stoichiometries. We find that whilst MoO2 is easily distinguished from MoO3, intermediate phases and phase mixtures have similar electronic structures. The effect of the different band structures is seen in the electrical conductivity and optical transmittance of the films. Insight into the oxide phase stability ranges and mixtures is not only important for understanding molybdenum oxide films for optoelectronic applications, but is also relevant to other transition metal oxides, such as WO3, which exist in analogous forms.

  12. Stability of molybdenum nanoparticles in Sn-3.8Ag-0.7Cu solder during multiple reflow and their influence on interfacial intermetallic compounds

    SciTech Connect

    Haseeb, A.S.M.A. Arafat, M.M. Johan, Mohd Rafie

    2012-02-15

    This work investigates the effects of molybdenum nanoparticles on the growth of interfacial intermetallic compound between Sn-3.8Ag-0.7Cu solder and copper substrate during multiple reflow. Molybdenum nanoparticles were mixed with Sn-3.8Ag-0.7Cu solder paste by manual mixing. Solder samples were reflowed on a copper substrate in a 250 Degree-Sign C reflow oven up to six times. The molybdenum content of the bulk solder was determined by inductive coupled plasma-optical emission spectrometry. It is found that upon the addition of molybdenum nanoparticles to Sn-3.8Ag-0.7Cu solder, the interfacial intermetallic compound thickness and scallop diameter decreases under all reflow conditions. Molybdenum nanoparticles do not appear to dissolve or react with the solder. They tend to adsorb preferentially at the interface between solder and the intermetallic compound scallops. It is suggested that molybdenum nanoparticles impart their influence on the interfacial intermetallic compound as discrete particles. The intact, discrete nanoparticles, by absorbing preferentially at the interface, hinder the diffusion flux of the substrate and thereby suppress the intermetallic compound growth. - Highlights: Black-Right-Pointing-Pointer Mo nanoparticles do not dissolve or react with the SAC solder during reflow. Black-Right-Pointing-Pointer Addition of Mo nanoparticles results smaller IMC thickness and scallop diameter. Black-Right-Pointing-Pointer Mo nanoparticles influence the interfacial IMC through discrete particle effect.

  13. Disulphide trapping of the GABAA receptor reveals the importance of the coupling interface in the action of benzodiazepines

    PubMed Central

    Hanson, Susan M; Czajkowski, Cynthia

    2011-01-01

    BACKGROUND AND SIGNIFICANCE Although the functional effects of benzodiazepines (BZDs) on GABAA receptors have been well characterized, the structural mechanism by which these modulators alter activation of the receptor by GABA is still undefined. EXPERIMENTAL APPROACH We used disulphide trapping between engineered cysteines to probe BZD-induced conformational changes within the γ2 subunit and at the α1/γ2 coupling interface (Loops 2, 7 and 9) of α1β2γ2 GABAA receptors. KEY RESULTS Crosslinking γ2Loop 9 to γ2β-strand 9 (via γ2S195C/F203C and γ2S187C/L206C) significantly decreased maximum potentiation by flurazepam, suggesting that modulation of GABA-induced current (IGABA) by flurazepam involves movements of γ2Loop 9 relative to γ2β-strand 9. In contrast, tethering γ2β-strand 9 to the γ2 pre-M1 region (via γ2S202C/S230C) significantly enhanced potentiation by both flurazepam and zolpidem, indicating γ2S202C/S230C trapped the receptor in a more favourable conformation for positive modulation by BZDs. Intersubunit disulphide bonds formed at the α/γ coupling interface between α1Loop 2 and γ2Loop 9 (α1D56C/γ2L198C) prevented flurazepam and zolpidem from efficiently modulating IGABA. Disulphide trapping α1Loop 2 (α1D56C) to γ2β-strand 1 (γ2P64C) decreased maximal IGABA as well as flurazepam potentiation. None of the disulphide bonds affected the ability of the negative modulator, 3-carbomethoxy-4-ethyl-6,7-dimethoxy-β-carboline (DMCM), to inhibit IGABA. CONCLUSIONS AND IMPLICATIONS Positive modulation of GABAA receptors by BZDs requires reorganization of the loops in the α1/γ2 coupling interface. BZD-induced movements at the α/γ coupling interface likely synergize with rearrangements induced by GABA binding at the β/α subunit interfaces to enhance channel activation by GABA. PMID:20942818

  14. A four-disulphide-bridged toxin, with high affinity towards voltage-gated K+ channels, isolated from Heterometrus spinnifer (Scorpionidae) venom.

    PubMed Central

    Lebrun, B; Romi-Lebrun, R; Martin-Eauclaire, M F; Yasuda, A; Ishiguro, M; Oyama, Y; Pongs, O; Nakajima, T

    1997-01-01

    A new toxin, named HsTX1, has been identified in the venom of Heterometrus spinnifer (Scorpionidae), on the basis of its ability to block the rat Kv1.3 channels expressed in Xenopus oocytes. HsTX1 has been purified and characterized as a 34-residue peptide reticulated by four disulphide bridges. HsTX1 shares 53% and 59% sequence identity with Pandinus imperator toxin1 (Pi1) and maurotoxin, two recently isolated four-disulphide-bridged toxins, whereas it is only 32-47% identical with the other scorpion K+ channel toxins, reticulated by three disulphide bridges. The amidated and carboxylated forms of HsTX1 were synthesized chemically, and identity between the natural and the synthetic amidated peptides was proved by mass spectrometry, co-elution on C18 HPLC and blocking activity on the rat Kv1.3 channels. The disulphide bridge pattern was studied by (1) limited reduction-alkylation at acidic pH and (2) enzymic cleavage on an immobilized trypsin cartridge, both followed by mass and sequence analyses. Three of the disulphide bonds are connected as in the three-disulphide-bridged scorpion toxins, and the two extra half-cystine residues of HsTX1 are cross-linked, as in Pi1. These results, together with those of CD analysis, suggest that HsTX1 probably adopts the same general folding as all scorpion K+ channel toxins. HsTX1 is a potent inhibitor of the rat Kv1.3 channels (IC50 approx. 12 pM). HsTX1 does not compete with 125I-apamin for binding to its receptor site on rat brain synaptosomal membranes, but competes efficiently with 125I-kaliotoxin for binding to the voltage-gated K+ channels on the same preparation (IC50 approx. 1 pM). PMID:9359871

  15. Redox state of low-molecular-weight thiols and disulphides during somatic embryogenesis of salt-treated suspension cultures of Dactylis glomerata L.

    PubMed

    Zagorchev, Lyuben; Seal, Charlotte E; Kranner, Ilse; Odjakova, Mariela

    2012-05-01

    The tripeptide antioxidant γ-L-glutamyl-L-cysteinyl-glycine, or glutathione (GSH), serves a central role in ROS scavenging and oxidative signalling. Here, GSH, glutathione disulphide (GSSG), and other low-molecular-weight (LMW) thiols and their corresponding disulphides were studied in embryogenic suspension cultures of Dactylis glomerata L. subjected to moderate (0.085 M NaCl) or severe (0.17 M NaCl) salt stress. Total glutathione (GSH + GSSG) concentrations and redox state were associated with growth and development in control cultures and in moderately salt-stressed cultures and were affected by severe salt stress. The redox state of the cystine (CySS)/2 cysteine (Cys) redox couple was also affected by developmental stage and salt stress. The glutathione half-cell reduction potential (E(GSSG/2 GSH)) increased with the duration of culturing and peaked when somatic embryos were formed, as did the half-cell reduction potential of the CySS/2 Cys redox couple (E(CySS/2 Cys)). The most noticeable relationship between cellular redox state and developmental state was found when all LMW thiols and disulphides present were mathematically combined into a 'thiol-disulphide redox environment' (E(thiol-disulphide)), whereby reducing conditions accompanied proliferation, resulting in the formation of pro-embryogenic masses (PEMs), and oxidizing conditions accompanied differentiation, resulting in the formation of somatic embryos. The comparatively high contribution of E(CySS/2 Cys) to E(thiol-disulphide) in cultures exposed to severe salt stress suggests that Cys and CySS may be important intracellular redox regulators with a potential role in stress signalling.

  16. Densification of molybdenum and molybdenum alloy powders using hot isostatic pressing. Final technical report

    SciTech Connect

    Barranco, J.; Ahmad, I.; Isserow, S.; Warenchak, R.

    1985-08-01

    This study was conducted to determine a superior erosion-resistant gun-barrel liner material with improved properties at higher temperatures. Four categories of powders were examined: 1. TZM spherical containing 0.5 titanium, 0.08 zirconium, and 0.02 carbon (wt. % nominally), balance molybdenum (Mo), produced by REP (Rotating Electrode Process), PREP (Plasma Rotating Electrode Process), and PMRS (Plasma Melted and Rapidly Solidified); 2. Mo reduced 2 and 5 microns; 3. Mo-0.1% cobalt, co-reduced; 4. Mo-5 wt. % alumina (A12O3), dispersion strengthened. Hot Isostatic Pressing (HIP) densification occurred at 15-30 Ksi, 1300-1600 C, for 1.5 to 3.0 hours. The TZM REP/PREP powders (220/74 microns) were not fully densified even at 1600 C, 30 Ksi, 3 hours. Point-particle contact prevented complete void elimination. TZM PMRS powder (24.7 microns) achieved 99% of theoretical density while maintaining a small grain size (10.4 ASTM eq.) Bend deflection and fracture energies were approximately three times those for PREP powder at a bend rupture strength of about 120 Ksi. Mo reduced and Mo-0.1% Co powders showed less (or the same) ductility with increasing HIP temperatures. Fractures were intergranular with decreased bend rupture and compression strength. The Mo-5A1/sub 2/O/sub 3/ powder maintained a fine grain size (13 ASTM eq.), but with fracture energies usually less than 0.6 in.-lbs. Included are results from bending and compression testing with metallographic and fracture mode interpretation.

  17. Potentiation of the reductase activity of protein disulphide isomerase (PDI) by 19-nortestosterone, bacitracin, fluoxetine, and ammonium sulphate.

    PubMed

    Hassan, Maya Haj; Alvarez, Eva; Cahoreau, Claire; Klett, Danièle; Lecompte, François; Combarnous, Yves

    2011-10-01

    Protein disulphide isomerase (PDI) in the endoplasmic reticulum catalyzes the rearrangement of disulphide bridges during folding of secreted proteins. It binds various molecules that inhibit its activity. But here, we looked for molecules that would potentiate its activity. PDI reductase activity was measured in vitro using di-eosin-oxidized glutathione as substrate. Its classical inhibitor bacitracin was found to exert a biphasic effect: stimulatory at low concentrations (∼10(-6) M) and inhibitory only at higher concentrations (∼10(-4)-10(-3) M). The weak oestrogenic molecule bisphenol A was found to exert a weak inhibitory effect on PDI reductase activity relative to the strong oestrogens, ethynylestradiol, and diethylstilbestrol. Like 19-nortestosterone, fluoxetine was found to exert a potentiating effect on PDI reductase activity and their potentiating effects could be reversed by increasing concentrations of oestrogens. In conclusion, this paper provides the first identification of potentiators of PDI activity that are potential pharmaceuticals against pathologies affecting protein folding such as Alzheimer's disease.

  18. Comparison of occupational exposure to carbon disulphide in a viscose rayon factory before and after technical adjustments.

    PubMed

    Bulat, Petar; Daemen, Edgard; Van Risseghem, Marleen; De Bacquer, Dirk; Tan, Xiaodong; Braeckman, Lutgart; Vanhoorne, Michel

    2002-01-01

    The objective of this follow-up study was to verify the efficacy of the technical adjustments gradually introduced in departments of a viscose rayon factory from 1989 onward. Personal exposure to carbon disulphide was assessed by means of personal monitoring through active sampling. Six job titles in three departments of the factory were sampled. Geometric means were calculated and used as estimates of time-weighted average (TWA) concentrations. The results from the present study were compared with similar measurements from a previous study in the same factory. Due to organizational changes, only three job titles (spinner, first spinner, and viscose preparator) could be compared directly. Two new job titles were identified, although tasks performed in these two job titles already existed. The measurements from one job title could not be compared, due to a substantial reorganization and automation of the tasks carried out in the department. The comparison before and after technical improvements shows that personal exposure of spinner and first spinner has been substantially reduced. Even the geometric means of measurements outside the fresh air mask are below the TWA-TLV (Threshold Limit Value). Despite the difficulties in comparing the results from the two studies, it is concluded that the technical measures reduced up to tenfold personal exposure to carbon disulphide and personal protection reduced it further by a factor two.

  19. Kinetics of molybdenum reduction to molybdenum blue by Bacillus sp. strain A.rzi.

    PubMed

    Othman, A R; Bakar, N A; Halmi, M I E; Johari, W L W; Ahmad, S A; Jirangon, H; Syed, M A; Shukor, M Y

    2013-01-01

    Molybdenum is very toxic to agricultural animals. Mo-reducing bacterium can be used to immobilize soluble molybdenum to insoluble forms, reducing its toxicity in the process. In this work the isolation of a novel molybdate-reducing Gram positive bacterium tentatively identified as Bacillus sp. strain A.rzi from a metal-contaminated soil is reported. The cellular reduction of molybdate to molybdenum blue occurred optimally at 4 mM phosphate, using 1% (w/v) glucose, 50 mM molybdate, between 28 and 30 °C and at pH 7.3. The spectrum of the Mo-blue product showed a maximum peak at 865 nm and a shoulder at 700 nm. Inhibitors of bacterial electron transport system (ETS) such as rotenone, sodium azide, antimycin A, and potassium cyanide could not inhibit the molybdenum-reducing activity. At 0.1 mM, mercury, copper, cadmium, arsenic, lead, chromium, cobalt, and zinc showed strong inhibition on molybdate reduction by crude enzyme. The best model that fitted the experimental data well was Luong followed by Haldane and Monod. The calculated value for Luong's constants p max, K(s), S(m), and n was 5.88 μmole Mo-blue hr(-1), 70.36 mM, 108.22 mM, and 0.74, respectively. The characteristics of this bacterium make it an ideal tool for bioremediation of molybdenum pollution.

  20. Evaluation of oxide dispersion strengthened (ODS) molybdenum and molybdenum-rhenium Alloys

    SciTech Connect

    Mueller, A.J.; Bianco, R.; Buckman, R.W. Jr.

    1999-10-22

    Oxide dispersion strengthened (ODS) molybdenum alloys being developed for high temperature applications possess excellent high temperature strength and creep resistance. In addition they exhibit a ductile-to-brittle transition temperature (DBIT) in the worked and stress-relieved condition under longitudinal tensile load well below room temperature. However, in the recrystallized condition, the DBTT maybe near or above room temperature, depending on the volume fraction of oxide dispersion and the amount of prior work. Dilute rhenium additions (7 and 14 wt.%) to ODS molybdenum were evaluated to determine their effect on low temperature ductility. The addition of 7 wt.% rhenium to the ODS molybdenum did not significantly enhance the mechanical properties. However, the addition of 14 wt.% rhenium to the ODS molybdenum resulted in a DBTT well below room temperature in both the stress-relieved and recrystallized condition. Additionally, the tensile strength of ODS Mo-14Re is greater than the base ODS molybdenum at 1,000 to 1,250 C.

  1. Shock compaction of molybdenum powder

    NASA Technical Reports Server (NTRS)

    Ahrens, T. J.; Kostka, D.; Vreeland, T., Jr.; Schwarz, R. B.; Kasiraj, P.

    1983-01-01

    Shock recovery experiments which were carried out in the 9 to 12 GPa range on 1.4 distension Mo and appear adequate to compact to full density ( 45 (SIGMA)m) powders were examined. The stress levels, however, are below those calculated to be from 100 to approx. 22 GPa which a frictional heating model predicts are required to consolidate approx. 10 to 50 (SIGMA)m particles. The model predicts that powders that have a distension of m=1.6 shock pressures of 14 to 72 GPa are required to consolidate Mo powders in the 50 to 10 (SIGMA)m range.

  2. Reactive melt infiltration of silicon-molybdenum alloys into microporous carbon preforms

    NASA Technical Reports Server (NTRS)

    Singh, M.; Behrendt, D. R.

    1995-01-01

    Investigations on the reactive melt infiltration of silicon-1.7 and 3.2 at.% molybdenum alloys into microporous carbon preforms have been carried out by modeling, differential thermal analysis (DTA), and melt infiltration experiments. These results indicate that the pore volume fraction of the carbon preform is a very important parameter in determining the final composition of the reaction-formed silicon carbide and the secondary phases. Various undesirable melt infiltration results, e.g. choking-off, specimen cracking, silicon veins, and lake formation, and their correlation with inadequate preform properties are presented. The liquid silicon-carbon reaction exotherm temperatures are influenced by the pore and carbon particle size of the preform and the compositions of infiltrants. Room temperature flexural strength and fracture toughness of materials made by the silicon-3.2 at.% molybdenum alloy infiltration of medium pore size preforms are also discussed.

  3. Enhanced superconductivity and superconductor to insulator transition in nano-crystalline molybdenum thin films

    NASA Astrophysics Data System (ADS)

    Sharma, Shilpam; Amaladass, E. P.; Sharma, Neha; Harimohan, V.; Amirthapandian, S.; Mani, Awadhesh

    2017-06-01

    Disorder driven superconductor to insulator transition via intermediate metallic regime is reported in nano-crystalline thin films of molybdenum. The nano-structured thin films have been deposited at room temperature using DC magnetron sputtering at different argon pressures. The grain size has been tuned using deposition pressure as the sole control parameter. A variation of particle sizes, room temperature resistivity and superconducting transition has been studied as a function of deposition pressure. The nano-crystalline molybdenum thin films are found to have large carrier concentration but very low mobility and electronic mean free path. Hall and conductivity measurements have been used to understand the effect of disorder on the carrier density and mobilities. Ioffe-Regel parameter is shown to correlate with the continuous metal-insulator transition in our samples.

  4. Molybdenum Sound Velocity and Shear Strength Softening

    NASA Astrophysics Data System (ADS)

    Nguyen, Jeffrey; Akin, Minta; Chau, Ricky; Fratandouno, Dayne; Ambrose, Pat; Fat'yanov, Oleg; Asimow, Paul; Holmes, Neil

    2013-06-01

    We recently carried out a series of light-gas gun experiments to measure molybdenum acoustic sound speed up to 5 Mbars on the Hugoniot. Our measured sound speeds increase linearly with pressure up to 2.6 Mbars and taper off near the melting pressure. The gradual leveling off of sound speed suggests a possible loss of shear strength near the melt. A linear extrapolation of our data to zero pressure is in good agreement with the sound speed measured at ambient condition. The results indicate that molybdenum remains in the bcc phase on the Hugoniot up to the melting pressure. There is no bcc solid phase transition on the Hugoniot as previously reported. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  5. Critical currents in sputtered copper molybdenum sulphide

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Woollam, J. A.; Kammerdiner, L.; Luo, H.-L.

    1977-01-01

    Critical currents in a sputtered Chevrel-phase copper molybdenum sulfide have been measured at 4.2 K as a function of applied magnetic field. Self-field critical-current values up to 10 to the 9th A/sq m were found, decreasing to 10 to the 8th A/sq m at 3 T. Graphs of pinning forces versus field were found to be independent of field direction, and the pinning mechanism is sample independent. Critical-current densities for sputtered lead molybdenum sulphide are estimated to be about 10 to the 8th A/sq m at 26 T based on a scaling law for pinning.

  6. Laser-assisted growth of molybdenum rods

    NASA Astrophysics Data System (ADS)

    Björklund, K. L.; Heszler, P.; Boman, M.

    2002-01-01

    In this paper, we report for the first time the laser-assisted growth of molybdenum rods via the H 2 reduction of MoF 6 with a focused Ar + laser beam as the heat source. By varying the gas composition, total pressure, and laser power rods with different morphologies were deposited on a tungsten wire. At low H 2/MoF 6 molar ratios crystal-like rods were obtained and at higher molar ratios the rods became dendrite-like. The activation energy for the process was determined to be 77±7 kJ mol -1 in the temperature range 705-840 K. The reaction order showed to be nearly 3 with respect to the hydrogen partial pressure and zero order with respect to the molybdenum hexafluoride partial pressure. Compositional and morphological characterisation were performed with scanning electron microscopy, energy dispersed X-ray spectroscopy and Auger electron spectroscopy.

  7. Reactively evaporated films of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Chi, K. C.; Dillon, R. O.; Bunshah, R. F.; Alterovitz, S.; Woollam, J. A.

    1978-01-01

    Films of superconducting Chevrel-phase copper molybdenum sulfide CuxMo6S8 were deposited on sapphire substrates by reactive evaporation using H2S as the reacting gas. Two superconducting temperatures (10.0 K and 5.0 K) of the films were found, corresponding to two different phases with different copper concentrations. All films were superconducting above 4.2 K and contained Chevrel-phase compound as well as free molybdenum. The critical current was measured as a function of applied field. One sample was found to deviate from the scaling law found for co-evaporated or sputtered samples, which possibly indicates a different pinning mechanism or inhomogeneity of the sample.

  8. Reactively evaporated films of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Chi, K. C.; Dillon, R. O.; Bunshah, R. F.; Alterovitz, S.; Woollam, J. A.

    1978-01-01

    Films of superconducting Chevrel-phase copper molybdenum sulfide CuxMo6S8 were deposited on sapphire substrates by reactive evaporation using H2S as the reacting gas. Two superconducting temperatures (10.0 K and 5.0 K) of the films were found, corresponding to two different phases with different copper concentrations. All films were superconducting above 4.2 K and contained Chevrel-phase compound as well as free molybdenum. The critical current was measured as a function of applied field. One sample was found to deviate from the scaling law found for co-evaporated or sputtered samples, which possibly indicates a different pinning mechanism or inhomogeneity of the sample.

  9. Critical currents in sputtered copper molybdenum sulphide

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Woollam, J. A.; Kammerdiner, L.; Luo, H.-L.

    1977-01-01

    Critical currents in a sputtered Chevrel-phase copper molybdenum sulfide have been measured at 4.2 K as a function of applied magnetic field. Self-field critical-current values up to 10 to the 9th A/sq m were found, decreasing to 10 to the 8th A/sq m at 3 T. Graphs of pinning forces versus field were found to be independent of field direction, and the pinning mechanism is sample independent. Critical-current densities for sputtered lead molybdenum sulphide are estimated to be about 10 to the 8th A/sq m at 26 T based on a scaling law for pinning.

  10. Breaking America's dependence on imported molybdenum.

    PubMed

    Einstein, Andrew J

    2009-03-01

    Approximately 9 million nuclear cardiology studies performed each year in the U.S. use technetium-99m, which is produced from the decay of molybdenum-99. The fragility of the worldwide technetium-99m supply chain has been underscored by current shortages caused by an unplanned shutdown of Europe's largest reactor. The majority of the U.S. supply derives from a reactor in Canada that is nearing the end of its lifespan and whose planned replacements have been cancelled recently. In this article, the clinical importance of technetium-99m and our tenuous dependence on the foreign supply of molybdenum are addressed, along with potential measures that may be taken to ensure that America's supply chain remains unbroken.

  11. A clock reaction based on molybdenum blue.

    PubMed

    Neuenschwander, Ulrich; Negron, Arnaldo; Jensen, Klavs F

    2013-05-30

    Clock reactions are rare kinetic phenomena, so far limited mostly to systems with ionic oxoacids and oxoanions in water. We report a new clock reaction in cyclohexanol that forms molybdenum blue from a noncharged, yellow molybdenum complex as precursor, in the presence of hydrogen peroxide. Interestingly, the concomitant color change is reversible, enabling multiple clock cycles to be executed consecutively. The kinetics of the clock reaction were experimentally characterized, and by adding insights from quantum chemical calculations, a plausible reaction mechanism was postulated. Key elementary reaction steps comprise sigmatropic rearrangements with five-membered or bicyclo[3.1.0] transition states. Importantly, numerical kinetic modeling demonstrated the mechanism's ability to reproduce the experimental findings. It also revealed that clock behavior is intimately connected to the sudden exhaustion of hydrogen peroxide. Due to the stoichiometric coproduction of ketone, the reaction bears potential for application in alcohol oxidation catalysis.

  12. Method for welding chromium molybdenum steels

    SciTech Connect

    Sikka, V.K.

    1986-09-16

    A process is described for welding chromium-molybdenum steels which consist of: subjecting the steel to normalization by heating to above the transformation temperature and cooling in air; subjecting the steel to a partial temper by heating to a temperature less than a full temper; welding the steel using an appropriate filler metal; subjecting the steel to a full temper by heating to a temperature sufficient to optimize strength, reduce stress, increase ductility and reduce hardness.

  13. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1973-01-01

    Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

  14. The alkaline earth intercalates of molybdenum disulfide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.; Samson, S.; Woollam, J. A.

    1975-01-01

    Molybdenum disulfide has been intercalated with calcium and strontium by means of the liquid ammonia technique. Chemical, X-ray, and superconductivity data are presented. The X-ray data reveal a lowering of crystal symmetry and increase of complexity of the structure upon intercalation with the alkaline earth metals. The Ca and Sr intercalates start to superconduct at 4 and 5.6 K, respectively, and show considerable anisotropy regarding the critical magnetic field.

  15. The alkaline earth intercalates of molybdenum disulfide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.; Samson, S.; Woollam, J. A.

    1975-01-01

    Molybdenum disulfide has been intercalated with calcium and strontium by means of the liquid ammonia technique. Chemical, X-ray, and superconductivity data are presented. The X-ray data reveal a lowering of crystal symmetry and increase of complexity of the structure upon intercalation with the alkaline earth metals. The Ca and Sr intercalates start to superconduct at 4 and 5.6 K, respectively, and show considerable anisotropy regarding the critical magnetic field.

  16. Reduced Grain Boundary Mobility and the Sintering of Molybdenum.

    DTIC Science & Technology

    1984-04-01

    rate of nickel activated molybdenum is further increased by 67% with the silica additions. The sintered material exl’Ibits a higher density and finer...molybdenum activated with nickel, and two levels of silica in activated molybdenum. The as-consolidated materials containing nickel were 100% dense...34, Sicence of Sintering, 1983, vol. 15, pp. 27-42. T. S. Wei and R. M. German, "The Pore-Grain Boundary Interaction in Intermediate Stage Sintering

  17. A solvent extraction study of molybdenum chloride and molybdenum thiocyanate complexes

    USGS Publications Warehouse

    Greenland, L.P.; Lillie, E.G.

    1974-01-01

    The effect of reducing agents on molybdenum(VI) solutions in hydrochloric acid was studied by a solvent extraction technique to elucidate the composition of the colored molybdenum thiocyanate complex. Neither copper(I) chloride nor ascorbic acid have any effect on the extraction of MoO2Cl2; it is inferred that tin(II) chloride reduces Mo(VI) stepwise to a polynuclear Mo(V)??Mo(VI) complex and then to Mo(V). The colored thiocyanate complex produced by copper(I) and by ascorbic acid differs only slightly in extraction characteristics from the uncolored Mo(VI) complex. It is suggested that the color may be produced by an isomerization reaction of MoO2(SCN)2, and thus that the colored species may be a hexavalent rather than pentavalent molybdenum complex. ?? 1974.

  18. Recovery of tungsten and molybdenum from sulfur--bearing material

    SciTech Connect

    Ritsko, J. E.; Acia, H. L.

    1984-11-13

    Tungsten and molybdenum are recovered from sulfur bearing material such as sulfide sludges by a pollution free process in which the sulfur bearing material is heated with agitation in an aqueous solution of sodium carbonate to form water soluble molybdenum and tungsten compounds without forming any appreciable amount of water soluble sulfur compounds. The reaction mixture is oxidized to convert partially reduced tungsten values or molybdenum values to sodium tungstate and sodium molybdate respectively. The liquid phase containing tungsten and molybdenum is separated from the solid phase containing free sulfur.

  19. Spectrophotometric determination of molybdenum in rocks with thiocyanate

    USGS Publications Warehouse

    Lillie, E.G.; Greenland, L.P.

    1974-01-01

    A rapid procedure for the determination of microgram amounts of molybdenum in rocks is described. After acid decomposition, molybdenum is extracted from a hydrochloric acid solution into xylene with tributyl phosphate. After back-extraction with water, molybdenum is extracted as the ??-benzoinoximate into chloroform, stripped into hydrochloric acid extracted as the thiocyanate into amyl alcohol, and determined spectrophotometrically. The molybdenum thiocyanate color produced is stable, sensitive, and reproducible. Results of analyses of several of the U.S. Geological Survey standard rocks are given. ?? 1974.

  20. Structure and Reversible Pyran Formation in Molybdenum Pyranopterin Dithiolene Models of the Molybdenum Cofactor

    PubMed Central

    Williams, Benjamin R.; Fu, Yichun; Yap, Glenn P. A.; Nieter Burgmayer, Sharon J.

    2012-01-01

    The syntheses and X-ray structures of two molybdenum pyranopterin dithiolene complexes in biologically relevant Mo(+4) and Mo(+5) states are reported. Crystallography reveals these complexes possess a pyran ring formed through a spontaneous cyclization reaction of a dithiolene side-chain hydroxyl group at a C=N bond of the pterin. NMR data on the Mo(+4) complex suggests a reversible pyran ring cyclization occurs in solution. These results provide experimental evidence that the pyranopterin dithiolene ligand in molybdenum and tungsten enzymes could participate in catalysis through dynamic processes modulated by the protein. PMID:23157708

  1. Selective cleavage of pepsin by molybdenum metallopeptidase

    SciTech Connect

    Yenjai, Sudarat; Malaikaew, Pinpinat; Liwporncharoenvong, Teerayuth; Buranaprapuk, Apinya

    2012-03-02

    Graphical abstract: Molybdenum metallopeptidase: the Mo(VI) cluster with six molybdenum cations has the ability to cleave protein under mild conditions (37 Degree-Sign C, pH 7) without reducing agents. The reaction required only low concentration of ammonium heptamolybdatetetrahydrate ((NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}{center_dot}4H{sub 2}O) (0.125 mM). The reaction undergoes possibly via a hydrolytic mechanism. This is the first demonstration of protein cleavage by a molybdenum cluster. Highlights: Black-Right-Pointing-Pointer This is the first demonstration of protein cleavage by a Mo(VI) cluster with six molybdenum cations. Black-Right-Pointing-Pointer The cleavage reaction undergoes at mild conditions. Black-Right-Pointing-Pointer No need of reducing agents. Black-Right-Pointing-Pointer Only low concentration of Mo(VI) cluster and short time of incubation are needed. -- Abstract: In this study, the cleavage of protein by molybdenum cluster is reported for the first time. The protein target used is porcine pepsin. The data presented in this study show that pepsin is cleaved to at least three fragments with molecular weights of {approx}23, {approx}19 and {approx}16 kDa when the mixture of the protein and ammonium heptamolybdate tetrahydrate ((NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}{center_dot}4H{sub 2}O) was incubated at 37 Degree-Sign C for 24 h. No self cleavage of pepsin occurs at 37 Degree-Sign C, 24 h indicating that the reaction is mediated by the metal ions. N-terminal sequencing of the peptide fragments indicated three cleavage sites of pepsin between Leu 112-Tyr 113, Leu 166-Leu 167 and Leu 178-Asn 179. The cleavage reaction occurs after incubation of the mixture of pepsin and (NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}{center_dot}4H{sub 2}O) only for 2 h. However, the specificity of the cleavage decreases when incubation time is longer than 48 h. The mechanism for cleavage of pepsin is expected to be hydrolytic chemistry of the amide bonds in the protein

  2. Disulphide-thiol chemistry: a multi-faceted tool for macromolecular design and synthesis of polyfunctional materials for specialized drug delivery.

    PubMed

    Kgesa, Teboho; Choonara, Yahya E; Tyagi, Charu; Tomar, Lomas K; Kumar, Pradeep; du Toit, Lisa C; Pillay, Viness

    2015-01-01

    This review highlights recent interests and applications of disulphide and thiol chemistry in creating contemporary macromolecular designs. Due to the chemical nature of disulphides and thiols a wide range of chemical species react with these functional groups to yield a variety of polymers extending their applications in chemical, biological, physical, material engineering and material sciences. The review aims to illustrate the versatility and demonstrate the potential of thiol-based chemistries. The focus is on exploring bio-cleavable disulphides and linking by "clicking" thiols via thiol/other functional group exchange reactions. Thiol synthesis, modification and functionalization are demonstrated to be highly attractive and efficient in polymer and material science which in turn have immense application in biological therapeutics and drug delivery. The review also illustrates the remarkable pliability of synthetic and natural approaches to designing, optimizing and functionalizing nanostructures and conjugates by thiol chermistry modification. The examples quoted in the review illustrate the power and versatility of thiols for site specific functionalization, the construction of complex macromolecules and the generation of both biodegradable disulphides and non-biodegradable bonds which are the tools for constructing specific therapeutic/drug delivery systems. In addition, the ability of thiols to react with various functional groups found in a variety of polymer science materials and biological entities such as peptide and related structures will also be demonstrated. Despite of the fact that research efforts in thiol chemistry are still at the early stages, it is likely that its true potential will be developed.

  3. Effect of introducing a disulphide bond between the A and C domains on the activity and stability of Saccharomycopsis fibuligera R64 α-amylase.

    PubMed

    Natalia, Dessy; Vidilaseris, Keni; Ismaya, Wangsa T; Puspasari, Fernita; Prawira, Iman; Hasan, Khomaini; Fibriansah, Guntur; Permentier, Hjalmar P; Nurachman, Zeily; Subroto, Toto; Dijkstra, Bauke W; Soemitro, Soetijoso

    2015-02-10

    Native enzyme and a mutant containing an extra disulphide bridge of recombinant Saccharomycopsis fibuligera R64 α-amylase, designated as Sfamy01 and Sfamy02, respectively, have successfully been overexpressed in the yeast Pichia pastoris KM71H. The purified α-amylase variants demonstrated starch hydrolysis resulting in a mixture of maltose, maltotriose, and glucose, similar to the wild type enzyme. Introduction of the disulphide bridge shifted the melting temperature (TM) from 54.5 to 56 °C and nearly tripled the enzyme half-life time at 65 °C. The two variants have similar kcat/KM values. Similarly, inhibition by acarbose was only slightly affected, with the IC50 of Sfamy02 for acarbose being 40 ± 3.4 μM, while that of Sfamy01 was 31 ± 3.9 μM. On the other hand, the IC50 of Sfamy02 for EDTA was 0.45 mM, nearly two times lower than that of Sfamy01 at 0.77 mM. These results show that the introduction of a disulphide bridge had little effect on the enzyme activity, but made the enzyme more susceptible to calcium ion extraction. Altogether, the new disulphide bridge improved the enzyme stability without affecting its activity, although minor changes in the active site environment cannot be excluded.

  4. UV-light exposure of insulin: pharmaceutical implications upon covalent insulin dityrosine dimerization and disulphide bond photolysis.

    PubMed

    Correia, Manuel; Neves-Petersen, Maria Teresa; Jeppesen, Per Bendix; Gregersen, Søren; Petersen, Steffen B

    2012-01-01

    In this work we report the effects of continuous UV-light (276 nm, ~2.20 W.m(-2)) excitation of human insulin on its absorption and fluorescence properties, structure and functionality. Continuous UV-excitation of the peptide hormone in solution leads to the progressive formation of tyrosine photo-product dityrosine, formed upon tyrosine radical cross-linkage. Absorbance, fluorescence emission and excitation data confirm dityrosine formation, leading to covalent insulin dimerization. Furthermore, UV-excitation of insulin induces disulphide bridge breakage. Near- and far-UV-CD spectroscopy shows that UV-excitation of insulin induces secondary and tertiary structure losses. In native insulin, the A and B chains are held together by two disulphide bridges. Disruption of either of these bonds is likely to affect insulin's structure. The UV-light induced structural changes impair its antibody binding capability and in vitro hormonal function. After 1.5 and 3.5 h of 276 nm excitation there is a 33.7% and 62.1% decrease in concentration of insulin recognized by guinea pig anti-insulin antibodies, respectively. Glucose uptake by human skeletal muscle cells decreases 61.7% when the cells are incubated with pre UV-illuminated insulin during 1.5 h. The observations presented in this work highlight the importance of protecting insulin and other drugs from UV-light exposure, which is of outmost relevance to the pharmaceutical industry. Several drug formulations containing insulin in hexameric, dimeric and monomeric forms can be exposed to natural and artificial UV-light during their production, packaging, storage or administration phases. We can estimate that direct long-term exposure of insulin to sunlight and common light sources for indoors lighting and UV-sterilization in industries can be sufficient to induce irreversible changes to human insulin structure. Routine fluorescence and absorption measurements in laboratory experiments may also induce changes in protein

  5. The roles of disulphide and non-covalent bonding in the functional properties of heat-induced whey protein gels.

    PubMed

    Havea, Palatasa; Carr, Alistair J; Creamer, Lawrence K

    2004-08-01

    Heat-induced gelation (80 degrees C, 30 min or 85 degrees C, 60 min) of whey protein concentrate (WPC) solutions was studied using transmission electron microscopy (TEM), dynamic rheology and polyacrylamide gel electrophoresis (PAGE). The WPC solutions (150 g/kg, pH 6.9) were prepared by dispersing WPC powder in water (control), 10 g/kg sodium dodecyl sulphate (SDS) solution or 10 mM-dithiothreitol (DTT) solution. The WPC gels containing SDS were more translucent than the control gels, which were slightly more translucent than the gels containing DTT. TEM analyses showed that the SDS-gels had finer aggregate structure (approximately equal to 10 nm) than the control gels (approximately equal to 100 nm), whereas the DTT-gels had a more particulate structure (approximately equal to 200 to 300 nm). Dynamic rheology measurements showed that the control WPC gels had storage modulus (G) values (approximately equal to 13,500 Pa) that were approximately equal to 25 times higher than those of the SDS-gels (approximately equal to 550 Pa) and less than half those of the DTT-gels after cooling. Compression tests showed that the DTT-gels were more rigid and more brittle than the control gels, whereas the SDS-gels were softer and more rubbery than either the control gels or the DTT-gels. PAGE analyses of WPC gel samples revealed that the control WPC solutions heated at 85 degrees C for 10 min contained both disulphide bonds and non-covalent linkages. In both the SDS-solutions and the DTT-solutions, the denatured whey protein molecules were in the form of monomers or small aggregates. It is likely that, on more extended heating, more disulphide linkages were formed in the SDS-gels whereas more hydrophobic aggregates were formed in the DTT-gels. These results demonstrate that the properties of heat-induced WPC gels are strongly influenced by non-covalent bonding. Intermolecular disulphide bonds appeared to give the rubbery nature of heat-induced WPC gels whereas non-covalent bonds

  6. UV-Light Exposure of Insulin: Pharmaceutical Implications upon Covalent Insulin Dityrosine Dimerization and Disulphide Bond Photolysis

    PubMed Central

    Correia, Manuel; Neves-Petersen, Maria Teresa; Jeppesen, Per Bendix; Gregersen, Søren; Petersen, Steffen B.

    2012-01-01

    In this work we report the effects of continuous UV-light (276 nm, ∼2.20 W.m−2) excitation of human insulin on its absorption and fluorescence properties, structure and functionality. Continuous UV-excitation of the peptide hormone in solution leads to the progressive formation of tyrosine photo-product dityrosine, formed upon tyrosine radical cross-linkage. Absorbance, fluorescence emission and excitation data confirm dityrosine formation, leading to covalent insulin dimerization. Furthermore, UV-excitation of insulin induces disulphide bridge breakage. Near- and far-UV-CD spectroscopy shows that UV-excitation of insulin induces secondary and tertiary structure losses. In native insulin, the A and B chains are held together by two disulphide bridges. Disruption of either of these bonds is likely to affect insulin’s structure. The UV-light induced structural changes impair its antibody binding capability and in vitro hormonal function. After 1.5 and 3.5 h of 276 nm excitation there is a 33.7% and 62.1% decrease in concentration of insulin recognized by guinea pig anti-insulin antibodies, respectively. Glucose uptake by human skeletal muscle cells decreases 61.7% when the cells are incubated with pre UV-illuminated insulin during 1.5 h. The observations presented in this work highlight the importance of protecting insulin and other drugs from UV-light exposure, which is of outmost relevance to the pharmaceutical industry. Several drug formulations containing insulin in hexameric, dimeric and monomeric forms can be exposed to natural and artificial UV-light during their production, packaging, storage or administration phases. We can estimate that direct long-term exposure of insulin to sunlight and common light sources for indoors lighting and UV-sterilization in industries can be sufficient to induce irreversible changes to human insulin structure. Routine fluorescence and absorption measurements in laboratory experiments may also induce changes in protein

  7. Involvement of disulphide bonds in the renal sodium/phosphate co-transporter NaPi-2.

    PubMed Central

    Xiao, Y; Boyer, C J; Vincent, E; Dugré, A; Vachon, V; Potier, M; Béliveau, R

    1997-01-01

    The rat renal brush border membrane sodium/phosphate co-transporter NaPi-2 was analysed in Western blots with polyclonal antibodies raised against its N-terminal and C-terminal segments. Under reducing conditions, proteins of 45-49 and 70-90 kDa (p45 and p70) were detected with N-terminal antibodies, and proteins of 40 and 70-90 kDa (p40 and p70) were detected with C-terminal antibodies. p40 and p45 apparently result from a post-translational cleavage of NaPi-2 but remain linked through one or more disulphide bonds. Glycosidase digestion showed that both polypeptides are glycosylated; the cleavage site could thus be located between Asn-298 and Asn-328, which have been shown to constitute the only two N-glycosylated residues in NaPi-2. In the absence of reducing agents, both N-terminal and C-terminal antibodies detected p70 and a protein of 180 kDa (p180), suggesting the presence of p70 dimers. Much higher concentrations of beta-mercaptoethanol were required to produce a given effect in intact membrane vesicles than in solubilized proteins, indicating that the affected disulphide bonds are not exposed at the surface of the co-transporter. Phosphate transport activity decreased with increasing concentrations of reducing agents [beta-mercaptoethanol, dithiothreitol and tris-(2-carboxyethyl)phosphine] and was linearly correlated with the amount of p180 detected. The target sizes estimated from the radiation-induced loss of intensity of p40, p70 and p180 were all approx. 190 kDa, suggesting that NaPi-2 exists as an oligomeric protein in which the subunits are sufficiently close to one another to allow substantial energy transfer between the monomers. When protein samples were pretreated with beta-mercaptoethanol [2.5% and 5% (v/v) to optimize the detection of p40 and p70] before irradiation, target sizes estimated from the radiation-induced loss of intensity of p40 and p70 were 74 and 92 kDa respectively, showing the presence of disulphide bridges in the molecular

  8. Extraction and determination of molybdenum with tributyl phosphate Application to analysis of copper-molybdenum ores.

    PubMed

    Caiozzi, M; Zunino, H; Sepúlveda, L

    1969-12-01

    A differential spectrophotometric method is described for the determination of molybdenum by means of solvent extraction with tributylphosphate of the peroxymolybdate complex formed with H(2)O(2) in 3.5N H(2)SO(4). The extraction parameters are studied, and the behaviour of some other ions is reported. The method is used for ore analysis.

  9. {alpha}' Subunit of soybean {beta}-conglycinin forms complex with rice glutelin via a disulphide bond in transgenic rice seeds.

    PubMed

    Motoyama, Takayasu; Maruyama, Nobuyuki; Amari, Yoshiki; Kobayashi, Kanna; Washida, Haruhiko; Higasa, Takahiko; Takaiwa, Fumio; Utsumi, Shigeru

    2009-01-01

    The alpha' and beta subunits of soybean beta-conglycinin were expressed in rice seeds in order to improve the nutritional and physiological properties of rice as a food. The alpha' subunit accumulated in rice seeds at a higher level than the beta subunit, but no detectable difference in mRNA transcription level between subunits was observed. Sequential extraction results indicate that the alpha' subunit formed one or more disulphide bonds with glutelin. Electron microscopic analysis showed that the alpha' subunit and the beta subunit were transported to PB-II together with glutelin. In mature transgenic seeds, the beta subunit accumulated in low electron density regions in the periphery of PB-II, whereas the alpha' subunit accumulated together with glutelin in high-density regions of the periphery. The subcellular localization of mutated alpha' subunits lacking one cysteine residue in the N-terminal mature region (alpha'DeltaCys1) or five cysteine residues in the pro and N-terminal mature regions (alpha'DeltaCys5) were also examined. Low-density regions were formed in PB-II in mature seeds of transgenic rice expressing alpha'DeltaCys 5 and alpha'DeltaCys1. alpha'DeltaCys5 was localized only in the low-density regions, whereas alpha'DeltaCys1 was found in both low- and high-density regions. These results suggest that the alpha' subunit could make a complex via one or more disulphide bonds with glutelin and accumulate together in PB-II of transgenic rice seeds.

  10. Cyst(e)ine residues of bovine white-matter proteolipid proteins. Role of disulphides in proteolipid conformation.

    PubMed Central

    Oteiza, P I; Adamo, A M; Aloise, P A; Paladini, A C; Paladini, A A; Soto, E F

    1987-01-01

    Cyst(e)ine residues of bovine white-matter proteolipid proteins were characterized in a highly purified preparation. From a total of 10.6 cyst(e)ine residues/molecule of protein, as determined by performic acid oxidation, 2.5-3 thiol groups were freely accessible to iodoacetamide, iodoacetic acid and 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB), when the proteins were solubilized in chloroform/methanol (C/M) (2:1, v/v). The presence of lipids had no effect on thiol-group exposure. One thiol group available to DTNB in C/M could not be detected when proteolipids were solubilized in the more polar solvent n-butanol. In a C/M solution of purified proteolipid proteins, SDS did not increase the number of reactive thiol groups, but the cleavage of one disulphide bridge made it possible to alkylate six more groups. C.d. and fluorescence studies showed that rupture of this disulphide bond changed the protein conformation, which was reflected in partial loss of helical structure and in a greater exposure to the solvent of at least one tryptophan residue. Cyst(e)ine residues were also characterized in the different components [PLP (principal proteolipid protein), DM20 and LMW (low-Mr proteins)] of the proteolipid preparation. Although the numbers of cyst(e)ine residues in PLP and DM20 were similar, in LMW fewer residues were alkylated under four different experimental conditions. The differences, however, are not simply related to differences in Mr. PMID:3663175

  11. Purification and characterization of Ak.1 protease, a thermostable subtilisin with a disulphide bond in the substrate-binding cleft.

    PubMed

    Toogood, H S; Smith, C A; Baker, E N; Daniel, R M

    2000-08-15

    Ak.1 protease, a thermostable subtilisin isolated originally from Bacillus st. Ak.1, was purified to homogeneity from the Escherichia coli clone PB5517. It is active against substrates containing neutral or hydrophobic branched-chain amino acids at the P(1) site, such as valine, alanine or phenylalanine. The K(m) and k(cat) of the enzyme decrease with decreasing temperature, though not to the same degree with all substrates, suggesting that specificity changes with temperature. The protease is markedly stabilized by Ca(2+) ions. At 70 degrees C, a 10-fold increase in Ca(2+) concentration increases the half-life by three orders of magnitude. Ak.1 protease is stabilized by Ca(2+) to a greater extent than is thermitase. This may be due, in part, to the presence of an extra Ca(2+)-binding site in Ak.1 protease. Other metal ions, such as Sr(2+), increase the thermostability of the enzyme, but to a significantly lower degree than does Ca(2+). The structure of the protease showed the presence of a disulphide bond located within the active-site cleft. This bond influences both enzyme activity and thermostability. The disulphide bond appears to have a dual role: maintaining the integrity of the substrate-binding cleft and increasing the thermostability of the protease. The protease was originally investigated to determine its usefulness in the clean-up of DNA at high temperatures. However, it was found that this protease has a limited substrate specificity, so this application was not explored further.

  12. Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

    DOEpatents

    Lowden, Richard A.

    1994-01-01

    A process for chemical vapor deposition of crystalline silicon nitride which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and thermally decomposing the mixture to deposit onto the substrate a coating comprising crystalline silicon nitride containing a dispersion of molybdenum silicide.

  13. Molybdenum In Cathodes Of Sodium/Metal Chloride Cells

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Attia, Alan I.; Halpert, Gerald

    1992-01-01

    Cyclic voltammetric curves of molybdenum wire in NaAlCl4 melt indicate molybdenum chloride useful as cathode material in rechargeable sodium/metal chloride electrochemical cells. Batteries used in electric vehicles, for electric-power load leveling, and other applications involving high energy and power densities.

  14. Molybdenum blue: binding to collagen fibres and microcrystal formation.

    PubMed

    Harris, J Robin; Reiber, Andreas; Therese, Helen Annal; Tremel, Wolfgang

    2005-01-01

    Collagen fibres have been shown by transmission electron microscopy to progressively bind the polyoxomolybdate ring-complex, termed molybdenum blue. Nucleation of cuboidal molybdenum blue microcrystals occurs on the surface of the collagen fibres, leading eventually to extensive coating of the fibres with microcrystals.

  15. Molybdenum limitation of asymbiotic nitrogen fixation in tropical forest soils

    NASA Astrophysics Data System (ADS)

    Barron, Alexander R.; Wurzburger, Nina; Bellenger, Jean Phillipe; Wright, S. Joseph; Kraepiel, Anne M. L.; Hedin, Lars O.

    2009-01-01

    Nitrogen fixation, the biological conversion of di-nitrogen to plant-available ammonium, is the primary natural input of nitrogen to ecosystems, and influences plant growth and carbon exchange at local to global scales. The role of this process in tropical forests is of particular concern, as these ecosystems harbour abundant nitrogen-fixing organisms and represent one third of terrestrial primary production. Here we show that the micronutrient molybdenum, a cofactor in the nitrogen-fixing enzyme nitrogenase, limits nitrogen fixation by free-living heterotrophic bacteria in soils of lowland Panamanian forests. We measured the fixation response to long-term nutrient manipulations in intact forests, and to short-term manipulations in soil microcosms. Nitrogen fixation increased sharply in treatments of molybdenum alone, in micronutrient treatments that included molybdenum by design and in treatments with commercial phosphorus fertilizer, in which molybdenum was a `hidden' contaminant. Fixation did not respond to additions of phosphorus that were not contaminated by molybdenum. Our findings show that molybdenum alone can limit asymbiotic nitrogen fixation in tropical forests and raise new questions about the role of molybdenum and phosphorus in the tropical nitrogen cycle. We suggest that molybdenum limitation may be common in highly weathered acidic soils, and may constrain the ability of some forests to acquire new nitrogen in response to CO2 fertilization.

  16. 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...

  17. Normal state properties of the ternary molybdenum sulfides

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Alterovitz, S. A.

    1978-01-01

    By making a large number of normal state and superconducting properties measurements, all on the same ternary molybdenum sulfide samples, we obtain values for Fermi surface and superconducting parameters. From these we conclude that sputtered ternary molybdenum sulfides are not completely in the dirty superconductor limit, and that they are d-band metals with a high electron carrier density.

  18. REDUCTION AND CONSOLIDATION OF SUPERIOR QUALITY MOLYBDENUM ALLOYS

    DTIC Science & Technology

    diameter bomb. Techniques were developed for the electron beam melting of hydrogen-reduced molybdenum powder. Although this material contains low... beam melting of the thermitically-reduced molybdenum presented difficulties; primarily because of the melting configuration. The use of a remote...interstitial elements, it exhibited severe grain boundary brittleness. Physical properties of these single crystals are being determined. The electron

  19. REDUCTION AND CONSOLIDATION OF SUPERIOR QUALITY MOLYBDENUM ALLOYS

    DTIC Science & Technology

    beam melting . Three electron-beammelted, hydrogen-reduced molybdenum billets were extruded. Sheets rolled to .030 inch from these extrusions had...temperature. This is the lowest recrystallization temperature reported for molybdenum and is attributed to the high purity obtainable by electron

  20. Structural state of native molybdenum in the lunar regolith

    NASA Astrophysics Data System (ADS)

    Mokhov, A. V.; Gornostaeva, T. A.; Kartashov, P. M.; Bogatikov, O. A.; Sakharov, O. A.; Trubkin, N. V.

    2016-11-01

    The structural state was determined for zero-valence molybdenum in the lunar regolith. The body- and face-centered molybdenum forms (BCC and FCC, respectively) were identified. Disruption of the structure down to complete amorphization was noted. This might be caused by the long-term influence of the solar wind.

  1. Normal state properties of the ternary molybdenum sulfides

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Alterovitz, S. A.

    1978-01-01

    By making a large number of normal state and superconducting properties measurements, all on the same ternary molybdenum sulfide samples, we obtain values for Fermi surface and superconducting parameters. From these we conclude that sputtered ternary molybdenum sulfides are not completely in the dirty superconductor limit, and that they are d-band metals with a high electron carrier density.

  2. Predicting Boron, Molybdenum, Selenium, and Arsenic Adsorption in Soil Systems

    USDA-ARS?s Scientific Manuscript database

    A chemical surface complexation model was applied to boron, molybdenum, selenium, and arsenic adsorption on up to 49 soils selected for variation in soil properties. The surface complexation model was able to fit boron, molybdenum, selenite, and arsenate adsorption on the soils. General regression...

  3. Kinetics of Molybdenum Reduction to Molybdenum Blue by Bacillus sp. Strain A.rzi

    PubMed Central

    Othman, A. R.; Bakar, N. A.; Halmi, M. I. E.; Johari, W. L. W.; Ahmad, S. A.; Jirangon, H.; Syed, M. A.; Shukor, M. Y.

    2013-01-01

    Molybdenum is very toxic to agricultural animals. Mo-reducing bacterium can be used to immobilize soluble molybdenum to insoluble forms, reducing its toxicity in the process. In this work the isolation of a novel molybdate-reducing Gram positive bacterium tentatively identified as Bacillus sp. strain A.rzi from a metal-contaminated soil is reported. The cellular reduction of molybdate to molybdenum blue occurred optimally at 4 mM phosphate, using 1% (w/v) glucose, 50 mM molybdate, between 28 and 30°C and at pH 7.3. The spectrum of the Mo-blue product showed a maximum peak at 865 nm and a shoulder at 700 nm. Inhibitors of bacterial electron transport system (ETS) such as rotenone, sodium azide, antimycin A, and potassium cyanide could not inhibit the molybdenum-reducing activity. At 0.1 mM, mercury, copper, cadmium, arsenic, lead, chromium, cobalt, and zinc showed strong inhibition on molybdate reduction by crude enzyme. The best model that fitted the experimental data well was Luong followed by Haldane and Monod. The calculated value for Luong's constants p max, K s, S m, and n was 5.88 μmole Mo-blue hr−1, 70.36 mM, 108.22 mM, and 0.74, respectively. The characteristics of this bacterium make it an ideal tool for bioremediation of molybdenum pollution. PMID:24369531

  4. Molybdenum oxide nanocubes: Synthesis and characterizations

    SciTech Connect

    Muthamizh, S.; Suresh, R.; Giribabu, K.; Manigandan, R.; Kumar, S. Praveen; Munusamy, S.; Narayanan, V.; Stephen, A.

    2015-06-24

    Molybdenum oxide nanoparticles were prepared by Solid state synthesis. The MoO{sub 3} nanoparticles were synthesized by using commercially available ammonium heptamolybdate. The XRD pattern reveals that the synthesized MoO{sub 3} has orthorhombic structure. In addition, lattice parameter values were also calculated using XRD data. The Raman analysis confirm the presence of Mo-O in MoO{sub 3} nanoparticles. DRS-UV analysis shows that MoO{sub 3} has a band gap of 2.89 eV. FE-SEM analysis confirms the material morphology in cubes with nano scale.

  5. Molybdenum protective coatings adhesion to steel substrate

    NASA Astrophysics Data System (ADS)

    Blesman, A. I.; Postnikov, D. V.; Polonyankin, D. A.; Teplouhov, A. A.; Tyukin, A. V.; Tkachenko, E. A.

    2017-06-01

    Protection of the critical parts, components and assemblies from corrosion is an urgent engineering problem and many other industries. Protective coatings’ forming on surface of metal products is a promising way of corrosionprevention. The adhesion force is one of the main characteristics of coatings’ durability. The paper presents theoretical and experimental adhesion force assessment for coatings formed by molybdenum magnetron sputtering ontoa steel substrate. Validity and reliability of results obtained by simulation and sclerometry method allow applying the developed model for adhesion force evaluation in binary «steel-coating» systems.

  6. Molybdenum oxide nanocubes: Synthesis and characterizations

    NASA Astrophysics Data System (ADS)

    Muthamizh, S.; Suresh, R.; Giribabu, K.; Manigandan, R.; Kumar, S. Praveen; Munusamy, S.; Stephen, A.; Narayanan, V.

    2015-06-01

    Molybdenum oxide nanoparticles were prepared by Solid state synthesis. The MoO3 nanoparticles were synthesized by using commercially available ammonium heptamolybdate. The XRD pattern reveals that the synthesized MoO3 has orthorhombic structure. In addition, lattice parameter values were also calculated using XRD data. The Raman analysis confirm the presence of Mo-O in MoO3 nanoparticles. DRS-UV analysis shows that MoO3 has a band gap of 2.89 eV. FE-SEM analysis confirms the material morphology in cubes with nano scale.

  7. Aspects of electroless nickel plating on molybdenum

    SciTech Connect

    Mikkola, R.D.; Daugherty, C.E.; Harris, G.E.; Neff, W.A.; Owens, W.W.

    1984-07-01

    A process for depositing an adherent coating of an electroless nickel-phosphorus alloy on molybdenum was developed. The required pretreatment processes included an anodic etch in a chromic acid-nitric acid solution, an anodic etch in a phosphonic acid solution, and an oxide stripping step in a chromic acid-nitric acid solution. Initiation of the electroless nickel plating was accomplished through a series of strikes in the nickel bath. Scale up from laboratory parts to large components involved optimization of parameters such as pretreat time, current density, anode to cathode ratio and strike time.

  8. Hot rolling of thick uranium molybdenum alloys

    DOEpatents

    DeMint, Amy L.; Gooch, Jack G.

    2015-11-17

    Disclosed herein are processes for hot rolling billets of uranium that have been alloyed with about ten weight percent molybdenum to produce cold-rollable sheets that are about one hundred mils thick. In certain embodiments, the billets have a thickness of about 7/8 inch or greater. Disclosed processes typically involve a rolling schedule that includes a light rolling pass and at least one medium rolling pass. Processes may also include reheating the rolling stock and using one or more heavy rolling passes, and may include an annealing step.

  9. The Role of Molybdenum in Agricultural Plant Production

    PubMed Central

    KAISER, BRENT N.; GRIDLEY, KATE L.; NGAIRE BRADY, JOANNE; PHILLIPS, THOMAS; TYERMAN, STEPHEN D.

    2005-01-01

    • Background The importance of molybdenum for plant growth is disproportionate with respect to the absolute amounts required by most plants. Apart from Cu, Mo is the least abundant essential micronutrient found in most plant tissues and is often set as the base from which all other nutrients are compared and measured. Molybdenum is utilized by selected enzymes to carry out redox reactions. Enzymes that require molybdenum for activity include nitrate reductase, xanthine dehydrogenase, aldehyde oxidase and sulfite oxidase. • Scope Loss of Mo-dependent enzyme activity (directly or indirectly through low internal molybdenum levels) impacts upon plant development, in particular, those processes involving nitrogen metabolism and the synthesis of the phytohormones abscisic acid and indole-3 butyric acid. Currently, there is little information on how plants access molybdate from the soil solution and redistribute it within the plant. In this review, the role of molybdenum in plants is discussed, focusing on its current constraints in some agricultural situations and where increased molybdenum nutrition may aid in agricultural plant development and yields. • Conclusions Molybdenum deficiencies are considered rare in most agricultural cropping areas; however, the phenotype is often misdiagnosed and attributed to other downstream effects associated with its role in various enzymatic redox reactions. Molybdenum fertilization through foliar sprays can effectively supplement internal molybdenum deficiencies and rescue the activity of molybdoenzymes. The current understanding on how plants access molybdate from the soil solution or later redistribute it once in the plant is still unclear; however, plants have similar physiological molybdenum transport phenotypes to those found in prokaryotic systems. Thus, careful analysis of existing prokaryotic molybdate transport mechanisms, as well as a re-examination of know anion transport mechanisms present in plants, will help to

  10. Biosynthesis of the iron-molybdenum cofactor and the molybdenum cofactor in Klebsiella pneumoniae: effect of sulfur source

    SciTech Connect

    Ugalde, R.A.; Imperial, J.; Shah, V.K.; Brill, W.J.

    1985-12-01

    NifQ/sup -/ and Mol/sup -/ mutants of Klebsiella pneumoniae show an elevated molybdenum requirement for nitrogen fixation. Substitution of cystine for sulfate as the sulfur source in the medium reduced the molybdenum requirement of these mutants to levels required by the wild type. Cystine also increased the intracellular molybdenum accumulation of NifQ/sup -/ and Mol/sup -/ mutants. Cystine did not affect the molybdenum requirement or accumulation in wild-type K. pneumoniae. Sulfate transport and metabolism in K. pneumoniae were repressed by cystine. However, the effect of cystine on the molybdenum requirement could not be explained by an interaction between sulfate and molybdate at the transport level. The data show that cystine does not have a generalized effect on molybdenum metabolism. Millimolar concentrations of molybdate inhibited nitrogenase and nitrate reductase derepression with sulfate as the sulfur source, but not with cystine. The inhibition was the result of a specific antagonism of sulfate metabolism by molybdate. This study suggests that a sulfur donor and molybdenum interact at an early step in the biosynthesis of the iron-molybdenum cofactor. This interaction might occur nonenzymatically when the levels of the reactants are high.

  11. Cell biology of molybdenum in plants.

    PubMed

    Mendel, Ralf R

    2011-10-01

    The transition element molybdenum (Mo) is of essential importance for (nearly) all biological systems as it is required by enzymes catalyzing important reactions within the cell. The metal itself is biologically inactive unless it is complexed by a special cofactor. With the exception of bacterial nitrogenase, where Mo is a constituent of the FeMo-cofactor, Mo is bound to a pterin, thus forming the molybdenum cofactor (Moco) which is the active compound at the catalytic site of all other Mo-enzymes. In plants, the most prominent Mo-enzymes are nitrate reductase, sulfite oxidase, xanthine dehydrogenase, aldehyde oxidase, and the mitochondrial amidoxime reductase. The biosynthesis of Moco involves the complex interaction of six proteins and is a process of four steps, which also includes iron as well as copper in an indispensable way. After its synthesis, Moco is distributed to the apoproteins of Mo-enzymes by Moco-carrier/binding proteins that also participate in Moco-insertion into the cognate apoproteins. Xanthine dehydrogenase and aldehyde oxidase, but not the other Mo-enzymes, require a final step of posttranslational activation of their catalytic Mo-center for becoming active.

  12. Climax-Type Porphyry Molybdenum Deposits

    USGS Publications Warehouse

    Ludington, Steve; Plumlee, Geoffrey S.

    2009-01-01

    Climax-type porphyry molybdenum deposits, as defined here, are extremely rare; thirteen deposits are known, all in western North America and ranging in age from Late Cretaceous to mainly Tertiary. They are consistently found in a postsubduction, extensional tectonic setting and are invariably associated with A-type granites that formed after peak activity of a magmatic cycle. The deposits consist of ore shells of quartz-molybdenite stockwork veins that lie above and surrounding the apices of cupola-like, highly evolved, calc-alkaline granite and subvolcanic rhyolite-porphyry bodies. These plutons are invariably enriched in fluorine (commonly >1 percent), rubidium (commonly >500 parts per million), and niobium-tantalum (Nb commonly >50 parts per million). The deposits are relatively high grade (typically 0.1-0.3 percent Mo) and may be very large (typically 100-1,000 million tons). Molybdenum, as MoS2, is the primary commodity in all known deposits. The effect on surface-water quality owing to natural influx of water or sediment from a Climax-type mineralized area can extend many kilometers downstream from the mineralized area. Waste piles composed of quartz-silica-pyrite altered rocks will likely produce acidic drainage waters. The potential exists for concentrations of fluorine or rare metals in surface water and groundwater to exceed recommended limits for human consumption near both mined and unmined Climax-type deposits.

  13. Segregation of carbon in iron and molybdenum

    NASA Astrophysics Data System (ADS)

    Arabczyk, W.; Narkiewicz, U.

    1996-05-01

    The segregation of nitrogen, phosphorus, sulphur and carbon in iron causes the formation of FeXX bonds on the surface. The system metal (Fe(111),Mo(100))-carbon has been studied using the AES method. The bonds FeC observed for lower surface coverages were transformed to FeCC bonds for higher coverages and the interaction between iron atoms and carbon atoms decreased. In the case of molybdenum the two different adsorption states were observed without a formation of CC bonding. The enthalpy of segregation for both adsorption states for iron and molybdenum has been determined using the Langmuir-McLean equation. The enthalpy of carbon segregation at the first adsorption state (lower carbon coverages) was - 140 and - 68 kJ/mol for Fe(111) and Mo(100) surfaces, respectively, and for the second adsorption state - 60 and - 47 kJ/mol, respectively. The further increase of the carbon surface concentration caused the formation of 3D graphite on the Fe(111) surface and of carbide-like compounds on the Mo(100) surface.

  14. Boron modified molybdenum silicide and products

    DOEpatents

    Meyer, Mitchell K.; Akinc, Mufit

    1999-02-02

    A boron-modified molybdenum silicide material having the composition comprising about 80 to about 90 weight % Mo, about 10 to about 20 weight % Si, and about 0.1 to about 2 weight % B and a multiphase microstructure including Mo.sub.5 Si.sub.3 phase as at least one microstructural component effective to impart good high temperature creep resistance. The boron-modified molybdenum silicide material is fabricated into such products as electrical components, such as resistors and interconnects, that exhibit oxidation resistance to withstand high temperatures in service in air as a result of electrical power dissipation, electrical resistance heating elements that can withstand high temperatures in service in air and other oxygen-bearing atmospheres and can span greater distances than MoSi.sub.2 heating elements due to improved creep resistance, and high temperature structural members and other fabricated components that can withstand high temperatures in service in air or other oxygen-bearing atmospheres while retaining creep resistance associated with Mo.sub.5 Si.sub.3 for structural integrity.

  15. Boron modified molybdenum silicide and products

    DOEpatents

    Meyer, M.K.; Akinc, M.

    1999-02-02

    A boron-modified molybdenum silicide material is disclosed having the composition comprising about 80 to about 90 weight % Mo, about 10 to about 20 weight % Si, and about 0.1 to about 2 weight % B and a multiphase microstructure including Mo{sub 5}Si{sub 3} phase as at least one microstructural component effective to impart good high temperature creep resistance. The boron-modified molybdenum silicide material is fabricated into such products as electrical components, such as resistors and interconnects, that exhibit oxidation resistance to withstand high temperatures in service in air as a result of electrical power dissipation, electrical resistance heating elements that can withstand high temperatures in service in air and other oxygen-bearing atmospheres and can span greater distances than MoSi{sub 2} heating elements due to improved creep resistance, and high temperature structural members and other fabricated components that can withstand high temperatures in service in air or other oxygen-bearing atmospheres while retaining creep resistance associated with Mo{sub 5}Si{sub 3} for structural integrity. 7 figs.

  16. "Non-hydrolytic" sol-gel synthesis of molybdenum sulfides

    NASA Astrophysics Data System (ADS)

    Leidich, Saskia; Buechele, Dominique; Lauenstein, Raphael; Kluenker, Martin; Lind, Cora

    2016-10-01

    Non-hydrolytic sol-gel reactions provide a low temperature solution based synthetic approach to solid-state materials. In this paper, reactions between molybdenum chloride and hexamethyldisilthiane in chloroform were explored, which gave access to both MoS2 and Mo2S3 after heat treatment of as-recovered amorphous samples to 600-1000 °C. Interesting morphologies were obtained for MoS2, ranging from fused spherical particles to well-defined nanoplatelets and nanoflakes. Both 2H- and 3R-MoS2 were observed, which formed thin hexagonal and triangular platelets, respectively. The platelets exhibited thicknesses of 10-30 nm, which corresponds to 15-50 MoS2 layers. No attempts to prevent agglomeration were made, however, well separated platelets were observed for many samples. Heating at 1000 °C led to formation of Mo2S3 for samples that showed well-defined MoS2 at lower temperatures, while less crystalline samples had a tendency to retain the MoS2 structure.

  17. Chill block melt spinning of nickel-molybdenum alloys

    NASA Technical Reports Server (NTRS)

    Hemker, Kevin J.; Glasgow, Thomas K.

    1987-01-01

    Samples of Ni-Mo alloys ranging in composition from pure nickel to Ni-40 at. pct molybdenum were cast by the chill block melt-spinning rapid solidification technique and examined by optical metallography, X-ray diffraction, and microhardness testing. Casting difficulties were encountered with lean alloys, but richer alloys spread more readily on the casting wheel. Alloy microstructures for 5 to 37.5 at. pct molybdenum ribbons were primarily cellular/dendritic; microstructure feature size decreased with increasing molybdenum content. Extended solubility of molybdenum in gamma-nickel, with fcc lattice parameter increasing with composition to the 1.05 power, was observed up to 37/5 at. pct molybdenum. Substoichiometric Ni-Mo (delta) nucleated on the wheel side of the ribbons of compositions 35, 37.5, and 40 at. pct molybdenum. The amount of partitionless delta-phase thus formed increased with increasing molybdenum content and quench rate. This substoichiometric delta transformed readily to a fine structure gamma-delta mixture.

  18. Chill block melt spinning of nickel-molybdenum alloys

    NASA Technical Reports Server (NTRS)

    Hemker, Kevin J.; Glasgow, Thomas K.

    1987-01-01

    Samples of Ni-Mo alloys ranging in composition from pure nickel to Ni-40 at. pct molybdenum were cast by the chill block melt-spinning rapid solidification technique and examined by optical metallography, X-ray diffraction, and microhardness testing. Casting difficulties were encountered with lean alloys, but richer alloys spread more readily on the casting wheel. Alloy microstructures for 5 to 37.5 at. pct molybdenum ribbons were primarily cellular/dendritic; microstructure feature size decreased with increasing molybdenum content. Extended solubility of molybdenum in gamma-nickel, with fcc lattice parameter increasing with composition to the 1.05 power, was observed up to 37/5 at. pct molybdenum. Substoichiometric Ni-Mo (delta) nucleated on the wheel side of the ribbons of compositions 35, 37.5, and 40 at. pct molybdenum. The amount of partitionless delta-phase thus formed increased with increasing molybdenum content and quench rate. This substoichiometric delta transformed readily to a fine structure gamma-delta mixture.

  19. Atomic layer deposition of molybdenum oxide using bis(tert-butylimido)bis(dimethylamido) molybdenum

    SciTech Connect

    Bertuch, Adam Sundaram, Ganesh

    2014-01-15

    Molybdenum trioxide films have been deposited using thermal atomic layer deposition techniques with bis(tert-butylimido)bis(dimethylamido)molybdenum. Films were deposited at temperatures from 100 to 300 °C using ozone as the oxidant for the process. The Mo precursor was evaluated for thermal stability and volatility using thermogravimetric analysis and static vapor pressure measurements. Film properties were evaluated with ellipsometry, x-ray photoelectron spectroscopy, secondary ion mass spectroscopy, and secondary electron microscopy. The growth rate per cycle was determined to extend from 0.3 to 2.4 Å/cycle with <4% nonuniformity (1-sigma) with-in-wafer across a 150 mm wafer for the investigated temperature range.

  20. Spreading of liquid Silver and Silver-Molybdenum alloys on molybdenum substrates

    SciTech Connect

    Rauch, Nicole; Saiz, Eduardo; Tomsia, Antoni P.

    2002-08-01

    The spreading of liquid Ag and Ag-Mo alloys on molybdenum substrates has been studied using a drop-transfer setup. Even though initial spreading velocities as fast as {approx}1 m/s have been recorded in some experiments, a large variation in the spreading dynamics has been observed, and there is no unique relationship between the contact angle and the spreading velocity. This can be attributed to the formation of ridges at the triple junction, the movement of which controls spreading. The fastest spreading rates are consistent with results reported for low temperature liquids; these can be described using a molecular-kinetic model. Spreading kinetics and final contact angles were similar for pure silver and silver-molybdenum liquids.

  1. Pterin chemistry and its relationship to the molybdenum cofactor

    PubMed Central

    Basu, Partha; Burgmayer, Sharon J.N.

    2011-01-01

    The molybdenum cofactor is composed of a molybdenum coordinated by one or two rather complicated ligands known as either molybdopterin or pyranopterin. Pterin is one of a large family of bicyclic N-heterocycles called pteridines. Such molecules are widely found in Nature, having various forms to perform a variety of biological functions. This article describes the basic nomenclature of pterin, their biological roles, structure, chemical synthesis and redox reactivity. In addition, the biosynthesis of pterins and current models of the molybdenum cofactor are discussed. PMID:21607119

  2. Field method for the determination of molybdenum in plants

    USGS Publications Warehouse

    Reichen, Laura E.; Ward, F.N.

    1951-01-01

    Fresh plant material is ashed directly by heating in nickel or platinum dishes over a "flame. An acid solution of 25 milligrams of ash is treated with stannous chloride and potassium thiocyanate. The amber-colored molybdenum thiocyanate complex ion is extracted with isopropyl ether, and the intensity of the color of the ether layer over a sample solution is compared with the ether layer over standard molybdenum solutions treated similarly. Field determinations can be made quickly and the method requires no special equipment. As little as 0.25 microgram or 0.001 percent molybdenum can be determined in plant ash.

  3. Mechanical properties of oxide dispersion strengthened (ODS) molybdenum alloys

    SciTech Connect

    Bianco, R.; Buckman, R.W. Jr.

    1998-03-01

    Oxide dispersion strengthened molybdenum, Mo-ODS, developed by a proprietary powder metallurgy process, exhibits a creep rupture life at 0.65T{sub m} (1,600 C) of three to five orders of magnitude greater than unalloyed molybdenum, while maintaining ductile fracture behavior at temperatures significantly below room temperature. In comparison, the creep rupture life of the Mo-50Re solid solution strengthened alloy at 1,600 C is only an order of magnitude greater than unalloyed molybdenum. The results of microstructural characterization and thermal stability and mechanical property testing are discussed.

  4. Superconducting properties of evaporated copper molybdenum sulfide films

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Chi, K. C.; Dillon, R. O.; Bunshah, R. F.; Alterovitz, S. A.

    1978-01-01

    Films of copper molybdenum sulfide were produced by coevaporation. Those that were superconducting contained only the ternary compound and free molybdenum. The range of copper content in the ternary compound was as large as that in polycrystalline material, that is, it includes either phase alone, or a mixture of the two phases of this material. This is in contrast with sputtered materials where copper concentration has been limited to a narrower range. The upper critical field and the critical current were measured as functions of external magnetic field, and found to be similar to those of sputtered copper molybdenum sulfide, when the comparison was made for samples having the same amount of copper.

  5. Superconducting properties of evaporated copper molybdenum sulfide films

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Chi, K. C.; Dillon, R. O.; Bunshah, R. F.; Alterovitz, S. A.

    1978-01-01

    Films of copper molybdenum sulfide were produced by coevaporation. Those that were superconducting contained only the ternary compound and free molybdenum. The range of copper content in the ternary compound was as large as that in polycrystalline material, that is, it includes either phase alone, or a mixture of the two phases of this material. This is in contrast with sputtered materials where copper concentration has been limited to a narrower range. The upper critical field and the critical current were measured as functions of external magnetic field, and found to be similar to those of sputtered copper molybdenum sulfide, when the comparison was made for samples having the same amount of copper.

  6. Recovery and upgrading bovine rumen protein by extrusion: effect of lipid content on protein disulphide cross-linking, solubility and molecular weight.

    PubMed

    Vaz, L C M A; Arêas, J A G

    2010-01-01

    Bovine rumen protein with two levels of residual lipids (1.9% or 3.8%) was subjected to thermoplastic extrusion under different temperatures and moisture contents. Protein solubility in different buffers, disulphide cross-linking and molecular weight distribution were determined on the extrudates. After extrusion, samples with 1.9% residual lipids content had a higher concentration of protein insoluble by undetermined forces, irrespective of feed moisture and processing temperature used. Lipid content of 3.8% in the feed material resulted in more protein participating in the extrudate network through non-covalent interactions (hydrophobic and electrostatic) and disulphide bonds. A small dependency of the extrusion process on moisture and temperature and a marked dependency on lipid content, especially phospholipid, was observed, Electrophoresis under non-reducing conditions showed that protein extrusion with low feed moisture promoted high molecular breakdown inside the barrel, probably due to intense shear force, and further protein aggregation at the die end.

  7. The extended family of hexagonal molybdenum oxide

    SciTech Connect

    Hartl, Monika; Daemen, Luke; Lunk, J H; Hartl, H; Frisk, A T; Shendervich, I; Mauder, D; Feist, M; Eckelt, R

    2009-01-01

    Over the last 40 years, a large number of isostructural compounds in the system MoO{sub 3}-NH{sub 3}-H{sub 2}O have been published. The reported molecular formulae of 'hexagonal molybdenum oxide' (HEMO) varied from MoO{sub 3}, MoO{sub 3} {center_dot} 0.33NH{sub 3}, MoO{sub 3} {center_dot} nH{sub 2}O (0.09 {le} n {le} 0.69) to MoO{sub 3} {center_dot} mNH{sub 3} {center_dot} nH{sub 2}O (0.09 {le} m {le} 0.20; 0.18 {le} n {le} 0.60). Samples, prepared by the acidification route, were investigated using thermal analysis coupled on-line to a mass spectrometer for evolved gas analysis; X-ray powder diffraction; Fourier Transform Infrared, Raman and Magic-Angle-Spinning {sup 1}H-NMR spectroscopy; Incoherent Inelastic Neutron Scattering. The X-ray study of a selected monocrystal confirmed the presence of the well-known framework of edge-sharing MoO{sub 6} octahedra: Space group P6{sub 3}/m, a = 10.527(1), c =3.7245(7) {angstrom}, {gamma} = 120{sup o}. The structure of the synthesized samples can best be described by the structural formula (NH{sub 4})[Mo{sub x}{open_square}{sub 1/2+p/2}(O{sub 3x + 1/2-p/2})(OH){sub p}] {center_dot} yH{sub 2}O (x 5.9-7.1; p {approx} 0.1; y = 1.2-2.6), which is consistent with the existence of one vacancy for 12-15 molybdenum sites. The 'chimie douce' reaction of MoO{sub 3} {center_dot} 0.155NH{sub 3} {center_dot} 0.440H{sub 2}O with a 1:1 mixture of NO/NO{sub 2} at 100 C resulted in the synthesis of MoO{sub 3} {center_dot} 0.539H{sub 2}O. Tailored nano-sized molybdenum powders can be produced using HEMO as precursor.

  8. Molybdenum enzymes, their maturation and molybdenum cofactor biosynthesis in Escherichia coli.

    PubMed

    Iobbi-Nivol, Chantal; Leimkühler, Silke

    2013-01-01

    Molybdenum cofactor (Moco) biosynthesis is an ancient, ubiquitous, and highly conserved pathway leading to the biochemical activation of molybdenum. Moco is the essential component of a group of redox enzymes, which are diverse in terms of their phylogenetic distribution and their architectures, both at the overall level and in their catalytic geometry. A wide variety of transformations are catalyzed by these enzymes at carbon, sulfur and nitrogen atoms, which include the transfer of an oxo group or two electrons to or from the substrate. More than 50 molybdoenzymes were identified in bacteria to date. In molybdoenzymes Mo is coordinated to a dithiolene group on the 6-alkyl side chain of a pterin called molybdopterin (MPT). The biosynthesis of Moco can be divided into four general steps in bacteria: 1) formation of the cyclic pyranopterin monophosphate, 2) formation of MPT, 3) insertion of molybdenum into molybdopterin to form Moco, and 4) additional modification of Moco with the attachment of GMP or CMP to the phosphate group of MPT, forming the dinucleotide variant of Moco. This review will focus on molybdoenzymes, the biosynthesis of Moco, and its incorporation into specific target proteins focusing on Escherichia coli. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Novel application of S-nitrosoglutathione-Sepharose to identify proteins that are potential targets for S-nitrosoglutathione-induced mixed-disulphide formation.

    PubMed Central

    Klatt, P; Pineda Molina , E; Pérez-Sala, D; Lamas, S

    2000-01-01

    Site-specific S-glutathionylation is emerging as a novel mechanism by which S-nitrosoglutathione (GSNO) may modify functionally important protein thiols. Here, we show that GSNO-Sepharose mimicks site-specific S-glutathionylation of the transcription factors c-Jun and p50 by free GSNO in vitro. Both c-Jun and p50 were found to bind to immobilized GSNO through the formation of a mixed disulphide, involving a conserved cysteine residue located in the DNA-binding domains of these transcription factors. Furthermore, we show that c-Jun, p50, glycogen phosphorylase b, glyceraldehyde-3-phosphate dehydrogenase, creatine kinase, glutaredoxin and caspase-3 can be precipitated from a mixture of purified thiol-containing proteins by the formation of a mixed-disulphide bond with GSNO-Sepharose. With few exceptions, protein binding to this matrix correlated well with the susceptibility of the investigated proteins to undergo GSNO- but not diamide-induced mixed-disulphide formation in vitro. Finally, it is shown that covalent GSNO-Sepharose chromatography of HeLa cell nuclear extracts results in the enrichment of proteins which incorporate glutathione in response to GSNO treatment. As suggested by DNA-binding assays, this group of nuclear proteins include the transcription factors activator protein-1, nuclear factor-kappaB and cAMP-response-element-binding protein. In conclusion, we introduce GSNO-Sepharose as a probe for site-specific S-glutathionylation and as a novel and potentially useful tool to isolate and identify proteins which are candidate targets for GSNO-induced mixed-disulphide formation. PMID:10880356

  10. Role of proline, cysteine and a disulphide bridge in the structure and activity of the anti-microbial peptide gaegurin 5.

    PubMed Central

    Park, Sang-Ho; Kim, Hyung-Eun; Kim, Chi-Man; Yun, Hee-Jeong; Choi, Eung-Chil; Lee, Bong-Jin

    2002-01-01

    Gaegurin 5 (GGN5) is a cationic 24-residue anti-microbial peptide isolated from the skin of a Korean frog, Rana rugosa. It contains a central proline residue and an intra-residue disulphide bridge in its C-terminus, which are common to the anti-microbial peptides found in Ranidae. We determined the solution structure of GGN5 bound to SDS micelles for the first time and investigated the role of proline, cysteine and a disulphide bridge on the structure and activity of GGN5. GGN5 adopts an amphipathic alpha-helical structure spanning residues 3-20 kinked around Pro-14, which allows the hydrophobic residues to reside in the concave helical region, and a disulphide-bridged loop-like conformation in its C-terminus. By replacement of proline with alanine (PAGGN5), a straight and rigid helix was formed in the central region and was more stable than the kinked helix. Reduction of a disulphide bridge in the C-terminus (GGN5SH) maintained the loosely ordered loop-like conformation, while the replacement of two cysteines with serines (CSGGN5) caused the C-terminal conformation to be completely disordered. The magnitude of anti-microbial activity of the peptides was closely related to their helical stability in the order PAGGN5>GGN5>GGN5SH>CSGGN5, suggesting that the helical stability of the peptides is important for anti-microbial activity. On the other hand, the significant increase of haemolytic activity of PAGGN5 implies that a helical kink of GGN5 could be involved in the selectivity of target cells. The location of GGN5 and PAGGN5, analysed using paramagnetic probes, was mainly at the surface of SDS micelles, although the location of the N-terminal region was slightly different between them. PMID:12164787

  11. Synthesis, Characterisation, and Evaluation of a Cross-Linked Disulphide Amide-Anhydride-Containing Polymer Based on Cysteine for Colonic Drug Delivery

    PubMed Central

    Lim, Vuanghao; Peh, Kok Khiang; Sahudin, Shariza

    2013-01-01

    The use of disulphide polymers, a low redox potential responsive delivery, is one strategy for targeting drugs to the colon so that they are specifically released there. The objective of this study was to synthesise a new cross-linked disulphide-containing polymer based on the amino acid cysteine as a colon drug delivery system and to evaluate the efficiency of the polymers for colon targeted drug delivery under the condition of a low redox potential. The disulphide cross-linked polymers were synthesised via air oxidation of 1,2-ethanedithiol and 3-mercapto-N-2-(3-mercaptopropionamide)-3-mercapto propionic anhydride (trithiol monomers) using different ratio combinations. Four types of polymers were synthesised: P10, P11, P151, and P15. All compounds synthesised were characterised by NMR, IR, LC-MS, CHNS analysis, Raman spectrometry, SEM-EDX, and elemental mapping. The synthesised polymers were evaluated in chemical reduction studies that were performed in zinc/acetic acid solution. The suitability of each polymer for use in colon-targeted drug delivery was investigated in vitro using simulated conditions. Chemical reduction studies showed that all polymers were reduced after 0.5–1.0 h, but different polymers had different thiol concentrations. The bacterial degradation studies showed that the polymers were biodegraded in the anaerobic colonic bacterial medium. Degradation was most pronounced for polymer P15. This result complements the general consensus that biodegradability depends on the swellability of polymers in an aqueous environment. Overall, these results suggest that the cross-linked disulphide-containing polymers described herein could be used as coatings for drugs delivered to the colon. PMID:24351841

  12. Novel application of S-nitrosoglutathione-Sepharose to identify proteins that are potential targets for S-nitrosoglutathione-induced mixed-disulphide formation.

    PubMed

    Klatt, P; Pineda Molina, E; Pérez-Sala, D; Lamas, S

    2000-07-15

    Site-specific S-glutathionylation is emerging as a novel mechanism by which S-nitrosoglutathione (GSNO) may modify functionally important protein thiols. Here, we show that GSNO-Sepharose mimicks site-specific S-glutathionylation of the transcription factors c-Jun and p50 by free GSNO in vitro. Both c-Jun and p50 were found to bind to immobilized GSNO through the formation of a mixed disulphide, involving a conserved cysteine residue located in the DNA-binding domains of these transcription factors. Furthermore, we show that c-Jun, p50, glycogen phosphorylase b, glyceraldehyde-3-phosphate dehydrogenase, creatine kinase, glutaredoxin and caspase-3 can be precipitated from a mixture of purified thiol-containing proteins by the formation of a mixed-disulphide bond with GSNO-Sepharose. With few exceptions, protein binding to this matrix correlated well with the susceptibility of the investigated proteins to undergo GSNO- but not diamide-induced mixed-disulphide formation in vitro. Finally, it is shown that covalent GSNO-Sepharose chromatography of HeLa cell nuclear extracts results in the enrichment of proteins which incorporate glutathione in response to GSNO treatment. As suggested by DNA-binding assays, this group of nuclear proteins include the transcription factors activator protein-1, nuclear factor-kappaB and cAMP-response-element-binding protein. In conclusion, we introduce GSNO-Sepharose as a probe for site-specific S-glutathionylation and as a novel and potentially useful tool to isolate and identify proteins which are candidate targets for GSNO-induced mixed-disulphide formation.

  13. Synthesis, characterisation, and evaluation of a cross-linked disulphide amide-anhydride-containing polymer based on cysteine for colonic drug delivery.

    PubMed

    Lim, Vuanghao; Peh, Kok Khiang; Sahudin, Shariza

    2013-12-18

    The use of disulphide polymers, a low redox potential responsive delivery, is one strategy for targeting drugs to the colon so that they are specifically released there. The objective of this study was to synthesise a new cross-linked disulphide-containing polymer based on the amino acid cysteine as a colon drug delivery system and to evaluate the efficiency of the polymers for colon targeted drug delivery under the condition of a low redox potential. The disulphide cross-linked polymers were synthesised via air oxidation of 1,2-ethanedithiol and 3-mercapto-N-2-(3-mercaptopropionamide)-3-mercapto propionic anhydride (trithiol monomers) using different ratio combinations. Four types of polymers were synthesised: P10, P11, P151, and P15. All compounds synthesised were characterised by NMR, IR, LC-MS, CHNS analysis, Raman spectrometry, SEM-EDX, and elemental mapping. The synthesised polymers were evaluated in chemical reduction studies that were performed in zinc/acetic acid solution. The suitability of each polymer for use in colon-targeted drug delivery was investigated in vitro using simulated conditions. Chemical reduction studies showed that all polymers were reduced after 0.5-1.0 h, but different polymers had different thiol concentrations. The bacterial degradation studies showed that the polymers were biodegraded in the anaerobic colonic bacterial medium. Degradation was most pronounced for polymer P15. This result complements the general consensus that biodegradability depends on the swellability of polymers in an aqueous environment. Overall, these results suggest that the cross-linked disulphide-containing polymers described herein could be used as coatings for drugs delivered to the colon.

  14. 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

  15. Enhanced dispersion and the reactivity of atomically thin Rh layers supported by molybdenum oxide films

    NASA Astrophysics Data System (ADS)

    Szenti, Imre; Bugyi, László; Kónya, Zoltán

    2015-11-01

    The behavior of rhodium layers deposited on oxidized, 0.15-20.0 ML thick Mo films formed on a nearly stoichiometric TiO2(110) single crystal was characterized by AES, TPD and work function (WF) measurements. The oxidation of 0.15-2.7 ML thick Mo deposits was performed via the redox reaction with the titania support at 1000 K. Molybdenum oxide supports of MoO3 and MoO2 surface composition were formed by the oxidation of 20 ML thick Mo multilayers by O2 at 650 K and 1000 K, respectively. Rh grows in a layer-by-layer fashion on a mixed titanium-molybdenum oxide produced in the reaction between titania and 0.15 ML Mo, corresponding to a considerably enhanced dispersion of rhodium as compared with that on the clean TiO2(110). The surface reactivity of Rh layers supported by molybdenum oxides as a function of pre-annealing temperature was followed by carbon monoxide adsorption-desorption cycles. The CO uptake of a 0.4 ML thick Rh film formed on the MoO3 support was strongly suppressed at 300 K, indicating the encapsulation of rhodium with MoOX species of low surface free energy. The CO adsorption capability of rhodium particles supported by both MoO3 and MoO2 layers was eliminated due to pre-annealing at 600 K, related to the extended decoration of metal particles by MoOX moiety. The encapsulation of the rhodium films proceeded above 600 K on both supports, and annealing to 1000 K resulted in nearly equal WF values, indicating the formation of MoOX overlayers of similar surface composition close to MoO2. AES depth profiles revealed that the 0.4 ML thick Rh deposits covered by MoOX at 1000 K preserved their island structure.

  16. Kinetic and thermodynamic consequences of the removal of the Cys-77-Cys-123 disulphide bond for the folding of TEM-1 beta-lactamase.

    PubMed Central

    Vanhove, M; Guillaume, G; Ledent, P; Richards, J H; Pain, R H; Frère, J M

    1997-01-01

    Class A beta-lactamases of the TEM family contain a single disulphide bond which connects cysteine residues 77 and 123. To clarify the possible role of the disulphide bond in the stability and folding kinetics of the TEM-1 beta-lactamase, this bond was removed by introducing a Cys-77-->Ser mutation, and the enzymically active mutant protein was studied by reversible guanidine hydrochloride-induced denaturation. The unfolding and refolding rates were monitored using tryptophan fluorescence. At low guanidine hydrochloride concentrations, the refolding of the wild-type and mutant enzymes followed biphasic time courses. The characteristics of the two phases were not significantly affected by the mutation. Double-jump experiments, in which the protein was unfolded in a high concentration of guanidine hydrochloride for a short time period and then refolded by diluting out the denaturant, indicated that, for both the wild-type and mutant enzymes, the two refolding phases could be ascribed to proline isomerization reactions. Equilibrium unfolding experiments monitored by fluorescence spectroscopy and far-UV CD indicated a three-state mechanism (N<-->H<--U). Both the folded mutant protein (N) and, to a lesser extent the thermodynamically stable intermediate, H. were destabilized relative to the fully unfolded state, U. Removal of the disulphide bond resulted in a decrease of 14.2 kJ/mol (3.4 kcal/mol) in the global free energy of stabilization. Similarly, the mutation also induced a drastic increase in the rate of thermal inactivation. PMID:9020874

  17. The conserved His8 of the Moloney murine leukemia virus Env SU subunit directs the activity of the SU-TM disulphide bond isomerase

    SciTech Connect

    Li Kejun; Zhang, Shujing; Kronqvist, Malin; Ekstroem, Maria; Wallin, Michael; Garoff, Henrik . E-mail: henrik.garoff@cbt.ki.se

    2007-04-25

    Murine leukemia virus (MLV) fusion is controlled by isomerization of the disulphide bond between the receptor-binding surface (SU) and fusion-active transmembrane subunits of the Env-complex. The bond is in SU linked to a CXXC motif. This carries a free thiol that upon receptor binding can be activated (ionized) to attack the disulphide and rearrange it into a disulphide isomer within the motif. To find out whether His8 in the conserved SPHQ sequence of Env directs thiol activation, we analyzed its ionization in MLV vectors with wtEnv and Env with His8 deleted or substituted for Tyr or Arg, which partially or completely arrests fusion. The ionization was monitored by following the pH effect on isomerization in vitro by Ca{sup 2+} depletion or in vivo by receptor binding. We found that wtEnv isomerized optimally at slightly basic pH whereas the partially active mutant required higher and the inactive mutants still higher pH. This suggests that His8 directs the ionization of the CXXC thiol.

  18. Environmental behavior of two molybdenum porphyry systems

    USGS Publications Warehouse

    Tuttle, M.L.W.; Wanty, R.B.; Berger, B.R.

    2004-01-01

    Our study focuses on the geology, hydrology, and geochemistry of a variety of molybdenum (Mo) porphyry systems. The systems are either high fluorine, granite, Climax-type, systems (e.g. Mount Emmons/ Redwell Mo deposit, Colorado and Questa Mo deposit, New Mexico) or low fluorine granodiorite systems (e.g. Buckingham Stockwork Mo deposit, Battle Mountain, Nevada and Cannivan Gulch Mo deposit, Montana). The water quality of streams, natural springs, mine discharge, and ground water from drill holes were assessed in the region of these deposits. The ultimate goal of our study is to understand the environmental behavior of these Mo porphyry systems in the context of geologic setting, hydrologic regime, and climate.

  19. Advances in rechargeable lithium molybdenum disulfide batteries

    NASA Technical Reports Server (NTRS)

    Brandt, K.; Stiles, J. A. R.

    1985-01-01

    The lithium molybdenum disulfide system as demonstrated in a C size cell, offers performance characteristics for applications where light weight and low volume are important. A gravimetric energy density of 90 watt hours per kilogram can be achieved in a C size cell package. The combination of charge retention capabilities, high energy density and a state of charge indicator in a rechargeable cell provides power package for a wide range of devices. The system overcomes the memory effect in Nicads where the full capacity of the battery cannot be utilized unless it was utilized on previous cycles. The development of cells with an advanced electrolyte formulation led to an improved rate capability especially at low temperatures and to a significantly improved life cycle.

  20. Molybdenum disulfide and water interaction parameters.

    PubMed

    Heiranian, Mohammad; Wu, Yanbin; Aluru, Narayana R

    2017-09-14

    Understanding the interaction between water and molybdenum disulfide (MoS2) is of crucial importance to investigate the physics of various applications involving MoS2 and water interfaces. An accurate force field is required to describe water and MoS2 interactions. In this work, water-MoS2 force field parameters are derived using the high-accuracy random phase approximation (RPA) method and validated by comparing to experiments. The parameters obtained from the RPA method result in water-MoS2 interface properties (solid-liquid work of adhesion) in good comparison to the experimental measurements. An accurate description of MoS2-water interaction will facilitate the study of MoS2 in applications such as DNA sequencing, sea water desalination, and power generation.

  1. Molybdenum disulfide and water interaction parameters

    NASA Astrophysics Data System (ADS)

    Heiranian, Mohammad; Wu, Yanbin; Aluru, Narayana R.

    2017-09-01

    Understanding the interaction between water and molybdenum disulfide (MoS2) is of crucial importance to investigate the physics of various applications involving MoS2 and water interfaces. An accurate force field is required to describe water and MoS2 interactions. In this work, water-MoS2 force field parameters are derived using the high-accuracy random phase approximation (RPA) method and validated by comparing to experiments. The parameters obtained from the RPA method result in water-MoS2 interface properties (solid-liquid work of adhesion) in good comparison to the experimental measurements. An accurate description of MoS2-water interaction will facilitate the study of MoS2 in applications such as DNA sequencing, sea water desalination, and power generation.

  2. Ultrafast response of monolayer molybdenum disulfide photodetectors

    PubMed Central

    Wang, Haining; Zhang, Changjian; Chan, Weimin; Tiwari, Sandip; Rana, Farhan

    2015-01-01

    The strong light emission and absorption exhibited by single atomic layer transitional metal dichalcogenides in the visible to near-infrared wavelength range make them attractive for optoelectronic applications. In this work, using two-pulse photovoltage correlation technique, we show that monolayer molybdenum disulfide photodetector can have intrinsic response times as short as 3 ps implying photodetection bandwidths as wide as 300 GHz. The fast photodetector response is a result of the short electron–hole and exciton lifetimes in this material. Recombination of photoexcited carriers in most two-dimensional metal dichalcogenides is dominated by nonradiative processes, most notable among which is Auger scattering. The fast response time, and the ease of fabrication of these devices, make them interesting for low-cost ultrafast optical communication links. PMID:26572726

  3. Measured oscillator strengths in singly ionized molybdenum

    NASA Astrophysics Data System (ADS)

    Mayo-García, R.; Aragón, C.; Aguilera, J. A.; Ortiz, M.

    2015-11-01

    In this article, 112 oscillator strengths from Mo II have been measured, 79 of which for the first time. The radiative parameters have been obtained by laser-induced breakdown spectroscopy (LIBS). The plasma is produced from a fused glass sample prepared from molybdenum oxide with a Mo atomic concentration of 0.1%. The plasma evolved in air at atmospheric pressure, and measurements were carried out with the following plasma parameters: an electron density of (2.5+/- 0.1)\\cdot {10}17 cm-3 and an electron temperature of 14,400+/- 200 K. In these conditions, a local thermodynamic equilibrium environment and an optically thin plasma were confirmed for the measurements. The relative intensities were placed on an absolute scale by combining branching fractions with the measured lifetimes and by comparing well-known lines using the plasma temperature. Comparisons were made to previously obtained experimental and theoretical values wherever possible.

  4. [Simultaneous determination of iron and molybdenum by extraction catalytic spectrophotometry].

    PubMed

    Zhu, Qing-ren; Sun, Deng-ming; Wang, Li

    2002-12-01

    In this paper, a new extraction catalytic spectrophotometric method for the simultaneous determination of iron and molybdenum has been studied. The method is based on the difference of the reaction rate of iron(III) and molybdenum(VI) catalyzed oxidation of o-aminophenol by hydrogen peroxide in weak acidic medium at pH 5.5. The reaction time, concentration of o-aminophenol in aqueous phase and degree of reaction are controlled by extraction equilibrium. The absorbance of organic phase is measured at 424 nm. The linear ranges of the method are 0.010-0.30 microgram.mL-1 (for iron) and 0.50-2.0 micrograms.mL-1 (for molybdenum). The method has been applied to the simultaneous determination of iron and molybdenum in soybean with satisfactory results.

  5. Improved molybdenum disulfide-silver motor brushes have extended life

    NASA Technical Reports Server (NTRS)

    Horton, J. C.; King, H. M.

    1964-01-01

    Motor brushes of proper quantities of molybdenum disulfide and copper or silver are manufactured by sintering techniques. Graphite molds are used. These brushes operate satisfactorily for long periods in normal atmosphere or in a high-vacuum environment.

  6. Electroplating and stripping copper on molybdenum and niobium

    NASA Technical Reports Server (NTRS)

    Power, J. L.

    1978-01-01

    Molybdenum and niobium are often electroplated and subsequently stripped of copper. Since general standard plating techniques produce poor quality coatings, general procedures have been optimized and specified to give good results.

  7. Synthesis of Dinitrogen and Dihydrogen Complexes of Molybdenum.

    ERIC Educational Resources Information Center

    Archer, Leonard J.; And Others

    1981-01-01

    Presents background information, safety notes, and laboratory procedures for synthesizing dinitrogen and dihydrogen complexes of molybdenum. The one-step method described is suitable for advanced inorganic chemistry classes. (SK)

  8. High Molybdenum availability for evolution in a Mesoproterozoic lacustrine environment.

    PubMed

    Parnell, John; Spinks, Samuel; Andrews, Steven; Thayalan, Wanethon; Bowden, Stephen

    2015-05-19

    Trace metal data for Proterozoic marine euxinic sediments imply that the expansion of nitrogen-fixing cyanobacteria and diversification of eukaryotes were delayed while the availability of bioessential metals such as molybdenum in the ocean was limited. However, there is increasing recognition that the Mesoproterozoic evolution of nitrogen fixation and eukaryotic life may have been promoted in marginal marine and terrestrial environments, including lakes, rather than in the deep ocean. Molybdenum availability is critical to life in lakes, just as it is in the oceans. It is, therefore, important to assess molybdenum availability to the lacustrine environment in the Mesoproterozoic. Here we show that the flux of molybdenum to a Mesoproterozoic lake was 1 to 2 orders of magnitude greater than typical fluxes in the modern and ancient marine environment. Thus, there was no barrier to availability to prevent evolution in the terrestrial environment, in contrast to the nutrient-limited Mesoproterozoic oceans.

  9. Molybdenum-A Key Component of Metal Alloys

    USGS Publications Warehouse

    Kropschot, S.J.

    2010-01-01

    Molybdenum, whose chemical symbol is Mo, was first recognized as an element in 1778. Until that time, the mineral molybdenite-the most important source of molybdenum-was believed to be a lead mineral because of its metallic gray color, greasy feel, and softness. In the late 19th century, French metallurgists discovered that molybdenum, when alloyed (mixed) with steel in small quantities, creates a substance that is remarkably tougher than steel alone and is highly resistant to heat. The alloy was found to be ideal for making tools and armor plate. Today, the most common use of molybdenum is as an alloying agent in stainless steel, alloy steels, and superalloys to enhance hardness, strength, and resistance to corrosion.

  10. Polarographic determination of tungsten and molybdenum in sedimentary rocks

    SciTech Connect

    Vakhobova, R.U.; Lykova, F.P.; Milyavskii, Yu. S.; Rachinskaya, G.F.

    1985-12-01

    In order to determine microamounts of tungsten and molybdenum, one the most sensitive versions of polarography is used in this paper, called catalytic currents. In the development of a procedure for the determination of tungsten and molybdenum in geochemical items, the reduction of hydroxylamine (HA) is used, catalyzed by tungsten and molybdenum compounds in the presence of pyrocatechol, as on a background of dicarboxylic acids and hydroxy acids the HA reduction half-wave potentials, catalyzed by these elements, coincide. The investigations were conducted on a PPT-1 polarograph in the classical regime in a thermostatically controlled cell with a mercury dripping electrode and a saturated calomel comparison electrode. The authors develop a procedure for the simultaneous determination of n.10/sup -5/-n.10/sup -4/% of tungsten and molybdenum in sedimentary rocks.

  11. Electroplating and stripping copper on molybdenum and niobium

    NASA Technical Reports Server (NTRS)

    Power, J. L.

    1978-01-01

    Molybdenum and niobium are often electroplated and subsequently stripped of copper. Since general standard plating techniques produce poor quality coatings, general procedures have been optimized and specified to give good results.

  12. Synthesis of Dinitrogen and Dihydrogen Complexes of Molybdenum.

    ERIC Educational Resources Information Center

    Archer, Leonard J.; And Others

    1981-01-01

    Presents background information, safety notes, and laboratory procedures for synthesizing dinitrogen and dihydrogen complexes of molybdenum. The one-step method described is suitable for advanced inorganic chemistry classes. (SK)

  13. High Molybdenum availability for evolution in a Mesoproterozoic lacustrine environment

    NASA Astrophysics Data System (ADS)

    Parnell, John; Spinks, Samuel; Andrews, Steven; Thayalan, Wanethon; Bowden, Stephen

    2015-05-01

    Trace metal data for Proterozoic marine euxinic sediments imply that the expansion of nitrogen-fixing cyanobacteria and diversification of eukaryotes were delayed while the availability of bioessential metals such as molybdenum in the ocean was limited. However, there is increasing recognition that the Mesoproterozoic evolution of nitrogen fixation and eukaryotic life may have been promoted in marginal marine and terrestrial environments, including lakes, rather than in the deep ocean. Molybdenum availability is critical to life in lakes, just as it is in the oceans. It is, therefore, important to assess molybdenum availability to the lacustrine environment in the Mesoproterozoic. Here we show that the flux of molybdenum to a Mesoproterozoic lake was 1 to 2 orders of magnitude greater than typical fluxes in the modern and ancient marine environment. Thus, there was no barrier to availability to prevent evolution in the terrestrial environment, in contrast to the nutrient-limited Mesoproterozoic oceans.

  14. Oxidation characteristics of molybdenum-zirconium oxide cermets

    NASA Technical Reports Server (NTRS)

    Heitzinger, B.

    1984-01-01

    The oxidation of molybdenum is affected by the factors of temperature, the oxygen pressure in the oxidizing atmosphere, and the time of exposure. Studies of the oxidation characteristics of Mo show that the oxidation rate increases strongly when the temperature exceeds 600 C. Investigations of the behavior of cermets with various percentages of zirconium oxide are discussed, taking into account oxidation conditions at temperatures under and above the melting point of molybdenum trioxide.

  15. Isotopically Modified Molybdenum: Production for Application in Nuclear Energy

    NASA Astrophysics Data System (ADS)

    Smirnov, A. Yu.; Bonarev, A. K.; Sulaberidze, G. A.; Borisevich, V. D.; Kulikov, G. G.; Shmelev, A. N.

    The possibility to use the isotopically modified molybdenum as a constructive material for the fuel rods of light water and fast reactors is discussed. The calculations demonstrate that the isotopically modified molybdenum with an average neutron absorption cross-section comparable to that of zirconium can be obtained with the reasonable for practice cost by a cascade of gas centrifuges, specially designed for separation of non-uranium isotopes.

  16. Oxidation-resistance Mechanism and Other Properties of Molybdenum Disilicide

    NASA Technical Reports Server (NTRS)

    Maxwell, W A

    1952-01-01

    The outstanding oxidation resistance of molybdenum disilicide at 2400 F and above was found to depend on the formation of a protective siliceous coating which a-cristobalie has been identified. Molybdenum disilicide is not inherently resistant to oxidation and in powdered form burns at low temperatures.Melting and casting experiments have demonstrated the decomposition of the material at the melting point. The room-temperature modulus of elasticity has been determined and electric-resistivity data are given to 2000 F.

  17. A rate-dependent constitutive model for molybdenum

    NASA Astrophysics Data System (ADS)

    Steinberg, Daniel J.

    1994-07-01

    The Steinberg-Guinan-Lund rate-dependent constitutive model has been successfully applied to molybdenum. The model reproduces yield strength vs strain-rate and temperature data and also successfully simulates rate-dependent phenomena, such as shock-smearing, precursor decay, and precursor on reshock, as observed in one-dimensional gas-gun experiments. The spall strength of molybdenum was determined to be 1.5 GPa.

  18. A study of the mechanisms of hydrogen embrittlement in molybdenum

    NASA Technical Reports Server (NTRS)

    Taheri, M.

    1978-01-01

    The mechanical properties of polycrystalline molybdenum samples in both the 'as annealed' and hydrogenized conditions were studied. The results indicate that hydrogen does not alter the yield stress of samples significantly although it reduces both the ultimate tensile strength and the ductility considerably. Fractographic study of samples shows a tendency to intercrystalline cracking of the hydrogenised molybdenum at low temperatures. In the light of the results, a mechanism involving grain boundary weakening is suggested.

  19. Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

    DOEpatents

    Lowden, R.A.

    1994-04-05

    A process for chemical vapor deposition of crystalline silicon nitride is described which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and thermally decomposing the mixture to deposit onto the substrate a coating comprising crystalline silicon nitride containing a dispersion of molybdenum silicide. 5 figures.

  20. A study of the mechanisms of hydrogen embrittlement in molybdenum

    NASA Technical Reports Server (NTRS)

    Taheri, M.

    1978-01-01

    The mechanical properties of polycrystalline molybdenum samples in both the 'as annealed' and hydrogenized conditions were studied. The results indicate that hydrogen does not alter the yield stress of samples significantly although it reduces both the ultimate tensile strength and the ductility considerably. Fractographic study of samples shows a tendency to intercrystalline cracking of the hydrogenised molybdenum at low temperatures. In the light of the results, a mechanism involving grain boundary weakening is suggested.

  1. Optimization of peroxynitrite-luminol chemiluminescence system for detecting peroxynitrite in cell culture solution exposed to carbon disulphide.

    PubMed

    Chen, Shao L; Jian, Le; Lang, Hui Q

    2003-01-01

    We established a peroxynitrite-luminol chemiluminescence system for detecting peroxynitrite in cell culture solution exposed to carbon disulphide (CS(2)). Three factors, including exposure time to ozone (Factor A), volume of peroxynitrite (ONOO(-)) solution (Factor B) and luminol concentrations (Factor C) at three levels were selected and the combinations were in accordance with orthogonal design L(9) (3(4)). Peroxynitrite was generated from the reaction of ozone and 0.01 mol/L sodium azide (NaN(3)) dissolved in carbonic acid buffer solution (pH 11), and it was reacted with luminol to yield chemiluminescence. The peak value, peak time and kinetic curve of the light emission were observed. The selected combination conditions were 50 s ozone, 800 micro L peroxynitrite and 0.001 mol/L luminol solution. Cell culture solution with CS(2) enhanced the emission intensity of chemiluminescence (F = 8.38, p = 0.018) and shortened the peak time to chemiluminescence (F = 139.00, p = 0.0001). The data demonstrated that this luminol chemiluminescence system is suitable for detecting peroxynitrite in cell culture solutions for evaluating the effect of CS(2) on endothelial cells. Copyright 2003 John Wiley & Sons, Ltd.

  2. Passively Q-switched dual-wavelength Yb:LSO laser based on tungsten disulphide saturable absorber

    NASA Astrophysics Data System (ADS)

    Jing-Hui, Liu; Jin-Rong, Tian; He-Yang, Guoyu; Run-Qin, Xu; Ke-Xuan, Li; Yan-Rong, Song; Xin-Ping, Zhang; Liang-Bi, Su; Jun, Xu

    2016-03-01

    We demonstrate a passively Q-switched Yb:LSO laser based on tungsten disulphide (WS2) saturable absorber operating at 1034 nm and 1056 nm simultaneously. The saturable absorbers were fabricated by spin coating method. With low speed, the WS2 nanoplatelets embedded in polyvinyl alcohol could be coated on a BK7 glass substrate coated with high-refractive-index thin polymer. The shortest pulse width of 1.6 μs with a repetition rate of 76.9 kHz is obtained. As the pump power increases to 9 W, the maximum output power is measured to be 250 mW, corresponding to a single pulse energy of 3.25 μJ. To the best of our knowledge, this is the first time to obtain dual-wavelength Q-switched solid-state laser using few-layer WS2 nanoplatelets. Project supported by the National Scientific Research Project of China (Grant No. 61177047), Beijing Municipal Natural Science Foundation, China (Grant No. 1102005), and the Basic Research Foundation of Beijing University of Technology, China (Grant No. X3006111201501).

  3. Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

    SciTech Connect

    Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Mukhopadhyay, K.; Prasad, N. E.; Gandhi, M. N.; Bhattacharyya, A. R.

    2016-05-06

    Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS{sub 2}) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS{sub 2} and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS{sub 2} and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

  4. Protein disulphide isomerase of Ostertagia ostertagi: an excretory-secretory product of L4 and adult worms?

    PubMed

    Geldhof, P; Vercauteren, I; Knox, D; Demaere, V; Van Zeveren, A; Berx, G; Vercruysse, J; Claerebout, E

    2003-02-01

    A pepstatin A-agarose column was used in an attempt to purify a previously described antibody-degrading aspartyl proteinase from excretory-secretory material from the L4 and the adult stages of the bovine abomasal nematode Ostertagia ostertagi. However, no aspartyl proteinase activity was detected in the eluted fractions (L4Pepst and AdPepst). Screening of cDNA libraries with polyclonal antibodies raised against L4Pepst and AdPepst showed that a protein disulphide isomerase (Ost-PDI2) was present in both antigen fractions. This multifunctional enzyme was detected in extracts of L3, L4 and adult parasites and, interestingly, also in excretory-secretory material of L4 and adult O. ostertagi. By immunohistochemistry, the Ost-PDI2 enzyme was localised in some parts of the hypodermis of L4 and adult worms and in the intestinal cells of all three parasitic life stages. Two-dimensional Western blot analysis indicated that Ost-PDI2 is recognised by calves during a natural O. ostertagi infection, which suggests that Ost-PDI2 could be used for immunological control of ostertagiosis.

  5. Large-Scale Phosphoproteome of Human Whole Saliva Using Disulphide-Thiol-Interchange Covalent Chromatography and Mass Spectrometry

    PubMed Central

    Salih, Erdjan; Siqueira, Walter L.; Helmerhorst, Eva J.; Oppenheim, Frank G.

    2010-01-01

    Thus far only a handful of phosphoproteins with important biological functions have been identified and characterized in oral fluids and these include some of the abundant protein constituents of saliva. Whole saliva (WS) samples were trypsin digested followed by chemical derivatization using dithiothreitol (DTT) of the phospho-serine/threonine containing peptides. The DTT-phosphopeptides were enriched by covalent disulphide-thiol-interchange chromatography and analysis by nano-flow LC-ESI-MS/MS. The specificity of DTT chemical derivatization was evaluated separately under different base-catalyzed conditions with NaOH and Ba(OH)2, blocking cysteine residues by iodoacetamide and enzymatic O-deglycosylation prior to DTT reaction. Further analysis of WS samples which were subjected to either of these conditions provided supporting evidence for phosphoprotein identifications. The combined chemical strategies and mass spectrometric analyses identified 65 phosphoproteins in WS of which 28 were based on two or more peptide identification criteria with high confidence, and 37 were based on a single phosphopeptide identification. Most of the identified proteins, ~80%, were hitherto unknown phosphoprotein components. This study represents the first large-scale documentation of phosphoproteins of WS. The origins and identity of WS phosphoproteome suggest significant implications for both basic science and the development of novel biomarkers/diagnostic tools for both systemic and oral disease states. PMID:20659418

  6. mRNA and Protein levels of rat pancreas specific protein disulphide isomerase are downregulated during Hyperglycemia.

    PubMed

    Gupta, Rajani; Bhar, Kaushik; Sen, Nandini; Bhowmick, Debajit; Mukhopadhyay, Satinath; Panda, Koustubh; Siddhanta, Anirban

    2016-02-01

    Diabetes (Type I and Type II) which affects nearly every organ in the body is a multi-factorial non-communicable disorder. Hyperglycemia is the most characteristic feature of this disease. Loss of beta cells is common in both types of diabetes whose detailed cellular and molecular mechanisms are yet to be elucidated. As this disease is complex, identification of specific biomarkers for its early detection, management and devising new therapies is challenging. Based on the fact that functionally defective proteins provide the biochemical basis for many diseases, in this study, we tried to identify differentially expressed proteins during hyperglycemia. For that, hyperglycemia was induced in overnight fasted rats by intra-peritoneal injection of streptozotocin (STZ). The pancreas was isolated from control and treated rats for subsequent analyses. The 2D-gel electrophoresis followed by MALDI-TOF-MS-MS analyses revealed several up- and down-regulated proteins in hyperglycemic rat pancreas including the downregulation of a pancreas specific isoform of protein disulphide isomerase a2 (Pdia2).This observation was validated by western blot. Quantitative PCR experiments showed that the level of Pdia2 mRNA is also proportionally reduced in hyperglycemic pancreas.

  7. Complexes of tetraethylthiuram disulphide with group 12 metals: single-source precursor in metal sulphide nanoparticles' synthesis

    NASA Astrophysics Data System (ADS)

    Shukla, Satyendra N.; Gaur, Pratiksha; Rai, Nidhi

    2015-06-01

    Six new complexes of Zn(II), Cd(II) and Hg(II) with sulphur containing ligand, tetraethylthiuram disulphide in 2:2 and 1:4 ratio have been synthesized. The resulting complexes have been characterized on the basis of molar conductance measurement, elemental analyses, FT-IR, 1H-NMR, and FAB/ESI-mass studies. The complexes were used as a single-source precursor for the synthesis of ZnS/CdS/HgS nanoparticles by their thermal decomposition in the presence of different surfactants. The precursor:surfactant ratio and temperature play an important role in determining the size of the nanoparticles. The size and morphology of nanoparticles have been ascertained by ultra violet-visible spectroscopy, X-ray diffraction measurements and transmission electron microscopy. Schiff bases, complexes and nanoparticles were tested for antibacterial activity and minimum inhibitory concentration values against Escherichia coli. The complexes were found more potent than the corresponding Schiff bases and nanoparticles.

  8. Complexes of tetraethylthiuram disulphide with group 12 metals: single-source precursor in metal sulphide nanoparticles' synthesis

    NASA Astrophysics Data System (ADS)

    Shukla, Satyendra N.; Gaur, Pratiksha; Rai, Nidhi

    2014-09-01

    Six new complexes of Zn(II), Cd(II) and Hg(II) with sulphur containing ligand, tetraethylthiuram disulphide in 2:2 and 1:4 ratio have been synthesized. The resulting complexes have been characterized on the basis of molar conductance measurement, elemental analyses, FT-IR, 1H-NMR, and FAB/ESI-mass studies. The complexes were used as a single-source precursor for the synthesis of ZnS/CdS/HgS nanoparticles by their thermal decomposition in the presence of different surfactants. The precursor:surfactant ratio and temperature play an important role in determining the size of the nanoparticles. The size and morphology of nanoparticles have been ascertained by ultra violet-visible spectroscopy, X-ray diffraction measurements and transmission electron microscopy. Schiff bases, complexes and nanoparticles were tested for antibacterial activity and minimum inhibitory concentration values against Escherichia coli. The complexes were found more potent than the corresponding Schiff bases and nanoparticles.

  9. Stability and activity of Dictyoglomus thermophilum GH11 xylanase and its disulphide mutant at high pressure and temperature.

    PubMed

    Li, He; Voutilainen, Sanni; Ojamo, Heikki; Turunen, Ossi

    2015-03-01

    The functional properties of extremophilic Dictyoglomus thermophilum xylanase (XYNB) and the N-terminal disulphide-bridge mutant (XYNB-DS) were studied at high pressure and temperature. The enzymes were quite stable even at the pressure of 500MPa at 80°C. The half-life of inactivation in these conditions was over 30h. The inactivation at 80°C in atmospheric pressure was only 3-times slower. The increase of pressure up to 500MPa at 80°C decreased only slightly the enzyme's stability, whereas in 500MPa the increase of temperature from 22 to 80°C decreased significantly more the enzyme's stability. While the high temperature (80-100°C) decreased the enzyme reaction with short xylooligosaccharides (xylotetraose and xylotriose), the high pressure (100-300MPa) had an opposite effect. The temperature of 100°C strongly increased the Km but did not affect the kcat to the same extent, thus indicating that the interaction of the substrate with the active site suffers before the catalytic reaction begins to decrease as the temperature rises. Circular dichroism spectroscopy showed the high structural stability of XYNB and XYNB-DS at 93°C.

  10. Separation of antigens by immunological specificity. Studies on the desorption of homologous antigen from disulphide-linked antibody immunosorbents

    PubMed Central

    Chidlow, J. W.; Stephen, J.; Smith, H.

    1970-01-01

    1. Glycine–hydrochloric acid buffer, pH2.2, desorbed 131I-labelled human serum albumin (100%), lysozyme (100%), ovalbumin (90%), fluorescent ovalbumin (50–60%) and fluorescent human γ-globulin (20%) from their respective homologous disulphide-linked antibody immunosorbents; reasons are suggested for the low recoveries of the fluorescently labelled proteins. 2. Approx. 40% of the recovered 131I-labelled human serum albumin and fluorescent ovalbumin was desorbed above pH6.0, but lysozyme was not eluted until the pH was 3.0 or below. 3. In all cases where high recoveries of antigen were obtained, the immunosorbents could be regenerated and recycled at least four times with full retention of specificity and minimal diminution of capacity. 4. The desorbed antigens were unchanged when compared with the original antigens by quantitative precipitin, specificradioactivity, fluorescent and enzymic analyses and by cellulose acetate electrophoresis. 5. Desorption of antigen with a variety of reagents was investigated. These reagents were less satisfactory than glycine–hydrochloric acid. PMID:5420956

  11. Minimisation of artefact formation of dimethyl disulphide during sampling and analysis of methanethiol in air using solid sorbent materials.

    PubMed

    Andersen, Kristin Barkve; Hansen, Michael Jørgen; Feilberg, Anders

    2012-07-06

    Methanethiol (MT) is a potent odorant that can be difficult to measure due to its high volatility and reactivity; it easily reacts to form dimethyl disulphide (DMDS) during sampling and/or analysis. This paper focuses on finding an optimal method for sampling and measuring MT with minimum artefact formation using sorbent materials and a thermal desorption-gas chromatography-mass spectrometry method (TD-GC-MS). Experiments were conducted to identify suitable sorbent materials and tubes for analysis. Breakthrough, desorption rate, the effects of storage and desorption temperatures were investigated and different drying methods were established with respect to quantitative sampling and formation of DMDS. Proton-transfer-reaction mass spectrometry (PTR-MS) was used in the development of the method and was an especially useful tool for determination of breakthrough. The results show that glass tubes packed with silica gel for pre-concentration of MT before analysis with TD-GC-MS give the best results. In addition, a combination of Tenax TA and carbonised molecular sieve or Tenax TA cooled to ≤0°C gives acceptable results. 80°C was found to be the optimal desorption temperature. For all the sampling methods tested, storage conditions were observed to be very critical for transformation of MT. Room temperature storage should be limited to few minutes and, in general, tubes should be kept at 0°C or lower during storage.

  12. Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

    NASA Astrophysics Data System (ADS)

    Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Gandhi, M. N.; Bhattacharyya, A. R.; Mukhopadhyay, K.; Prasad, N. E.

    2016-05-01

    Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

  13. A chemical approach toward low temperature alloying of immiscible iron and molybdenum metals

    SciTech Connect

    Nazir, Rabia; Ahmed, Sohail; Mazhar, Muhammad; Akhtar, Muhammad Javed; Siddique, Muhammad; Khan, Nawazish Ali; Shah, Muhammad Raza; Nadeem, Muhammad

    2013-11-15

    Graphical abstract: - Highlights: • Low temperature pyrolysis of [Fe(bipy){sub 3}]Cl{sub 2} and [Mo(bipy)Cl{sub 4}] homogeneous powder. • Easy low temperature alloying of immiscible metals like Fe and Mo. • Uniform sized Fe–Mo nanoalloy with particle size of 48–68 nm. • Characterization by EDXRF, AFM, XRPD, magnetometery, {sup 57}Fe Mössbauer and impedance. • Alloy behaves as almost superparamagnetic obeying simple –R(CPE)– circuit. - Abstract: The present research is based on a low temperature operated feasible method for the synthesis of immiscible iron and molybdenum metals’ nanoalloy for technological applications. The nanoalloy has been synthesized by pyrolysis of homogeneous powder precipitated, from a common solvent, of the two complexes, trisbipyridineiron(II)chloride, [Fe(bipy){sub 3}]Cl{sub 2}, and bipyridinemolybedenum(IV) chloride, [Mo(bipy)Cl{sub 4}], followed by heating at 500 °C in an inert atmosphere of flowing argon gas. The resulting nanoalloy has been characterized by using EDXRF, AFM, XRD, magnetometery, {sup 57}Fe Mössbauer and impedance spectroscopies. These results showed that under provided experimental conditions iron and molybdenum metals, with known miscibility barrier, alloy together to give (1:1) single phase material having particle size in the range of 48–66 nm. The magnetism of iron is considerably reduced after alloy formation and shows its trend toward superparamagnetism. The designed chemical synthetic procedure is equally feasible for the fabrication of other immiscible metals.

  14. Solvent extraction, ion chromatography, and mass spectrometry of molybdenum isotopes.

    PubMed

    Dauphas, N; Reisberg, L; Marty, B

    2001-06-01

    A procedure was developed that allows precise determination of molybdenum isotope abundances in natural samples. Purification of molybdenum was first achieved by solvent extraction using di(2-ethylhexyl) phosphate. Further separation of molybdenum from isobar nuclides was obtained by ion chromatography using AG1-X8 strongly basic anion exchanger. Finally, molybdenum isotopic composition was measured using a multiple collector inductively coupled plasma hexapole mass spectrometer. The abundances of molybdenum isotopes 92, 94, 95, 96, 97, 98, and 100 are 14.8428(510), 9.2498(157), 15.9303(133), 16.6787(37), 9.5534(83), 24.1346(394), and 9.6104(312) respectively, resulting in an atomic mass of 95.9304(45). After internal normalization for mass fractionation, no variation of the molybdenum isotopic composition is observed among terrestrial samples within a relative precision on the order of 0.00001-0.0001. This demonstrates the reliability of the method, which can be applied to searching for possible isotopic anomalies and mass fractionation.

  15. Electron accelerator-based production of molybdenum-99: Bremsstrahlung and photoneutron generation from molybdenum vs. tungsten

    NASA Astrophysics Data System (ADS)

    Tsechanski, A.; Bielajew, A. F.; Archambault, J. P.; Mainegra-Hing, E.

    2016-01-01

    A new "one-stage" approach for production of 99Mo and other radioisotopes by means of an electron linear accelerator is described. It is based on using a molybdenum target both as a bremsstrahlung converter and as a radioisotope producing target for the production of 99Mo via the photoneutron reaction 100Mo(γ,n)99Mo. Bremsstrahlung characteristics, such as bremsstrahlung efficiency, angular distribution, and energy deposition for molybdenum targets were obtained by means of the EGSnrc Monte Carlo simulation code system. As a result of our simulations, it is concluded that a 60 MeV electron beam incident on a thick Mo target will have greater bremsstrahlung efficiency than the same thickness (in units of r0) W target, for target thickness z > 1.84r0, where r0 is the electron range. A 50 MeV electron beam incident on a Mo target will result in greater bremsstrahlung efficiency than the same thickness W target (in units of r0) for target thickness case: z ⩾ 2.0r0. It is shown for the one-stage approach with thicknesses of (1.84-2.0)r0, that the 99Mo-production bremsstrahlung efficiency of a molybdenum target is greater by ∼100% at 30 MeV and by ∼70% at 60 MeV compared to the values for tungsten of the same thickness (in units of the appropriate r0) in the traditional two-stage approach (W converter and separate 99Mo producing target). This advantage of the one-stage approach arises from the fact that the bremsstrahlung produced is attenuated only once from attenuation in the molybdenum converter/target. In the traditional, two-stage approach, the bremsstrahlung generated in the W-converter/target is attenuated both in the converter in the 99Mo-producing molybdenum target. The photoneutron production yield of molybdenum and tantalum (as a substitute for tungsten) target was calculated by means of the MCNP5 transport code. On the basis of these data, the specific activity for the one-stage approach of three enriched 100Mo-targets of a 2 cm diameter and

  16. Molybdenum oxide and molybdenum oxide-nitride back contacts for CdTe solar cells

    SciTech Connect

    Drayton, Jennifer A. Geisthardt, Russell M. Sites, James R.; Williams, Desiree D. Cramer, Corson L. Williams, John D.

    2015-07-15

    Molybdenum oxide (MoO{sub x}) and molybdenum oxynitride (MoON) thin film back contacts were formed by a unique ion-beam sputtering and ion-beam-assisted deposition process onto CdTe solar cells and compared to back contacts made using carbon–nickel (C/Ni) paint. Glancing-incidence x-ray diffraction and x-ray photoelectron spectroscopy measurements show that partially crystalline MoO{sub x} films are created with a mixture of Mo, MoO{sub 2}, and MoO{sub 3} components. Lower crystallinity content is observed in the MoON films, with an additional component of molybdenum nitride present. Three different film thicknesses of MoO{sub x} and MoON were investigated that were capped in situ in Ni. Small area devices were delineated and characterized using current–voltage (J-V), capacitance–frequency, capacitance–voltage, electroluminescence, and light beam-induced current techniques. In addition, J-V data measured as a function of temperature (JVT) were used to estimate back barrier heights for each thickness of MoO{sub x} and MoON and for the C/Ni paint. Characterization prior to stressing indicated the devices were similar in performance. Characterization after stress testing indicated little change to cells with 120 and 180-nm thick MoO{sub x} and MoON films. However, moderate-to-large cell degradation was observed for 60-nm thick MoO{sub x} and MoON films and for C/Ni painted back contacts.

  17. Biosynthesis and Insertion of the Molybdenum Cofactor.

    PubMed

    Magalon, Axel; Mendel, Ralf R

    2015-01-01

    The transition element molybdenum (Mo) is of primordial importance for biological systems, because it is required by enzymes catalyzing key reactions in the global carbon, sulfur, and nitrogen metabolism. To gain biological activity, Mo has to be complexed by a special cofactor. With the exception of bacterial nitrogenase, all Mo-dependent enzymes contain a unique pyranopterin-based cofactor coordinating a Mo atom at their catalytic site. Various types of reactions are catalyzed by Mo-enzymes in prokaryotes including oxygen atom transfer, sulfur or proton transfer, hydroxylation, or even nonredox reactions. Mo-enzymes are widespread in prokaryotes and many of them were likely present in the Last Universal Common Ancestor. To date, more than 50--mostly bacterial--Mo-enzymes are described in nature. In a few eubacteria and in many archaea, Mo is replaced by tungsten bound to the same unique pyranopterin. How Mo-cofactor is synthesized in bacteria is reviewed as well as the way until its insertion into apo-Mo-enzymes.

  18. Vertically aligned biaxially textured molybdenum thin films

    SciTech Connect

    Krishnan, Rahul; Riley, Michael; Lee, Sabrina; Lu, Toh-Ming

    2011-09-15

    Vertically aligned, biaxially textured molybdenum nanorods were deposited using dc magnetron sputtering with glancing flux incidence (alpha = 85 degrees with respect to the substrate normal) and a two-step substrate-rotation mode. These nanorods were identified with a body-centered cubic crystal structure. The formation of a vertically aligned biaxial texture with a [110] out-of-plane orientation was combined with a [-110] in-plane orientation. The kinetics of the growth process was found to be highly sensitive to an optimum rest time of 35 seconds for the two-step substrate rotation mode. At all other rest times, the nanorods possessed two separate biaxial textures each tilted toward one flux direction. While the in-plane texture for the vertical nanorods maintains maximum flux capture area, inclined Mo nanorods deposited at alpha = 85 degrees without substrate rotation display a [-1-1-4] in-plane texture that does not comply with the maximum flux capture area argument. Finally, an in situ capping film was deposited with normal flux incidence over the biaxially textured vertical nanorods resulting in a thin film over the porous nanorods. This capping film possessed the same biaxial texture as the nanorods and could serve as an effective substrate for the epitaxial growth of other functional materials.

  19. Molybdenum disilicide composites produced by plasma spraying

    SciTech Connect

    Castro, R.G.; Hollis, K.J.; Kung, H.H.; Bartlett, A.H.

    1998-05-25

    The intermetallic compound, molybdenum disilicide (MoSi{sub 2}) is being considered for high temperature structural applications because of its high melting point and superior oxidation resistance at elevated temperatures. The lack of high temperature strength, creep resistance and low temperature ductility has hindered its progress for structural applications. Plasma spraying of coatings and structural components of MoSi{sub 2}-based composites offers an exciting processing alternative to conventional powder processing methods due to superior flexibility and the ability to tailor properties. Laminate, discontinuous and in situ reinforced composites have been produced with secondary reinforcements of Ta, Al{sub 2}O{sub 3}, SiC, Si{sub 3}N{sub 4} and Mo{sub 5}Si{sub 3}. Laminate composites, in particular, have been shown to improve the damage tolerance of MoSi{sub 2} during high temperature melting operations. A review of research which as been performed at Los Alamos National Laboratory on plasma spraying of MoSi{sub 2}-based composites to improve low temperature fracture toughness, thermal shock resistance, high temperature strength and creep resistance will be discussed.

  20. Amorphous molybdenum silicon superconducting thin films

    SciTech Connect

    Bosworth, D. Sahonta, S.-L.; Barber, Z. H.; Hadfield, R. H.

    2015-08-15

    Amorphous superconductors have become attractive candidate materials for superconducting nanowire single-photon detectors due to their ease of growth, homogeneity and competitive superconducting properties. To date the majority of devices have been fabricated using W{sub x}Si{sub 1−x}, though other amorphous superconductors such as molybdenum silicide (Mo{sub x}Si{sub 1−x}) offer increased transition temperature. This study focuses on the properties of MoSi thin films grown by magnetron sputtering. We examine how the composition and growth conditions affect film properties. For 100 nm film thickness, we report that the superconducting transition temperature (Tc) reaches a maximum of 7.6 K at a composition of Mo{sub 83}Si{sub 17}. The transition temperature and amorphous character can be improved by cooling of the substrate during growth which inhibits formation of a crystalline phase. X-ray diffraction and transmission electron microscopy studies confirm the absence of long range order. We observe that for a range of 6 common substrates (silicon, thermally oxidized silicon, R- and C-plane sapphire, x-plane lithium niobate and quartz), there is no variation in superconducting transition temperature, making MoSi an excellent candidate material for SNSPDs.

  1. Structural phase transitions in monolayer molybdenum dichalcogenides

    NASA Astrophysics Data System (ADS)

    Choe, Duk-Hyun; Sung, Ha June; Chang, Kee Joo

    2015-03-01

    The recent discovery of two-dimensional materials such as graphene and transition metal dichalcogenides (TMDs) has provided opportunities to develop ultimate thin channel devices. In contrast to graphene, the existence of moderate band gap and strong spin-orbit coupling gives rise to exotic electronic properties which vary with layer thickness, lattice structure, and symmetry. TMDs commonly appear in two structures with distinct symmetries, trigonal prismatic 2H and octahedral 1T phases which are semiconducting and metallic, respectively. In this work, we investigate the structural and electronic properties of monolayer molybdenum dichalcogenides (MoX2, where X = S, Se, Te) through first-principles density functional calculations. We find a tendency that the semiconducting 2H phase is more stable than the metallic 1T phase. We show that a spontaneous symmetry breaking of 1T phase leads to various distorted octahedral (1T') phases, thus inducing a metal-to-semiconductor transition. We discuss the effects of carrier doping on the structural stability and the modification of the electronic structure. This work was supported by the National Research Foundation of Korea (NRF) under Grant No. NRF-2005-0093845 and Samsung Science and Technology Foundation under Grant No. SSTFBA1401-08.

  2. The dynamics of copper intercalated molybdenum ditelluride

    NASA Astrophysics Data System (ADS)

    Onofrio, Nicolas; Guzman, David; Strachan, Alejandro

    2016-11-01

    Layered transition metal dichalcogenides are emerging as key materials in nanoelectronics and energy applications. Predictive models to understand their growth, thermomechanical properties, and interaction with metals are needed in order to accelerate their incorporation into commercial products. Interatomic potentials enable large-scale atomistic simulations connecting first principle methods and devices. We present a ReaxFF reactive force field to describe molybdenum ditelluride and its interactions with copper. We optimized the force field parameters to describe the energetics, atomic charges, and mechanical properties of (i) layered MoTe2, Mo, and Cu in various phases, (ii) the intercalation of Cu atoms and small clusters within the van der Waals gap of MoTe2, and (iii) bond dissociation curves. The training set consists of an extensive set of first principles calculations computed using density functional theory (DFT). We validate the force field via the prediction of the adhesion of a single layer MoTe2 on a Cu(111) surface and find good agreement with DFT results not used in the training set. We characterized the mobility of the Cu ions intercalated into MoTe2 under the presence of an external electric field via finite temperature molecular dynamics simulations. The results show a significant increase in drift velocity for electric fields of approximately 0.4 V/Å and that mobility increases with Cu ion concentration.

  3. Special nerve functions and colour discrimination in workers with long term low level exposure to carbon disulphide.

    PubMed Central

    Ruijten, M W; Sallé, H J; Verberk, M M; Muijser, H

    1990-01-01

    Certain functions of the peripheral and autonomic nervous systems, and colour discrimination were examined in 45 workers (mean age 49; mean exposure to carbon disulphide (CS2) 20 years) and 37 controls (mean age 48). Conduction velocity and refractory period of the peroneal and sural nerves were determined. The conduction velocity of the slower fibres of the peroneal nerve was measured by means of an improved method that makes use of the refractory period. Function of autonomic nerves was assessed by measuring the variation in heart rate during rest, during deep breathing, and during isometric muscle contraction. Colour discrimination was evaluated by the Lanthony desaturated test. Individual cumulative exposure to CS2 was calculated on the basis of exposure in the past and individual job history. Mean cumulative exposure was 165 ppm-years. The peroneal nerves of exposed workers showed a decrease (-1.0 m/s) in conduction velocity of the slow fibres and a prolongation (0.1 ms) of the refractory period (mean 1.6 ms) compared with controls. These effects were related to cumulative exposure. No impairment of function of the sural nerve or of colour discrimination was found. The muscle heart reflex was decreased in the exposed group, but this was not related to cumulative exposure. This study has established more firmly that a decrease in conduction velocity of slow motor fibres occurs at low levels of exposure to CS2. Extrapolation of the results suggests that small effects may occur after 40 years of exposure to concentrations below the present threshold limit value (10 ppm). PMID:2207029

  4. D-penicillamine and D-penicillamine-protein disulphide in plasma and synovial fluid of patients with rheumatoid arthritis.

    PubMed

    Joyce, D A; Day, R O

    1990-10-01

    1. The plasma pharmacokinetics of D-penicillamine (D-pen) and D-penicillamine-albumin disulphide (D-pen-alb) were examined over a dosage interval in six patients with rheumatoid arthritis. In two of these, 24 h synovial fluid profiles of D-pen and D-pen-alb were also obtained. 2. D-pen was undetectable in plasma at the beginning of the study. The peak concentration (5.4 +/- 1.2 microM) occurred at between 45 min and 2 h and the mean elimination half-life was 0.6 h. D-pen-alb, however, was present at a mean plasma concentration of 19.1 microM prior to dosage, peaked at 26.2 microM and was eliminated with a half-life of 40 h. 3. D-pen concentrations in synovial fluid rose more slowly and peaked lower than in plasma. D-pen-alb was present in synovial fluid of the patients at 50.1% and 83.6%, respectively, of the simultaneous plasma concentration prior to dosage. Concentrations varied during the study interval, corresponding to changes in plasma concentrations. 4. These results demonstrate that D-pen forms stable conjugates with protein in treated patients. The presence of D-pen-alb in relatively high concentrations throughout the dosage interval contrasts with the low concentrations and rapid elimination of D-pen. Both D-pen and D-pen-alb were also shown to be present at the putative site of drug action (the inflamed synovial joint) in concentrations lower than those in plasma.

  5. D-penicillamine prevents ram sperm agglutination by reducing the disulphide bonds of a copper-binding sperm protein.

    PubMed

    Leahy, T; Rickard, J P; Aitken, R J; de Graaf, S P

    2016-05-01

    Head-to-head agglutination of ram spermatozoa is induced by dilution in the Tyrode's capacitation medium with albumin, lactate and pyruvate (TALP) and ameliorated by the addition of the thiol d-penicillamine (PEN). To better understand the association and disassociation of ram spermatozoa, we investigated the mechanism of action of PEN in perturbing sperm agglutination. PEN acts as a chelator of heavy metals, an antioxidant and a reducing agent. Chelation is not the main mechanism of action, as the broad-spectrum chelator ethylenediaminetetraacetic acid and the copper-specific chelator bathocuproinedisulfonic acid were inferior anti-agglutination agents compared with PEN. Oxidative stress is also an unlikely mechanism of sperm association, as PEN was significantly more effective in ameliorating agglutination than the antioxidants superoxide dismutase, ascorbic acid, α-tocopherol and catalase. Only the reducing agents cysteine and DL-dithiothreitol displayed similar levels of non-agglutinated spermatozoa at 0 h compared with PEN but were less effective after 3 h of incubation (37 °C). The addition of 10 µM Cu(2+) to 250 µM PEN + TALP caused a rapid reversion of the motile sperm population from a non-agglutinated state to an agglutinated state. Other heavy metals (cobalt, iron, manganese and zinc) did not provoke such a strong response. Together, these results indicate that PEN prevents sperm association by the reduction of disulphide bonds on a sperm membrane protein that binds copper. ADAM proteins are possible candidates, as targeted inhibition of the metalloproteinase domain significantly increased the percentage of motile, non-agglutinated spermatozoa (52.0% ± 7.8) compared with TALP alone (10.6% ± 6.1).

  6. Rational mutagenesis by engineering disulphide bonds improves Kluyveromyces lactis beta-galactosidase for high-temperature industrial applications

    PubMed Central

    Rico-Díaz, Agustín; Álvarez-Cao, María-Efigenia; Escuder-Rodríguez, Juan-José; González-Siso, María-Isabel; Cerdán, M. Esperanza; Becerra, Manuel

    2017-01-01

    Kluyveromyces lactis β-galactosidase (Kl-β-Gal) is one of the most important enzymes in the dairy industry. The poor stability of this enzyme limits its use in the synthesis of galactooligosaccharides (GOS) and other applications requiring high operational temperature. To obtain thermoresistant variants, a rational mutagenesis strategy by introducing disulphide bonds in the interface between the enzyme subunits was used. Two improved mutants, R116C/T270C and R116C/T270C/G818C, had increased half-lives at 45 °C compared to Kl-β-Gal (2.2 and 6.8 fold increases, respectively). Likewise, Tm values of R116C/T270C and R116C/T270C/G818C were 2.4 and 8.5 °C, respectively, higher than Kl-β-Gal Tm. Enrichment in enzymatically active oligomeric forms in these mutant variants also increased their catalytic efficiency, due to the reinforcement of the interface contacts. In this way, using an artificial substrate (p-nitrophenyl-β-D-galactopyranoside), the Vmax values of the mutants were ~1.4 (R116C/T270C) and 2 (R116C/T270C/G818C) fold higher than that of native Kl-β-Gal. Using the natural substrate (lactose) the Vmax for R116C/T270C/G818C almost doubled the Vmax for Kl-β-Gal. Validation of these mutant variants of the enzyme for their use in applications that depend on prolonged incubations at high temperatures was achieved at the laboratory scale by monitoring their catalytic activity in GOS synthesis. PMID:28361909

  7. Aquatic acute toxicity assessments of molybdenum (+VI) to Daphnia magna.

    PubMed

    Wang, Chi-Wei; Liang, Chenju; Yeh, Hui-Ju

    2016-03-01

    Generally, molybdenum (Mo) metals in the environment are very rare, but wastewater discharges from industrial processes may contain high concentrations of Mo, which has the potential to contaminate water or soil if not handled properly. In this study, the impact of three common compounds of hexavalent Mo (sodium molybdate (Na2MoO4‧2H2O), ammonium molybdate ((NH4)6Mo7O24‧4H2O) and molybdenum trioxide (MoO3)) in an aquatic system were assessed based on 48-h exposure acute toxicity to Daphnia magna (D. magna). The LC50 toxicities for associated conjugate ions including Na(+), Cl(-), SO4(2-), and NH4(+) were determined. Furthermore, the LC50 values for the three forms of hexavalent Mo were determined, and the acute toxicities of the Mo forms were found to follow the order: (NH4)6Mo7O24‧4H2O > MoO3 > Na2MoO4‧2H2O in solution. (NH4)6Mo7O24‧4H2O exhibited the lowest LC50 of 43.3 mg L(-1) (corresponding to 23.5 mg Mo L(-1)) among the three molybdenum salts. The research confirmed that the toxicity of molybdenum in the aquatic system is highly dependent on the form of molybdenum salts used, and is also associated with the influence of the background water quality.

  8. METHOD FOR FORMING A COATING OF MOLYBDENUM CARBIDE ON A CARBON BODY

    DOEpatents

    Simnad, M.T.

    1962-04-01

    A method is described for coating a carbon bodywith molybdenum carbide in such a manner that the carbon body is rendered less permeable to the flow of gases and has increased resistance to corrosion and erosion. The method includes coating a carbon body with molybdenum trioxide by contacting it at a temperature below the condensation temperature with molybdenum trioxide vapors and thereafter carburizing the molybdenum trioxide in situ in an inert atmosphere on the carhon body. (AEC)

  9. Effect of Molybdenum Starvation and Tungsten on the Synthesis of Nitrogenase Components in Klebsiella pneumoniae

    PubMed Central

    Brill, Winston J.; Steiner, Ann L.; Shah, Vinod K.

    1974-01-01

    Klebsiella pneumoniae M5a1 grows well in the presence or absence of molybdenum in media containing excess NH4+. However, growth on N2 is completely dependent on the presence of molybdenum in the medium. Tungstate competes with the molybdate requirement during growth on N2. In molybdenum-depleted medium, neither protein component of nitrogenase is active and neither component can be detected antigenically. These data provide evidence that molybdenum is an inducer of nitrogenase synthesis. PMID:4598014

  10. Active Site and Electronic Structure Elucidation of Pt Nanoparticles Supported on Phase-Pure Molybdenum Carbide Nanotubes.

    PubMed

    Tan, Shuai; Wang, Lucun; Saha, Shibely; Fushimi, Rebecca R; Li, Dongmei

    2017-03-22

    We recently showed that phase-pure molybdenum carbide nanotubes can be durable supports for platinum (Pt) nanoparticles in hydrogen evolution reaction (HER). In this paper we further characterize surface properties of the same Pt/β-Mo2C catalyst platform using carbon monoxide (CO)-Pt and CO-Mo2C bond strength of different Pt particle sizes in the <3 nm range. Results from diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temporal analysis of products (TAP) revealed the existence of different active sites as Pt particle size increases. Correlation between the resultant catalyst activity and deposited Pt particle size was further investigated using water-gas-shift (WGS) as a probe reaction, suggesting that precise control of particle diameter and thickness is needed for optimized catalytic activity.

  11. Molybdenum oxide nanosheets prepared by an anodizing-exfoliation process and observation of photochromic properties

    NASA Astrophysics Data System (ADS)

    Ranjbar, M.; Delalat, F.; Salamati, H.

    2017-02-01

    Anodizing-exfoliation of molybdenum foil was performed in 0.02 M HCl electrolyte at 30 V. In this process, the electrolyte rapidly turned into a blue colloidal solution of molybdenum oxide nanosheets with fragmented edges observed on transmission electron microscope (TEM). X-ray Diffraction (XRD) pattern of particles was free of peak while annealing at a temperature range of 100-500 °C led to formation of monoclinic (for T < 300 °C) and orthorhombic (for T > 300 °C) phases of MoO3. Moreover, addition of PdCl2 (0.2 g/l) salt solution caused a spontaneous bleaching of the initial blue colloid. Annealing of powders extracted from these bleached solutions with different PdCl2 concentrations at 500 °C led to a preferential growth of (0k0) orientation. X-ray photoelectron spectroscopy (XPS) revealed that the blue nanosheets solution contains mainly Mo5+ with slightly Mo6+ oxidation states and each of annealing or salt bleaching procedures can entirely convert Mo5+ to Mo6+. When the bleached solutions was exposed to KrF laser beam (λ = 248 nm) a strong photochromic coloration with a deep blue color was occurred. Regardless of Pd:Mo ratio, the primary and laser irradiated solutions showed analogues optical absorption bands in the 1-3 nm photon energy range while the photochromic process led to a broader absorption band.

  12. Tyrosine phosphorylation of P-selectin in intact platelets and in a disulphide-linked complex with immunoprecipitated pp60c-src.

    PubMed Central

    Modderman, P W; von dem Borne, A E; Sonnenberg, A

    1994-01-01

    P-selectin is a 140 kDa membrane glycoprotein found in secretory granules of platelets and endothelial cells where it is rapidly translocated to the plasma membrane upon cell activation. It then functions as a receptor for various types of leucocytes. Metabolic labelling of resting platelets with 32Pi showed that P-selectin is primarily phosphorylated on serine residues, although some tyrosine phosphorylation was observed as well. However, tyrosine phosphorylation of P-selectin was greatly stimulated by treatment with the permeating phosphatase inhibitor, pervanadate. When P-selectin immunoprecipitates were incubated with [gamma-32P]ATP (in vitro kinase assay), a fraction of P-selectin was phosphorylated on its tyrosine residues by a co-precipitated kinase. P-selectin phosphorylated in vitro co-migrated with 140 kDa surface-labelled 125I-P-selectin during SDS/PAGE under reducing conditions. Under non-reducing conditions, however, phosphorylated P-selectin was disulphide-linked to unknown protein(s) in a 205 kDa complex. In vitro kinase assays of the most abundant platelet tyrosine kinase, pp60c-src, demonstrated the presence of similar 140 and 205 kDa phosphorylated proteins in SDS/PAGE under reducing and non-reducing conditions respectively. Extraction and reprecipitation studies with proteins phosphorylated in vitro indicated that P-selectin and pp60c-src form a 205 kDa 1:1 disulphide-linked complex. In the complex, pp60c-src autophosphorylation is inhibited and P-selectin is phosphorylated on tyrosine residues. As protein disulphides in the cytoplasm of intact cells are extremely rare, our results suggest that P-selectin and pp60c-src, which co-localize in platelet dense granules, may be non-covalently associated and spontaneously form disulphide bridges during lysis. In addition, the observed tyrosine phosphorylation of P-selectin in intact platelets suggests that its function might be regulated by phosphorylation by pp60c-src. Images Figure 1 Figure 2 Figure 3

  13. X-ray Diffraction Study of Molybdenum to 900 GPa

    NASA Astrophysics Data System (ADS)

    Wang, J.; Coppari, F.; Smith, R.; Eggert, J.; Boehly, T.; Collins, G. W.; Duffy, T. S.

    2013-12-01

    Molybdenum (Mo) is a transition metal that is important as a high-pressure standard. Its equation of state, structure, and melting behavior have been explored extensively in both experimental and theoretical studies. Melting data up to the Mbar pressure region from static compression experiments in the diamond anvil cell [Errandonea et al. 2004] are inconsistent with shock wave sound velocity measurements [Hixson et al., 1989]. There are also conflicting reports as to whether body-centered cubic (BCC) Mo transforms to a face-centered cubic (FCC), hexagonal close packed (HCP) or double hexagonal close packed (DHCP) structure at either high pressure or high pressure and temperature conditions [Belonoshko et al. 2008, Mikhaylushkin et al., 2008 and Cazorla et al., 2008]. Recently, a phase transition from BCC to the DHCP phase at 660 GPa and 0 K was predicted using the particle swam optimization (PSO) method (Wang et al, 2013). Here we report an x-ray diffraction study of dynamically compressed molybdenum. Experiments were conducted using the Omega laser at the Laboratory for Laser Energetics at the University of Rochester. Mo targets were either ramp or shock compressed using a laser drive. In ramp loading, the sample is compressed sufficiently slowly that a shock wave does not form. This results in lower temperatures, keeping the sample in the solid state to higher pressures. X-ray diffraction measurements were performed using quasi-monochromatic x-rays from a highly ionized He-α Cu source and image plate detectors. Upon ramp compression, we found no evidence of phase transition in solid Mo up to 900 GPa. The observed peaks can be assigned to the (110) and (200) or (220) reflections of BCC Mo up to the highest pressure, indicating that Mo does not melt under ramp loading to maximum pressure reached. Under shock loading, we did not observe any evidence for the solid-solid phase transformation around 210 GPa as reported in previous work (Hixson et al, 1989). The BCC

  14. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  15. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  16. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  17. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  18. 40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

  19. 40 CFR 421.220 - Applicability: Description of the secondary molybdenum and vanadium subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... secondary molybdenum and vanadium subcategory. 421.220 Section 421.220 Protection of Environment... POINT SOURCE CATEGORY Secondary Molybdenum and Vanadium Subcategory § 421.220 Applicability: Description of the secondary molybdenum and vanadium subcategory. The provisions of this subpart are applicable...

  20. 40 CFR 421.220 - Applicability: Description of the secondary molybdenum and vanadium subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... secondary molybdenum and vanadium subcategory. 421.220 Section 421.220 Protection of Environment... POINT SOURCE CATEGORY Secondary Molybdenum and Vanadium Subcategory § 421.220 Applicability: Description of the secondary molybdenum and vanadium subcategory. The provisions of this subpart are applicable...

  1. 40 CFR 421.220 - Applicability: Description of the secondary molybdenum and vanadium subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... secondary molybdenum and vanadium subcategory. 421.220 Section 421.220 Protection of Environment... POINT SOURCE CATEGORY Secondary Molybdenum and Vanadium Subcategory § 421.220 Applicability: Description of the secondary molybdenum and vanadium subcategory. The provisions of this subpart are applicable...

  2. 40 CFR 421.220 - Applicability: Description of the secondary molybdenum and vanadium subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... secondary molybdenum and vanadium subcategory. 421.220 Section 421.220 Protection of Environment... POINT SOURCE CATEGORY Secondary Molybdenum and Vanadium Subcategory § 421.220 Applicability: Description of the secondary molybdenum and vanadium subcategory. The provisions of this subpart are applicable...

  3. 40 CFR 421.220 - Applicability: Description of the secondary molybdenum and vanadium subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... secondary molybdenum and vanadium subcategory. 421.220 Section 421.220 Protection of Environment... POINT SOURCE CATEGORY Secondary Molybdenum and Vanadium Subcategory § 421.220 Applicability: Description of the secondary molybdenum and vanadium subcategory. The provisions of this subpart are applicable...

  4. Groundwater Molybdenum from Emerging Industries in Taiwan.

    PubMed

    Tsai, Kuo-Sheng; Chang, Yu-Min; Kao, Jimmy C M; Lin, Kae-Long

    2016-01-01

    This study determined the influence of emerging industries development on molybdenum (Mo) groundwater contamination. A total of 537 groundwater samples were collected for Mo determination, including 295 samples from potentially contaminated areas of 3 industrial parks in Taiwan and 242 samples from non-potentially contaminated areas during 2008-2014. Most of the high Mo samples are located downstream from a thin film transistor-liquid crystal display (TFT-LCD) panel factory. Mean groundwater Mo concentrations from potentially contaminated areas (0.0058 mg/L) were significantly higher (p < 0.05) than those from non-potentially contaminated areas (0.0022 mg/L). The highest Mo wastewater concentrations in the effluent from the optoelectronics industry and following wastewater batch treatment were 0.788 and 0.0326 mg/L, respectively. This indicates that wastewater containing Mo is a possible source of both groundwater and surface water contamination. Nine samples of groundwater exceed the World Health Organization's suggested drinking water guideline of 0.07 mg/L. A non-carcinogenic risk assessment for Mo in adults and children using the Mo concentration of 0.07 mg/L yielded risks of 0.546 and 0.215, respectively. These results indicate the importance of the development of a national drinking water quality standard for Mo in Taiwan to ensure safe groundwater for use. According to the human health risk calculation, the groundwater Mo standard is suggested as 0.07 mg/L. Reduction the discharge of Mo-contaminated wastewater from factories in the industrial parks is also the important task in the future.

  5. Isotopic delta values of molybdenum reference solutions

    NASA Astrophysics Data System (ADS)

    Wen, Hanjie; Carignan, Jean; Cloquet, Christophe; Zhu, Xiangkun; Zhang, Yuxu

    2010-05-01

    We report the isotopic composition of five molybdenum (Mo) standard reference solutions and four fractions from one of these solutions eluted through anion resin column relative to a sixth reference solution. Measurements were conducted using Isoprobe multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) at the Centre de Recherches Pétrographiques et Géochimiques (France) and Nu Plasma MC-ICP-MS at either the Ecole Normale Supérieure de Lyon (France) or the Laboratory of Isotope Geology in the Ministry of Land and Resources (China). The sample-standard bracketing method was employed to correct the mass bias for Mo isotopes during instrumental measurement. Except for the Merck Mo solution, all the Mo solutions were identical in isotopic composition within error. Although the JMC Mo solution has been used as the internal reference material by various groups, uncertainty may still occur with different lot numbers and availability might be limited. Here, we propose the NIST 3134 Mo solution as a new candidate for delta zero reference material, used for reporting Mo isotopic composition of natural samples. Isotopic compositions for four eluted fractions of the Sigma-Aldrich Mo solution range from 2.2 ‰ to -2.0 ‰ for δ97/95Mo relative to the NIST Mo standard. These values span the range of reported isotopic composition for natural terrestrial and experimental samples (approximately -0.5‰ to 1.6‰ for δ97/95Mo). We propose these eluted fractions to be used as secondary reference for Mo isotope measurements.

  6. Recent Developments in Homogeneous Dinitrogen Reduction by Molybdenum and Iron

    PubMed Central

    MacLeod, K. Cory; Holland, Patrick L.

    2013-01-01

    The reduction of gaseous nitrogen (N2) is a challenge for industrial, biological and synthetic chemists, who want to understand the formation of ammonia (NH3) for agriculture and also want to form N-C and N-Si bonds for fine chemical synthesis. The iron-molybdenum active site of nitrogenase has inspired chemists to explore the ability of iron and molybdenum complexes to bring about transformations related to N2 reduction. This area of research has gained significant momentum, and the last two years have witnessed a number of significant advances in synthetic Fe-N2 and Mo-N2 chemistry. In addition, the identities of all atoms in the iron-molybdenum cofactor of nitrogenase have finally been elucidated, and the discovery of a carbide has generated new questions and targets for coordination chemists. This Perspective summarizes the recent work on iron and molydenum complexes, and highlights the opportunities for continued research. PMID:23787744

  7. Achieving the ideal strength in annealed molybdenum nanopillars

    SciTech Connect

    Lowry, M. B.; Kiener, D.; LeBlanc, M. M.; Chisholm, Claire; Florando, Jeff; Morris, J. W.; Minor, Andrew

    2010-01-01

    The theoretical strength of a material is the stress required to deform an infinite, defect-free crystal. Achieving the theoretical strength of a material experimentally is hindered by the ability to create and mechanically test an absolutely defect-free material. Here we show that through annealing it is possible to employ the versatility of the focused ion beam (FIB) but recover a mechanically pristine limited volume. Starting with FIB-milled molybdenum pillars, we anneal them in situ in a transmission electron microscope (TEM) producing a molybdenum pillar with a spherical cap. This geometry allows for the maximum stress to occur in the interior of the spherical cap and is ideally suited for experimentally achieving the ideal strength. During in situ compression testing in the TEM the annealed pillars show initial elastic loading followed by catastrophic failure at, or very near, the calculated theoretical strength of molybdenum. Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

  8. Microstructures define melting of molybdenum at high pressures

    NASA Astrophysics Data System (ADS)

    Hrubiak, Rostislav; Meng, Yue; Shen, Guoyin

    2017-03-01

    High-pressure melting anchors the phase diagram of a material, revealing the effect of pressure on the breakdown of the ordering of atoms in the solid. An important case is molybdenum, which has long been speculated to undergo an exceptionally steep increase in melting temperature when compressed. On the other hand, previous experiments showed nearly constant melting temperature as a function of pressure, in large discrepancy with theoretical expectations. Here we report a high-slope melting curve in molybdenum by synchrotron X-ray diffraction analysis of crystalline microstructures, generated by heating and subsequently rapidly quenching samples in a laser-heated diamond anvil cell. Distinct microstructural changes, observed at pressures up to 130 gigapascals, appear exclusively after melting, thus offering a reliable melting criterion. In addition, our study reveals a previously unsuspected transition in molybdenum at high pressure and high temperature, which yields highly textured body-centred cubic nanograins above a transition temperature.

  9. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

    NASA Astrophysics Data System (ADS)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  10. A molybdenum disulfide/carbon nanotube heterogeneous complementary inverter.

    PubMed

    Huang, Jun; Somu, Sivasubramanian; Busnaina, Ahmed

    2012-08-24

    We report a simple, bottom-up/top-down approach for integrating drastically different nanoscale building blocks to form a heterogeneous complementary inverter circuit based on layered molybdenum disulfide and carbon nanotube (CNT) bundles. The fabricated CNT/MoS(2) inverter is composed of n-type molybdenum disulfide (MOS(2)) and p-type CNT transistors, with a high voltage gain of 1.3. The CNT channels are fabricated using directed assembly while the layered molybdenum disulfide channels are fabricated by mechanical exfoliation. This bottom-up fabrication approach for integrating various nanoscale elements with unique characteristics provides an alternative cost-effective methodology to complementary metal-oxide-semiconductors, laying the foundation for the realization of high performance logic circuits.

  11. [Determination of trace molybdenum by extraction catalytic kinetic spectrophotometry].

    PubMed

    Zhu, Qing-ren; Sun, Deng-ming; Li, Hai-yan

    2002-02-01

    A new extraction catalytic kinetic spectrophotometric method for the determination of trace molybdenum is studied. The method is based on the molybdenum (VI) catalytic oxidation of o-aminophenol by hydrogen peroxide in week acidic medium at pH 5.5. The reaction is carried out at room temperature. The reaction time, concentration of o-aminophenol in aqueous phase and degree of reaction are controlled by extraction equilibrium. The absorbance of organic phase is measured at 424 nm. Under the optimum experiment conditions, the linear range of the determination is 0.0050-2.0 mg.L-1, the detection limit is 2.0 x 10(-6) g.L-1. Combining with separation of ionic exchange, the method has been applied to the determination of trace molybdenum in bean samples with satisfactory results. The kinetic equation of extraction catalytic reaction is discussed.

  12. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions.

    PubMed

    Koh, Ming Joo; Nguyen, Thach T; Lam, Jonathan K; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R; Hoveyda, Amir H

    2017-02-02

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  13. Dynamic Shear Strength Measurements in Shock-Loaded Molybdenum

    NASA Astrophysics Data System (ADS)

    Stirk, S. M.; Millett, J. C. F.; Bourne, N. K.; Whiteman, G.; Park, N. T.

    2009-12-01

    Dynamic shear strength measurements in shock-loaded molybdenum have been performed in the stress range 1-12 GPa using plate impact techniques. Shear strength is deduced using manganin stress gauges mounted such that they are sensitive to the longitudinal lateral components of stress. In previous work on the shock response of body-centred-cubic (bcc) metals, increases in lateral stress with duration behind the shock front have been interpreted as a decrease in shear strength. In tantalum, this interpretation has been supported by post-shock microstructural analysis which reveals only a minor increase in dislocation density. However, our current observations in molybdenum reveal a flatter response with duration behind the shock front. It is postulated that this behaviour is a consequence of deformation twinning in molybdenum, the motion interaction of dislocations already present in the as-received material.

  14. Microstructures define melting of molybdenum at high pressures

    PubMed Central

    Hrubiak, Rostislav; Meng, Yue; Shen, Guoyin

    2017-01-01

    High-pressure melting anchors the phase diagram of a material, revealing the effect of pressure on the breakdown of the ordering of atoms in the solid. An important case is molybdenum, which has long been speculated to undergo an exceptionally steep increase in melting temperature when compressed. On the other hand, previous experiments showed nearly constant melting temperature as a function of pressure, in large discrepancy with theoretical expectations. Here we report a high-slope melting curve in molybdenum by synchrotron X-ray diffraction analysis of crystalline microstructures, generated by heating and subsequently rapidly quenching samples in a laser-heated diamond anvil cell. Distinct microstructural changes, observed at pressures up to 130 gigapascals, appear exclusively after melting, thus offering a reliable melting criterion. In addition, our study reveals a previously unsuspected transition in molybdenum at high pressure and high temperature, which yields highly textured body-centred cubic nanograins above a transition temperature. PMID:28248309

  15. Influence of the conserved disulphide bond, exposed to the putative binding pocket, on the structure and function of the immunoglobulin-like molecular chaperone Caf1M of Yersinia pestis.

    PubMed

    Zav'yalov, V P; Chernovskaya, T V; Chapman, D A; Karlyshev, A V; MacIntyre, S; Zavialov, A V; Vasiliev, A M; Denesyuk, A I; Zav'yalova, G A; Dudich, I V; Korpela, T; Abramov, V M

    1997-06-01

    The Yersinia pestis protein Caf1M is a typical representative of a subfamily of periplasmic molecular chaperones with characteristic structural and functional features, one of which is the location of two conserved cysteine residues close to the putative binding pocket. We show that these residues form a disulphide bond, the reduction and alkylation of which significantly increases the dissociation constant of the Caf1M-Caf1 (where Caf 1 is a polypeptide subunit of the capsule) complex [from a Kd of (4.77+/-0.50)x10(-9) M for the intact protein to one of (3.68+/-0.68)x10(-8) M for the modified protein]. The importance of the disulphide bond for the formation of functional Caf1M in vivo was demonstrated using an Escherichia coli dsbA mutant carrying the Y. pestis f1 operon. In accordance with the CD and fluorescence measurements, the disulphide bond is not important for maintenance of the overall structure of the Caf1M molecule, but would appear to affect the fine structural properties of the subunit binding site. A three-dimensional model of the Caf1M-Caf1 complex was designed based on the published crystal structure of PapD (a chaperone required for Pap pili assembly) complexed with a peptide corresponding to the C-terminus of the papG subunit. In the model the disulphide bond is in close proximity to the invariant Caf1M Arg-23 and Lys-142 residues that are assumed to anchor the C-terminal group of the subunit. The importance of this characteristic disulphide bond for the orchestration of the binding site and subunit binding, as well as for the folding of the protein in vivo, is likely to be a common feature of this subfamily of Caf1M-like chaperones. A possible model for the role of the disulphide bond in Caf1 assembly is discussed.

  16. Femtosecond laser surface structuring of molybdenum thin films

    NASA Astrophysics Data System (ADS)

    Kotsedi, L.; Mthunzi, P.; Nuru, Z. Y.; Eaton, S. M.; Sechoghela, P.; Mongwaketsi, N.; Ramponi, R.; Maaza, M.

    2015-10-01

    This contribution reports on the femtosecond surface structuring of molybdenum thin coatings deposited by electron beam evaporation onto Corning glass substrates. The 1-D type periodic grating lines created by such an ablation showed that the widths of the shallow grooves followed a logarithmic dependence with the laser energy incident on the molybdenum film. The electronic valence "x" of the created oxide surface layer MoOx was found to be incident laser power dependent via Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy and X-ray diffraction investigations. Such a photo-induced MoOx-Mo nanocomposite exhibited effective selective solar absorption in the UV-vis-IR spectral range.

  17. Selective emission multilayer coatings for a molybdenum thermophotovoltaic radiator

    DOEpatents

    Cockeram, Brian Vern

    2004-01-27

    Multilayer coating designs have been developed to provide selective emission for a molybdenum thermophotovoltaic (TPV) radiator surface. These coatings increase the surface emissivity of a molybdenum TPV radiator substrate in the wavelength range that matches the bandgap of the TPV cells to increase the power density of the TPV system. Radiator emission at wavelengths greater than the bandgap energy of the TPV cells is greatly reduced through the use of these coatings, which significantly increases the efficiency of the TPV system. The use of this coating greatly improves the performance of a TPV system, and the coating can be tailored to match the bandgap of any practical TPV system.

  18. HEU and LEU comparison in the production of Molybdenum-99

    SciTech Connect

    Cestau, Daniel; Novello, Ariel; Cristini, Pablo; Bronca, Marcelo; Centurion, Roberto; Bavaro, Ricardo; Cestau, Julian; Carranza, Eduardo

    2008-07-15

    Fission Molybdenum-99 from LEU targets is being produced in Argentina, at the Ezeiza Atomic Centre, since 2002. Before 2002, Argentina produced for more than 15 years fission molybdenum-99 from HEU targets. Both production procedures involve the irradiation of the targets composed by an Uranium-Aluminium compound 'meat' cladded with aluminum and a chemical processing of the targets. A statistic relative efficiency analysis of the production results, a brief description of the LEU method and quality control data of both procedures will be presented. (author)

  19. Nitrogen incorporation in sputter deposited molybdenum nitride thin films

    SciTech Connect

    Stöber, Laura Patocka, Florian Schneider, Michael Schmid, Ulrich; Konrath, Jens Peter Haberl, Verena

    2016-03-15

    In this paper, the authors report on the high temperature performance of sputter deposited molybdenum (Mo) and molybdenum nitride (Mo{sub 2}N) thin films. Various argon and nitrogen gas compositions are applied for thin film synthetization, and the amount of nitrogen incorporation is determined by Auger measurements. Furthermore, effusion measurements identifying the binding conditions of the nitrogen in the thin film are performed up to 1000 °C. These results are in excellent agreement with film stress and scanning electron microscope analyses, both indicating stable film properties up to annealing temperatures of 500 °C.

  20. A review of chromium, molybdenum, and tungsten alloys

    NASA Technical Reports Server (NTRS)

    Klopp, W. D.

    1975-01-01

    The mechanical properties of chromium, molybdenum, and tungsten alloys are reviewed with particular emphasis on high-temperature strength and low-temperature ductility. Precipitate strengthening is highly effective at 0.4 to 0.8 times the melting temperature in these metals, with HfC being most effective in tungsten and molybdenum, and Ta(B,C) most effective in chromium. Low-temperature ductility can be improved by alloying to promote rhenium ductilizing or solution softening. The low-temperature mechanical properties of these alloys appear related to electronic interactions rather than to the usual metallurgical considerations.

  1. Magnetoresistance measurements of superconducting molybdenum nitride thin films

    SciTech Connect

    Baskaran, R. Arasu, A. V. Thanikai; Amaladass, E. P.

    2016-05-23

    Molybdenum nitride thin films have been deposited on aluminum nitride buffered glass substrates by reactive DC sputtering. GIXRD measurements indicate formation of nano-crystalline molybdenum nitride thin films. The transition temperature of MoN thin film is 7.52 K. The transition width is less than 0.1 K. The upper critical field Bc{sub 2}(0), calculated using GLAG theory is 12.52 T. The transition width for 400 µA current increased initially upto 3 T and then decreased, while that for 100 µA current transition width did not decrease.

  2. A review of chromium, molybdenum, and tungsten alloys

    NASA Technical Reports Server (NTRS)

    Klopp, W. D.

    1975-01-01

    The mechanical properties of chromium, molybdenum, and tungsten alloys are reviewed with particular emphasis on high-temperature strength and low-temperature ductility. Precipitate strengthening is highly effective at 0.4 to 0.8 times the melting temperature in these metals, with HfC being most effective in tungsten and molybdenum, and Ta(B,C) most effective in chromium. Low-temperature ductility can be improved by alloying to promote rhenium ductilizing or solution softening. The low-temperature mechanical properties of these alloys appear related to electronic interactions rather than to the usual metallurgical considerations.

  3. Breaking America’s Dependence on Foreign…Molybdenum

    PubMed Central

    Einstein, Andrew J.

    2009-01-01

    Brief Unstructured Abstract Approximately 9 million nuclear cardiology studies performed each year in the United States employ technetium-99m, which is produced from the decay of molybdenum-99. The fragility of the worldwide technetium-99m supply chain has been underscored by current shortages caused by an unplanned shutdown of Europe’s largest reactor. The majority of the United States’ supply derives from a reactor in Canada nearing the end of its lifespan, whose planned replacements have been recently cancelled. In this article, the clinical importance of technetium-99m and our tenuous dependence on foreign supply of Molybdenum is addressed. PMID:19356583

  4. The nairovirus nairobi sheep disease virus/ganjam virus induces the translocation of protein disulphide isomerase-like oxidoreductases from the endoplasmic reticulum to the cell surface and the extracellular space.

    PubMed

    Lasecka, Lidia; Baron, Michael D

    2014-01-01

    Nairobi sheep disease virus (NSDV) of the genus Nairovirus causes a haemorrhagic gastroenteritis in sheep and goats with mortality up to 90%; the virus is found in East and Central Africa, and in India, where the virus is called Ganjam virus. NSDV is closely related to the human pathogen Crimean-Congo haemorrhagic fever virus, which also causes a haemorrhagic disease. As with other nairoviruses, replication of NSDV takes place in the cytoplasm and the new virus particles bud into the Golgi apparatus; however, the effect of viral replication on cellular compartments has not been studied extensively. We have found that the overall structure of the endoplasmic reticulum (ER), the ER-Golgi intermediate compartment and the Golgi were unaffected by infection with NSDV. However, we observed that NSDV infection led to the loss of protein disulphide isomerase (PDI), an oxidoreductase present in the lumen of the endoplasmic reticulum (ER) and which assists during protein folding, from the ER. Further investigation showed that NSDV-infected cells have high levels of PDI at their surface, and PDI is also secreted into the culture medium of infected cells. Another chaperone from the PDI family, ERp57, was found to be similarly affected. Analysis of infected cells and expression of individual viral glycoproteins indicated that the NSDV PreGn glycoprotein is involved in redistribution of these soluble ER oxidoreductases. It has been suggested that extracellular PDI can activate integrins and tissue factor, which are involved respectively in pro-inflammatory responses and disseminated intravascular coagulation, both of which manifest in many viral haemorrhagic fevers. The discovery of enhanced PDI secretion from NSDV-infected cells may be an important finding for understanding the mechanisms underlying the pathogenicity of haemorrhagic nairoviruses.

  5. An Unsaturated Four-Coordinate Dimethyl Dimolybdenum Complex with a Molybdenum-Molybdenum Quadruple Bond.

    PubMed

    Curado, Natalia; Carrasco, Mario; Campos, Jesús; Maya, Celia; Rodríguez, Amor; Ruiz, Eliseo; Álvarez, Santiago; Carmona, Ernesto

    2017-01-01

    We describe the synthesis and the molecular and electronic structures of the complex [Mo2 Me2 {μ-HC(NDipp)2 }2 ] (2; Dipp=2,6-iPr2 C6 H3 ), which contains a dimetallic core with an Mo-Mo quadruple bond and features uncommon four-coordinate geometry and has a fourteen-electron count for each molybdenum atom. The coordination polyhedron approaches a square pyramid, with one of the molybdenum atoms nearly co-planar with the basal square plane, in which the trans coordination position with respect to the Mo-Me bond is vacant. The other three sites are occupied by two trans nitrogen atoms of different amidinate ligands and the methyl group. The second Mo atom occupies the apex of the pyramid and forms an Mo-Mo bond of length 2.080(1) Å, consistent with a quadruple bond. Compound 2 reacts with tetrahydrofuran (THF) and trimethylphosphine to yield the mono-adducts [Mo2 Me(μ-Me){μ-HC(NDipp)2 }2 (L)] (3⋅THF and 3⋅PMe3 , respectively) with one terminal and one bridging methyl group. In contrast, 4-dimethylaminopyridine (dmap) forms the bis-adduct [Mo2 Me2 {μ-HC(NDipp)2 }2 (dmap)2 ] (4), with terminally coordinated methyl groups. Hydrogenolysis of complex 2 leads to the bis(hydride) [Mo2 H2 {μ-HC(NDipp)2 }2 (thf)2 ] (5⋅THF) with elimination of CH4 . Computational, kinetic, and mechanistic studies, which included the use of D2 and of complex 2 labelled with (13) C (99 %) at the Mo-CH3 sites, supported the intermediacy of a methyl-hydride reactive species. A computational DFT analysis of the terminal and bridging coordination of the methyl groups to the Mo≣Mo core is also reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Heterogeneous nuclear ribonucleoprotein E1 regulates protein disulphide isomerase translation in oxidized low-density lipoprotein-activated endothelial cells.

    PubMed

    Meng, N; Peng, N; Huang, S; Wang, S Q; Zhao, J; Su, L; Zhang, Y; Zhang, S; Zhao, B; Miao, J

    2015-03-01

    Endothelium-derived protein disulphide isomerase (PDI) is required for thrombus formation in vivo. But, how to control PDI overproduction in oxidized low-density lipoprotein (oxLDL)-activated vascular endothelial cells (VECs) is not well understood. In this study, we try to answer this question using our newly identified activator of mTOC1 3-benzyl-5-((2-nitrophenoxy) methyl)-dihydrofuran-2 (3H)-one (3BDO) that has been shown to protect VECs. First, we performed a proteomics analysis on the oxLDL-activated vascular VECs in the presence or absence of 3BDO. Next, we constructed the heterogeneous nuclear ribonucleoprotein E1 (hnRNP E1) mutants at Ser43 and used the RNA-ChIP technique to investigate the relationship between hnRNP E1 and PDI production. Furthermore, we examined the effect of 3BDO on oxLDL-altered phosphorylation of Akt1 and Akt2. Finally, we studied the effect of 3BDO on oxLDL-altered PDI protein level in apolipoprotein E(-/-) mice with advanced atherosclerosis. In VECs, oxLDL-increased PDI protein level, induced hnRNP E1 phosphorylation at Ser43, suppressed the binding of hnRNP E1 to PDI 5'UTR and induced the phosphorylation of Akt2 but not Akt1. All of these processes were blocked by 3BDO. Importantly, Ser43 mutant of hnRNP E1 inhibited the increase of PDI protein level and the decrease of the binding of hnRNP E1 and PDI 5'UTR induced by oxLDL. Furthermore, 3BDO suppressed oxLDL-induced PDI protein increase in the serum and plaque endothelium of apolipoprotein E(-/-) mice. hnRNP E1 is a new regulator of PDI translation in oxLDL-activated VECs, and 3BDO is a powerful agent for controlling PDI overproduction. © 2014 Scandinavian Physiological Society. Published by John Wiley & Sons Ltd.

  7. Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

    SciTech Connect

    Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; Glatzel, Uwe

    2015-01-31

    Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is more than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.

  8. Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

    DOE PAGES

    Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

    2015-01-31

    Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

  9. Alloy hardening and softening in binary molybdenum alloys as related to electron concentration

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.; Witzke, W. R.

    1972-01-01

    An investigation was conducted to determine the effects of alloy additions of hafnium, tantalum, tungsten, rhenium, osmium, iridium, and platinum on hardness of molybdenum. Special emphasis was placed on alloy softening in these binary molybdenum alloys. Results showed that alloy softening was produced by those elements having an excess of s+d electrons compared to molybdenum, while those elements having an equal number or fewer s+d electrons that molybdenum failed to produce alloy softening. Alloy softening and alloy hardening can be correlated with the difference in number of s+d electrons of the solute element and molybdenum.

  10. Chemical bonding topology of superconductors. 1. Ternary molybdenum chalcogenides (Chevrel phases)

    NASA Astrophysics Data System (ADS)

    King, R. B.

    1987-03-01

    Models for the chemical bonding topologies of ternary molybdenum chalcogenides (Chevrel phases) are derived using methods based on graph theory. The molybdenum sulfite Chevrel phases as well as their selenium analogs are viewed as three-dimensional lattices of edge-localized discrete molybdenum octahedra through face-sharing leads successively to the Mo9S11 napthalene analog and the Mo12S14 anathracene analog with increasing fusion leading to increasing delocalization of the chemical bonding topology within individual molybdenum cluster units. The infinite limit of such fusion of molybdenum octahedra corresponds to the infinite chain pseudo-one-dimensional metals which are formulated with globally delocalized octahedral cavities.

  11. Immunization with a synthetic robustoxin derivative lacking disulphide bridges protects against a potentially lethal challenge with funnel-web spider (Atrax robustus) venom.

    PubMed

    Comis, Alfio; Tyler, Margaret; Mylecharane, Ewan; Spence, Ian; Howden, Merlin

    2009-03-01

    The venom of male Atrax robustus spiders is potentially lethal to primates. These spiders have been responsible for a number of human deaths. Robustoxin is the lethal toxin in the venom. It is a highly cross-linked polypeptide that has 42 amino acid residues and four disulphide bridges. If these bridges are broken, the resulting polypeptide is non-toxic. Robustoxin was chemically synthesized with all of its eight cysteine residues protected with acetamidomethyl groups in order to avoid formation of disulphide bridges. The resulting derivative was co-polymerized with keyhole limpet haemocyanin. Two Macaca fascicularis monkeys were immunized with this conjugate. The monkeys were challenged,under anaesthesia,with a potentially lethal dose of male A.robustus crude venom. Both monkeys showed some minor symptoms of intoxication but recovered fully with no adverse after-effects. Immunization with the same immunogen, in the absence of keyhole limpet haemocyanin, did not protect a third monkey. The N-terminal 23 amino acid peptide derived from the sequence of robustoxin was synthesized and conjugated with ovalbumin. A fourth monkey was immunized with this conjugate. However,it was not protected against challenge.The implications of these results for the preparation of synthetic peptide vaccines are discussed.

  12. A critical survey on the preferred conformations of diphenyl disulphone, dimethyl- and diphenyl-dichalcogenides, bis(3-thienyl)-disulphide and -disulphone

    NASA Astrophysics Data System (ADS)

    Lumbroso, H.; Catel, J.-M.; Le Coustumer, G.; Andrieu, C. G.

    1999-12-01

    A detailed analysis of the dipole moments of diphenyl disulphone as a benzene solute showed that the compound in solution exists as an equimolecular mixture of ψ-enantiomers characterized by a (O 2)S-S(O 2) rotational angle of ψ=118° in modulum, whilst in the crystal phase the molecules exhibit the s- trans structure ( ψ=180°) (C.H. Kiers, A. Vos, Rec. Trav. Chim. Pays-Bas 91 (1972) 126). Also from a dipole moment analysis, the preferred conformations in solution of dimethyl- and diphenyl-dichalcogenides, R 2X 2 with X=S, Se or Te, are determined and the results compared with previous studies. The actual structures of all these compounds in the non-condensed phase can be explained on classical grounds, at least qualitatively. The 1H and 13C NMR spectra of various 3-thienyl sulphides and sulphones, disulphides and disulphones including bis(3-thienyl)-disulphide and -disulphone, two novel compounds, were recorded and analysed in terms of the sulphur or sulphonyl mesomeric effect. Rotational isomerism for these compounds is also discussed, in the light for the sulphones of a molecular modelling for bis(3-thienyl) disulphone.

  13. Role of disulphide linkages between protein-coated lipid droplets and the protein matrix in the rheological properties of porcine myofibrillar protein-peanut oil emulsion composite gels.

    PubMed

    Wu, Mangang; Xiong, Youling L; Chen, Jie

    2011-07-01

    The objective of the study was to establish disulphide interaction between protein-coated oil droplets and the surrounding protein matrix in myofibrillar protein (MP)-emulsion composite gels. An MP-stabilized peanut oil emulsion was treated with 0, 1, 3, 5 and 10 mM N-ethylmaleimide (NEM, a sulphydryl-blocking agent) and subsequently incorporated into a bulk MP sol to produce 5%-lipid, 2%-protein composites at pH 6.2. About 69% of sulphydryls in the emulsion (1% protein) were blocked by 1 mM NEM, and almost all were bound at ≥3 mM NEM. The loss of free sulphydryls resulted in a significant drop in the storage modulus (G') and rupture force of the composite gels. Microstructural examination revealed pores and oil leakage from emulsion droplets by NEM treatments, corresponding to declining rheological properties of the MP-emulsion composites. The results supported the hypothesis that disulphide cross-linking between MP-coated oil droplets and protein matrix contributed to the stabilization and reinforcement of protein-emulsion composite gels formed in comminuted muscle foods. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Mass spectrometry analysis of the oxidation states of the pro-oncogenic protein anterior gradient-2 reveals covalent dimerization via an intermolecular disulphide bond.

    PubMed

    Clarke, David J; Murray, Euan; Faktor, Jakub; Mohtar, Aiman; Vojtesek, Borek; MacKay, C Logan; Smith, Pat Langridge; Hupp, Ted R

    2016-05-01

    Anterior Gradient-2 (AGR2) is a component of a pro-oncogenic signalling pathway that can promote p53 inhibition, metastatic cell migration, limb regeneration, and cancer drug-resistance. AGR2 is in the protein-disulphide isomerase superfamily containing a single cysteine (Cys-81) that forms covalent adducts with its client proteins. We have found that mutation of Cysteine-81 attenuates its biochemical activity in its sequence-specific peptide docking function, reduces binding to Reptin, and reduces its stability in cells. As such, we evaluated how chemical oxidation of its cysteine affects its biochemical properties. Recombinant AGR2 spontaneously forms covalent dimers in the absence of reductant whilst DTT promotes dimer to monomer conversion. Mutation of Cysteine-81 to alanine prevents peroxide catalysed dimerization of AGR2 in vitro, suggesting a reactive cysteine is central to covalent dimer formation. Both biochemical assays and ESI mass spectrometry were used to demonstrate that low levels of a chemical oxidant promote an intermolecular disulphide bond through formation of a labile sulfenic acid intermediate. However, higher levels of oxidant promote sulfinic or sulfonic acid formation thus preventing covalent dimerization of AGR2. These data together identify the single cysteine of AGR2 as an oxidant responsive moiety that regulates its propensity for oxidation and its monomeric-dimeric state. This has implications for redox regulation of the pro-oncogenic functions of AGR2 protein in cancer cells. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. The disulphide mapping, folding and characterisation of recombinant Ber e 1, an allergenic protein, and SFA8, two sulphur-rich 2S plant albumins.

    PubMed

    Alcocer, Marcos J C; Murtagh, Gareth J; Bailey, Kevin; Dumoulin, Mireille; Meseguer, Amparo Sarabia; Parker, Martin J; Archer, David B

    2002-11-15

    We have cloned and expressed genes encoding the allergenic brazil nut 2S albumin (Ber e 1) and the sunflower albumin 8 (SFA8) in the methylotrophic yeast Pichia pastoris. We show that both proteins were secreted at high levels and that the purified proteins were properly folded. We also showed that Ber e 1 is glycosylated during secretion and that the glycan does not interfere with the folding or immunoreactivity. The disulphide map of the Ber e 1 protein was experimentally established and is in agreement with the conserved disulphide structure of other members of the 2S albumin family. A model three-dimensional structure of the allergen was generated. During the expression studies and through mutation we have also shown that alteration of the sequences around the Kex2 endoproteolytic processing site in the expressed fusion protein can compromise the secretion by targeting part of the protein for possible degradation. The secreted production of these properly folded sulphur-rich plant albumins presents an opportunity to delineate the attributes that make an allergen and to facilitate the diagnosis and therapy of type I allergy.

  16. Disulphide bonds in wheat gluten: further cystine peptides from high molecular weight (HMW) and low molecular weight (LMW) subunits of glutenin and from gamma-gliadins.

    PubMed

    Köhler, P; Belitz, H D; Wieser, H

    1993-03-01

    Glutenin was prepared from gluten of the wheat variety Rektor by extraction of gliadin with aqueous ethanol. It was cleaved successively into soluble peptides by the enzymes trypsin and thermolysin. Separation of the peptide mixtures was performed by gel permeation chromatography (GPC) on Sephadex G25 and reversed phase high performance liquid chromatography (RP-HPLC) on ODS-Hypersil. Cystine peptides were detected by differential chromatography of the samples prior to and after reduction. After isolation by multi-step RP-HPLC, the cystine peptides were reduced. The resulting cysteine peptides were alkylated with 4-vinylpyridine, separated by RP-HPLC and sequenced by means of the Edman degradation. The isolated cystine peptides represented a considerable portion of the total cysteine in glutenin: four out of seven cysteine residues of HMW subunits, and eight out of nine cysteine residues of LMW subunits are documented by at least one cystine peptide. Most of the peptides corresponded to known sequences of gluten protein components. From the structures of some tryptic peptides, inter- and intramolecular disulphide bonds for HMW subunits of glutenin have been proven. Cystine peptides from the thermolytic digest have been assigned to LMW subunits of glutenin and to gamma-gliadins. Other peptides have been closely related to partial sequences of these protein components. The results have allowed several conclusions about the arrangement of intra- and intermolecular disulphide bridges in gluten proteins.

  17. Corrosion Evaluation of RERTR Uranium Molybdenum Fuel

    SciTech Connect

    A K Wertsching

    2012-09-01

    As part of the National Nuclear Security Agency (NNSA) mandate to replace the use of highly enriched uranium (HEU) fuel for low enriched uranium (LEU) fuel, research into the development of LEU fuel for research reactors has been active since the late 1970’s. Originally referred to as the Reduced Enrichment for Research and Test Reactor (RERTR) program the new effort named Global Threat Reduction Initiative (GTRI) is nearing the goal of replacing the standard aluminum clad dispersion highly enriched uranium aluminide fuel with a new LEU fuel. The five domestic high performance research reactors undergoing this conversion are High Flux Isotope reactor (HFIR), Advanced Test Reactor (ATR), National Institute of Standards and Technology (NIST) Reactor, Missouri University Research Reactor (MURR) and the Massachusetts Institute of Technology Reactor II (MITR-II). The design of these reactors requires a higher neutron flux than other international research reactors, which to this point has posed unique challenges in the design and development of the new mandated LEU fuel. The new design utilizes a monolithic fuel configuration in order to obtain sufficient 235U within the LEU stoichoimetry to maintain the fission reaction within the domestic test reactors. The change from uranium aluminide dispersion fuel type to uranium molybdenum (UMo) monolithic configuration requires examination of possible corrosion issues associated with the new fuel meat. A focused analysis of the UMo fuel under potential corrosion conditions, within the ATR and under aqueous storage indicates a slow and predictable corrosion rate. Additional corrosion testing is recommended for the highest burn-up fuels to confirm observed corrosion rate trends. This corrosion analysis will focus only on the UMo fuel and will address corrosion of ancillary components such as cladding only in terms of how it affects the fuel. The calculations and corrosion scenarios are weighted with a conservative bias to

  18. Synthesis and characterization of zinc-molybdenum oxide photocatalysts using an electrochemical-thermal process

    NASA Astrophysics Data System (ADS)

    Goveas, J. J.; Gonsalves, R. A.; Rao, P.; Pinto, R.

    2016-05-01

    Dyes act as major pollutants in water and can be degraded by photocatalysis. This paper establishes the role of electrochemically generated nanostructures of Zinc-Molybdenum oxides (ZMO) as photocatalysts by degrading EBT (Eriochrome Black- T) taken as a model pollutant under UV light. A facile, rapid and low cost process to synthesize these nanostructures (ZMO) is presented. Various factors that affect the synthesis and photocatalytic activity of these nanostructures are discussed. The role of calcination temperature and pulverization on the photocatalytic action has also been established. Particles have been synthesized in pure form as well as using surfactants such as cetrimide (cetyl trimethyl ammonium bromide), polyethylene glycol (PEG) and SDS (sodium dodecyl sulphate) to enhance their photocatalytic action. This paper also discusses the characterization of these nanoparticles by powder XRD, SEM, FT-IR and UV-Visible spectroscopy. Decolourisation was achieved to completion under optimum experimental conditions at room temperature ascertaining the application of these nanostructures as effective photocatalysts.

  19. Fretting wear in titanium, Monel-400, and cobalt 25-percent-molybdenum using scanning electron microscopy

    NASA Technical Reports Server (NTRS)

    Bill, R. C.

    1972-01-01

    Damage scar volume measurements taken from like metal fretting pairs combined with scanning electron microscopy observations showed that three sequentially operating mechanisms result in the fretting of titanium, Monel-400, and cobalt - 25-percent molybdenum. Initially, adhesion and plastic deformation of the surface played an important role. This was followed after a few hundred cycles by a fatigue mechanism which produced spall-like pits in the damage scar. Finally, a combination of oxidation and abrasion by debris particles became most significant. Damage scar measurements made on several elemental metals after 600,000 fretting cycles suggested that the ratio of oxide hardness to metal hardness was a measure of the susceptibility of a metal to progressive damage by fretting.

  20. Molybdenum disulfide nanoparticles decorated reduced graphene oxide: highly sensitive and selective hydrogen sensor.

    PubMed

    Venkatesan, A; Rathi, Servin; Lee, In-Yeal; Park, Jinwoo; Lim, Dongsuk; Kang, Moonshik; Joh, Han-Ik; Kim, Gil-Ho; Kannan, E S

    2017-09-08

    In this work, we report on the hydrogen (H2) sensing behavior of reduced graphene oxide (RGO)/molybdenum disulfide (MoS2) nano particles (NPs) based composite film. The RGO/MoS2 composite exhibited a highly enhanced H2 response (∼15.6%) for 200 ppm at an operating temperature of 60 °C. Furthermore, the RGO/MoS2 composite showed excellent selectivity to H2 with respect to ammonia (NH3) and nitric oxide (NO) which are highly reactive gas species. The composite's response to H2 is 2.9 times higher than that of NH3 whereas for NO it is 3.5. This highly improved H2 sensing response and selectivity of RGO/MoS2 at low operating temperatures were attributed to the structural integration of MoS2 nanoparticles in the nanochannels and pores in the RGO layer.

  1. Formation of the phase composition of a multicomponent molybdenum oxide catalyst in the course of regeneration

    SciTech Connect

    Yakovleva, T.N.; Chibirova, F. Kh.; Tarasova, D.V.

    1995-09-01

    Formation of the phase composition of a multicomponent molybdenum oxide catalyst (supported on silica gel), which was deactivated during the ammoxidation of propene, is studied by means of chemical and X-ray phase analyses, Moessbauer spectroscopy, and ESR in the course of the regeneration using ammonium paramolybdate followed by thermal treatment at 100 - 650{degrees}C. The formation of iron(III) molybdate is shown to occur in the temperature range 350 - 650{degrees}C via the oxidation of iron(II) molybdate by air to form Fe{sub 2}O{sub 3} clusters, which transform into the hematite particles, and the interaction of the latter with MoO{sub 3}.

  2. Molybdenum disulfide nanoparticles decorated reduced graphene oxide: highly sensitive and selective hydrogen sensor

    NASA Astrophysics Data System (ADS)

    Venkatesan, A.; Rathi, Servin; Lee, In-yeal; Park, Jinwoo; Lim, Dongsuk; Kang, Moonshik; Joh, Han-Ik; Kim, Gil-Ho; Kannan, E. S.

    2017-09-01

    In this work, we report on the hydrogen (H2) sensing behavior of reduced graphene oxide (RGO)/molybdenum disulfide (MoS2) nano particles (NPs) based composite film. The RGO/MoS2 composite exhibited a highly enhanced H2 response (∼15.6%) for 200 ppm at an operating temperature of 60 °C. Furthermore, the RGO/MoS2 composite showed excellent selectivity to H2 with respect to ammonia (NH3) and nitric oxide (NO) which are highly reactive gas species. The composite’s response to H2 is 2.9 times higher than that of NH3 whereas for NO it is 3.5. This highly improved H2 sensing response and selectivity of RGO/MoS2 at low operating temperatures were attributed to the structural integration of MoS2 nanoparticles in the nanochannels and pores in the RGO layer.

  3. Synthesis and characterization of zinc-molybdenum oxide photocatalysts using an electrochemical-thermal process

    SciTech Connect

    Goveas, J. J. Gonsalves, R. A.; Rao, P.; Pinto, R.

    2016-05-23

    Dyes act as major pollutants in water and can be degraded by photocatalysis. This paper establishes the role of electrochemically generated nanostructures of Zinc-Molybdenum oxides (ZMO) as photocatalysts by degrading EBT (Eriochrome Black- T) taken as a model pollutant under UV light. A facile, rapid and low cost process to synthesize these nanostructures (ZMO) is presented. Various factors that affect the synthesis and photocatalytic activity of these nanostructures are discussed. The role of calcination temperature and pulverization on the photocatalytic action has also been established. Particles have been synthesized in pure form as well as using surfactants such as cetrimide (cetyl trimethyl ammonium bromide), polyethylene glycol (PEG) and SDS (sodium dodecyl sulphate) to enhance their photocatalytic action. This paper also discusses the characterization of these nanoparticles by powder XRD, SEM, FT-IR and UV-Visible spectroscopy. Decolourisation was achieved to completion under optimum experimental conditions at room temperature ascertaining the application of these nanostructures as effective photocatalysts.

  4. Storage and Bioavailability of Molybdenum in Soils Increased by Organic Matter Complexation

    SciTech Connect

    Wichard, T.; Mishra, B; Myneni, S; Bellenger, J; Kraepiel, A

    2009-01-01

    The micronutrient molybdenum is a necessary component of the nitrogen-fixing enzyme nitrogenase1, 2. Molybdenum is very rare in soils, and is usually present in a highly soluble form, making it susceptible to leaching3, 4. However, it is generally thought that molybdenum attaches to mineral surfaces in acidic soils; this would prevent its escape into the groundwater, but would also impede uptake by microbes3. Here we use X-ray spectroscopy to examine the chemical speciation of molybdenum in soil samples from forests in Arizona and New Jersey. We show that in the leaf litter layer, most of the molybdenum forms strong complexes with plant-derived tannins and tannin-like compounds; molybdenum binds to these organic ligands across a wide pH range. In deeper soils, molybdenum binds to both iron oxides and natural organic matter. We suggest that the molybdenum bound to organic matter can be captured by small complexing agents that are released by nitrogen-fixing bacteria; the molybdenum can then be incorporated into nitrogenase. We conclude that the binding of molybdenum to natural organic matter helps prevent leaching of molybdenum, and is thus a critical step in securing new nitrogen in terrestrial ecosystems.

  5. Storage and bioavailability of molybdenum in soils increased by organic matter complexation

    NASA Astrophysics Data System (ADS)

    Wichard, Thomas; Mishra, Bhoopesh; Myneni, Satish C. B.; Bellenger, Jean-Philippe; Kraepiel, Anne M. L.

    2009-09-01

    The micronutrient molybdenum is a necessary component of the nitrogen-fixing enzyme nitrogenase. Molybdenum is very rare in soils, and is usually present in a highly soluble form, making it susceptible to leaching. However, it is generally thought that molybdenum attaches to mineral surfaces in acidic soils; this would prevent its escape into the groundwater, but would also impede uptake by microbes. Here we use X-ray spectroscopy to examine the chemical speciation of molybdenum in soil samples from forests in Arizona and New Jersey. We show that in the leaf litter layer, most of the molybdenum forms strong complexes with plant-derived tannins and tannin-like compounds; molybdenum binds to these organic ligands across a wide pH range. In deeper soils, molybdenum binds to both iron oxides and natural organic matter. We suggest that the molybdenum bound to organic matter can be captured by small complexing agents that are released by nitrogen-fixing bacteria; the molybdenum can then be incorporated into nitrogenase. We conclude that the binding of molybdenum to natural organic matter helps prevent leaching of molybdenum, and is thus a critical step in securing new nitrogen in terrestrial ecosystems.

  6. Electrodeposition of low contraction chromium/molybdenum alloys using pulse-reverse plating. Final report

    SciTech Connect

    Miller, M.D.; Langston, S.

    1994-12-01

    The use of modulated pulse periodic reverse (pulse-reverse) current to electrodeposit a low contraction (LC) chromium/molybdenum alloy has been evaluated. When using one full pulse-reverse plating cycle, the percent molybdenum in the deposit increased almost 400 percent (from 1 to 4 percent) as the current in the reverse cycle was increased from 0 to 10 amps. However, when the pulse reverse current was carried to six full plating cycles, the percent molybdenum in the deposit was not dependent upon the current and remained constant at about 1 percent. This is about the same percent molybdenum that could be expected in direct current-plated LC chromium/molybdenum alloy and about half the percent molybdenum that could be expected in an on/off pulse-plated LC chromium/molybdenum alloy.

  7. Molybdenum-platinum-oxide electrodes for thermoelectric generators

    DOEpatents

    Schmatz, Duane J.

    1990-01-01

    The invention is directed to a composite article suitable for use in thermoelectric generators. The article comprises a solid electrolyte carrying a thin film comprising molybdenum-platinum-oxide as an electrode deposited by physical deposition techniques. The invention is also directed to the method of making same.

  8. Molybdenum disilicide composites reinforced with zirconia and silicon carbide

    DOEpatents

    Petrovic, John J.

    1995-01-01

    Compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

  9. Molybdenum disilicide composites reinforced with zirconia and silicon carbide

    DOEpatents

    Petrovic, J.J.

    1995-01-17

    Compositions are disclosed consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

  10. Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

    NASA Astrophysics Data System (ADS)

    Li, Yongli; Yang, Jinhong; Zhao, Zhongwei

    2017-10-01

    With most high-quality tungsten ores being exhausted, the enhancement of low-grade scheelite concentrates processing has attracted a great deal of attention. The objective of this study is to develop a method to maximize the recovery tungsten and molybdenum from a low-grade scheelite via a new acid leaching process followed by solvent extraction. Under optimal conditions (350 g/L H2SO4, 95°C, and 2 h), approximately 99.8% of tungsten and 98% of molybdenum were leached out. In the subsequent solvent extraction process, more than 99% of the tungsten and molybdenum were extracted with a co-extraction system (50% TBP, 30% HDEHP, and 10% 2-octanol in kerosene) using a three-stage cross-flow extraction. The raffinate can be recycled for the next leaching process after replenishing the H2SO4 to the initial value (approximately 350 g/L). Based on these results, a conceptual flowsheet is presented to recover tungsten and molybdenum from the low-grade scheelite.

  11. Discovery of rubidium, strontium, molybdenum, and rhodium isotopes

    SciTech Connect

    Parker, A.M.; Thoennessen, M.

    2012-07-15

    Currently, 31 rubidium, 35 strontium, 35 molybdenum, and 38 rhodium isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

  12. Iron-molybdenum cofactor synthesis in Azotobacter vinelandii Nif- mutants.

    PubMed Central

    Imperial, J; Shah, V K; Ugalde, R A; Ludden, P W; Brill, W J

    1987-01-01

    Nif- mutants of Azotobacter vinelandii defective in dinitrogenase activity synthesized iron-molybdenum cofactor (FeMo-co) and accumulated it in two protein-bound forms: inactive dinitrogenase and a possible intermediate involved in the FeMo-co biosynthetic pathway. FeMo-co from both these proteins could activate apo-dinitrogenase from FeMo-co-deficient mutants. PMID:3470286

  13. Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

    NASA Astrophysics Data System (ADS)

    Ho, Li-Ngee; Ikegawa, Tasuku; Nishiguchi, Hiroyasu; Nagaoka, Katsutoshi; Takita, Yusaku

    2006-07-01

    A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of 27Al and 31P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m 2/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo 4+ and Mo 6+ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.

  14. Molybdenum disilicide composites reinforced with zirconia and silicon carbide

    SciTech Connect

    Petrovic, J.J.

    1992-12-31

    This patent pertains to compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia. Fabrication, fracture toughness, and bend strength are covered.

  15. Dissolution kinetics of a sintered molybdenum coating applied on ceramics

    SciTech Connect

    Kuz`ko, V.S.

    1994-11-01

    Using weighing and corrosion diagrams, the etching parameters are determined for a sintered M-21 molybdenum coating applied to VK 94-1 vacuum-tight ceramics. Dissolution of M-21 in an alkaline solution of potassium hexacyanoferrate(III) can be treated as a corrosion process proceeding with kinetic control.

  16. Flexible Molybdenum Electrodes towards Designing Affinity Based Protein Biosensors

    PubMed Central

    Kamakoti, Vikramshankar; Panneer Selvam, Anjan; Radha Shanmugam, Nandhinee; Muthukumar, Sriram; Prasad, Shalini

    2016-01-01

    Molybdenum electrode based flexible biosensor on porous polyamide substrates has been fabricated and tested for its functionality as a protein affinity based biosensor. The biosensor performance was evaluated using a key cardiac biomarker; cardiac Troponin-I (cTnI). Molybdenum is a transition metal and demonstrates electrochemical behavior upon interaction with an electrolyte. We have leveraged this property of molybdenum for designing an affinity based biosensor using electrochemical impedance spectroscopy. We have evaluated the feasibility of detection of cTnI in phosphate-buffered saline (PBS) and human serum (HS) by measuring impedance changes over a frequency window from 100 mHz to 1 MHz. Increasing changes to the measured impedance was correlated to the increased dose of cTnI molecules binding to the cTnI antibody functionalized molybdenum surface. We achieved cTnI detection limit of 10 pg/mL in PBS and 1 ng/mL in HS medium. The use of flexible substrates for designing the biosensor demonstrates promise for integration with a large-scale batch manufacturing process. PMID:27438863

  17. Irradiation testing of a niobium-molybdenum developmental thermocouple

    SciTech Connect

    Knight, R.C.; Greenslade, D.L.

    1991-10-01

    A need exists for a radiation-resistant thermocouple capable of monitoring temperatures in excess of the limits of the chromel/alumel system. Tungsten/rhenium and platinum/rhodium thermocouples have sufficient temperature capability but have proven to be unstable because of irradiation-induced decalibration. The niobium/molybdenum system is believed to hold great potential for nuclear applications at temperatures up to 2000 K. However, the fragility of pure niobium and fabrication problems with niobium/molybdenum alloys have limited development of this system. Utilizing the Fast Flux Test Facility, a developmental thermocouple with a thermoelement pair consisting of a pure molybdenum and a niobium-1%zirconium alloy wire was irradiated fro 7200 hours at a temperature of 1070 K. The thermocouple performed flawlessly for the duration of the experiment and exhibited stability comparable to a companion chromel/alumel unit. A second thermocouple, operating at 1375 K, is currently being employed to monitor a fusion materials experiment in the Fast Flux Test Facility. This experiment, also scheduled for 7200 hours, will serve to further evaluate the potential of the niobium-1%zirconium/molybdenum thermoelement system. 7 refs., 7 figs.

  18. Flexible Molybdenum Electrodes towards Designing Affinity Based Protein Biosensors.

    PubMed

    Kamakoti, Vikramshankar; Panneer Selvam, Anjan; Radha Shanmugam, Nandhinee; Muthukumar, Sriram; Prasad, Shalini

    2016-07-18

    Molybdenum electrode based flexible biosensor on porous polyamide substrates has been fabricated and tested for its functionality as a protein affinity based biosensor. The biosensor performance was evaluated using a key cardiac biomarker; cardiac Troponin-I (cTnI). Molybdenum is a transition metal and demonstrates electrochemical behavior upon interaction with an electrolyte. We have leveraged this property of molybdenum for designing an affinity based biosensor using electrochemical impedance spectroscopy. We have evaluated the feasibility of detection of cTnI in phosphate-buffered saline (PBS) and human serum (HS) by measuring impedance changes over a frequency window from 100 mHz to 1 MHz. Increasing changes to the measured impedance was correlated to the increased dose of cTnI molecules binding to the cTnI antibody functionalized molybdenum surface. We achieved cTnI detection limit of 10 pg/mL in PBS and 1 ng/mL in HS medium. The use of flexible substrates for designing the biosensor demonstrates promise for integration with a large-scale batch manufacturing process.

  19. Low solvothermal synthesis and characterization of hollow nanospheres molybdenum sulfide.

    PubMed

    Akram, H; Mateos-Pedrero, C; Gallegos-Suárez, E; Allali, N; Chafik, T; Rodriguez-Ramos, I; Guerrero Ruiz, A

    2012-08-01

    Hollow nanospheres of molybdenum disulfide have been synthesized by a novel solvothermal method under low temperature (180 degrees C). These nanomaterials were characterized by X-ray diffraction (XRD), Fourier transformation infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM, HRTEM) and X-ray Photoelectron Spectroscopy (XPS). A mechanism for the synthesis reaction is tentatively proposed and discussed.

  20. Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

    NASA Astrophysics Data System (ADS)

    Li, Yongli; Yang, Jinhong; Zhao, Zhongwei

    2017-07-01

    With most high-quality tungsten ores being exhausted, the enhancement of low-grade scheelite concentrates processing has attracted a great deal of attention. The objective of this study is to develop a method to maximize the recovery tungsten and molybdenum from a low-grade scheelite via a new acid leaching process followed by solvent extraction. Under optimal conditions (350 g/L H2SO4, 95°C, and 2 h), approximately 99.8% of tungsten and 98% of molybdenum were leached out. In the subsequent solvent extraction process, more than 99% of the tungsten and molybdenum were extracted with a co-extraction system (50% TBP, 30% HDEHP, and 10% 2-octanol in kerosene) using a three-stage cross-flow extraction. The raffinate can be recycled for the next leaching process after replenishing the H2SO4 to the initial value (approximately 350 g/L). Based on these results, a conceptual flowsheet is presented to recover tungsten and molybdenum from the low-grade scheelite.

  1. Preparation of isotopic molybdenum foils utilizing small quantities of material

    NASA Astrophysics Data System (ADS)

    Lipski, A. R.; Lee, L. L.; Liang, J. F.; Mahon, J. C.

    1993-09-01

    A simple method utilizing a small amount of isotopic material for production of molybdenum foils is discussed. An e-gun is used in the procedure. The Mo powder undergoes reduction-sintering and melting-solidifying steps leading to the creation of a metallic droplet suitable for further cold rolling or vacuum deposition.

  2. Optimization of the dissolution of molybdenum disks. FY-16 results

    SciTech Connect

    Tkac, Peter; Rotsch, David A.; Chemerisov, Sergey D.; Bailey, James L.; Krebs, John F.; Vandegrift, George F.

    2016-09-01

    Argonne National Laboratory is providing technical development assistance to NorthStar Medical Technologies LLC in its pursuit of two pathways for production of molybdenum-99: the 98Mo(n,γ) 99Mo reaction and the photonuclear reaction, 100Mo(γ,n)99Mo. Processing of irradiated targets, from either production mode, requires dissolution of the target material in H2O2 followed by a concentration step, addition of ferric ion to precipitate impurities, and conversion of the final solution to 5M potassium hydroxide solution of potassium molybdate. Currently, NorthStar is using pressed and sintered Mo disks as targets. Several options are being considered for the design of Mo targets for the production of 99Mo using the (γ,n) reaction. In the current design, the target holder contains a series of sintered Mo disks lined up perpendicular to two incident electron beams, one entering from each side of the target stack. In this configuration, the front-most disks absorb most of the heat from the electron beam and need to be thinner to allow for better cooling, while the middle of the target can be thicker. Distribution of the total mass of Mo allows for larger masses of Mo material and thus larger production batches of 99Mo. A limitation of the sintering approach is the production of very thin disks. Recent advances in 3D printing allow for much thinner target components can be achieved than when the traditional press-and-sinter approach is used. We have demonstrated that several factors can play important roles in dissolution behavior: particle size of Mo metal used for production of targets, sintering conditions, degree of open porosity, and thickness of the sintered Mo targets. Here we report experimental results from studies of small-scale dissolution of sintered Mo disks fabricated from various recycled and commercial Mo materials, and dissolution of 3D-printed Mo disks that were

  3. Small-angle neutron scattering by the tungsten and molybdenum oxides synthesized from polymer-salt complexes in acidic medium

    NASA Astrophysics Data System (ADS)

    Bogdanov, S.; Valiev, E.; Pirogov, A.; Teplykh, A.; Ostroushko, A.

    2004-07-01

    The peculiarities of oxide phase formation processes under the pyrolysis of salt and polymer-salt compounds based on polyvinyl alcohol and molybdenum and tungsten salts acidified by nitric acid have been studied. For that samples were prepared by annealing in a temperature range of 100-600°C and investigated by small-angle neutron scattering and X-ray diffraction methods. Similar samples with no polymer in their composition were studied for comparison. A size distribution of oxide phase particles, a specific surface area, a volume fraction and a mean particle size were found to be dependent on an annealing temperature and availability of the polymer. The characteristics of the above samples were compared with those of the earlier samples synthesized from solutions with a naturally established acidity. A mechanism of oxide particle formation under a thermal decomposition of the acidic compounds is provided.

  4. Characterization of Rhodobacter capsulatus genes encoding a molybdenum transport system and putative molybdenum-pterin-binding proteins.

    PubMed Central

    Wang, G; Angermüller, S; Klipp, W

    1993-01-01

    The alternative, heterometal-free nitrogenase of Rhodobacter capsulatus is repressed by traces of molybdenum in the medium. Strains carrying mutations located downstream of nifB copy II were able to express the alternative nitrogenase even in the presence of high molybdate concentrations. DNA sequence analysis of a 5.5-kb fragment of this region revealed six open reading frames, designated modABCD, mopA, and mopB. The gene products of modB and modC are homologous to ChlJ and ChlD of Escherichia coli and represent an integral membrane protein and an ATP-binding protein typical of high-affinity transport systems, respectively. ModA and ModD exhibited no homology to known proteins, but a leader peptide characteristic of proteins cleaved during export to the periplasm is present in ModA, indicating that ModA might be a periplasmic molybdate-binding protein. The MopA and MopB proteins showed a high degree of amino acid sequence homology to each other. Both proteins contained a tandem repeat of a domain encompassing 70 amino acid residues, which had significant sequence similarity to low-molecular-weight molybdenum-pterin-binding proteins from Clostridium pasteurianum. Compared with that for the parental nifHDK deletion strain, the molybdenum concentrations necessary to repress the alternative nitrogenase were increased 4-fold in a modD mutant and 500-fold in modA, modB, and modC mutants. No significant inhibition of the heterometal-free nitrogenase by molybdate was observed for mopA mopB double mutants. The uptake of molybdenum by mod and mop mutants was estimated by measuring the activity of the conventional molybdenum-containing nitrogenase. Molybdenum transport was not affected in a mopA mopB double mutant, whereas strains carrying lesions in the binding-protein-dependent transport system were impaired in molybdenum uptake. PMID:8491722

  5. Rhenium and Molybdenum in Rivers and Estuaries.

    NASA Astrophysics Data System (ADS)

    Walker, B. D.; Peucker-Ehrenbrink, B.

    2004-12-01

    Due to their redox-sensitive nature, the geochemical cycles of Re and Mo are linked to the global organic carbon cycle. Reducing sediments constitute a globally important sink and weathering of organic-rich sediments is responsible for a large portion of the Re and - to a lesser extent - Mo flux to the oceans (Colodner et al., 1993; Jaffe et al., 2002). Riverine concentrations of Re and Mo are a function of the river basin lithology, but are also likely to be affected by anthropogenic contributions (Colodner et al., 1995). Current estimates of global natural riverine Re flux are restricted to single analyses of four major rivers, which characterize only 23%\\ of the global freshwater flux (Colodner et al., 1993). Annual variability of Re and Mo concentrations in rivers has not been studied. A single study of Re concentrations along the salinity gradient of the Amazon shelf is suggestive of conservative mixing, but scatter in the data do not allow to exclude the possibility of Re addition in the low-salinity end of the profile (Colodner et al., 1993). Careful evaluation of samples from the Hudson River estuary using a variety of extraction techniques indicates that spike-sample equilibration was not fully achieved using commonly used methods. We have therefore developed a simple, clean and efficient method of extracting Re from filtered water samples. Our method utilizes syringe filtration, prolonged heating to achieve spike-sample equilibration, batch equilibration with TEVA resin, and extraction of Re and Mo using syringe filtration. Rhenium concentrations in the Hudson, Housatonic and Connecticut rivers are 38 pM, 6.6 pM and 14 pM, respectively, much higher than the estimated global average of 2.1 pM (Colodner et al., 1993). Molybdenum concentrations are 4.6 nM, 5.5 nM, 7.8 nM, respectively. These rivers drain basins of Precambrian basement as well as predominantly Paleozoic sediments and have been substantially urbanized. Data for a salinity profile along the

  6. Uranium-Molybdenum Dissolution Flowsheet Studies

    SciTech Connect

    Pierce, R. A.

    2007-03-01

    The Super Kukla (SK) Prompt Burst Reactor operated at the Nevada Test Site from 1964 to 1978. The SK material is a uranium-molybdenum (U-Mo) alloy material of 90% U/10% Mo by weight at approximately 20% 235U enrichment. H-Canyon Engineering (HCE) requested that the Savannah River National Lab (SRNL) define a flowsheet for safely and efficiently dissolving the SK material. The objective is to dissolve the material in nitric acid (HNO3) in the H-Canyon dissolvers to a U concentration of 15-20 g/L (3-4 g/L 235U) without the formation of precipitates or the generation of a flammable gas mixture. Testing with SK material validated the applicability of dissolution and solubility data reported in the literature for various U and U-Mo metals. Based on the data, the SK material can be dissolved in boiling 3.0-6.0 M HNO3 to a U concentration of 15-20 g/L and a corresponding Mo concentration of 1.7-2.2 g/L. The optimum flowsheet will use 4.0-5.0 M HNO3 for the starting acid. Any nickel (Ni) cladding associated with the material will dissolve readily. After dissolution is complete, traditional solvent extraction flowsheets can be used to recover and purify the U. Dissolution rates for the SK material are consistent with those reported in the literature and are adequate for H-Canyon processing. When the SK material dissolved at 70-100 o C in 1-6 M HNO3, the reaction bubbled vigorously and released nitrogen oxide (NO) and nitrogen dioxide (NO2) gas. Gas generation tests in 1 M and 2 M HNO3 at 100 o C generated less than 0.1 volume percent hydrogen (H2) gas. It is known that higher HNO3 concentrations are less favorable for H2 production. All tests at 70-100 o C produced sufficient gas to mix the solutions without external agitation. At room temperature in 5 M HNO3, the U-Mo dissolved slowly and the U-laden solution sank to the bottom of the dissolution vessel because of its greater density. The effect of the density difference insures that the SK material cannot dissolve and

  7. Reflectance, Optical Properties, and Stability of Molybdenum/Strontium and Molybdenum/Yttrium Multilayer Mirrors

    SciTech Connect

    Kjornrattanawanich, Benjawan

    2002-09-01

    The motivation of this work is to develop high reflectance normal-incidence multilayer mirrors in the 8-12 nm wavelength region for applications in astronomy and extreme ultraviolet lithography. To achieve this goal, Mo/Sr and Mo/Y multilayers were studied. These multilayers were deposited with a UHV magnetron sputtering system and their reflectances were measured with synchrotron radiation. High normal-incidence reflectances of 23% at 8.8 nm, 40.8% at 9.4 nm, and 48.3% at 10.5 nm were achieved. However, the reflectance of Mo/Sr multilayers decreased rapidly after exposure to air. Attempts to use thin layers of carbon to passivate the surface of Mo/Sr multilayers were unsuccessful. Experimental results on the refractive index $\\tilde{n}$ = 1-δ + iβ of yttrium and molybdenum in the 50-1300 eV energy region are reported in this work. This is the first time ever that values on the refractive index of yttrium are measured in this energy range. The absorption part β was determined through transmittance measurements. The dispersive part δ was calculated by means of the Kramers-Kronig formalism. The newly determined values of the refractive index of molybdenum are in excellent agreement with the published data. Those of yttrium are more accurate and contain fine structures around the yttrium M-absorption edges where Mo/Y multilayers operate. These improved sets of optical data lead to better design and modeling of the optical properties of Mo/Y multilayers. The reflectance quality of Mo/Y multilayers is dependent on their optical and structural properties. To correlate these properties with the multilayer reflectance, x-ray diffraction, Rutherford backscattering spectrometry, and transmission electron microscopy were used to analyze samples. Normal-incidence reflectances of 32.6% at 9.27 nm, 38.4% at 9.48 nm, and 29.6% at 9.46 nm were obtained from three representative Mo/Y multilayers which had about 0%, 25%, and 39% atomic oxygen assimilated in their yttrium layers

  8. Preparation of molybdenum carbides with multiple morphologies using surfactants as carbon sources

    SciTech Connect

    Wang, Hongfen; Wang, Zhiqi; Chen, Shougang

    2012-10-15

    Molybdenum carbides with surfactants as carbon sources were prepared using the carbothermal reduction of the appropriate precursors (molybdenum oxides deposited on surfactant micelles) at 1023 K under hydrogen gas. The carburized products were characterized using scanning electron microscopy (SEM), X-ray diffraction and BET surface area measurements. From the SEM images, hollow microspherical and rod-like molybdenum carbides were observed. X-ray diffraction patterns showed that the annealing time of carburization had a large effect on the conversion of molybdenum oxides to molybdenum carbides. And BET surface area measurements indicated that the difference of carbon sources brought a big difference in specific surface areas of molybdenum carbides. - Graphical abstract: Molybdenum carbides having hollow microspherical and hollow rod-like morphologies that are different from the conventional monodipersed platelet-like morphologies. Highlights: Black-Right-Pointing-Pointer Molybdenum carbides were prepared using surfactants as carbon sources. Black-Right-Pointing-Pointer The kinds of surfactants affected the morphologies of molybdenum carbides. Black-Right-Pointing-Pointer The time of heat preservation at 1023 K affected the carburization process. Black-Right-Pointing-Pointer Molybdenum carbides with hollow structures had larger specific surface areas.

  9. Low molybdenum state induced by tungsten as a model of molybdenum deficiency in rats.

    PubMed

    Yoshida, Munehiro; Nakagawa, Mikihito; Hosomi, Ryota; Nishiyama, Toshimasa; Fukunaga, Kenji

    2015-05-01

    Organ molybdenum (Mo) concentration and the activity of hepatic sulfite oxidase and xanthine oxidase were compared in tungsten-administered rats as well as rats fed with a low Mo diet to evaluate the use of tungsten-administered rats as a model of Mo deficiency. Twenty-four male 6-week-old Wistar rats were divided into four groups according to diet (AIN93G diet (control diet) or the control diet minus ammonium molybdate (low Mo diet)) and drinking water (deionized water or deionized water containing 200 μg/mL tungsten in the form of sodium tungstate). Mo content in the control and low Mo diets were 196 and 42 ng/g, respectively. Intake of the low Mo diet significantly reduced the Mo content of several organs and serum. Decrease in hepatic sulfite oxidase activity was also induced by the low Mo diet. The administration of tungsten induced marked decreases in organ Mo content and the activity of hepatic sulfite oxidase and xanthine oxidase. These decreases induced by tungsten administration were more pronounced than those induced by just a low Mo diet. Serum uric acid was also reduced by tungsten administration irrespective of Mo intake. Although a comparatively high accumulation of tungsten (3 to 9 μg/g) was observed in the kidneys and liver, adverse effects of tungsten accumulation on liver and kidney function were not observed in serum biochemical tests. These results indicate that tungsten-administered animals may be used as a model of Mo deficiency.

  10. Laser synthesis, structure and chemical properties of colloidal nickel-molybdenum nanoparticles for the substitution of noble metals in heterogeneous catalysis.

    PubMed

    Marzun, Galina; Levish, Alexander; Mackert, Viktor; Kallio, Tanja; Barcikowski, Stephan; Wagener, Philipp

    2017-03-01

    Platinum and iridium are rare and expensive noble metals that are used as catalysts for different sectors including in heterogeneous chemical automotive emission catalysis and electrochemical energy conversion. Nickel and its alloys are promising materials to substitute noble metals. Nickel based materials are cost-effective with good availability and show comparable catalytic performances. The nickel-molybdenum system is a very interesting alternative to platinum in water electrolysis. We produced ligand-free nickel-molybdenum nanoparticles by laser ablation in water and acetone. Our results show that segregated particles were formed in water due to the oxidation of the metals. X-ray diffraction shows a significant change in the lattice parameter due to a diffusion of molybdenum atoms into the nickel lattice with increasing activity in the electrochemical oxygen evolution reaction. Even though the solubility of molecular oxygen in acetone is higher than in water, there were no oxides and a more homogeneous metal distribution in the particles in acetone as seen by TEM-EDX. This showed that dissolved molecular oxygen does not control oxide formation. Overall, the laser ablation of pressed micro particulate mixtures in liquids offers a combinational synthesis approach that allows the screening of alloy nanoparticles for catalytic testing and can convert micro-mixtures into nano-alloys.

  11. Molybdenum isotope fractionation in the mantle

    NASA Astrophysics Data System (ADS)

    Liang, Yu-Hsuan; Halliday, Alex N.; Siebert, Chris; Fitton, J. Godfrey; Burton, Kevin W.; Wang, Kuo-Lung; Harvey, Jason

    2017-02-01

    We report double-spike molybdenum (Mo) isotope data for forty-two mafic and fifteen ultramafic rocks from diverse locations and compare these with results for five chondrites. The δ98/95Mo values (normalized to NIST SRM 3134) range from -0.59 ± 0.04 to +0.10 ± 0.08‰. The compositions of one carbonaceous (CI) and four ordinary chondrites are relatively uniform (-0.14 ± 0.01‰, 95% ci (confidence interval)) in excellent agreement with previous data. These values are just resolvable from the mean of 10 mid-ocean ridge basalts (MORBs) (0.00 ± 0.02‰, 95% ci). The compositions of 13 mantle-derived ultramafic xenoliths from Kilbourne Hole, Tariat and Vitim are more diverse (-0.39 to -0.07‰) with a mean of -0.22 ± 0.06‰ (95% ci). On this basis, the isotopic composition of the bulk silicate Earth (BSE or Primitive Mantle) is within error identical to chondrites. The mean Mo concentration of the ultramafic xenoliths (0.19 ± 0.07 ppm, 95% ci) is similar in magnitude to that of MORB (0.48 ± 0.13 ppm, 95% ci), providing evidence, either for a more compatible behaviour than previously thought or for selective Mo enrichment of the subcontinental lithospheric mantle. Intraplate and ocean island basalts (OIBs) display significant isotopic variability within a single locality from MORB-like to strongly negative (-0.59 ± 0.04‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. δ98/95Mo correlates negatively with Ce/Pb and U/Pb, and positively with Mo/Ce, explicable if a phase such as an oxide or a sulphide liquid selectively retains isotopically heavy Mo in the mantle and fractionates its isotopic composition in low degree partial melts. If residual phases retain Mo during partial melting, it is possible that the [Mo] for the BSE may be misrepresented by values estimated from basalts. This would be consistent with the high Mo

  12. Gene design, fusion technology and TEV cleavage conditions influence the purification of oxidized disulphide-rich venom peptides in Escherichia coli.

    PubMed

    Sequeira, Ana Filipa; Turchetto, Jeremy; Saez, Natalie J; Peysson, Fanny; Ramond, Laurie; Duhoo, Yoan; Blémont, Marilyne; Fernandes, Vânia O; Gama, Luís T; Ferreira, Luís M A; Guerreiro, Catarina I P I; Gilles, Nicolas; Darbon, Hervé; Fontes, Carlos M G A; Vincentelli, Renaud

    2017-01-17

    Animal venoms are large, complex libraries of bioactive, disulphide-rich peptides. These peptides, and their novel biological activities, are of increasing pharmacological and therapeutic importance. However, recombinant expression of venom peptides in Escherichia coli remains difficult due to the significant number of cysteine residues requiring effective post-translational processing. There is also an urgent need to develop high-throughput recombinant protocols applicable to the production of reticulated peptides to enable efficient screening of their drug potential. Here, a comprehensive study was developed to investigate how synthetic gene design, choice of fusion tag, compartment of expression, tag removal conditions and protease recognition site affect levels of solubility of oxidized venom peptides produced in E. coli. The data revealed that expression of venom peptides imposes significant pressure on cysteine codon selection. DsbC was the best fusion tag for venom peptide expression, in particular when the fusion was directed to the bacterial periplasm. While the redox activity of DsbC was not essential to maximize expression of recombinant fusion proteins, redox activity did lead to higher levels of correctly folded target peptides. With the exception of proline, the canonical TEV protease recognition site tolerated all other residues at its C-terminus, confirming that no non-native residues, which might affect activity, need to be incorporated at the N-terminus of recombinant peptides for tag removal. This study reveals that E. coli is a convenient heterologous host for the expression of soluble and functional venom peptides. Using the optimal construct design, a large and diverse range of animal venom peptides were produced in the µM scale. These results open up new possibilities for the high-throughput production of recombinant disulphide-rich peptides in E. coli.

  13. One-electron oxidation pathway of thiols by peroxynitrite in biological fluids: bicarbonate and ascorbate promote the formation of albumin disulphide dimers in human blood plasma.

    PubMed Central

    Scorza, G; Minetti, M

    1998-01-01

    Recent studies have shown that peroxynitrite oxidizes thiol groups through competing one- and two-electron pathways. The two-electron pathway is mediated by the peroxynitrite anion and prevails quantitatively over the one-electron pathway, which is mediated by peroxynitrous acid or a reactive species derived from it. In CO2-containing fluids the oxidation of thiols might follow a different mechanism owing to the rapid formation of a different oxidant, the nitrosoperoxycarbonate anion (ONOOCO2(-)). Here we present evidence that in blood plasma peroxynitrite induces the formation of a disulphide cross-linked protein identified by immunological (anti-albumin antibodies) and biochemical criteria (peptide mapping) as a dimer of serum albumin. The albumin dimer did not form in plasma devoid of CO2 and its formation was enhanced by ascorbate. However, analysis of thiol groups showed that reconstituting dialysed plasma with NaHCO3 protected protein thiols against the oxidation mediated by peroxynitrite and that the simultaneouspresence of ascorbate provided further protection. Ascorbate alone did not protect thiol groups from peroxynitrite-mediated oxidation. ESR spin-trapping studies with N-t-butyl-alpha-phenylnitrone (PBN) revealed that peroxynitrite induced the formation of protein thiyl radicals and their intensity was markedly decreased by plasma dialysis and restored by reconstitution with NaHCO3. PBN completely inhibited the formation of albumin dimer. Moreover, the addition of iron-diethyldithiocarbamate to plasma demonstrated that peroxynitrite induced the formation of protein S-nitrosothiols and/or S-nitrothiols. Our results are consistent with the hypothesis that NaHCO3 favours the one-electron oxidation of thiols by peroxynitrite with formation of thiyl radicals, ;NO2, and RSNOx. Thiyl radicals, in turn, are involved in chain reactions by which thiols are oxidized to disulphides. PMID:9425126

  14. Armet/Manf and Creld2 are components of a specialized ER stress response provoked by inappropriate formation of disulphide bonds: implications for genetic skeletal diseases

    PubMed Central

    Hartley, Claire L.; Edwards, Sarah; Mullan, Lorna; Bell, Peter A.; Fresquet, Maryline; Boot-Handford, Raymond P.; Briggs, Michael D.

    2013-01-01

    Mutant matrilin-3 (V194D) forms non-native disulphide bonded aggregates in the rER of chondrocytes from cell and mouse models of multiple epiphyseal dysplasia (MED). Intracellular retention of mutant matrilin-3 causes endoplasmic reticulum (ER) stress and induces an unfolded protein response (UPR) including the upregulation of two genes recently implicated in ER stress: Armet and Creld2. Nothing is known about the role of Armet and Creld2 in human genetic diseases. In this study, we used a variety of cell and mouse models of chondrodysplasia to determine the genotype-specific expression profiles of Armet and Creld2. We also studied their interactions with various mutant proteins and investigated their potential roles as protein disulphide isomerases (PDIs). Armet and Creld2 were up-regulated in cell and/or mouse models of chondrodysplasias caused by mutations in Matn3 and Col10a1, but not Comp. Intriguingly, both Armet and Creld2 were also secreted into the ECM of these disease models following ER stress. Armet and Creld2 interacted with mutant matrilin-3, but not with COMP, thereby validating the genotype-specific expression. Substrate-trapping experiments confirmed Creld2 processed PDI-like activity, thus identifying a putative functional role. Finally, alanine substitution of the two terminal cysteine residues from the A-domain of V194D matrilin-3 prevented aggregation, promoted mutant protein secretion and reduced the levels of Armet and Creld2 in a cell culture model. We demonstrate that Armet and Creld2 are genotype-specific ER stress response proteins with substrate specificities, and that aggregation of mutant matrilin-3 is a key disease trigger in MED that could be exploited as a potential therapeutic target. PMID:23956175

  15. Critical evaluation of molybdenum and its alloys for use in space reactor core heat pipes

    SciTech Connect

    Lundberg, L.B.

    1981-01-01

    The choice of pure molybdenum as the prime candidate material for space reactor core heat pipes is examined, and the advantages and disadvantages of this material are brought into focus. Even though pure molybdenum heat pipes have been built and tested, this metal's high ductile-brittle transition temperature and modest creep strength place significant design restrictions on a core heat pipe made from it. Molybdenum alloys are examined with regard to their promise as potential replacements for pure molybdenum. The properties of TZM and molybdenum-rhenium alloys are examined, and it appears that Mo-Re alloys with 10 to 15 wt % rhenium offer the most advantage as an alternative to pure molybdenum in space reactor core heat pipes.

  16. Molybdenum as a contact material in zinc tin oxide thin film transistors

    SciTech Connect

    Hu, W.; Peterson, R. L.

    2014-05-12

    Amorphous oxide semiconductors are of increasing interest for a variety of thin film electronics applications. Here, the contact properties of different source/drain electrode materials to solution-processed amorphous zinc tin oxide (ZTO) thin-film transistors are studied using the transmission line method. The width-normalized contact resistance between ZTO and sputtered molybdenum is measured to be 8.7 Ω-cm, which is 10, 20, and 600 times smaller than that of gold/titanium, indium tin oxide, and evaporated molybdenum electrodes, respectively. The superior contact formed using sputtered molybdenum is due to a favorable work function lineup, an insulator-free interface, bombardment of ZTO during molybdenum sputtering, and trap-assisted tunneling. The transfer length of the sputtered molybdenum/ZTO contact is 0.34 μm, opening the door to future radio-frequency sub-micron molybdenum/ZTO thin film transistors.

  17. Low-energy electron collisions with molybdenum atoms.

    NASA Astrophysics Data System (ADS)

    Bartschat, K.; Dasgupta, A.; Giuliani, J. L.

    2002-10-01

    Reliable cross-section data for electron collisions with molybdenum atoms are important for various applications, such as monitoring the impurity influx in tokamaks or the modeling of a high-intensity metal-oxide discharge that represents a promising candidate for mercury-free lighting concepts. We have therefore extended our recent work on electron collisions with Mo I atoms in their ground state [1] and will present new results for electron-induced transitions between the lowest 15 septet and quintet states of neutral molybdenum. The dependence of our results from a non-relativistic R-matrix (close-coupling) approach on the details of the theoretical model, particularly on the structure description and the number of coupled states, is analyzed, with particular emphasis on the relevant transitions in a moly-oxide discharge lamp. [1.] K. Bartschat, A. Dasgupta, and J.L. Giuliani, J. Phys. B 35, in press (scheduled for July 2002).

  18. Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis

    SciTech Connect

    Bullock, R. Morris

    2010-11-01

    Homogeneous catalytic hydrogenation of the C=O bond of ketones has a long and successful history in catalysis, but has been almost exclusively been carried out with precious metals such as rhodium or ruthenium. It is now possible to carry out catalytic hydrogenation of ketones using organometallic complexes of inexpensive, abundant metals like molybdenum or tungsten. In most cases, these reactions proceed by an ionic hydrogenation mechanism, in which a metal hydride bond serves as a proton donor and a different metal hydride serves as a hydride donor. Reaction of the metal complex with dihydrogen regenerates the metal hydride bonds and completes the catalytic cycle. This chapter will review the development of this new class of catalyst, and will summarize the activity and lifetimes of molybdenum and tungsten catalysts. This work was supported by the US Department of energy's Office of Basic Energy Sciences' Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for US Department of Energy.

  19. Production of Molybdenum-99 using Neutron Capture Methods

    SciTech Connect

    Toth, James J; Greenwood, Lawrence R; Soderquist, Chuck Z; Wittman, Richard S; Pierson, Bruce D; Burns, Kimberly A; Lavender, Curt A; Painter, Chad L; Love, Edward F; Wall, Donald E

    2011-01-01

    Pacific Northwest National Laboratory (PNNL), operated by Battelle, has identified a reference process for the production of molybdenum-99 (99Mo) for use in a chromatographic generator to separate the daughter product, technetium-99m (99mTc). The reference process uses the neutron capture reaction of natural or enriched molybdenum oxide via the reaction 98Mo(n,γ)99Mo. The irradiated molybdenum is dissolved in an alkaline solution, whereby the molybdenum, dissolved as the molybdate anion, is loaded on a proprietary ion exchange material in the chromatographic generator. The approach of this investigation is to provide a systematic collection of technologies to make the neutron capture method for Mo-99 production economically viable. This approach would result in the development of a technetium Tc99m generator and a new type of target. The target is comprised of molybdenum, either natural or enriched, and is tailored to the design of currently operating U.S. research reactors. The systematic collection of technologies requires evaluation of new metallurgical methods to produce the target, evaluation of target geometries tailored to research reactors, and chemical methods to dissolve the irradiated target materials for use in a chromatographic generator. A Technical specification for testing the target and neutron capture method in a research reactor is also required. This report includes identification of research and demonstration activities needed to enable deployment of neutron capture production method, including irradiations of prototypic targets, chemical processing of irradiated targets, and loading and extraction tests of Mo99 and Tc99m on the sorbent material in a prototypic generator design. The prototypical generator design is based on the proprietary method and systems for isotope product generation. The proprietary methods and systems described in this report are clearly delineated with footnotes. Ultimately, the Tc-99m generator solution provided by

  20. Spectrophotometric determination of molybdenum by extraction of its thiosulphate complex.

    PubMed

    Yatirajam, V; Ram, J

    1974-12-01

    A simple and rapid spectrophotometric determination of molybdenum is described. The molybdenum thiosulphate complex is extracted into isoamyl alcohol from 1.0-1.5M hydrochloric acid containing 36-40 mg of Na(2)S(2)O(3).5H(2)O per ml. The absorbance at lambda(max) = 475 nm obeys Beer's law over the range 0-32 microg of Mo per ml of solvent phase. Up to 5 mg/ml of Ti(IV), V(V), Cr(VI), Fe(III), Co(II), Ni(II), U(VI), W(VI), Sb(III), 1 mg/ml of Cu(II), Sn(II), Bi(V) and 10 microg/ml of Pt(IV) and Pd(II) do not interfere. Large amounts of complexing agents interfere. The method has been applied to analysis of synthetic and industrial samples.

  1. Molybdenum-UO2 cerment irradiation at 1145 K

    NASA Technical Reports Server (NTRS)

    Mcdonald, G.

    1971-01-01

    Two molybdenum-UO2 cermet fuel pins were fission heated in a helium-cooled loop at a temperature of 1145 K and to a total burnup of 5.3 % of the U-235. After irradiation the fuel pins were measured to check dimensional stability, punctured at the plenums to determine fission gas release, and examined metallographically to determine the effect of irradiation. Burnup was determined in several sections of the fuel pin. The results of the postirradiation examination indicated: (1) There was no visible change in the fuel pins on irradiation under the above conditions. (2) The maximum swelling of the fuel pins was less than 1%. (3) There was no migration of UO2 and no visible interaction between the molybdenum and the UO2. (4) Approximately 12% of the fission gas formed was released from the cermet cone into the gas plenum.

  2. Solar thermal thruster made of single crystal molybdenum

    NASA Astrophysics Data System (ADS)

    Shimizu, Morio; Itoh, Katsuya; Sato, Hitoshi; Fujii, Tadayuki; Igarashi, Tadashi; Okamoto, Ken-ichi

    1997-07-01

    The heart element of solar thermal propulsion (STP) system is a thruster made of refractory metals such as tungsten, tantalum and molybdenum or advance high temperature ceramics because of the high operating temperature (1000-2500 K) involved. In this paper, design, fabrication and preliminary experimental results in the JSUS Research Plan are presented, using 20 mm diameter of thrusters made of single crystal molybdenum which NRIM has patented and is a perfect (non-defect) material, namely no brittleness due to recrystallization under high operating temperature conditions. The working gas temperature within the thruster chamber reached higher than 1850 K (namely, the Isp is approximately 700 s for hydrogen gas propellant) at 0.2 MPa of the plenum chamber pressure, using the small solar concentrator (1.6 m diameter of half paraboloid and 0.65 m of the focal length).

  3. Predicting molybdenum toxicity to higher plants: influence of soil properties.

    PubMed

    McGrath, S P; Micó, C; Curdy, R; Zhao, F J

    2010-10-01

    The effect of soil properties on the toxicity of molybdenum (Mo) to four plant species was investigated. Soil organic carbon or ammonium-oxalate extractable Fe oxides were found to be the best predictors of the 50% effective dose (ED50) of Mo in different soils, explaining>65% of the variance in ED50 for four species except for ryegrass (26-38%). Molybdenum concentrations in soil solution and consequently plant uptake were increased when soil pH was artificially raised because sorption of Mo to amorphous oxides is greatly reduced at high pH. The addition of sulphate significantly decreased Mo uptake by oilseed rape. For risk assessment, we suggest that Mo toxicity values for plants should be normalised using soil amorphous iron oxide concentrations.

  4. Layered Vanadium and Molybdenum Oxides: Batteries and Electrochromics

    SciTech Connect

    Chernova, N. A.; Roppolo, M.; Dillon, A. C.; Whittingham, M. S.

    2009-01-01

    The layered oxides of vanadium and molybdenum have been studied for close to 40 years as possible cathode materials for lithium batteries or electrochromic systems. The highly distorted metal octahedra naturally lead to the formation of a wide range of layer structures, which can intercalate lithium levels exceeding 300 Ah/kg. They have found continuing success in medical devices, such as pacemakers, but many challenges remain in their application in long-lived rechargeable devices. Their high-energy storage capability remains an encouragement to researchers to resolve the stability concerns of vanadium dissolution and the tendency of lithium and vanadium to mix changing the crystal structure on cycling the lithium in and out. Nanomorphologies have enabled higher reactivities to be obtained for both vanadium and molybdenum oxides, and with the latter show promise for electrochromic displays.

  5. Characterization of molybdenum interfacial crud in a uranium mill that employs tertiary-amine solvent extraction

    SciTech Connect

    Moyer, B.; McDowell, W.J.

    1983-01-01

    In the present work, samples of a molybdenum-caused green gummy interfacial crud from an operating western US uranium mill have been physically and chemically examined. Formaton of cruds of this description has been a long-standing problem in the use of tertiary amine solvent extraction for the recovery of uranium from low-grade ores (Amex Process). The crud is essentially an organic-continuous dispersion containing about 10 wt % aqueous droplets and about 37 wt % greenish-yellow crystalline solids suspended in kerosene-amine process solvent. The greenish-yellow crystals were found to be a previously unknown double salt of tertiary amine molybdophosphate with three tertiary amine chlorides having the empirical formula (R/sub 3/NH)/sub 3/(PMo/sub 12/O/sub 40/).3(R/sub 3/NH)Cl. To confirm the identification of the compound, a pure trioctylamine (TOA) analog was synthesized. In laboratory extraction experiments, it was demonstrated that organic-soluble amine molydophosphate forms slowly upon contact of TOA solvent with dilute sulfuric acid solutions containing low concentrations of molybdate and phosphate. If the organic solutions of amine molybdophosphate were then contacted with aqueous NaCl solutions, a greenish-yellow precipitate of (TOAH)/sub 3/(PMo/sub 12/O/sub 40/).3(TOAH)Cl formed at the interface. The proposed mechanism for the formation of the crud under process conditions involves build up of molybdenum in the solvent, followed by reaction with extracted phosphate to give dissolved amine molybdophosphate. The amine molybdophosphate then co-crystallizes with amine chloride, formed during the stripping cycle, to give the insoluble double salt, which precipitates as a layer of small particles at the interface. The proposed solution to the problem is the use of branched-chain, instead of straight-chain, tertiary amine extractants under the expectation that branching would increase the solubility of the double salt. 2 figures, 5 tables.

  6. Molybdenum-99/technetium-99m management: race against time.

    PubMed

    Ahmad, Mushtaq

    2011-11-01

    Molybdenum-99 is a parent of diagnostic nuclear medicine. It decays to technetium-99m, which used in over 30 million investigations per year around the world. Supplies of Tc-99m remained fragile in the last few years, which may occur again in the short and long term. Few suggestions have been registered in this letter to cope inadequate supply of the most wanted radionuclide for patient care.

  7. Structural properties of molybdenum-lead-borate glasses.

    PubMed

    Rada, M; Rada, S; Pascuta, P; Culea, E

    2010-11-01

    Glasses and glass ceramics in the system xMoO₃·(100 - x)[3B₂O₃·PbO] with 0 ≤ x ≤ 30 mol% have been prepared from melt quenching method and characterized by means of X-ray diffraction, FTIR, UV-VIS and EPR spectroscopy. We have examined and analyzed the effects of systematic molybdenum ions intercalation on lead-borate glasses and glass ceramics with interesting results. The observations present in these mechanisms show the lead ions bonded ionic have a strong affinity towards [BO₃] units containing non-bridging oxygens and [MoO₄]²⁻ molybdate units. The pronounced affinity towards molybdate anions yields the formation of the PbMoO₄ crystalline phase. Then, the excess of oxygen can be supported into the glass network by the formation of [MoO₆] and [Mo₂O₇] structural units. Pb²(+) ions with 6s² configuration show strong absorption in the ultraviolet due to parity allowed s²-sp transition and yield an absorption band centered at about 310 nm. The changes in the features of the absorption bands centered at about 310 nm can be explained as a consequence of the appearance of additional absorption shoulder due to photoinduced color centers in the glass such as the formation of borate-molybdate and lead-molybdate paramagnetic defect centers in the glasses. The concentration of molybdenum ions influences the shape and width of the EPR signals located at g ∼ 1.86, 1.91 and 5.19. The microenvironment of molybdenum ions in glasses is expected to have mainly sixfold coordination. However, there is a possibility of reduction of a part of molybdenum ions from the Mo⁶(+) to the Mo⁵(+) and Mo⁴(+) to the Mo³(+) states.

  8. Structural properties of molybdenum-lead-borate glasses

    NASA Astrophysics Data System (ADS)

    Rada, M.; Rada, S.; Pascuta, P.; Culea, E.

    2010-11-01

    Glasses and glass ceramics in the system xMoO 3·(100 - x)[3B 2O 3·PbO] with 0 ≤ x ≤ 30 mol% have been prepared from melt quenching method and characterized by means of X-ray diffraction, FTIR, UV-VIS and EPR spectroscopy. We have examined and analyzed the effects of systematic molybdenum ions intercalation on lead-borate glasses and glass ceramics with interesting results. The observations present in these mechanisms show the lead ions bonded ionic have a strong affinity towards [BO 3] units containing non-bridging oxygens and [MoO 4] 2- molybdate units. The pronounced affinity towards molybdate anions yields the formation of the PbMoO 4 crystalline phase. Then, the excess of oxygen can be supported into the glass network by the formation of [MoO 6] and [Mo 2O 7] structural units. Pb 2+ ions with 6s 2 configuration show strong absorption in the ultraviolet due to parity allowed s 2-sp transition and yield an absorption band centered at about 310 nm. The changes in the features of the absorption bands centered at about 310 nm can be explained as a consequence of the appearance of additional absorption shoulder due to photoinduced color centers in the glass such as the formation of borate-molybdate and lead-molybdate paramagnetic defect centers in the glasses. The concentration of molybdenum ions influences the shape and width of the EPR signals located at g ˜ 1.86, 1.91 and 5.19. The microenvironment of molybdenum ions in glasses is expected to have mainly sixfold coordination. However, there is a possibility of reduction of a part of molybdenum ions from the Mo 6+ to the Mo 5+ and Mo 4+ to the Mo 3+ states.

  9. The calculations of thermophysical properties of molybdenum plasma

    NASA Astrophysics Data System (ADS)

    Apfelbaum, E. M.

    2017-05-01

    The thermophysical properties (pressure, internal energy, conductivity, thermal conductivity, and thermal power) of molybdenum plasma at temperatures 10-60 kK and densities less than 2 g/cm3 have been calculated. The corresponding model has been developed on the basis of the chemical approach and relaxation time approximation. The approximations used in our model are valid under these conditions. A comparison with available experimental data on conductivity has shown good agreement in this area.

  10. Retention of Sputtered Molybdenum on Ion Engine Discharge Chamber Surfaces

    NASA Technical Reports Server (NTRS)

    Sovey, James S.; Dever, Joyce A.; Power, John L.

    2001-01-01

    Grit-blasted anode surfaces are commonly used in ion engines to ensure adherence of sputtered coatings. Next generation ion engines will require higher power levels, longer operating times, and thus there will likely be thicker sputtered coatings on their anode surfaces than observed to date on 2.3 kW-class xenon ion engines. The thickness of coatings on the anode of a 10 kW, 40-centimeter diameter thruster, for example, may be 22 micrometers or more after extended operation. Grit-blasted wire mesh, titanium, and aluminum coupons were coated with molybdenum at accelerated rates to establish coating stability after the deposition process and after thermal cycling tests. These accelerated deposition rates are roughly three orders of magnitude more rapid than the rates at which the screen grid is sputtered in a 2.3 kW-class, 30-centimeter diameter ion engine. Using both RF and DC sputtering processes, the molybdenum coating thicknesses ranged from 8 to 130 micrometers, and deposition rates from 1.8 micrometers per hour to 5.1 micrometers per hour. In all cases, the molybdenum coatings were stable after the deposition process, and there was no evidence of spalling of the coatings after 20 cycles from about -60 to +320 C. The stable, 130 micrometer molybdenum coating on wire mesh is 26 times thicker than the thickest coating found on the anode of a 2.3 kW, xenon ion engine that was tested for 8200 hr. Additionally, this coating on wire mesh coupon is estimated to be a factor of greater than 4 thicker than one would expect to obtain on the anode of the next generation ion engine which may have xenon throughputs as high as 550 kg.

  11. Bulk molybdenum field emitters by inductively coupled plasma etching.

    PubMed

    Zhu, Ningli; Cole, Matthew T; Milne, William I; Chen, Jing

    2016-12-07

    In this work we report on the fabrication of inductively coupled plasma (ICP) etched, diode-type, bulk molybdenum field emitter arrays. Emitter etching conditions as a function of etch mask geometry and process conditions were systematically investigated. For optimized uniformity, aspect ratios of >10 were achieved, with 25.5 nm-radius tips realised for masks consisting of aperture arrays some 4.45 μm in diameter and whose field electron emission performance has been herein assessed.

  12. Performance and Safety Characteristics of Lithium-molybdenum Disulfide Cells

    NASA Technical Reports Server (NTRS)

    Stiles, J. A.

    1984-01-01

    The lithium-molybdenum disulfide system offers attractive characteristics including high rate capability, successful operation up to 75 C, a very low self-discharge rate, a good cycle life and safety characteristics which compare favorably to those of other lithium cells. Moreover, the materials and manufacturing costs for the system is effectively controlled, so the cells should ultimately be competitive with currently marketed rechargeable cells.

  13. Concentrations of boron, molybdenum, and selenium in chinook salmon

    USGS Publications Warehouse

    Hamilton, Steven J.; Wiedmeyer, Raymond H.

    1990-01-01

    The concentrations of boron, molybdenum, and selenium in young chinook salmon Oncorhynchus tshawytscha were determined in three partial life cycle chronic toxicity studies. In each study, fish were exposed to a mixture of boron, molybdenum, selenate, and selenite in the proportions found in subsurface agricultural drainage water in the basin of the San Joaquin Valley, California. Tests were conducted in well water and in site-specific fresh and brackish waters. No boron or molybdenum was detected in fish exposed to concentrations as high as 6,046 μg boron/L and 193 μg molybdenum/L for 90 d in well water or fresh water; however, whole-body concentrations of selenium increased with increasing exposure concentrations in well water and fresh water, but not in brackish water. Concentrations of selenium in chinook salmon were strongly correlated with reduced survival and growth of fish in well water and with reduced survival in a 15-d seawater challenge test of fish from fresh water. Concentrations of selenium in fish seemed to reach a steady state after 60 d of exposure in well water or fresh water. Fish in brackish water had only background concentrations of selenium after 60 d of exposure, and no effects on survival and growth in brackish water or on survival in a 10-d seawater challenge test were exhibited. This lack of effect in brackish water was attributed to initiation of the study with advanced fry, which were apparently better able to metabolize the trace element mixture than were the younger fish used in studies with well water and fresh water. In all three experimental waters, concentration factors (whole-body concentration/waterborne concentration) for selenium decreased with increasing exposure concentrations, suggesting decreased uptake or increased excretion, or both, of selenium at the higher concentrations.

  14. The nuclear response of molybdenum to supernova neutrinos

    SciTech Connect

    Ydrefors, E.; Suhonen, J.

    2011-12-16

    Neutrino-nucleus interactions play a prominent role in many astrophysical applications. Knowledge about nuclear responses to neutrinos is therefore of paramount importance. We present cross sections for neutral-current neutrino-nucleus scattering off the stable (A = 92,94,95,96,97,98,100) molybdenum isotopes. The nuclear responses for these nuclei are additionally computed by folding the computed cross sections with a Fermi-Dirac distribution.

  15. Evaluation of Oxide Dispersion Strengthened (ODS) Molybdenum Alloys

    DTIC Science & Technology

    1997-01-01

    containing 4 parts concentrated sulfuric acid and 1 part distilled water using a Type 304 stainless steel cathode and a direct current accelerating...Ductile-to-Brittle Transition Temperature ( DBTT ): The following mechanical properties were measured from the ODS molybdenum alloy rods: (a) 0.2...and to determine the DBTT . Elevated Temperature Tensile Tests: Elevated temperature tensile specimens of each as- swaged alloy were equilibrated

  16. Criticality experiments and analysis of molybdenum reflected cylindrical uranyl fluoride water solution reactors

    NASA Technical Reports Server (NTRS)

    Fieno, D.; Fox, T.; Mueller, R.

    1972-01-01

    Clean criticality data were obtained from molybdenum-reflected cylindrical uranyl-fluoride-water solution reactors. Using ENDF/B molybdenum cross sections, a nine energy group two-dimensional transport calculation of a reflected reactor configuration predicted criticality to within 7 cents of the experimental value. For these reactors, it was necessary to compute the reflector resonance integral by a detailed transport calculation at the core-reflector interface volume in the energy region of the two dominant resonances of natural molybdenum.

  17. Electrochromic properties of molybdenum trioxide thin films prepared by chemical vapor deposition

    SciTech Connect

    Maruyama, Toshiro; Kanagawa, Tetsuya

    1995-05-01

    Electrochromic molybdenum trioxide thin films were prepared by chemical vapor deposition. The source material was molybdenum carbonyl. Amorphous molybdenum trioxide thin films were produced at a substrate temperature 300 C. Reduction and oxidation of the films in a 0.3M LiClO{sub 4} propylene carbonate solution caused desirable changes in optical absorption. Coulometry indicated that the coloration efficiency was 25.8 cm{sup 2}/C.

  18. Mechanical properties of electron-beam-melted molybdenum and dilute Mo-Re alloys.

    NASA Technical Reports Server (NTRS)

    Klopp, W. D.; Witzke, W. R.

    1973-01-01

    Study of Mo-Re alloys aimed at examining the effects of small rhenium additions on the low-temperature ductility of molybdenum and determining the mechanical properties of dilute Mo-Re alloys. The results obtained indicate that high-purity Mo-Re alloys have ductile-brittle transition temperatures considerably lower than those for unalloyed molybdenum and that rhenium promotes normal solid-solution strengthening in molybdenum at elevated temperatures.

  19. Feasibility of preparing patterned molybdenum coatings on bismuth telluride thermoelectric modules.

    SciTech Connect

    Sarobol, Pylin; Hall, Aaron Christopher; Miller, Stephen Samuel; Knight, Marlene E.; LePage, William S.; Sobczak, Catherine Elizabeth.; Wesolowski, Daniel Edward

    2013-09-01

    Molybdenum electrical interconnects for thermoelectric modules were produced by air plasma spraying a 30%CE%BCm size molybdenum powder through a laser-cut Kapton tape mask. Initial feasibility demonstrations showed that the molybdenum coating exhibited excellent feature and spacing retention (~170%CE%BCm), adhered to bismuth-telluride, and exhibited electrical conductivity appropriate for use as a thermoelectric module interconnect. A design of experiments approach was used to optimize air plasma spray process conditions to produce a molybdenum coating with low electrical resistivity. Finally, a molybdenum coating was successfully produced on a fullscale thermoelectric module. After the addition of a final titanium/gold layer deposited on top of the molybdenum coating, the full scale module exhibited an electrical resistivity of 128%CE%A9, approaching the theoretical resistivity value for the 6mm module leg of 112%CE%A9. Importantly, air plasma sprayed molybdenum did not show significant chemical reaction with bismuth-telluride substrate at the coating/substrate interface. The molybdenum coating microstructure consisted of lamellar splats containing columnar grains. Air plasma sprayed molybdenum embedded deeply (several microns) into the bismuth-telluride substrate, leading to good adhesion between the coating and the substrate. Clusters of round pores (and cracks radiating from the pores) were found immediately beneath the molybdenum coating. These pores are believed to result from tellurium vaporization during the spray process where the molten molybdenum droplets (2623%C2%B0C) transferred their heat of solidification to the substrate at the moment of impact. Substrate cooling during the molybdenum deposition process was recommended to mitigate tellurium vaporization in future studies.

  20. Molybdate Reduction to Molybdenum Blue by an Antarctic Bacterium

    PubMed Central

    Ahmad, S. A.; Shukor, M. Y.; Shamaan, N. A.; Mac Cormack, W. P.; Syed, M. A.

    2013-01-01

    A molybdenum-reducing bacterium from Antarctica has been isolated. The bacterium converts sodium molybdate or Mo6+ to molybdenum blue (Mo-blue). Electron donors such as glucose, sucrose, fructose, and lactose supported molybdate reduction. Ammonium sulphate was the best nitrogen source for molybdate reduction. Optimal conditions for molybdate reduction were between 30 and 50 mM molybdate, between 15 and 20°C, and initial pH between 6.5 and 7.5. The Mo-blue produced had a unique absorption spectrum with a peak maximum at 865 nm and a shoulder at 710 nm. Respiratory inhibitors such as antimycin A, sodium azide, potassium cyanide, and rotenone failed to inhibit the reducing activity. The Mo-reducing enzyme was partially purified using ion exchange and gel filtration chromatography. The partially purified enzyme showed optimal pH and temperature for activity at 6.0 and 20°C, respectively. Metal ions such as cadmium, chromium, copper, silver, lead, and mercury caused more than 95% inhibition of the molybdenum-reducing activity at 0.1 mM. The isolate was tentatively identified as Pseudomonas sp. strain DRY1 based on partial 16s rDNA molecular phylogenetic assessment and the Biolog microbial identification system. The characteristics of this strain would make it very useful in bioremediation works in the polar and temperate countries. PMID:24381945

  1. Basic ammonothermal GaN growth in molybdenum capsules

    NASA Astrophysics Data System (ADS)

    Pimputkar, S.; Speck, J. S.; Nakamura, S.

    2016-12-01

    Single crystal, bulk gallium nitride (GaN) crystals were grown using the basic ammonothermal method in a high purity growth environment created using a non-hermetically sealed molybdenum (Mo) capsule and compared to growths performed in a similarly designed silver (Ag) capsule and capsule-free René 41 autoclave. Secondary ion mass spectrometry (SIMS) analysis revealed transition metal free (<1×1017 cm-3) GaN crystals. Anomalously low oxygen concentrations ((2-6)×1018 cm-3) were measured in a {0001} seeded crystal boule grown using a Mo capsule, despite higher source material oxygen concentrations ((1-5)×1019 cm-3) suggesting that molybdenum (or molybdenum nitrides) may act to getter oxygen under certain conditions. Total system pressure profiles from growth runs in a Mo capsule system were comparable to those without a capsule, with pressures peaking within 2 days and slowly decaying due to hydrogen diffusional losses. Measured Mo capsule GaN growth rates were comparable to un-optimized growth rates in capsule-free systems and appreciably slower than in Ag-capsule systems. Crystal quality replicated that of the GaN seed crystals for all capsule conditions, with high quality growth occurring on the (0001) Ga-face. Optical absorption and impurity concentration characterization suggests reduced concentrations of hydrogenated gallium vacancies (VGa-Hx).

  2. Structure of Molybdenum Under Dynamic Compression to 1 TPa

    NASA Astrophysics Data System (ADS)

    Duffy, Thomas; Wang, Jue; Coppari, Federica; Smith, Raymond; Eggert, Jon; Lazicki, Amy; Fratanduono, Dayne; Rygg, Ryan; Boehly, Thomas; Collins, Gilbert

    2015-06-01

    Molybdenum (Mo) is a refractory 4d transition metal that is widely used as a standard in static and dynamic high-pressure experiments. However, there are significant unanswered questions and unresolved discrepancies about the melting curve and high-pressure phase stability of this fundamental material. Similar questions surround the melting curve and phase stabilities of other transition metals including Ta and Fe, and so a better understanding of Mo has broad implications for high-pressure science and geophysics. Here we use x-ray diffraction to determine the crystal structure of molybdenum under both shock and ramp compression to pressures as high as 1 TPa. Under shock loading, we find that Mo remains in body centered cubic (BCC) structure until melting begins at near 390 GPa. Our results are in good agreement with recent theoretical calculations and recent re-measurement of sound speeds along the Hugoniot. We also carried out x-ray diffraction measurements of ramp-loaded molybdenum up to 1050 GPa. Our x-ray diffraction patterns are consistent with the persistence of the BCC phase up to the highest pressure achieved. The measured densities under ramp loading are intermediate between those achieved under shock compression and those expected from extrapolation of room-temperature data. We do not observe evidence for the theoretically predicted transition to face centered cubic or double hexagonal close packed phases above 600 GPa.

  3. Ion beam-induced hydroxylation controls molybdenum disulfide growth

    NASA Astrophysics Data System (ADS)

    Bartolucci, Stephen F.; Kaplan, Daniel; Maurer, Joshua A.

    2017-06-01

    2D materials, such as graphene and transition metal dichalcogenides, are a promising class of nanomaterials for next generation electronics, photovoltaics, electrocatalysts, sensors, and optoelectronic devices. Molybdenum disulfide (MoS2) is of particular interest due to its direct bandgap in the visible spectrum, high electron mobility, and chemical stability. Here, we demonstrate that alterations in the density of surface hydroxyl groups on silicon dioxide substrates can control nucleation and growth in molybdenum disulfide thin films produced by atmospheric-pressure chemical vapor deposition. The extent of MoS2 nucleation is linearly correlated to the density of surface hydroxyl groups. Controlling the density of surface hydroxyl groups on the initial substrate provides a method of growing patterned molybdenum disulfide. Furthermore, we establish that the surface density of hydroxyl groups on silicon dioxide (SiO2) is altered using conventional gallium focused ion beam (FIB) patterning. Upon gallium-ion beam exposure, the number of hydroxyl groups generated on the surface is directly proportional to the ion dosage. This work establishes a means of patterning large-area monolayer MoS2 on silicon dioxide substrates, which is a critical step for realizing applications in imaging, catalysis, biosensing, chemical detection, electronics and optoelectronics.

  4. The mammalian molybdenum enzymes of mARC.

    PubMed

    Ott, Gudrun; Havemeyer, Antje; Clement, Bernd

    2015-03-01

    The "mitochondrial amidoxime reducing component" (mARC) is the most recently discovered molybdenum-containing enzyme in mammals. All mammalian genomes studied to date contain two mARC genes: MARC1 and MARC2. The proteins encoded by these genes are mARC-1 and mARC-2 and represent the simplest form of eukaryotic molybdenum enzymes, only binding the molybdenum cofactor. In the presence of NADH, mARC proteins exert N-reductive activity together with the two electron transport proteins cytochrome b5 type B and NADH cytochrome b5 reductase. This enzyme system is capable of reducing a great variety of N-hydroxylated substrates. It plays a decisive role in the activation of prodrugs containing an amidoxime structure, and in detoxification pathways, e.g., of N-hydroxylated purine and pyrimidine bases. It belongs to a group of drug metabolism enzymes, in particular as a counterpart of P450 formed N-oxygenated metabolites. Its physiological relevance, on the other hand, is largely unknown. The aim of this article is to summarize our current knowledge of these proteins with a special focus on the mammalian enzymes and their N-reductive activity.

  5. Molybdenum accumulation, tolerance and molybdenum-selenium-sulfur interactions in Astragalus selenium hyperaccumulator and nonaccumulator species.

    PubMed

    DeTar, Rachael Ann; Alford, Élan R; Pilon-Smits, Elizabeth A H

    2015-07-01

    Some species hyperaccumulate selenium (Se) upwards of 0.1% of dry weight. This study addressed whether Se hyperaccumulators also accumulate and tolerate more molybdenum (Mo). A field survey revealed on average 2-fold higher Mo levels in three hyperaccumulator Astragali compared to three nonaccumulator Astragali, which were not significantly different. Next, a controlled study was performed where hyperaccumulators Astragalus racemosus and Astragalus bisulcatus were compared with nonaccumulators Astragalus drummondii and Astragalus convallarius for Mo accumulation and tolerance, alone or in the presence of Se. When grown on agar media with 0, 12, 24 or 48 mg L(-1) molybdate and/or 0, 1.6 or 3.2 mg L(-1) selenate, all species decreased in biomass with increasing Mo supply. Selenium did not impact biomass at the supplied levels. All Astragali accumulated Mo upwards of 0.1% of dry weight. Selenium levels were up to 0.08% in Astragalus racemosus and 0.04% Se in the other species. Overall, there was no correlation between Se hyperaccumulation and Mo accumulation capacity. However, the hyperaccumulators and nonaccumulators differed in some respects. While none of the species had a higher tissue Mo to sulfur (S) ratio than the growth medium, nonaccumulators had a higher Mo/S ratio than hyperaccumulators. Also, while molybdate and selenate reduced S accumulation in nonaccumulators, it did not in hyperaccumulators. Furthermore, A. racemosus had a higher Se/S ratio than its medium, while the other species did not. Additionally, Mo and Se treatment affected S levels in nonaccumulators, but not in hyperaccumulators. In conclusion, there is no evidence of a link between Se and Mo accumulation and tolerance in Astragalus. Sulfate transporters in hyperaccumulating Astragali appear to have higher sulfate specificity over other oxyanions, compared to nonaccumulators, and A. racemosus may have a transporter with enhanced selenate specificity relative to sulfate or molybdate.

  6. Hypersensitivity to molybdenum as a possible trigger of ANA-negative systemic lupus erythematosus.

    PubMed Central

    Federmann, M; Morell, B; Graetz, G; Wyss, M; Elsner, P; von Thiessen, R; Wüthrich, B; Grob, D

    1994-01-01

    After implantation of two metal plates a 24 year old woman developed fever of unknown origin and successively more symptoms of an ANA-negative systemic lupus erythematosus (SLE). These symptoms resolved after removal of the plates and recurred during patch testing of the metal components, which showed a reaction to molybdenum. A lymphocyte transformation test indicated a delayed-type hypersensitivity to molybdenum. Subsequent progressive flare ups of SLE appeared without molybdenum reexposure. This is the first report suggesting the existence of a hypersensitivity to molybdenum, which may act as another environmental trigger for SLE. PMID:8037499

  7. A STUDY OF DISLOCATION STRUCTURE OF SUBBOUNDARIES IN MOLYBDENUM SINGLE CRYSTALS,

    DTIC Science & Technology

    MOLYBDENUM, *DISLOCATIONS), GRAIN STRUCTURES(METALLURGY), SINGLE CRYSTALS, ZONE MELTING, ELECTRON BEAM MELTING , GRAIN BOUNDARIES, MATHEMATICAL ANALYSIS, ETCHED CRYSTALS, ETCHING, ELECTROEROSIVE MACHINING, CHINA

  8. Determination of iron and molybdenum in a dietetic preparation by flame AAS after dry ashing.

    PubMed

    Canfranc, E; Abarca, A; Sierra, I; Marina, M L

    2001-04-01

    Methods for the determination of iron and molybdenum in a dietetic pharmaceutical preparation by flame atomic absorption spectrometry (FAAS) after dry ashing at 600 degrees C have been validated. Linearity, precision, accuracy, detection and quantification limits, specificity and robustness have been determined. Linearity of response was verified for concentrations ranging from 0.50 to 4.00 mg l(-1) of iron and 1.00 to 6.00 mg l(-1) of molybdenum. Precision of the methods, performed under conditions of repeatability and reproducibility, gave relative standard deviations of 0.4 and 1.1%, respectively, for the iron determination and of 1.0 and 6.5%, respectively, for the molybdenum determination. Mean recoveries determined after spiking dietetic preparation placebos ranged from 97.1 to 102.6% for iron and 95.2 to 102.9% for molybdenum. The limit of detection for iron was 126 microg g(-1) and for molybdenum 129 microg l(-1). Quantification limits were 420 and 433microg l(-1) for iron and molybdenum, respectively. No interference in the iron and molybdenum determination due to other components present in the dietetic capsules was found. Day-to-day and analyst-to-analyst variability was less than 1.1% for iron and 4.5% for molybdenum. Results show the suitability of the method for measurement of iron and molybdenum in a complex matrix sample such as a dietetic pharmaceutical preparation.

  9. GEMAS: Molybdenum Spatial Distribution Patterns in European Soil

    NASA Astrophysics Data System (ADS)

    Cicchella, Domenico; Zuzolo, Daniela; Demetriades, Alecos; De Vivo, Benedetto; Eklund, Mikael; Ladenberger, Anna; Negrel, Philippe; O'Connor, Patrick

    2017-04-01

    Molybdenum is an essential trace element for both plants and animals as well as for human being. It is one such trace element for which potential health concerns have been raised but for which few data exist and little investigation or interpretation of distributions in soils has been made. The main goal of this study was to fill this gap. Molybdenum (Mo) concentrations are reported for the <2 mm fraction of soil samples from agricultural (Ap horizon, 0-20 cm; N=2218) and grazing land (Gr, 0-10 cm; N=2127). The survey covers 33 European countries and 5.6 million km2 at a sample density of 1 site/2500 km2. All samples were analysed by ICP-MS following an aqua regia extraction. The European median Mo concentration is 0.416 mg/kg in agricultural soil and 0.424 mg/kg in grazing land soil. Molybdenum geochemical maps for both land use types (Ap and Gr) show overall similar spatial distribution patterns mainly governed by geology (parent material and mineralisation), as well as weathering, soil formation and climate since the last glaciations period. The dominant feature is represented by low Mo concentrations over the coarse-grained sandy deposits of the last glaciations in central northern Europe while the most extensive anomalies occur in Scandinavian soils. The highest Mo concentration value occurs to the North of Oslo close to one of the largest porphyry Mo deposit of the World. Some interesting anomalous patterns occur also in Italy in correspondence with alkaline volcanics, in Spain and Greece associated with sulfides mineralizations and in Slovenia and Croatia where are probably related to the long weathering history of karstic residual soils. Anomalous concentrations in some areas of Ireland represent a clear example of how an excess of molybdenum has produced potentially toxic pastures. In fact, these give rise to problems particularly in young cattle when excess molybdenum in the herbage acts as an antagonist, which militates against efficient copper

  10. Performance of thermionic converters with smooth and grooved molybdenum electrodes

    NASA Astrophysics Data System (ADS)

    Momozaki, Yoichi

    Experiments are conducted to investigate the performance of thermionic converters with (a) smooth electrodes, (b) a grooved emitter and a smooth collector, (c) a smooth emitter and a grooved collector, and (d) grooved emitter and collector. The electrodes are made of molybdenum (Mo) and the inter-electrode gap is 0.5 mm. Experiments are performed at TE = 1473 K--1773 K, TC = 773 K--1023 K, and PCs = 10 Pa--500 Pa. For the smooth electrodes converter, the maximum electric power density is 2.25 to 4.24 We/cm2 and the maximum efficiency is 13.8 to 17.0%. Because the effective work function of Mo decreases with decreasing TE, the performance of the converter with smooth Mo electrodes at low temperatures (≤1773 K) is shown to be superior to that reported for a TI converter with a W emitter. The measured electric power density of the former is as much as 90% higher than of the latter. At TE = 1673 K, increasing T C, beyond its optimum of 873 K, to 1023 K causes PMAXD and etaMAX for the smooth electrodes converter to decrease from 3.74 W/cm2 and 17% to ˜1.6 W/cm 2 and ˜10%, respectively. At this high collector temperature, the grooved collector converter gives the highest PMAXD (˜2.4 We/cm2) and eta MAX (14%). Visual observations of the plasma discharge in the interelectrode gap of the converter with a grooved collector show that the plasma discharge forms first near the emitter and becomes brighter and extends toward the collector with increasing current. At high discharge current, the plasma discharge stops expanding due to electron scattering, but increases in brightness. The Cs plasma discharge model developed in this research solves the particle, momentum, and energy conservation equations and calculates the output voltage, current, and the spatial distributions of the electron temperature, Te, electron number density, ne, ion number density, n+, and the electron potential, φ e. The source-sink terms in the governing equations are calculated using an ionization

  11. Influence of the conserved disulphide bond, exposed to the putative binding pocket, on the structure and function of the immunoglobulin-like molecular chaperone Caf1M of Yersinia pestis.

    PubMed Central

    Zav'yalov, V P; Chernovskaya, T V; Chapman, D A; Karlyshev, A V; MacIntyre, S; Zavialov, A V; Vasiliev, A M; Denesyuk, A I; Zav'yalova, G A; Dudich, I V; Korpela, T; Abramov, V M

    1997-01-01

    The Yersinia pestis protein Caf1M is a typical representative of a subfamily of periplasmic molecular chaperones with characteristic structural and functional features, one of which is the location of two conserved cysteine residues close to the putative binding pocket. We show that these residues form a disulphide bond, the reduction and alkylation of which significantly increases the dissociation constant of the Caf1M-Caf1 (where Caf 1 is a polypeptide subunit of the capsule) complex [from a Kd of (4.77+/-0.50)x10(-9) M for the intact protein to one of (3.68+/-0.68)x10(-8) M for the modified protein]. The importance of the disulphide bond for the formation of functional Caf1M in vivo was demonstrated using an Escherichia coli dsbA mutant carrying the Y. pestis f1 operon. In accordance with the CD and fluorescence measurements, the disulphide bond is not important for maintenance of the overall structure of the Caf1M molecule, but would appear to affect the fine structural properties of the subunit binding site. A three-dimensional model of the Caf1M-Caf1 complex was designed based on the published crystal structure of PapD (a chaperone required for Pap pili assembly) complexed with a peptide corresponding to the C-terminus of the papG subunit. In the model the disulphide bond is in close proximity to the invariant Caf1M Arg-23 and Lys-142 residues that are assumed to anchor the C-terminal group of the subunit. The importance of this characteristic disulphide bond for the orchestration of the binding site and subunit binding, as well as for the folding of the protein in vivo, is likely to be a common feature of this subfamily of Caf1M-like chaperones. A possible model for the role of the disulphide bond in Caf1 assembly is discussed. PMID:9182720

  12. Feasibility study of accelerator based production of molybdenum-99/technetium-99m

    NASA Astrophysics Data System (ADS)

    Tchelidze, Lali

    Stability of supply in the medical radioisotope market is now of overriding importance. One of the most commonly used radioisotopes is 99mTc, which is produced from 99Mo decay. 99Mo has been produced in nuclear reactors before, however these reactors are aging and have been not reliable lately and there is a great need to find an alternative for the production. In the current project, photo-neutron production of 99Mo/ 99mTc was investigated. An electron linear accelerator at the Idaho Accelerator Center was used to study the feasibility of 99mTc production using bremsstrahlung photon beams from the accelerator. The kinematic recoil process that occurs with every photo nuclear reaction was exploited. With the emission of a neutron in a photo nuclear reaction, the parent nucleus recoils in order to conserve momentum. This recoil can be used to separate 99Mo from 100Mo, at which point one has a very pure and very high specific activity source of 99Mo. We verified the photo-neutron production rates for 99Mo. Also, the kinematic recoil process was modeled and separation efficiencies were measured experimentally. We concluded that it is feasible to produce high 99Mo activities, however nano-particles of molybdenum have to be used and a clean nano-particle separation method has to be achieved.

  13. Synthesizing aluminum particles towards controlling electrostatic discharge ignition sensitivity

    SciTech Connect

    Eric S. Collins; Jeffery P. Gesner; Michelle L. Pantoya; Michael A. Daniels

    2014-02-01

    Aluminum particles were synthesized with shell thicknesses ranging from 2.7 to 8.3 nm and a constant diameter of 95 nm. These fuel particles were combined with molybdenum trioxide particles and the electrostatic discharge (ESD) sensitivity of the mixture was measured. Results show ignition delay increased as the alumina shell thickness increased. These results correlated with electrical resistivity measurements of the mixture which increased with alumina concentration. A model was developed using COMSOL for ignition of a single Al particle. The ignition delay in the model was consistent with the experimental results suggesting that the primary ESD ignition mechanism is joule heating.

  14. Inorganic polarography in organic solvents-II: polarographic examination of the molybdenum(V) thiocyanate complex in diethyl ether.

    PubMed

    Afghan, B K; Dagnall, R M

    1967-02-01

    A procedure involving the solvent extraction of molybdenum(V) thiocyanate into diethyl ether followed by a direct polarographic examination of the organic phase offers a selective method for the determination of molybdenum down to 0.5 ppm. Only molybdenum, amongst 21 elements examined, is observed to give a reduction wave under the recommended conditions. The method is evaluated with respect to various experimental factors and is applied to the determination of molybdenum in mild and alloy steels.

  15. Experimental investigation of the behaviour of tungsten and molybdenum alloys at high strain-rate and temperature

    NASA Astrophysics Data System (ADS)

    Scapin, Martina; Fichera, Claudio; Carra, Federico; Peroni, Lorenzo

    2015-09-01

    The introduction in recent years of new, extremely energetic particle accelerators such as the Large Hadron Collider (LHC) gives impulse to the development and testing of refractory metals and alloys based on molybdenum and tungsten to be used as structural materials. In this perspective, in this work the experimental results of a tests campaign on Inermet® IT180 and pure Molybdenum (sintered by two different producers) are presented. The investigation of the mechanical behaviour was performed in tension varying the strain-rates, the temperatures and both of them. Overall six orders of magnitude in strain-rate (between 10-3 and 103 s-1) were covered, starting from quasi-static up to high dynamic loading conditions. The high strain-rate tests were performed using a direct Hopkinson Bar setup. Both in quasi-static and high strain-rate conditions, the heating of the specimens was obtained with an induction coil system, controlled in feedback loop, based on measurements from thermocouples directly welded on the specimen. The temperature range varied between 25 and 1000°C. The experimental data were, finally, used to extract the parameters of the Zerilli-Armstrong model used to reproduce the mechanical behaviour of the investigated materials.

  16. 10 CFR 35.2204 - Records of molybdenum-99, strontium-82, and strontium-85 concentrations.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... concentrations. 35.2204 Section 35.2204 Energy NUCLEAR REGULATORY COMMISSION MEDICAL USE OF BYPRODUCT MATERIAL Records § 35.2204 Records of molybdenum-99, strontium-82, and strontium-85 concentrations. A licensee shall maintain a record of the molybdenum-99 concentration or strontium-82 and strontium-85...

  17. 10 CFR 35.2204 - Records of molybdenum-99, strontium-82, and strontium-85 concentrations.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... concentrations. 35.2204 Section 35.2204 Energy NUCLEAR REGULATORY COMMISSION MEDICAL USE OF BYPRODUCT MATERIAL Records § 35.2204 Records of molybdenum-99, strontium-82, and strontium-85 concentrations. A licensee shall maintain a record of the molybdenum-99 concentration or strontium-82 and strontium-85...

  18. 10 CFR 35.2204 - Records of molybdenum-99, strontium-82, and strontium-85 concentrations.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... concentrations. 35.2204 Section 35.2204 Energy NUCLEAR REGULATORY COMMISSION MEDICAL USE OF BYPRODUCT MATERIAL Records § 35.2204 Records of molybdenum-99, strontium-82, and strontium-85 concentrations. A licensee shall maintain a record of the molybdenum-99 concentration or strontium-82 and strontium-85...

  19. 10 CFR 35.2204 - Records of molybdenum-99, strontium-82, and strontium-85 concentrations.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... concentrations. 35.2204 Section 35.2204 Energy NUCLEAR REGULATORY COMMISSION MEDICAL USE OF BYPRODUCT MATERIAL Records § 35.2204 Records of molybdenum-99, strontium-82, and strontium-85 concentrations. A licensee shall maintain a record of the molybdenum-99 concentration or strontium-82 and strontium-85...

  20. 10 CFR 35.2204 - Records of molybdenum-99, strontium-82, and strontium-85 concentrations.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... concentrations. 35.2204 Section 35.2204 Energy NUCLEAR REGULATORY COMMISSION MEDICAL USE OF BYPRODUCT MATERIAL Records § 35.2204 Records of molybdenum-99, strontium-82, and strontium-85 concentrations. A licensee shall maintain a record of the molybdenum-99 concentration or strontium-82 and strontium-85...

  1. The effect of molybdenum on the in vitro development of mouse preimplantation embryos.

    PubMed

    Bi, Cong-Ming; Zhang, Yu-Ling; Liu, Feng-Jun; Zhou, Tie-Zhong; Yang, Zi-Jun; Gao, Shen-Yang; Wang, Shu-De; Chen, Xiao-Li; Zhai, Xiao-Wei; Ma, Xue-Gang; Jin, Li-Jun; Wang, Shen

    2013-04-01

    The object of this study was to investigate the effect of molybdenum on the development of mouse preimplantation embryos cultured in vitro. Zygotes were flushed from one outbred mouse strain (Kunming), and then were cultured in potassium simplex optimized medium (KSOM) containing 0, 5, 10, 20, 40, 80, 120, and 160 µg/ml of molybdenum for 5 days until the mid-blastocyst stage. The addition of ≤ 20 µg/ml molybdenum did not affect the blastocyst and birth rates. Molybdenum at doses of 40 µg/ml and higher significantly decreased the cleavage, blastocyst and birth rates, the average cell number, and significantly increased the proportion of degenerative blastocysts. At 120 µg/ml molybdenum inhibited the blastocysts development to birth. At 160 µg/ml molybdenum caused overall developmental arrest (up to 16-cells) of embryos and their massive degeneration. In conclusion, molybdenum negatively affected the development of embryos in a dose-dependent manner. With lower doses (≤ 20 µg/ml), mouse embryos were not apparently damaged. With very high doses (≥ 40 µg/ml), embryo quality significantly decreased. This assessment of the effect of molybdenum on the preimplantation embryo is an initial survey of toxicological risk.

  2. ELECTRON MICROSCOPIC AND MICRODIFFRACTION INVESTIGATION OF NONMETALLIC IMPURITIES IN MOLYBDENUM AND ITS ALLOYS,

    DTIC Science & Technology

    and distribution of the inclusions were determined in specimens of molybdenum produced by electron - beam melting and in molybdenum alloys containing...specimens. The electron - beam melting and annealing were done in a vacuum of 10-4-10-5 Hg mm. (Author)

  3. Synthesis of nanocrystalline molybdenum carbide (Mo{sub 2}C) by solution route

    SciTech Connect

    Patel, Manish Subrahmanyam, J.

    2008-08-04

    Nanocrystalline molybdenum carbide (Mo{sub 2}C) of less than 10 nm size was synthesized by solution route. The process temperature and composition of raw materials were optimized by thermodynamic equilibrium calculation. The raw materials as well as synthesized nanocrystalline molybdenum carbide were characterized by X-ray diffraction (XRD) and thermogravimetric analysis/differential thermal analysis (TGA/DTA)

  4. 40 CFR 440.100 - Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... copper, lead, zinc, gold, silver, and molybdenum ores subcategory. 440.100 Section 440.100 Protection of... DRESSING POINT SOURCE CATEGORY Copper, Lead, Zinc, Gold, Silver, and Molybdenum Ores Subcategory § 440.100 Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory. (a)...

  5. 40 CFR 440.100 - Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... copper, lead, zinc, gold, silver, and molybdenum ores subcategory. 440.100 Section 440.100 Protection of... DRESSING POINT SOURCE CATEGORY Copper, Lead, Zinc, Gold, Silver, and Molybdenum Ores Subcategory § 440.100 Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory. (a)...

  6. 40 CFR 440.100 - Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... copper, lead, zinc, gold, silver, and molybdenum ores subcategory. 440.100 Section 440.100 Protection of... MINING AND DRESSING POINT SOURCE CATEGORY Copper, Lead, Zinc, Gold, Silver, and Molybdenum Ores Subcategory § 440.100 Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum...

  7. 40 CFR 440.100 - Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... copper, lead, zinc, gold, silver, and molybdenum ores subcategory. 440.100 Section 440.100 Protection of... MINING AND DRESSING POINT SOURCE CATEGORY Copper, Lead, Zinc, Gold, Silver, and Molybdenum Ores Subcategory § 440.100 Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum...

  8. Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

    USGS Publications Warehouse

    Helz, G.R.; Miller, C.V.; Charnock, J.M.; Mosselmans, J.F.W.; Pattrick, R.A.D.; Garner, C.D.; Vaughan, D.J.

    1996-01-01

    Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10

  9. Measurement of Actinides in Molybdenum-99 Solution Analytical Procedure

    SciTech Connect

    Soderquist, Chuck Z.; Weaver, Jamie L.

    2015-11-01

    This document is a companion report to a previous report, PNNL 24519, Measurement of Actinides in Molybdenum-99 Solution, A Brief Review of the Literature, August 2015. In this companion report, we report a fast, accurate, newly developed analytical method for measurement of trace alpha-emitting actinide elements in commercial high-activity molybdenum-99 solution. Molybdenum-99 is widely used to produce 99mTc for medical imaging. Because it is used as a radiopharmaceutical, its purity must be proven to be extremely high, particularly for the alpha emitting actinides. The sample of 99Mo solution is measured into a vessel (such as a polyethylene centrifuge tube) and acidified with dilute nitric acid. A gadolinium carrier is added (50 µg). Tracers and spikes are added as necessary. Then the solution is made strongly basic with ammonium hydroxide, which causes the gadolinium carrier to precipitate as hydrous Gd(OH)3. The precipitate of Gd(OH)3 carries all of the actinide elements. The suspension of gadolinium hydroxide is then passed through a membrane filter to make a counting mount suitable for direct alpha spectrometry. The high-activity 99Mo and 99mTc pass through the membrane filter and are separated from the alpha emitters. The gadolinium hydroxide, carrying any trace actinide elements that might be present in the sample, forms a thin, uniform cake on the surface of the membrane filter. The filter cake is first washed with dilute ammonium hydroxide to push the last traces of molybdate through, then with water. The filter is then mounted on a stainless steel counting disk. Finally, the alpha emitting actinide elements are measured by alpha spectrometry.

  10. Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase.

    PubMed

    Wu, Sheng-Yi; Rothery, Richard A; Weiner, Joel H

    2015-10-09

    We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser(719), NarG-His(1163), and NarG-His(1184)); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His(1092) and NarG-His(1098)). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of -88 and -36 mV, respectively). Ala variants of His(1092) and His(1098) also elicit large ΔEm values of -143 and -101 mV, respectively. An Arg variant of His(1092) elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  11. Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase*

    PubMed Central

    Wu, Sheng-Yi; Rothery, Richard A.; Weiner, Joel H.

    2015-01-01

    We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser719, NarG-His1163, and NarG-His1184); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His1092 and NarG-His1098). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of −88 and −36 mV, respectively). Ala variants of His1092 and His1098 also elicit large ΔEm values of −143 and −101 mV, respectively. An Arg variant of His1092 elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. PMID:26297003

  12. Application of Molybdenum isotopes as proxy for weathering conditions

    NASA Astrophysics Data System (ADS)

    Siebert, C.; Pett-Ridge, J.; Burton, K.; Halliday, A. N.

    2008-12-01

    Molybdenum isotopes have become an important tracer for paleo-redox conditions in the oceans and paleo- oceans. Mo is also an essential enzyme co-factor in organisms and therefore important in studies of nitrogen fixation and reduction. With an increasing amount of data on the biogeochemical behavior of Mo in the oceans, it is now possible to better constrain the general behavior of Mo in the marine environment. However, the terrestrial geochemistry of Mo remains very poorly understood. For example, in contrast to earlier assumptions, recent measurements of river-waters (Archer & Vance(2008) Nature Geoscience, Vol. 1, P. 597; Pearce et al. (2008) Geology, Vol. 36, 3, P. 231) suggest that the Mo isotopic input into the oceans is more variable and more enriched in heavy isotopes then previously assumed. So far these variations do not easily correlate with the isotope composition of the source rocks in the catchment area of rivers. Therefore, fractionation during weathering and transport does indeed occur and it is essential to understand the processes controlling the Mo isotope composition of rivers, if one wants to utilize Mo isotopes as quantitative (paleo-)proxy for marine redox-conditions. The aim of this study is to investigate the biogeochemistry of molybdenum in weathering profiles. Results are promising and suggest that molybdenum isotopes may also become useful tracers for redox-conditions during weathering. Results show a clear correlation of Mo isotope compositions with rainfall gradients (i.e. redox conditions) in saprolites from Hawaii. Weathering profiles from Puerto Rico also imply a strong dependence of the Mo isotope composition on pH shifts within a weathering profile. More data are necessary to judge the influence of these processes on the overall Mo isotope composition of rivers and therefore the Mo input to the oceans. However, it becomes clear that the processes affecting Mo isotopes in the terrestrial environment might be complex and need to be

  13. Molybdenum intake of adults in Germany and Mexico.

    PubMed

    Holzinger, S; Anke, M; Röhrig, B; Gonzalez, D

    1998-03-01

    Molybdenum is an essential micronutrient. It plays a complex role in the ecosystem, because the metal is a part of a cofactor for several important enzymes in human, animal and plant metabolism. The physiological requirement for this element is relatively low. Our investigations were aimed at determining the Mo intake of adults in Germany and Mexico by means of duplicate portion technique. Molybdenum was estimated in the food duplicate samples by inductively coupled plasma atomic emission spectrometry. In 1988, 1992 and 1996 the Mo consumption of humans was investigated in 14 test groups of persons with mixed diets. Each test population consisted of seven men and seven women. Furthermore, in 1996 the Mo intake of 10 female and 10 male vegetarians and of two Mexican test groups was also determined. Different factors, such as sex, time of investigation, location and eating habits have an effect on the individual Mo intake, Molybdenum intake of adults with mixed diets has increased significantly from 1988 to 1996. Furthermore, results of our study showed that Mo intake of German adults differs depending on location and the kind of diet. German women with a mixed diet consumed 89 micrograms d-1 in 1996 and men 100 micrograms d-1. In comparison, female and male vegetarians consumed 179 micrograms d-1 and 170 micrograms d-1, respectively. There was a significant difference in Mo consumption between German and Mexican test persons. Mexican women consumed on average 162 micrograms d-1 and Mexican men 208 micrograms d-1. The Mo requirement of adults amounts to about 25 micrograms d-1. Our investigations showed that the Mo requirement is met by normal intake. An intake of 150 micrograms kg-1 body weight may be toxic for humans. Therefore, people in Germany and Mexico are not endangered by Mo exposure.

  14. Evaluation of Molybdenum as a Surrogate for Iridium in the GPHS Weld Development

    SciTech Connect

    Stine, Andrew Martin; Pierce, Stanley W.; Moniz, Paul F.

    2015-10-17

    The welding equipment used for welding iridium containers (clads) at Los Alamos National Laboratory is twenty five years old and is undergoing an upgrade. With the upgrade, there is a requirement for requalification of the welding process, and the opportunity for process improvement. Testing of the new system and requalification will require several welds on iridium test parts and clads, and any efforts to improve the process will add to the need for iridium parts. The extreme high cost of iridium imposes a severe limitation on the extent of test welding that can be done. The 2 inch diameter, 0.027 inch thick, iridium blank disc that the clad cup is formed from, is useful for initial weld trials, but it costs $5000. The development clad sets needed for final tests and requalification cost $15,000 per set. A solution to iridium cost issue would be to do the majority of the weld development on a less expensive surrogate metal with similar weld characteristics. One such metal is molybdenum. Since its melting index (melting temperature x thermal conductivity) is closest to iridium, welds on molybdenum should be similar in size for a given weld power level. Molybdenum is inexpensive; a single 2 inch molybdenum disc costs only $9. In order to evaluate molybdenum as a surrogate for iridium, GTA welds were first developed to provide full penetration on 0.030 inch thick molybdenum discs at speeds of 20, 25, and 30 inches per minute (ipm). These weld parameters were then repeated on the standard 0.027 inch thick iridium blanks. The top surface and bottom surface (root) width and grain structure of the molybdenum and iridium welds were compared, and similarities were evident between the two metals. Due to material and thickness differences, the iridium welds were approximately 35% wider than the molybdenum welds. A reduction in iridium weld current of 35% produce welds slightly smaller than the molybdenum welds yet showed that current could be scaled according to molybdenum

  15. Molybdenum and copper levels in white-tailed deer near uranium mines in Texas

    USGS Publications Warehouse

    King, K.A.; LeLeux, J.; Mulhern, B.M.

    1984-01-01

    Molybdenum toxicity, molybdenosis, in ruminant animals has been identified in at least 15 states and in Canada, England, Australia, and New Zealand. In most western states, molybdenosis has been associated with strip-mine spoil deposits. Molybdenum toxicity has been diagnosed in cattle pastured near uranium strip-mine spoils in several Texas counties. Recent reports from hunters and the authors' observations indicated that white-tailed deer (Odocoileus virginianus ) that fed near uranium-mine spoil deposits may also have been exposed to high levels of molybdenum. The objectives of this study were to determine if white-tailed deer from a South Texas uranium mining district were accumulating harmful levels of molybdenum and to compare molybdenum and copper levels with antler development in deer from the mined area vs. an unmined control area.

  16. Acidic ammonothermal growth of gallium nitride in a liner-free molybdenum alloy autoclave

    NASA Astrophysics Data System (ADS)

    Malkowski, Thomas F.; Pimputkar, Siddha; Speck, James S.; DenBaars, Steven P.; Nakamura, Shuji

    2016-12-01

    This paper discusses promising materials for use as internal, non-load bearing components as well as molybdenum-based alloys for autoclave structural components for an ammonothermal autoclave. An autoclave was constructed from the commercial titanium-zirconium-molybdenum (TZM) alloy and was found to be chemically inert and mechanically stable under acidic ammonothermal conditions. Preliminary seeded growth of GaN was demonstrated with negligible incorporation of transition metals (including molybdenum) into the grown material (<1017 cm-3). Molybdenum and TZM were exposed to a basic ammonothermal environment, leading to slight degradation through formation of molybdenum nitride powders on their surface at elevated temperatures (T>560 °C). The possibility of a 'universal', inexpensive, liner-free ammonothermal autoclave capable of exposure to basic and acidic chemistry is demonstrated.

  17. Influence of Chromium and Molybdenum on the Corrosion of Nickel Based Alloys

    SciTech Connect

    Hayes, J R; Gray, J; Szmodis, A W; Orme, C A

    2005-08-02

    The addition of chromium and molybdenum to nickel creates alloys with exceptional corrosion resistance in a diverse range of environments. This study examines the complementary roles of Cr and Mo in Ni alloy passivation. Four nickel alloys with varying amounts of chromium and molybdenum were studied in 1 molar salt solutions over a broad pH range. The passive corrosion and breakdown behavior of the alloys suggests that chromium is the primary element influencing general corrosion resistance. The breakdown potential was nearly independent of molybdenum content, while the repassivation potential is strongly dependant on the molybdenum content. This indicates that chromium plays a strong role in maintaining the passivity of the alloy, while molybdenum acts to stabilize the passive film after a localized breakdown event.

  18. Leaching of molybdenum and arsenic from uranium ore and mill tailings

    USGS Publications Warehouse

    Landa, E.R.

    1984-01-01

    A sequential, selective extraction procedure was used to assess the effects of sulfuric acid milling on the geochemical associations of molybdenum and arsenic in a uranium ore blend, and the tailings derived therefrom. The milling process removed about 21% of the molybdenum and 53% of the arsenic initially present in the ore. While about one-half of the molybdenum in the ore was water soluble, only about 14% existed in this form in the tailings. The major portion of the extractable molybdenum in the tailings appears to be associated with hydrous oxides of iron, and with alkaline earth sulfate precipitates. In contrast with the pattern seen for molybdenum, the partitioning of arsenic into the various extractable fractions differs little between the ore and the tailings. ?? 1984.

  19. Adjacency of molybdenum redox sites and the oxidation of butene

    SciTech Connect

    Racine, B.N.; Sorensen, C.M.; Weber, R.S. )

    1993-08-01

    The authors have attempted to determine the structure sensitivity of C-H activation and oxygen insertion during the oxidation of 1-butene by measuring how the rates of the reactions depend on variations in the sizes of very small ensembles of redox centers in a catalyst. The authors have employed polyoxometalate cluster compounds in which 3 or 12 of the tungsten ions initially present in a Keggin framework were replaced with molybdenum ions. As in previous work with methanol oxidation, the catalyst derived from the parent Keggin anion, [PW[sub 12]O[sub 40

  20. Procedure for Uranium-Molybdenum Density Measurements and Porosity Determination

    SciTech Connect

    Prabhakaran, Ramprashad; Devaraj, Arun; Joshi, Vineet V.; Lavender, Curt A.

    2016-08-13

    The purpose of this document is to provide guidelines for preparing uranium-molybdenum (U-Mo) specimens, performing density measurements, and computing sample porosity. Typical specimens (solids) will be sheared to small rectangular foils, disks, or pieces of metal. A mass balance, solid density determination kit, and a liquid of known density will be used to determine the density of U-Mo specimens using the Archimedes principle. A standard test weight of known density would be used to verify proper operation of the system. By measuring the density of a U-Mo sample, it is possible to determine its porosity.