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Sample records for sub-100nm molybdenum disulfide

  1. Sub-100 nm wrinkling of polydimethylsiloxane by double frontal oxidation.

    Science.gov (United States)

    Nania, Manuela; Foglia, Fabrizia; Matar, Omar K; Cabral, João T

    2017-02-02

    We demonstrate nanoscale wrinkling on polydimethylsiloxane (PDMS) at sub-100 nm length scales via a (double) frontal surface oxidation coupled with a mechanical compression. The kinetics of the glassy skin propagation is resolved by neutron and X-ray reflectivity, and atomic force microscopy, combined with mechanical wrinkling experiments to evaluate the resulting pattern formation. In conventional PDMS surface oxidation, the smallest wrinkling patterns attainable have an intrinsic lower wavelength limit due to the coupling of skin formation and front propagation at fixed strain εprestrain, whose maximum is, in turn, set by material failure. However, combining two different oxidative processes, ultra-violet ozonolysis followed by air plasma exposure, we break this limit by fabricating trilayer laminates with excellent interfacial properties and a sequence of moduli and layer thicknesses able to trivially reduce the surface topography to sub-100 nm dimensions. This method provides a powerful, yet simple, non-lithographic approach to extend surface patterning from visible to the deep UV range.

  2. Hardmask technology for sub-100 nm lithographic imaging

    Science.gov (United States)

    Babich, Katherina; Mahorowala, Arpan P.; Medeiros, David R.; Pfeiffer, Dirk; Petrillo, Karen E.; Angelopoulos, Marie; Grill, Alfred; Patel, Vishnubhai; Halle, Scott; Brunner, Timothy A.; Conti, Richard; Allen, Scott D.; Wise, Richard

    2003-06-01

    The importance of hardmask technology is becoming increasingly evident as the demand for high-resolution imaging dictates the use of ever-thinner resist films. An appropriately designed etch resistant hardmask used in conjunction with a thin resist can provide the combined lithographic and etch performance needed for sub-100 nm device fabrication. We have developed a silicon-based, plasma-enhanced chemical vapor deposition (PECVD) prepared material that performs both as an antireflective coating (ARC) and a hardmask and thus enables the use of thin resists for device fabrication. This ARC/hardmask material offers several advantages over organic bottom antireflective coatings (BARC). These benefits include excellent tunability of the material's optical properties, which allows superior substrate reflectivity control, and high etch selectivity to resist, exceeding 2:1. In addition, this material can serve as an effective hardmask etch barrier during the plasma etching of dielectric stacks, as the underlying silicon oxide etches eight times faster than this material in typical fluorocarbon plasma. These properties enable the pattering of features in 1-2 μm dielectric stacks using thin resists, imaging that would otherwise be impossible with conventional processing. Potential extendibility of this approach to feature sizes below 100nm has been also evaluated. High resolution images as small as 50nm, have been transferred into a 300nm thick SiO2 layer by using Si ARC/hardmask material as an etch mask. Lithographic performance and etch characteristics of a thin resist process over both single layer and index-graded ARC/hardmask materials will be shown.

  3. Molybdenum disulfide and water interaction parameters

    Science.gov (United States)

    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.

  4. CONTROLLABLE PREPARATION OF NANO MOLYBDENUM DISULFIDE BY HYDROTHERMAL METHOD

    Directory of Open Access Journals (Sweden)

    Suo Xia Hou

    2017-03-01

    Full Text Available Nano molybdenum disulfide possesses unique chemical and physical properties. In this paper molybdenum disulfide nanoparticles with spherical and flower-like structure are prepared via a hydrothermal method. Sodium molybdate and thioacetamide are taken as precursors, polyethylene glycol (PEG-20000, hexadecyl trimethyl ammonium chloride (CTAC and anhydrous ethanol are used as additives. The properties of the product are characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. The results showed that under acidic conditions, molybdenum disulfide nanoparticles with spherical shape are obtained when PEG-20000 and CTAC are added. The nanoparticles are uniform in size with a diameter of about 100 nm. Molybdenum disulfide nanoparticles with a flower-like structure are obtained when anhydrous ethanol is added. Their diameters under sulfuric acid and hydrochloric acid conditions are 190 nm and 70 nm, respectively. Yield analysis reveals that the highest yield (which can be up to 79 % occurs by adding polyethylene glycol in a sulfuric acid environment.

  5. Formation and characterization of low resistivity sub-100 nm copper films deposited by electroless on SAM

    Energy Technology Data Exchange (ETDEWEB)

    Asher, T. [Dept. of Physical Electronics, Faculty of Engineering, Tel-Aviv University, Ramat-Aviv 69978, Tel-Aviv (Israel)], E-mail: tamaras3@tau.ac.il; Inberg, A.; Glickman, E.; Fishelson, N.; Shacham-Diamand, Y. [Dept. of Physical Electronics, Faculty of Engineering, Tel-Aviv University, Ramat-Aviv 69978, Tel-Aviv (Israel)

    2009-10-30

    Thin Cu films of microelectronic quality and low electrical resistivity were created by electroless deposition (ELD) onto SiO{sub 2} surface modified first with self-assembled monolayer (SAM) of 3-aminopropyltrimethoxysilane (APTMS) and activated then by 5 nm gold nano-particles (AuNPs). The presence of highly oriented amino-terminated SAM was revealed by XPS and ToF-SIMS analyses. The Cu films were deposited in boron- and phosphorous-free tartrate/formaldehyde electrolyte. Controlling the deposition rate via the solution pH permitted a minimum value in resistivity {rho}. XPS depth profile revealed that diffusion of Cu into SiO{sub 2} modified by APTMS did not take place after annealing at 220 deg. C, 4 h. Moreover, annealing resulted in the drop of electrical resistivity to {rho} = 4 {+-} 0.4 {mu}{omega} cm for the films with the thickness of 35-100 nm. This value of {rho} is several times smaller than those reported in literature for sub-100 nm Cu films deposited by electroless on different SAMs. It is speculated that nano-scale porosity and corrugated structure observed by HRTEM and AFM in the ELD Cu films contribute to the resistivity. The obtained results demonstrate a viable route for formation of low resistivity, sub-100 nm Cu films on dielectrics for microelectronic application.

  6. Chemical Vapor Deposition of Atomically-Thin Molybdenum Disulfide (MoS2)

    Science.gov (United States)

    2015-03-01

    DISULFIDE ( MoS2 ) Daniel Kaplan Kendall Mills Venkataraman Swaminathan March 2015 Approved for public release...4. TITLE AND SUBTITLE CHEMICAL VAPOR DEPOSITION OF ATOMICALLY-THIN MOLYBDENUM DISULFIDE ( MoS2 ) 5a. CONTRACT NUMBER 5b. GRANT NUMBER...distribution is unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT A method of synthesizing monolayers of molybdenum disulfide ( MoS2 ) via

  7. Experimental determination of the impact of polysilicon LER on sub-100-nm transistor performance

    Science.gov (United States)

    Patterson, Kyle; Sturtevant, John L.; Alvis, John R.; Benavides, Nancy; Bonser, Douglas; Cave, Nigel; Nelson-Thomas, Carla; Taylor, William D.; Turnquest, Karen L.

    2001-08-01

    Photoresist line edge roughness (LER) has long been feared as a potential limitation to the application of various patterning technologies to actual devices. While this concern seems reasonable, experimental verification has proved elusive and thus LER specifications are typically without solid parametric rationale. We report here the transistor device performance impact of deliberate variations of polysilicon gate LER. LER magnitude was attenuated by more than a factor of 5 by altering the photoresist type and thickness, substrate reflectivity, masking approach, and etch process. The polysilicon gate LER for nominally 70 - 150 nm devices was quantified using digital image processing of SEM images, and compared to gate leakage and drive current for variable length and width transistors. With such comparisons, realistic LER specifications can be made for a given transistor. It was found that subtle cosmetic LER differences are often not discernable electrically, thus providing hope that LER will not limit transistor performance as the industry migrates to sub-100 nm patterning.

  8. Impact of agglomeration on the bioaccumulation of sub-100 nm sized TiO₂.

    Science.gov (United States)

    Kwon, Dongwook; Jeon, Soo Kyung; Yoon, Tae Hyun

    2014-04-01

    To improve our understanding on the impact of extrinsic properties of NPs on their bioaccumulation and toxicity, we have investigated the bioaccumulation of sub 100 nm sized P25 TiO₂ nanoparticles (NPs) by Daphnia magna (D. magna) in toxicity testing media. Based on our quantitative ICP-MS measurements as well as spectromicroscopic observations, we found that the bioaccumulation by D. magna were strongly influenced by the extrinsic properties of NPs as well as the biological uptake characteristics of D. magna. New sets of effective dosimetry parameters well correlated with the amount of NPs bioaccumulated within D. magna were also proposed. Based on these findings, we suggested that the extrinsic physicochemical properties of NPs (e.g., interfacial and colloidal properties of NPs) and biological characteristics for NPs (e.g., uptake cutoff sizes of testing organisms) should be considered and included when developing alternative dosimetry of NPs. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Tribological performance of sub-100-nm femtosecond laser-induced periodic surface structures on titanium

    Energy Technology Data Exchange (ETDEWEB)

    Bonse, J., E-mail: joern.bonse@bam.de [BAM Bundesanstalt für Materialforschung und -prüfung, Unter den Eichen 87, D-12205 Berlin (Germany); Höhm, S. [Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie (MBI), Max-Born-Straße 2A, D-12489 Berlin (Germany); Koter, R.; Hartelt, M.; Spaltmann, D.; Pentzien, S. [BAM Bundesanstalt für Materialforschung und -prüfung, Unter den Eichen 87, D-12205 Berlin (Germany); Rosenfeld, A. [Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie (MBI), Max-Born-Straße 2A, D-12489 Berlin (Germany); Krüger, J. [BAM Bundesanstalt für Materialforschung und -prüfung, Unter den Eichen 87, D-12205 Berlin (Germany)

    2016-06-30

    Graphical abstract: - Highlights: • Large areas covered with sub-100 nm LIPSS (HSFL) were manufactured by fs-laser irradiation on titanium surfaces. • Tribological performance of HSFL covered areas was qualified in reciprocal sliding tests in two different lubricating oils. • HSFL on titanium do not endure the tribological tests. • For a beneficial tribological performance, the tribological sample deformation must be smaller than the LIPSS modulation depth. - Abstract: Sub-100-nm laser-induced periodic surface structures (LIPSS) were processed on bulk titanium (Ti) surfaces by femtosecond laser pulse irradiation in air (30 fs pulse duration, 790 nm wavelength). The laser peak fluence, the spatial spot overlap, and the number of overscans were optimized in a sample-scanning geometry in order to obtain large surface areas (5 mm × 5 mm) covered homogeneously by the LIPSS. The laser-processed regions were characterized by optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM). The friction coefficient of the nanostructured surfaces was tested during 1000 cycles under reciprocal sliding conditions (1 Hz, 1.0 N normal load) against a 10-mm diameter ball of hardened 100Cr6 steel, both in paraffin oil and in engine oil used as lubricants. Subsequently, the corresponding wear tracks were qualified by OM, SEM, and energy dispersive X-ray analyses (EDX). The results of the tribological tests are discussed and compared to that obtained for near wavelength-sized fs-LIPSS, processed under somewhat different irradiation conditions. Some constraints for a beneficial effect of LIPSS on the tribological performance are provided.

  10. Manipulation and in situ transmission electron microscope characterization of sub-100 nm nanostructures using a microfabricated nanogripper

    DEFF Research Database (Denmark)

    Cagliani, Alberto; Wierzbicki, Rafal; Occhipini, Luigi

    2010-01-01

    We present here a polysilicon electrothermal microfabricated nanogripper capable of manipulating nanowires and nanotubes in the sub-100 nm range. The nanogripper was fabricated with a mix and match microfabrication process, combining high throughput of photolithography with 10 nm resolution...

  11. New approach for pattern collapse problem by increasing contact area at sub-100nm patterning

    Science.gov (United States)

    Lee, Sung-Koo; Jung, Jae Chang; Lee, Min Suk; Lee, Sung K.; Kim, Sam Young; Hwang, Young-Sun; Bok, Cheol K.; Moon, Seung-Chan; Shin, Ki S.; Kim, Sang-Jung

    2003-06-01

    To accomplish minimizing feature size to sub 100nm, new light sources for photolithography are emerging, such as ArF(193nm), F2(157nm), and EUV(13nm). However as the pattern size decreases to sub 100nm, a new obstacle, that is pattern collapse problem, becomes most serious bottleneck to the road for the sub 100 nm lithography. The main reason for this pattern collapse problem is capillary force that is increased as the pattern size decreases. As a result there were some trials to decrease this capillary force by changing developer or rinse materials that had low surface tension. On the other hands, there were other efforts to increase adhesion between resists and sub materials (organic BARC). In this study, we will propose a novel approach to solve pattern collapse problems by increasing contact area between sub material (organic BARC) and resist pattern. The basic concept of this approach is that if nano-scale topology is made at the sub material, the contact area between sub materials and resist will be increased. The process scheme was like this. First after coating and baking of organic BARC material, the nano-scale topology (3~10nm) was made by etching at this organic BARC material. On this nano-scale topology, resist was coated and exposed. Finally after develop, the contact area between organic BARC and resist could be increased. Though nano-scale topology was made by etching technology, this 20nm topology variation induced large substrate reflectivity of 4.2% and as a result the pattern fidelity was not so good at 100nm 1:1 island pattern. So we needed a new method to improve pattern fidelity problem. This pattern fidelity problem could be solved by introducing a sacrificial BARC layer. The process scheme was like this. First organic BARC was coated of which k value was about 0.64 and then sacrificial BARC layers was coated of which k value was about 0.18 on the organic BARC. The nano-scale topology (1~4nm) was made by etching of this sacrificial BARC layer

  12. Tribological performance of sub-100-nm femtosecond laser-induced periodic surface structures on titanium

    Science.gov (United States)

    Bonse, J.; Höhm, S.; Koter, R.; Hartelt, M.; Spaltmann, D.; Pentzien, S.; Rosenfeld, A.; Krüger, J.

    2016-06-01

    Sub-100-nm laser-induced periodic surface structures (LIPSS) were processed on bulk titanium (Ti) surfaces by femtosecond laser pulse irradiation in air (30 fs pulse duration, 790 nm wavelength). The laser peak fluence, the spatial spot overlap, and the number of overscans were optimized in a sample-scanning geometry in order to obtain large surface areas (5 mm × 5 mm) covered homogeneously by the LIPSS. The laser-processed regions were characterized by optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM). The friction coefficient of the nanostructured surfaces was tested during 1000 cycles under reciprocal sliding conditions (1 Hz, 1.0 N normal load) against a 10-mm diameter ball of hardened 100Cr6 steel, both in paraffin oil and in engine oil used as lubricants. Subsequently, the corresponding wear tracks were qualified by OM, SEM, and energy dispersive X-ray analyses (EDX). The results of the tribological tests are discussed and compared to that obtained for near wavelength-sized fs-LIPSS, processed under somewhat different irradiation conditions. Some constraints for a beneficial effect of LIPSS on the tribological performance are provided.

  13. Near-field coupling of gold plasmonic antennas for sub-100 nm magneto-thermal microscopy

    Science.gov (United States)

    Karsch, Jonathan C.; Bartell, Jason M.; Fuchs, Gregory D.

    2017-08-01

    The development of spintronic technology with increasingly dense, high-speed, and complex devices will be accelerated by accessible microscopy techniques capable of probing magnetic phenomena on picosecond time scales and at deeply sub-micron length scales. A recently developed time-resolved magneto-thermal microscope provides a path towards this goal if it is augmented with a picosecond, nanoscale heat source. We theoretically study adiabatic nanofocusing and near-field heat induction using conical gold plasmonic antennas to generate sub-100 nm thermal gradients for time-resolved magneto-thermal imaging. Finite element calculations of antenna-sample interactions reveal focused electromagnetic loss profiles that are either peaked directly under the antenna or are annular, depending on the sample's conductivity, the antenna's apex radius, and the tip-sample separation. We find that the thermal gradient is confined to 40 nm to 60 nm full width at half maximum for realistic ranges of sample conductivity and apex radius. To mitigate this variation, which is undesirable for microscopy, we investigate the use of a platinum capping layer on top of the sample as a thermal transduction layer to produce heat uniformly across different sample materials. After determining the optimal capping layer thickness, we simulate the evolution of the thermal gradient in the underlying sample layer and find that the temporal width is below 10 ps. These results lay a theoretical foundation for nanoscale, time-resolved magneto-thermal imaging.

  14. Inclusion of a cobalt tetraazamacrocycle into layered molybdenum disulfide

    Energy Technology Data Exchange (ETDEWEB)

    Bissessur, Rabin, E-mail: rabissessur@upei.ca [Department of Chemistry, University of Prince Edward Island, Charlottetown, PEI, C1A 4P3 (Canada); Haines, Robert I.; Gallant, David [Department of Chemistry, University of Prince Edward Island, Charlottetown, PEI, C1A 4P3 (Canada); Bruening, Ralf [Department of Physics, Mount Allison University, Sackville, New Brunswick, E4L 1E6 (Canada)

    2010-08-01

    We report on the intercalation of meso-5, 5, 7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-1,8-diacetate complexed with Co (III) into layered molybdenum disulfide. This is achieved by using the exfoliation and re-stacking properties of LiMoS{sub 2}. The cobalt complex dissolves readily in a water/acetone solvent mixture. Addition of this solution to an aqueous suspension of single MoS{sub 2} layers results in the entrapment of the cobalt macrocycle between the sheets of MoS{sub 2}. The resulting intercalate was characterized by powder X-ray diffraction and thermogravimetric analysis.

  15. Chemical vapor deposition growth of bilayer graphene in between molybdenum disulfide sheets

    NARCIS (Netherlands)

    Kwieciñski, Wojciech; Sotthewes, Kai; Poelsema, Bene; Zandvliet, Harold J.W.; Bampoulis, Pantelis

    2017-01-01

    Direct growth of flat micrometer-sized bilayer graphene islands in between molybdenum disulfide sheets is achieved by chemical vapor deposition of ethylene at about 800 °C. The temperature assisted decomposition of ethylene takes place mainly at molybdenum disulfide step edges. The carbon atoms

  16. Characterization of strain in sub-100 nm silicon transistors by convergent-beam electron diffraction

    Science.gov (United States)

    Zhang, Peng

    As silicon devices shrink further beyond the 65 nm technology node, strain is increasingly important for the fabrication and operation of nano-devices. According to the latest International Technology Roadmap for Semiconductors, however, the detection and mapping of strain at the required nanometer spatial resolution has yet to be achieved. The project is to evaluate the convergent-beam electron diffraction (CBED) technique in a transmission electron microscope (TEM) as a nanoscale strain metrology. In this work, by using energy-filtered CBED under scanning TEM (STEM) mode, we have successfully measured strain in two types of sub-100 nm semiconductor structures: 90 nm node and 65 nm node shallow trench isolation (STI) structures, and a 65 nm node locally strained p-type metal-oxide semiconductor field-effect transistor (P-MOSFET, or PMOS) featuring SiGe source and drain (S/D). In the 90 nm STI structures, the strain is generally less than 0.1%. Nevertheless, CBED is sensitive enough to tell the strain difference in two 90 nm STI structures with different oxide trench filling conditions. In the 65 nm STI structure, the strain tensors at different positions around the oxide trench filling are measured. The experimental results are compared with finite element modeling based on isotropic elasticity theory. A large discrepancy is found between experiments and simulation, which suggests that a more sophisticated model is necessary for accurate modeling, and more importantly that CBED strain measurements can be used to check the applicability of models at nanometer scale. In the 65 nm node uniaxially strained PMOS, the lattice parameters of silicon at a distance of 25 nm to 55nm below the gate are measured. It is found that at 25 below the gate, the major stress component, 1.1 GPa, is compressive along the source-drain axis. It is also noticed that in the strained silicon area, all three diagonal components of the strain tensor are compressive. Thus the CBED strain

  17. Simple Formation of Nanostructured Molybdenum Disulfide Thin Films by Electrodeposition

    Directory of Open Access Journals (Sweden)

    S. K. Ghosh

    2013-01-01

    Full Text Available Nanostructured molybdenum disulfide thin films were deposited on various substrates by direct current (DC electrolysis form aqueous electrolyte containing molybdate and sulfide ions. Post deposition annealing at higher temperatures in the range 450–700°C transformed the as-deposited amorphous films to nanocrystalline structure. High temperature X-ray diffraction studies clearly recorded the crystal structure transformations associated with grain growth with increase in annealing temperature. Surface morphology investigations revealed featureless structure in case of as-deposited surface; upon annealing it converts into a surface with protruding nanotubes, nanorods, or dumbbell shape nanofeatures. UV-visible and FTIR spectra confirmed about the presence of Mo-S bonding in the deposited films. Transmission electron microscopic examination showed that the annealed MoS2 films consist of nanoballs, nanoribbons, and multiple wall nanotubes.

  18. Raman investigation of molybdenum disulfide with different polytypes

    Science.gov (United States)

    Lee, Jae-Ung; Kim, Kangwon; Han, Songhee; Ryu, Gyeong Hee; Lee, Zonghoon; Cheong, Hyeonsik

    The Raman spectra of molybdenum disulfide (MoS2) with different polytypes are investigated. Although 2H-MoS2 is most common in nature, the 3R phase can exist due to a small difference in the formation energy. However, only a few studies are reported for the 3R phase, and most studies have focused on the 2H phase. We found the 2H, 3R and mixed phases of exfoliated few-layer MoS2 from natural molybdenite crystals. The crystal structures of 2H- and 3R-MoS2 are confirmed by the HR-TEM measurements. By using 3 different excitation energies, we compared the Raman spectra of different polytypes in detail. We show that the Raman spectroscopy can be used to identify not only the number of layers but also the polytypes of MoS2.

  19. Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

    Science.gov (United States)

    Niyitanga, Theophile; Jeong, Hae Kyung

    2017-10-01

    Graphite oxide and molybdenum disulfide (GO-MoS2) composite is prepared through a wet process by using hydrolysis of ammonium tetrathiomolybdate, and it exhibits excellent catalytic activity of the hydrogen evolution reaction (HER) with a low overpotential of -0.47 V, which is almost two and three times lower than those of precursor MoS2 and GO. The high performance of HER of the composite attributes to the reduced GO supporting MoS2, providing a conducting network for fast electron transport from MoS2 to electrodes. The composite also shows high stability after 500 cycles, demonstrating a synergistic effect of MoS2 and GO for efficient HER.

  20. Piezoelectricity in two dimensions: Graphene vs. molybdenum disulfide

    Science.gov (United States)

    Song, Xiaoxue; Hui, Fei; Knobloch, Theresia; Wang, Bingru; Fan, Zhongchao; Grasser, Tibor; Jing, Xu; Shi, Yuanyuan; Lanza, Mario

    2017-08-01

    The synthesis of piezoelectric two-dimensional (2D) materials is very attractive for implementing advanced energy harvesters and transducers, as these materials provide enormously large areas for the exploitation of the piezoelectric effect. Among all 2D materials, molybdenum disulfide (MoS2) has shown the largest piezoelectric activity. However, all research papers in this field studied just a single material, and this may raise concerns because different setups could provide different values depending on experimental parameters (e.g., probes used and areas analyzed). By using conductive atomic force microscopy, here we in situ demonstrate that the piezoelectric currents generated in MoS2 are gigantic (65 mA/cm2), while the same experiments in graphene just showed noise currents. These results provide the most reliable comparison yet reported on the piezoelectric effect in graphene and MoS2.

  1. Active terahertz wave modulator based on molybdenum disulfide

    Science.gov (United States)

    Liu, Xin; Zhang, Bo; Wang, Guocui; Wang, Wei; Ji, Hongyu; Shen, Jingling

    2017-11-01

    A high-efficiency active terahertz wave modulator based on a molybdenum disulfide (MoS2)/germanium (Ge) structure was investigated. Spectrally broadband modulation of the THz transmission was obtained using optical control over the frequency range from 0.2 to 2.6 THz. The MoS2 monolayer structure on germanium demonstrated enhancement of the terahertz modulation depth when compared with those of bare Ge and the graphene/Ge structures. The results show that the MoS2-based modulator demonstrated even higher modulation efficiency than the graphene-based device. The modulation enhancement mechanism that originated from increased conductivity was analyzed. The optical modulation properties of the MoS2/Ge device show tremendous promise for applications in terahertz modulation and switching.

  2. Novel alkyl substituted polyanilines/molybdenum disulfide nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Bissessur, Rabin [Department of Chemistry, University of Prince Edward Island, Charlottetown, PEI, C1A 4P3 (Canada)]. E-mail: rabissessur@upei.ca; White, Wade [Department of Chemistry, University of Prince Edward Island, Charlottetown, PEI, C1A 4P3 (Canada)

    2006-10-10

    Polyaniline (PANI), poly(N-methyl aniline) (PMA), poly(ethyl aniline) (PEA) and poly(propyl aniline) (PPA) were synthesized in their salt form, and then characterized by FT-IR spectroscopy and charge transport measurements. The solubility of the polymers was tested in a variety of solvents and N-methylformamide (NMF) was found to be the best solvent. While polyaniline gave a colloidal suspension in NMF, the solubility of the polymer increased with increasing length of the alkyl group, resulting in a concomitant decrease in electrical conductivity. The solubility of the polymers was exploited and their intercalation was performed in molybdenum disulfide by using the exfoliating/restacking property of LiMoS{sub 2}. Powder X-ray diffraction showed that genuine intercalation compounds were formed. The resulting nanocomposites were also characterized by thermogravimetric analysis (TGA)

  3. Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

    Science.gov (United States)

    Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G.

    2016-01-01

    Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials. PMID:27767030

  4. Wet chemical thinning of molybdenum disulfide down to its monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Amara, Kiran Kumar [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Chu, Leiqiang; Kumar, Rajeev [Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Graphene Research Centre, National University of Singapore, 2 Science Drive 3, Singapore 117542 (Singapore); Toh, Minglin [Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Eda, Goki, E-mail: g.eda@nus.edu.sg [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117551 (Singapore); Graphene Research Centre, National University of Singapore, 2 Science Drive 3, Singapore 117542 (Singapore)

    2014-09-01

    We report on the preparation of mono- and bi-layer molybdenum disulfide (MoS{sub 2}) from a bulk crystal by facile wet chemical etching. We show that concentrated nitric acid (HNO{sub 3}) effectively etches thin MoS{sub 2} crystals from their edges via formation of MoO{sub 3}. Interestingly, etching of thin crystals on a substrate leaves behind unreacted mono- and bilayer sheets. The flakes obtained by chemical etching exhibit electronic quality comparable to that of mechanically exfoliated counterparts. Our findings indicate that the self-limiting chemical etching is a promising top-down route to preparing atomically thin crystals from bulk layer compounds.

  5. Selective and efficient electrochemical biosensing of ultrathin molybdenum disulfide sheets.

    Science.gov (United States)

    Narayanan, Tharangattu N; Vusa, Chiranjeevi S R; Alwarappan, Subbiah

    2014-08-22

    Atomically thin molybdenum disulfide (MoS₂) sheets were synthesized and isolated via solvent-assisted chemical exfoliation. The charge-dependent electrochemical activities of these MoS₂ sheets were studied using positively charged hexamine ruthenium (III) chloride and negatively charged ferricyanide/ferrocyanide redox probes. Ultrathin MoS₂ sheet-based electrodes were employed for the electrochemical detection of an important neurotransmitter, namely dopamine (DA), in the presence of ascorbic acid (AA). MoS₂ electrodes were identified as being capable of distinguishing the coexistence of the DA and the AA with an excellent stability. Moreover, the enzymatic detection of the glucose was studied by immobilizing glucose oxidase on the MoS₂. This study opens enzymatic and non-enzymatic electrochemical biosensing applications of atomic MoS₂ sheets, which will supplement their established electronic applications.

  6. Large-area patterning of sub-100 nm epitaxial L10 FePt dots array via nanoimprint lithography

    Directory of Open Access Journals (Sweden)

    Zheng Li

    2015-08-01

    Full Text Available Bit-patterned media, a promising candidate for next generation high density magnetic recording, requires sub-100 nm dots array on a wafer scale, a high degree of patterning control of the size distribution, and a material with high perpendicular anisotropy. In this work, large area (0.75 cm × 0.75 cm dots array was achieved by nanoimprint lithography and ion milling from L10 FePt thin films that are pre-sputtered at 450 °C with both high crystalline quality and good chemical order. The sub-100 nm dots are decoupled from each other and show both narrow size distributions and high coercivity values on the order of 11 kOe. Our work would cast light for the application of bit-patterned media.

  7. Edge eigen-stress and eigen-displacement of armchair molybdenum disulfide nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Quan; Li, Xi [Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing 100083 (China); Volinsky, Alex A., E-mail: volinsky@usf.edu [Department of Mechanical Engineering, University of South Florida, Tampa, FL 33620 (United States); Su, Yanjing, E-mail: yjsu@ustb.edu.cn [Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing 100083 (China)

    2017-05-10

    Edge effects on mechanical properties of armchair molybdenum disulfide nanoribbons were investigated using first principles calculations. The edge eigen-stress model was applied to explain the relaxation process of forming molybdenum disulfide nanoribbon. Edge effects on surface atoms fluctuation degree were obtained from each fully relaxed nanoribbon with different width. Changes of the relaxed armchair molybdenum disulfide nanoribbons structure can be expressed using hexagonal perimeters pattern. Based on the thickness change, relaxed armchair molybdenum disulfide nanoribbons tensile/compression tests were simulated, providing intrinsic edge elastic parameters, such as eigen-stress, Young's modulus and Poisson's ratio. - Highlights: • Edge effects on mechanical properties of armchair MoS{sub 2} nanoribbons were investigated. • Structure changes of different width armchair MoS{sub 2} nanoribbons were obtained. • Tensile/compressive tests were conducted to determine elastic constants. • Mechanical properties are compared for two and three dimensional conditions.

  8. Graphene oxide – molybdenum disulfide hybrid membranes for hydrogen separation

    KAUST Repository

    Ostwal, Mayur

    2017-12-24

    Graphene oxide – molybdenum disulfide hybrid membranes were prepared using vacuum filtration technique. The thickness and the MoS2 content in the membranes were varied and their H2 permeance and H2/CO2 selectivity are reported. A 60nm hybrid membrane containing ~75% by weight of MoS2 exhibited the highest H2 permeance of 804×10−9mol/m2·s·Pa with corresponding H2/CO2 selectivity of 26.7; while a 150nm hybrid membrane with ~29% MoS2 showed the highest H2/CO2 selectivity of 44.2 with corresponding H2 permeance of 287×10−9mol/m2·s·Pa. The hybrid membranes exhibited much higher H2 permeance compared to graphene oxide membranes and higher selectivity compared to MoS2 membranes, which fully demonstrated the synergistic effect of both nanomaterials. The membranes also displayed excellent operational long-term stability.

  9. Aqueous Medium Synthesis Route for Randomly Stacked Molybdenum Disulfide

    Directory of Open Access Journals (Sweden)

    Pravas Kumar Panigrahi

    2013-01-01

    Full Text Available Synthesis of poorly crystalline, randomly oriented rag-like structures of molybdenum disulfide has been reported starting from aqueous solutions of ammonium molybdate, and thioacetamide in presence of sodium dodecyl sulfate via calcination of the amorphous precipitates, obtained through acidification of the in situ generated intermediate of ammonium tetrathiomolybdate. X-ray photoelectron spectroscopy, UV-visible spectroscopy, and X-ray diffraction of the calcined samples reveal the formation of single-phase MoS2, while the amorphous precipitates have been found to be a mixture of Mo2S5, MoS3, and a trace amount of H2MoS4. Highly folded and disordered layers of rag-like MoS2 have been confirmed through high-resolution transmission electron microscopy. The electrical conductivity for the cold pressed pellet of the MoS2 sample is found to be significantly higher than that of 2H-MoS2 and increases further on annealing.

  10. DNA origami deposition on native and passivated molybdenum disulfide substrates

    Directory of Open Access Journals (Sweden)

    Xiaoning Zhang

    2014-04-01

    Full Text Available Maintaining the structural fidelity of DNA origami structures on substrates is a prerequisite for the successful fabrication of hybrid DNA origami/semiconductor-based biomedical sensor devices. Molybdenum disulfide (MoS2 is an ideal substrate for such future sensors due to its exceptional electrical, mechanical and structural properties. In this work, we performed the first investigations into the interaction of DNA origami with the MoS2 surface. In contrast to the structure-preserving interaction of DNA origami with mica, another atomically flat surface, it was observed that DNA origami structures rapidly lose their structural integrity upon interaction with MoS2. In a further series of studies, pyrene and 1-pyrenemethylamine, were evaluated as surface modifications which might mitigate this effect. While both species were found to form adsorption layers on MoS2 via physisorption, 1-pyrenemethylamine serves as a better protective agent and preserves the structures for significantly longer times. These findings will be beneficial for the fabrication of future DNA origami/MoS2 hybrid electronic structures.

  11. Metallic molybdenum disulfide nanosheet-based electrochemical actuators

    Science.gov (United States)

    Acerce, Muharrem; Akdoğan, E. Koray; Chhowalla, Manish

    2017-09-01

    Actuators that convert electrical energy to mechanical energy are useful in a wide variety of electromechanical systems and in robotics, with applications such as steerable catheters, adaptive wings for aircraft and drag-reducing wind turbines. Actuation systems can be based on various stimuli, such as heat, solvent adsorption/desorption, or electrochemical action (in systems such as carbon nanotube electrodes, graphite electrodes, polymer electrodes and metals). Here we demonstrate that the dynamic expansion and contraction of electrode films formed by restacking chemically exfoliated nanosheets of two-dimensional metallic molybdenum disulfide (MoS2) on thin plastic substrates can generate substantial mechanical forces. These films are capable of lifting masses that are more than 150 times that of the electrode over several millimetres and for hundreds of cycles. Specifically, the MoS2 films are able to generate mechanical stresses of about 17 megapascals—higher than mammalian muscle (about 0.3 megapascals) and comparable to ceramic piezoelectric actuators (about 40 megapascals)—and strains of about 0.6 per cent, operating at frequencies up to 1 hertz. The actuation performance is attributed to the high electrical conductivity of the metallic 1T phase of MoS2 nanosheets, the elastic modulus of restacked MoS2 layers (2 to 4 gigapascals) and fast proton diffusion between the nanosheets. These results could lead to new electrochemical actuators for high-strain and high-frequency applications.

  12. Toward barrier free contact to molybdenum disulfide using graphene electrodes.

    Science.gov (United States)

    Liu, Yuan; Wu, Hao; Cheng, Hung-Chieh; Yang, Sen; Zhu, Enbo; He, Qiyuan; Ding, Mengning; Li, Dehui; Guo, Jian; Weiss, Nathan O; Huang, Yu; Duan, Xiangfeng

    2015-05-13

    Two-dimensional layered semiconductors such as molybdenum disulfide (MoS2) have attracted tremendous interest as a new class of electronic materials. However, there are considerable challenges in making reliable contacts to these atomically thin materials. Here we present a new strategy by using graphene as the back electrodes to achieve ohmic contact to MoS2. With a finite density of states, the Fermi level of graphene can be readily tuned by a gate potential to enable a nearly perfect band alignment with MoS2. We demonstrate for the first time a transparent contact to MoS2 with zero contact barrier and linear output behavior at cryogenic temperatures (down to 1.9 K) for both monolayer and multilayer MoS2. Benefiting from the barrier-free transparent contacts, we show that a metal-insulator transition can be observed in a two-terminal MoS2 device, a phenomenon that could be easily masked by Schottky barriers found in conventional metal-contacted MoS2 devices. With further passivation by boron nitride (BN) encapsulation, we demonstrate a record-high extrinsic (two-terminal) field effect mobility up to 1300 cm(2)/(V s) in MoS2 at low temperature.

  13. Effect of molybdenum disulfide nanoribbon on quantum transport of graphene

    Science.gov (United States)

    Gao, Guanyi; Li, Zhongyao; Chen, Mingyan; Xie, Yiqun; Wang, Yin

    2017-11-01

    Based on the density functional theory method in combination with the nonequilibrium green’s function formalism, the quantum transport properties in graphene–MoS2 vertical heterojunction were investigated in this work. The leads are boron doped graphene and seamlessly connect to the graphene nanoribbon in central scattering region. Although there is a weak graphene–MoS2 interaction, molybdenum disulfide can smooth the electrostatic potential and enlarge the transport properties of the whole device. However, another competitive factor is that of the edge states of the MoS2 nanoribbon. When the transport is along the zigzag direction of graphene, the armchair MoS2 nanoribbon simply enlarges the transmission coefficient. Nevertheless, in the armchair transport system, there is an asymmetric electrostatic potential induced by the different atomic potentials of S and Mo atoms at both edges in the zigzag MoS2 nanoribbon, whose potential can lead to obvious scattering from graphene to MoS2 and suppress the transmission probability. Therefore, it also suppresses the influence of zigzag MoS2 nanoribbon on the transmission coefficient. Our first principles simulations provide useful predictions for the application of graphene based emerging electronics, which may stimulate further experimental exploration.

  14. Exciton-plasmon coupling in monolayer molybdenum disulfide

    Science.gov (United States)

    Ziegler, Jed; Newaz, A. K. M.; Bolotin, Kirill; Haglund, Richard

    2013-03-01

    Two-dimensional materials such as monolayer molybdenum disulfide (MoS2) represent a unique platform for investigating the dynamics of exciton-plasmon coupling. We report on the generation and modulation of coherent and incoherent coupled states between excitons in monolayer MoS2 and plasmons in an array of gold nanoparticle deposited onto the surface of MoS2. We study the behavior of these coherent states, termed plexcitons using a combination of photoluminescence, extinction and ultrafast spectroscopies. The close proximity of the two characteristic exciton bands of MoS2 presents multiple coherent coupling configurations, including A-or-B exciton-plasmon, and A-and-B exciton-plasmon interactions. These configurations of plexciton formation that are shown to modulate both the extinction and photoluminescence spectra of the hybrid system. This includes broadband photoluminescence and Fano-type resonances. This behavior is distinct from the spectral response of the MoS2 and plasmonic components of the system. Incoherent exciton-plasmon coupling, achieved by detuning from the plasmon extinction peaks, enhances the interaction of MoS2 with light by focusing the plasmon energy. Depending on which coupling configuration is chosen, our results show that the MoS2/plasmon hybrid systems can act as high efficiency light harvesters, broadband emitters and as tunable visible and NIR photodetectors. Support by Defense Threat Reduction Agency (HDTRA1-1-10-1-0047) and NSF DMR-1056859

  15. On the feasibility of sub-100 nm rad emittance measurement in plasma accelerators using permanent magnetic quadrupoles

    Science.gov (United States)

    Li, F.; Wu, Y. P.; Nie, Z.; Guo, B.; Zhang, X. H.; Huang, S.; Zhang, J.; Cheng, Z.; Ma, Y.; Fang, Y.; Zhang, C. J.; Wan, Y.; Xu, X. L.; Hua, J. F.; Pai, C. H.; Lu, W.; Gu, Y. Q.

    2018-01-01

    Low emittance (sub-100 nm rad) measurement of electron beams in plasma accelerators has been a challenging issue for a while. Among various measurement schemes, measurements based on single-shot quad-scan using permanent magnetic quadrupoles (PMQs) has been recently reported with emittance as low as ∼200 nm Weingartner (2012 Phys. Rev. Spec. Top. Accel. Beams 15 111302). However, the accuracy and reliability of this method have not been systematically analyzed. Such analysis is critical for evaluating the potential of sub-100 nm rad emittance measurement using any scheme. In this paper, we analyze the effects of various nonideal physical factors on the accuracy and reliability using the PMQ method. These factors include aberration induced by a high order field, PMQ misalignment and angular fluctuation of incoming beams. Our conclusions are as follows: (i) the aberrations caused by high order fields of PMQs are relatively weak for low emittance measurement as long as the PMQs are properly constructed. A series of PMQs were manufactured and measured at Tsinghua University, and using numerical simulations their high order field effects were found to be negligible . (ii) The largest measurement error of emittance is caused by the angular misalignment between PMQs. For low emittance measurement of ∼100 MeV beams, an angular alignment accuracy of 0.1° is necessary. This requirement can be eased for beams with higher energies. (iii) The transverse position misalignment of PMQs and angular fluctuation of incoming beams only cause a translational and rotational shift of measured signals, respectively, therefore, there is no effect on the measured value of emittance. (iv) The spatial resolution and efficiency of the detection system need to be properly designed to guarantee the accuracy of sub-100 nm rad emittance measurement.

  16. Multiscale structural and electronic control of molybdenum disulfide foam for highly efficient hydrogen production

    Science.gov (United States)

    Deng, Jiao; Li, Haobo; Wang, Suheng; Ding, Ding; Chen, Mingshu; Liu, Chuan; Tian, Zhongqun; Novoselov, K. S.; Ma, Chao; Deng, Dehui; Bao, Xinhe

    2017-04-01

    Hydrogen production through water splitting has been considered as a green, pure and high-efficient technique. As an important half-reaction involved, hydrogen evolution reaction is a complex electrochemical process involving liquid-solid-gas three-phase interface behaviour. Therefore, new concepts and strategies of material design are needed to smooth each pivotal step. Here we report a multiscale structural and electronic control of molybdenum disulfide foam to synergistically promote the hydrogen evolution process. The optimized three-dimensional molybdenum disulfide foam with uniform mesopores, vertically aligned two-dimensional layers and cobalt atoms doping demonstrated a high hydrogen evolution activity and stability. In addition, density functional theory calculations indicate that molybdenum disulfide with moderate cobalt doping content possesses the optimal activity. This study demonstrates the validity of multiscale control in molybdenum disulfide via overall consideration of the mass transport, and the accessibility, quantity and capability of active sites towards electrocatalytic hydrogen evolution, which may also be extended to other energy-related processes.

  17. Mechanochemical preparation of stable sub-100 nm γ-cyclodextrin:Buckminsterfullerene (C60) nanoparticles by electrostatic or steric stabilization.

    Science.gov (United States)

    Van Guyse, Joachim; De la Rosa, Victor R; Hoogenboom, Richard

    2017-12-12

    Buckminsterfullerene (C60)'s main hurdle to enter the field of biomedicine is its low bioavailability, which results from its extremely low water solubility. A well-known approach to increase the water solubility of C60 is by complexation with γ-cyclodextrins. However, the formed complexes are not stable in time as they rapidly aggregate and eventually precipitate due to attractive intermolecular forces, a common problem in inclusion complexes of cyclodextrins. In this study we attempt to overcome the attractive intermolecular forces between the complexes by designing custom γ-cyclodextrin (γCD)-based supramolecular hosts for C60 that inhibit the aggregation found in native γCD-C60 complexes. The approach entails the introduction of either repulsive electrostatic forces or increased steric hindrance to prevent aggregation, thus enhancing the biomedical application potential of C60. These modifications have led to new sub-100 nm nanostructures that show long-term stability in solution. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Poly(vinyl alcohol) nanocomposite films containing chemically exfoliated molybdenum disulfide

    Energy Technology Data Exchange (ETDEWEB)

    Batista Mancinelli, Ketlin Cristine; Lisboa, Fabio da Silva [Centro de Pesquisa em Quimica Aplicada - CEPESQ, Laboratorio de Quimica de Materiais Avancados, Universidade Federal do Parana, Departamento de Quimica, Caixa Postal 19081, 81531-980 Curitiba, PR (Brazil); Soares, Jaisa Fernandes [Laboratorio de Quimica Bioinorganica, Universidade Federal do Parana, Departamento de Quimica, Caixa Postal 19081, 81531-980 Curitiba, PR (Brazil); Zawadzki, Sonia Faria [Laboratorio de Polimeros Sinteticos, Universidade Federal do Parana, Departamento de Quimica, Caixa Postal 19081, 81531-980 Curitiba, PR (Brazil); Wypych, Fernando, E-mail: wypych@ufpr.br [Centro de Pesquisa em Quimica Aplicada - CEPESQ, Laboratorio de Quimica de Materiais Avancados, Universidade Federal do Parana, Departamento de Quimica, Caixa Postal 19081, 81531-980 Curitiba, PR (Brazil)

    2013-01-15

    Molybdenum disulfide (2H-MoS{sub 2}) was exfoliated in water after reaction with n-butyl-lithium. Using either alkaline or neutral conditions, different amounts of the resulting single-layer suspension were employed as filler for the production of poly(vinyl alcohol) films containing distinct disulfide contents. These nanocomposite films were obtained by wet casting and were further characterized by powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) and Raman spectroscopies. The mechanical properties of the films were also evaluated. Characterization studies revealed the attainment of homogeneous nanocomposite films in both alkaline and neutral conditions, indicating good distribution and interaction of the hydrophilic filler with the polyhydroxylated polymer. Improved Young's (tensile) modulus (+57%) and tensile strength (+9%) as well as reduced elongation (-78%) were achieved only when the neutral suspension of single layers was utilized. Increased MoS{sub 2} content diminished the crystallinity of the polymer, while enhanced mechanical properties were obtained in the presence of intermediate filler content (around 1 wt%). Highlights: Black-Right-Pointing-Pointer Molybdenum disulfide (2H-MoS{sub 2}) was chemically exfoliated in water. Black-Right-Pointing-Pointer MoS{sub 2} single-layer suspension was used as filler for poly(vinyl alcohol) films. Black-Right-Pointing-Pointer Increased MoS{sub 2} content diminished the crystallinity of the polymer. Black-Right-Pointing-Pointer Enhanced mechanical properties were obtained with intermediate filler content.

  19. Chemically exfoliated large-area two-dimensional flakes of molybdenum disulfide for device applications

    Directory of Open Access Journals (Sweden)

    Vivek Pachauri

    2013-09-01

    Full Text Available A solution-based exfoliation method for obtaining large-area two-dimensional flakes of molybdenum disulfide, followed by the fabrication of electrical devices is presented in this manuscript. The exfoliation method is based on the use of an aprotic solvent, namely, acetonitrile under mild sonication steps. In order to fabricate devices, a dielectrophoresis technique is used for transferring MoS2 flakes site-specifically on to the electrode pairs pre-written on the glass chips. The devices fabricated thus can be operated as chemical sensor in liquids while investigations under photo illumination indicate that such devices can also efficiently function as photodetectors.

  20. Differences in the Toxicological Potential of Two-Dimensional versus Aggregated Molybdenum Disulfide in the Lung

    OpenAIRE

    Wang, Xiang; Mansukhani, Nikhita D.; Guiney, Linda M.; Ji, Zhaoxia; Chang, Chong Hyun; Wang, Meiying; Liao, Yu-Pei; Song, Tze-Bin; Sun, Bingbing; Li, Ruibin; Xia, Tian; Hersam, Mark C.; Nel, André E.

    2015-01-01

    Two-dimensional molybdenum disulfide (MoS2) has distinct optical and electronic properties compared to aggregated MoS2, enabling wide use of these materials for electronic and biomedical applications. However, the hazard potential of MoS2 has not been studied extensively. Here, we present a comprehensive analysis of the pulmonary hazard potential of three aqueous suspended forms of MoS2: aggregated MoS2 (Agg-MoS2), MoS2 exfoliated by lithiation (Lit-MoS2) and MoS2 dispersed by Pluronic F87 (P...

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

    Science.gov (United States)

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

    2017-02-01

    Transition metal dichalcogenides (TMDs) are becoming significant because of their interesting semiconducting and photonic properties. In particular, TMDs such as molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2), tungsten disulfide (WS2), tungsten diselenide (WSe2), titanium disulfide (TiS2), tantalum sulfide (TaS2), and niobium selenide (NbSe2) are increasingly attracting attention for their applications in solar cell devices. In this review, we give a brief introduction to TMDs with a focus on MoS2; and thereafter, emphasize the role of atomically thin MoS2 layers in fabricating solar cell devices, including bulk-heterojunction, organic, and perovskites-based solar cells. Layered MoS2 has been used as the hole-transport layer (HTL), electron-transport layer (ETL), interfacial layer, and protective layer in fabricating heterojunction solar cells. The trilayer graphene/MoS2/n-Si solar cell devices exhibit a power-conversion efficiency of 11.1%. The effects of plasma and chemical doping on the photovoltaic performance of MoS2 solar cells have been analyzed. After doping and electrical gating, a power-conversion efficiency (PCE) of 9.03% has been observed for the MoS2/h-BN/GaAs heterostructure solar cells. The MoS2-containing perovskites-based solar cells show a PCE as high as 13.3%. The PCE of MoS2-based organic solar cells exceeds 8.40%. The stability of MoS2 solar cells measured under ambient conditions and light illumination has been discussed. The MoS2-based materials show a great potential for solar cell devices along with high PCE; however, in this connection, their long-term environmental stability is also of equal importance for commercial applications.

  2. The effects of morphology re-arrangements on the pseudocapacitive properties of mesoporous molybdenum disulfide (MoS2) nanoflakes

    CSIR Research Space (South Africa)

    Khawula, TNY

    2016-07-01

    Full Text Available Mesoporous molybdenum disulfide (MoS(sub2)) with different morphologies have been prepared via hydrothermal method using different solvents, water or water/acetone mixture. The MoS(sub2) obtained with water alone gave a graphene-like nanoflakes (g...

  3. Molybdenum Disulfide as a Protection Layer and Catalyst for Gallium Indium Phosphide Solar Water Splitting Photocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Britto, Reuben J.; Benck, Jesse D.; Young, James L.; Hahn, Christopher; Deutsch, Todd G.; Jaramillo, Thomas F.

    2016-06-02

    Gallium indium phosphide (GaInP2) is a semiconductor with promising optical and electronic properties for solar water splitting, but its surface stability is problematic as it undergoes significant chemical and electrochemical corrosion in aqueous electrolytes. Molybdenum disulfide (MoS2) nanomaterials are promising to both protect GaInP2 and to improve catalysis since MoS2 is resistant to corrosion and also possesses high activity for the hydrogen evolution reaction (HER). In this work, we demonstrate that GaInP2 photocathodes coated with thin MoS2 surface protecting layers exhibit excellent activity and stability for solar hydrogen production, with no loss in performance (photocurrent onset potential, fill factor, and light limited current density) after 60 hours of operation. This represents a five-hundred fold increase in stability compared to bare p-GaInP2 samples tested in identical conditions.

  4. High-resolution transmission electron microscopy of hexagonal and rhombohedral molybdenum disulfide crystals.

    Science.gov (United States)

    Isshiki, T; Nishio, K; Saijo, H; Shiojiri, M; Yabuuchi, Y; Takahashi, N

    1993-07-01

    Natural (molybdenite) and synthesized molybdenum disulfide crystals have been studied by high-resolution transmission electron microscopy. The image simulation demonstrates that the [0001] and [0110] HRTEM images of hexagonal and rhombohedral MoS2 crystals hardly disclose their stacking sequences, and that the [2110] images can distinguish the Mo and S columns along the incident electron beam and enable one to determine not only the crystal structure but also the fault structure. Observed [0001] images of cleaved molybdenite and synthesized MoS2 crystals, however, reveal the strain field around partial dislocations limiting an extended dislocation. A cross-sectional image of a single molecular (S-Mo-S) layer cleaved from molybdenite has been observed. Synthesized MoS2 flakes which were prepared by grinding have been found to be rhombohedral crystals containing many stacking faults caused by glides between S/S layers.

  5. van der Waals screening by single-layer graphene and molybdenum disulfide.

    Science.gov (United States)

    Tsoi, Stanislav; Dev, Pratibha; Friedman, Adam L; Stine, Rory; Robinson, Jeremy T; Reinecke, Thomas L; Sheehan, Paul E

    2014-12-23

    A sharp tip of atomic force microscope is employed to probe van der Waals forces of a silicon oxide substrate with adhered graphene. Experimental results obtained in the range of distances from 3 to 20 nm indicate that single-, double-, and triple-layer graphenes screen the van der Waals forces of the substrate. Fluorination of graphene, which makes it electrically insulating, lifts the screening in the single-layer graphene. The van der Waals force from graphene determined per layer decreases with the number of layers. In addition, increased hole doping of graphene increases the force. Finally, we also demonstrate screening of the van der Waals forces of the silicon oxide substrate by single- and double-layer molybdenum disulfide.

  6. Controlled growth of large-area and high-quality molybdenum disulfide

    Science.gov (United States)

    Kim, Ja-Yeon; Kim, Doo-Hyung; Kwon, Min-Ki

    2017-11-01

    We describe a method of synthesizing large-area and uniform molybdenum disulfide (MoS2) films with control over the size and layer number at predetermined locations, using a step-edge mediated growth technique with simple lithography. Controlling various growth parameters such as temperature and pressure enables the synthesis of high quality, crystalline, monolayer MoS2, with electrical and optical properties that are comparable to those of exfoliated MoS2. This approach to the precise control of the size and orientation of MoS2 atomic layers can open a path toward the scalable production of high-quality devices based on MoS2 for applications in flexible displays.

  7. Influences of water molecules on the electronic properties of atomically thin molybdenum disulfide

    Science.gov (United States)

    Zhang, Kang; Wang, Xingli; Sun, Leimeng; Zou, Jianping; Wang, Jingyuan; Liu, Zheng; Chen, Tupei; Tay, Beng Kang; Zhang, Qing

    2017-07-01

    Although it is well known that the performances of two-dimensional transition metal dichalcogenide (2D-TMD) based devices are strongly affected by humidity, the roles of water molecules in the electronic properties of 2D-TMDs are still unclear. In this work, the influence of water molecules on the electrical properties of monolayer molybdenum disulfide (MoS2) is studied systemically using the dielectric force microscopy (DFM) technique. Taking the advantage of the DFM technique and other nondestructive characterization techniques, the electronic properties (surface potential, dielectrics, and carrier mobility) of atomically thin MoS2 exposed to different levels of humidity are investigated. Furthermore, Raman spectroscopy manifested the correlation between the optical phonon and the mobility drop of MoS2 flakes when subjected to humidity variations. Our results provide an in-depth understanding of the mechanism of water molecules interacting with MoS2.

  8. Rational design of multifunctional devices based on molybdenum disulfide and graphene hybrid nanostructures

    Science.gov (United States)

    Lim, Yi Rang; Lee, Young Bum; Kim, Seong Ku; Kim, Seong Jun; Kim, Yooseok; Jeon, Cheolho; Song, Wooseok; Myung, Sung; Lee, Sun Sook; An, Ki-Seok; Lim, Jongsun

    2017-01-01

    We rationally designed a new type of hybrid materials, molybdenum disulfide (MoS2) synthesized by Mo pre-deposition followed by subsequent sulfurization process directly on thermal chemical vapor deposition (TCVD)-grown graphene, for applications in a multifunctional device. The synthesis of stoichiometric and uniform multilayer MoS2 and high-crystalline monolayer graphene was evaluated by X-ray photoelectron spectroscopy and Raman spectroscopy. To examine the electrical transport and photoelectrical properties of MoS2-graphene hybrid films, field effect transistors (FETs) and visible-light photodetectors based on MoS2-graphene were both fabricated. As a result, the extracted mobility for MoS2-graphene hybrid FETs was two times higher than that of MoS2 FETs. In addition, the MoS2-graphene photodetectors revealed a significant photocurrent with abrupt switching behavior under periodic illumination.

  9. Molybdenum disulfide nanoparticles decorated reduced graphene oxide: highly sensitive and selective hydrogen sensor

    Science.gov (United States)

    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.

  10. First-principles studies of chromium line-ordered alloys in a molybdenum disulfide monolayer

    Science.gov (United States)

    Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

    2017-08-01

    Density functional theory calculations have been performed to study the thermodynamic stability, structural and electronic properties of various chromium (Cr) line-ordered alloy configurations in a molybdenum disulfide (MoS2) hexagonal monolayer for band gap engineering. Only the molybdenum (Mo) sites were substituted at each concentration in this study. For comparison purposes, different Cr line-ordered alloy and random alloy configurations were studied and the most thermodynamically stable ones at each concentration were identified. The configurations formed by the nearest neighbor pair of Cr atoms are energetically most favorable. The line-ordered alloys are constantly lower in formation energy than the random alloys at each concentration. An increase in Cr concentration reduces the lattice constant of the MoS2 system following the Vegard’s law. From density of states analysis, we found that the MoS2 band gap is tunable by both the Cr line-ordered alloys and random alloys with the same magnitudes. The reduction of the band gap is mainly due to the hybridization of the Cr 3d and Mo 4d orbitals at the vicinity of the band edges. The band gap engineering and magnitudes (1.65 eV to 0.86 eV) suggest that the Cr alloys in a MoS2 monolayer are good candidates for nanotechnology devices.

  11. Dissulfeto de molibdênio, um material multifuncional e surpreendente Molybdenum disulfide, a multifunctional and remarkable material

    Directory of Open Access Journals (Sweden)

    Fernando Wypych

    2002-02-01

    Full Text Available The aim of this work is to review the chemical and physical properties of layered molybdenum disulfide. The three polymorphic/polytypic modifications of the compound were found, the polytypes 2H (molybdenite and 3R are semiconductors while the polymorph 1T is an electronic conductor. 2H-MoS2 has several important industrial applications as hydrotreatment catalysts, energy storage devices, solar cells, solid lubricants, among others. When intercalated, the 2H phase changes to a distorted 1T phase, producing unstable intercalation compounds that can be exfoliated in solution, producing single layers and consequently nanocomposites. The direct synthesis of the 1T phase produces stable intercalation compounds. Recently molybdenum disulfide was prepared as nanotubes and fulerene-like structures that bring new insights in the investigation of this important material.

  12. Fabrication of sub-micrometer PMOSFETs with sub-100 nm p sup + -n shallow junctions using Group III dual ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Lin, C.-M. (Intel Corp., Santa Clara, CA (USA)); Steckl, A.J. (Cincinnati Univ., OH (USA). Dept. of Electrical and Computer Engineering)

    1990-04-01

    Fabrication of sub-micrometer PMOSFETs with sub-100 nm p{sup +}-n source/drain junctions using all Group III ({sup 69}Ga, {sup 115}In, {sup 11}B, {sup 49}BF{sub 2}) dual ion implantation is reported. We have obtained low leakage p{sup +}-n shallow junctions with a depth less than 70 nm by implanting various combinations of Group III species in conjunction with low temperature rapid thermal annealing (25/3 keV Ga/B implant annealed at 600{sup 0}C for 30 s; 50/5 keV and 30/3 keV, In/B implants annealed at 900{sup 0}C for 10 s). Sub-micrometer (0.6-0.95 {mu}m) PMOSFETs have been fabricated with this technique. The Ga/B-implanted transistors exhibit a subthreshold slope of 95-105 mV/decade and yield a maximum transconductance of 35-45 mS/mm. The corresponding values for the In/B-implanted FETs are 100-110 mV/decade and 30-40 mS/mm. (author).

  13. Photoelectrochemical Cell of Hybrid Regioregular POLY(3-HEXYLTHIOPHENE-2,5-DIYL) and Molybdenum Disulfide Film

    Science.gov (United States)

    Abdelmola, Fatmaelzahraa M.; Ram, Manoj K.; Takshi, Arash; Stafanakos, Elias; Kumar, Ashok; Goswami, D. Yogi

    The photoelectrochemical cell attracts attention worldwide due to conversion of optical energy into electricity, production of hydrogen through water splitting and use in photodetector and photo-sensor applications. We have been working on the photochemical cell based on regioregular polyhexylthiophenes hybrid-structured films for photoelectrochemical and photovoltaic applications. This paper discusses the hybrid film studies on regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT) with 2D molybdenum disulfide (MoS2) for photoelectrochemical cell. The hybrid P3HT/MoS2 films deposited over indium tin oxide (ITO)-coated glass plate or n-type silicon substrates were characterized using FTIR, UV/vis, electrochemical and scanning electron microscopy (SEM) techniques. The optical measurements showed a higher absorption magnitude with low reflection properties of P3HT/MoS2 hybrid films revealing a superior photocurrent compared to both P3HT and MoS2 films. The P3HT/MoS2 hybrid-based photoelectrochemical cell yielded a short-circuit current (Isc) of 183.16μAṡcm-2, open-circuit voltage (Voc) of 0.92V, fill factor (FF) of 25% and power conversion efficiency (η) of 0.18% under the light intensity of 242Wṡm-2. The estimated power conversion efficiency and fill factor are comparable to organic-based photovoltaic devices.

  14. Cathode based on molybdenum disulfide nanoflakes for lithium-oxygen batteries.

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Mohammad; Kumar, Bijandra; Liu, Cong; Phillips, Patrick; Yasaei, Poya; Behranginia, Amirhossein; Zapol, Peter; Klie, Robert F.; Curtiss, Larry A.; Salehi-Khojin, Amin

    2016-02-01

    Lithium-oxygen (Li-O-2) batteries have been recognized as an emerging technology for energy storage systems owing to their high theoretical specific energy. One challenge is to find an electrolyte/cathode system that is efficient, stable, and cost-effective. We present such a system based on molybdenum disulfide (MoS2) nanoflakes combined with an ionic liquid (IL) that work together as an effective cocatalyst for discharge and charge in a Li-O-2 battery. Cyclic voltammetry results show superior catalytic performance for this cocatalyst for both oxygen reduction and evolution reactions compared to Au and Pt catalysts. It also performs remarkably well in the Li-O-2 battery system with 85% round-trip efficiency and reversibility up to 50 cycles. Density functional calculations provide a mechanistic understanding of the MoS2 nanoflakes/IL system. cocatalyst reported in this work could open the way for exploiting the unique properties of ionic liquids in Li-air batteries in combination with nanostructured MoS2 as a cathode material.

  15. Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Abbasi, Pedram; Asadi, Mohammad; Liu, Cong; Sharifi-Asl, Soroosh; Sayahpour, Baharak; Behranginia, Amirhossein; Zapol, Peter; Shahbazian-Yassar, Reza; Curtiss, Larry A.; Salehi-Khojin, Amin

    2017-01-24

    Electrocatalytic conversion of carbon dioxide (CO2) into energy-rich fuels is considered to be the most efficient approach to achieve a carbon neutral cycle. Transition-metal dichalcogenides (TMDCs) have recently shown a very promising catalytic performance for CO2 reduction reaction in an ionic liquid electrolyte. Here, we report that the catalytic performance of molybdenum disulfide (MoS2), a member of TMDCs, can be significantly improved by using an appropriate dopant. Our electrochemical results indicate that 5% niobium (Nb)-doped vertically aligned MoS2 in ionic liquid exhibits 1 order of magnitude higher CO formation turnover frequency (TOF) than pristine MoS2 at an overpotential range of 50-150 mV. The TOF of this catalyst is also 2 orders of magnitude higher than that of Ag nanoparticles over the entire range of studied overpotentials (100-650 mV). Moreover, the in situ differential electrochemical mass spectrometry experiment shows the onset overpotential of 31 mV for this catalyst, which is the lowest onset potential for CO2 reduction reaction reported so far. Our density functional theory calculations reveal that low concentrations of Nb near the Mo edge atoms can enhance the TOF of CO formation by modifying the binding energies of intermediates to MoS2 edge atoms.

  16. Cytotoxicity and Efflux Pump Inhibition Induced by Molybdenum Disulfide and Boron Nitride Nanomaterials with Sheetlike Structure.

    Science.gov (United States)

    Liu, Su; Shen, Zhuoyan; Wu, Bing; Yu, Yue; Hou, Hui; Zhang, Xu-Xiang; Ren, Hong-Qiang

    2017-09-19

    Sheetlike molybdenum disulfide (MoS 2 ) and boron nitride (BN) nanomaterials have attracted attention in the past few years due to their unique material properties. However, information on adverse effects and their underlying mechanisms for sheetlike MoS 2 and BN nanomaterials is rare. In this study, cytotoxicities of sheetlike MoS 2 and BN nanomaterials on human hepatoma HepG2 cells were systematically investigated at different toxic end points. Results showed that MoS 2 and BN nanomaterials decreased cell viability at 30 μg/mL and induced adverse effects on intracellular ROS generation (≥2 μg/mL), mitochondrial depolarization (≥4 μg/mL), and membrane integrity (≥8 μg/mL for MoS 2 and ≥2 μg/mL for BN). Furthermore, this study first found that low exposure concentrations (0.2-2 μg/mL) of MoS 2 and BN nanomaterials could increase plasma membrane fluidity and inhibit transmembrane ATP binding cassette (ABC) efflux transporter activity, which make both nanomaterials act as a chemosensitizer (increasing arsenic toxicity). Damage to plasma membrane and release of soluble Mo or B species might be two reasons that both nanomaterials inhibit efflux pump activities. This study provides a systematic understanding of the cytotoxicity of sheetlike MoS 2 and BN nanomaterials at different exposure levels, which is important for their safe use.

  17. Few-layer molybdenum disulfide transistors and circuits for high-speed flexible electronics.

    Science.gov (United States)

    Cheng, Rui; Jiang, Shan; Chen, Yu; Liu, Yuan; Weiss, Nathan; Cheng, Hung-Chieh; Wu, Hao; Huang, Yu; Duan, Xiangfeng

    2014-10-08

    Two-dimensional layered materials, such as molybdenum disulfide, are emerging as an exciting material system for future electronics due to their unique electronic properties and atomically thin geometry. Here we report a systematic investigation of MoS2 transistors with optimized contact and device geometry, to achieve self-aligned devices with performance including an intrinsic gain over 30, an intrinsic cut-off frequency fT up to 42 GHz and a maximum oscillation frequency fMAX up to 50 GHz, exceeding the reported values for MoS2 transistors to date (fT~0.9 GHz, fMAX~1 GHz). Our results show that logic inverters or radio frequency amplifiers can be formed by integrating multiple MoS2 transistors on quartz or flexible substrates with voltage gain in the gigahertz regime. This study demonstrates the potential of two-dimensional layered semiconductors for high-speed flexible electronics.

  18. Monolayer-molybdenum-disulfide-based nano-optomechanical transistor and tunable nonlinear responses

    Science.gov (United States)

    Huajun, Chen; Changzhao, Chen; Yang, Li; Xianwen, Fang

    2016-11-01

    Atomically thin two-dimensional semiconductor nanomaterials have attained considerable attention currently. Here, we present a nano-optomechanical system based on a suspended monolayer molybdenum disulfide (MoS2). The linear and nonlinear coherent optical properties of this system, and the phenomenon of phonon-induced transparency are demonstrated. The transmission of the probe field can be manipulated by the power of a second ‘gating’ (pump) field, which indicates a promising candidate for an optical transistor. We further study the nonlinear effect of the system, and the optical Kerr effect of the monolayer MoS2 resonator can be regulated under different parameter regimes. This scheme proposed here may indicate potential chip-scale applications of monolayer MoS2 resonator in quantum information with the currently popular pump-probe technology. Project supported by the National Natural Science Foundation of China (Nos. 11404005, 51502005, 61272153, 61572035), the Key Foundation for Young Talents in College of Anhui Province (No. 2013SQRL026ZD), and the Foundation for PhD in Anhui University of Science and Technology.

  19. Highly conductive carbon black supported amorphous molybdenum disulfide for efficient hydrogen evolution reaction

    Science.gov (United States)

    Cao, Pengfei; Peng, Jing; Li, Jiuqiang; Zhai, Maolin

    2017-04-01

    Molybdenum disulfide (MoS2) is a promising electrocatalyst for hydrogen evolution reaction (HER), however, the catalytic activity of reported MoS2-based materials towards HER still can't satisfy the requirement of practical application. Herein, highly conductive carbon black (CB) supported amorphous MoS2 nanocomposite is synthesized by a facile one-pot hydrothermal process. XRD and TEM analysis proves the amorphous morphology of MoS2. XPS further confirms both hexagonal and orthorhombic S ligands exist in the amorphous MoS2. Compared with crystalline MoS2, amorphous MoS2/CB shows an onset overpotential of 78 mV and current density of 470 mA cm-2 at the overpotential of 200 mV, which is even 50% higher than that of the commercial 20% Pt/C catalyst. Furthermore, a fairly stable performance can be achieved even after 5000 CV cycles. The outstanding HER activity and stability of the amorphous MoS2/CB nanocomposite can be attributed to these advantages: (1) amorphous structure offers more active sites in MoS2; (2) highly conductive CB reduces the charge transfer resistance (RCT); (3) relative hydrophilic CB can largely reduce the resistance between catalyst/electrolyte interface and allows rapid mass transport; (4) electron penetration effect between amorphous MoS2 and CB increases the intrinsic activity of amorphous MoS2 by two orders of magnitude.

  20. Molybdenum disulfide for ultra-low detection of free radicals: electrochemical response and molecular modeling

    Science.gov (United States)

    Gupta, Ankur; Rawal, Takat B.; Neal, Craig J.; Das, Soumen; Rahman, Talat S.; Seal, Sudipta

    2017-06-01

    Two-dimensional (2D) molybdenum disulfide (MoS2) offers attractive properties due to its band gap modulation and has led to significant research-oriented applications (i.e. DNA and protein detection, cell imaging (fluorescent label) etc.). In biology, detection of free radicals (i.e. reactive oxygen species and reactive nitrogen (NO*) species are very important for early discovery and treatment of diseases. Herein, for the first time, we demonstrate the ultra-low (pico-molar) detection of pharmaceutically relevant free radicals using MoS2 for electrochemical sensing. We present pico- to nano- molar level sensitivity in smaller MoS2 with S-deficiency as revealed by x-ray photoelectron spectroscopy. Furthermore, the detection mechanism and size-dependent sensitivity have been investigated by density functional theory (DFT) showing the change in electronic density of states of Mo atoms at edges which lead to the preferred adsorption of H2O2 on Mo edges. The DFT analysis signifies the role of size and S-deficiency in the higher catalytic activity of smaller MoS2 particles and, thus, ultra-low detection.

  1. Tuning the Schottky rectification in graphene-hexagonal boron nitride-molybdenum disulfide heterostructure.

    Science.gov (United States)

    Liu, Biao; Zhao, Yu-Qing; Yu, Zhuo-Liang; Wang, Lin-Zhi; Cai, Meng-Qiu

    2017-12-04

    It was still a great challenge to design high performance of rectification characteristic for the rectifier diode. Lately, a new approach was proposed experimentally to tune the Schottky barrier height (SBH) by inserting an ultrathin insulated tunneling layer to form metal-insulator-semiconductor (MIS) heterostructures. However, the electronic properties touching off the high performance of these heterostructures and the possibility of designing more efficient applications for the rectifier diode were not presently clear. In this paper, the structural, electronic and interfacial properties of the novel MIS diode with the graphene/hexagonal boron nitride/monolayer molybdenum disulfide (GBM) heterostructure had been investigated by first-principle calculations. The calculated results showed that the intrinsic properties of graphene and MoS 2 were preserved due to the weak van der Waals contact. The height of interfacial Schottky barrier can be tuned by the different thickness of hBN layers. In addition, the GBM Schottky diode showed more excellent rectification characteristic than that of GM Schottky diode due to the interfacial band bending caused by the epitaxial electric field. Based on the electronic band structure, we analyzed the relationship between the electronic structure and the nature of the Schottky rectifier, and revealed the potential of utilizing GBM Schottky diode for the higher rectification characteristic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Rational design of multifunctional devices based on molybdenum disulfide and graphene hybrid nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Yi Rang; Lee, Young Bum; Kim, Seong Ku; Kim, Seong Jun [Thin Film Materials Research Center, Korea Research Institute of Chemical Technology, Yuseong, Post Office Box 107, Daejeon 305-600 (Korea, Republic of); Kim, Yooseok; Jeon, Cheolho [Nano-Surface Research Group, Korea Basic Science Institute, Daejeon, 302-333 (Korea, Republic of); Song, Wooseok, E-mail: wssong@krict.re.kr [Thin Film Materials Research Center, Korea Research Institute of Chemical Technology, Yuseong, Post Office Box 107, Daejeon 305-600 (Korea, Republic of); Myung, Sung; Lee, Sun Sook; An, Ki-Seok [Thin Film Materials Research Center, Korea Research Institute of Chemical Technology, Yuseong, Post Office Box 107, Daejeon 305-600 (Korea, Republic of); Lim, Jongsun, E-mail: jslim@krict.re.kr [Thin Film Materials Research Center, Korea Research Institute of Chemical Technology, Yuseong, Post Office Box 107, Daejeon 305-600 (Korea, Republic of)

    2017-01-15

    Highlights: • We fabricated MoS{sub 2}-graphene hybrid thin films for multifunctional applications. • Large-area, uniform multilayer MoS{sub 2} was synthesized on TCVD-grown graphene. • The mobility and photocurrent of the hybrid devices were improved significantly. - Abstract: We rationally designed a new type of hybrid materials, molybdenum disulfide (MoS{sub 2}) synthesized by Mo pre-deposition followed by subsequent sulfurization process directly on thermal chemical vapor deposition (TCVD)-grown graphene, for applications in a multifunctional device. The synthesis of stoichiometric and uniform multilayer MoS{sub 2} and high-crystalline monolayer graphene was evaluated by X-ray photoelectron spectroscopy and Raman spectroscopy. To examine the electrical transport and photoelectrical properties of MoS{sub 2}-graphene hybrid films, field effect transistors (FETs) and visible-light photodetectors based on MoS{sub 2}-graphene were both fabricated. As a result, the extracted mobility for MoS{sub 2}-graphene hybrid FETs was two times higher than that of MoS{sub 2} FETs. In addition, the MoS{sub 2}-graphene photodetectors revealed a significant photocurrent with abrupt switching behavior under periodic illumination.

  3. Contact research strategy for emerging molybdenum disulfide and other two-dimensional field-effect transistors

    Directory of Open Access Journals (Sweden)

    Yuchen Du

    2014-09-01

    Full Text Available Layered two-dimensional (2D semiconducting transition metal dichalcogenides (TMDs have been widely isolated, synthesized, and characterized recently. Numerous 2D materials are identified as the potential candidates as channel materials for future thin film technology due to their high mobility and the exhibiting bandgaps. While many TMD filed-effect transistors (FETs have been widely demonstrated along with a significant progress to clearly understand the device physics, large contact resistance at metal/semiconductor interface still remain a challenge. From 2D device research point of view, how to minimize the Schottky barrier effects on contacts thus reduce the contact resistance of metals on 2D materials is very critical for the further development of the field. Here, we present a review of contact research on molybdenum disulfide and other TMD FETs from the fundamental understanding of metal-semiconductor interfaces on 2D materials. A clear contact research strategy on 2D semiconducting materials is developed for future high-performance 2D FETs with aggressively scaled dimensions.

  4. Atomistic simulations of nanoindentation on the basal plane of crystalline molybdenum disulfide (MoS2)

    Science.gov (United States)

    Stewart, J. A.; Spearot, D. E.

    2013-06-01

    In the present work, nanoindentation on the basal surface of a crystalline molybdenum disulfide (MoS2) thin film is investigated by molecular statics (MS) calculations. A previously parameterized interatomic potential combining the reactive empirical bond-order and Lennard-Jones potentials is implemented into the LAMMPS molecular simulation package and refined for improved prediction of the mechanical properties of MoS2 at athermal conditions. Nanoindentation simulations are performed using three indenter sizes with specific focus on the incipient plastic deformation event within the MoS2single crystal. MS calculations show that a local phase transformation occurs beneath the indenter at plastic yield without the presence of broken Mo-S bonds. The structural characteristics of the phase transformation are captured using a slip vector analysis. The nanoindentation simulations provide insight into the mechanical response of MoS2 during contact deformation characteristic of both synthesis and application for better design of MoS2 nanoparticle lubricants.

  5. Grain boundary-mediated nanopores in molybdenum disulfide grown by chemical vapor deposition.

    Science.gov (United States)

    Elibol, Kenan; Susi, Toma; O Brien, Maria; Bayer, Bernhard C; Pennycook, Timothy J; McEvoy, Niall; Duesberg, Georg S; Meyer, Jannik C; Kotakoski, Jani

    2017-01-26

    Molybdenum disulfide (MoS 2 ) is a particularly interesting member of the family of two-dimensional (2D) materials due to its semiconducting and tunable electronic properties. Currently, the most reliable method for obtaining high-quality industrial scale amounts of 2D materials is chemical vapor deposition (CVD), which results in polycrystalline samples. As grain boundaries (GBs) are intrinsic defect lines within CVD-grown 2D materials, their atomic structure is of paramount importance. Here, through atomic-scale analysis of micrometer-long GBs, we show that covalently bound boundaries in 2D MoS 2 tend to be decorated by nanopores. Such boundaries occur when differently oriented MoS 2 grains merge during growth, whereas the overlap of grains leads to boundaries with bilayer areas. Our results suggest that the nanopore formation is related to stress release in areas with a high concentration of dislocation cores at the grain boundaries, and that the interlayer interaction leads to intrinsic rippling at the overlap regions. This provides insights for the controlled fabrication of large-scale MoS 2 samples with desired structural properties for applications.

  6. Stability and thermal behavior of molybdenum disulfide nanotubes: Nonequilibrium molecular dynamics simulation using REBO potential

    Science.gov (United States)

    Ahadi, Zohreh; Shadman Lakmehsari, Muhammad; Kumar Singh, Sandeep; Davoodi, Jamal

    2017-12-01

    This study is an attempt to perform equilibrium molecular dynamics and non-equilibrium molecular dynamics (NEMD) to evaluate the stability and thermal behavior of molybdenum disulfide nanotubes (MoS2NTs) by reactive empirical bond order potential. The stability of nanotubes, cohesive energy, isobaric heat capacity, and enthalpies of fusion in armchair and zigzag structures with different radii were calculated. The observed results illustrate that SWMoS2NTs, which have larger diameters, are more stable with more negative energy than the smaller ones. Moreover, it was found that the melting point is increased with an increase in the nanotube's radius. During the melting process, the structural transformation of nanotubes was investigated using a mean-square displacement and radial distribution function diagrams. Afterwards, using a NEMD simulation, the thermal conductivity of nanotubes with various diameters was calculated at a constant nanotube length. The obtained results show that the thermal conductivity coefficient increases with increasing nanotube diameters when the nanotube length is constant.

  7. Ferroelectric transistors with monolayer molybdenum disulfide and ultra-thin aluminum-doped hafnium oxide

    Science.gov (United States)

    Yap, Wui Chung; Jiang, Hao; Liu, Jialun; Xia, Qiangfei; Zhu, Wenjuan

    2017-07-01

    In this letter, we demonstrate ferroelectric memory devices with monolayer molybdenum disulfide (MoS2) as the channel material and aluminum (Al)-doped hafnium oxide (HfO2) as the ferroelectric gate dielectric. Metal-ferroelectric-metal capacitors with 16 nm thick Al-doped HfO2 are fabricated, and a remnant polarization of 3 μC/cm2 under a program/erase voltage of 5 V is observed. The capability of potential 10 years data retention was estimated using extrapolation of the experimental data. Ferroelectric transistors based on embedded ferroelectric HfO2 and MoS2 grown by chemical vapor deposition are fabricated. Clockwise hysteresis is observed at low program/erase voltages due to slow bulk traps located near the 2D/dielectric interface, while counterclockwise hysteresis is observed at high program/erase voltages due to ferroelectric polarization. In addition, the endurances of the devices are tested, and the effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, are observed. Reliable writing/reading in MoS2/Al-doped HfO2 ferroelectric transistors over 2 × 104 cycles is achieved. This research can potentially lead to advances of two-dimensional (2D) materials in low-power logic and memory applications.

  8. The influence of molybdenum disulfide nanoplatelets on the dispersion of nano silica in natural rubber composites

    Energy Technology Data Exchange (ETDEWEB)

    Weng, Peijin; Wei, Qiuyan; Tang, Zhenghai; Lin, Tengfei; Guo, Baochun, E-mail: psbcguo@scut.edu.cn

    2015-12-30

    Graphical abstract: - Highlights: • The dispersion of silica in rubber is improved by incorporating MoS{sub 2} nanoplatelets. • The charge transferring between MoS{sub 2} and silica is verified. • The mechanical performance of the composites are enhanced by incorporating MoS{sub 2} plates. • The heat build-up of the composites is decreased by incorporating MoS{sub 2} plates. - Abstract: The dispersion of nanofiller in polymer composites is critical in governing the ultimate performances. Present study aimed to improve the dispersion of silica in elastomeric materials based on natural rubber (NR) composites using the nanoplatelets of molybdenum disulfide (MoS{sub 2}), a graphene-like layered inorganic. NR latex was co-coagulated with MoS{sub 2} suspension to form NR/MoS{sub 2} compounds (1∼5 phr). Then silica (30 phr) was incorporated into NR/MoS{sub 2} compounds, followed by curing with sulfur, to obtained NR/MoS{sub 2}/silica composites. The dispersion state of silica in the composites was examined by TEM and the effects of MoS{sub 2} on the performance of the composites were investigated. It was found that a small amount of MoS{sub 2} nanoplatelets significantly improved the silica dispersion. Consequently, the static and dynamic mechanical properties of the crosslinked natural rubber materials were greatly enhanced. The improved dispersion of silica is associated with charge transfer interaction, giving rise to electrostatic repulsion among silica.

  9. Electronic Structure and Surface Physics of Two-dimensional Material Molybdenum Disulfide

    Science.gov (United States)

    Jin, Wencan

    The interest in two-dimensional materials and materials physics has grown dramatically over the past decade. The family of two-dimensional materials, which includes graphene, transition metal dichalcogenides, phosphorene, hexagonal boron nitride, etc., can be fabricated into atomically thin films since the intralayer bonding arises from their strong covalent character, while the interlayer interaction is mediated by weak van der Waals forces. Among them, molybdenum disulfide (MoS2) has attracted much interest for its potential applications in opto-electronic and valleytronics devices. Previously, much of the experimental studies have concentrated on optical and transport measurements while neglecting direct experimental determination of the electronic structure of MoS2, which is crucial to the full understanding of its distinctive properties. In particular, like other atomically thin materials, the interactions with substrate impact the surface structure and morphology of MoS2, and as a result, its structural and physical properties can be affected. In this dissertation, the electronic structure and surface structure of MoS2 are directly investigated using angle-resolved photoemission spectroscopy and cathode lens microscopy. Local-probe angle-resolved photoemission spectroscopy measurements of monolayer, bilayer, trilayer, and bulk MoS 2 directly demonstrate the indirect-to-direct bandgap transition due to quantum confinement as the MoS2 thickness is decreased from multilayer to monolayer. The evolution of the interlayer coupling in this transition is also investigated using density functional theory calculations. Also, the thickness-dependent surface roughness is characterized using selected-area low energy electron diffraction (LEED) and the surface structural relaxation is investigated using LEED I-V measurements combined with dynamical LEED calculations. Finally, bandgap engineering is demonstrated via tuning of the interlayer interactions in van der Waals

  10. Tribological properties of adaptive phosphate composite coatings with addition of silver and molybdenum disulfide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cancan [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); University of Chinese Academy of Sciences, Beijing (China); Chen, Lei, E-mail: chenlei@lzb.ac.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); Zhou, Jiansong, E-mail: jszhou@licp.cas.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); Zhou, Huidi; Chen, Jianmin [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China)

    2014-05-01

    Highlights: • A new kind of adaptive coatings was fabricated using relatively simple spraying techniques. • The tribological properties of Ag/MoS{sub 2} phosphate composite coatings were investigated at the temperature from 20 °C to 700 °C. • The composition and wear mechanisms of Ag/MoS{sub 2} phosphate composite coatings were also discussed. • The Ag/MoS{sub 2} phosphate composite coatings have self-repairing capability in the rubbing process at 700 °C. - Abstract: Adaptive phosphate composite coatings with addition of solid lubricants of molybdenum disulfide (MoS{sub 2}) and silver (Ag) using aluminum chromium phosphate as the binder were fabricated on high-temperature steel. The tribological properties of phosphate composite coatings were evaluated from room temperature (RT) to 700 °C. The phase composition and microstructure were investigated according to the characterization by power X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The results show that the composite coating with the Ag/MoS{sub 2} mass ratio of 2:1 exhibits the stable and low friction coefficients from RT to 700 °C and relative low wear rates at all testing temperatures. The tribo-chemical reaction between Ag and MoS{sub 2} occurred in the rubbing process to form silver molybdates compounds lubricating film. The temperature-adaptive tribological properties were attributed to the formation of lubricating films composed of lubricants silver, MoS{sub 2} and silver molybdates phases on the worn surfaces of the composites coatings in a wide-temperature range.

  11. Vertical 2D/3D Semiconductor Heterostructures Based on Epitaxial Molybdenum Disulfide and Gallium Nitride.

    Science.gov (United States)

    Ruzmetov, Dmitry; Zhang, Kehao; Stan, Gheorghe; Kalanyan, Berc; Bhimanapati, Ganesh R; Eichfeld, Sarah M; Burke, Robert A; Shah, Pankaj B; O'Regan, Terrance P; Crowne, Frank J; Birdwell, A Glen; Robinson, Joshua A; Davydov, Albert V; Ivanov, Tony G

    2016-03-22

    When designing semiconductor heterostructures, it is expected that epitaxial alignment will facilitate low-defect interfaces and efficient vertical transport. Here, we report lattice-matched epitaxial growth of molybdenum disulfide (MoS2) directly on gallium nitride (GaN), resulting in high-quality, unstrained, single-layer MoS2 with strict registry to the GaN lattice. These results present a promising path toward the implementation of high-performance electronic devices based on 2D/3D vertical heterostructures, where each of the 3D and 2D semiconductors is both a template for subsequent epitaxial growth and an active component of the device. The MoS2 monolayer triangles average 1 μm along each side, with monolayer blankets (merged triangles) exhibiting properties similar to that of single-crystal MoS2 sheets. Photoluminescence, Raman, atomic force microscopy, and X-ray photoelectron spectroscopy analyses identified monolayer MoS2 with a prominent 20-fold enhancement of photoluminescence in the center regions of larger triangles. The MoS2/GaN structures are shown to electrically conduct in the out-of-plane direction, confirming the potential of directly synthesized 2D/3D semiconductor heterostructures for vertical current flow. Finally, we estimate a MoS2/GaN contact resistivity to be less than 4 Ω·cm(2) and current spreading in the MoS2 monolayer of approximately 1 μm in diameter.

  12. Valley- and spin-switch effects in molybdenum disulfide superconducting spin valve

    Science.gov (United States)

    Majidi, Leyla; Asgari, Reza

    2014-10-01

    We propose a hole-doped molybdenum disulfide (MoS2) superconducting spin valve (F/S/F) hybrid structure in which the Andreev reflection process is suppressed for all incoming waves with a determined range of the chemical potential in ferromagnetic (F) region and the cross-conductance in the right F region depends crucially on the configuration of magnetizations in the two F regions. Using the scattering formalism, we find that the transport is mediated purely by elastic electron cotunneling (CT) process in a parallel configuration and changes to the pure crossed Andreev reflection (CAR) process in the low-energy regime, without fixing of a unique parameter, by reversing the direction of magnetization in the right F region. This suggests both valley- and spin-switch effects between the perfect elastic CT and perfect CAR processes and makes the nonlocal charge current to be fully valley- and spin-polarized inside the right F region where the type of the polarizations can be changed by reversing the magnetization direction in the right F region. We further demonstrate that the presence of the strong spin-orbit interaction λ and an additional topological term (β ) in the Hamiltonian of MoS2 result in an enhancement of the charge conductance of the CT and CAR processes and make them to be present for long lengths of the superconducting region. Besides, we find that the thermal conductance of the structure with a small length of the highly doped superconducting region exhibits linear dependence on the temperature at low temperatures, whereas it enhances exponentially at higher temperatures. In particular, we demonstrate that the thermal conductance versus the strength of the exchange field (h ) in F region displays a maximum value at h <λ , which moves towards larger exchange fields by increasing the temperature.

  13. Molybdenum disulfide nanoflower-chitosan-Au nanoparticles composites based electrochemical sensing platform for bisphenol A determination

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Ke-Jing, E-mail: kejinghuang@163.com [College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000 (China); State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Liu, Yu-Jie; Liu, Yan-Ming; Wang, Ling-Ling [College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000 (China)

    2014-07-15

    Highlights: • This work constructs a novel electrochemical biosensor for bisphenol A detection. • Flower-like MoS{sub 2} are prepared by a simple hydrothermal procedure. • AuNPs are assembled on MoS{sub 2} nanoflowers modified electrode for signal amplification. • The developed sensor exhibits low detection limit and wide linear range. - Abstract: Two-dimensional transition metal dichalcogenide are attracting increasing attention in electrochemical sensing due to their unique electronic properties. In this work, flower-like molybdenum disulfide (MoS{sub 2}) was prepared by a simple hydrothermal method. The scanning electron microscopy and transmission electron microscopy images showed the MoS{sub 2} nanoflower had sizes with diameter of about 200 nm and was constructed with many irregular sheets as a petal-like structure with thickness of several nanometers. A novel electrochemical sensor was constructed for the determination of bisphenol A (BPA) based on MoS{sub 2} and chitosan-gold nanoparticles composites modified electrode. The sensor showed an efficient electrocatalytic role for the oxidation of BPA, and the oxidation overpotentials of BPA decreased significantly and the peak current increased greatly compared with bare GCE and other modified electrode. A good linear relationship between the oxidation peak current and BPA concentration was obtained in the range from 0.05 to 100 μM with a detection limit of 5.0 × 10{sup −9} M (S/N = 3). The developed sensor exhibited high sensitivity and long-term stability, and it was successfully applied for the determination of BPA in different samples. This work indicated MoS{sub 2} nanoflowers were promising in electrochemical sensing and catalytic applications.

  14. Swift tuning from spherical molybdenum microspheres to hierarchical molybdenum disulfide nanostructures by switching from solvothermal to hydrothermal synthesis route

    Science.gov (United States)

    Qureshi, Nilam; Arbuj, Sudhir; Shinde, Manish; Rane, Sunit; Kulkarni, Milind; Amalnerkar, Dinesh; Lee, Haiwon

    2017-09-01

    Herein, we report the synthesis of metallic molybdenum microspheres and hierarchical MoS2 nanostructures by facile template-free solvothermal and hydrothermal approach, respectively. The morphological transition of the Mo microspheres to hierarchical MoS2 nanoflower architectures is observed to be accomplished with change in solvent from ethylenediamine to water. The resultant marigold flower-like MoS2 nanostructures are few layers thick with poor crystallinity while spherical ball-like molybdenum microspheres exhibit better crystalline nature. This is the first report pertaining to the synthesis of Mo microspheres and MoS2 nanoflowers without using any surfactant, template or substrate in hydro/solvothermal regime. It is opined that such nanoarchitectures of MoS2 are useful candidates for energy related applications such as hydrogen evolution reaction, Li ion battery and pseudocapacitors. Inquisitively, metallic Mo can potentially act as catalyst as well as fairly economical Surface Enhanced Raman Spectroscopy (SERS) substrate in biosensor applications.

  15. Recent Advancement on the Optical Properties of Two-Dimensional Molybdenum Disulfide (MoS2 Thin Films

    Directory of Open Access Journals (Sweden)

    Mingxiao Ye

    2015-03-01

    Full Text Available The emergence of two-dimensional (2D materials has led to tremendous interest in the study of graphene and a series of mono- and few-layered transition metal dichalcogenides (TMDCs. Among these TMDCs, the study of molybdenum disulfide (MoS2 has gained increasing attention due to its promising optical, electronic, and optoelectronic properties. Of particular interest is the indirect to direct band-gap transition from bulk and few-layered structures to mono-layered MoS2, respectively. In this review, the study of these properties is summarized. The use of Raman and Photoluminescence (PL spectroscopy of MoS2 has become a reliable technique for differentiating the number of molecular layers in 2D MoS2.

  16. Broad-spectrum enhanced absorption of graphene-molybdenum disulfide photovoltaic cells in Metal-Mirror Microcavity.

    Science.gov (United States)

    Liu, Jiang Tao; Cao, Yunkai; Tong, Hong; Wang, Dahai; Wu, Zhenhua

    2018-01-29

    We investigate theoretically the optical absorption of graphene-molybdenum disulfide photovoltaic cells (GM-PVc) in wedge-shaped metal-mirror microcavities (w-MMCs) combined with spectrum-splitting structure. Results show that the combination of spectrum-splitting structure and w-MMC can enable the light absorption of GM-PVc to reach about 65% in the broad spectrum. The influence of processing errors on the absorption of GM-PVc in w-MMCs is effectively suppressed, i.e., 3 ~14 times lower than that of GM-PVc in common wedge photonic crystal microcavities. The light absorption of GM-PVc reaches 60% in broad spectrum even with the processing errors. This proposal of GM-PVc structure is easy to implement and has potentially important applications in the development of ultra-thin and high-efficiency solar cells and optoelectronic devices. © 2018 IOP Publishing Ltd.

  17. Development of self-lubricating composite materials of nickel with molybdenum disulfide, graphite and hexagonal boron nitride processed by powder metallurgy: preliminary study

    OpenAIRE

    Parucker, Moisés Luiz; Klein, Aloisio Nelmo; Binder, Cristiano; Ristow Junior, Walter; Binder, Roberto

    2013-01-01

    The purpose of this work was to develop nickel self-lubricating composites using solid lubricant as second phase and obtained by powder metallurgy. The work involved the study of chemical stability and chemical interaction between the nickel alloy matrix and solid lubricating additives (molybdenum disulfide, graphite and hexagonal boron nitride). The results showed a thermodynamic stability during sintering for the composites containing the phases of graphite and hexagonal boron nitride. The ...

  18. Variations of Contact Resistance in Dual-Gated Monolayer Molybdenum Disulfide Transistors Depending on Gate Bias Selection

    Science.gov (United States)

    Tran, P. X.

    2017-06-01

    Monolayer molybdenum disulfide (MoS2) is considered an alternative two-dimensional material for high performance ultra-thin field-effect transistors. MoS2 is a triple atomic layer with a direct 1.8 eV bandgap. Bulk MoS2 has an additional indirect bandgap of 1.2 eV, which leads to high current on/off ratio around 108. Flakes of MoS2 can be obtained by mechanical exfoliation or grown by chemical vapor deposition. Intrinsic cut-off frequency of multilayer MoS2 transistor has reached 42 GHz. Chemical doping of MoS2 is challenging and results in reduction of contact resistance. This paper focuses on modeling of dual-gated monolayer MoS2 transistors with effective mobility of carriers varying from 0.6 cm2/V s to 750 cm2/V s. In agreement with experimental data, the model demonstrates that in back-gate bias devices, the contact resistance decreases almost exponentially with increasing gate bias, whereas in top-gate bias devices, the contact resistance stays invariant when varying gate bias.

  19. Hierarchical Polyphosphazene@Molybdenum Disulfide Hybrid Structure for Enhancing the Flame Retardancy and Mechanical Property of Epoxy Resins.

    Science.gov (United States)

    Zhou, Xia; Qiu, Shuilai; Xing, Weiyi; Gangireddy, Chandra Sekhar Reddy; Gui, Zhou; Hu, Yuan

    2017-08-30

    A novel polyphosphazene (PZS) microsphere@molybdenum disulfide nanoflower (MoS 2 ) hierarchical hybrid architecture was first synthesized and applied for enhancing the mechanical performance and flame retardancy of epoxy (EP) resin via a cooperative effect. Herein, using PZS microsphere as the template, a layer of MoS 2 nanoflowers were anchored to PZS spheres via a hydrothermal strategy. The well-designed PZS@MoS 2 exhibits excellent fire retardancy and a reinforcing effect. The obtained PZS@MoS 2 significantly enhanced the flame-retardant performance of EP composites, which can be proved by thermogravimetric and cone calorimeter results. For instance, the incorporation of 3 wt % PZS@MoS 2 brought about a 41.3% maximum reduction in the peak heat-release rate and decreased by 30.3% maximum in the total heat release, accompanying the higher graphitized char layer. With regard to mechanical property, the storage modulus of EP/PZS@MoS 2 3.0 in the glassy state was dramatically increased to 22.4 GPa in comparison with that of pure EP (11.15 GPa). It is sensible to know that the improved flame-retardant performance for EP composites is primarily assigned to a physical barrier effect of the MoS 2 nanoflowers and the polyphosphazene structure has an positive impact on promoting char formation in the condensed phase.

  20. Catalytic chemical vapor deposition of large-area uniform two-dimensional molybdenum disulfide using sodium chloride

    Science.gov (United States)

    Song, Jeong-Gyu; Ryu, Gyeong Hee; Kim, Youngjun; Woo, Whang Je; Ko, Kyung Yong; Kim, Yongsung; Lee, Changseung; Oh, Il-Kwon; Park, Jusang; Lee, Zonghoon; Kim, Hyungjun

    2017-11-01

    The effective synthesis of atomically thin molybdenum disulfides (MoS2) of high quality and uniformity over a large area is essential for their use in electronic and optical devices. In this work, we synthesize MoS2 that exhibit a high quality and large area uniformity using chemical vapor deposition (CVD) with volatile S organic compound and NaCl catalysts. In the latter process, the NaCl enhances the growth rate (5 min for synthesis of monolayer MoS2) and purity of the synthesized MoS2. The optical microscopy, Raman spectroscopy, x-ray photoemission spectroscopy, photoluminescence, and transmission electron microscopy measurements indicate that the NaCl-CVD MoS2 has a large grain size, clear Raman shift, strong photoluminescence, good stoichiometry, and 6-fold coordination symmetry. Moreover, we demonstrate that the electron mobility (10.4 cm2 V‑1 s‑1) and on/off current ratio (3 × 107) of monolayer MoS2 measured using a field-effect transistor are comparable to those of previously reported MoS2 synthesized using CVD.

  1. Elastic and thermal properties of free-standing molybdenum disulfide membranes measured using ultrafast transient grating spectroscopy

    Science.gov (United States)

    Kim, Taeyong; Ding, Ding; Yim, Jong-Hyuk; Jho, Young-Dahl; Minnich, Austin J.

    2017-08-01

    Molybdenum disulfide (MoS2), a member of transition-metal dichalcogenide family, is of intense interest due to its unique electronic and thermoelectric properties. However, reports of its in-plane thermal conductivity vary due to the difficulty of in-plane thermal conductivity measurements on thin films, and an experimental measurement of the in-plane sound velocity has not been reported. Here, we use time-resolved transient grating spectroscopy to simultaneously measure the in-plane elastic and thermal properties of free-standing MoS2 membranes at room temperature. We obtain a longitudinal acoustic phonon velocity of 7000 ± 40 m s-1 and an in-plane thermal conductivity of 74 ± 21 W m-1K-1. Our measurements provide useful insights into the elastic and thermal properties of MoS2 and demonstrate the capability of transient grating spectroscopy to investigate the in-plane vibrational properties of van der Waals materials that are challenging to characterize with conventional methods.

  2. Elemental Sulfur and Molybdenum Disulfide Composites for Li-S Batteries with Long Cycle Life and High-Rate Capability.

    Science.gov (United States)

    Dirlam, Philip T; Park, Jungjin; Simmonds, Adam G; Domanik, Kenneth; Arrington, Clay B; Schaefer, Jennifer L; Oleshko, Vladimir P; Kleine, Tristan S; Char, Kookheon; Glass, Richard S; Soles, Christopher L; Kim, Chunjoong; Pinna, Nicola; Sung, Yung-Eun; Pyun, Jeffrey

    2016-06-01

    The practical implementation of Li-S technology has been hindered by short cycle life and poor rate capability owing to deleterious effects resulting from the varied solubilities of different Li polysulfide redox products. Here, we report the preparation and utilization of composites with a sulfur-rich matrix and molybdenum disulfide (MoS2) particulate inclusions as Li-S cathode materials with the capability to mitigate the dissolution of the Li polysulfide redox products via the MoS2 inclusions acting as "polysulfide anchors". In situ composite formation was completed via a facile, one-pot method with commercially available starting materials. The composites were afforded by first dispersing MoS2 directly in liquid elemental sulfur (S8) with sequential polymerization of the sulfur phase via thermal ring opening polymerization or copolymerization via inverse vulcanization. For the practical utility of this system to be highlighted, it was demonstrated that the composite formation methodology was amenable to larger scale processes with composites easily prepared in 100 g batches. Cathodes fabricated with the high sulfur content composites as the active material afforded Li-S cells that exhibited extended cycle lifetimes of up to 1000 cycles with low capacity decay (0.07% per cycle) and demonstrated exceptional rate capability with the delivery of reversible capacity up to 500 mAh/g at 5 C.

  3. Elastic and thermal properties of free-standing molybdenum disulfide membranes measured using ultrafast transient grating spectroscopy

    Directory of Open Access Journals (Sweden)

    Taeyong Kim

    2017-08-01

    Full Text Available Molybdenum disulfide (MoS2, a member of transition-metal dichalcogenide family, is of intense interest due to its unique electronic and thermoelectric properties. However, reports of its in-plane thermal conductivity vary due to the difficulty of in-plane thermal conductivity measurements on thin films, and an experimental measurement of the in-plane sound velocity has not been reported. Here, we use time-resolved transient grating spectroscopy to simultaneously measure the in-plane elastic and thermal properties of free-standing MoS2 membranes at room temperature. We obtain a longitudinal acoustic phonon velocity of 7000 ± 40 m s−1 and an in-plane thermal conductivity of 74 ± 21 W m−1K−1. Our measurements provide useful insights into the elastic and thermal properties of MoS2 and demonstrate the capability of transient grating spectroscopy to investigate the in-plane vibrational properties of van der Waals materials that are challenging to characterize with conventional methods.

  4. Molybdenum Disulfide (MoS2 Coating on AISI 316 Stainless Steel by Thermo-Diffusion Method

    Directory of Open Access Journals (Sweden)

    Akbarzadeh M.

    2017-09-01

    Full Text Available Molybdenum disulfide (MoS2 is one of the most widely used solid lubricants applied in different ways on the surfaces under friction. In this work, AISI 316 austenitic stainless steel was coated with MoS2, using thermo-diffusion method at different temperatures and times. Coatings properties were investigated using SEM, EDX, XRD and FTIR, Hardness Tester and Roughness tester. The results illustrated the formation of a uniform layer on the surface, containing MoS2 and MoO3-X phases. The thickness, grain size and the hardness of the coatings were 20-50 μm, 400-1000 nm and 350- 550 HV respectively. Friction tests carried out using ball-on-disc method under normal loads of 10 N under ambient conditions showed values of the friction coefficient 0.30-0.40. In addition, the kinetics of diffusion layers between the substrate and the coating were also investigated. It was found that there at steady temperature there is a parabolic relationship between the thickness of the diffusion layer and the treatment time. The activation energy for the process was estimated to be 143 kJ mol−1. Depending on the treatment time and temperature, the thicknesses of diffusion layer varied between 0.5 and 2.5 microns.

  5. Hydrogen Evolution Reaction Property in Alkaline Solution of Molybdenum Disulfide Modified by Surface Anchor of Nickel–Phosphorus Coating

    Directory of Open Access Journals (Sweden)

    Jun He

    2017-06-01

    Full Text Available Molybdenum disulfide (MoS2 is unfavorable for practical application in the hydrogen evolution reaction (HER process due to its inert basal surface, inferior conductivity, and limited amount of active edge sites. For the purpose of enhancing the HER performance of this catalyst, the HER activity of its basal surface should be increased. Herein, three types of nickel-phosphorus (Ni–P coatings—namely, low phosphorus (LP, medium phosphorus (MP and high phosphorus (HP —were anchored onto the surfaces of MoS2 nanoparticles via an electroless plating process; thus, three Ni–P/MoS2 composites (Ni–LP/MoS2, Ni–MP/MoS2, and Ni–HP/MoS2 were fabricated. Crystal structures, morphologies, chemical components, and HER performances of each in an alkaline solution were characterized. Both Ni–LP/MoS2 and Ni–MP/MoS2 showed a crystal nature, while the amorphous feature for Ni–HP/MoS2 was validated. The three Ni–P/MoS2 composites exhibited a higher HER activity than the pure MoS2. The HER performance of the Ni–MP/MoS2 composite was more outstanding than those of other two composites, which could be attributed to the presence of metastable nickel phosphides, and the excellent conductivity of Ni–MP coating anchored on the basal surface of MoS2.

  6. Highly efficient hydrogen evolution reaction using crystalline layered three-dimensional molybdenum disulfides grown on graphene film.

    Energy Technology Data Exchange (ETDEWEB)

    Behranginia, Amirhossein; Asadi, Mohammad; Liu, Cong; Yasaei, Poya; Kumar, Bijandra; Phillips, Patrick; Foroozan, Tara; Waranius, Joseph C.; Kim, Kibum; Abiade, Jeremiah; Klie, Robert F.; Curtiss, Larry A.; Salehi-Khojin, Amin

    2016-01-26

    Electrochemistry is central to applications in the field of energy storage and generation. However, it has advanced far more slowly over the last two decades, mainly because of a lack of suitable and affordable catalysts. Here, we report the synthesis of highly crystalline layered three-dimensional (3D) molybdenum disulfide (MoS2) catalysts with bare Mo-edge atoms and demonstrate their remarkable performance for the hydrogen evolution reaction (HER). We found that Mo-edge-terminated 3D MoS2 directly grown on graphene film exhibits a remarkable exchange current density (18.2 mu A cm(-2)) and turnover frequency (>4 S-1) for HER. The obtained exchange current density is 15.2 and 2.3 times higher than that of MoS2/graphene and MoS2/Au catalysts, respectively, both with sulfided Mo-edge atoms. An easily scalable and robust growth process on a wide variety of substrates, along with prolonged stability, suggests that this material is a promising catalyst in energy-related applications.

  7. Effects of γ-ray radiation on two-dimensional molybdenum disulfide (MoS{sub 2}) nanomechanical resonators

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jaesung; Feng, Philip X.-L., E-mail: philip.feng@case.edu [Department of Electrical Engineering and Computer Science, Case School of Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106 (United States); Krupcale, Matthew J. [Department of Electrical Engineering and Computer Science, Case School of Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106 (United States); Department of Physics, College of Arts and Sciences, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106 (United States)

    2016-01-11

    We report on experimental investigation and analysis of γ-ray radiation effects on two-dimensional molybdenum disulfide (MoS{sub 2}) drumhead nanomechanical resonators vibrating at megahertz frequencies. Given calibrated dosages of γ-ray radiation of ∼5000 photons with energy at 662 keV, upon exposure over 24 or 12 h, all the MoS{sub 2} resonators exhibit ∼0.5–2.1% resonance frequency upshifts due to the ionizing γ-ray induced charges and their interactions. The devices show γ-ray photon responsivity of ∼30–82 Hz/photon, with an intrinsic γ-ray sensitivity (limit of detection) estimated to approach ∼0.02–0.05 photon. After exposure expires, resonance frequencies return to an ordinary tendency where the frequency variations are dominated by long-term drift. These γ-ray radiation induced frequency shifts are distinctive from those due to pressure variation or surface adsorption mechanisms. The measurements and analyses show that MoS{sub 2} resonators are robust yet sensitive to very low dosage γ-ray, demonstrating a potential for ultrasensitive detection and early alarm of radiation in the very low dosage regime.

  8. Cationic surfactant-assisted hydrothermal synthesis of few-layer molybdenum disulfide/graphene composites: Microstructure and electrochemical lithium storage

    Science.gov (United States)

    Ma, Lin; Huang, Guochuang; Chen, Weixiang; Wang, Zhen; Ye, Jianbo; Li, Haiyang; Chen, Dongyun; Lee, Jim Yang

    2014-10-01

    Few-layer molybdenum disulfide/graphene (FL-MoS2/GNS) composites are fabricated by a facile hydrothermal route and a post-annealing with the assistance of various cationic surfactants (dodecyltrimethylammonium bromide, DTAB; octyltrimethylammonium bromide, OTAB; and tetrabutylammonium bromide, TBAB), which have different alkyl-chain lengths and stereo configurations. The effects of these cationic surfactants on the microstructures and electrochemical performances of the FL-MoS2/GNS for lithium storage are investigated. It is demonstrated the cationic surfactants show some ability to control the microstructure (layer number) of FL-MoS2 in composites. The electrochemical performances of FL-MoS2/GNS composites for lithium storage are greatly improved compared to the bare MoS2. Especially, FL-MoS2/GNS with ∼6 MoS2 layers prepared with the assistance of OTAB exhibits very high reversible capacity of ∼1200 mAh g-1 with excellent cycle stability and enhanced rate capability. Electrochemical impedance spectrum also confirms that the FL-MoS2/GNS composite electrodes exhibit much lower electron-transfer resistance than the MoS2. The remarkable electrochemical performances of FL-MoS2/GNS composites can be attributed to the synergistic interaction between FL-MoS2 and graphene and their quasi-3D architectures, which promote lithium diffusion, electron transfer and electrolyte access.

  9. Evidence from in situ X-ray absorption spectroscopy for the involvement of terminal disulfide in the reduction of protons by an amorphous molybdenum sulfide electrocatalyst.

    Science.gov (United States)

    Lassalle-Kaiser, Benedikt; Merki, Daniel; Vrubel, Heron; Gul, Sheraz; Yachandra, Vittal K; Hu, Xile; Yano, Junko

    2015-01-14

    The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoSx) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as the precatalytic and catalytic states. The as prepared material is very similar to MoS3 and remains unmodified under functional conditions (pH = 2 aqueous HNO3) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (-0.3 V vs RHE), the film is reduced to an amorphous form of MoS2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. These results show the implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.

  10. The coupled effects of environmental composition, temperature and contact size-scale on the tribology of molybdenum disulfide

    Science.gov (United States)

    Khare, Harmandeep S.

    Liquid lubricants are precluded in an exceedingly large number of consumer as well as extreme applications as a means to reduce friction and wear at the sliding interface of two bodies. The extraterrestrial environment is one such example of an extreme environment which has motivated the development of advanced solid lubricant materials. Mechanical systems for space require fabrication, assembly, transportation and testing on earth before launch and deployment. Solid lubricants for space are expected to not only operate efficiently in the hard vacuum of space but also withstand interactions with moisture or oxygen during the terrestrial storage, transportation and assembly prior to deployment and launch. Molybdenum disulfide (MoS2) is considered the gold standard in solid lubricants for space due to its excellent tribological properties in ultra-high vacuum. However in the presence of environmental species such as water and oxygen or at elevated temperatures, the lubricity and endurance of MoS2 is severely limited. Past studies have offered several hypotheses for the breakdown of lubrication of MoS2 under the influence of water and oxygen, although exact mechanisms remain unknown. Furthermore, it is unclear if temperature acts as a driver solely for oxidation or for thermally activated slip and thermally activated desorption as well. The answers to these questions are of fundamental importance to improving the reliability of existing MoS2-based solid lubricants for space, as well as for guiding the design of advanced lamellar solid lubricant coatings. This dissertation aims to elucidate: (1) the role of water on MoS2 oxidation, (2) the role of water on MoS2 friction, (3) the role of oxygen on MoS2 friction, (4) the contribution of thermal activation to ambient-temperature friction, and (5) effects of length-scale. The results of this study showed that water does not cause oxidation of MoS2. Water increases ambient-temperature friction of MoS2 directly through a

  11. A sensitive electrochemical aptasensor based on palladium nanoparticles decorated graphene–molybdenum disulfide flower-like nanocomposites and enzymatic signal amplification

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Pei; Yi, Huayu; Xue, Shuyan; Chai, Yaqin; Yuan, Ruo; Xu, Wenju, E-mail: xwju@swu.edu.cn

    2015-01-01

    Highlights: • PDDA–G–MoS{sub 2} nanoflowers were firstly used for the fabrication of thrombin aptasensor. • MoS{sub 2} was adopted to enhance the surface area of graphene and accelerate the electron transfer. • GOD, PdNPs and hemin/G-quadruplex could amplify the electrochemical signal through synergetic catalysis. • The proposed aptasensor displayed an improved sensitivity. - Abstract: In the present study, with the aggregated advantages of graphene and molybdenum disulfide (MoS{sub 2}), we prepared poly(diallyldimethylammonium chloride)–graphene/molybdenum disulfide (PDDA–G–MoS{sub 2}) nanocomposites with flower-like structure, large surface area and excellent conductivity. Furthermore, an advanced sandwich-type electrochemical assay for sensitive detection of thrombin (TB) was fabricated using palladium nanoparticles decorated PDDA–G–MoS{sub 2} (PdNPs/PDDA–G–MoS{sub 2}) as nanocarriers, which were functionalized by hemin/G-quadruplex, glucose oxidase (GOD), and toluidine blue (Tb) as redox probes. The signal amplification strategy was achieved as follows: Firstly, the immobilized GOD could effectively catalyze the oxidation of glucose to gluconolactone, coupling with the reduction of the dissolved oxygen to H{sub 2}O{sub 2}. Then, both PdNPs and hemin/G-quadruplex acting as hydrogen peroxide (HRP)-mimicking enzyme could further catalyze the reduction of H{sub 2}O{sub 2}, resulting in significant electrochemical signal amplification. So the proposed aptasensor showed high sensitivity with a wide dynamic linear range of 0.0001 to 40 nM and a relatively low detection limit of 0.062 pM for TB determination. The strategy showed huge potential of application in protein detection and disease diagnosis.

  12. Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S

    Energy Technology Data Exchange (ETDEWEB)

    Mane, Anil U. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Letourneau, Steven [Micron School of Materials Science and Engineering, Boise State University, 1910 University Dr., Boise, Idaho 83725; Mandia, David J. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Liu, Jian [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208; Libera, Joseph A. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Lei, Yu [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Peng, Qing [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439; Graugnard, Elton [Micron School of Materials Science and Engineering, Boise State University, 1910 University Dr., Boise Idaho 83725; Elam, Jeffrey W. [Energy Systems Division, Argonne National Laboratory, 9700 S. Cass Ave, Argonne, Illinois 60439

    2018-01-01

    Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 degrees C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 angstrom/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFx residues in the films. Annealing the films at 350 degrees C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc. Published by the AVS

  13. Manipulation of local optical properties and structures in molybdenum-disulfide monolayers using electric field-assisted near-field techniques.

    Science.gov (United States)

    Nozaki, Junji; Fukumura, Musashi; Aoki, Takaaki; Maniwa, Yutaka; Yomogida, Yohei; Yanagi, Kazuhiro

    2017-04-05

    Remarkable optical properties, such as quantum light emission and large optical nonlinearity, have been observed in peculiar local sites of transition metal dichalcogenide monolayers, and the ability to tune such properties is of great importance for their optoelectronic applications. For that purpose, it is crucial to elucidate and tune their local optical properties simultaneously. Here, we develop an electric field-assisted near-field technique. Using this technique we can clarify and tune the local optical properties simultaneously with a spatial resolution of approximately 100 nm due to the electric field from the cantilever. The photoluminescence at local sites in molybdenum-disulfide (MoS2) monolayers is reversibly modulated, and the inhomogeneity of the charge neutral points and quantum yields is suggested. We successfully etch MoS2 crystals and fabricate nanoribbons using near-field techniques in combination with an electric field. This study creates a way to tune the local optical properties and to freely design the structural shapes of atomic monolayers using near-field optics.

  14. A novel molybdenum disulfide nanosheet self-assembled flower-like monolithic sorbent for solid-phase extraction with high efficiency and long service life.

    Science.gov (United States)

    Ran, Fanpeng; Liu, Hongmei; Wang, Xiaoqi; Guo, Yong

    2017-07-21

    A novel material consisting of molybdenum disulfide (MoS2) nanosheet that self-assemble into flower-like microspheres which aggregate to form a monolithic matrix with a micro or nano-scaled mesopore structure was successfully synthesized and used as an efficient sorbent for solid-phase extraction (SPE) due to its large specific adsorption area and good stability. The extraction properties of the as-prepared sorbent were evaluated by high-performance liquid chromatography with variable wavelength detection (HPLC-VWD) by analyzing four flavonoids (apigenin, quercetin, luteolin, and kaempferol). Under optimal conditions, the LODs and LOQs were found to be in the ranges of 0.1-0.25 and 0.4-0.5μgL-1, respectively, and wide linear ranges were obtained with correlation coefficients (R) ranging from 0.9991 to 0.9996. Compared with commercial C18 and Alumina-N sorbents, the as-prepared sorbent showed high extraction efficiency at different concentrations of flavonoids. After 100 uses, the extraction ability of the self-assembled MoS2 nanosheet monolithic sorbent had no evident decline, denoting a long service life. Finally, the SPE-HPLC-VWD method using the as-prepared sorbent was applied to flavonoid analysis in beverage samples with satisfactory results. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Space-Confined Growth of Defect-Rich Molybdenum Disulfide Nanosheets Within Graphene: Application in The Removal of Smoke Particles and Toxic Volatiles.

    Science.gov (United States)

    Wang, Dong; Xing, Weiyi; Song, Lei; Hu, Yuan

    2016-12-21

    In this work, molybdenum disulfide/reduced graphene oxide (MoS2/RGO) hybrids are synthesized by a spatially confined reaction to insert the growth of defect-rich MoS2 nanosheets within graphene to enable incorporation into the polymer matrix for the application in the removal of smoke particles and toxic volatiles. The steady-state tube furnace result demonstrates that MoS2/RGO hybrid could considerably reduce the yield of CO and smoke particles. The TG-IR coupling technique was utilized to identify species of toxic volatiles including aromatic compounds, CO, and hydrocarbons and to investigate the removal effect of MoS2/RGO hybrids on reducing toxic volatiles. The removal of smoke particles and toxic volatiles was attributed to the adsorption capacity derived from edges sites of MoS2 and the honeycomb lattice of graphene, as well as the inhibition of nanobarrier resulting from two-dimensional structure. The work will offer a strategy for fabricating graphene-based hybrids by the space-confined synthesis and exploiting the application of space-confined graphene-based hybrid.

  16. Lignin-assisted exfoliation of molybdenum disulfide in aqueous media and its application in lithium ion batteries

    Science.gov (United States)

    Liu, Wanshuang; Zhao, Chenyang; Zhou, Rui; Zhou, Dan; Liu, Zhaolin; Lu, Xuehong

    2015-05-01

    In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 +/- 0.08 mg mL-1, which is much higher than the typical reported concentrations (polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications.In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 +/- 0.08 mg mL-1, which is much higher than the typical reported concentrations (polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral

  17. The Two-Dimensional Nanocomposite of Molybdenum Disulfide and Nitrogen-Doped Graphene Oxide for Efficient Counter Electrode of Dye-Sensitized Solar Cells

    Science.gov (United States)

    Cheng, Chao-Kuang; Lin, Che-Hsien; Wu, Hsuan-Chung; Ma, Chen-Chi M.; Yeh, Tsung-Kuang; Chou, Huei-Yu; Tsai, Chuen-Horng; Hsieh, Chien-Kuo

    2016-02-01

    In this study, we reported the synthesis of the two-dimensional (2D) nanocomposite of molybdenum disulfide and nitrogen-doped graphene oxide (MoS2/nGO) as a platinum-free counter electrode (CE) for dye-sensitized solar cells (DSSCs). X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy were used to examine the characteristics of the 2D nanocomposite of MoS2/nGO. The cyclic voltammetry (CV), electrochemical impedance spectra (EIS), and the Tafel polarization measurements were carried out to examine the electrocatalytic abilities. XPS and Raman results showed the 2D behaviors of the prepared nanomaterials. HRTEM micrographs showed the direct evidence of the 2D nanocomposite of MoS2/nGO. The results of electrocatalytic examinations indicated the MoS2/nGO owning the low charge transfer resistance, high electrocatalytic activity, and fast reaction kinetics for the reduction of triiodide to iodide on the electrolyte-electrode interface. The 2D nanocomposite of MoS2/nGO combined the advantages of the high specific surface of nGO and the plenty edge sites of MoS2 and showed the promoted properties different from those of their individual constituents to create a new outstanding property. The DSSC with MoS2/nGO nanocomposite CE showed a photovoltaic conversion efficiency (PCE) of 5.95 % under an illumination of AM 1.5 (100 mW/cm2), which was up to 92.2 % of the DSSC with the conventional platinum (Pt) CE (PCE = 6.43 %). These results reveal the potential of the MoS2/nGO nanocomposite in the use of low-cost, scalable, and efficient Pt-free CEs for DSSCs.

  18. Enhanced Efficiency of Dye-Sensitized Solar Counter Electrodes Consisting of Two-Dimensional Nanostructural Molybdenum Disulfide Nanosheets Supported Pt Nanoparticles

    Directory of Open Access Journals (Sweden)

    Chao-Kuang Cheng

    2017-10-01

    Full Text Available This paper reports architecturally designed nanocomposites synthesized by hybridizing the two-dimensional (2D nanostructure of molybdenum disulfide (MoS2 nanosheet (NS-supported Pt nanoparticles (PtNPs as counter electrodes (CEs for dye-sensitized solar cells (DSSCs. MoS2 NSs were prepared using the hydrothermal method; PtNPs were subsequently reduced on the MoS2 NSs via the water–ethylene method to form PtNPs/MoS2 NSs hybrids. The nanostructures and chemical states of the PtNPs/MoS2 NSs hybrids were characterized by high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Detailed electrochemical characterizations by electrochemical impedance spectroscopy, cyclic voltammetry, and Tafel-polarization measurement demonstrated that the PtNPs/MoS2 NSs exhibited excellent electrocatalytic activities, afforded a higher charge transfer rate, a decreased charge transfer resistance, and an improved exchange current density. The PtNPs/MoS2 NSs hybrids not only provided the exposed layers of 2D MoS2 NSs with a great deal of catalytically active sites, but also offered PtNPs anchored on the MoS2 NSs enhanced I3− reduction. Accordingly, the DSSCs that incorporated PtNPs/MoS2 NSs CE exhibited an outstanding photovoltaic conversion efficiency (PCE of 7.52%, which was 8.7% higher than that of a device with conventional thermally-deposited platinum CE (PCE = 6.92%.

  19. Characterization and study of reduction and sulfurization processing in phase transition from molybdenum oxide (MoO{sub 2}) to molybdenum disulfide (MoS{sub 2}) chalcogenide semiconductor nanoparticles prepared by one-stage chemical reduction method

    Energy Technology Data Exchange (ETDEWEB)

    Shomalian, K.; Bagheri-Mohagheghi, M.M.; Ardyanian, M. [Damghan University, School of Physics, Damghan (Iran, Islamic Republic of)

    2017-01-15

    In this research, molybdenum disulfide (MoS{sub 2}) nanoparticles were prepared by chemical reduction method using MoO{sub 3} and thiourea as a precursor. The physical properties of the synthesized MoO{sub 2}-MoS{sub 2} nanoparticles annealed at different temperatures of 200, 300, 750 C have been investigated, before and after exposure to sulfur vapor. The nanostructure of nanoparticles has been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM) analyses and UV-Vis spectrophotometer. The X-ray diffraction analysis showed the formation of MoS{sub 2} single phase at annealing temperature of 750 C in the presence of sulfur vapor. The Raman spectrum of the nanoparticles revealed that the formation of MoS{sub 2} at 750 C after annealing in sulfur vapor. The values of band gap were obtained in the range of 3.64-3.17 eV and 3.47-1.95 eV for MoS{sub 2} nanoparticles before and after exposure to sulfur vapor, respectively. According to SEM images, the grain size decreases with increasing annealing temperature up to 750 C. Also, nanoplate-nanoparticles of MoS{sub 2} are formed at annealing temperature of 200-750 C. The TEM images of MoS{sub 2} nanoparticles at T{sub a} = 750 C confirm that the nanoparticles have a homogeneous distribution with a hexagonal structure. The FTIR spectra of the MoS{sub 2} nanoparticles showed the peaks at about 467 cm {sup -1} belong to the characteristic bands of Mo-S. (orig.)

  20. An ultrasensitive detection of miRNA-155 in breast cancer via direct hybridization assay using two-dimensional molybdenum disulfide field-effect transistor biosensor.

    Science.gov (United States)

    Majd, Samira Mansouri; Salimi, Abdollah; Ghasemi, Foad

    2018-05-15

    MicroRNAs (miRNAs), critical biomarkers of acute and chronic diseases, play key regulatory roles in many biological processes. As a result, robust assay platforms to enable an accurate and efficient detection of low-level miRNAs in complex biological samples are of great significance. In this work, a label-free and direct hybridization assay using molybdenum disulfide (MoS 2 ) field-effect transistor (FET) biosensor has been developed for ultrasensitive detection of miRNA-155 as a breast cancer biomarker in human serum and cell-line samples. MoS 2 , the novel 2D layered material with excellent physical and chemical properties, was prepared through sequential solvent exchange method and was used as an active channel material. MoS 2 was comprehensively characterized by spectroscopic and microscopic methods and it was applied for fabrication of FET device by drop-casting MoS 2 flacks suspension onto the FET surface. MoS 2 FET device showed a relatively low subthreshold swing of 48.10mV/decade and a high mobility of 1.98 × 10 3 cm 2 V -1 s -1 . Subsequently, probe miRNA-155 strands were immobilized on the surface of the MoS 2 FET device. Under optimized conditions detection limit of 0.03fM and concentration range 0.1fM to 10nM were achieved. The developed biosensor not only was capable to identification of fully matched versus one-base mismatch miRNA-155 sequence, but also it could detect target miRNA-155 in spiked real human serum and extracts from human breast cancer cell-line samples. This approach paves a way for label-free, early detection of miRNA as a biomarker in cancer diagnostics with very high sensitivity and good specificity, thus offering a significant potential for clinical application. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Injection molding of high aspect ratio sub-100 nm nanostructures

    DEFF Research Database (Denmark)

    Matschuk, Maria; Larsen, Niels B

    2013-01-01

    We have explored the use of mold coatings and optimized processing conditions to injection mold high aspect ratio nanostructures (height-to-width >1) in cyclic olefin copolymer (COC). Optimizing the molding parameters on uncoated nickel molds resulted in slight improvements in replication quality...... as described by height, width and uniformity of the nanoscopic features. Use of a mold temperature transiently above the polymer glass transition temperature (Tg) was the most important factor in increasing the replication fidelity. Surface coating of the nickel molds with a fluorocarbon-containing thin film...... (FDTS) greatly enhanced the quality of replicated features, in particular at transient mold temperatures above Tg. Injection molding using the latter mold temperature regime resulted in a bimodal distribution of pillar heights, corresponding to either full or very poor replication of the individual...

  2. Switching Properties of sub-100 nm Perpendicular Magnetic Tunnel Junctions

    Science.gov (United States)

    Tryputen, Larysa; Piotrowski, Stephan; Bapna, Mukund; Chien, Chia-Ling; Wang, Weigang; Majetich, Sara; Ross, Caroline

    2015-03-01

    Perpendicular magnetic tunnel junctions (p-MTJs) have great potential for realizing high-density non-volatile memory and logic devices. It is critical to solve scalability problem to implement such devices, to achieve low resistance area and to reduce switching current density while maintaining thermal stability. We present our recent results on fabrication of high resolution Ta/CoFeB/MgO/CoFeB/Ta p-MTJ devices and characterization of their switching properties as well as topography and current mapping by using nanoscale Conductive Atomic Force Microscopy. Our patterning method is based on using hydrogen silsesquioxane resist mask combined with ion beam etching. It allows to fabricate p-MTJ devices down to 40 nm in diameter while maintaining the magnetic quality of the multilayers. Repeatable, consistent switching behaviour has been observed in the obtained p-MTJ devices of 500 nm down to 40 nm with 10 - 800 mV voltage applied. Switching field increased as device diameter decreased, from 580 Oe at 500 nm (MR = 10%) to 410 Oe at 80 nm (MR = 9%). We discuss the effect of device sizes on the switching properties. This work was supported in part by C-SPIN, one of the six centers of STARnet, a Semiconductor Research Corporation Program sponsored by MARCO and DARPA and in part through the National Science Foundation through NCN-Needs Program, Contract 12207020-EEC.

  3. A fluorescence turn-on biosensor based on graphene quantum dots (GQDs) and molybdenum disulfide (MoS2) nanosheets for epithelial cell adhesion molecule (EpCAM) detection.

    Science.gov (United States)

    Shi, Jingyu; Lyu, Jing; Tian, Feng; Yang, Mo

    2017-07-15

    This paper presents a "turn-on" fluorescence biosensor based on graphene quantum dots (GQDs) and molybdenum disulfide (MoS 2 ) nanosheets for rapid and sensitive detection of epithelial cell adhesion molecule (EpCAM). PEGylated GQDs were used as donor molecules, which could not only largely increase emission intensity but also prevent non-specific adsorption of PEGylated GQD on MoS 2 surface. The sensing platform was realized by adsorption of PEGylated GQD labelled EpCAM aptamer onto MoS 2 surface via van der Waals force. The fluorescence signal of GQD was then quenched by MoS 2 nanosheets via fluorescence resonance energy transfer (FRET) mechanism. In the presence of EpCAM protein, the stronger specific affinity interaction between aptamer and EpCAM protein could detach GQD labelled EpCAM aptamer from MoS 2 nanosheets, leading to the restoration of fluorescence intensity. By monitoring the change of fluorescence signal, the target EpCAM protein could be detected sensitively and selectively with a linear detection range from 3nM to 54nM and limit of detection (LOD) around 450pM. In addition, this nanobiosensor has been successfully used for EpCAM-expressed breast cancer MCF-7 cell detection. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. One-step construction of a molybdenum disulfide/multi-walled carbon nanotubes/polypyrrole nanocomposite biosensor for the ex-vivo detection of dopamine in mouse brain tissue.

    Science.gov (United States)

    Vijayaraj, Kathiresan; Dinakaran, Thirumalai; Lee, Yujeong; Kim, Suhkmann; Kim, Hyung Sik; Lee, Jaewon; Chang, Seung-Cheol

    2017-12-09

    We developed a new strategy for construction of a biosensor for the neurotransmitter dopamine. The biosensor was constructed by one-step electrochemical deposition of a nanocomposite in aqueous solution at pH 7.0, consisting of molybdenum disulfide, multi-walled carbon nanotubes, and polypyrrole. A series of analytical methods was performed to investigate the surface characteristics and the improved electrocatalytic effect of the nanocomposite, including cyclic voltammetry, electrochemical impedance spectroscopy, field-emission scanning electron microscopy, atomic force microscopy, and Raman spectroscopy. The constructed biosensor showed high sensitivity (1.130 μAμM-1cm-2) with a dynamic linearity range of 25-1000 nM and a detection limit of 10 nM. Additionally, the designed sensor exhibited strong anti-interference ability and satisfactory reproducibility. The practical application of the sensor was manifested for the ex vivo determination of dopamine neurotransmitters using brain tissue samples of a mouse Parkinson's disease model. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Growth of three dimensional flower-like molybdenum disulfide hierarchical structures on graphene/carbon nanotube network: An advanced heterostructure for energy storage devices

    Science.gov (United States)

    Lingappan, Niranjanmurthi; Van, Ngoc Huynh; Lee, Suok; Kang, Dae Joon

    2015-04-01

    We report the design and synthesis of three dimensional flower-like molybdenum disulphide (f-MoS2) hierarchical structures, on reduced graphene oxide (RGO)/oxidized multi-walled carbon nanotube (o-MWCNT) backbone (f-MoS2/RGO/o-MWCNT), through one-pot hydrothermal method. Control experiments reveal that the homogenously distributed o-MWCNTs on RGO play an essential role for the formation of such morphology. As an anode for lithium ion batteries, the f-MoS2/RGO/o-MWCNT hybrid delivers a high reversible capacity of 1275 mAh g-1 at the current density of 100 mA g-1, superior rate capability and excellent long cycle life, with capacity retention of 93% after 100 cycles. The outstanding electrochemical performance can be attributed to the large surface area, short diffusion length and continuous electron transport pathway, as a consequence of the intimate contact between f-MoS2, graphene, and o-MWCNTs.

  6. A molybdenum disulfide/reduced graphene oxide fiber coating coupled with gas chromatography-mass spectrometry for the saponification-headspace solid-phase microextraction of polychlorinated biphenyls in food.

    Science.gov (United States)

    Lv, Fangying; Gan, Ning; Cao, Yuting; Zhou, You; Zuo, Rongjie; Dong, Youren

    2017-11-24

    In this work, the molybdenum disulfide/reduced graphene oxide (MoS2/RGO) composite material was synthesized as a fiber coating to extract seven indicator polychlorinated biphenyls (PCBs; PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) present in food via a saponification-headspace solid-phase microextraction assay (saponification-HS-SPME). The MoS2/RGO coating was prepared and deposited on a stainless steel wire with the help of a silicone sealant and used as an SPME fiber. The alkali solution dissolved the fat and helped in releasing the PCBs present in milk to the headspace for extraction under 100°C. Following desorption in the inlet, the targets were quantified by gas chromatography-mass spectrometry. The effects of sorbent dosage, extraction time, added salts, and stirring rate on the extraction efficiency were investigated. The new coating was able to adsorb a higher amount of analytes, which was about 1.1-2.9 times in comparison with the commercially available SPME fiber (coated with divinylbenzene/carboxen/polydimethylsiloxane). It also showed the highest adsorption capability toward PCBs, which was 1.5-2.7 times that of the prepared RGO modified fiber. Moreover, MoS2 also showed a strong affinity toward PCBs in a manner similar to its affinity for graphene. The developed method is simple and environmentally friendly as it does not require any organic solvents. Furthermore, it exhibits good sensitivity with detection limits less than 0.1ngmL-1, linearity (0.25-100ngmL-1), and reproducibility (relative standard deviation below 10% for n=3). The novel SPME fibers are inexpensive, reusable, and can be easily prepared and manipulated. In addition, the saponification-HS-SPME assay was also found to be suitable for screening persistent organic pollutants in dairy products. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Ultrahigh pressure superconductivity in molybdenum disulfide

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Zhenhua [Chinese Academy of Sciences (CAS), Hefei (China); Yen, Feihsiang [Chinese Academy of Sciences (CAS), Hefei (China); Peng, Feng [Luoyang Normal Univ., Luoyang (China); Zhu, Jinlong [Univ. of Nevada, Las Vegas, NV (United States); Zhang, Yijin [Univ. of Tokyo, Tokyo (Japan); Chen, Xuliang [Chinese Academy of Sciences (CAS), Hefei (China); Yang, Zhaorong [Chinese Academy of Sciences (CAS), Hefei (China); Nanjing Univ., Nanjing (China); Liu, Xiaodi [Chinese Academy of Sciences (CAS), Hefei (China); Ma, Yaming [Jilin Univ., Changchun (China); Zhao, Yusheng [Univ. of Nevada, Las Vegas, NV (United States); Kagayama, Tomoko [Osaka Univ., Osaka (Japan); Iwasa, Yoshihiro [Univ. of Tokyo, Tokyo (Japan); RIKEN Center for Emergent Matter Science (CEMS), Wako (Japan)

    2015-03-18

    Superconductivity commonly appears under pressure in charge densit wave (CDW)-bearing transition metal dichalcogenides (TMDs)1,2, but ha emerged so far only via either intercalation with electron donors3 or electrostati doping4 in CDW-free TMDs. Theoretical calculations have predicted that th latter should be metallized through bandgap closure under pressure5,6, bu superconductivity remained elusive in pristine 2H-MoS2 upon substantia compression, where a pressure of up to 60 GPa only evidenced the metalli state7,8. Here we report the emergence of superconductivity in pristine 2H-MoS at 90 GPa. The maximum onset transition temperature Tc(onset) of 11.5 K, th highest value among TMDs and nearly constant from 120 up to 200 GPa, is wel above that obtained by chemical doping3 but comparable to that obtained b electrostatic doping4. Tc(onset) is more than an order of magnitude larger tha present theoretical expectations, raising questions on either the curren calculation methodologies or the mechanism of the pressure-induced pairin state. Lastly, our findings strongly suggest further experimental and theoretical effort directed toward the study of the pressure-induced superconductivity in all CDWfre TMDs.

  8. Materials and device issues in the formation of sub-100-nm junctions

    Science.gov (United States)

    Osburn, C. M.; Chevacharoenkul, S.; Wang, Q. F.; Markus, K.; McGuire, G. E.; Smith, P. L.

    1993-04-01

    This paper compares the materials and device issues associated with two alternative techniques for the formation of ultrashallow junctions: 1) the use of preamorphization and low energy dopant implantation, combined with rapid, low-temperature annealing; and 2) the use of metal suicides as a diffusion source (SADS) where dopants are implanted into CoSi 2 and subsequently diffused into silicon. For conventionally-formed, ultrashallow junctions, preamorphization with either silicon or germanium does not result in shallower junctions. The enhanced diffusion associated with the preamorphization implant damage compensates for the reduction in channeling. Preamorphization does, however, give low sheet resistance junctions and high dopant activation after recrystallization at 550°C. Considerable dopant motion (˜ 50 nm) is observed in the tail region, near the junction, after 10 s of annealing at a relatively low temperature (800°C). The SADS process is seen to produce low leakage n + and p + diodes with less than 10 nm of dopant diffusion beyond the silicide/silicon interface, using a very low thermal budget process. By confining the implantation to within the suicide, no crystal defects are created in the underlying silicon. With the SADS process, the limitation on scaling the junction depth lies in producing thin, stable suicide films. Agglomeration of the silicide and pullback along feature edges restrict the maximum thermal cycle and the minimum allowable film thickness.

  9. Investigation of Sub-100 nm Gold Nanoparticles for Laser-Induced Thermotherapy of Cancer

    Directory of Open Access Journals (Sweden)

    Ruth Signorell

    2013-01-01

    Full Text Available Specialized gold nanostructures are of interest for the development of alternative treatment methods in medicine. Photothermal therapy combined with gene therapy that supports hyperthermia is proposed as a novel multimodal treatment method for prostate cancer. In this work, photothermal therapy using small (<100 nm gold nanoparticles and near-infrared (NIR laser irradiation combined with gene therapy targeting heat shock protein (HSP 27 was investigated. A series of nanoparticles: nanoshells, nanorods, core-corona nanoparticles and hollow nanoshells, were synthesized and examined to compare their properties and suitability as photothermal agents. In vitro cellular uptake studies of the nanoparticles into prostate cancer cell lines were performed using light scattering microscopy to provide three-dimensional (3D imaging. Small gold nanoshells (40 nm displayed the greatest cellular uptake of the nanoparticles studied and were used in photothermal studies. Photothermal treatment of the cancer cell lines with laser irradiation at 800 nm at 4 W on a spot size of 4 mm (FWHM for 6 or 10 min resulted in an increase in temperature of ~12 °C and decrease in cell viability of up to 70%. However, in vitro studies combining photothermal therapy with gene therapy targeting HSP27 did not result in additional sensitization of the prostate cancer cells to hyperthermia.

  10. Intercalation doping of narrow multilayer graphene interconnects with sub-100 nm widths

    Science.gov (United States)

    Katagiri, Masayuki; Miyazaki, Hisao; Matsumoto, Rika; Kajita, Akihiro; Sakai, Tadashi

    2017-07-01

    An intercalation process for narrow graphene interconnects with linewidths of graphene flakes of >5 µm size induced partial delamination of the graphene layers and insufficient intercalation in some graphene interconnects with linewidths of graphene layers and provided improved doping characteristics with a higher yield in narrow graphene interconnects with linewidths of graphene interconnects under suitable conditions was confirmed by Raman scattering spectroscopy. These results indicate that intercalation using MoCl5 is promising for the fabrication of narrow graphene interconnects.

  11. Experimental study of contact edge roughness on sub-100 nm various circular shapes

    Science.gov (United States)

    Lee, Tae Y.; Ihm, Dongchul; Kang, Hyo C.; Lee, Jum B.; Lee, Byoung H.; Chin, Soo B.; Cho, Do H.; Song, Chang L.

    2005-05-01

    The measurement of edge roughness has become a hot issue in the semiconductor industry. Especially the contact roughness is being more critical as design rule shrinks. Major vendors offer a variety of features to measure the edge roughness in their CD-SEMs. For the line and space patterns, features such as Line Edge Roughness (LER) and Line Width Roughness (LWR) are available in current CD-SEMs. However the features currently available in commercial CD-SEM cannot provide a proper solution in monitoring the contact roughness. We had introduced a new parameter R, measurement algorithm and definition of contact edge roughness to quantify CER and CSR in previous paper. The parameter, R could provide an alternative solution to monitor contact or island pattern roughness. In this paper, we investigated to assess optimum number of CD measurement (1-D) and fitting method for CER or CSR. The study was based on a circular contact shape. Some new ideas to quantify CER or CSR were also suggested with preliminary experimental results.

  12. Experimental methodology of contact edge roughness on sub-100-nm pattern

    Science.gov (United States)

    Lee, Tae Yong; Ihm, Dongchul; Kang, Hyo Chun; Lee, Jun Bum; Lee, Byoung-Ho; Chin, Soo-Bok; Cho, Do-Hyun; Kim, Yang Hyong; Yang, Ho Dong; Yang, Kyoung Mo

    2004-05-01

    The measurement of edge roughness has become a hot issue in the semiconductor industry. Major vendors offer a variety of features to measure the edge roughness in their CD-SEMs. However, most of the features are limited by the applicable pattern types. For the line and space patterns, features such as Line Edge Roughness (LER) and Line Width Roughness (LWR) are available in current CD-SEMs. The edge roughness is more critical in contact process. However the measurement of contact edge roughness (CER) or contact space roughness (CSR) is more complicated than that of LER or LWR. So far, no formal standard measurement algorithm or definition of contact roughness measurement exists. In this article, currently available features are investigated to assess their representability for CER or CSR. Some new ideas to quantify CER and CSR were also suggested with preliminary experimental results.

  13. Protein disulfide engineering.

    Science.gov (United States)

    Dombkowski, Alan A; Sultana, Kazi Zakia; Craig, Douglas B

    2014-01-21

    Improving the stability of proteins is an important goal in many biomedical and industrial applications. A logical approach is to emulate stabilizing molecular interactions found in nature. Disulfide bonds are covalent interactions that provide substantial stability to many proteins and conform to well-defined geometric conformations, thus making them appealing candidates in protein engineering efforts. Disulfide engineering is the directed design of novel disulfide bonds into target proteins. This important biotechnological tool has achieved considerable success in a wide range of applications, yet the rules that govern the stabilizing effects of disulfide bonds are not fully characterized. Contrary to expectations, many designed disulfide bonds have resulted in decreased stability of the modified protein. We review progress in disulfide engineering, with an emphasis on the issue of stability and computational methods that facilitate engineering efforts. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  14. Quantum transport in molybdenum disulfide and germanane transistors

    NARCIS (Netherlands)

    Chen, Qihong

    2017-01-01

    In the past decades, electronic devices are getting smaller and more powerful, following the Moore’s Law. Nevertheless, silicon-based field effect transistors are rapidly approaching their scaling limit. Thus, exploring new channel materials as well as novel device architectures are highly demanded

  15. Two optically active molybdenum disulfide quantum dots as tetracycline sensors

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhuosen; Lin, Jintai [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Gao, Jinwei [Institute for Advanced Materials, Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006 (China); Wang, Qianming, E-mail: qmwang@scnu.edu.cn [Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, 510006 (China)

    2016-08-01

    In this work, we use the hydrothermal method to develop two luminescent MoS{sub 2} quantum dots (QDs) from L-cysteine and glutathione as sulfur precursors. The special blue emissions give rise to an instantaneous determination of tetracycline (TC) through the quenching of its luminescence. The accessibility of the optical materials and recognition mechanism have been extensively studied. This strategy demonstrated that MoS{sub 2} could act as a new platform for anchoring bioactive species or particular functional moieties. - Highlights: • MoS{sub 2} nanostructures with water solubility have been fabricated. • Blue emission has been achieved. • It displays selective detection to tetracyclines in water.

  16. Origin of the phase transition in lithiated molybdenum disulfide

    KAUST Repository

    Cheng, Yingchun

    2014-11-25

    Phase transitions and phase engineering in two-dimensional MoS2 are important for applications in electronics and energy storage. By in situ transmission electron microscopy, we find that H-MoS2 transforms to T-LiMoS2 at the early stages of lithiation followed by the formation of Mo and Li2S phases. The transition from H-MoS2 to T-LiMoS2 is explained in terms of electron doping and electron - phonon coupling at the conduction band minima. Both are essential for the development of two-dimensional semiconductor-metal contacts based on MoS2 and the usage of MoS2 as anode material in Li ion batteries. (Figure Presented).

  17. Structure and properties of molybdenum disulfide : based inclusion materials

    OpenAIRE

    Cetnarowski, Gregory

    2008-01-01

    The use of exfoliated MoS2 layers as surfaces for adsorption have been examined. The properties of exfoliated and restacked MoS2-malachite green (MG) inclusion compounds have been examined to provide insight into the MG-MoS2 interactions that characterize these materials. The results of X-ray diffraction experiments indicate that MG included into the restacked structure adopts a flat orientation approximately parallel to the MoS2 sheets. Second-harmonic generation (SHG) experiments conducted ...

  18. Self-propelled Janus mesoporous silica nanomotors with sub-100 nm diameters for drug encapsulation and delivery.

    Science.gov (United States)

    Xuan, Mingjun; Shao, Jingxin; Lin, Xiankun; Dai, Luru; He, Qiang

    2014-08-04

    The synthesis of an innovative self-propelled Janus nanomotor with a diameter of about 75 nm that can be used as a drug carrier is described. The Janus nanomotor is based on mesoporous silica nanoparticles (MSNs) with chromium/platinum metallic caps and propelled by decomposing hydrogen peroxide to generate oxygen as a driving force with speeds up to 20.2 μm s(-1) (about 267 body lengths per second). The diffusion coefficient (D) of nanomotors with different H2 O2 concentrations is calculated by tracking the movement of individual particles recorded by means of a self-assembled fluorescence microscope and is significantly larger than free Brownian motion. The traction of a single Janus MSN nanomotor is estimated to be about 13.47×10(-15) N. Finally, intracellular localization and drug release in vitro shows that the amount of Janus MSN nanomotors entering the cells is more than MSNs with same culture time and particle concentrations, meanwhile anticancer drug doxorubicin hydrochloride loaded in Janus MSNs can be slowly released by biodegradation of lipid bilayers in cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Multiple ways to make disulfides

    DEFF Research Database (Denmark)

    Bulleid, Neil J; Ellgaard, Lars

    2011-01-01

    -localized protein disulfide isomerase peroxidases and vitamin K epoxide reductase might all contribute to disulfide formation. Here we discuss these various pathways for disulfide formation in the mammalian ER and highlight the central role played by glutathione in regulating this process.......Our concept of how disulfides form in proteins entering the secretory pathway has changed dramatically in recent years. The discovery of endoplasmic reticulum (ER) oxidoreductin 1 (ERO1) was followed by the demonstration that this enzyme couples oxygen reduction to de novo formation of disulfides...

  20. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar affinities. Thus...

  1. Organometallic Chemistry of Molybdenum.

    Science.gov (United States)

    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)

  2. Molybdenum sulfides-efficient and viable materials for electro - and photoelectrocatalytic hydrogen evolution

    DEFF Research Database (Denmark)

    Laursen, Anders Bo; Kegnæs, Søren; Dahl, Søren

    2012-01-01

    This perspective covers the use of molybdenum disulfide and related compounds, generally termed MoSx, as electro- or photoelectrocatalysts for the hydrogen evolution reaction (HER). State of the art solutions as well as the most illustrative results from the extensive electro- and photoelectrocat......This perspective covers the use of molybdenum disulfide and related compounds, generally termed MoSx, as electro- or photoelectrocatalysts for the hydrogen evolution reaction (HER). State of the art solutions as well as the most illustrative results from the extensive electro...... sites of the catalyst, and (3) improving the electrical contact to these sites. These postulations are substantiated by examples from the existing literature and some new results. To demonstrate the electrocatalytic properties of a highly conductive MoS2 hybrid material, we present the HER activity data...

  3. Novel Disulfide Formation Strategies in Peptide Synthesis

    OpenAIRE

    Postma, Tobias Maria

    2014-01-01

    Cysteine (Cys) is a unique amino acid due to its ability to form reversible covalent disulfide bonds. These bonds cause conformational constraints which make peptides or proteins more rigid and stable. In addition, the conformational constraints induced by disulfide bonds can result in highly potent molecules as illustrated by the vast number of disulfide-rich plant and animal peptide toxins. Furthermore, disulfide-rich peptides are gaining importance as pharmaceuticals and therefore powerful...

  4. Molybdenum Tube Characterization report

    Energy Technology Data Exchange (ETDEWEB)

    Beaux II, Miles Frank [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Usov, Igor Olegovich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-02-07

    Chemical vapor deposition (CVD) techniques have been utilized to produce free-standing molybdenum tubes with the end goal of nuclear fuel clad applications. In order to produce tubes with properties desirable for this application, deposition rates were lowered requiring long deposition durations on the order of 50 hours. Standard CVD methods as well as fluidized-bed CVD (FBCVD) methods were applied towards these objectives. Characterization of the tubes produced in this manner revealed material suitable for fuel clad applications, but lacking necessary uniformity across the length of the tubes. The production of freestanding Mo tubes that possess the desired properties across their entire length represents an engineering challenge that can be overcome in a next iteration of the deposition system.

  5. Nitrogen reduction: Molybdenum does it again

    Science.gov (United States)

    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.

  6. Conformal SiO2 coating of sub-100 nm diameter channels of polycarbonate etched ion-track channels by atomic layer deposition

    Directory of Open Access Journals (Sweden)

    Nicolas Sobel

    2015-02-01

    Full Text Available Polycarbonate etched ion-track membranes with about 30 µm long and 50 nm wide cylindrical channels were conformally coated with SiO2 by atomic layer deposition (ALD. The process was performed at 50 °C to avoid thermal damage to the polymer membrane. Analysis of the coated membranes by small angle X-ray scattering (SAXS reveals a homogeneous, conformal layer of SiO2 in the channels at a deposition rate of 1.7–1.8 Å per ALD cycle. Characterization by infrared and X-ray photoelectron spectroscopy (XPS confirms the stoichiometric composition of the SiO2 films. Detailed XPS analysis reveals that the mechanism of SiO2 formation is based on subsurface crystal growth. By dissolving the polymer, the silica nanotubes are released from the ion-track membrane. The thickness of the tube wall is well controlled by the ALD process. Because the track-etched channels exhibited diameters in the range of nanometres and lengths in the range of micrometres, cylindrical tubes with an aspect ratio as large as 3000 have been produced.

  7. Comparative study between REAP 200 and FEP171 CAR with 50-kV raster e-beam system for sub-100-nm technology

    Science.gov (United States)

    Baik, Ki-Ho; Lem, Homer Y.; Dean, Robert L.; Osborne, Stephen; Mueller, Mark; Abboud, Frank E.

    2003-08-01

    In this paper, a process established with a positive-tone chemically amplified resist (CAR) from TOK REAP200 and Fujifilm Arch FEP171 and 50kV MEBES system is discussed. This TOK resist is developed for raster scan 50 kV e-beam systems. It has high contrast, good coating characteristics, good dry etch selectivity, and high environmental stability. In the mask industries, the most popular positive tone CAR is FEP171, which is a high activation energy type CAR. REAP (Raster E-beam Advanced Process) 200 is low activation energy type and new acetal protecting polymer. In this study, we compared to these different type resists in terms of contrast, PAB and PEB latitude, resist profile, footing, T-topping, PED stability, LER, Global CDU (Critical Dimension Uniformity) and resolution. The REAP200 Resist obtained 75nm isolated lines and spaces, 90nm dense patterns with vertical profile, and a good stability of delay time.

  8. REAP (raster e-beam advanced process) using 50-kV raster e-beam system for sub-100-nm node mask technology

    Science.gov (United States)

    Baik, Ki-Ho; Dean, Robert L.; Mueller, Mark; Lu, Maiying; Lem, Homer Y.; Osborne, Stephen; Abboud, Frank E.

    2002-07-01

    A chemically amplified resist (CAR) process has been recognized as an approach to meet the demanding critical dimension (CD) specifications of 100nm node technology and beyond. Recently, significant effort has been devoted to optimizing CAR materials, which offer the characteristics required for next generation photomask fabrication. In this paper, a process established with a positive-tone CAR from TOK and 50kV MEBES eXara system is discussed. This resist is developed for raster scan 50 kV e-beam systems. It has high contrast, good coating characteristics, good dry etch selectivity, and high environmental stability. The coating process is conducted in an environment with amine concentration less than 2 ppb. A nitrogen environment is provided during plate transfer steps. Resolution using a 60nm writing grid is 90nm line and space patterns. CD linearity is maintained down to 240nm for isolated lines or spaces by applying embedded proximity effect correction (emPEC). Optimizations of post-apply bake (PAB) and post-expose bake (PEB) time, temperature, and uniformity are completed to improve adhesion, coating uniformity, and resolution. A puddle develop process is optimized to improve line edge roughness, edge slope, and resolution. Dry etch process is optimized on a TetraT system to transfer the resist image into the chrome layer with minimum etch bias.

  9. Amino Acid Patterns around Disulfide Bonds

    Science.gov (United States)

    Marques, José R. F.; da Fonseca, Rute R.; Drury, Brett; Melo, André

    2010-01-01

    Disulfide bonds provide an inexhaustible source of information on molecular evolution and biological specificity. In this work, we described the amino acid composition around disulfide bonds in a set of disulfide-rich proteins using appropriate descriptors, based on ANOVA (for all twenty natural amino acids or classes of amino acids clustered according to their chemical similarities) and Scheffé (for the disulfide-rich proteins superfamilies) statistics. We found that weakly hydrophilic and aromatic amino acids are quite abundant in the regions around disulfide bonds, contrary to aliphatic and hydrophobic amino acids. The density distributions (as a function of the distance to the center of the disulfide bonds) for all defined entities presented an overall unimodal behavior: the densities are null at short distances, have maxima at intermediate distances and decrease for long distances. In the end, the amino acid environment around the disulfide bonds was found to be different for different superfamilies, allowing the clustering of proteins in a biologically relevant way, suggesting that this type of chemical information might be used as a tool to assess the relationship between very divergent sets of disulfide-rich proteins. PMID:21151463

  10. Amino acid patterns around disulfide bonds.

    Science.gov (United States)

    Marques, José R F; da Fonseca, Rute R; Drury, Brett; Melo, André

    2010-11-18

    Disulfide bonds provide an inexhaustible source of information on molecular evolution and biological specificity. In this work, we described the amino acid composition around disulfide bonds in a set of disulfide-rich proteins using appropriate descriptors, based on ANOVA (for all twenty natural amino acids or classes of amino acids clustered according to their chemical similarities) and Scheffé (for the disulfide-rich proteins superfamilies) statistics. We found that weakly hydrophilic and aromatic amino acids are quite abundant in the regions around disulfide bonds, contrary to aliphatic and hydrophobic amino acids. The density distributions (as a function of the distance to the center of the disulfide bonds) for all defined entities presented an overall unimodal behavior: the densities are null at short distances, have maxima at intermediate distances and decrease for long distances. In the end, the amino acid environment around the disulfide bonds was found to be different for different superfamilies, allowing the clustering of proteins in a biologically relevant way, suggesting that this type of chemical information might be used as a tool to assess the relationship between very divergent sets of disulfide-rich proteins.

  11. HYDROGEN VACANCY INTERACTION IN MOLYBDENUM

    NARCIS (Netherlands)

    Abd El Keriem, M.S.; van der Werf, D.P.; Pleiter, F

    1993-01-01

    Vacancy-hydrogen interaction in molybdenum was investigated by means of the perturbed angular correlation technique, using the isotope In-111 as a probe. The complex InV2 turned out to trap up to two hydrogen atoms: trapping of a single hydrogen atom gives rise to a decrease of the quadrupole

  12. Gel Fabrication of Molybdenum “Beads”

    Energy Technology Data Exchange (ETDEWEB)

    Lowden, Richard Andrew [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Armstrong, Beth L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Cooley, Kevin M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

    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.

  13. The folding of disulfide-rich proteins.

    Science.gov (United States)

    Craik, David J

    2011-01-01

    The articles in this forum issue describe various aspects of the folding of disulfide-rich proteins. They include review articles using proteins such as bovine pancreatic trypsin inhibitor as models to highlight the range of folding pathways seen in disulfide-rich proteins, along with a detailed analysis of the methods used to study them. Following two comprehensive reviews on the methods and applications of protein folding, three original articles in this issue focus on two specific classes of disulfide-rich proteins that have applications in drug design and development, namely cyclotides and conotoxins. Cyclotides are head-to-tail cyclic and disulfide-rich proteins from plants and function as a defense against insect attack. Conotoxins are the disulfide-rich components of the venom of marine cone snails that is used to capture prey. These research articles report on factors that modulate protein folding pathways in these molecules and determine the outcomes of protein folding, that is, yield and heterogeneity of products. Finally, the issue concludes with a comprehensive review on a different type of disulfide bond, namely those that have a functional rather than structural role in proteins, with a particular focus on allosteric disulfide bonds that modify protein function.

  14. New concept of energy storage material. ; Disulfide polymer. Atarashii gainen no energy chozo zairyo. ; Disulfide polymer

    Energy Technology Data Exchange (ETDEWEB)

    Visco, S.; Jonghe, L. (Lawrence Berkeley Laboratory, Cyclotron Road, CA, (United States)); Ue, M. (Mitsubishi Petrochemical Co. Ltd., Tokyo (Japan))

    1994-04-05

    This review article introduces new type cells, which are based on a new concept of electrochemical polymerization and depolymerization of disulfide polymer. For the disulfide polymer, chemical molecular designing can be conducted. Additionally, the disulfide polymer has low price and low toxicity. High theoretical electric capacity of the disulfide polymer is attractive from the viewpoint of the energy storage. It is illustrated that the middle temperature lithium solid polymer electrolyte cell and sodium solid polymer electrolyte cell, and the room temperature lithium gel electrolyte cell have high performances. Especially, it is shown that the lithium/polyethylene oxide/disulfide polymer cell has an excellent performance in the cycle characteristics and power density. It is also verified that the sodium/[beta][prime][prime]-alumina/disulfide polymer cell has a high reversibility in the oxidation-reduction polymerization and depolymerization reaction. 23 refs., 2 figs., 2 tabs.

  15. Neutron scattering and models : molybdenum.

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. 40 CFR 721.1745 - Ethoxybenzothiazole disulfide.

    Science.gov (United States)

    2010-07-01

    ....1745 Section 721.1745 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... to reporting. (1) The chemical substance generically identified as ethoxybenzothiazole disulfide (PMN... except as modified by this paragraph. (1) Recordkeeping requirements. Requirements as specified in § 721...

  17. Thiol/disulfide homeostasis in postmenopausal osteoporosis.

    Science.gov (United States)

    Korkmaz, V; Kurdoglu, Z; Alisik, M; Turgut, E; Sezgın, O O; Korkmaz, H; Ergun, Y; Erel, O

    2017-04-01

    To evaluate the impact of postmenopausal osteoporosis on thiol/disulfide homeostasis. A total of 75 participants were divided into two groups: Group 1 (n = 40) was composed of healthy postmenopausal women, and group 2 (n = 35) was composed of women with postmenopausal osteoporosis. Clinical findings and thiol/disulfide homeostasis were compared between the two groups. The disulfide/native thiol ratio was 8.6% ± 3.6 in group 1 and 12.7% ± 8.4 in group 2 (p = 0.04). The disulfide/native thiol percent ratio was significantly higher in group 2 after adjustment for the years since menopause and age (p osteoporosis.

  18. Shedding light on disulfide bond formation

    DEFF Research Database (Denmark)

    Ostergaard, H; Henriksen, A; Hansen, F G

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease in the i......To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within the physiological range...

  19. Zirconia-molybdenum disilicide composites

    Science.gov (United States)

    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.

  20. Accelerated ageing of molybdenum oxide

    Science.gov (United States)

    Jorge, Marina; Cooil, Simon; Edmonds, Mark T.; Thomsen, Lars; Nematollahi, Mohammadreza; Mazzola, Federico; Wells, Justin W.

    2017-11-01

    The stability and lifetime of materials proposed for photovoltaic applications are important parameters, because such devices should offer long-term reliable performance whilst operating in a harsh environment. In this work, we present a powerful approach to accelerate and study the degradation mechanisms of molybdenum oxide, a material which has shown promise for next generation photovoltaics, and for enhanced hole extraction in organic photovoltaics. We use UV and soft x-rays to drive accelerated ageing, boosting the ageing time by a factor of up to 1000. Using this method, we find that molybdenum oxide does not offer reliable performance in environments in which heating or ionising radiation are present, because of its propensity to reduce, thus strongly modifying its electronic properties. We estimate that  ≈100 d of unfiltered sunlight exposure would be sufficient to reduce this material into metallic MoO2. We also show that a very similar degradation can be driven by thermally, and that in both cases, the creation of oxygen vacancies is responsible. A lack of robustness to harsh operating conditions (i.e. UV and/or heat) brings the suitability of unprotected molybdenum oxide in photovoltaic applications into question.

  1. Role of charged impurities in thermoelectric transport in molybdenum disulfide monolayers

    Science.gov (United States)

    Patil, Sukanya B.; Sankeshwar, N. S.; Mulimani, B. G.

    2017-12-01

    A theoretical study of the electronic properties, namely, electrical conductivity (EC), electronic thermal conductivity (ETC) and thermoelectric power (TEP) in 2D MoS2 monolayers (MLs), over a wide range of temperatures (10  TEP presented for supported and free-standing MLs with high electron concentrations, as a function of temperature, bring out the relative importance of the various scattering mechanisms operative. The role of CIs, with regard to both concentration and separation from the substrate-ML interface, in determining the properties of supported MLs is demonstrated for the first time. Validity of Wiedemann–Franz law and Mott formula are examined for supported and free standing MLs. Calculations are in consonance with recent experimental data on mobility and TEP of exfoliated SiO2-supported MoS2 ML samples. In the case of TEP it is found that though the diffusion contribution is dominant the inclusion of the drag component, incorporating contributions from all relevant phonon scattering mechanisms, is needed to obtain good agreement with the data.

  2. Optimized expanding of interlayer distance for molybdenum disulfide towards enhanced hydrogen evolution reaction

    Science.gov (United States)

    Chai, Yong-Ming; Shang, Xiao; Hu, Wen-Hui; Dong, Bin; Liu, Zi-Zhang; Chi, Jing-Qi; Yan, Kai-Li; Gao, Wen-Kun; Liu, Chen-Guang

    2018-01-01

    Adjusting the hydrogen-binding free energy (ΔGH*) of two dimensional (2D) MoS2 by changing the interlayer distance has been an effective strategy to improve the intrinsic activity for hydrogen evolution reaction (HER). Herein, a facile solvothermal access via various ratio of N, N-dimethylformamide (DMF)/H2O has been used to modulate interlayer distance of nanostructured MoS2. With increasing of DMF, the interlayer distance of MoS2 can be expanded to 9.4 Å with smaller sizes, which may be derived from intercalation effect of DMF. The certain ratio of DMF/H2O (volume ratio of 19/1, MoS2-D19H1) leads to the largest interlayer distances of 10.0 Å and the smallest size of nanospheres with less stacking than counterparts synthesized at other ratios of DMF/H2O. The expanded interlayer distance of MoS2-D19H1 may change electronic structure of active sites for HER, implying the improved ΔGH* and the intrinsic activity of MoS2. The smallest size also suggests the more exposure of active sites for HER. The electrochemical measurements demonstrate that MoS2-D19H1 shows the best electrocatalytic performances than MoS2 samples synthesized at other ratio of DMF/H2O. This work may provide a promising strategy to tune the interlayer distance of 2D-layered transition metal dichalcogenide for efficient HER.

  3. Direct Imaging of Kinetic Pathways of Atomic Diffusion in Monolayer Molybdenum Disulfide.

    Science.gov (United States)

    Hong, Jinhua; Pan, Yuhao; Hu, Zhixin; Lv, Danhui; Jin, Chuanhong; Ji, Wei; Yuan, Jun; Zhang, Ze

    2017-06-14

    Direct observation of atomic migration both on and below surfaces is a long-standing but important challenge in materials science as diffusion is one of the most elementary processes essential to many vital material behaviors. Probing the kinetic pathways, including metastable or even transition states involved down to atomic scale, holds the key to the underlying physical mechanisms. Here, we applied aberration-corrected transmission electron microscopy (TEM) to demonstrate direct atomic-scale imaging and quasi-real-time tracking of diffusion of Mo adatoms and vacancies in monolayer MoS2, an important two-dimensional transition metal dichalcogenide (TMD) system. Preferred kinetic pathways and the migration potential-energy landscape are determined experimentally and confirmed theoretically. The resulting three-dimensional knowledge of the atomic configuration evolution reveals the different microscopic mechanisms responsible for the contrasting intrinsic diffusion rates for Mo adatoms and vacancies. The new insight will benefit our understanding of material processes such as phase transformation and heterogeneous catalysis.

  4. Enhanced piezoelectric effect at the edges of stepped molybdenum disulfide nanosheets.

    Science.gov (United States)

    Song, Xiaoxue; Hui, Fei; Gilmore, Keith; Wang, Bingru; Jing, Guangyin; Fan, Zhongchao; Grustan-Gutierrez, Enric; Shi, Yuanyuan; Lombardi, Lucia; Hodge, Stephen A; Ferrari, Andrea C; Lanza, Mario

    2017-05-18

    The development of piezoelectric layered materials may be one of the key elements enabling expansion of nanotechnology, as they offer a solution for the construction of efficient transducers for a wide range of applications, including self-powered devices. Here, we investigate the piezoelectric effect in multilayer (ML) stepped MoS 2 flakes obtained by liquid-phase exfoliation, which is especially interesting because it may allow the scalable fabrication of electronic devices using large area deposition techniques (e.g. solution casting, spray coating, inkjet printing). By using a conductive atomic force microscope we map the piezoelectricity of the MoS 2 flakes at the nanoscale. Our experiments demonstrate the presence of electrical current densities above 100 A cm -2 when the flakes are strained in the absence of bias, and the current increases proportional to the bias. Simultaneously collected topographic and current maps demonstrate that the edges of stepped ML MoS 2 flakes promote the piezoelectric effect, where the largest currents are observed. Density functional theory calculations are consistent with the ring-like piezoelectric potential generated when the flakes are strained, as well as the enhanced piezoelectric effect at edges. Our results pave the way to the design of piezoelectric devices using layered materials.

  5. Tunable spin and valley dependent magneto-optical absorption in molybdenum disulfide quantum dots

    Science.gov (United States)

    Qu, Fanyao; Dias, A. C.; Fu, Jiyong; Villegas-Lelovsky, L.; Azevedo, David L.

    2017-01-01

    Photonic quantum computer, quantum communication, quantum metrology and quantum optical technologies rely on the single-photon source (SPS). However, the SPS with valley-polarization remains elusive and the tunability of magneto-optical transition frequency and emission/absorption intensity is restricted, in spite of being highly in demand for valleytronic applications. Here we report a new class of SPSs based on carriers spatially localized in two-dimensional monolayer transition metal dichalcogenide quantum dots (QDs). We demonstrate that the photons are absorbed (or emitted) in the QDs with distinct energy but definite valley-polarization. The spin-coupled valley-polarization is invariant under either spatial or magnetic quantum quantization. However, the magneto-optical absorption peaks undergo a blue shift as the quantization is enhanced. Moreover, the absorption spectrum pattern changes considerably with a variation of Fermi energy. This together with the controllability of absorption spectrum by spatial and magnetic quantizations, offers the possibility of tuning the magneto-optical properties at will, subject to the robust spin-coupled valley polarization.

  6. Two-Dimensional Material Molybdenum Disulfides as Electrocatalysts for Hydrogen Evolution

    Directory of Open Access Journals (Sweden)

    Lei Yang

    2017-09-01

    Full Text Available Recently, transition metal dichalcogenides (TMDs, represented by MoS2, have been proven to be a fascinating new class of electrocatalysts in hydrogen evolution reaction (HER. The rich chemical activities, combined with several strategies to regulate its morphologies and electronic properties, make MoS2 very attractive for understanding the fundamentals of electrocatalysis. In this review, recent developments in using MoS2 as electrocatalysts for the HER with high activity are presented. The effects of edges on HER activities of MoS2 are briefly discussed. Then we demonstrate strategies to further enhance the catalytic performance of MoS2 by improving its conductivity or engineering its structure. Finally, the key challenges to the industrial application of MoS2 in electrocatalytic hydrogen evolution are also pointed out.

  7. Origin of Improved Optical Quality of Monolayer Molybdenum Disulfide Grown on Hexagonal Boron Nitride Substrate.

    Science.gov (United States)

    Wan, Yi; Zhang, Hui; Wang, Wei; Sheng, Bowen; Zhang, Kun; Wang, Yilun; Song, Qingjun; Mao, Nannan; Li, Yanping; Wang, Xinqiang; Zhang, Jin; Dai, Lun

    2016-01-13

    Monolayer MoS2 is synthesized on hexagonal boron nitride (h-BN) flakes with a simple, high-yield method. Monolayer MoS2 on h-BN exhibits improved optical quality. Combining the theoretical and experimental analysis, it is concluded that the enhanced photoluminescence and Raman intensities of monolayer MoS2 probably originate from the relatively weak doping effect from the h-BN substrate rather than the optical interference effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Pressure-dependent optical and vibrational properties of monolayer molybdenum disulfide

    KAUST Repository

    Nayak, Avinash P.

    2015-01-14

    Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T′) and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structure-property relation due to the rich band structure of MoS2. Remarkably, the metastable 1T′-MoS2 metallic state remains invariant with pressure, with the J2, A1g, and E2g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

  9. Metallic modification of molybdenum disulfide monolayer via doping charge carriers: A DFT investigation

    Science.gov (United States)

    Shekaari, Ashkan; Abolhassani, Mohammad Reza

    2017-09-01

    Density-functional theory has been applied to investigate the effect of doping charge carriers on the electronic structure of single-layer MoS2. The charge of the super cell changes from zero to n = ± 3 e with e the absolute value of the elementary electric charge. Results firmly support the view that such an effect is manifested in the form of semiconductor-metal transition in addition to shift in the Fermi level. Examining the total number of allowed states at the Fermi level also reveals that the more positive/negative the charge of the super cell, the higher the electrical conductivity of the monolayer.

  10. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction.

    Science.gov (United States)

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin

    2016-02-10

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm(-1) in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm(-2) at a low potential of -175 mV and a Tafel slope of 41 mV per decade.

  11. High-quality molybdenum disulfide nanosheets with 3D structure for electrochemical sensing

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Aiping, E-mail: aipingyin1964@163.com [Department of chemistry, Xinzhou Teachers University, Xinzhou, Shanxi (China); Wei, Xuehong [College of Chemistry and Chemical Engineering, Shanxi University, Taiyuan, Shanxi (China); Cao, Yexia; Li, Huiqing [Department of chemistry, Xinzhou Teachers University, Xinzhou, Shanxi (China)

    2016-11-01

    Graphical abstract: MoS{sub 2} ultrathin nanosheets are successfully synthesized via a facile strategy, one-step pyrolysis of ammonium molybdate, thiourea and layered g-C{sub 3}N{sub 4} template. Possessing hierarchical porous structure and large pore volume as well as good conductivity, MoS{sub 2} ultrathin nanosheets demonstrates significantly improved electrocatalytic activity toward oxidation of AA, DA, and UA. Display Omitted - Highlights: • MoS{sub 2} ultrathin nanosheets are achieved via a facile strategy, one-step pyrolysis of ammonium molybdate, thiourea and layered g-C{sub 3}N{sub 4} template. • The sacrificial template (g-C{sub 3}N{sub 4}) plays a significant role in this synthetic process, which brings ultrathin structure and three-dimensional porous network for MoS{sub 2} materials. • The MoS{sub 2} ultrathin nanosheets sample displays significantly improved electrocatalytic performance toward oxidation of AA, DA, and UA, manifesting enlarged peak separation and increased peak current. • Meantime, simultaneous determination of these biomolecules is achieved in a wide concentration rang with high sensitivity, selectivity, stability and good reproducibility on modified electrode of the MoS{sub 2} nanosheets. - Abstract: An electrochemical sensor has been developed for simultaneous detection of dopamine (DA), uric acid (UA) and ascorbic acid (AA) based on pure MoS{sub 2} nanosheets modified electrode. The MoS{sub 2} nanosheets are achieved via a facile strategy, one-step pyrolysis of ammonium molybdate, thiourea and layered g-C{sub 3}N{sub 4} template. Possessing hierarchical porous structure and large pore volume as well as good conductivity, MoS{sub 2} nanosheets demonstrates significantly improved electrocatalytic activity toward oxidation of AA, DA, and UA. In the coexisting system, the peak separation of AA–DA, DA–UA and AA–UA is 208.3 mV, 128.0 mV and 336.3 mV, respectively, which is much larger than for other MoS{sub 2}-based catalyst. On the basis of large potential separation and high current response, selective and sensitive simultaneous determination of AA, DA, and UA was successfully accomplished by DPV, displaying a linear response from 5 to 1200 μM, from 1 to 900 μM, and from 1 to 60 μM with a detection limit (S/N = 3) of 0.82, 0.15, and 0.06 μM. This work highlights the importance of Mo-edge sites of MoS{sub 2} and hierarchical porous structure for efficient catalysis.

  12. Simple Synthesis of Molybdenum Disulfide/Reduced Graphene Oxide Composite Hollow Microspheres as Supercapacitor Electrode Material

    Directory of Open Access Journals (Sweden)

    Wei Xiao

    2016-09-01

    Full Text Available MoS2/RGO composite hollow microspheres were hydrothermally synthesized by using SiO2/GO microspheres as a template, which were obtained via the sonication-assisted interfacial self-assembly of tiny GO sheets on positively charged SiO2 microspheres. The structure, morphology, phase, and chemical composition of MoS2/RGO hollow microspheres were systematically investigated by a series of techniques such as FE-SEM, TEM, XRD, TGA, BET, and Raman characterizations, meanwhile, their electrochemical properties were carefully evaluated by CV, GCD, and EIS measurements. It was found that MoS2/RGO hollow microspheres possessed unique porous hollow architecture with high-level hierarchy and large specific surface area up to 63.7 m2·g−1. When used as supercapacitor electrode material, MoS2/RGO hollow microspheres delivered a maximum specific capacitance of 218.1 F·g−1 at the current density of 1 A·g−1, which was much higher than that of contrastive bare MoS2 microspheres developed in the present work and most of other reported MoS2-based materials. The enhancement of supercapacitive behaviors of MoS2/RGO hollow microspheres was likely due to the improved conductivity together with their distinct structure and morphology, which not only promoted the charge transport but also facilitated the electrolyte diffusion. Moreover, MoS2/RGO hollow microsphere electrode displayed satisfactory long-term stability with 91.8% retention of the initial capacitance after 1000 charge/discharge cycles at the current density of 3 A·g−1, showing excellent application potential.

  13. Simple Synthesis of Molybdenum Disulfide/Reduced Graphene Oxide Composite Hollow Microspheres as Supercapacitor Electrode Material.

    Science.gov (United States)

    Xiao, Wei; Zhou, Wenjie; Feng, Tong; Zhang, Yanhua; Liu, Hongdong; Tian, Liangliang

    2016-09-20

    MoS₂/RGO composite hollow microspheres were hydrothermally synthesized by using SiO₂/GO microspheres as a template, which were obtained via the sonication-assisted interfacial self-assembly of tiny GO sheets on positively charged SiO₂ microspheres. The structure, morphology, phase, and chemical composition of MoS₂/RGO hollow microspheres were systematically investigated by a series of techniques such as FE-SEM, TEM, XRD, TGA, BET, and Raman characterizations, meanwhile, their electrochemical properties were carefully evaluated by CV, GCD, and EIS measurements. It was found that MoS₂/RGO hollow microspheres possessed unique porous hollow architecture with high-level hierarchy and large specific surface area up to 63.7 m²·g-1. When used as supercapacitor electrode material, MoS₂/RGO hollow microspheres delivered a maximum specific capacitance of 218.1 F·g-1 at the current density of 1 A·g-1, which was much higher than that of contrastive bare MoS₂ microspheres developed in the present work and most of other reported MoS₂-based materials. The enhancement of supercapacitive behaviors of MoS₂/RGO hollow microspheres was likely due to the improved conductivity together with their distinct structure and morphology, which not only promoted the charge transport but also facilitated the electrolyte diffusion. Moreover, MoS₂/RGO hollow microsphere electrode displayed satisfactory long-term stability with 91.8% retention of the initial capacitance after 1000 charge/discharge cycles at the current density of 3 A·g-1, showing excellent application potential.

  14. Piezoelectric effect in chemical vapour deposition-grown atomic-monolayer triangular molybdenum disulfide piezotronics

    KAUST Repository

    Qi, Junjie

    2015-06-25

    High-performance piezoelectricity in monolayer semiconducting transition metal dichalcogenides is highly desirable for the development of nanosensors, piezotronics and photo-piezotransistors. Here we report the experimental study of the theoretically predicted piezoelectric effect in triangle monolayer MoS2 devices under isotropic mechanical deformation. The experimental observation indicates that the conductivity of MoS2 devices can be actively modulated by the piezoelectric charge polarization-induced built-in electric field under strain variation. These polarization charges alter the Schottky barrier height on both contacts, resulting in a barrier height increase with increasing compressive strain and decrease with increasing tensile strain. The underlying mechanism of strain-induced in-plane charge polarization is proposed and discussed using energy band diagrams. In addition, a new type of MoS2 strain/force sensor built using a monolayer MoS2 triangle is also demonstrated. Our results provide evidence for strain-gating monolayer MoS2 piezotronics, a promising avenue for achieving augmented functionalities in next-generation electronic and mechanical–electronic nanodevices.

  15. Interlayer expanded molybdenum disulfide nanosheets assembly for electrochemical supercapacitor with enhanced performance

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Huaqing; Wang, Shutao; Zhang, Shuo; Wang, Yihe; Xu, Qingfei; Hu, Wenjie [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); Zhou, Yan, E-mail: yanzhou@upc.edu.cn [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); Wang, Zhaojie [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); An, Changhua [College of Science, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China); College of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin, 300384 (China); Zhang, Jun, E-mail: zhangj@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), 66 Changjiang West Road, Qingdao Economic Development Zone, Qingdao, Shandong, 266580 (China)

    2017-05-01

    Rational structural design for electrode materials is essential for fabricating high performance supercapacitors. In this work, we demonstrated a novel way to prepare incompact MoS{sub 2} nanosheets assembled nanorods with the interlayer of MoS{sub 2} nanosheets expanded to 0.89 nm, namely layer expanded MoS{sub 2} nanorods (LE-MoS{sub 2} NRs). The material was characterized by XRD, XPS and electron microscopes. The XRD data and HRTEM images confirmed the existence of expanded interlayer of MoS{sub 2} nanosheets. N{sub 2} adsorption-desorption isotherms of LE-MoS{sub 2} NRs indicated high specific area up to 37.0 m{sup 2} g{sup −1}. It was found that the expanded interlayer spacing can benefit the ion transportation within the MoS{sub 2} interlayers. The as-prepared electrode material showed capacitance up to 231 F g{sup −1} at 1 A g{sup −1} charge-discharge current and cycling stability test indicated high capacitance of 177 F g{sup −1} was retained after 1000 cycles. - Highlights: • High performance electrochemical supercapacitor electrode material. • Interlayer expanded MoS{sub 2} to achieve enhanced capacitance. • Facile hydrothermal synthesis of interlayer expanded MoS{sub 2}. • MoS{sub 2} nanosheets assembled incompact nanorods.

  16. Upconversion nanoparticles grafted molybdenum disulfide nanosheets platform for microcystin-LR sensing.

    Science.gov (United States)

    Lv, Jiajia; Zhao, Sen; Wu, Shijia; Wang, Zhouping

    2017-04-15

    Water safety is one of the most pervasive problems afflicting people throughout the world. Microcystin-LR (MC-LR), a representative toxin released by cyanobacteria, poses an increasing and serious threat to water safety. In order to develop facile, specific and sensitive detection methods for MC-LR, we fabricated an ultrasensitive fluorescence aptasensor using the enhanced fluorescence of UCNP and the effective quenching ability, high affinity toward single strand DNA (ssDNA) of MoS2 (termed as FAUM). This assay specifically determined MC-LR in the linear range of 0.01-50ng/ml with a limit of detection (LOD) of 0.002ng/ml. The real water sample results indicated that this FAUM assay owns well enough reliability and feasibility to allow the determination of MC-LR. This aptamer-based method might be a promising strategy for a variety of sensing applications. Copyright © 2016. Published by Elsevier B.V.

  17. Density functional theory study on water-gas-shift reaction over molybdenum disulfide

    DEFF Research Database (Denmark)

    Shi, X. R.; Wang, Shengguang; Hu, J.

    2009-01-01

    species HCOO formation is the surface CO2 reaction with H as a side reaction of CO2 desorption on S-termination with 50% S coverage. The formed HCOO species will react further with adsorbed hydrogen yielding H2COO followed by breaking its C-O bond to form the surface CH2O and O species.......Density functional theory calculations have been carried out to investigate the adsorption of reaction intermediates appearing during water-gas-shift reaction at the sulfur covered MoS2 (1 0 0)surfaces, Mo-termination with 37.5% S coverage and S-termination with 50% S coverage using periodic slabs....... The pathway for water-gas-shift reaction on both terminations has been carefully studied where the most favorable reaction path precedes the redox mechanism, namely the reaction takes place as follows: CO + H2O --> CO + OH + H --> CO + O + 2H --> CO2 + H-2. The most likely reaction candidates for the formate...

  18. Effects of Growth Conditions on the Measured Electrical Properties of Monolayer Molybdenum Disulfide

    Science.gov (United States)

    2017-02-01

    point probe (4PP) conductance measured on sample 104C in both a dark and illuminated condition. Upon illumination, both the current and conductance...increase. The conductance measured in the dark is drawn in red, the illuminated conductance is plotted in purple. The current measured in the dark is...DJ, Liu B, Matte HSSR, Dravid VP, Rao CNR. Hysteresis in single-layer MoS2 field effect transistors. ACS Nano. 2012 June;6(6):5635–5641. 20. Shah

  19. On the photostability of the disulfide bond

    DEFF Research Database (Denmark)

    Stephansen, Anne Boutrup; Larsen, Martin Alex Bjørn; Klein, Liv Bærenholdt

    2014-01-01

    Photostability is an essential property of molecular building blocks of nature. Disulfides are central in the structure determination of proteins, which is in striking contradiction to the result that the S-S bond is a photochemically labile structural entity that cleaves to form free radicals upon...... on a sub 50 fs timescale without further ado. In a cyclic motif resembling the cysteine-disulfide bond in proteins, light can perturb the S-S bond to generate short-lived diradicaloid species, but the sulfur atoms are conformationally restricted by the ring that prevents the sulfur atoms from flying apart...... the photostability of disulfide-bonds must be ascribed a cyclic structural arrangement....

  20. Disulfide by Design 2.0: a web-based tool for disulfide engineering in proteins.

    Science.gov (United States)

    Craig, Douglas B; Dombkowski, Alan A

    2013-12-01

    Disulfide engineering is an important biotechnological tool that has advanced a wide range of research. The introduction of novel disulfide bonds into proteins has been used extensively to improve protein stability, modify functional characteristics, and to assist in the study of protein dynamics. Successful use of this technology is greatly enhanced by software that can predict pairs of residues that will likely form a disulfide bond if mutated to cysteines. We had previously developed and distributed software for this purpose: Disulfide by Design (DbD). The original DbD program has been widely used; however, it has a number of limitations including a Windows platform dependency. Here, we introduce Disulfide by Design 2.0 (DbD2), a web-based, platform-independent application that significantly extends functionality, visualization, and analysis capabilities beyond the original program. Among the enhancements to the software is the ability to analyze the B-factor of protein regions involved in predicted disulfide bonds. Importantly, this feature facilitates the identification of potential disulfides that are not only likely to form but are also expected to provide improved thermal stability to the protein. DbD2 provides platform-independent access and significantly extends the original functionality of DbD. A web server hosting DbD2 is provided at http://cptweb.cpt.wayne.edu/DbD2/.

  1. Voltammetric studies of poly(carbon disulfide)

    Energy Technology Data Exchange (ETDEWEB)

    Geng, L.; Xu, J.; Prasad, S.; Skotheim, T.A. [Moltech Corp., Stony Brook, NY (United States); Lee, H.S.; McBreen, J. [Brookhaven National Lab., Upton, NY (United States)

    1992-12-31

    Poly(carbon disulfide) was studied by cyclic voltammetry using glassy carbon and platinum macro- and microdisk electrodes. The electron transfer kinetics is significantly faster at glassy carbon electrodes than at Pt electrodes. It is chemically reversible with moderate electron transfer rates. Voltammetric results of poly(carbon disulfide) are in good agreement with battery testing data. The k{sup 0} value measured at a Pt microdisk electrode is 7{times}10{sup 3} cm/sec. Electrochemical data suggest that PCS can be a potential cathode material for low current density lithium batteries.

  2. Disulfide-Functionalized Diblock Copolymer Worm Gels.

    Science.gov (United States)

    Warren, Nicholas J; Rosselgong, Julien; Madsen, Jeppe; Armes, Steven P

    2015-08-10

    Two strategies for introducing disulfide groups at the outer surface of RAFT-synthesized poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA, or Gx-Hy for brevity) diblock copolymer worms are investigated. The first approach involved statistical copolymerization of GMA with a small amount of disulfide dimethacrylate (DSDMA, or D) comonomer to afford a G54-D0.50 macromolecular chain transfer agent (macro-CTA); this synthesis was conducted in relatively dilute solution in order to ensure mainly intramolecular cyclization and hence the formation of linear chains. Alternatively, a new disulfide-based bifunctional RAFT agent (DSDB) was used to prepare a G45-S-S-G45 (or (G45-S)2) macro-CTA. A binary mixture of a non-functionalized G55 macro-CTA was utilized with each of these two disulfide-based macro-CTAs in turn for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). By targeting a PHPMA DP of 130 and systematically varying the molar ratio of the two macro-CTAs, a series of disulfide-functionalized diblock copolymer worm gels were obtained. For both formulations, oscillatory rheology studies confirmed that higher disulfide contents led to stronger gels, presumably as a result of inter-worm covalent bond formation via disulfide/thiol exchange. Using the DSDB-based macro-CTA led to the strongest worm gels, and this formulation also proved to be more effective in suppressing the thermosensitive behavior that is observed for the nondisulfide-functionalized control worm gel. However, macroscopic precipitation occurred when the proportion of DSDB-based macro-CTA was increased to 50 mol %, whereas the DSDMA-based macro-CTA could be utilized at up to 80 mol %. Finally, the worm gel modulus could be reduced to that of a nondisulfide-containing worm gel by reductive cleavage of the inter-worm disulfide bonds using excess tris(2-carboxyethyl)phosphine (TCEP) to yield thiol groups. These new biomimetic worm gels are

  3. Disulfide Bond Oxidoreductase DsbA2 of Legionella pneumophila Exhibits Protein Disulfide Isomerase Activity

    OpenAIRE

    Kpadeh, Zegbeh Z.; Jameson-Lee, Max; Anthony J. Yeh; Chertihin, Olga; Shumilin, Igor A.; Dey, Rafik; Day, Shandra R.; Hoffman, Paul S.

    2013-01-01

    The extracytoplasmic assembly of the Dot/Icm type IVb secretion system (T4SS) of Legionella pneumophila is dependent on correct disulfide bond (DSB) formation catalyzed by a novel and essential disulfide bond oxidoreductase DsbA2 and not by DsbA1, a second nonessential DSB oxidoreductase. DsbA2, which is widely distributed in the microbial world, is phylogenetically distinct from the canonical DsbA oxidase and the DsbC protein disulfide isomerase (PDI)/reductase of Escherichia coli. Here we s...

  4. The human protein disulfide isomerase gene family

    Directory of Open Access Journals (Sweden)

    Galligan James J

    2012-07-01

    Full Text Available Abstract Enzyme-mediated disulfide bond formation is a highly conserved process affecting over one-third of all eukaryotic proteins. The enzymes primarily responsible for facilitating thiol-disulfide exchange are members of an expanding family of proteins known as protein disulfide isomerases (PDIs. These proteins are part of a larger superfamily of proteins known as the thioredoxin protein family (TRX. As members of the PDI family of proteins, all proteins contain a TRX-like structural domain and are predominantly expressed in the endoplasmic reticulum. Subcellular localization and the presence of a TRX domain, however, comprise the short list of distinguishing features required for gene family classification. To date, the PDI gene family contains 21 members, varying in domain composition, molecular weight, tissue expression, and cellular processing. Given their vital role in protein-folding, loss of PDI activity has been associated with the pathogenesis of numerous disease states, most commonly related to the unfolded protein response (UPR. Over the past decade, UPR has become a very attractive therapeutic target for multiple pathologies including Alzheimer disease, Parkinson disease, alcoholic and non-alcoholic liver disease, and type-2 diabetes. Understanding the mechanisms of protein-folding, specifically thiol-disulfide exchange, may lead to development of a novel class of therapeutics that would help alleviate a wide range of diseases by targeting the UPR.

  5. Functional differences in yeast protein disulfide isomerases

    DEFF Research Database (Denmark)

    Nørgaard, P; Westphal, V; Tachibana, C

    2001-01-01

    PDI1 is the essential gene encoding protein disulfide isomerase in yeast. The Saccharomyces cerevisiae genome, however, contains four other nonessential genes with homology to PDI1: MPD1, MPD2, EUG1, and EPS1. We have investigated the effects of simultaneous deletions of these genes. In several c...

  6. Large-Batch Reduction of Molybdenum Trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Kiggans, Jr, James O. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lowden, Richard Andrew [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Menchhofer, Paul A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Nunn, Stephen D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bryan, Chris [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-01

    Unconverted, isotopically-enriched molybdenum metal must be recovered from the spent radiopharmaceutical solution used in NorthStar’s Technetium-99m generator and reused. The recycle process begins by recovering the metal from the aqueous potassium molybdate (K2MoO4) solutions as molybdenum trioxide (MoO3) employing a process developed at Argonne National Laboratory. The MoO3 powder is subsequently reduced to molybdenum metal powder which can be blended with new powder and further processed into a flowable form to be used to produce target disks for irradiation. The molybdenum oxide reduction process has been examined and scaled to produce kilogram quantities of metal powder suitable for processing into a useable form employing spray drying or similar technique and ultimately used for target fabrication.

  7. Disulfide Bonds: A Key Modification in Bacterial Extracytoplasmic Proteins.

    Science.gov (United States)

    Lee, S F; Davey, L

    2017-12-01

    Disulfide bonds are a common posttranslational modification that contributes to the folding and stability of extracytoplasmic proteins. Almost all organisms, from eukaryotes to prokaryotes, have evolved enzymes to make and break these bonds. Accurate and efficient disulfide bond formation can be vital for protein function; therefore, the enzymes that catalyze disulfide bond formation are involved in multiple biological processes. Recent advances clearly show that oral bacteria also have the ability to from disulfide bonds, and this ability has an effect on a range of dental plaque-related phenotypes. In the gram-positive Streptococcus gordonii, the ability to form disulfide bonds affected autolysis, extracellular DNA release, biofilm formation, genetic competence, and bacteriocin production. In Actinomyces oris, disulfide bond formation is needed for pilus assembly, coaggregation, and biofilm formation. In other gram-positive bacteria, such as Enterococcus faecalis, disulfide bonds are formed in secreted bacteriocins and required for activity. In these oral bacteria, the enzymes that catalyze the disulfide bonds are quite diverse and share little sequence homology, but all contain a CXXC catalytic active site motif and a conserved C-terminal cis-proline, signature features of a thiol-disulfide oxidoreductase. Emerging evidence also indicates that gram-negative oral bacteria, such as Porphyromonas gingivalis and Tannerella forsythia, use disulfide bonds to stabilize their outer membrane porin proteins. Bioinformatic screens reveal that these gram-negative bacteria carry genes coding for thiol-disulfide oxidoreductases in their genomes. In conclusion, disulfide bond formation in oral bacteria is an emerging field, and the ability to form disulfide bonds plays an important role in dental plaque formation and fitness for the bacteria.

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

    Science.gov (United States)

    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.

  9. Why is DsbA such an oxidizing disulfide catalyst?

    DEFF Research Database (Denmark)

    Grauschopf, U; Winther, Jakob R.; Korber, P

    1995-01-01

    DsbA, a member of the thioredoxin family of disulfide oxidoreductases, acts in catalyzing disulfide bond formation by donating its disulfide to newly translocated proteins. We have found that the two central residues within the active site Cys-30-Pro-31-His-32-Cys-33 motif are critical in determi......DsbA, a member of the thioredoxin family of disulfide oxidoreductases, acts in catalyzing disulfide bond formation by donating its disulfide to newly translocated proteins. We have found that the two central residues within the active site Cys-30-Pro-31-His-32-Cys-33 motif are critical......Ka of Cys-30 varied dramatically from mutant to mutant and could accurately predict the oxidizing power of each DsbA mutant protein....

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  11. Prenatal brain disruption in molybdenum cofactor deficiency.

    Science.gov (United States)

    Carmi-Nawi, Nirit; Malinger, Gustavo; Mandel, Hanna; Ichida, Kimiyoshi; Lerman-Sagie, Tally; Lev, Dorit

    2011-04-01

    Molybdenum cofactor deficiency is a rare autosomal recessive disorder that may present during the neonatal period with intractable seizures and be mistaken for ischemic encephalopathy. We describe a patient whose prenatal sonography at 35 weeks' gestation revealed diffuse brain damage with multiple subcortical cavities, ventriculomegaly, dysgenesis of the corpus callosum, and a hypoplastic cerebellum with an enlarged cisterna magna. Magnetic resonance imaging (MRI) later revealed brain atrophy, and multicystic encephalomalacia with hypoplastic vermis and cerebellum. Neurological examination at 10 months showed microcephaly, profound mental retardation, and spasticity. Uric acid was low, and taurine and xanthine were increased in the urine. A sulfite test was positive. The diagnosis of molybdenum cofactor deficiency was made. Sulfite oxidase activity in fibroblasts was undetectable. The patient was found to be homozygous for the 251-418del in the MOCS1 gene. This is the first description of the prenatal development of severe brain disruption in molybdenum cofactor deficiency.

  12. Manufacture of molybdenum ingot and its utilization

    Energy Technology Data Exchange (ETDEWEB)

    Rhee, Kang In; Yu, Hyo Shin; Youn, In Ju; Choi, Good Sun; Lee, Churl Kyoung; Seo, Chang Youl; Yang, Dong Hyo [Korea Inst. of Geology Mining and Materials, Taejon (Korea, Republic of)

    1995-12-01

    The pure molybdenum metal ingot was obtained from sintered molybdenum and/or molybdenum wire scrap through operating optimum conditions of electron beam melting. And a sputtering target through precise cutting, abrading and lapping was fabricated and compared to the commercial target made by a conventional PM process. For the utilization of molybdenum ingot, vacuum forging process was tested to modify the cast structure. Molybdenum ingot of 50 and 100 mm in diameter were obtained from sintered Mo bars and molybdenum wire scrap by EB drip melting technique. Macroscopic observation of EB remelted ingot indicates that coarse and columnar grains grow in the direction parallel to ingot pulling direction. This can be explained by slow solidification (3 mm/min), large temperature gradient and heat flow to this direction. The orientation of columnar structure was found to be <110>, <200> and <211> by the analysis of x-ray diffraction patterns. The contents of typical metallic impurities in Mo sintered bar are 1.2 ppm Cr, 3 ppm Fe, 44 ppm Zr, 150 ppm W. Most of metallic impurities were reduced below the order of ppm except zirconium and tungsten by the selective evaporation. In the removal of nonmetallic impurities, oxygen and carbon impurities were lowered from 120 to 6 ppm and from 157 to 106 ppm, respectively, after first melting. Although the purification effect was not significant with the number of remelting, Vickers hardness was reduced from 217 to 195 and 184 in sequence with increasing the number of remelting. Grain refinement and high temperature workability was also tested at the temperature of 800-1300 degree using an induction heating and optical pyrometer and the deformation was measured. The sputtering target from 100 mm ingot made by EB melting was highly pure compared to the PM product. (author). 24 figs., 7 tabs.

  13. Disulfide Chromophore and Its Optical Activity

    Czech Academy of Sciences Publication Activity Database

    Maloň, Petr; Bednárová, Lucie; Straka, Michal; Krejčí, Lucie; Kumprecht, Lukáš; Kraus, Tomáš; Kubáňová, M.; Baumruk, V.

    2010-01-01

    Roč. 22, 1E (2010), E47-E55 ISSN 0899-0042 R&D Projects: GA ČR(CZ) GA203/07/1335; GA ČR GA203/06/1550; GA ČR GA203/09/2037; GA ČR GAP208/10/0376; GA AV ČR IAA400550810 Institutional research plan: CEZ:AV0Z40550506 Keywords : disulfide chromophore * Raman optical activity * vibrational optical activity * circular dichroism Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.892, year: 2010

  14. Several nanosecond Nd:YVO4 lasers Q-switched by two dimensional materials: tungsten disulfide, molybdenum disulfide, and black phosphorous.

    Science.gov (United States)

    Liu, Huan; Sun, Zhe; Wang, Xi; Wang, Yonggang; Cheng, Guanghua

    2017-03-20

    Graphene-like two-dimensional (2D) materials have shown remarkable broadband saturable absorption properties. These materials were successfully applied into mode locked lasers to generate laser pulses with the pulse duration from picosecond to femtosecond. However, these novel materials have not shown good performance as far in another important aspect: Q-switched lasers. Solid-state or fiber lasers Q-switched with broadband absorbers usually generated pulses of one hundred nanosecond to several microsecond, which show weak competitiveness compared to traditional absorbers such as Cr: YAG and semiconductor saturable absorption mirror (SESAM). In this paper we utilized BP, WS2 and MoS2 solutions as saturable absorbers (SAs) to construct the passively Q-switched Nd:YVO4 lasers. The pulse durations as short as 2.86 nanosecond was obtained. To the best of our knowledge, it was the first report that the pulse durations approached several nanosecond level in Q-switched lasers with liquid-form of BP, WS2 and MoS2 SAs.

  15. Exploring atomic defects in molybdenum disulphide monolayers

    KAUST Repository

    Hong, Jinhua

    2015-02-19

    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 × 10 13 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.

  16. Molybdenum Valence in Basaltic Silicate Melts

    Science.gov (United States)

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

    2010-03-01

    XANES analyses of molybdenum were performed on basaltic glass run products experiments conducted at varying P, T, and fO2. The transition from Mo6+ to Mo4+ occurs around IW, only Mo4+ remains at IW-1 and below, conditions relevant to core formation.

  17. Molybdenum-catalyzed deoxydehydration of vicinal diols

    DEFF Research Database (Denmark)

    Dethlefsen, Johannes Rytter; Lupp, Daniel; Oh, Byung Chang

    2014-01-01

    The commercially available (NH4)6Mo7O24 and other molybdenum compounds are shown to be viable substitutes for the typically employed rhenium compounds in the catalytic deoxydehydration of aliphatic diols into the corresponding alkenes. The transformation, which represents a model system for the v...

  18. 21 CFR 524.2101 - Selenium disulfide suspension.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Selenium disulfide suspension. 524.2101 Section 524.2101 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... § 524.2101 Selenium disulfide suspension. (a) Specifications. The product contains 0.9-percent weight in...

  19. Compact conformations of human protein disulfide isomerase.

    Directory of Open Access Journals (Sweden)

    Shang Yang

    Full Text Available Protein disulfide isomerase (PDI composed of four thioredoxin-like domains a, b, b', and a', is a key enzyme catalyzing oxidative protein folding in the endoplasmic reticulum. Large scale molecular dynamics simulations starting from the crystal structures of human PDI (hPDI in the oxidized and reduced states were performed. The results indicate that hPDI adopts more compact conformations in solution than in the crystal structures, which are stabilized primarily by inter-domain interactions, including the salt bridges between domains a and b' observed for the first time. A prominent feature of the compact conformations is that the two catalytic domains a and a' can locate close enough for intra-molecular electron transfer, which was confirmed by the characterization of an intermediate with a disulfide between the two domains. Mutations, which disrupt the inter-domain interactions, lead to decreased reductase activity of hPDI. Our molecular dynamics simulations and biochemical experiments reveal the intrinsic conformational dynamics of hPDI and its biological impact.

  20. Oxidation behavior of multiphase molybdenum-molybdenum silicide-molybdenum silicide boride intermetallics

    Science.gov (United States)

    Dheeradhada, Voramon Supatarawanich

    coefficients for Mo, Si, B, and O in various phases were also determined. The motion of the (metal/Mo+glass) and (Mo+glass/glass) interfaces was examined. An average effective interdiffusion coefficient of silicon in molybdenum at 1300°C was estimated as 10 -17 m2/s. Moreover, interdiffusion coefficients for each component in the Mo+glass layer were evaluated on the basis of Mishin's analysis.

  1. Thiol-Disulfide Exchange between Glutaredoxin and Glutathione

    DEFF Research Database (Denmark)

    Iversen, Rasmus; Andersen, Peter Anders; Jensen, Kristine Steen

    2010-01-01

    Glutaredoxins are ubiquitous thiol-disulfide oxidoreductases which catalyze the reduction of glutathione-protein mixed disulfides. Belonging to the thioredoxin family, they contain a conserved active site CXXC motif. The N-proximal active site cysteine can form a mixed disulfide with glutathione ...... has been replaced with serine. The exchange reaction between the reduced protein and oxidized glutathione leading to formation of the mixed disulfide could readily be monitored by isothermal titration calorimetry (ITC) due to the enthalpic contributions from the noncovalent interactions...... potential of -295 mV for the mixed disulfide. In another set of experiments, the pKa value of the active site cysteine was determined. In line with what has been observed for other glutaredoxins, this cysteine was found to have a very low pKa value. The glutathionylation of glutaredoxin was shown to have...

  2. Disulfide Linkage Characterization of Disulfide Bond-Containing Proteins and Peptides by Reducing Electrochemistry and Mass Spectrometry

    DEFF Research Database (Denmark)

    Cramer, Christian N; Haselmann, Kim F; Olsen, Jesper V

    2016-01-01

    Unravelling of disulfide linkage patterns is a crucial part of protein characterization, whether it is for a previously uncharacterized protein in basic research or a recombinant pharmaceutical protein. In the biopharmaceutical industry, elucidation of the cysteine connectivities is a necessity...... to avoid disulfide scrambled and incorrectly folded forms in the final product. Mass spectrometry (MS) is a highly utilized analytical tool for this due to fast and accurate characterization. However, disulfide bonds being an additional covalent bond in the protein structure represent a challenge...... in protein sequencing by tandem MS (MS/MS). Electrochemical (EC) reduction of disulfide bonds has recently been demonstrated to provide efficient reduction efficiencies, significantly enhancing sequence coverages in online coupling with MS characterization. In this study, the potential use of EC disulfide...

  3. Twin disulfides for orthogonal disulfide pairing and the directed folding of multicyclic peptides

    Science.gov (United States)

    Wu, Chuanliu; Leroux, Jean-Christophe; Gauthier, Marc A.

    2012-12-01

    Multicyclic peptides are emerging as an exciting platform for drug and targeted ligand discovery owing to their expected greater target affinity/selectivity/stability versus linear or monocyclic peptides. However, although the precise pairing of cysteine residues in proteins is routinely achieved in nature, the rational pairing of cysteine residues within polypeptides is a long-standing challenge for the preparation of multicyclic species containing several disulfide bridges. Here, we present an efficient and straightforward approach for directing the intermolecular and intramolecular pairing of cysteine residues within peptides using a minimal CXC motif. Orthogonal disulfide pairing can be exploited in complex redox media to rationally produce dimeric peptides and bi/tricyclic peptides from fully reduced peptides containing 1-6 cysteine residues. This strategy, which does not rely on extensive manipulation of the primary sequence, post-translational modification or protecting groups, should greatly benefit the development of multicyclic peptide therapeutics and targeting ligands.

  4. Ferromagnetism in exfoliated tungsten disulfide nanosheets

    Science.gov (United States)

    2013-01-01

    Two-dimensional-layered transition metal dichalcogenides nanosheets have attracted tremendous attention for their promising applications in spintronics because the atomic-thick nanosheets can not only enhance the intrinsic properties of their bulk counterparts, but also give birth to new promising properties. In this paper, ultrathin tungsten disulfide (WS2) nanosheets were gotten by liquid exfoliation route from its bulk form using dimethylformamide (DMF). Compared to the antiferromagnetism bulk WS2, ultrathin WS2 nanosheets show intrinsic room-temperature ferromagnetism (FM) with the maximized saturation magnetization of 0.004 emu/g at 10 K, where the appearance of FM in the nanosheets is partly due to the presence of zigzag edges in the magnetic ground state at the grain boundaries. PMID:24134699

  5. Thiol/disulfide homeostasis in untreated schizophrenia patients.

    Science.gov (United States)

    Topcuoglu, Canan; Bakirhan, Abdurrahim; Yilmaz, Fatma Meric; Neselioglu, Salim; Erel, Ozcan; Sahiner, Safak Yalcin

    2017-05-01

    The aim of the study was to investigate dynamic thiol/disulfide (SH/SS) homeostasis in untreated schizophrenia. Blood thiol/disulfide homeostasis status, which reflects native thiol-disulfide exchanges, was investigated in 87 untreated patients (52 males, 35 females), and the obtained results were compared with 86 healthy controls. Blood serum native thiol and total thiol (ToSH) concentrations were measured in a paired test. The half value of the difference between native thiol and ToSH concentrations was calculated as the disulfide bond amount. SH and ToSH concentrations were found to be significantly lower (pschizophrenia compared with the control group, whereas disulfide levels were significantly higher (pSchizophrenia patients had significantly higher SS/ToSH and SS/SH ratios and a significantly lower SH/ToSH ratio compared to those of healthy individuals. SH and ToSH amounts were found to be insufficient in untreated schizophrenia patients. Additionally, according to the results of the study, thiol/disulfide homeostasis was also disturbed by a shift to the disulfide bond formation side. This might affect the neurotransmission processes, which are known to be related with many symptoms observed in schizophrenia. The replacement of the thiol gap and the reduction of excess SS amounts might have a positive effect in supporting therapy for schizophrenia patients. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

  6. Conformational characterization of disulfide bonds: a tool for protein classification.

    Science.gov (United States)

    Marques, José Rui Ferreira; da Fonseca, Rute R; Drury, Brett; Melo, André

    2010-12-07

    Throughout evolution, mutations in particular regions of some protein structures have resulted in extra covalent bonds that increase the overall robustness of the fold: disulfide bonds. The two strategically placed cysteines can also have a more direct role in protein function, either by assisting thiol or disulfide exchange, or through allosteric effects. In this work, we verified how the structural similarities between disulfides can reflect functional and evolutionary relationships between different proteins. We analyzed the conformational patterns of the disulfide bonds in a set of disulfide-rich proteins that included twelve SCOP superfamilies: thioredoxin-like and eleven superfamilies containing small disulfide-rich proteins (SDP). The twenty conformations considered in the present study were characterized by both structural and energetic parameters. The corresponding frequencies present diverse patterns for the different superfamilies. The least-strained conformations are more abundant for the SDP superfamilies, while the "catalytic" +/-RHook is dominant for the thioredoxin-like superfamily. The "allosteric" -RHSaple is moderately abundant for BBI, Crisp and Thioredoxin-like superfamilies and less frequent for the remaining superfamilies. Using a hierarchical clustering analysis we found that the twelve superfamilies were grouped in biologically significant clusters. In this work, we carried out an extensive statistical analysis of the conformational motifs for the disulfide bonds present in a set of disulfide-rich proteins. We show that the conformational patterns observed in disulfide bonds are sufficient to group proteins that share both functional and structural patterns and can therefore be used as a criterion for protein classification. Copyright © 2010 Elsevier Ltd. All rights reserved.

  7. Selective reduction of the disulfide bonds of ovine placental lactogen.

    Science.gov (United States)

    Caridad, J J; Wolfenstein-Todel, C

    1988-01-01

    Reduction and carbamidomethylation of two of the three disulfide bridges of ovine placental lactogen was accomplished by the use of 20-fold molar excess of dithiothreitol over protein disulfide content. The derivative retained its binding capacity to somatogenic as well as lactogenic rat liver receptors, although the latter was somewhat diminished. The two disulfide bonds exposed to the reducing agent are those located near the carboxy- and amino-terminus, while the larger loop remained intact after reduction. This behaviour is similar to that of bovine growth hormone, where the larger loop was also more resistant to reduction.

  8. Preparation of single phase molybdenum boride

    Energy Technology Data Exchange (ETDEWEB)

    Camurlu, Hasan Erdem, E-mail: erdemcamurlu@gmail.com [Akdeniz University, Mechanical Engineering Department, 07058, Antalya (Turkey)

    2011-04-28

    Highlights: > Formation of Mo and a mixture of molybdenum boride phases take place in preparation of molybdenum borides. > It is intricate to prepare single phase molybdenum borides. > Formation of single phase MoB from MoO{sub 3} + B{sub 2}O{sub 3} + Mg mixtures has not been reported previously. > Single phase MoB was successfully prepared through a combination of mechanochemical synthesis and annealing process. - Abstract: The formation of MoB through volume combustion synthesis (VCS), and through mechanochemical synthesis (MCS) followed by annealing has been investigated. MoO{sub 3}, B{sub 2}O{sub 3} and Mg were used as reactants while MgO and NaCl were introduced as diluents. Products were leached in dilute HCl solution and were subjected to X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) examinations. Mo was the major phase component in the VCS products under all the experimental conditions. Mo{sub 2}B, MoB, MoB{sub 2} and Mo{sub 2}B{sub 5} were found as minor phases. Products of MCS contained a mixture of Mo{sub 2}B, MoB, MoB{sub 2} and Mo. After annealing the MCS product at 1400 deg. C for 3 h, single phase {alpha}-MoB was obtained.

  9. Deformation localization and cyclic strength in polycrystalline molybdenum

    Energy Technology Data Exchange (ETDEWEB)

    Sidorov, O.T.; Rakshin, A.F.; Fenyuk, M.I.

    1983-06-01

    Conditions of deformation localization and its interrelation with cyclic strength in polycrystalline molybdenum were investigated. A fatigue failure of polycrystalline molybdenum after rolling and in an embrittled state reached by recrystallization annealing under cyclic bending at room temperature takes place under nonuniform distribution of microplastic strain resulting in a temperature rise in separate sections of more than 314 K. More intensive structural changes take place in molybdenum after rolling than in recrystallized state.

  10. Versatile molybdenum disulfide based antibacterial composites for in vitro enhanced sterilization and in vivo focal infection therapy

    Science.gov (United States)

    Zhang, Wentao; Shi, Shuo; Wang, Yanru; Yu, Shaoxuan; Zhu, Wenxin; Zhang, Xu; Zhang, Daohong; Yang, Baowei; Wang, Xin; Wang, Jianlong

    2016-06-01

    Biologically, MoS2-based nanostructures have been intensely applied for the photothermal therapy of cancer, but rarely for antibacterial uses. In this contribution, a multifunctional chitosan (CS) functionalized magnetic MoS2 (abbreviated to CFM) was constructed to nonspecifically combat bacterial infection by integrating bacterial conjugation and enrichment, and NIR-triggered photothermal sterilization. Owing to the abundant introduced amino groups, the CFM complex offers a significantly enhanced conjugation efficiency without obvious specificity towards both Gram-positive and -negative bacteria compared to amino-free magnetic MoS2. The magnetic properties of CFM obtained from iron oxide facilitate the enrichment of a CFM-bacteria conjugate, improving the photothermal efficiency of CFM as a photothermal antibacterial agent. Specifically, after being trapped together with bacteria cells, CFM shows an enhanced in vitro photothermal sterilization ability. In vivo S. aureus-induced abscess treatment studies show faster healing when CFM is used as subcutaneous nano-localized heating sources with the assistance of an external magnet to concentrate the CFM-bacteria conjugate. This work establishes an innovative solution and a novel antimicrobial agent for combating bacterial infections without the use of antibiotics, which may open a new area of application and research for MoS2-based nanostructures.Biologically, MoS2-based nanostructures have been intensely applied for the photothermal therapy of cancer, but rarely for antibacterial uses. In this contribution, a multifunctional chitosan (CS) functionalized magnetic MoS2 (abbreviated to CFM) was constructed to nonspecifically combat bacterial infection by integrating bacterial conjugation and enrichment, and NIR-triggered photothermal sterilization. Owing to the abundant introduced amino groups, the CFM complex offers a significantly enhanced conjugation efficiency without obvious specificity towards both Gram-positive and -negative bacteria compared to amino-free magnetic MoS2. The magnetic properties of CFM obtained from iron oxide facilitate the enrichment of a CFM-bacteria conjugate, improving the photothermal efficiency of CFM as a photothermal antibacterial agent. Specifically, after being trapped together with bacteria cells, CFM shows an enhanced in vitro photothermal sterilization ability. In vivo S. aureus-induced abscess treatment studies show faster healing when CFM is used as subcutaneous nano-localized heating sources with the assistance of an external magnet to concentrate the CFM-bacteria conjugate. This work establishes an innovative solution and a novel antimicrobial agent for combating bacterial infections without the use of antibiotics, which may open a new area of application and research for MoS2-based nanostructures. Electronic supplementary information (ESI) available: Experimental details, characterization and supporting figures. See DOI: 10.1039/c6nr01243d

  11. A molybdenum disulfide/reduced oxide-graphene nanoflakelet-on-sheet structure for lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiayu; Zhao, Xianmin; Fu, Yongsheng, E-mail: fuyongsheng0925@163.com; Wang, Xin, E-mail: wangx@njust.edu.cn

    2017-03-31

    Highlights: • Graphene/MoS{sub 2} hybrid was successfully prepared via a facile solvothermal method. • A novel nanoflakelet-on-sheet morphology was obtained by controlling solvent. • The hybrid showed high capacity, excellent cycling stability and rate capability. • The synergistic effect remarkably improved electrochemical properties. - Abstract: A MoS{sub 2} nanoflakelet/graphene hybrid (MoS{sub 2}/G) is designed and successfully synthesized via a simple and cost-effective strategy. It is found that the MoS{sub 2}/G hybrids prepared using and without using ethanol (EtOH) show different morphologies and EtOH plays a crucial role in the formation of MoS{sub 2} nanoflakelets on graphene. The resulting nanoflakelet-on-sheet structure can be used as a high-performance anode material for lithium ion batteries, because it not only offers plenty of pores and pathways for lithium ions to shuttle back and forth, but also withstands lithium ion intercalation/de-intercalation process without collapse or deformation. The MoS{sub 2}/G hybrid synthesized in EtOH/H{sub 2}O exhibits remarkable reversible capacities of 1902 mAh g{sup −1} and 1454 mAh g{sup −1} in the first discharging and charging cycle, respectively, with a high coulombic efficiency of 76.45%. The hybrid also shows excellent cycle and rate performance. The superior Li storage performance of the MoS{sub 2}/G hybrid is mainly attributed to the intrinsic properties of MoS{sub 2} nanoflakelets and the synergistic effect of the MoS{sub 2} nanoflakelets and graphene.

  12. Solution-phase epitaxial growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide nanosheets.

    Science.gov (United States)

    Huang, Xiao; Zeng, Zhiyuan; Bao, Shuyu; Wang, Mengfei; Qi, Xiaoying; Fan, Zhanxi; Zhang, Hua

    2013-02-05

    Compared with the conventional deposition techniques used for the epitaxial growth of metallic structures on a bulk substrate, wet-chemical synthesis based on the dispersible template offers several advantages, including relatively low cost, high throughput, and the capability to prepare metal nanostructures with controllable size and morphology. Here we demonstrate that the solution-processable two-dimensional MoS(2) nanosheet can be used to direct the epitaxial growth of Pd, Pt and Ag nanostructures at ambient conditions. These nanostructures show the major (111) and (101) orientations on the MoS(2)(001) surface. Importantly, the Pt-MoS(2) hybrid nanomaterials exhibit much higher electrocatalytic activity towards the hydrogen evolution reaction compared with the commercial Pt catalysts with the same Pt loading. We believe that nanosheet-templated epitaxial growth of nanostructures via wet-chemical reaction is a promising strategy towards the facile and high-yield production of novel functional materials.

  13. Self-optimization of the active site of molybdenum disulfide by an irreversible phase transition during photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Longlu; Duan, Xidong; Liu, Chengbin; Zhang, Shuqu; Zeng, Yunxiong [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha (China); Liu, Xia; Pei, Yong [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University (China); Luo, Jinming; Crittenden, John [Brook Byers Institute for Sustainable Systems and School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA (United States); Duan, Xiangfeng [Department of Chemistry and Biochemistry, University of California, Los Angeles, CA (United States)

    2017-06-19

    The metallic 1T-MoS{sub 2} has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS{sub 2} and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS{sub 2} by hydrothermal exfoliation of MoS{sub 2} nanosheets vertically rooted into rigid one-dimensional TiO{sub 2} nanofibers. The 1T-MoS{sub 2} can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a ''catalytic site self-optimization''. Hydrogen atom adsorption is the major driving force for this phase transition. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Human IgG2 Antibody Disulfide Rearrangement in Vivo*

    OpenAIRE

    Liu, Y. Diana; CHEN, XIAOYU; Enk, Jian Zhang-van; Plant, Matt; Dillon, Thomas M.; Flynn, Gregory C.

    2008-01-01

    Proteins destined to circulate in the blood are first folded and assembled in the endoplasmic reticulum of secretory cells. For antibodies, like many other serum proteins, the folding and assembly steps involve the formation of disulfide bonds. Such bonds have been thought to be static features of proteins, stabilizing domains, and linking polypeptide chains, although some cases of extracellular disulfide bond cleavage have been noted. Recently, the human IgG2 antibody...

  15. Regulation of a phage endolysin by disulfide caging.

    Science.gov (United States)

    Kuty, Gabriel F; Xu, Min; Struck, Douglas K; Summer, Elizabeth J; Young, Ry

    2010-11-01

    In contrast to canonical phage endolysins, which require holin-mediated disruption of the membrane to gain access to attack the cell wall, signal anchor release (SAR) endolysins are secreted by the host sec system, where they accumulate in an inactive form tethered to the membrane by their N-terminal SAR domains. SAR endolysins become activated by various mechanisms upon release from the membrane. In its inactive form, the prototype SAR endolysin, Lyz(P1), of coliphage P1, has an active-site Cys covalently blocked by a disulfide bond; activation involves a disulfide bond isomerization driven by a thiol in the newly released SAR domain, unblocking the active-site Cys. Here, we report that Lyz(103), the endolysin of Erwinia phage ERA103, is also a SAR endolysin. Although Lyz(103) does not have a catalytic Cys, genetic evidence suggests that it also is activated by a thiol-disulfide isomerization triggered by a thiol in the SAR domain. In this case, the inhibitory disulfide in nascent Lyz(103) is formed between cysteine residues flanking a catalytic glutamate, caging the active site. Thus, Lyz(P1) and Lyz(103) define subclasses of SAR endolysins that differ in the nature of their inhibitory disulfide, and Lyz(103) is the first enzyme found to be regulated by disulfide bond caging of its active site.

  16. Characterization of Defects in Copper Antimony Disulfide

    Energy Technology Data Exchange (ETDEWEB)

    Zakutayev, Andriy A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); De Souza Lucas, Francisco Willian [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Johnston, Steven [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Dippo, Patricia C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lany, Stephan [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Peng, Haowei [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Mascaro, Lucia H. [Federal University of Sao Carlos

    2017-09-19

    Copper antimony disulfide (CuSbS2) with chalcostibite structure is a promising photovoltaic (PV) absorber material with several excellent measured optoelectronic properties, such as solar matched band gap and tunable hole concentration. However, much less is known from experimental perspective about defects in CuSbS2, even though the defects are critical for solar cell performance. Here, we explore the defect properties in CuSbS2 thin film materials and photovoltaic devices using photoluminescence and capacitance-based spectroscopies, as well as first principles theoretical calculations. We measured three electrically and optically active acceptor defects in CuSbS2, and assigned them to the copper vacancies, sulfur vacancies, and/or copper on antimony antisites by comparison with theoretical calculations. Their activation energies, concentrations, and capture cross sections have been determined and compared to other chalcogenide absorber materials. These fundamental parameters should enable more accurate simulations of CuSbS2 PV devices, paving the way to the future improvements in CuSbS2 solar cell efficiencies.

  17. The Effect of Molybdenum Fertilization on Arachis Glabrata Biomass ...

    African Journals Online (AJOL)

    The effect of molybdenum fertilization on biomass and the number of nodules of Arachis glabrata was assessed at the Teaching and Research Farm of the University of Dschang in 2011 at different periods of mowing. A factorial design comparing four doses of molybdenum as ammonium molybdate (0, 0.75, 1.5 and 2.25 ...

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

    Science.gov (United States)

    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.

  19. the influence of molybdenum and sulphur on sheep receiving high ...

    African Journals Online (AJOL)

    THE INFLUENCE OF MOLYBDENUM AND SULPHUR ON SHEEP RECEIVING HIGH LEVELS. OF COPPER AND BROILER LITTER IN THEIR RATIONS. Receipr of MS 06-09-1978. J.B.J. van RYSSEN. Department of Animol Science, University of Natal, Pietermoritzburg, 3200. (Key words: Molybdenum, sulphur, copper ...

  20. Dioxobridged complexes of molybdenum (IV) and tungsten (IV) with ...

    Indian Academy of Sciences (India)

    Abstract. Six new dioxobridged complexes of molybdenum (IV) and tungsten (IV) with N-alkylphenothiazines having the general formula M2O4(L)2(H2O)2 [where M = molybdenum or tungsten and L = N-alkylphenothiazines] have been synthesised. The complexes have been characterised on the basis of analytical, molar ...

  1. Study of molybdenum precipitation in steels using thermoelectric power measurement

    Energy Technology Data Exchange (ETDEWEB)

    Houze, Marc [INSA LYON, GEMPPM, UMR CNRS 5510, Bat Blaise Pascal, 20 Avenue A. Einstein, 69621 Villeurbanne Cedex (France); Kleber, Xavier [INSA LYON, GEMPPM, UMR CNRS 5510, Bat Blaise Pascal, 20 Avenue A. Einstein, 69621 Villeurbanne Cedex (France)]. E-mail: xavier.kleber@insa-lyon.fr; Fouquet, Francis [INSA LYON, GEMPPM, UMR CNRS 5510, Bat Blaise Pascal, 20 Avenue A. Einstein, 69621 Villeurbanne Cedex (France); Delnondedieu, Marc [EDF R and D, MMC, Ecuelles BP 1, 77818 Moret-sur-Loing Cedex (France)

    2004-12-15

    The precipitation of molybdenum in iron has been investigated using thermoelectric power measurement. We found an increase of the thermoelectric power of iron with the molybdenum content and a coefficient of its influence has been determined. A correlation between secondary hardening due to the precipitation of Mo{sub 2}C carbides and thermoelectric power variations has been established.

  2. Behaviour of helium after implantation in molybdenum

    Energy Technology Data Exchange (ETDEWEB)

    Viaud, C. [Commissariat a l' Energie Atomique (CEA), Cadarache (France)], E-mail: viaud@dircad.cea.fr; Maillard, S.; Carlot, G.; Valot, C. [Commissariat a l' Energie Atomique (CEA), Cadarache (France); Gilabert, E. [Chimie Nucleaire Analytique and Bio-environnementale (CNAB), Gradignan (France); Sauvage, T. [CEMHTI-CNRS, Orleans (France); Peaucelle, C.; Moncoffre, N. [Institut de Physique Nucleaire de Lyon (IPNL), Lyon (France)

    2009-03-31

    This study deals with the behaviour of helium in a molybdenum liner dedicated to the retention of fission products. More precisely this work contributes to evaluate the release of implanted helium when the gas has precipitated into nanometric bubbles close to the free surface. A simple model dedicated to calculate the helium release in such a condition is presented. The specificity of this model lays on the assumption that the gas is in equilibrium with a simple distribution of growing bubbles. This effort is encouraging since the calculated helium release fits an experimental dataset with a set of parameters in good agreement with the literature.

  3. Electrochemical ammonia production on molybdenum nitride nanoclusters

    DEFF Research Database (Denmark)

    Howalt, Jakob Geelmuyden; Vegge, Tejs

    2013-01-01

    energy profile for electrochemical protonation of N2 and N adatoms on cuboctahedral Mo13 nanoparticles. Pathways for electrochemical ammonia production via direct protonation of N adatoms and N2 admolecules with an onset potential as low as -0.5 V and generally lower than -0.8 V on both a nitrogen......Theoretical investigations of electrochemical production of ammonia at ambient temperature and pressure on nitrogen covered molybdenum nanoparticles are presented. Density functional theory calculations are used in combination with the computational hydrogen electrode approach to calculate the free...

  4. Low-molecular-weight oxidants involved in disulfide bond formation.

    Science.gov (United States)

    Ruddock, Lloyd W

    2012-05-15

    The biogenesis of most secreted and outer membrane proteins involves the formation of structure stabilizing disulfide bonds. Hence knowledge of the mechanisms for their formation is critical for understanding a myriad of cellular processes and associated disease states. Until recently it was thought that members of the Ero1 sulfhydryl oxidase family were responsible for catalyzing the majority of disulfide bond formation in the endoplasmic reticulum. However, multiple eukaryotic organisms are now known to show no or minor phenotypes when these enzymatic pathways are disrupted, suggesting that other pathways can catalyze disulfide bond formation to an extent sufficient to maintain normal physiology. This lack of a strong phenotype raises multiple questions regarding what pathways are acting and whether they themselves constitute the major route for disulfide bond formation. This review critically examines the potential low molecular oxidants that maybe involved in the catalyzed or noncatalyzed formation of disulfide bonds, with an emphasis on the mammalian endoplasmic reticulum, via an examination of their thermodynamics, kinetics, and availability and gives pointers to help guide future experimental work.

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

    Science.gov (United States)

    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

  6. Chill block melt spinning of nickel-molybdenum alloys

    Science.gov (United States)

    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.

  7. Low molecular mass thiols, disulfides and protein mixed disulfides in rat tissues: influence of sample manipulation, oxidative stress and ageing.

    Science.gov (United States)

    Giustarini, Daniela; Dalle-Donne, Isabella; Milzani, Aldo; Rossi, Ranieri

    2011-04-01

    Most of the data in studies investigating the contribution of oxidative stress to some human diseases and to ageing derive from measurements carried out in blood, on the basis of the assumption that any alteration of the hematic thiol/disulfide balance should reflect a corresponding alteration in other less accessible tissues. But it is evident that the information that can be gleaned from a direct analysis in specific tissues is largely greater. Nevertheless, the accurate measurement of disulfides is frequently hampered by the artifactual oxidation occurring during sample manipulation as a consequence of the presence of heme-proteins. Therefore, the levels of disulfide forms of low molecular mass thiols in tissues are still poorly investigated, even if their measurements could represent a powerful index of the oxidative status. Here we have used an artifact-free procedure to measure low molecular mass thiols and their disulfides in different rat tissues. Our findings suggest that disulfides are a reliable biomarker of even slight oxidative damage. In tissues of aged rats we observed that either oxidative stress or glutathione depletion alone can occur in different tissues during ageing. Interestingly, among the investigated thiols, only homocysteine showed a tendency to increase in some organs with ageing. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  8. Chemical shift and coupling constant analysis of dibenzyloxy disulfides.

    Science.gov (United States)

    Stoutenburg, Eric G; Gryn'ova, Ganna; Coote, Michelle L; Priefer, Ronny

    2015-02-05

    Dialkoxy disulfides have found applications in the realm of organic synthesis as an S2 or alkoxy donor, under thermal and photolytic decompositions conditions, respectively. Spectrally, dibenzyloxy disulfides possess an ABq in the (1)H NMR, which can shift by over 1.1ppm depending on the substituents present on the aromatic ring, as well as the solvent employed. The effect of the said substituents and solvent were analyzed and compared to the center of the ABq, geminal coupling, and the differences in chemical shifts of the individual doublets. Additionally, quantum-chemical calculations demonstrated the intramolecular H-bonding arrangement, found within the dibenzyloxy disulfides. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Quantifying the global cellular thiol-disulfide status

    DEFF Research Database (Denmark)

    Hansen, Rosa E; Roth, Doris; Winther, Jakob R

    2009-01-01

    It is widely accepted that the redox status of protein thiols is of central importance to protein structure and folding and that glutathione is an important low-molecular-mass redox regulator. However, the total cellular pools of thiols and disulfides and their relative abundance have never been...... determined. In this study, we have assembled a global picture of the cellular thiol-disulfide status in cultured mammalian cells. We have quantified the absolute levels of protein thiols, protein disulfides, and glutathionylated protein (PSSG) in all cellular protein, including membrane proteins. These data...... cell types. However, when cells are exposed to a sublethal dose of the thiol-specific oxidant diamide, PSSG levels increase to >15% of all protein cysteine. Glutathione is typically characterized as the "cellular redox buffer"; nevertheless, our data show that protein thiols represent a larger active...

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

    Energy Technology Data Exchange (ETDEWEB)

    Bertuch, Adam, E-mail: abertuch@ultratech.com; Sundaram, Ganesh [Ultratech/Cambridge NanoTech, 130 Turner Street, Waltham, Massachusetts 02453 (United States); Saly, Mark; Moser, Daniel; Kanjolia, Ravi [SAFC Hitech, 1429 Hilldale Avenue, Haverhill, Massachusetts 01832 (United States)

    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.

  11. The extended family of hexagonal molybdenum oxide

    Energy Technology Data Exchange (ETDEWEB)

    Hartl, Monika [Los Alamos National Laboratory; Daemen, Luke [Los Alamos National Laboratory; Lunk, J H [NON LANL; Hartl, H [NON LANL; Frisk, A T [NON LANL; Shendervich, I [NON LANL; Mauder, D [NON LANL; Feist, M [NON LANL; Eckelt, R [NON LANL

    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.

  12. Structures and related properties of helical, disulfide-stabilized peptides

    Energy Technology Data Exchange (ETDEWEB)

    Pagel, Mark D. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1993-11-01

    The three dimensional structure of several peptides were determined by NMR spectroscopy and distance geometry calculations. Each peptide formed a predictable, rigid structure, consisting of an α-helix, a "scaffold" region which packed along one face of the helix, and two disulfide bridges which covalently connect the helix and scaffold regions. The peptide Apa-M5 was designed to constrain the M5 peptide from MLCK in a helical geometry using the apamin disulfide scaffold. This scaffold constrains the N- terminal end of the helix with two disulfide bridges and a reverse turn. Like the M5 peptide, Apa-M5 was found to bind calmodulin in a Ca2+-dependent 1:1 stoichiometry. However, the dissociation constant of the (Apa-M5)-calmodulin complex, 107 nM, was 100-fold higher than the dissociation constant of the M5-calmodulin complex. This difference was due to a putative steric overlap between the Apa-M5 scaffold and calmodulin. The peptide Apa-Cro was designed to replace the large structural protein matrix of λ Cro with the apamin disulfide scaffold. However, Apa-Cro did not bind the consensus DNA operator half-site of λ Cro, probably due to a steric overlap between the Apa-Cro disulfide framework and the DNA. The amino acid sequence of the scaffold-disulfide bridge arrangement of the peptide Max was derived from the core sequence of scyllatoxin, which contains an α-helix constrained at the C-terminal end by two disulfide bridges and a two-stranded βsheet scaffold. Max was shown to fold with >84% yield to form a predictable, stable structure that is similar to scyllatoxin. The folding and stability properties of Max make this scaffold and disulfide bridge arrangement an ideal candidate for the development of hybrid sequence peptides. The dynamics of a fraying C-terminal end of the helix of the peptide Apa-AlaN was determined by analysis of 15N NMR relaxation properties.

  13. Microplastic relaxations of single and polycrystalline molybdenum

    Energy Technology Data Exchange (ETDEWEB)

    Pichl, W.; Weiss, B. [Wien Univ. (Austria). Inst. fuer Materialphysik; Chen, D.L.

    1998-05-01

    The microplasticity of high-purity molybdenum single crystals and of Mo polycrystals of technical purity has been investigated by relaxation step tests in uniaxial compression. A new model for the evaluation of relaxation tests in the microplastic range of b.c.c metals is presented which takes into account the decrease of the mobile dislocation density due to exhaustion of non-screw dislocations. The model allows an independent determination of the activation volume and of the microstructure parameters controlling dislocation exhaustion. The results indicate that in the high-purity single crystals the deformation rate is controlled by interactions of non-screw dislocations with the grown-in network. In the polycrystals additional interactions with impurity atoms seem to occur. In the single crystals the activity and subsequent exhaustion of two different glide systems was observed, followed by a gradual onset of screw dislocation motion. (orig.) 26 refs.

  14. Simulations of intergranular fracture in nanocrystalline molybdenum

    DEFF Research Database (Denmark)

    Frederiksen, Søren Lund; Jacobsen, Karsten Wedel; Schiøtz, Jakob

    2004-01-01

    with density-functional calculations. The simulations show the plastic deformation to involve both grain boundary processes and dislocation migration which in some cases lead to twin boundary formation. A large component of the strain is accommodated through the formation of cracks in the grain boundaries......Using molecular dynamics simulations we investigate the plastic deformation of nanocrystalline molybdenum with a grain size of 12 nm at high strain rates. The simulations are performed with an interatomic potential which is obtained through matching of atomic forces to a database generated....... This behavior is very different from what has been seen earlier in simulations of fee metals where grain boundary sliding is the dominant mechanism for very small grain sizes. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved....

  15. Chemical and Photochemical Reactions of Thioctic Acid and RelatedDisulfides

    Energy Technology Data Exchange (ETDEWEB)

    Calvin, Melvin

    1954-06-10

    The carbon cycle of photosynthesis is briefly reviewed in its entirety and the experiments involving it which led to the implication of disulfide rupture in photosynthesis are indicated. A review of the organic, physical and photochemistry of disulfides, with particular reference to the five-membered disulfide rings as they appear in thioctic acid, is given.

  16. Disulfide-containing poly (beta-amino ester)s for gene delivery

    NARCIS (Netherlands)

    Lin, C.; Hennink, W.E.; Lammens, T.M.; Feijen, J.; Zhong, Zhiyuan; Sam, T; Gu, H.; Lok, M.C.; Jiang, X.; Feijen, Jan; Engbersen, Johannes F.J.

    2006-01-01

    A group of new disulfide-containing poly(β-amino ester)s was synthesized and evaluated as non-viral gene delivery vectors. These linear polymers were obtained by Michael addition of a number of selected amines to bis(2-acryloyloxyethyl) disulfide. It was shown that the disulfide-containing

  17. GEMAS: Molybdenum Spatial Distribution Patterns in European Soil

    Science.gov (United States)

    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 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 absorption by the animal.

  18. Innovative Molybdenum Alloy for Extreme Operating Conditions Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Molybdenum has been identified as a promising material for many high temperature NASA applications due to its high melting temperature, resistance to liquid metals,...

  19. Recovering and recycling uranium used for production of molybdenum-99

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, Sean Douglas; May, Iain; Copping, Roy; Dale, Gregory Edward

    2017-12-12

    A processes for recycling uranium that has been used for the production of molybdenum-99 involves irradiating a solution of uranium suitable for forming fission products including molybdenum-99, conditioning the irradiated solution to one suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina. Another process involves irradiation of a solid target comprising uranium, forming an acidic solution from the irradiated target suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina.

  20. Binary and Ternary Explorations of the Molybdenum Boride System

    OpenAIRE

    Dismukes, Avalon Hope

    2015-01-01

    Refractory metal borides have recently generated intense interest in materials chemistry. These compounds have been shown to possess many advantageous properties, such as exceptionally high hardness, electrical conductivity, and even superconductivity. Higher molybdenum borides are discussed as compounds of interest in this category of materials. However, the complex phase relationships in the molybdenum-boron system complicate the preparation of phase-pure samples. MoB2 and Mo2B4 have both b...

  1. Alpha-cyclodextrins reversibly capped with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Kumprecht, Lukáš; Buděšínský, Miloš; Bouř, Petr; Kraus, Tomáš

    2010-01-01

    Roč. 34, č. 10 (2010), s. 2254-2260 ISSN 1144-0546 R&D Projects: GA AV ČR IAA400550810 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclodextrin s * disulfide bond * dynamic covalent bond Subject RIV: CC - Organic Chemistry Impact factor: 2.631, year: 2010

  2. Metal-free oxidative coupling of thiols to disulfides using ...

    Indian Academy of Sciences (India)

    SiO2OSO3H) as a new oxidizing system is able to oxidize a variety of aliphatic or aromatic thiols to the corresponding disulfides. The process reported here is operationally simple, environmentally benign and reactions have been mildly and ...

  3. Metal-free oxidative coupling of thiols to disulfides using ...

    Indian Academy of Sciences (India)

    454. Arash Ghorbani-Choghamarani et al. Table 1. Oxidative coupling of thiols to the corresponding disulfides using combination of guanidinium nitrate I or nitro urea II in the presence of silica sulfuric acid III in dichloromethane at room temperature. Entry. Substrate. Product. Substrate/Reagents (mmol)a. Time. Yield. Mp (.

  4. Impaired Thiol-Disulfide Balance in Acute Brucellosis.

    Science.gov (United States)

    Kolgelier, Servet; Ergin, Merve; Demir, Lutfi Saltuk; Inkaya, Ahmet Cagkan; Aktug Demir, Nazlim; Alisik, Murat; Erel, Ozcan

    2017-05-24

    The objective of this study was to examine a novel profile: thiol-disulfide homeostasis in acute brucellosis. The study included 90 patients with acute brucellosis, and 27 healthy controls. Thiol-disulfide profile tests were analyzed by a recently developed method, and ceruloplasmin levels were determined. Native thiol levels were 256.72 ± 48.20 μmol/L in the acute brucellosis group and 461.13 ± 45.37 μmol/L in the healthy group, and total thiol levels were 298.58 ± 51.78 μmol/L in the acute brucellosis group and 504.83 ± 51.05 μmol/L in the healthy group (p brucellosis than in the healthy controls (p brucellosis. The strong associations between thiol-disulfide parameters and a positive acute-phase reactant reflected the disruption of the balance between the antioxidant and oxidant systems. Since thiol groups act as anti-inflammatory mediators, the alteration in the thiol-disulfide homeostasis may be involved in brucellosis.

  5. Fmoc-based synthesis of disulfide-rich cyclic peptides.

    Science.gov (United States)

    Cheneval, Olivier; Schroeder, Christina I; Durek, Thomas; Walsh, Phillip; Huang, Yen-Hua; Liras, Spiros; Price, David A; Craik, David J

    2014-06-20

    Disulfide-rich cyclic peptides have exciting potential as leads or frameworks in drug discovery; however, their use is faced with some synthetic challenges, mainly associated with construction of the circular backbone and formation of the correct disulfides. Here we describe a simple and efficient Fmoc solid-phase peptide synthesis (SPPS)-based method for synthesizing disulfide-rich cyclic peptides. This approach involves SPPS on 2-chlorotrityl resin, cyclization of the partially protected peptide in solution, cleavage of the side-chain protecting groups, and oxidization of cysteines to yield the desired product. We illustrate this method with the synthesis of peptides from three different classes of cyclic cystine knot motif-containing cyclotides: Möbius (M), trypsin inhibitor (T), and bracelet (B). We show that the method is broadly applicable to peptide engineering, illustrated by the synthesis of two mutants and three grafted analogues of kalata B1. The method reduces the use of highly caustic and toxic reagents and is better suited for high-throughput synthesis than previously reported methods for producing disulfide-rich cyclic peptides, thus offering great potential to facilitate pharmaceutical optimization of these scaffolds.

  6. Computational design of disulfide cyclic peptide as potential ...

    African Journals Online (AJOL)

    This research studied and evaluated the interaction of ligands and the enzyme in the hydrate state using molecular dynamics simulations at two different temperatures. Simulations were performed using two disulfide cyclic peptide inhibitors KRK and RKR, along with one linear peptide Bz-Nle-K-R-R-H as standard ligand.

  7. A simplified approach to disulfide connectivity prediction from protein sequences

    Science.gov (United States)

    Vincent, Marc; Passerini, Andrea; Labbé, Matthieu; Frasconi, Paolo

    2008-01-01

    Background Prediction of disulfide bridges from protein sequences is useful for characterizing structural and functional properties of proteins. Several methods based on different machine learning algorithms have been applied to solve this problem and public domain prediction services exist. These methods are however still potentially subject to significant improvements both in terms of prediction accuracy and overall architectural complexity. Results We introduce new methods for predicting disulfide bridges from protein sequences. The methods take advantage of two new decomposition kernels for measuring the similarity between protein sequences according to the amino acid environments around cysteines. Disulfide connectivity is predicted in two passes. First, a binary classifier is trained to predict whether a given protein chain has at least one intra-chain disulfide bridge. Second, a multiclass classifier (plemented by 1-nearest neighbor) is trained to predict connectivity patterns. The two passes can be easily cascaded to obtain connectivity prediction from sequence alone. We report an extensive experimental comparison on several data sets that have been previously employed in the literature to assess the accuracy of cysteine bonding state and disulfide connectivity predictors. Conclusion We reach state-of-the-art results on bonding state prediction with a simple method that classifies chains rather than individual residues. The prediction accuracy reached by our connectivity prediction method compares favorably with respect to all but the most complex other approaches. On the other hand, our method does not need any model selection or hyperparameter tuning, a property that makes it less prone to overfitting and prediction accuracy overestimation. PMID:18194539

  8. A simplified approach to disulfide connectivity prediction from protein sequences

    Directory of Open Access Journals (Sweden)

    Frasconi Paolo

    2008-01-01

    Full Text Available Abstract Background Prediction of disulfide bridges from protein sequences is useful for characterizing structural and functional properties of proteins. Several methods based on different machine learning algorithms have been applied to solve this problem and public domain prediction services exist. These methods are however still potentially subject to significant improvements both in terms of prediction accuracy and overall architectural complexity. Results We introduce new methods for predicting disulfide bridges from protein sequences. The methods take advantage of two new decomposition kernels for measuring the similarity between protein sequences according to the amino acid environments around cysteines. Disulfide connectivity is predicted in two passes. First, a binary classifier is trained to predict whether a given protein chain has at least one intra-chain disulfide bridge. Second, a multiclass classifier (plemented by 1-nearest neighbor is trained to predict connectivity patterns. The two passes can be easily cascaded to obtain connectivity prediction from sequence alone. We report an extensive experimental comparison on several data sets that have been previously employed in the literature to assess the accuracy of cysteine bonding state and disulfide connectivity predictors. Conclusion We reach state-of-the-art results on bonding state prediction with a simple method that classifies chains rather than individual residues. The prediction accuracy reached by our connectivity prediction method compares favorably with respect to all but the most complex other approaches. On the other hand, our method does not need any model selection or hyperparameter tuning, a property that makes it less prone to overfitting and prediction accuracy overestimation.

  9. [Effects of carbon disulfide on cardiovascular system of workers occupationally exposed to carbon disulfide].

    Science.gov (United States)

    Li, Kui-rong; Wang, Si-hua; Wang, Jing; Su, Dong-mei; Gu, Gui-zhen; Cui, Shou-ming; Yu, Shan-fa

    2012-06-01

    To study the effects of long-term exposure to carbon disulfide (SC(2)) on cardiovascular system of workers. The concentrations of CS(2) were detected in the representative workshops with different exposure levels. The indicators related to cardiovascular system were tested in 633 workers occupationally exposed to CS(2), which included blood pressure, electrocardiogram, blood routine (blood RT), cholesterol (TCHO), triglyceride (TG) and so on. The data were analyzed by chi-square test and multiple logistic regression analysis. The exposure concentration of CS(2) for 389 workers was less than or equal to 5 mg/m(3), which for other 244 workers was higher than 5 mg/m(3). The maximum exposure concentration of CS(2) was 15.73 mg/m(3). There were no significant effects of CS(2) on the electrocardiogram, red blood cells, white blood cells, blood platelet, TCHO and TG of workers. However, the positive effects of CS(2) on blood pressure and negative effects of CS(2) on hemoglobin were found. The rates of high TCHO, TG and hypertension in male workers were significantly higher than those in female workers (P 30 years old) (P cardiovascular system of workers.

  10. Chemical methods for producing disulfide bonds in peptides and proteins to study folding regulation.

    Science.gov (United States)

    Okumura, Masaki; Shimamoto, Shigeru; Hidaka, Yuji

    2014-04-01

    Disulfide bonds play a critical role in the folding of secretory and membrane proteins. Oxidative folding reactions of disulfide bond-containing proteins typically require several hours or days, and numerous misbridged disulfide isomers are often observed as intermediates. The rate-determining step in refolding is thought to be the disulfide-exchange reaction from nonnative to native disulfide bonds in folding intermediates, which often precipitate during the refolding process because of their hydrophobic properties. To overcome this, chemical additives or a disulfide catalyst, protein disulfide isomerase (PDI), are generally used in refolding experiments to regulate disulfide-coupled peptide and protein folding. This unit describes such methods in the context of the thermodynamic and kinetic control of peptide and protein folding, including (1) regulation of disulfide-coupled peptides and protein folding assisted by chemical additives, (2) reductive unfolding of disulfide-containing peptides and proteins, and (3) regulation of disulfide-coupled peptide and protein folding using PDI. Copyright © 2014 John Wiley & Sons, Inc.

  11. Kinetic analysis of the mechanism and specificity of protein-disulfide isomerase using fluorescence-quenched peptides

    DEFF Research Database (Denmark)

    Westphal, V; Spetzler, J C; Meldal, M

    1998-01-01

    Protein-disulfide isomerase (PDI) is an abundant folding catalyst in the endoplasmic reticulum of eukaryotic cells. PDI introduces disulfide bonds into newly synthesized proteins and catalyzes disulfide bond isomerizations. We have synthesized a library of disulfide-linked fluorescence-quenched...

  12. Evaluation of dynamic thiol-disulfide homeostasis in very low-birth-weighted preterms.

    Science.gov (United States)

    Unal, Sezin; Ulubas Isik, Dilek; Bas, Ahmet Yagmur; Erol, Sara; Arifoglu, İlter; Alisik, Murat; Erel, Ozcan; Demirel, Nihal

    2017-11-13

    Thiols are organic compounds containing sulfhydryl groups which exert antioxidant effects via dynamic thiol-disulfide homeostasis. The shift towards disulfides indicates the presence of oxidative environment. Thiol-disulfide homeostasis has not been evaluated in neonates. We aimed to evaluate dynamic thiol-disulfide homeostasis in preterm infants. Preterm infants with birth weight less than 1500 g (25-32 weeks of gestation) were included. Infants with major congenital anomaly, perinatal asphyxia, twin to twin transfusion and infants who were mechanically ventilated and nil by mouth for more than 3 days or fed with formula, had intraventricular hemorrhage ≥ grade 2 or sepsis, received blood/blood product transfusion or inotrope treatment and developed bronchopulmonary dysplasia or retinopathy of prematurity (≥ stage 3), and died were excluded thereafter. Serum thiol-disulfide homeostasis was evaluated for three times: (Baseline, first week, third week). Serum native thiol, total thiol and disulfide were measured (µmol/Lt), disulfide:native thiol, disulfide:total thiol, and native thiol:total thiol ratios were calculated. Wilcoxon's test was used to analyze the significance of change in measurements. Baseline results were analyzed for gender and mode of delivery. Eighty preterm infants [1255 (1080-1415) grams] were included. Baseline values were native thiol: 209.54 ± 41.83 µmol/L; total thiol: 251.70 ± 45.82 µmol/L; disulfide: 21.08 ± 7.43 µmol/Lt; disulfide:native thiol: 10.49 ± 4.62; disulfide:total thiol: 8.45 ± 2.93; native thiol:total thiol: 83.10 ± 5.87. Thiol levels increased in each measurement, disulfide and disulfide/thiol ratios increased in the first week, decreased in the third week, ratio of native/total thiol decreased in the first week, increased in the third week. No effect of gender or mode of delivery on baseline thiol-disulfide homeostasis was detected. The shift in the thiol-disulfide equilibrium

  13. A molybdenum-isotope perspective on Phanerozoic deoxygenation events

    Science.gov (United States)

    Dickson, Alexander J.

    2017-10-01

    The expansion and contraction of sulfidic depositional conditions in the oceans can be tracked with the isotopic composition of molybdenum in marine sediments. However, molybdenum-isotope data are often subject to multiple conflicting interpretations. Here I present a compilation of molybdenum-isotope data from three time intervals: the Toarcian Oceanic Anoxic Event about 183 million years ago, Oceanic Anoxic Event 2 about 94 million years ago, and two early Eocene hyperthermal events from 56 to 54 million years ago. A comparison of data from sites located in different hydrographic settings tightly constrains the molybdenum cycle for these intervals, allowing a direct comparison of the expanse of sulfidic conditions in each interval compared to today. Nonetheless, tracing rates of redox change over such rapid climatic events using molybdenum isotopes remains challenging. Future efforts to achieve this goal might be accomplished by analysing specific mineral phases, using complementary redox-sensitive geochemical techniques and by linking isotopic observations with Earth system modelling. Such improvements will make it possible to more fully assess the links between ocean deoxygenation, climatic and oceanographic changes, and biotic turnover.

  14. Reactive copolymers based on N-vinyl lactams with pyridyl disulfide side groups via RAFT polymerization and postmodification via thiol-disulfide exchange reaction

    NARCIS (Netherlands)

    Peng, Huan; Rübsam, Kristin; Huang, Xiaobin; Jakob, Felix; Karperien, Marcel; Schwaneberg, Ulrich; Pich, Andrij

    2016-01-01

    Herein, we report the synthesis of a series of novel pyridyl disulfide (PDS)-functionalized statistical reactive copolymers that enable facile access to complex polymeric architectures through highly selective thiol-disulfide exchange reaction with thiol-containing ligands or proteins. Functional

  15. The Variation of Disulfides in the Progression of Type 2 Diabetes Mellitus.

    Science.gov (United States)

    Ergin, Merve; Aydin, Cevdet; Yurt, Emine Feyza; Cakir, Bekir; Erel, Ozcan

    2018-01-29

    The purpose of this study was to examine thiol-disulfide balance in patients with type 2 diabetes mellitus. This study included 32 subjects with known type 2 diabetes mellitus without complications, 30 patients with type 2 diabetes mellitus with complications, 28 newly diagnosed patients with type 2 diabetes mellitus, and 45 healthy individuals. Thiol-disulfide profile tests were quantified in all groups. Compared to the control group, patients in each of the diabetic groups had significantly lower native and total thiol levels, higher disulfide levels, and higher disulfide/native thiol and disulfide/total thiol ratios (p<0.05 for all). Disulfide levels were significantly lower in the newly diagnosed group than in other diabetic groups (p<0.05). There were significant associations between glycemic parameters and thiol-disulfide tests (p<0.05). A disequilibrium between thiol-disulfide pairs occurs in patients with type 2 diabetes mellitus, and a gradual increase to disulfide levels may contribute to the disease's severity. Deteriorated thiol-disulfide homeostasis may be relevant to the pathophysiology of type 2 diabetes mellitus. © Georg Thieme Verlag KG Stuttgart · New York.

  16. A degradable polydopamine coating based on disulfide-exchange reaction

    Science.gov (United States)

    Hong, Daewha; Lee, Hojae; Kim, Beom Jin; Park, Taegyun; Choi, Ji Yu; Park, Matthew; Lee, Juno; Cho, Hyeoncheol; Hong, Seok-Pyo; Yang, Sung Ho; Jung, Sun Ho; Ko, Sung-Bo; Choi, Insung S.

    2015-11-01

    Although the programmed degradation of biocompatible films finds applications in various fields including biomedical and bionanotechnological areas, coating methods have generally been limited to be substrate-specific, not applicable to any kinds of substrates. In this paper, we report a dopamine derivative, which allows for both universal coating of various substrates and stimuli-responsive film degradation, inspired by mussel-adhesive proteins. Two dopamine moieties are linked together by the disulfide bond, the cleavage of which enables the programmed film degradation. Mechanistic analysis of the degradable films indicates that the initial cleavage of the disulfide linkage causes rapid uptake of water molecules, hydrating the films, which leads to rapid degradation. Our substrate-independent coating of degradable films provides an advanced tool for drug delivery systems, tissue engineering, and anti-fouling strategies.Although the programmed degradation of biocompatible films finds applications in various fields including biomedical and bionanotechnological areas, coating methods have generally been limited to be substrate-specific, not applicable to any kinds of substrates. In this paper, we report a dopamine derivative, which allows for both universal coating of various substrates and stimuli-responsive film degradation, inspired by mussel-adhesive proteins. Two dopamine moieties are linked together by the disulfide bond, the cleavage of which enables the programmed film degradation. Mechanistic analysis of the degradable films indicates that the initial cleavage of the disulfide linkage causes rapid uptake of water molecules, hydrating the films, which leads to rapid degradation. Our substrate-independent coating of degradable films provides an advanced tool for drug delivery systems, tissue engineering, and anti-fouling strategies. Electronic supplementary information (ESI) available: Synthesis, characterization, and other additional details. See DOI: 10

  17. Quantification of small cyclic disulfide-rich peptides.

    Science.gov (United States)

    Conibear, Anne C; Daly, Norelle L; Craik, David J

    2012-01-01

    Cyclic disulfide-rich peptides ranging in size from ∼14 to 29 amino acids have been found in a wide variety of organisms and have exciting biological and medicinal applications due to their stability and structure. Many of these peptides can be chemically synthesized, but their small size and limited number of chromophore-containing amino acids make them difficult to quantify by methods routinely used for large proteins. A comparison of the precision and accuracy of gravimetric, UV- and NMR-based methods in current use for the quantification of small peptides is presented for a representative set of cyclic disulfide-rich peptides. The study shows that gravimetric and UV absorbance methods should be used with caution for small peptides and all methods should be carefully validated. For the routine quantification of small disulfide-rich peptides, we recommend comparison of the analytical reverse-phase high-performance liquid chromatography trace or UV absorbance at 214 nm with that of a standard peptide solution quantified by amino acid analysis. An accurate quantification method that is simple and cost effective will assist in comparison of inhibition and activity data between different laboratories and peptides and correct calculation of synthesis yields. Copyright © 2012 Wiley Periodicals, Inc.

  18. Molybdenum Cycling During Crust Formation and Destruction

    Science.gov (United States)

    Greaney, A. T.; Rudnick, R. L.

    2016-12-01

    Molybdenum geochemistry has become an important tool for tracking the redox state of the early atmosphere and oceans as well as the emergence and sustainability of Mo-cofactored enzymes. However, in order for Mo to be enriched in the oceans, it must first be weathered out of the crust. Sulfides that weather in the presence of atmospheric O2have historically been deemed the predominant crustal source of Mo. Here, we test this assumption by determining the mineralogical hosts of Mo in Archean, Proterozoic, and Phanerozoic upper crustal rocks, using LA-ICP-MS. We also investigate Mo behavior during igneous differentiation and continental crust formation. We find that molybdenite, MoS2, is a weatherable sulfide source of Mo, but common igneous sulfides are not because their Mo concentrations are too low. However, molybdenite is uncommon in the upper continental crust. By contrast, volcanic glass is much more abundant and is a significant weatherable source of Mo that readily breaks down to release oxidized, soluble Mo whether or not atmospheric O2is present. Other common crustal mineral hosts of Mo are Ti-bearing phases like titanite, ilmenite, magnetite, and rutile that are resistant to weathering. Significant Mo depletion (relative to Ce and Pr) is observed in nearly every granitic rock analyzed in our study, but is not observed in OIB or MORB (Jenner and O'Neill, 2012). There are two possible reasons for this: 1) Mo is removed from cooling plutons during fluid expulsion, or 2) Mo is fractionated during igneous differentiation. The first scenario is a likely explanation given the solubility of oxidized Mo. However, correlations between Mo/Ce and Nb/La in several plutonic suites suggest a fractionating phase like rutile may sequester Mo in the lower crust. Additionally, a correlation between Mo/Ce and inferred tectonic setting (enrichments observed in rift-related plutons) suggest an overall tectonic influence on the availability of Mo in the upper crust.

  19. High heat load test of molybdenum

    Energy Technology Data Exchange (ETDEWEB)

    Tanabe, T. (Faculty of Engineering, Osaka Univ., Suita (Japan)); Fujine, M.; Noguchi, H. (Daido Steel Co. Ltd., Nagoya (Japan)); Yagi, Y.; Hirano, Y.; Shimizu, H. (Electrotechnical Lab., Umezono, Tsukuba (Japan)); Akiba, M.; Araki, M. (Japan Atomic Energy Research Inst., Naka, Ibaraki (Japan)); Kubota, Y.; Miyahara, A. (National Inst. for Fusion Science, Nagoya (Japan))

    1993-03-01

    Three different types of molybdenum, powder metallurgical polycrystalline (PM-Mo), and as-forged polycrystalline and single crystalline of highly purified electron-beam-melted Mo (AFEB-Mo and SCEB-Mo), have been subjected to high heat load test with neutral beam injection (NBI) stands at Japan Atomic Energy Research Institute (JAERI) and National Institute for Fusion Science (NIFS). These materials have also been tested as a movable limiter in a reversed field pinch machine (RFP:TPE-1RM15) in Electrotechnical Laboratory (ETL). The results are summarized as follows. The SCEB-Mo shows the least damage with slight local melting after a very high heat load of 260 MW/m[sup 2] for 250 ms with NBI, while for the PM-Mo the whole irradiated area melt with many craters due to impurity gas evaporation under less heat load (200 ms). All movable limiter heads of the RFP are severely damaged with partial melting. The appearance of the SCEB-Mo limiter after melting is not good and shows the crystalline cleavage. However, SEM observation of the microstructure opposes the surface appearance. In the SCEB-Mo, appreciable recrystallization is not observed and hence no crack is seen to go into the bulk except the crystalline cleavage. In the PM-Mo, on the other hand, the resolidification to columnar grains as well as the recrystallization is apparent, and the cracks not only go along the columnar grains but also separate the recrystallized region from the matrix. In the AFEB-Mo, a slight grain growth occurs and several cracks enter deep along the grain boundaries. Thus the SCEB-Mo is a very nice plasma-facing material if used under the critical heat load for melting. (orig.).

  20. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

    Science.gov (United States)

    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.

  1. The behaviour of molybdenum dialkyldithiocarbamate friction modifier additives

    CERN Document Server

    Graham, J C H

    2001-01-01

    In recent years there has been growing concern to produce energy-efficient lubricated components and modem engine oil specifications require lubricants to demonstrate fuel efficiency in standardised engine tests. One important method of producing low friction and thus fuel-efficient lubricants is to use oil-soluble, molybdenum-containing, friction modifier additives. In optimal conditions these additives are able to produce very low friction coefficients, in the range 0.045 to 0.075 in boundary lubrication conditions. Very little is known about the chemical and physical mechanisms by which oil soluble molybdenum additives form low friction films in tribological contacts. Information about their activity could lead to optimal use of these additives in lubricants and, therefore, more efficient engine running. The work outlined in this thesis investigated the behaviour of oil-soluble molybdenum additives and showed that these additives were able to effectively reduce friction in the absence of other additives su...

  2. Supported molybdenum carbide for higher alcohol synthesis from syngas

    DEFF Research Database (Denmark)

    Wu, Qiongxiao; Christensen, Jakob Munkholt; Chiarello, Gian Luca

    2013-01-01

    carbide, while the selectivity to methanol follows the opposite trend. The effect of Mo2C loading on the alcohol selectivity at a fixed K/Mo molar ratio of 0.14 could be related to the amount of K2CO3 actually on the active Mo2C phase and the size, structure and composition of the supported carbide......Molybdenum carbide supported on active carbon, carbon nanotubes, and titanium dioxide, and promoted by K2CO3, has been prepared and tested for methanol and higher alcohol synthesis from syngas. At optimal conditions, the activity and selectivity to alcohols (methanol and higher alcohols) over...... supported molybdenum carbide are significantly higher compared to the bulk carbide. The CO conversion reaches a maximum, when about 20wt% Mo2C is loaded on active carbon. The selectivity to higher alcohols increases with increasing Mo2C loading on active carbon and reaches a maximum over bulk molybdenum...

  3. Molybdenum cofactor deficiency mimics cerebral palsy: differentiating factors for diagnosis.

    Science.gov (United States)

    Kikuchi, Kenjiro; Hamano, Shin-ichiro; Mochizuki, Hiroshi; Ichida, Kimiyoshi; Ida, Hiroyuki

    2012-08-01

    We describe an infant with molybdenum cofactor deficiency, initially diagnosed as cerebral palsy. Clinical features of molybdenum cofactor deficiency, e.g., neonatal seizures, hypertonus/hypotonus, and feeding and respiratory difficulties, resemble those of neonatal hypoxic-ischemic encephalopathy. Our patient, a 2-year-old boy, presented with spastic quadriplegia and mental retardation. He manifested intractable neonatal seizures and diffuse cerebral atrophy. When admitted with bronchitis at age 18 months, his uric acid levels in blood and urine were undetectable. A urinary sulfite test revealed positive results. Further tests revealed elevated urinary levels of xanthine, hypoxanthine, and S-sulfocystein. Sequencing of the MOCS2A gene revealed heterozygosity for c.[265T>C] + [266A>G], diagnosed as molybdenum cofactor deficiency type B. Neonatal seizures, progressive cerebral atrophy, and low serum levels of uric acid may provide diagnostic clues in patients with cerebral palsy of undetermined cause. Copyright © 2012 Elsevier Inc. All rights reserved.

  4. 10 CFR 35.2204 - Records of molybdenum-99, strontium-82, and strontium-85 concentrations.

    Science.gov (United States)

    2010-01-01

    ... 10 Energy 1 2010-01-01 2010-01-01 false Records of molybdenum-99, strontium-82, and strontium-85... 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...

  5. Molybdenum--substrate interactions in nitrogenase: an EXAFS study

    Energy Technology Data Exchange (ETDEWEB)

    Smith, J.P.

    1978-07-01

    The sensitivity of x-ray absorption edge spectra and extended x-ray absorption fine structure (EXAFS) to the environment of metal atoms make x-ray absorption spectroscopy a useful probe of the environment of the molybdenum in nitrogenase. It is of particular interest to investigate any perturbations of the environment of the molybdenum due to the presence of nitrogenase substrates. The results of measurements of the x-ray absorption spectra of nitrogenase samples by the absorption and fluorescence detection techniques are compared. The procedures used for the growth of Azotobacter vinelandii for the production of nitrogenase and the procedures used for the purification of nitrogenase are described in detail.

  6. A review of chromium, molybdenum, and tungsten alloys

    Science.gov (United States)

    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.

  7. [Xanthine oxidase deficiency (hereditary xanthinuria), molybdenum cofactor deficiency].

    Science.gov (United States)

    Sumi, S; Wada, Y

    1996-12-01

    Hereditary xanthinuria is a rare autosomal recessive disorder, with xanthine oxidase deficiency. Patients often display renal symptoms because they excrete a large amounts of xanthine in urine. An high-fluid-intake, alow-purine-food, and alkalinization of urine are effective in the patients. Molybdenum cofactor is essential for xanthine oxidase, sulfite oxidase and aldehyde oxidase. Patients with molybdenum cofactor deficiency display severe neurological symptoms, such as severe convulsions. The patients increase urinary excretions of xanthine and sulfite. Treatments are ineffective for neurological symptoms.

  8. Detection of disulfide bonds in bovine brain tubulin and their role in protein folding and microtubule assembly in vitro: a novel disulfide detection approach.

    Science.gov (United States)

    Chaudhuri, A R; Khan, I A; Ludueña, R F

    2001-07-31

    Cysteine residues in tubulin are actively involved in regulating ligand interactions and microtubule formation both in vivo and in vitro. These cysteine residues are sensitive reporters in determining the conformation of tubulin. Although some of the cysteines are critical in modulating drug binding and microtubule assembly, it is not clear how many of these normally exist as disulfides. The controversy regarding the disulfide bonds led us to develop a disulfide detection assay to reexamine the presence of the disulfide linkages in purified alphabeta tubulin and explore their possible biological functions in vitro. The accessible cysteine residues in alphabeta tubulin were alkylated with an excess of iodoacetamide to prevent artifactual generation of disulfide linkages in tubulin. After removal of excess iodoacetamide, tubulin was unfolded in 8 M urea. Half of the unfolded tubulin was treated with dithiothreitol to reduce any disulfide bonds present. The aliquots were then treated with iodo[(14)C]acetamide and the incorporation of radioactivity was measured. We also used the same approach to detect the disulfide linkages in the tubulin in a whole-cell extract. We found in both cases that the samples which were not treated with dithiothreitol had little or no incorporation of iodo[(14)C]acetamide, while the others that were treated with dithiothreitol had significant amounts of (14)C incorporation into tubulin. Moreover, the reduction of the disulfide linkages in tubulin resulted in inhibition of microtubule assembly (29-54%) and markedly affected refolding of the tubulin from both an intermediate and a completely unfolded state. All these data therefore suggest that tubulin has intrachain disulfide bonds in the alpha- and beta-subunits and that these disulfides assist in correct refolding of tubulin from the intermediate unfolded state or help to recover the hydrophobic domains from the completely unfolded state. These disulfides also regulate microtubule assembly

  9. Identification of thioredoxin target disulfides in proteins released from barley aleurone layers

    DEFF Research Database (Denmark)

    Hägglund, Per; Bunkenborg, J.; Yang, Fen

    2010-01-01

    Thioredoxins are ubiquitous disulfide reductases involved in a wide range of cellular processes including DNA synthesis, oxidative stress response and apoptosis. In cereal seeds thioredoxins are proposed to facilitate the germination process by reducing disulfide bonds in storage proteins and oth...... targets in the starchy endosperm. Here we have applied a thiol-specific labeling approach to identify specific disulfide targets of barley thioredoxin in proteins released from barley aleurone layers incubated in buffer containing gibberellic acid....

  10. Tungsten-molybdenum fractionation in estuarine environments

    Science.gov (United States)

    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 sequestration on river-borne particles and its subsequent release to sulfidic pore waters after the particles are deposited in the delta and become subject to reductive

  11. Corrosion Evaluation of RERTR Uranium Molybdenum Fuel

    Energy Technology Data Exchange (ETDEWEB)

    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

  12. Cortamidine oxide, a novel disulfide metabolite from the New Zealand basidiomycete (mushroom) Cortinarius species.

    Science.gov (United States)

    Nicholas, G M; Blunt, J W; Munro, M H

    2001-03-01

    Three disulfide metabolites were isolated from the fruiting bodies of the basidiomycete (mushroom) Cortinarius sp., collected in the Catlins, New Zealand. The structures of these compounds were determined as the unsymmetrical disulfide cortamidine oxide (1), 2,2'-dithiobis(pyridine N-oxide) (2), and the symmetrical disulfide 3. Both 1 and 2 showed significant antimicrobial activity and cytotoxicity. 2,2'-Dithiobis(pyridine N-oxide) (2) and the symmetrical disulfide 3 are assumed to be artifacts of the isolation procedure.

  13. Cleavage and formation of molecular dinitrogen in a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine.

    Science.gov (United States)

    Miyazaki, Takamasa; Tanaka, Hiromasa; Tanabe, Yoshiaki; Yuki, Masahiro; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-10-20

    The N≡N bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molecular dinitrogen induced by a pair of two different external stimuli using a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine under ambient conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Friction stir surfacing of cast A356 aluminium–silicon alloy with boron carbide and molybdenum disulphide powders

    Directory of Open Access Journals (Sweden)

    R. Srinivasu

    2015-06-01

    Full Text Available Good castability and high strength properties of Al–Si alloys are useful in defence applications like torpedoes, manufacture of Missile bodies, and parts of automobile such as engine cylinders and pistons. Poor wear resistance of the alloys is major limitation for their use. Friction stir processing (FSP is a recognized surfacing technique as it overcomes the problems of fusion route surface modification methods. Keeping in view of the requirement of improving wear resistance of cast aluminium–silicon alloy, friction stir processing was attempted for surface modification with boron carbide (B4C and molybdenum disulfide (MoS2 powders. Metallography, micro compositional analysis, hardness and pin-on-disc wear testing were used for characterizing the surface composite coating. Microscopic study revealed breaking of coarse silicon needles and uniformly distributed carbides in the A356 alloy matrix after FSP. Improvement and uniformity in hardness was obtained in surface composite layer. Higher wear resistance was achieved in friction stir processed coating with carbide powders. Addition of solid lubricant MoS2 powder was found to improve wear resistance of the base metal significantly.

  15. Storage and Bioavailability of Molybdenum in Soils Increased by Organic Matter Complexation

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. The oxidation product of molybdenum cofactor from milk xanthine oxidase

    NARCIS (Netherlands)

    van Spanning, R J; Wansell-Bettenhaussen, C W; Oltmann, L F; Stouthamer, A.H.

    In extracts of acid treated molybdenum cofactor containing xanthine oxidase, fluorescence is maximally developed upon a three hours incubation. Analysis by means of reversed phase HPLC revealed the presence of several fluorescent compounds, the main one being a blue fluorescent compound with an

  17. Research on the effect of phosphorus and molybdenum applications ...

    African Journals Online (AJOL)

    STORAGESEVER

    2008-05-02

    May 2, 2008 ... Research on the effect of phosphorus and molybdenum applications on the yield and yield parameters in lentil. (Lens culinaris Medic.) .... 0.020. 0.021. Organic matter (%)F. 1.81 ... fertilizer was applied in bands 3 cm below lentil rows. The lentil ..... A Critical Examination of a Rapid Method for. Determining ...

  18. Flexible Molybdenum Electrodes towards Designing Affinity Based Protein Biosensors.

    Science.gov (United States)

    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. Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

    Science.gov (United States)

    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.

  20. Growth of molybdenum disulphide using iodine as transport material

    Indian Academy of Sciences (India)

    In the present paper an attempt has been made to describe the chemical vapor transport (CVT) technique used for the growth of molybdenum disulphide (MoS2) single crystals. Iodine (I2) is used as transporting material for this purpose. The energy dispersive analysis by X-ray (EDAX) confirmed the stoichiometry of the ...

  1. Growth of molybdenum disulphide using iodine as transport material

    Indian Academy of Sciences (India)

    Abstract. In the present paper an attempt has been made to describe the chemical vapor transport (CVT) technique used for the growth of molybdenum disulphide (MoS2) single crystals. Iodine (I2) is used as transporting material for this purpose. The energy dispersive analysis by X-ray (EDAX) confirmed the stoichiometry ...

  2. Extraction and purification of molybdenum cofactor from milk xanthine oxidase

    NARCIS (Netherlands)

    van Spanning, R J; Wansell-Bettenhaussen, C W; Oltmann, L F; Stouthamer, A.H.

    1987-01-01

    Molybdenum cofactor (mocofactor) is extracted efficiently, free of impurities and in high concentrations, by acid treatment of xanthine oxidase and subsequent incubation of the precipitate with phosphate buffer containing EDTA, molybdate and oxygen. It is suggested that cofactor is bound to the

  3. Directional uv photoemission from (100) and (110) molybdenum surfaces

    DEFF Research Database (Denmark)

    Cinti, R. C.; Khoury, E. Al; Chakraverty, B. K.

    1976-01-01

    A study of the (100) and (110) molybdenum surfaces by directional photoemission spectroscopy is presented. Energy distribution spectra formed by photoelectrons emitted normal to the surfaces have been measured for photon energies between 10.2 and 21.2 eV. The results are discussed in terms of cal...

  4. Femtosecond laser surface structuring of molybdenum thin films

    Energy Technology Data Exchange (ETDEWEB)

    Kotsedi, L., E-mail: Kotsedi@tlabs.ac.za [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa); Mthunzi, P. [Council for Scientific and Industrial Research (CSIR), Biophotonics Lab: National Laser Centre Pretoria, 0001 (South Africa); Nuru, Z.Y. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa); Eaton, S.M. [Physics Department, Politecnico di Milano, Piazza Leonardo Da Vinci, 32, 20133 Milano (Italy); Center for Nano Science and Technology, Istituto Italiano di Tecnologia, Via Pascoli 70/3, 20133 Milano, Itala (Italy); Sechoghela, P.; Mongwaketsi, N. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa); Ramponi, R. [Institute for Photonics and Nanotechnologies (IFN)–CNR, Piazza Leanardo Da Vinci, 32, 20133 Milano (Italy); Maaza, M. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa)

    2015-10-30

    Highlights: • Color change of the molybdenum thin film from shinny to violet–yellowish color after laser irradiation at various laser powers. • Formation of the molybdenum dioxide coating after laser exposure, as confirmed by the X-ray diffraction spectrometry. • Selective solar absorbing nature of the laser exposed films. • Study of the binding energies is presented in this contribution using the XPS spectrometry. - Abstract: 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 MoO{sub x} 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 MoO{sub x}–Mo nanocomposite exhibited effective selective solar absorption in the UV–vis–IR spectral range.

  5. Visible light photocatalytic properties of novel molybdenum treated ...

    Indian Academy of Sciences (India)

    It was found that the photocatalytic degradation of a methylene blue solution could be attributed to the combined effects caused by the photo-degradation of titania, the electron assistance of carbon nanotube network, and the enhancement of molybdenum. The proposed redox mechanism of the photodegradation of ...

  6. Molybdenum incorporation in tungsten aldehyde oxidoreductase enzymes from Pyrococcus furiosus

    NARCIS (Netherlands)

    Sevcenco, A.M.; Bevers, L.E.; Pinkse, M.W.H.; Krijger, G.C.; Wolterbeek, H.T.; Verhaert, P.D.E.M.; Hagen, W.R.; Hagedoorn, P.L.

    2010-01-01

    The hyperthermophilic archaeon Pyrococcus furiosus expresses five aldehyde oxidoreductase (AOR) enzymes, all containing a tungsto-bispterin cofactor. The growth of this organism is fully dependent on the presence of tungsten in the growth medium. Previous studies have suggested that molybdenum is

  7. Research on the effect of phosphorus and molybdenum applications ...

    African Journals Online (AJOL)

    Lentil is one of the oldest domesticated crops grown and used mostly in human diets in Turkey. The trial was laid out in a factorial randomized complete block design with three replications. Sazak-91 lentil variety was applied at three different phosphorus levels (0, 30 and 60 kg ha-1) and four different molybdenum levels (0, ...

  8. Visible light photocatalytic properties of novel molybdenum treated ...

    Indian Academy of Sciences (India)

    Visible light photocatalytic properties of novel molybdenum treated carbon nanotube/titania composites. FENG-JUN ZHANG† and WON-CHUN OH. ∗. School of Materials and Chemical Engineering, Anhui University of Architecture, Anhui Hefei 230022,. P. R. China. †Department of Advanced Materials & Engineering, ...

  9. Rewiring Chemical Networks Based on Dynamic Dithioacetal and Disulfide Bonds.

    Science.gov (United States)

    Orrillo, A Gastón; La-Venia, Agustina; Escalante, Andrea M; Furlan, Ricardo L E

    2018-01-18

    The control of the connectivity between nodes of synthetic networks is still largely unexplored. To address this point we take advantage of a simple dynamic chemical system with two exchange levels that are mutually connected and can be activated simultaneously or sequentially. Dithioacetals and disulfides can be exchanged simultaneously under UV light in the presence of a sensitizer. Crossover reactions between both exchange processes produce a fully connected chemical network. On the other hand, the use of acid, base or UV light connects different nodes allowing network rewiring. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Molecular dynamics simulations of human serum albumin and role of disulfide bonds.

    Science.gov (United States)

    Castellanos, Maria Monica; Colina, Coray M

    2013-10-10

    Atomistic molecular dynamics simulations of human serum albumin in the presence and absence of disulfide bonds are presented. Simulations of 70 ns duration provide information on the relevance of disulfide bonds in the dynamics and structural conformation of HSA. Significant conformational changes are observed in the absence of disulfide bonds after 35 ns that could impact the functionality and stability of the protein. Changes in the secondary structure, hydrogen bonds, B factors, and cross-correlations reveal which disulfide bonds are important for keeping the secondary and tertiary structure and dynamics of the protein (e.g., Cys168-Cys177, Cys278-Cys289) and which have little effect on the local structure and dynamics (e.g., Cys200-Cys246, Cys461-Cys477). Removing all disulfide bonds in the protein appears to be a practical prescreening tool for identifying disulfide bonds relevant to structure and dynamics. In the absence of disulfide bonds, certain hydrogen bonds and correlated motions vanish, affecting the structure of neighboring residues. The structure of the primary binding sites of HSA is partially affected when disulfide bonds are removed. For the native structure, simulations clearly reveal the conformational changes that allow the only free cysteine to be exposed on the protein surface to form intermolecular disulfide bonds; this information could not be resolved from the static crystal structure alone. The absence of specific disulfide bonds could lead to partially unfolded structures; such structures are known to be prone to protein aggregation. Removing disulfide bonds could have similar consequences in other proteins of interest, such as immunoglobulin G.

  11. Complete Mapping of Complex Disulfide Patterns with Closely-Spaced Cysteines by In-Source Reduction and Data-Dependent Mass Spectrometry

    DEFF Research Database (Denmark)

    Cramer, Christian N; Kelstrup, Christian D; Olsen, Jesper V

    2017-01-01

    bonds are present in complicated patterns. This includes the presence of disulfide bonds in nested patterns and closely spaced cysteines. Unambiguous mapping of such disulfide bonds typically requires advanced MS approaches. In this study, we exploited in-source reduction (ISR) of disulfide bonds during...... of individual disulfide bonds could be done in species containing closely spaced disulfide bonds. The strength of this methodology was demonstrated by complete mapping of all four disulfide bonds in lysozyme and all 17 disulfide bonds in human serum albumin, including nested disulfide bonds and motifs...

  12. Kinetic and Thermodynamic Aspects of Cellular Thiol-Disulfide Redox Regulation

    DEFF Research Database (Denmark)

    Jensen, Kristine Steen; Hansen, Rosa Erritzøe; Winther, Jakob R

    2009-01-01

    that affect the rate of thiol-disulfide exchange and stability of disulfide bonds are discussed within the framework of the underlying chemical foundations. This includes the effect of thiol acidity (pKa), the local electrostatic environment, molecular strain and entropy. Even though a thiol...

  13. 21 CFR 520.1802 - Piperazine-carbon disulfide complex oral dosage forms.

    Science.gov (United States)

    2010-04-01

    ... HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS ORAL DOSAGE FORM NEW ANIMAL DRUGS § 520.1802 Piperazine-carbon disulfide complex oral dosage forms. ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Piperazine-carbon disulfide complex oral dosage...

  14. Extracellular Disulfide Bridges Serve Different Purposes in Two Homologous Chemokine Receptors, CCR1 and CCR5

    DEFF Research Database (Denmark)

    Rummel, Pia Cwarzko; Thiele, Stefanie; Hansen, Lærke Smidt

    2013-01-01

    In addition to the 7 transmembrane receptor (7TM)-conserved disulfide bridge between transmembrane (TM) helix 3 and extracellular loop (ECL)-2, chemokine receptors (CCR) contain a disulfide bridge between the N terminus and what previously was believed to be ECL-3. Recent crystal and NMR structur...

  15. Structural basis for target protein recognition by the protein disulfide reductase thioredoxin

    DEFF Research Database (Denmark)

    Maeda, Kenji; Hägglund, Per; Finnie, Christine

    2006-01-01

    of this mixed disulfide shows a conserved hydrophobic motif in thioredoxin interacting with a sequence of residues from BASI through van der Waals contacts and backbone-backbone hydrogen bonds. The observed structural complementarity suggests that the recognition of features around protein disulfides plays...

  16. Inhibition of carbon disulfide on bio-desulfurization in the process of ...

    African Journals Online (AJOL)

    Biological desulfurization is a novel technology for the removal of hydrogen sulfide from some biogas or sour gas, in which there are always a certain amounts of carbon disulfide together with much hydrogen sulfide. Nowadays, carbon disulfide is found to have negative effect on the biological desulfurization, but seldom ...

  17. Preparation of Vesicles and Nanoparticles of Amphiphilic Cyclodextrins Containing Labile Disulfide Bonds

    NARCIS (Netherlands)

    Nolan, Darren; Darcy, Raphael; Ravoo, B.J.

    2003-01-01

    Amphiphilic cyclodextrin derivatives were prepared in which a disulfide bond connects the hydrophobic substituents to the macrocycle. These compounds were obtained by 1,3-dicyclohexylcarbodiimide-mediated coupling reactions of heptakis(6-amino-6-deoxy)-B-cyclodextrins and disulfide-containing

  18. Diversity of the Epsilonproteobacteria Dsb (disulfide bond systems

    Directory of Open Access Journals (Sweden)

    Katarzyna Marta Bocian-Ostrzycka

    2015-06-01

    Full Text Available The bacterial proteins of the Dsb family – important components of the posttranslational protein modification system – catalyze the formation of disulfide bridges, a process that is crucial for protein structure stabilization and activity. Dsb systems play an essential role in the assembly of many virulence factors. Recent rapid advances in global analysis of bacteria have thrown light on the enormous diversity among bacterial Dsb systems. While the Escherichia coli disulfide bond-forming system is quite well understood, the mechanisms of action of Dsb systems in other bacteria, including members of class Epsilonproteobacteria that contain pathogenic and non-pathogenic bacteria colonizing extremely diverse ecological niches, are poorly characterized. Here we present a review of current knowledge on Epsilonproteobacteria Dsb systems. We have focused on the Dsb systems of Campylobacter spp. and Helicobacter spp. because our knowledge about Dsb proteins of Wolinella and Arcobacter spp. is still scarce and comes mainly from bioinformatic studies. Helicobacter pylori is a common human pathogen that colonizes the gastric epithelium of humans with severe consequences. Campylobacter spp. is a leading cause of zoonotic enteric bacterial infections in most developed and developing nations. We focus on various aspects of the diversity of the Dsb systems and their influence on pathogenicity, particularly because Dsb proteins are considered as potential targets for a new class of anti-virulence drugs to treat human infections by Campylobacter or Helicobacter spp.

  19. Lithium/disulfide cells capable of long cycle life

    Science.gov (United States)

    Kaun, T. D.; Holifield, T. F.; Deluca, W. H.

    The lithium-alloy/disulfide cell has undergone improvements to provide a very stable, high performance Upper-Plateau (UP) FeS2 electrode. Prismatic UP FeS2 cell tests (12 to 24 Ah capacity) with a LiCl-LiBr-KBr eutectic electrolyte have demonstrated 1000 deep discharge cycles at 400 C with less than a 20 percent drop in capacity and without reduced power capability. Previous lithium-alloy/disulfide cells, which were based on a two voltage-plateau FeS2 electrode and LiCl-KCl eutectic electrolyte had a life expectancy of only 100 cycles. Both time- and cycle-related capacity loss mechanisms have been eliminated with the improved cell design. In addition, new cell design features of overcharge tolerance and overdischarge safeguarding enhance battery durability. The performance prospects of a Li-alloy/UP FeS2 battery for an IDSEP van application are discussed. A specific energy of 150 Wh/kg for this battery after 1000 cycles of operation is projected.

  20. Lithium/disulfide cells capable of long cycle life

    Energy Technology Data Exchange (ETDEWEB)

    Kaun, T.D.; Holifield, T.F.; DeLuca, W.H.

    1988-01-01

    The lithium-alloy/disulfide cell has undergone improvements to provide a very stable, high performance upper-plateau (UP) FeS/sub 2/ electrode. Prismatic UP FeS/sub 2/ cell tests (12--24 Ah capacity) with a LiCl-LiBr-KBr eutectic electrolyte have demonstrated 1000 deep discharge cycles at 400/degree/C with less than a 20% drop in capacity and without reduced power capability. Previous lithium-alloy/disulfide cells, which were based on a two voltage-plateau FeS/sub 2/ electrode and LiCl-KCl eutectic electrolyte had a life expectancy of only 100 cycles. Both time- and cycle-related capacity loss mechanisms have been eliminated with the improved cell design. In addition, new cell design features of overcharge tolerance and overdischarge safeguarding enhance battery durability. The performance prospects of a Li-alloy/UP FeS/sub 2/ battery for an IDSEP van application are discussed. A specific energy of 150 Wh/kg for this battery after 1000 cycles of operation is projected. 8 refs., 5 figs., 1 tab.

  1. Interplay of chemical microenvironment and redox environment on thiol-disulfide exchange kinetics.

    Science.gov (United States)

    Wu, Chuanliu; Belenda, Cristina; Leroux, Jean-Christophe; Gauthier, Marc A

    2011-08-29

    The interplay between the chemical microenvironment surrounding disulfides and the redox environment of the media on thiol-disulfide exchange kinetics was examined by using a peptide platform. Exchange kinetics of up to 34 cysteine-containing peptides were measured in several redox buffers. The electrostatic attraction/repulsion between charged peptides and reducing agents such as glutathione was found to have a very pronounced effect on thiol-disulfide exchange kinetics (differences of ca. three orders of magnitude). Exchange kinetics could be directly correlated to peptide charge over the entire range examined. This study highlights the possibility of finely and predictably tuning thiol-disulfide exchange, and demonstrates the importance of considering both the local environment surrounding the disulfide and the nature of the major reducing species present in the environment for which their use is intended (e.g., in drug delivery systems, sensors, etc). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Chemical methods and approaches to the regioselective formation of multiple disulfide bonds.

    Science.gov (United States)

    Shimamoto, Shigeru; Katayama, Hidekazu; Okumura, Masaki; Hidaka, Yuji

    2014-04-01

    Disulfide-bond formation plays an important role in the stabilization of the native conformation of peptides and proteins. In the case of multidisulfide-containing peptides and proteins, numerous folding intermediates are produced, including molecules that contain non-native and native disulfide bonds during in vitro folding. These intermediates can frequently be trapped covalently during folding and subsequently analyzed. The structural characterization of these kinetically trapped disulfide intermediates provides a clue to understanding the oxidative folding pathway. To investigate the folding of disulfide-containing peptides and proteins, in this unit, chemical methods are described for regulating regioselective disulfide formation (1) by using a combination of several types of thiol protecting groups, (2) by incorporating unique SeCys residues into a protein or peptide molecule, and (3) by combining with post-translational modification. Copyright © 2014 John Wiley & Sons, Inc.

  3. Increasing the reactivity of an artificial dithiol-disulfide pair through modification of the electrostatic milieu

    DEFF Research Database (Denmark)

    Hansen, Rosa E; Østergaard, Henrik; Winther, Jakob R

    2005-01-01

    to play a key role in determining the rates of thiol disulfide exchange reactions. While modest reactivity effects have previously been seen in peptide model studies, here, we show that introduction of positive charges can have dramatic effects on disulfide bond formation on a structurally restricted......K(a) value of Cys149, as well as favorable electrostatic interactions with the negatively charged reagents. The results presented here show that the electrostatic milieu of cysteine thiols in proteins can have substantial effects on the rates of the thiol-disulfide exchange reactions.......The thiol-disulfide exchange reaction plays a central role in the formation of disulfide bonds in newly synthesized proteins and is involved in many aspects of cellular metabolism. Because the thiolate form of the cysteine residue is the key reactive species, its electrostatic milieu is thought...

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

    Science.gov (United States)

    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.

  5. The Disulfide Bonds within BST-2 Enhance Tensile Strength during Viral Tethering.

    Science.gov (United States)

    Du Pont, Kelly E; McKenzie, Aidan M; Kokhan, Oleksandr; Sumner, Isaiah; Berndsen, Christopher E

    2016-02-16

    Human BST-2/tetherin is a host factor that inhibits the release of enveloped viruses, including HIV-1, HIV-2, and SIV, from the cell surface by tethering viruses to the host cell membrane. BST-2 has an α-helical ectodomain that forms disulfide-linked dimers between two monomers forming a coiled coil. The ectodomain contains three cysteine residues that can participate in disulfide bond formation and are critical for viral tethering. The role of the disulfides in viral tethering is unknown but proposed to be for maintaining the dimer. We explored the role of the disulfides in the structure of BST-2 using experimental, biophysical methods. To understand the role of the disulfides in viral tethering, we used a new approach in viral tethering, steered molecular dynamics. We find that the disulfides coordinate the unfolding of the BST-2 monomers, which adds tensile strength to the coiled coil. Structural differences between oxidized and reduced BST-2 are apparent during unfolding, showing the monomers slide past each other in the absence of the disulfides. We found no evidence to support dissociation of the dimer upon reduction of the disulfide bonds. Moreover, the structure of BST-2 in the absence of the disulfides is similar to that of the oxidized form of BST-2, supporting previous X-ray crystallography and cellular work that showed the disulfides are not required for expression of BST-2. These data provide new insights into viral tethering by using novel techniques in the analysis of BST-2 to give amino acid level insight into functions of BST-2.

  6. In-Depth Characterization of Protein Disulfide Bonds by Online Liquid Chromatography-Electrochemistry-Mass Spectrometry

    Science.gov (United States)

    Switzar, Linda; Nicolardi, Simone; Rutten, Julie W.; Oberstein, Saskia A. J. Lesnik; Aartsma-Rus, Annemieke; van der Burgt, Yuri E. M.

    2016-01-01

    Disulfide bonds are an important class of protein post-translational modifications, yet this structurally crucial modification type is commonly overlooked in mass spectrometry (MS)-based proteomics approaches. Recently, the benefits of online electrochemistry-assisted reduction of protein S-S bonds prior to MS analysis were exemplified by successful characterization of disulfide bonds in peptides and small proteins. In the current study, we have combined liquid chromatography (LC) with electrochemistry (EC) and mass analysis by Fourier transform ion cyclotron resonance (FTICR) MS in an online LC-EC-MS platform to characterize protein disulfide bonds in a bottom-up proteomics workflow. A key advantage of a LC-based strategy is the use of the retention time in identifying both intra- and interpeptide disulfide bonds. This is demonstrated by performing two sequential analyses of a certain protein digest, once without and once with electrochemical reduction. In this way, the "parent" disulfide-linked peptide detected in the first run has a retention time-based correlation with the EC-reduced peptides detected in the second run, thus simplifying disulfide bond mapping. Using this platform, both inter- and intra-disulfide-linked peptides were characterized in two different proteins, ß-lactoglobulin and ribonuclease B. In order to prevent disulfide reshuffling during the digestion process, proteins were digested at a relatively low pH, using (a combination of) the high specificity proteases trypsin and Glu-C. With this approach, disulfide bonds in ß-lactoglobulin and ribonuclease B were comprehensively identified and localized, showing that online LC-EC-MS is a useful tool for the characterization of protein disulfide bonds.

  7. Molybdenum isotope fractionation in the mantle

    Science.gov (United States)

    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

  8. Protein Disulfide Levels and Lens Elasticity Modulation: Applications for Presbyopia.

    Science.gov (United States)

    Garner, William H; Garner, Margaret H

    2016-05-01

    The purpose of the experiments described here was to determine the effects of lipoic acid (LA)-dependent disulfide reduction on mouse lens elasticity, to synthesize the choline ester of LA (LACE), and to characterize the effects of topical ocular doses of LACE on mouse lens elasticity. Eight-month-old mouse lenses (C57BL/6J) were incubated for 12 hours in medium supplemented with selected levels (0-500 μM) of LA. Lens elasticity was measured using the coverslip method. After the elasticity measurements, P-SH and PSSP levels were determined in homogenates by differential alkylation before and after alkylation. Choline ester of LA was synthesized and characterized by mass spectrometry and HPLC. Eight-month-old C57BL/6J mice were treated with 2.5 μL of a formulation of 5% LACE three times per day at 8-hour intervals in the right eye (OD) for 5 weeks. After the final treatment, lenses were removed and placed in a cuvette containing buffer. Elasticity was determined with a computer-controlled instrument that provided Z-stage upward movements in 1-μm increments with concomitant force measurements with a Harvard Apparatus F10 isometric force transducer. The elasticity of lenses from 8-week-old C57BL/6J mice was determined for comparison. Lipoic acid treatment led to a concentration-dependent decrease in lens protein disulfides concurrent with an increase in lens elasticity. The structure and purity of newly synthesized LACE was confirmed. Aqueous humor concentrations of LA were higher in eyes of mice following topical ocular treatment with LACE than in mice following topical ocular treatment with LA. The lenses of the treated eyes of the old mice were more elastic than the lenses of untreated eyes (i.e., the relative force required for similar Z displacements was higher in the lenses of untreated eyes). In most instances, the lenses of the treated eyes were even more elastic than the lenses of the 8-week-old mice. As the elasticity of the human lens decreases with age

  9. Production of Molybdenum-99 using Neutron Capture Methods

    Energy Technology Data Exchange (ETDEWEB)

    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

  10. Predicting molybdenum toxicity to higher plants: Influence of soil properties

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, S.P., E-mail: steve.mcgrath@bbsrc.ac.u [Soil Science Department, Centre for Soils and Ecosystems Functions, Rothamsted Research, Harpenden, Hertfordshire AL5 2JQ (United Kingdom); Mico, C. [Soil Science Department, Centre for Soils and Ecosystems Functions, Rothamsted Research, Harpenden, Hertfordshire AL5 2JQ (United Kingdom); Curdy, R. [Laboratory for Environmental Biotechnology (LBE), Swiss Federal Institute of Technology Lausanne (EPFL) Station 6 CH, 1015 Lausanne (Switzerland); Zhao, F.J. [Soil Science Department, Centre for Soils and Ecosystems Functions, Rothamsted Research, Harpenden, Hertfordshire AL5 2JQ (United Kingdom)

    2010-10-15

    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 (ED{sub 50}) of Mo in different soils, explaining > 65% of the variance in ED{sub 50} 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. - Amorphous iron oxides or organic carbon were found to be the best predictors of the toxicity threshold values of Mo to higher plants on different soils.

  11. In situ hydrogenation of molybdenum oxide nanowires for enhanced supercapacitors

    KAUST Repository

    Shakir, Imran

    2014-01-01

    In situ hydrogenation of orthorhombic molybdenum trioxide (α-MoO 3) nanowires has been achieved on a large scale by introducing alcohol during the hydrothermal synthesis for electrochemical energy storage supercapacitor devices. The hydrogenated molybdenum trioxide (H xMoO3) nanowires yield a specific capacitance of 168 F g-1 at 0.5 A g-1 and maintain 108 F g-1 at 10 A g-1, which is 36-fold higher than the capacitance obtained from pristine MoO3 nanowires at the same conditions. The electrochemical devices made with HxMoO3 nanowires exhibit excellent cycling stability by retaining 97% of their capacitance after 3000 cycles due to an enhanced electronic conductivity and increased density of hydroxyl groups on the surface of the MoO3 nanowires. This journal is © The Royal Society of Chemistry.

  12. Effects of molybdenum on fertility of male rats.

    Science.gov (United States)

    Pandey, Ratna; Singh, S P

    2002-03-01

    Sodium molybdate was administered orally to adult male rat at dose level of 10, 30, and 50 mg kg body weight (5 days per week) for 60 days. At higher dose levels significant decrease in absolute and organ-to-body weight ratios of testes, epididymides, seminal vesicles and ventral prostate was observed. The sperm abnormality, associated with decrease in sperm motility and sperm count was also observed. Significant alterations in the activities of marker testicular enzymes, viz. sorbitol dehydrogenase (decreases), lactate dehydrogenase (increases) and gamma-glutamyl transpeptidase (increases) associated with histopathological changes in testes was also observed. Accumulation of molybdenum in testes, epididymides and seminal vesicles was also observed. The study reveals that the oral ingestion of molybdenum may affect the histoarchitecture of testes and sperm morphology. The testicular and spermatotoxic changes may be responsible for observed male mediated developmental toxic effects.

  13. Ternary cobalt-molybdenum-zirconium coatings for alternative energies

    Science.gov (United States)

    Yar-Mukhamedova, Gulmira; Ved', Maryna; Sakhnenko, Nikolay; Koziar, Maryna

    2017-11-01

    Consistent patterns for electrodeposition of Co-Mo-Zr coatings from polyligand citrate-pyrophosphate bath were investigated. The effect of both current density amplitude and pulse on/off time on the quality, composition and surface morphology of the galvanic alloys were determined. It was established the coating Co-Mo-Zr enrichment by molybdenum with current density increasing up to 8 A dm-2 as well as the rising of pulse time and pause duration promotes the content of molybdenum because of subsequent chemical reduction of its intermediate oxides by hydrogen ad-atoms. It was found that the content of the alloying metals in the coating Co-Mo-Zr depends on the current density and on/off times extremely and maximum Mo and Zr content corresponds to the current density interval 4-6 A dm-2, on-/off-time 2-10 ms. Chemical resistance of binary and ternary coatings based on cobalt is caused by the increased tendency to passivity and high resistance to pitting corrosion in the presence of molybdenum and zirconium, as well as the acid nature of their oxides. Binary coating with molybdenum content not less than 20 at.% and ternary ones with zirconium content in terms of corrosion deep index are in a group ;very proof;. It was shown that Co-Mo-Zr alloys exhibits the greatest level of catalytic properties as cathode material for hydrogen electrolytic production from acidic media which is not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2-4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for red-ox processes activating by oxygen as well as electrode materials for red-ox batteries.

  14. Characterization of molybdenum-doped indium oxide thin films by ...

    Indian Academy of Sciences (India)

    index, extension coefficient and bandgap of these films also were investigated. Keywords. Molybdenum-doped indium oxide; spray pyrolysis; thin films. 1. Introduction. Transparent conducting oxide (TCOs) films such as In2O3,. ZnO, SnO2 and In2O3:Sn (ITO), In2O3:Mo (IMO), etc due to their high optical transparency in the ...

  15. Fabrication of organic light emitting diode using Molybdenum ...

    Indian Academy of Sciences (India)

    65

    as PEDOT: PSS and sulfonated polyaniline can be used to reduce the potential barrier for FTO based OLED [31, 32]. But till now no any report was found to be published on the effect of molybdenum trioxide (MoO3) over non-conventional FTO surface. MoO3 is a transition metal oxide which forms a better ohmic contact w.r.t. ...

  16. Molybdenum species on alumina and silica supports for soot combustion

    OpenAIRE

    Braun, Silvana; Appel, Lúcia Gorenstin; Schmal,Martin

    2010-01-01

    Mo/A1203 and Mo/Si02 catalysts with different molybdenum species were tested in diesel soot combustion. These catalysts have shown different performances due to the presence of different species, being the most active those dispersed onto silica surface. which are similar to M020~- ion. The thermal stability was evaluated by differential thermal analyses and the results have shown that Mo species formed on silica-supported catalysts are thermally stable under the reaction conditions....

  17. Subcellular distribution of molybdenum, ultrastructural and antioxidative responses in soybean seedlings under excess molybdenum stress.

    Science.gov (United States)

    Xu, Shoujun; Hu, Chengxiao; Tan, Qiling; Qin, Shiyu; Sun, Xuecheng

    2017-12-05

    Some studies have shown that excess molybdenum (Mo) could produce toxic effects on plants. However, little is known about the subcellular distribution of Mo and cell ultrastructure within plants under excess Mo stress. Here, we comprehensively analyzed the changes of Mo distribution in subcellular fractions, cell ultrastructure and antioxidant enzymes in leaves and roots of soybean seedlings in response to excess Mo stress. The results showed that roots exhibited higher Mo accumulation than leaves at the 100 mg L-1 Mo level, about 38.58-, 171.48- and 52.99-fold higher in cell walls, cell organelles and soluble fractions, respectively. Subcellular fractionations of Mo-containing tissues indicated that approximately 90% of Mo was accumulated in the soluble fractions and cell walls of the roots and leaves, and soluble fractions (accumulated 66.3-72.2% Mo) might serve as an effective storage site for excess Mo. Furthermore, excess Mo caused ultrastructural alterations in roots and leaves of soybean seedlings, leading to structural abnormality of chloroplast in leaf cells, plasmolysis, cellular deformity, vacuole enlargement and the swelling of cell wall and cytoplasm in root cells. Meanwhile, under excess Mo stress, the activity of POD, CAT and APX enzymes in roots was 1.43, 2.35 and 1.23 times that under standard Mo condition, while that of SOD and CAT enzymes in leaves was 1.23 and 1.94 times, respectively. This study provided novel insights into the mechanisms of excess Mo toxicity in soybean seedlings. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  18. Molybdate Reduction to Molybdenum Blue by an Antarctic Bacterium

    Directory of Open Access Journals (Sweden)

    S. A. Ahmad

    2013-01-01

    Full Text Available 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.

  19. Chemical vapour deposition of diamond coatings onto molybdenum dental tools

    Science.gov (United States)

    Amar, M.; Ahmed, W.; Sein, H.; Jones, A. N.; Rego, C. A.

    2003-10-01

    The growth of polycrystalline diamond films onto molybdenum rods and dental burrs by using a new hot filament chemical vapour deposition (CVD) system has been investigated. Negative dc bias voltage relative to the filament was applied to the molybdenum substrate prior to deposition. This led to much improved film adhesion and increased nucleation density. There was a factor of four improvement in the adhesive force from 20 to 80 N when a bias voltage of -300 V was employed to the substrate. The CVD coated molybdenum dental burr was found to give much improved performance and lifetime compared to the conventional sintered diamond burr. The CVD diamond burr showed no signs of deterioration even after 1000 operations whereas the conventional sintered diamond burrs were ineffective after between 30 and 60 operations. This represents a 30-fold improvement when CVD is applied. CVD diamond growth onto dental burrs has the potential for replacing exciting technology by achieving better performance and lifetime in a cost-effective manner.

  20. Bandgap tunability at single-layer molybdenum disulphide grain boundaries

    KAUST Repository

    Huang, Yu Li

    2015-02-17

    Two-dimensional transition metal dichalcogenides have emerged as a new class of semiconductor materials with novel electronic and optical properties of interest to future nanoelectronics technology. Single-layer molybdenum disulphide, which represents a prototype two-dimensional transition metal dichalcogenide, has an electronic bandgap that increases with decreasing layer thickness. Using high-resolution scanning tunnelling microscopy and spectroscopy, we measure the apparent quasiparticle energy gap to be 2.40±0.05 eV for single-layer, 2.10±0.05 eV for bilayer and 1.75±0.05 eV for trilayer molybdenum disulphide, which were directly grown on a graphite substrate by chemical vapour deposition method. More interestingly, we report an unexpected bandgap tunability (as large as 0.85±0.05 eV) with distance from the grain boundary in single-layer molybdenum disulphide, which also depends on the grain misorientation angle. This work opens up new possibilities for flexible electronic and optoelectronic devices with tunable bandgaps that utilize both the control of two-dimensional layer thickness and the grain boundary engineering.

  1. Dynamic Combinatorial Chemistry with Diselenides, Disulfides, Imines and Metal Coordination

    DEFF Research Database (Denmark)

    Sørensen, Anne

    The design and preparation of strong and selective artificial receptors, especially biomi-metic receptors that function in aqueous solution, has proved truly challenging. In this thesis it will be described how the strengths of dynamic combinatorial chemistry can be used to great advantage...... in this field. The aim of this project has therefore been to develop new ways of using dynamic combinatorial libraries for molecular recognition in aqueous media. The focus has been on using what has been learned from the well-established di-sulfide exchange chemistry to incorporate a new reaction into dynamic...... combinatorial chemistry, namely the reversible diselenide exchange reaction. The first part of the thesis describes the development of a thermally induced OAr → SeAr migration reaction. Here, it was proven possible to rearrange a variety of substituted O-aryl selenocarbamates into the corresponding Se...

  2. Surprising Intrinsic Photostability of the Disulfide Bridge Common in Proteins

    DEFF Research Database (Denmark)

    Stephansen, Anne Boutrup; Brogaard, Rasmus Yding; Kuhlman, Thomas Scheby

    2012-01-01

    on the femtosecond time scale and found the reason for the existence of the S–S bridge as a natural building block in folded structures. The sulfur atoms will indeed move apart on the excited state but only to oscillate around the S–S center of mass. At long S–S distances, there is a strong coupling to the ground......For a molecule to survive evolution and to become a key building block in nature, photochemical stability is essential. The photolytically weak S–S bond does not immediately seem to possess that ability. We mapped the real-time motion of the two sulfur radicals that result from disulfide photolysis...

  3. Internal disulfide bond acts as a switch for intein activity.

    Science.gov (United States)

    Nicastri, Michael C; Xega, Kristina; Li, Lingyun; Xie, Jian; Wang, Chunyu; Linhardt, Robert J; Reitter, Julie N; Mills, Kenneth V

    2013-08-27

    Inteins are intervening polypeptides that catalyze their own removal from flanking exteins, concomitant to the ligation of the exteins. The intein that interrupts the DP2 (large) subunit of DNA polymerase II from Methanoculleus marisnigri (Mma) can promote protein splicing. However, protein splicing can be prevented or reduced by overexpression under nonreducing conditions because of the formation of a disulfide bond between two internal intein Cys residues. This redox sensitivity leads to differential activity in different strains of E. coli as well as in different cell compartments. The redox-dependent control of in vivo protein splicing in an intein derived from an anaerobe that can occupy multiple environments hints at a possible physiological role for protein splicing.

  4. Feasibility of preparing patterned molybdenum coatings on bismuth telluride thermoelectric modules.

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Disulfide bonds regulate binding of exogenous ligand to human cytoglobin.

    Science.gov (United States)

    Tsujino, Hirofumi; Yamashita, Taku; Nose, Azusa; Kukino, Kaori; Sawai, Hitomi; Shiro, Yoshitsugu; Uno, Tadayuki

    2014-06-01

    Cytoglobin (Cgb) was discovered a decade ago and is a fourth member of the group of hexacoordinated globin-folded proteins. Although some crystal structures have been reported and several functions have been proposed for Cgb, its physiological role remains uncertain. In this study, we measured cyanide binding to the ferric state of the wild-type (WT) Cgb, and found that the binding consisted of multiple steps. These results indicated that Cgb may be comprised of several forms, and the presence of monomers, dimers, and tetramers was subsequently confirmed by SDS-PAGE. Remarkably, each species contained two distinguishable forms, and, in the monomer, analyses of alternative cysteine states suggested the presence of an intramolecular disulfide bond (monomer SS form) and a structure with unpaired thiol groups (monomer SH form). These confirmed that forms were separated by gel-exclusion chromatography, and that the cyanide binding of the separated fractions was again measured; they showed different affinities for cyanide, with the monomer fraction showing the highest affinity. In addition, the ferrous state in each fraction showed distinct carbon monoxide (CO)-binding properties, and the affinities for cyanide and CO suggested a linear correlation. Furthermore, we also prepared several variants involving the two cysteine residues. The C38S and C83S variants showed a binding affinity for cyanide similar to the value for the monomer SH form, and hence the fraction with the highest affinity for exogenous ligands was designated as a monomer SS form. We concluded that polymerization could be a mechanism that triggers the exertion of various physiological functions of this protein and that an appropriate disulfide bond between the two cysteine residues was critical for regulating the binding affinity of Cgb, which can act as a ROS scavenger, for exogenous ligands. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Modified electrophoretic and digestion conditions allow a simplified mass spectrometric evaluation of disulfide bonds.

    Science.gov (United States)

    Pompach, Petr; Man, Petr; Kavan, Daniel; Hofbauerová, Katerina; Kumar, Vinay; Bezouska, Karel; Havlícek, Vladimír; Novák, Petr

    2009-11-01

    Proper formation of disulfide bonds in proteins is a prerequisite to their stability and function. Information on disulfide pattern may therefore serve as an indication of the proper folding of recombinant proteins, and can also be used in protein homology modeling for the purpose of structure refinement. Protein handling and digestion at basic pH leads to disulfide bond scrambling. That is why the samples are usually treated and digested at low pH where no scrambling occurs. Unfortunately, the specific proteases used in protein research are active at high pH values. Here, we present a complete sample handling protocol, which allows processing of disulfide containing proteins at basic pH. We modified the standard SDS gel electrophoresis and protein digestion conditions by the addition of an oxidative agent, cystamine. This modification prevented disulfide scrambling, which we otherwise observed in the samples handled according to the general protocol. Lysozyme from hen egg was used as a model protein for the development of the method. We then applied our protocol to human leukocyte antigen CD69, for which the disulfide bonding is known, but only for its monomeric form. In addition, the disulfide arrangement was then 'de novo' identified in the recombinant murine leukocyte receptor NKR-P1A and in the larger glycosylated proteins beta-N-acetylhexosaminidases from Aspergillus oryzae and Penicillium oxalicum. Copyright 2009 John Wiley & Sons, Ltd.

  7. PADLOC: a powerful tool to assign disulfide bond connectivities in peptides and proteins by NMR spectroscopy.

    Science.gov (United States)

    Poppe, Leszek; Hui, John O; Ligutti, Joseph; Murray, Justin K; Schnier, Paul D

    2012-01-03

    The determination of the disulfide bond connectivity in a peptide or protein represents a significant challenge. It is notoriously difficult to use NMR spectroscopy to assign disulfide connectivities because NMR spectra lack direct evidence for disulfide bonds. These bonds are typically inferred from three-dimensional structure calculations, which can result in ambiguous disulfide assignment. Here, we present a new NMR based methodology, in which the disulfide connectivity is obtained by applying Bayesian rules of inference to the local topology of cysteine residues. We illustrate how this approach successfully predicts the disulfide connectivity in proteins for which crystal structures are available in the protein data bank (PDB). We also demonstrate how this methodology is used with experimental NMR data for peptides with complex disulfide topologies, including hepcidin, Kalata-B1, and μ-Conotoxin KIIIA. In the case of μ-Conotoxin KIIIA, the PADLOC connectivity (1-15,2-9,4-16) differs from previously published results; additional evidence is presented demonstrating unequivocally that this newly proposed connectivity is correct. © 2011 American Chemical Society

  8. Determination of disulfide bridges of two spider toxins: hainantoxin-III and hainantoxin-IV

    Directory of Open Access Journals (Sweden)

    W Wang

    2009-01-01

    Full Text Available Peptide toxins are usually highly bridged proteins with multipairs of intrachain disulfide bonds. Analysis of disulfide connectivity is an important facet of protein structure determination. In this paper, we successfully assigned the disulfide linkage of two novel peptide toxins, called HNTX-III and HNTX-IV, isolated from the venom of Ornithoctonus hainana spider. Both peptides are useful inhibitors of TTX-sensitive voltage-gated sodium channels and are composed of six cysteine residues that form three disulfide bonds, respectively. Firstly, the peptides were partially reduced by tris(2-carboxyethyl-phosphine (TCEP in 0.1 M citrate buffer containing 6 M guanidine-HCl at 40° C for ten minutes. Subsequently, the partially reduced intermediates containing free thiols were separated by reversed-phase high-performance liquid chromatography (RP-HPLC and alkylated by rapid carboxamidomethylation. Then, the disulfide bonds of the intermediates were analyzed by Edman degradation. By using the strategy above, disulfide linkages of HNTX-III and HNTX-IV were determined as I-IV, II-V and III-VI pattern. In addition, this study also showed that this method may have a great potential for determining the disulfide bonds of spider peptide toxins.

  9. The influence of disulfide bonds on the mechanical stability of proteins is context dependent.

    Science.gov (United States)

    Manteca, Aitor; Alonso-Caballero, Álvaro; Fertin, Marie; Poly, Simon; De Sancho, David; Perez-Jimenez, Raul

    2017-08-11

    Disulfide bonds play a crucial role in proteins, modulating their stability and constraining their conformational dynamics. A particularly important case is that of proteins that need to withstand forces arising from their normal biological function and that are often disulfide bonded. However, the influence of disulfides on the overall mechanical stability of proteins is poorly understood. Here, we used single-molecule force spectroscopy (smFS) to study the role of disulfide bonds in different mechanical proteins in terms of their unfolding forces. For this purpose, we chose the pilus protein FimG from Gram-negative bacteria and a disulfide-bonded variant of the I91 human cardiac titin polyprotein. Our results show that disulfide bonds can alter the mechanical stability of proteins in different ways depending on the properties of the system. Specifically, disulfide-bonded FimG undergoes a 30% increase in its mechanical stability compared with its reduced counterpart, whereas the unfolding force of I91 domains experiences a decrease of 15% relative to the WT form. Using a coarse-grained simulation model, we rationalized that the increase in mechanical stability of FimG is due to a shift in the mechanical unfolding pathway. The simple topology-based explanation suggests a neutral effect in the case of titin. In summary, our results indicate that disulfide bonds in proteins act in a context-dependent manner rather than simply as mechanical lockers, underscoring the importance of considering disulfide bonds both computationally and experimentally when studying the mechanical properties of proteins. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  10. Reactivity of disulfide bonds is markedly affected by structure and environment

    DEFF Research Database (Denmark)

    Karimi, Maryam; Ignasiak, Marta T; Chan, Bun

    2016-01-01

    with multiple oxidants and is shown to arise from favorable electrostatic stabilization of the incipient positive charge on the sulfur reaction center by remote groups, or by the neighboring sulfur for conformations in which the orbitals are suitably aligned. Controlling these factors should allow the design......Disulfide bonds play a key role in stabilizing protein structures, with disruption strongly associated with loss of protein function and activity. Previous data have suggested that disulfides show only modest reactivity with oxidants. In the current study, we report kinetic data indicating...... of efficient scavengers and high-stability proteins. These data are consistent with selective oxidative damage to particular disulfides, including those in some proteins....

  11. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    OpenAIRE

    Hoskins, J.T.; Zhou, Z.; Harding, P A

    2008-01-01

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser108/121, HB-EGF-Cys/Ser116/132, and HB-EGF-Cys/Ser134/143) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with Mr of 6.5, 21 and 24kDa were observed from lys...

  12. Structure, activity and kinetics of supported molybdenum oxide and mixed molybdenum-vanadium oxide catalysts prepared by flame spray pyrolysis for propane OHD

    DEFF Research Database (Denmark)

    Høj, Martin; Kessler, Thomas; Beato, Pablo

    2013-01-01

    . The catalytic experiments showed that the most selective molybdenum oxide catalysts for the ODH reaction were those with high Mo loadings of 7 to 15 wt% Mo, while the most selective mixed molybdenum-vanadium oxide catalyst were at 4 wt% Mo, where separate surface species of molybdenum and vanadium oxide were...... observed by Raman spectroscopy. A simple kinetic model based on the propane ODH reaction, parallel combustion of propane and sequential combustion of propene described the experimental results well and could be used to determine the optimal reaction conditions. © 2013 Elsevier B.V....

  13. Synthesis and structural characterization of coaxial nano tubes intercalated of molybdenum disulfide with carbon; Sintesis y caracterizacion estructural de nanotubos coaxiales intercalados de disulfuro de molibdeno con carbono

    Energy Technology Data Exchange (ETDEWEB)

    Reza San German, C.M

    2005-07-01

    In this work the study of some fundamental aspects in the growth of unidimensional systems of coaxial nano tubes from the mold method is approached. This method is an inclusion technique of a precursor reagent into oxide nano porous alumina film (mold), and later applying some processes of synthesis it is gotten to obtain the wished material. The synthesized structures are identified later because they take place by means of the initial formation of nano tubes of MoS{sub 2}, enclosing to carbon nano tubes by the same method, with propylene flow which generates a graphitization process that 'copy' the mold through as it flows. Binary phase MoS{sub 2} + C nano tubes were synthesized by propylene pyrolysis inside MoS{sub 2} nano tubes prepared by template assisted technique. The large coaxial nano tubes constituted of graphite sheets inserted between the MoS{sub 2} layers forming the outer part, and coaxial multi wall carbon nano tubes (MWCNT) intercalated with MoS{sub 2} inside. High resolution electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), high angle annular dark field (HAADF), gatan image filter (GIF), nano beam electron diffraction patterns (NBEDP), along with molecular dynamics simulation and quantum mechanical calculations were used to characterize the samples. The one-dimensional structures exhibit diverse morphologies such as long straight and twisted nano tubes with several structural irregularities. The inter-planar spacing between MoS{sub 2} layers was found to increase from 6.3 to 7.4 A due to intercalation with carbon. Simulated HREM images revealed the presence of these twisted nano structures, with mechanical stretch into intercalate carbon between MoS{sub 2} layers. Our results open up the possibility of using MoS{sub 2} nano tubes as templates for the synthesis of new one- dimensional binary phase systems. (Author)

  14. Self-assembly of exfoliated molybdenum disulfide (MoS2) nanosheets and layered double hydroxide (LDH): Towards reducing fire hazards of epoxy.

    Science.gov (United States)

    Zhou, Keqing; Gao, Rui; Qian, Xiaodong

    2017-09-15

    In present study, LDH/MoS2 hybrids were facilely prepared by self-assembly of exfoliated MoS2 nanosheets and LDH via electrostatic force. The structure and morphology of the LDH/MoS2 hybrids were characterized and then introduced into epoxy for reducing its fire hazards. Compared with single MoS2, LDH/MoS2 hybrids showed a more homogeneous dispersion in the epoxy matrix and no obvious agglomerates were observed. Compared with MoS2, the addition of LDH/MoS2 hybrids endowed more excellent fire resistance to epoxy matrix, which was reflected by the significantly reduced peak heat release rate, total heat release and total smoke production. A rational flame retardant mode of action for LDH/MoS2 hybrids was proposed based on the analysis of pyrolysis fragments and char residues. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Manipulation of local optical properties and structures in molybdenum-disulfide monolayers using electric field-assisted near-field techniques

    OpenAIRE

    Junji Nozaki; Musashi Fukumura; Takaaki Aoki; Yutaka Maniwa; Yohei Yomogida; Kazuhiro Yanagi

    2017-01-01

    Remarkable optical properties, such as quantum light emission and large optical nonlinearity, have been observed in peculiar local sites of transition metal dichalcogenide monolayers, and the ability to tune such properties is of great importance for their optoelectronic applications. For that purpose, it is crucial to elucidate and tune their local optical properties simultaneously. Here, we develop an electric field-assisted near-field technique. Using this technique we can clarify and tune...

  16. Symmetric pseudocapacitors based on molybdenum disulfide (MoS2)-modified carbon nanospheres: correlating physicochemistry and synergistic interaction on energy storage

    CSIR Research Space (South Africa)

    Khawula, TNY

    2016-03-01

    Full Text Available (FTIR) spectroscopy, and advanced electrochemistry, including cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), long-hour voltage-holding tests, and electrochemical impedance spectroscopy (EIS). The two different MoS(sub2...

  17. Process Development for Reactive-Ion Etching of Molybdenum Disulfide (MoS2) Utilizing a Poly(methyl methacrylate) (PMMA) Etch Mask

    Science.gov (United States)

    2017-10-01

    solvents and additional dry etching steps. The first approach relied on post-etch treatments utilizing different solvents and heating of the solvents...applications with flexible substrates this heat treatment is often not allowed. Since polymer interaction with 2-D layers often leads to residues that...Acknowledgments vi 1. Introduction 1 2. Methods/Procedures 2 3. Results 3 3.1 PMMA Age and Composition 4 3.2 RIE Treatment 5 3.3 MoS2 Etch

  18. Inactivation of barley limit dextrinase inhibitor by thioredoxin-catalysed disulfide reduction

    DEFF Research Database (Denmark)

    Jensen, Johanne Mørch; Hägglund, Per; Christensen, Hans Erik Mølager

    2012-01-01

    and one glutathionylated cysteine. Here, thioredoxin is shown to progressively reduce disulfide bonds in LDI accompanied by loss of activity. A preferential reduction of the glutathionylated cysteine, as indicated by thiol quantification and molecular mass analysis using electrospray ionisation mass...

  19. Insulin analog with additional disulfide bond has increased stability and preserved activity

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Norrman, Mathias; Ribel, Ulla

    2013-01-01

    bond may enhance insulin structural stability which would be highly desirable in a pharmaceutical use. To address this hypothesis, we designed insulin with an additional interchain disulfide bond in positions A10/B4 based on Cα-Cα distances, solvent exposure, and side-chain orientation in human insulin......Insulin is a key hormone controlling glucose homeostasis. All known vertebrate insulin analogs have a classical structure with three 100% conserved disulfide bonds that are essential for structural stability and thus the function of insulin. It might be hypothesized that an additional disulfide...... (HI) structure. This insulin analog had increased affinity for the insulin receptor and apparently augmented glucodynamic potency in a normal rat model compared with HI. Addition of the disulfide bond also resulted in a 34.6°C increase in melting temperature and prevented insulin fibril formation...

  20. The role of disulfide bonds in structure and activity of chlorotoxin.

    Science.gov (United States)

    Ojeda, Paola G; Chan, Lai Y; Poth, Aaron G; Wang, Conan K; Craik, David J

    2014-10-01

    Chlorotoxin is a small scorpion peptide that inhibits glioma cell migration. We investigated the importance of a major component of chlorotoxin's chemical structure - four disulfide bonds - to its tertiary structure and biological function. Five disulfide bond analogs of chlorotoxin were synthesized, with l-α-aminobutyric acid residues replacing each or all of the disulfide bonds. Chemical oxidation and circular dichroism experiments revealed that Cys III-VII and Cys V-VIII were essential for native structure formation. Cys I-IV and Cys II-VI were important for stability of enzymatic proteolysis but not for the inhibition of human umbilical vein endothelial cell migration. The disulfide bonds of chlorotoxin are important for its structure and stability and have a minor role in its activity against cell migration.

  1. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease in the i......To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... as a structural reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within...

  2. Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

    DEFF Research Database (Denmark)

    Diemer, Sanna L.; Kristensen, Morten; Rasmussen, Brian

    2015-01-01

    that operate simultaneously or two reversible reactions that operate independently. Both these scenarios have advantages and disadvantages. In this contribution, we show how disulfide exchange and boronic ester transesterification can function simultaneous in dynamic combinatorial libraries under appropriate...

  3. The Mitochondrial Disulfide Relay System: Roles in Oxidative Protein Folding and Beyond

    Directory of Open Access Journals (Sweden)

    Manuel Fischer

    2013-01-01

    Full Text Available Disulfide bond formation drives protein import of most proteins of the mitochondrial intermembrane space (IMS. The main components of this disulfide relay machinery are the oxidoreductase Mia40 and the sulfhydryl oxidase Erv1/ALR. Their precise functions have been elucidated in molecular detail for the yeast and human enzymes in vitro and in intact cells. However, we still lack knowledge on how Mia40 and Erv1/ALR impact cellular and organism physiology and whether they have functions beyond their role in disulfide bond formation. Here we summarize the principles of oxidation-dependent protein import mediated by the mitochondrial disulfide relay. We proceed by discussing recently described functions of Mia40 in the hypoxia response and of ALR in influencing mitochondrial morphology and its importance for tissue development and embryogenesis. We also include a discussion of the still mysterious function of Erv1/ALR in liver regeneration.

  4. Site‐Selective Disulfide Modification of Proteins: Expanding Diversity beyond the Proteome

    OpenAIRE

    Kuan, Seah Ling; Wang, Tao; Weil, Tanja

    2016-01-01

    Abstract The synthetic transformation of polypeptides with molecular accuracy holds great promise for providing functional and structural diversity beyond the proteome. Consequently, the last decade has seen an exponential growth of site‐directed chemistry to install additional features into peptides and proteins even inside living cells. The disulfide rebridging strategy has emerged as a powerful tool for site‐selective modifications since most proteins contain disulfide bonds. In this Revie...

  5. Aeropyrum pernix membrane topology of protein VKOR promotes protein disulfide bond formation in two subcellular compartments.

    Science.gov (United States)

    Hibender, Stijntje; Landeta, Cristina; Berkmen, Mehmet; Beckwith, Jon; Boyd, Dana

    2017-11-15

    Disulfide bonds confer stability and activity to proteins. Bioinformatic approaches allow predictions of which organisms make protein disulfide bonds and in which subcellular compartments disulfide bond formation takes place. Such an analysis, along with biochemical and protein structural data, suggests that many of the extremophile Crenarachaea make protein disulfide bonds in both the cytoplasm and the cell envelope. We have sought to determine the oxidative folding pathways in the sequenced genomes of the Crenarchaea, by seeking homologues of the enzymes known to be involved in disulfide bond formation in bacteria. Some Crenarchaea have two homologues of the cytoplasmic membrane protein VKOR, a protein required in many bacteria for the oxidation of bacterial DsbAs. We show that the two VKORs of Aeropyrum pernix assume opposite orientations in the cytoplasmic membrane, when expressed in E. coli. One has its active cysteines oriented toward the E. coli periplasm (ApVKORo) and the other toward the cytoplasm (ApVKORi). Furthermore, the ApVKORo promotes disulfide bond formation in the E. coli cell envelope, while the ApVKORi promotes disulfide bond formation in the E. coli cytoplasm via a co-expressed archaeal protein ApPDO. Amongst the VKORs from different archaeal species, the pairs of VKORs in each species are much more closely related to each other than to the VKORs of the other species. The results suggest two independent occurrences of the evolution of the two topologically inverted VKORs in archaea. Our results suggest a mechanistic basis for the formation of disulfide bonds in the cytoplasm of Crenarchaea.

  6. Preventing Disulfide Bond Formation Weakens Non-Covalent Forces among Lysozyme Aggregates

    OpenAIRE

    Vijay Kumar Ravi; Mohit Goel; Hema Chandra Kotamarthi; Sri Rama Koti Ainavarapu; Rajaram Swaminathan

    2014-01-01

    Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL) at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescenc...

  7. The role of intra-domain disulfide bonds in heat-induced irreversible denaturation of camelid single domain VHH antibodies.

    Science.gov (United States)

    Akazawa-Ogawa, Yoko; Uegaki, Koichi; Hagihara, Yoshihisa

    2016-01-01

    Camelid-derived single domain VHH antibodies are highly heat resistant, and the mechanism of heat-induced VHH denaturation predominantly relies on the chemical modification of amino acids. Although chemical modification of disulfide bonds has been recognized as a cause for heat-induced denaturation of many proteins, there have been no mutagenesis studies, in which the number of disulfide bonds was controlled. In this article, we examined a series of mutants of two different VHHs with single, double or no disulfide bonds, and scrutinized the effects of these disulfide bond modifications on VHH denaturation. With the exception of one mutant, the heat resistance of VHHs decreased when the number of disulfide bonds increased. The effect of disulfide bonds on heat denaturation was more striking if the VHH had a second disulfide bond, suggesting that the contribution of disulfide shuffling is significant in proteins with multiple disulfide bonds. Furthermore, our results directly indicate that removal of a disulfide bond can indeed increase the heat resistance of a protein, irrespective of the negative impact on equilibrium thermodynamic stability. © The Authors 2015. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.

  8. Measurement of Actinides in Molybdenum-99 Solution Analytical Procedure

    Energy Technology Data Exchange (ETDEWEB)

    Soderquist, Chuck Z. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Weaver, Jamie L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    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.

  9. Structure and photoluminescence of molybdenum selenide nanomaterials grown by hot filament chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Wang, B.B. [College of Chemistry and Chemical Engineering, Chongqing University of Technology, 69 Hongguang Rd, Lijiatuo, Banan District, Chongqing 400054 (China); Plasma Nanoscience Laboratories, Manufacturing Flagship, Commonwealth Scientific and Industrial Research Organization, P. O. Box 218, Lindfield, NSW 2070 (Australia); Zhu, M.K. [College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124 (China); Ostrikov, K., E-mail: kostya.ostrikov@qut.edu.au [Plasma Nanoscience Laboratories, Manufacturing Flagship, Commonwealth Scientific and Industrial Research Organization, P. O. Box 218, Lindfield, NSW 2070 (Australia); Institute for Future Environments, School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, QLD 4000 (Australia); Plasma Nanoscience, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Shao, R.W.; Zheng, K. [Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing 100124 (China)

    2015-10-25

    Molybdenum selenide nanomaterials with different structures are synthesized on silicon substrates coated with gold films by hot filament chemical vapor deposition (HFCVD) in nitrogen environment, where molybdenum trioxide and selenium powders are used as source materials. The structure and composition of the synthesized molybdenum selenide nanomaterials are studied using field emission scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the structures of molybdenum selenide change from nanoflakes to nanoparticles with the increase of content of molybdenum trioxide precursor. The photoluminescence (PL) excitation using the 325 nm line of He–Cd laser as the excitation source generates green light with the wavelength of about 512–516 nm. The formation of molybdenum selenide nanomaterials is determined by the decomposition rates of molybdenum trioxide in HFCVD. The possible factors that affect the generation of green PL bands are analyzed. These outcomes of this work enrich our knowledge on the synthesis of transition metal dichalcogenides and contribute to the development of applications of these materials in optoelectronic devices. - Highlights: • Molybdenum selenide nanoflakes, nanoparticles and hybrids produced by HFCVD. • Uncommon MoO{sub 3} and Se precursor co-location and mixing and effective MoO{sub 3} decomposition. • Morphology change from nanoflakes to nanoparticles with higher ratio of MoO{sub 3} precursor. • Strong photoluminescence emission of green light with a wavelength of ∼512–516 nm.

  10. Effect of dietary molybdenum and sulphur on the copper status of ...

    African Journals Online (AJOL)

    DICK, A.T., 1956. Molybdenum and copper relationships in animal nutrition. In: Inorganic Nitrogen Metabolism. Eds. McElroy,. W.D. & Glass, B. John Hopkins Press, Baltimore. p.445. DICK, A.T., DEWEY, D.W. & GAWTHORNE, J.M., 1975. Thiomolybdates and the copper-molybdenum-sulphur interaction in ruminant nutrition.

  11. Effect of high levels of dietary molybdenum and sulphate on SA ...

    African Journals Online (AJOL)

    1988-10-29

    Oct 29, 1988 ... Effect of high levels of dietary molybdenum and sulphate on SA Mutton Merino sheep. I. Minerai status and ... reliable diagnostic index of copper deficiency in sheep in the presence of high concentrations of molybdenum and sulphate in ..... dates are poorly excreted by both the urinary and faecal routes in ...

  12. 10 CFR 35.204 - Permissible molybdenum-99, strontium-82, and strontium-85 concentrations.

    Science.gov (United States)

    2010-01-01

    ... 10 Energy 1 2010-01-01 2010-01-01 false Permissible molybdenum-99, strontium-82, and strontium-85... Unsealed Byproduct Material-Written Directive Not Required § 35.204 Permissible molybdenum-99, strontium-82, and strontium-85 concentrations. (a) A licensee may not administer to humans a radiopharmaceutical...

  13. Effect of liming on the molybdenum content in the root and leaf of ...

    African Journals Online (AJOL)

    Three liming treatments were employed (1, 3 and 4 t/ha CaCO3). The liming operation used on pseudogley induced a statistically significant increase in molybdenum ion absorption into the root system of tomato. Independently from the aforementioned, the values for the root and leaf molybdenum content of tomato in each ...

  14. Stabilization of cyclohexanone monooxygenase by a computationally designed disulfide bond spanning only one residue

    Directory of Open Access Journals (Sweden)

    Hugo L. van Beek

    2014-01-01

    Full Text Available Enzyme stability is an important parameter in biocatalytic applications, and there is a strong need for efficient methods to generate robust enzymes. We investigated whether stabilizing disulfide bonds can be computationally designed based on a model structure. In our approach, unlike in previous disulfide engineering studies, short bonds spanning only a few residues were included. We used cyclohexanone monooxygenase (CHMO, a Baeyer–Villiger monooxygenase (BVMO from Acinetobacter sp. NCIMB9871 as the target enzyme. This enzyme has been the prototype BVMO for many biocatalytic studies even though it is notoriously labile. After creating a small library of mutant enzymes with introduced cysteine pairs and subsequent screening for improved thermostability, three stabilizing disulfide bonds were identified. The introduced disulfide bonds are all within 12 Å of each other, suggesting this particular region is critical for unfolding. This study shows that stabilizing disulfide bonds do not have to span many residues, as the most stabilizing disulfide bond, L323C–A325C, spans only one residue while it stabilizes the enzyme, as shown by a 6 °C increase in its apparent melting temperature.

  15. The disulfide proteome and other reactive cysteine proteomes: analysis and functional significance.

    Science.gov (United States)

    Lindahl, Marika; Mata-Cabana, Alejandro; Kieselbach, Thomas

    2011-06-15

    Ten years ago, proteomics techniques designed for large-scale investigations of redox-sensitive proteins started to emerge. The proteomes, defined as sets of proteins containing reactive cysteines that undergo oxidative post-translational modifications, have had a particular impact on research concerning the redox regulation of cellular processes. These proteomes, which are hereafter termed "disulfide proteomes," have been studied in nearly all kingdoms of life, including animals, plants, fungi, and bacteria. Disulfide proteomics has been applied to the identification of proteins modified by reactive oxygen and nitrogen species under stress conditions. Other studies involving disulfide proteomics have addressed the functions of thioredoxins and glutaredoxins. Hence, there is a steadily growing number of proteins containing reactive cysteines, which are probable targets for redox regulation. The disulfide proteomes have provided evidence that entire pathways, such as glycolysis, the tricarboxylic acid cycle, and the Calvin-Benson cycle, are controlled by mechanisms involving changes in the cysteine redox state of each enzyme implicated. Synthesis and degradation of proteins are processes highly represented in disulfide proteomes and additional biochemical data have established some mechanisms for their redox regulation. Thus, combined with biochemistry and genetics, disulfide proteomics has a significant potential to contribute to new discoveries on redox regulation and signaling.

  16. Bovicin HJ50-like lantibiotics, a novel subgroup of lantibiotics featured by an indispensable disulfide bridge.

    Directory of Open Access Journals (Sweden)

    Jian Wang

    Full Text Available Lantibiotics are ribosomally-synthesized and posttranslationally modified peptides with potent antimicrobial activities. Discovery of novel lantibiotics has been greatly accelerated with the soaring release of genomic information of microorganisms. As a unique class II lantibiotic, bovicin HJ50 is produced by Streptococcus bovis HJ50 and contains one rare disulfide bridge. By using its precursor BovA as a drive sequence, 16 BovA-like peptides were revealed in a wide variety of species. From them, three representative novel lan loci from Clostridium perfringens D str. JGS1721, Bacillus cereus As 1.348 and B. thuringiensis As 1.013 were identified by PCR screening. The corresponding mature lantibiotics designated perecin, cerecin and thuricin were obtained and structurally elucidated to be bovicin HJ50-like lantibiotics especially by containing a conserved disulfide bridge. The disulfide bridge was substantiated to be essential for the function of bovicin HJ50-like lantibiotics as its disruption eliminated their antimicrobial activities. Further analysis indicated that the disulfide bridge played a crucial role in maintaining the hydrophobicity of bovicin HJ50, which might facilitate it to exert antimicrobial function. This study unveiled a novel subgroup of disulfide-containing lantibiotics from bacteria of different niches and further demonstrated the indispensable role of disulfide bridge in these novel bovicin HJ50-like lantibiotics.

  17. Procedure for Uranium-Molybdenum Density Measurements and Porosity Determination

    Energy Technology Data Exchange (ETDEWEB)

    Prabhakaran, Ramprashad [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Devaraj, Arun [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Joshi, Vineet V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lavender, Curt A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    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.

  18. Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

    OpenAIRE

    Efremova, Olga A.; Vorotnikov, Yuri A.; Brylev, Konstantin A.; Vorotnikova, Natalya A.; Novozhilov, Igor N.; Kuratieva, Natalia V.; Edeleva, Mariya V.; Benoit, David M.; Kitamura, Noboru; Mironov, Yuri V.; Shestopalov, Michael A.; Sutherland, Andrew J.

    2016-01-01

    This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>...

  19. Disposition of plutonium-239 via production of fission molybdenum-99.

    Science.gov (United States)

    Mushtaq, A

    2011-04-01

    A heritage of physical consequences of the U.S.-Soviet arms race has accumulated, the weapons-grade plutonium (WPu), which will become excess as a result of the dismantlement of the nuclear weapons under the arms reduction agreements. Disposition of Pu has been proposed by mixing WPu with high-level radioactive waste with subsequent vitrification into large, highly radioactive glass logs or fabrication into mixed oxide fuel with subsequent irradiation in existing light water reactors. A potential option may be the production of medical isotope molybdenum-99 by using Pu-239 targets. Copyright © 2011 Elsevier Ltd. All rights reserved.

  20. Disposition of plutonium-239 via production of fission molybdenum-99

    Energy Technology Data Exchange (ETDEWEB)

    Mushtaq, A., E-mail: muahtaq_a1953@hotmail.co [Isotope Production Division, Pakistan Institute of Nuclear Science and Technology, P.O. Nilore, Islamabad (Pakistan)

    2011-04-15

    A heritage of physical consequences of the U.S.-Soviet arms race has accumulated, the weapons-grade plutonium (WPu), which will become excess as a result of the dismantlement of the nuclear weapons under the arms reduction agreements. Disposition of Pu has been proposed by mixing WPu with high-level radioactive waste with subsequent vitrification into large, highly radioactive glass logs or fabrication into mixed oxide fuel with subsequent irradiation in existing light water reactors. A potential option may be the production of medical isotope molybdenum-99 by using Pu-239 targets.

  1. Physicochemical investigation of NiAl with small molybdenum additions

    Science.gov (United States)

    Troshkina, V. A.; Kucherenko, L. A.; Fadeeva, V. I.; Aristova, N. M.

    1982-01-01

    Specimens of four cast NiAl alloys, three of them containing 0.5, 1.0 and 1.5 at. % Mo., were homogenized for 10, 10, and 140 hr at 1373, 1523 and 1273 K, respectively, then kept at 1073, 1173 and 1323 K for 60, 120 and 3 hr, respectively, and quenched in icy water. The precipitation of a metastable Ni3Mo phase was observed at temperatures between 1073 and 1523 K. Molybdenum substituted for nickel was found to inhibit the lattice disordering in NiAl at 1073 and 1523 K.

  2. Leaching of molybdenum and arsenic from uranium ore and mill tailings

    Science.gov (United States)

    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.

  3. Influence of Chromium and Molybdenum on the Corrosion of Nickel Based Alloys

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Biotechnology for removal of carbon disulfide emissions. Final report

    Energy Technology Data Exchange (ETDEWEB)

    McIntosh, M.J.

    1995-07-01

    Biological removal in a ``biofilter`` plant of carbon disulfide and hydrogen sulfide from the air effluent of a viscose plant at Teepak, Inc., is analyzed from process and economic standpoints by use of the Aspen Plus simulation program. The metabolic product from the biofilter, 3% sulfuric acid, must be transformed at the source into either a marketable or recyclable commodity (such as 95% sulfuric acid, high-quality sulfur, or high-quality gypsum) or a material with reasonable landfill costs (such as sulfur or gypsum). The simulations indicate that the total capital requirement for production of concentrated sulfuric acid is $48.9 million; for high-quality gypsum, $40.4 million; and for high-quality sulfur, $29.4 million. Production of concentrated sulfur for landfill is not economically practical. The process to neutralize the 3% acid effluent with limestone and landfill the resulting low-quality gypsum requires the lowest total investment of the processes simulated, $8.7 million, including the biofilter plant.

  5. Oxidation Effect in Octahedral Hafnium Disulfide Thin Film.

    Science.gov (United States)

    Chae, Sang Hoon; Jin, Youngjo; Kim, Tae Soo; Chung, Dong Seob; Na, Hyunyeong; Nam, Honggi; Kim, Hyun; Perello, David J; Jeong, Hye Yun; Ly, Thuc Hue; Lee, Young Hee

    2016-01-26

    Atomically smooth van der Waals materials are structurally stable in a monolayer and a few layers but are susceptible to oxygen-rich environments. In particular, recently emerging materials such as black phosphorus and perovskite have revealed stronger environmental sensitivity than other two-dimensional layered materials, often obscuring the interesting intrinsic electronic and optical properties. Unleashing the true potential of these materials requires oxidation-free sample preparation that protects thin flakes from air exposure. Here, we fabricated few-layer hafnium disulfide (HfS2) field effect transistors (FETs) using an integrated vacuum cluster system and study their electronic properties and stability under ambient conditions. By performing all the device fabrication and characterization procedure under an oxygen- and moisture-free environment, we found that few-layer AA-stacking HfS2-FETs display excellent field effect responses (Ion/Ioff ≈ 10(7)) with reduced hysteresis compared to the FETs prepared under ambient conditions. Oxidation of HfS2 occurs uniformly over the entire area, increasing the film thickness by 250% at a prolonged oxidation time of >120 h, while defects on the surface are the preferential initial oxidation sites. We further demonstrated that the stability of the device in air is significantly improved by passivating FETs with BN in a vacuum cluster.

  6. The flexibility and dynamics of protein disulfide isomerase.

    Science.gov (United States)

    Römer, Rudolf A; Wells, Stephen A; Emilio Jimenez-Roldan, J; Bhattacharyya, Moitrayee; Vishweshwara, Saraswathi; Freedman, Robert B

    2016-12-01

    We have studied the mobility of the multidomain folding catalyst, protein disulfide isomerase (PDI), by a coarse-graining approach based on flexibility. We analyze our simulations of yeast PDI (yPDI) using measures of backbone movement, relative positions and orientations of domains, and distances between functional sites. We find that there is interdomain flexibility at every interdomain junction but these show very different characteristics. The extent of interdomain flexibility is such that yPDI's two active sites can approach much more closely than is found in crystal structures-and indeed hinge motion to bring these sites into proximity is the lowest energy normal mode of motion of the protein. The flexibility predicted for yPDI (based on one structure) includes the other known conformation of yPDI and is consistent with (i) the mobility observed experimentally for mammalian PDI and (ii) molecular dynamics. We also observe intradomain flexibility and clear differences between the domains in their propensity for internal motion. Our results suggest that PDI flexibility enables it to interact with many different partner molecules of widely different sizes and shapes, and highlights considerable similarities of yPDI and mammalian PDI. Proteins 2016; 84:1776-1785. © 2016 Wiley Periodicals, Inc. © 2016 The Authors. The Authors Proteins: Structure, Function, and Bioinformatics Published by Wiley Periodicals, Inc.

  7. Impairment of thiol-disulfide homeostasis in preeclampsia.

    Science.gov (United States)

    Korkmaz, Vakkas; Kurdoglu, Zehra; Alisik, Murat; Cetin, Orkun; Korkmaz, Hilal; Surer, Hatice; Erel, Ozcan

    2016-12-01

    To investigate the effects of severity of preeclampsia on thiol-disulfide homeostasis (TDH). A total of 108 participants were divided into three groups: Group 1 was composed of pregnant women with no obstetric complications, Group 2 included pregnant women with mild preeclampsia, and Group 3 consisted of pregnant women with severe preeclampsia. TDH parameters were determined, and comparisons of clinical and routine laboratory test findings were made in all groups. The serum native thiol level was 347.9 ± 27.4 in the control group, 237.2 ± 44.2 in the mild preeclampsia group, and 227.9 ± 53.1 in the severe preeclampsia group (p preeclampsia group, and 248.3 ± 57.4 in the severe preeclampsia group (p preeclampsia group, and 10.2 ± 4.8 in the severe preeclampsia group (p = 0.001). A significant correlation between impairment in degree of TDH and severity of preeclampsia was observed. TDH was impaired in women with preeclampsia, and this impairment increased with disease severity. Therefore, impaired TDH may have a role in the etiopathogenesis of the disease.

  8. Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

    Science.gov (United States)

    Pan, Hui

    2016-02-01

    Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

  9. Plant growth in amended molybdenum mine waste rock.

    Science.gov (United States)

    Burney, Owen T; Redente, Edward F; Lambert, Charles E

    2017-04-01

    This greenhouse study examined the use of organic and inorganic soil amendments in waste rock material from the former Questa Molybdenum Mine in northern New Mexico to promote beneficial soil properties. Waste rock material was amended with 11 soil amendment treatments that included municipal composted biosolids, Biosol®, inorganic fertilizer, and two controls (pure waste rock and sand). Elymus trachycaulus and Robinia neomexicana growth performance and plant chemistry were assessed across all treatments over a period of 99 and 141 days, respectively. Even though waste rock material had more than 200 times the molybdenum concentration of native soils, adverse effects were not observed for either species. The two main limiting factors in this study were soil nutritional status and soil water retention. The biosolid amendment was found to provide the greatest buffer against these limiting factors due to significant increases in both nutrition and soil water retention. As a result, both species responded with the highest levels of biomass production and the least amount of required water demands. Use of organic amendments such as biosolids, even though short lived in the soil, may provide plants the necessary growth stimulus to become more resilient to the harsh conditions found on many mine reclamation sites.

  10. Synthesis and characterization of several molybdenum chloride cluster compounds

    Energy Technology Data Exchange (ETDEWEB)

    Beers, W.W.

    1983-06-01

    Investigation into the direct synthesis of Mo/sub 4/Cl/sub 8/(P(C/sub 2/H/sub 5/)/sub 3/)/sub 4/ from Mo/sub 2/(OAc)/sub 4/ led to a synthetic procedure that produces yields greater than 80%. The single-crystal structure disclosed a planar rectangular cluster of molybdenum atoms. Metal-metal bond distances suggest that the long edges of the rectangular cluster should be considered to be single bonds and the short metal-metal bonds to be triple bonds. This view is reinforced by an extended Hueckel calculation. Attempts to add a metal atom to Mo/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ to form Mo/sub 5/Cl/sub 10/(PR/sub 3/)/sub 3/ led instead to a compound with the composition Mo/sub 8/Cl/sub 16/(PR/sub 3/)/sub 4/. Solution and reflectance uv-visible spectra and x-ray photoelectron spectra suggest that tetranuclear molybdenum units are present. The facile reaction between Mo/sub 8/Cl/sub 16/(PR/sub 3/)/sub 4/ and PR/sub 3/ imply that the linkage between tetrameric units is weak.

  11. Sulphur shuttling across a chaperone during molybdenum cofactor maturation.

    Science.gov (United States)

    Arnoux, Pascal; Ruppelt, Christian; Oudouhou, Flore; Lavergne, Jérôme; Siponen, Marina I; Toci, René; Mendel, Ralf R; Bittner, Florian; Pignol, David; Magalon, Axel; Walburger, Anne

    2015-02-04

    Formate dehydrogenases (FDHs) are of interest as they are natural catalysts that sequester atmospheric CO2, generating reduced carbon compounds with possible uses as fuel. FDHs activity in Escherichia coli strictly requires the sulphurtransferase EcFdhD, which likely transfers sulphur from IscS to the molybdenum cofactor (Mo-bisPGD) of FDHs. Here we show that EcFdhD binds Mo-bisPGD in vivo and has submicromolar affinity for GDP-used as a surrogate of the molybdenum cofactor's nucleotide moieties. The crystal structure of EcFdhD in complex with GDP shows two symmetrical binding sites located on the same face of the dimer. These binding sites are connected via a tunnel-like cavity to the opposite face of the dimer where two dynamic loops, each harbouring two functionally important cysteine residues, are present. On the basis of structure-guided mutagenesis, we propose a model for the sulphuration mechanism of Mo-bisPGD where the sulphur atom shuttles across the chaperone dimer.

  12. Reprocessability of molybdenum and magnesia based inert matrix fuels

    Directory of Open Access Journals (Sweden)

    Ebert Elena L.

    2015-12-01

    Full Text Available This work focuses on the reprocessability of metallic 92Mo and ceramic MgO, which is under investigation for (Pu,MA-oxide (MA = minor actinide fuel within a metallic 92Mo matrix (CERMET and a ceramic MgO matrix (CERCER. Magnesium oxide and molybdenum reference samples have been fabricated by powder metallurgy. The dissolution of the matrices was studied as a function of HNO3 concentration (1-7 mol/L and temperature (25-90°C. The rate of dissolution of magnesium oxide and metallic molybdenum increased with temperature. While the MgO rate was independent of the acid concentration (1-7 mol/L, the rate of dissolution of Mo increased with acid concentration. However, the dissolution of Mo at high temperatures and nitric acid concentrations was accompanied by precipitation of MoO3. The extraction of uranium, americium, and europium in the presence of macro amounts of Mo and Mg was studied by three different extraction agents: tri-n-butylphosphate (TBP, N,Nʹ-dimethyl-N,Nʹ-dioctylhexylethoxymalonamide (DMDOHEMA, and N,N,N’,N’- -tetraoctyldiglycolamide (TODGA. With TBP no extraction of Mo and Mg occurred. Both matrix materials are partly extracted by DMDOHEMA. Magnesium is not extracted by TODGA (D < 0.1, but a weak extraction of Mo is observed at low Mo concentration.

  13. Molybdenum-containing nitrite reductases: Spectroscopic characterization and redox mechanism.

    Science.gov (United States)

    Wang, Jun; Keceli, Gizem; Cao, Rui; Su, Jiangtao; Mi, Zhiyuan

    2017-01-01

    This review summarizes the spectroscopic results, which will provide useful suggestions for future research. In addition, the fields that urgently need more information are also advised. Nitrite-NO-cGMP has been considered as an important signaling pathway of NO in human cells. To date, all the four known human molybdenum-containing enzymes, xanthine oxidase, aldehyde oxidase, sulfite oxidase, and mitochondrial amidoxime-reducing component, have been shown to function as nitrite reductases under hypoxia by biochemical, cellular, or animal studies. Various spectroscopic techniques have been applied to investigate the structure and catalytic mechanism of these enzymes for more than 20 years. We summarize the published data on the applications of UV-vis and EPR spectroscopies, and X-ray crystallography in studying nitrite reductase activity of the four human molybdenum-containing enzymes. UV-vis has provided useful information on the redox active centers of these enzymes. The utilization of EPR spectroscopy has been critical in determining the coordination and redox status of the Mo center during catalysis. Despite the lack of substrate-bound crystal structures of these nitrite reductases, valuable structural information has been obtained by X-ray crystallography. To fully understand the catalytic mechanisms of these physiologically/pathologically important nitrite reductases, structural studies on substrate-redox center interaction are needed.

  14. Materials and Breakdown Phenomena: Heterogeneous Molybdenum Metallic Films

    Directory of Open Access Journals (Sweden)

    Augusto Marcelli

    2017-05-01

    Full Text Available Technological activities to design, manufacture, and test new accelerating devices using different materials and methods is under way all over the world. The main goal of these studies is to increase the accelerating gradients and reduce the probability of radio-frequency (RF breakdown. Indeed, it is still not clear why, by increasing the intensity of the applied field, intense surface damage is observed in copper structures, limiting the lifetime and, therefore, the practical applications. A possible solution is represented by a coating of a relatively thick layer of molybdenum in order to improve the breakdown rate. molybdenum can be reliably grown on different substrates with a negligible strain and, for thicknesses up to 600 nm, with a resistivity < 100–150·μΩ cm. Moreover, Mo coatings with controlled composition, internal stress, and roughness may allow improving thermo-mechanical properties reaching values not attainable by uncoated copper. Although the Mo conductivity remains lower compared to Cu, a Mo coating represents a very interesting option for high gradient accelerator components manufactured in copper.

  15. Preventing disulfide bond formation weakens non-covalent forces among lysozyme aggregates.

    Directory of Open Access Journals (Sweden)

    Vijay Kumar Ravi

    Full Text Available Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescence anisotropy, atomic force microscopy and single-molecule force spectroscopy to quantify the size, morphology and non-covalent interaction forces among the aggregates, respectively. These measurements were performed under conditions when disulfide bond formation was allowed (control and alternatively when it was prevented by alkylation of free thiols using iodoacetamide. Blocking disulfide bond formation affected growth but not growth kinetics of aggregates which were ∼50% reduced in volume, flatter in vertical dimension and non-fibrillar in comparison to control. Interestingly, single-molecule force spectroscopy data revealed that preventing disulfide bond formation weakened the non-covalent interaction forces among monomers in the aggregate by at least ten fold, thereby stalling their growth and yielding smaller aggregates in comparison to control. We conclude that while constrained protein chain dynamics in correctly disulfide bonded amyloidogenic proteins may protect them from venturing into partial folded conformations that can trigger entry into aggregation pathways, aberrant disulfide bonds in non-amyloidogenic proteins (like HEWL on the other hand, may strengthen non-covalent intermolecular forces among monomers and promote their aggregation.

  16. Carbon disulfide exposure and neurotoxic sequelae among viscose rayon workers

    Energy Technology Data Exchange (ETDEWEB)

    Aaserud, O.; Hommeren, O.J.; Tvedt, B.; Nakstad, P.; Mowe, G.; Efskind, J.; Russell, D.; Joergensen, E.B.N.; Nyberg-Hansen, R.; Rootwelt, K. (Univ. of Oslo (Norway))

    1990-01-01

    In Norway's only viscose rayon plant, carbon disulfide (CS2) concentrations in ambient air usually were between 30 and 50 mg/m3 during the first 23 years of production. From 1970/1971 until the factory was closed in 1982, corresponding values were 10-25 mg/m3. Through all of these years, high peak exposures of CS2 and H2S occurred. In 1986, 16 of the 24 men still at work in 1982 and with at least 10 years' experience in the spinning room agreed to participate in this study. Clinical neurological examination demonstrated abnormalities in 15; neuropsychological tests showed impairments of probable organic origin in 14. Thirteen had cerebral atrophy demonstrated by cerebral computed tomography (CT). Electromyography (EMG) was abnormal in six, neurography in 11. Regional cerebral blood flow measurements indicated flow asymmetries in eight, whereas Doppler investigation of the extracranial carotid and vertebral arteries, electroencephalography (EEG), and evoked response investigations were mostly normal. Based on these results and the exposure data, a diagnosis of CS2-induced encephalopathy was reached in eight workers; another six had an encephalopathy in which CS2 exposure was regarded as a partial cause. Correspondingly, seven had a neuropathy probably caused by CS2 exposure alone; in three others, CS2 was found to be the partial cause of a neuropathy. This indicates that long-term, relatively moderate exposure to CS2 in association with high peak exposures to CS2 and H2S involves a substantial risk of developing neurotoxic disease.

  17. Kinetic measurements on single-molecule disulfide bond cleavage.

    Science.gov (United States)

    Liang, Jian; Fernández, Julio M

    2011-03-16

    We use single-molecule force clamp spectroscopy (SMFCS) to explore the reactivity of tris(2-carboxyethyl)phosphine (TCEP), 1, 4-dl-dithiothreitol (DTT) and hydrosulfide anion (HS(-)) on disulfide bonds within a mechanically stretched polypeptide. The single-bond level bimolecular nucleophilic substitution (S(N)2) events are recorded at a series of precisely controlled temperatures so that the Arrhenius kinetic parameters, that is, the height of the activation energy barrier (E(a)) and the attempting frequency (A) of the chemical reactions, can be determined. The values of A are typically at the order of 10(7) M(-1) s(-1), which is far lower than that predicted by the transition-state theory, in which A is given by k(B)T/h and around 10(12) M(-1) s(-1) at room temperature. Furthermore, E(a) is derived to be 30-40 kJ/mol, which can be lowered by ∼6-8% with every 100 pN mechanical force applied. The correlation of the A and E(a) with the molecular structures reveals that the relative magnitude of these two parameters cannot be simply judged from the size of the molecule or the nucleophilicity of the attacking atom. The comparison of the influences on the reaction rate induced by force and temperature indicates an equivalent accelerating effect by every 50 pN or 10 K increment, giving for the first time the relationship between mechanical and thermal effects on a single-molecule S(N)2 chemical reaction.

  18. Highly dispersed molybdenum carbide as non-noble electrocatalyst for PEM fuel cells: Performance for CO electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Guil-Lopez, R.; Martinez-Huerta, M.V.; Pena, M.A.; Fierro, J.L.G. [Instituto de Catalisis y Petroleoquimica (CSIC), Marie Curie 2, Cantoblanco, E-28049 Madrid (Spain); Guillen-Villafuerte, O.; Pastor, E. [Departamento de Quimica Fisica, Universidad de La Laguna, Astrofisico Francisco Sanchez s/n, E-38071 La Laguna, Tenerife (Spain)

    2010-08-15

    CO electrooxidation on nanocrystalline molybdenum carbide has been studied through CO stripping measurements using cyclic voltammetry. The active molybdenum carbide was obtained from the carbothermic reduction of really very small molybdenum oxide particles supported on Vulcan XC-72 carbon black (CB). In order to obtain highly dispersed molybdenum carbide particles, low molybdenum loading and control of the carbothermic reduction conditions of CB-supported molybdenum oxide were employed to avoid Mo sintering during the carburization process. This work provides experimental evidence on the CO electrooxidation capability of the Mo carbide phase, which to the best of our knowledge is reported for the first time. The small particle size of carbide electrocatalyst exhibited better performance for CO electrooxidation than the commercial bulk molybdenum carbide sample. (author)

  19. Environmental Benign Process for Production of Molybdenum Metal from Sulphide Based Minerals

    Science.gov (United States)

    Rajput, Priyanka; Janakiram, Vangada; Jayasankar, Kalidoss; Angadi, Shivakumar; Bhoi, Bhagyadhar; Mukherjee, Partha Sarathi

    2017-10-01

    Molybdenum is a strategic and high temperature refractory metal which is not found in nature in free state, it is predominantly found in earth's crust in the form of MoO3/MoS2. The main disadvantage of the industrial treatment of Mo concentrate is that the process contains many stages and requires very high temperature. Almost in every step many gaseous, liquid, solid chemical substances are formed which require further treatment. To overcome the above drawback, a new alternative one step novel process is developed for the treatment of sulphide and trioxide molybdenum concentrates. This paper presents the results of the investigations on molybdenite dissociation (MoS2) using microwave assisted plasma unit as well as transferred arc thermal plasma torch. It is a single step process for the preparation of pure molybdenum metal from MoS2 by hydrogen reduction in thermal plasma. Process variable such as H2 gas, Ar gas, input current, voltage and time have been examined to prepare molybdenum metal. Molybdenum recovery of the order of 95% was achieved. The XRD results confirm the phases of molybdenum metal and the chemical analysis of the end product indicate the formation of metallic molybdenum (Mo 98%).

  20. Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

    Science.gov (United States)

    Rosenthal-Kim, Emily Quinn

    The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight

  1. Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-07

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi2) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi2 was identified based on its high temperature oxidation resistance in O2 atmospheres (e.g. air and “wet air”). However, its behavior in H2O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O2) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670

  2. Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

    Science.gov (United States)

    Hilsenbeck, S.J.; McCarley, R.E.; Schrader, G.L.; Xie, X.B.

    1999-02-16

    New amorphous molybdenum/tungsten sulfides with the general formula M{sup n+}{sub 2x/n}(L{sub 6}S{sub 8})S{sub x}, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M{sub 6}S{sub 8}){sup 0} cluster units are present. Vacuum thermolysis of the amorphous Na{sub 2x}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH first produces poorly crystalline NaMo{sub 6}S{sub 8} by disproportionation at 800 C and well-crystallized NaMo{sub 6}S{sub 8} at {>=} 900 C. Ion-exchange of the sodium material in methanol with soluble M{sup 2+} and M{sup 3+} salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M{sup n+}{sub 2x/n}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M{sup n+}{sub 2x/n}Mo{sub 6}S{sub 8+x}(MeOH){sub y}[MMOS] (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as ``Chevrel phase-like`` in that both contain Mo{sub 6}S{sub 8} cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst is shown to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS{sub 2} catalysts. 9 figs.

  3. Design of an in vivo cleavable disulfide linker in recombinant fusion proteins.

    Science.gov (United States)

    Chen, Xiaoying; Bai, Yun; Zaro, Jennica L; Shen, Wei-Chiang

    2010-07-01

    In order to achieve optimal biological activity and desired pharmacokinetic profiles, a dithiocyclopeptide linker was designed for in vivo release of protein domains from a recombinant fusion protein. This novel in vivo cleavable disulfide linker, based on a dithiocyclopeptide containing a thrombin-sensitive sequence and an intramolecular disulfide bond, was inserted between transferrin and granulocyte colony-stimulating factor (G-CSF) recombinant fusion protein domains. After expression of the fusion protein, G-C-T, from HEK293 cells, thrombin treatment in vitro generated a fusion protein linked via a reversible disulfide bond that was quickly cleaved in vivo, separating the protein domains. After release from the fusion protein, free G-CSF exhibited an improved biological activity in a cell proliferation assay. Although reversible disulfide bonds are commonly used in protein chemical conjugation methods, to our knowledge this report is the first example of the construction of a recombinant fusion protein with a disulfide linkage for the release of the functional domain. This linker design can be adapted to diverse recombinant fusion proteins in which in vivo separation of protein domains is required to achieve an improved therapeutic effect and a desirable pharmacokinetic profile and biodistribution of the functional domain.

  4. Functional Analysis of Paralogous Thiol-disulfide Oxidoreductases in Streptococcus gordonii*

    Science.gov (United States)

    Davey, Lauren; Ng, Crystal K. W.; Halperin, Scott A.; Lee, Song F.

    2013-01-01

    Disulfide bonds are important for the stability of many extracellular proteins, including bacterial virulence factors. Formation of these bonds is catalyzed by thiol-disulfide oxidoreductases (TDORs). Little is known about their formation in Gram-positive bacteria, particularly among facultative anaerobic Firmicutes, such as streptococci. To investigate disulfide bond formation in Streptococcus gordonii, we identified five putative TDORs from the sequenced genome. Each of the putative TDOR genes was insertionally inactivated with an erythromycin resistance cassette, and the mutants were analyzed for autolysis, extracellular DNA release, biofilm formation, bacteriocin production, and genetic competence. This analysis revealed a single TDOR, SdbA, which exhibited a pleiotropic mutant phenotype. Using an in silico analysis approach, we identified the major autolysin AtlS as a natural substrate of SdbA and showed that SdbA is critical to the formation of a disulfide bond that is required for autolytic activity. Analysis by BLAST search revealed homologs to SdbA in other Gram-positive species. This study provides the first in vivo evidence of an oxidoreductase, SdbA, that affects multiple phenotypes in a Gram-positive bacterium. SdbA shows low sequence homology to previously identified oxidoreductases, suggesting that it may belong to a different class of enzymes. Our results demonstrate that SdbA is required for disulfide bond formation in S. gordonii and indicate that this enzyme may represent a novel type of oxidoreductase in Gram-positive bacteria. PMID:23615907

  5. Disulfide bond formation and ToxR activity in Vibrio cholerae.

    Directory of Open Access Journals (Sweden)

    Vera H I Fengler

    Full Text Available Virulence factor production in Vibrio cholerae is complex, with ToxRS being an important part of the regulatory cascade. Additionally, ToxR is the transcriptional regulator for the genes encoding the major outer membrane porins OmpU and OmpT. ToxR is a transmembrane protein and contains two cysteine residues in the periplasmic domain. This study addresses the influence of the thiol-disulfide oxidoreductase system DsbAB, ToxR cysteine residues and ToxR/ToxS interaction on ToxR activity. The results show that porin production correlates with ToxR intrachain disulfide bond formation, which depends on DsbAB. In contrast, formation of ToxR intrachain or interchain disulfide bonds is dispensable for virulence factor production and in vivo colonization. This study further reveals that in the absence of ToxS, ToxR interchain disulfide bond formation is facilitated, whereat cysteinyl dependent homo- and oligomerization of ToxR is suppressed if ToxS is coexpressed. In summary, new insights into gene regulation by ToxR are presented, demonstrating a mechanism by which ToxR activity is linked to a DsbAB dependent intrachain disulfide bond formation.

  6. Role of Disulfide Bonds on DNA Packaging Forces in Bull Sperm Chromatin.

    Science.gov (United States)

    Hutchison, James M; Rau, Donald C; DeRouchey, Jason E

    2017-11-07

    Short arginine-rich proteins called protamines mediate the near crystalline DNA packaging in most vertebrate sperm cells. Protamines are synthesized during spermiogenesis and condense the paternal genome into a transcriptionally inactive state in late-stage spermatids. Protamines from eutherian mammals, including bulls and humans, also contain multiple cysteine residues that form intra- and interprotamine sulfur-sulfur bonds during the final stages of sperm maturation. Although the cross-linked protamine network is known to stabilize the resulting nucleoprotamine structure, little is known about the role of disulfide bonds on DNA condensation in the mammalian sperm. Using small angle x-ray scattering, we show that isolated bull nuclei achieve slightly lower DNA packing densities compared to salmon nuclei despite salmon protamine lacking cysteine residues. Surprisingly, reduction of the intermolecular sulfur-sulfur bonds of bull protamine results in tighter DNA packing. Complete reduction of the intraprotamine disulfide bonds ultimately leads to decondensation, suggesting that disulfide-mediated secondary structure is also critical for proper protamine function. Lastly, comparison of multiple bull collections showed some to have aberrant x-ray scattering profiles consistent with incorrect disulfide bond formation. Together, these observations shed light on the biological functions of disulfide linkages for in vivo DNA packaging in sperm chromatin. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  7. Immediate stabilization of human blood for delayed quantification of endogenous thiols and disulfides

    Science.gov (United States)

    Giustarini, Daniela; Galvagni, Federico; Orlandini, Maurizio; Fanti, Paolo; Rossi, Ranieri

    2016-01-01

    Endogenous thiols undergo rapid and reversible oxidation to disulfides when exposed to oxidants and are, therefore, suitable biomarkers of oxidative stress. However, accurate analysis of thiols in blood is frequently compromised by their artifactual oxidation during sample manipulation, which spuriously elevates the disulfide levels. Here, we describe a validated pre-analytical procedure that prevents both artifactual oxidation of thiols during sample manipulation and their oxidative decay for months in biosamples that are stored at −80°C. Addition of N-ethylmaleimide to blood samples from healthy donors was used to stabilize whole blood, red blood cells, platelets and plasma disulfides, whereas addition of citrate buffer followed by dilution of plasma with H2O was used to stabilize plasma thiols. The concentrations of thiols and disulfides were stable in all biosamples for at least 6 months when analyzed by UV/Vis HPLC at regular intervals. Only 3 ml of blood were needed to perform the analyses of thiols and disulfides in the different blood fractions. This pre-analytical procedure is reliable for use in both animal and human prospective studies. Its ease of implementation makes the method suitable for application to multicenter studies where blood samples are collected by different sites and personnel and are shipped to specific specialized laboratories. PMID:26896310

  8. Active carbon supported molybdenum carbides for higher alcohols synthesis from syngas

    DEFF Research Database (Denmark)

    Wu, Qiongxiao; Chiarello, Gian Luca; Christensen, Jakob Munkholt

    This work provides an investigation of the high pressure CO hydrogenation to higher alcohols on K2CO3 promoted active carbon supported molybdenum carbide. Both activity and selectivity to alcohols over supported molybdenum carbides increased significantly compared to bulk carbides in literatures....... The optimal loadings of both molybdenum carbide and the K2CO3 promoter on active carbon have been investigated. The catalysts were characterized using BET surface area measurements, transmission electron microscopy and X-ray diffraction. Additionally, in-situ X-ray diffraction and in-situ X-ray absorption...

  9. Acidic ammonothermal growth of gallium nitride in a liner-free molybdenum alloy autoclave

    Science.gov (United States)

    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 (560 °C). The possibility of a 'universal', inexpensive, liner-free ammonothermal autoclave capable of exposure to basic and acidic chemistry is demonstrated.

  10. Neutronic and thermal hydraulic analysis for production of fission molybdenum-99 at Pakistan Research Reactor-1

    Energy Technology Data Exchange (ETDEWEB)

    Mushtaq, A. [Isotope Production Division, Pakistan Institute of Nuclear Science and Technology, P.O. Nilore, Islamabad (Pakistan)], E-mail: mushtaqa@pinstech.org.pk; Iqbal, Massod; Bokhari, Ishtiaq Hussain; Mahmood, Tariq; Mahmood, Tayyab; Ahmad, Zahoor; Zaman, Qamar [Nuclear Engineering Division, Pakistan Institute of Nuclear Science and Technology, P.O. Nilore, Islamabad (Pakistan)

    2008-02-15

    Neutronic and thermal hydraulic analysis for the fission molybdenum-99 production at PARR-1 has been performed. Low enriched uranium foil (<20% {sup 235}U) will be used as target material. Annular target designed by ANL (USA) will be irradiated in PARR-1 for the production of 100 Ci of molybdenum-99 at the end of irradiation, which will be sufficient to prepare required {sup 99}Mo/{sup 99m}Tc generators at PINSTECH and its supply in the country. Neutronic and thermal hydraulic analysis were performed using various codes. Data shows that annular targets can be safely irradiated in PARR-1 for production of required amount of fission molybdenum-99.

  11. Synthesis of molybdenum oxide microsheets via close-spaced vapor transport

    Energy Technology Data Exchange (ETDEWEB)

    Goiz, O., E-mail: ogoiza@gmail.com [Department of Electrical Engineering, CINVESTAV-IPN, 07360 Mexico, D.F. (Mexico); Chavez, F. [Department of Physical-Chemical Materials, ICUAP-BUAP, 72050 Puebla, Pue. (Mexico); Felipe, C. [Department of Biosciences and Engineering, CIIEMAD-IPN, 07340 Mexico, D.F. (Mexico); Morales, N. [Department of Physical-Chemical Materials, ICUAP-BUAP, 72050 Puebla, Pue. (Mexico); Pena-Sierra, R. [Department of Electrical Engineering, CINVESTAV-IPN, 07360 Mexico, D.F. (Mexico)

    2010-10-25

    Growth of molybdenum oxide microsheets on silicon (1 0 0) substrates using the close-spaced vapor transport (CSVT) technique is proposed. Molybdenum oxide powder is employed as source, the synthesis is carried out at atmospheric pressure with a nitrogen ambient by employing short times (a few minutes), water as reactant and moderate temperatures. The growth process is efficient, fast, and without the use of catalysts. Changes in morphology and structure of products when temperature varies are reported. The produced molybdenum oxide microsheets are analyzed with SEM, XRD and micro-Raman techniques.

  12. Development of Solvent Extraction Approach to Recycle Enriched Molybdenum Material

    Energy Technology Data Exchange (ETDEWEB)

    Tkac, Peter [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Brown, M. Alex [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Sen, Sujat [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Bowers, Delbert L. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Wardle, Kent [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Copple, Jacqueline M. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Pupek, Krzysztof Z. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Dzwiniel, Trevor L. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Pereira, Candido [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Krumdick, Gregory K. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division

    2016-06-01

    Argonne National Laboratory, in cooperation with Oak Ridge National Laboratory and NorthStar Medical Technologies, LLC, is developing a recycling process for a solution containing valuable Mo-100 or Mo-98 enriched material. Previously, Argonne had developed a recycle process using a precipitation technique. However, this process is labor intensive and can lead to production of large volumes of highly corrosive waste. This report discusses an alternative process to recover enriched Mo in the form of ammonium heptamolybdate by using solvent extraction. Small-scale experiments determined the optimal conditions for effective extraction of high Mo concentrations. Methods were developed for removal of ammonium chloride from the molybdenum product of the solvent extraction process. In large-scale experiments, very good purification from potassium and other elements was observed with very high recovery yields (~98%).

  13. Mn-Promoted Growth and Photoluminescence of Molybdenum Disulphide Monolayer

    Directory of Open Access Journals (Sweden)

    Shengzhong Jin

    2017-06-01

    Full Text Available Molybdenum disulphide (MoS2 monolayer is a two-dimensional semiconductor material with potential applications in nano electronic devices. However, it is still a challenge to reproducibly synthesize single layer MoS2 in high quality. Herein, we report the growth of monolayer of MoS2 on the SiO2/Si substrate with manganese heterogeneous nucleation. It was shown that the Mn promotes the growth of monolayer MoS2 via heterogeneous nucleation. The growth temperature range expanded two-fold, the nucleation density increased as well. The monolayer prepared in the presence of Mn exhibits a unique red emission peak at 732 nm at room temperature compared to the sample in the absence of Mn.

  14. Structural and electrical properties of DC sputtered molybdenum films

    Energy Technology Data Exchange (ETDEWEB)

    Gordillo, G.; Grizalez, M.; Hernandez, L.C. [Laboratorio de Celdas Solares, Departamento de Fisica, Universidad Nacional de Colombia, Bogota (Colombia)

    1998-02-27

    A method is described for the fabrication of low-resistivity molybdenum films on soda-lime glass substrates. Films have been deposited using a DC magnetron sputtering system with a S-gun configuration, and have been characterized through X-ray diffraction, electrical conductivity, and Hall mobility measurements. The influence of the deposition parameters on both the resistivity of the Mo and on the contact resistivity of the Mo/CuInSe{sub 2}/Mo structure has been studied. Values of resistivity ranging from 1.2x10{sup -5} to 36x10{sup -5} {Omega} cm and of contact resistivity ranging from 0.025 to 0.15 {Omega} cm{sup 2} were found

  15. The history of development of molybdenum alloys for structural applications

    Energy Technology Data Exchange (ETDEWEB)

    Wadsworth, J. [Lawrence Livermore National Lab., CA (United States); Wittenauer, J.P. [Lockheed Missiles and Space Co., Inc., Palo Alto, CA (United States). Research and Development Div.

    1993-02-01

    Molybdenum was first isolated as an element in 1893 and found initial commercial application as a filament support for incandescent lamps in 1910. The advent of arc melting practice in the 1940s led to an increase in availability of Mo sheet, bar, and plate products. Alloy development programs were heavily supported starting in the 1950s and several key alloys emerged over the next twenty years that remain in use to the present time such as Mo-TZM, unalloyed Mo, and Mo-Re. In recent years, improved understanding of the role of oxygen and carbide distributions at grain boundaries have led to increased reliability and use of Mo in aerospace products. Current developmental programs in areas of propulsion and energy conversion will ensure the prominent position of Mo as a high-temperature structural material. This paper highlights some of these key developments in the evolution of Mo alloys.

  16. Powder Metallurgy Fabrication of Molybdenum Accelerator Target Disks

    Energy Technology Data Exchange (ETDEWEB)

    Lowden, Richard Andrew [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kiggans Jr., James O. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Nunn, Stephen D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Parten, Randy J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-07-01

    Powder metallurgy approaches for the fabrication of accelerator target disks are being examined to support the development of Mo-99 production by NorthStar Medical Technologies, LLC. An advantage of powder metallurgy is that very little material is wasted and, at present, dense, quality parts are routinely produced from molybdenum powder. The proposed targets, however, are thin wafers, 29 mm in diameter with a thickness of 0.5 mm, with very stringent dimensional tolerances. Although tooling can be machined to very high tolerance levels, the operations of powder feed, pressing and sintering involve complicated mechanisms, each of which affects green density and shrinkage, and therefore the dimensions and shape of the final product. Combinations of powder morphology, lubricants and pressing technique have been explored to produce target disks with minimal variations in thickness and little or no distortion. In addition, sintering conditions that produce densities for optimum target dissolvability are being determined.

  17. Predicting the stability of surface phases of molybdenum selenides

    Energy Technology Data Exchange (ETDEWEB)

    Roma, Guido [Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg Universität, D-55128, Mainz (Germany); CEA, DEN, Service de Recherches de Métallurgie Physique, F-91191, Gif sur Yvette (France); Ghorbani, Elaheh [Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg Universität, D-55128, Mainz (Germany); IBM Mainz (Germany); Mirhosseini, Hossein; Kühne, Thomas D. [Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg Universität, D-55128, Mainz (Germany); Kiss, Janos; Felser, Claudia [Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg Universität, D-55128, Mainz (Germany); Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden (Germany)

    2014-02-10

    The selenization of molybdenum might become an important step in the production of nanostructures based on the layered compound MoSe{sub 2}. It is already technologically relevant for the production of thin film chalcopyrite solar cells. However, the control of the process is still very poor, due to the lack of basic knowledge of the surface thermodynamics of the system. Here, we present a theoretical study on the stability of surface adlayers of Se on the Mo(110) surface, predicting surface patterns and their stability range in terms of temperature and selenium partial pressure. Our results, based on density functional theory, show that the attainable Se coverages range from 1/4 to 3/4 of a monolayer for systems in equilibrium with a gas formed of Se molecules. We provide simulated scanning tunneling microscopy images to help the experimental characterization of adsorbed surface patterns.

  18. Molybdenum isotope fractionation during adsorption to organic matter

    Science.gov (United States)

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

    2018-02-01

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

  19. Molybdenum isotope fractionation during adsorption to organic matter

    Science.gov (United States)

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

    2018-01-01

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

  20. Molecular Simulations of Disulfide-Rich Venom Peptides with Ion Channels and Membranes

    Directory of Open Access Journals (Sweden)

    Evelyne Deplazes

    2017-02-01

    Full Text Available Disulfide-rich peptides isolated from the venom of arthropods and marine animals are a rich source of potent and selective modulators of ion channels. This makes these peptides valuable lead molecules for the development of new drugs to treat neurological disorders. Consequently, much effort goes into understanding their mechanism of action. This paper presents an overview of how molecular simulations have been used to study the interactions of disulfide-rich venom peptides with ion channels and membranes. The review is focused on the use of docking, molecular dynamics simulations, and free energy calculations to (i predict the structure of peptide-channel complexes; (ii calculate binding free energies including the effect of peptide modifications; and (iii study the membrane-binding properties of disulfide-rich venom peptides. The review concludes with a summary and outlook.

  1. Failure life determination of oilfield elastomer seals in sour gas/dimethyl disulfide environments

    Energy Technology Data Exchange (ETDEWEB)

    Kennelley, K.J.; Abrams, P.I. (Exxon Production Research Co., Houston, TX (US)); Vicic, J.C. (FMC Corp., Central Engineering Labs., Santa Clara, CA (US)); Cain, D. (FMC Corp., Wellhead Equipment, Houston, TX (US))

    1989-01-01

    Previous screening tests of various oilfield elastomers in sour gas/dimethyl disulfide environments indicated that hydrogenated nitrile (HNBR), tetrafluoroethylene-propylene (TFE/P), ethylene-propylene-diene (EPDM), and perfluorinated rubber (FFKM) elastomers may perform satisfactorily in these environments. This paper describes subsequent failure life tests conducted with the subject elastomers in the sour gas/dimethyl disulfide test environment at several elevated temperatures (> 135{degrees}C). The materials were tested in the form of O-rings (size 214), which were used to seal an autoclave containing the test environment at 14 MPa gas pressure. The results were used to extrapolate time to failure at a common reference temperature of 135{degrees}C. The performance of EPDM and HNBR in the sour gas/dimethyl disulfide mixture substantially exceeded a projected 20-year service life at 135{degrees}C, while FFKM and TFE/P did not.

  2. Rapid expansion of the protein disulfide isomerase gene family facilitates the folding of venom peptides

    DEFF Research Database (Denmark)

    Safavi-Hemami, Helena; Li, Qing; Jackson, Ronneshia L.

    2016-01-01

    Formation of correct disulfide bonds in the endoplasmic reticulum is a crucial step for folding proteins destined for secretion. Protein disulfide isomerases (PDIs) play a central role in this process. We report a previously unidentified, hypervariable family of PDIs that represents the most...... diverse gene family of oxidoreductases described in a single genus to date. These enzymes are highly expressed specifically in the venom glands of predatory cone snails, animals that synthesize a remarkably diverse set of cysteine-rich peptide toxins (conotoxins). Enzymes in this PDI family, termed...... conotoxin-specific PDIs, significantly and differentially accelerate the kinetics of disulfide-bond formation of several conotoxins. Our results are consistent with a unique biological scenario associated with protein folding: The diversification of a family of foldases can be correlated with the rapid...

  3. Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Salbo, Rune; Ploug, Michael

    2014-01-01

    requires a high concentration (>200 mM) of the chemical reducing agent Tris(2-carboxyethyl)phosphine (TCEP) as its reduction rate constant is decreased at low pH and temperature. Serious adverse effects on chromatographic and mass spectrometric performances have been reported when using high concentrations......Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

  4. Molecular Simulations of Disulfide-Rich Venom Peptides with Ion Channels and Membranes.

    Science.gov (United States)

    Deplazes, Evelyne

    2017-02-27

    Disulfide-rich peptides isolated from the venom of arthropods and marine animals are a rich source of potent and selective modulators of ion channels. This makes these peptides valuable lead molecules for the development of new drugs to treat neurological disorders. Consequently, much effort goes into understanding their mechanism of action. This paper presents an overview of how molecular simulations have been used to study the interactions of disulfide-rich venom peptides with ion channels and membranes. The review is focused on the use of docking, molecular dynamics simulations, and free energy calculations to (i) predict the structure of peptide-channel complexes; (ii) calculate binding free energies including the effect of peptide modifications; and (iii) study the membrane-binding properties of disulfide-rich venom peptides. The review concludes with a summary and outlook.

  5. On the relevance of sophisticated structural annotations for disulfide connectivity pattern prediction.

    Science.gov (United States)

    Becker, Julien; Maes, Francis; Wehenkel, Louis

    2013-01-01

    Disulfide bridges strongly constrain the native structure of many proteins and predicting their formation is therefore a key sub-problem of protein structure and function inference. Most recently proposed approaches for this prediction problem adopt the following pipeline: first they enrich the primary sequence with structural annotations, second they apply a binary classifier to each candidate pair of cysteines to predict disulfide bonding probabilities and finally, they use a maximum weight graph matching algorithm to derive the predicted disulfide connectivity pattern of a protein. In this paper, we adopt this three step pipeline and propose an extensive study of the relevance of various structural annotations and feature encodings. In particular, we consider five kinds of structural annotations, among which three are novel in the context of disulfide bridge prediction. So as to be usable by machine learning algorithms, these annotations must be encoded into features. For this purpose, we propose four different feature encodings based on local windows and on different kinds of histograms. The combination of structural annotations with these possible encodings leads to a large number of possible feature functions. In order to identify a minimal subset of relevant feature functions among those, we propose an efficient and interpretable feature function selection scheme, designed so as to avoid any form of overfitting. We apply this scheme on top of three supervised learning algorithms: k-nearest neighbors, support vector machines and extremely randomized trees. Our results indicate that the use of only the PSSM (position-specific scoring matrix) together with the CSP (cysteine separation profile) are sufficient to construct a high performance disulfide pattern predictor and that extremely randomized trees reach a disulfide pattern prediction accuracy of [Formula: see text] on the benchmark dataset SPX[Formula: see text], which corresponds to [Formula: see text

  6. On the relevance of sophisticated structural annotations for disulfide connectivity pattern prediction.

    Directory of Open Access Journals (Sweden)

    Julien Becker

    Full Text Available Disulfide bridges strongly constrain the native structure of many proteins and predicting their formation is therefore a key sub-problem of protein structure and function inference. Most recently proposed approaches for this prediction problem adopt the following pipeline: first they enrich the primary sequence with structural annotations, second they apply a binary classifier to each candidate pair of cysteines to predict disulfide bonding probabilities and finally, they use a maximum weight graph matching algorithm to derive the predicted disulfide connectivity pattern of a protein. In this paper, we adopt this three step pipeline and propose an extensive study of the relevance of various structural annotations and feature encodings. In particular, we consider five kinds of structural annotations, among which three are novel in the context of disulfide bridge prediction. So as to be usable by machine learning algorithms, these annotations must be encoded into features. For this purpose, we propose four different feature encodings based on local windows and on different kinds of histograms. The combination of structural annotations with these possible encodings leads to a large number of possible feature functions. In order to identify a minimal subset of relevant feature functions among those, we propose an efficient and interpretable feature function selection scheme, designed so as to avoid any form of overfitting. We apply this scheme on top of three supervised learning algorithms: k-nearest neighbors, support vector machines and extremely randomized trees. Our results indicate that the use of only the PSSM (position-specific scoring matrix together with the CSP (cysteine separation profile are sufficient to construct a high performance disulfide pattern predictor and that extremely randomized trees reach a disulfide pattern prediction accuracy of [Formula: see text] on the benchmark dataset SPX[Formula: see text], which corresponds to

  7. Two temperature approach to femtosecond laser oxidation of molybdenum and morphological study

    Science.gov (United States)

    Kotsedi, L.; Kaviyarasu, K.; Fuku, X. G.; Eaton, S. M.; Amara, E. H.; Bireche, F.; Ramponi, R.; Maaza, M.

    2017-11-01

    The two-temperature model was used to gain insight into the thermal evolution of the hot electrons and the crystal lattice of the molybdenum thin coating during femtosecond laser treatment. The heat from the laser raised the bulk temperature of the sample through heat transfer from the hot electron to the crystal lattice of the material, which then led to the melting of the top layer of the film. This process resulted in the hot melt reacting ambient oxygen, which in turn oxidized the surface of molybdenum coating. The topological study and morphology of the oxidized film was conducted using high-resolution scanning electron microscope, with micrographs taken in both the cross-sectional geometry and normal incidence to the electron beam. The molybdenum oxide nanorods were clearly observed and the x-ray diffraction patterns showed the diffraction peaks due to molybdenum oxide.

  8. FY16 Status Report for the Uranium-Molybdenum Fuel Concept

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, Wendy D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Doherty, Ann L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Henager, Charles H. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lavender, Curt A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Montgomery, Robert O. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Omberg, Ronald P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Smith, Mark T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Webster, Ryan A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-09-22

    The Fuel Cycle Research and Development program of the Office of Nuclear Energy has implemented a program to develop a Uranium-Molybdenum metal fuel for light water reactors. Uranium-Molybdenum fuel has the potential to provide superior performance based on its thermo-physical properties. With sufficient development, it may be able to provide the Light Water Reactor industry with a melt-resistant, accident-tolerant fuel with improved safety response. The Pacific Northwest National Laboratory has been tasked with extrusion development and performing ex-reactor corrosion testing to characterize the performance of Uranium-Molybdenum fuel in both these areas. This report documents the results of the fiscal year 2016 effort to develop the Uranium-Molybdenum metal fuel concept for light water reactors.

  9. Formation of molybdenum boride cermet coating by the detonation spray process

    Science.gov (United States)

    Yang, Gao; Zu-Kun, Hei; Xiaolei, Xu; Gang, Xin

    2001-09-01

    The effects of the powder particle size and the acetylene/oxygen gas flow ratio during the detonation spray process on the amount of molybdenum phase, porosity, and hardness of the coatings using MoB powder were investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), etc. The results show that the presence of metallic molybdenum in the coating results from decomposition of MoB powder during thermal spray. The compositions of the coatings are metallic Mo, MoB, and Mo2B, which are different from the phases of the original powder. The amount of molybdenum phase increases monotonously with the oxygen/acetylene ratio, but the increasing rate for the fine powder is faster than that for the coarse powder. The porosity and hardness of the coating are related to the amount of molybdenum phase. The phase constitution of the coating is discussed.

  10. Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Botar, Bogdan; Ellern, Arkady; Kogerler, Paul

    2012-05-18

    The self-assembly of soluble molybdenum blue species from simple molybdate solutions has primarily been associated with giant mixed-valent wheel-shaped cluster anions, derived from the {MoV/VI154/176} archetypes, and a {MoV/VI368} lemon-shaped cluster. The combined use of Raman spectroscopy and kinetic precipitation as self-assembly monitoring techniques and single-crystal X-ray diffraction is key to mapping the realm of molybdenum blue species by establishing spherical {MoV/VI102}-type Keplerates as an important giant molybdenum blue-type species. We additionally rationalize the empirical effect of reducing agent concentration on the formation of all three relevant skeletal types: wheel, lemon and spheres. Whereas both wheels and the lemon-shaped {MoV/VI368} cluster are obtained from weakly reduced molybdenum blue solutions, considerably higher reduced solutions lead to {MoV/VI102}-type Keplerates.

  11. Quantitation of protein S-glutathionylation by liquid chromatograph-tandem mass spectrometry: Correction for contaminating glutathione and glutathione disulfide

    Science.gov (United States)

    Protein S-glutathionylation is a posttranslational modification that links oxidative stimuli to reversible changes in cellular function. Protein-glutathione mixed disulfides (PSSG) are commonly quantified by the reduction of the disulfide and detection of the resultant glutathione species. This met...

  12. Minor element distribution in iron disulfides in coal: a geochemical review

    Science.gov (United States)

    Kolker, Allan

    2012-01-01

    Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe3S4), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to

  13. The electrochemical oxidation of dimethyl disulfide-Anodic methylsulfanylation of phenols and aromatic ethers

    Energy Technology Data Exchange (ETDEWEB)

    Quang Tho Do [Laboratoire d' Electrochimie et Environnement, CEREA, Universite Catholique de l' Ouest, BP 10808, 49008 ANGERS Cedex 01 (France); Elothmani, Driss [Laboratoire GRAPPE, Ecole Superieure d' Agriculture d' Angers, BP 30748, 49007 ANGERS Cedex 01 (France); Simonet, Jacques [Laboratoire d' Electrochimie Moleculaire (UMR CNRS 6510), Universite de RENNES 1, 35042 RENNES Cedex (France); Guillanton, Georges Le [Laboratoire d' Electrochimie et Environnement, CEREA, Universite Catholique de l' Ouest, BP 10808, 49008 ANGERS Cedex 01 (France)]. E-mail: gleguill@uco.fr

    2005-08-30

    The electrochemical oxidation of dimethyl disulfide was investigated in acetonitrile and dichloromethane. The nature of the oxidation strongly depends on the nucleophilicity of the solvent. In acetonitrile a one-electron oxidation is observed and the consecutive species did not exhibit any reactivity towards aromatic compounds subject to electrophile substitution. On the contrary, the oxidation of dimethyl disulfide in methylene chloride afforded a two-electron process with the formation of a species consistent with CH{sub 3} -S{sup +}. Its reactivity towards phenols and aromatic ethers was confirmed and showed a selective monomethylsulfanylation in most of the cases.

  14. Denaturation and unfolding of human anaphylatoxin C3a: an unusually low covalent stability of its native disulfide bonds.

    Science.gov (United States)

    Chang, Jui-Yoa; Lin, Curtis C-J; Salamanca, Silvia; Pangburn, Michael K; Wetsel, Rick A

    2008-12-15

    The complement C3a anaphylatoxin is a major molecular mediator of innate immunity. It is a potent activator of mast cells, basophils and eosinophils and causes smooth muscle contraction. Structurally, C3a is a relatively small protein (77 amino acids) comprising a N-terminal domain connected by 3 native disulfide bonds and a helical C-terminal segment. The structural stability of C3a has been investigated here using three different methods: Disulfide scrambling; Differential CD spectroscopy; and Reductive unfolding. Two uncommon features regarding the stability of C3a and the structure of denatured C3a have been observed in this study. (a) There is an unusual disconnection between the conformational stability of C3a and the covalent stability of its three native disulfide bonds that is not seen with other disulfide proteins. As measured by both methods of disulfide scrambling and differential CD spectroscopy, the native C3a exhibits a global conformational stability that is comparable to numerous proteins with similar size and disulfide content, all with mid-point denaturation of [GdmCl](1/2) at 3.4-5M. These proteins include hirudin, tick anticoagulant protein and leech carboxypeptidase inhibitor. However, the native disulfide bonds of C3a is 150-1000 fold less stable than those proteins as evaluated by the method of reductive unfolding. The 3 native disulfide bonds of C3a can be collectively and quantitatively reduced with as low as 1mM of dithiothreitol within 5 min. The fragility of the native disulfide bonds of C3a has not yet been observed with other native disulfide proteins. (b) Using the method of disulfide scrambling, denatured C3a was shown to consist of diverse isomers adopting varied extent of unfolding. Among them, the most extensively unfolded isomer of denatured C3a is found to assume beads-form disulfide pattern, comprising Cys(36)-Cys(49) and two disulfide bonds formed by two pair of consecutive cysteines, Cys(22)-Cys(23) and Cys(56)-Cys(57), a

  15. Molybdenum-copper and tungsten-copper alloys and method of making

    Science.gov (United States)

    Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

    1989-05-23

    Molybdenum-copper and tungsten-copper alloys are prepared by a consumable electrode method in which the electrode consists of a copper matrix with embedded strips of refractory molybdenum or tungsten. The electrode is progressively melted at its lower end with a superatmospheric inert gas pressure maintained around the liquifying electrode. The inert gas pressure is sufficiently above the vapor pressure of copper at the liquidus temperature of the alloy being formed to suppress boiling of liquid copper.

  16. Synthesis of high active catalytic systems based on double molybdenum carbides

    OpenAIRE

    Dolmatov Vladimir; Kuznetsov Sergey; Rebrov Evgeny; Schouten Jacob Cornelis

    2015-01-01

    A new two-stage synthesis of double molybdenum and nickel carbides and high active and stable catalytic coatings of nickelpromoter molybdenum carbide in molten salts is developed. The first stage includes the formation of molybdenum–nickel alloys by an electrolytic method and currentless transfer in chloride melts. The second stage consists in the carbonization of the alloys in chloride-carbonate melt under various synthesis conditions. The stabilities of the nickel-promoter catalyti...

  17. Molybdenum-containing acidic catalysts to convert cellulosic biomass to glycolic acid

    KAUST Repository

    Han, Yu

    2014-09-30

    Embodiments of the present invention include methods and compositions related to catabolic conversion of cellulosic biomass to glycolic acid using molybdenum-containing acidic catalysts. The invention includes the use of heteropoly and isopoly acids and salts as the molybdenum-containing multi-functional catalysts for biomass conversion. In embodiments of the invention, the reactions employ successive hydrolysis, retro-aldol fragmentation, and selective oxidation in a noble metal-free system.

  18. Material and Energy Flows Associated with Select Metals in GREET 2. Molybdenum, Platinum, Zinc, Nickel, Silicon

    Energy Technology Data Exchange (ETDEWEB)

    Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dai, Qiang [Argonne National Lab. (ANL), Argonne, IL (United States); Sullivan, John L. [Argonne National Lab. (ANL), Argonne, IL (United States); Kelly, Jarod C. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-09-01

    In this work, we analyzed the material and energy consumption from mining to production of molybdenum, platinum, zinc, and nickel. We also analyzed the production of solar- and semiconductor-grade silicon. We described new additions to and expansions of the data in GREET 2. In some cases, we used operating permits and sustainability reports to estimate the material and energy flows for molybdenum, platinum, and nickel, while for zinc and silicon we relied on information provided in the literature.

  19. Carbon disulfide exposure estimate and prevalence of chronic diseases after carbon disulfide poisoning-related occupational diseases.

    Science.gov (United States)

    Chung, Hweemin; Youn, Kanwoo; Kim, Kyuyeon; Park, Kyunggeun

    2017-01-01

    In Korea, Carbon disulfide (CS2) toxicity was an important social problem from the late 1980s to the early 1990s but there have been few large-scale studies examining the prevalence of diseases after CS2 exposure discontinuance. So we investigated past working exposure to CS2 characteristics from surviving ex-workers of a rayon manufacturing plant including cumulative CS2 exposure index. Furthermore, we studied the prevalence of their chronic diseases recently after many years. We interviewed 633 ex-workers identified as CS2 poisoning-related occupational diseases to determine demographic and occupational characteristics and reviewed their medical records. The work environment measurement data from 1992 was used as a reference. Based on the interviews and foreign measurement documents, weights were assigned to the reference concentrations followed by calculation of individual exposure index, the sum of the portion of each time period multiplied by the concentrations of CS2 during that period. The cumulative exposure index was 128.2 ppm on average. Workers from the spinning, electrical equipment repair, and motor repair departments were exposed to high concentrations of ≥10 ppm. Workers from the maintenance of the ejector, manufacturing of CS2, post-process, refining, maintenance and manufacturing of viscose departments were exposed to low concentrations below 10 ppm. The prevalence for hypertension, coronary artery disease, cerebrovascular disease, diabetes, arrhythmia, psychoneurotic disorder, disorders of the nervous system and sensory organ were 69.2%, 13.9%, 24.8%, 24.5%, 1.3%, 65.7%, 72.4% respectively. We estimated the individual cumulative CS2 exposure based on interviews and foreign measurement documents, and work environment measurement data. Comparing the work environment measurement data from 1992, these values were similar to them. After identified as CS2 poisoning, there are subjects over 70 years of average age with disorders of the nervous

  20. The road to the first, fully active and more stable human insulin variant with an additional disulfide bond

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Kjeldsen, Thomas B.; Jensen, Knud Jørgen

    2015-01-01

    variants in vertebrates consist of two peptide chains and have six cysteine residues, which form three disulfide bonds, two of them link the two chains and a third is an intra-chain bond in the A-chain. This classical insulin fold appears to have been conserved over half a billion years of evolution. We...... addressed the question whether a human insulin variant with four disulfide bonds could exist and be fully functional. In this review, we give an overview of the road to engineering four-disulfide bonded insulin analogs. During our journey, we discovered several active four disulfide bonded insulin analogs......Insulin, a small peptide hormone, is crucial in maintaining blood glucose homeostasis. The stability and activity of the protein is directed by an intricate system involving disulfide bonds to stabilize the active monomeric species and by their non-covalent oligomerization. All known insulin...

  1. Environmental exposure to metals and male reproductive hormones: circulating testosterone is inversely associated with blood molybdenum.

    Science.gov (United States)

    Meeker, John D; Rossano, Mary G; Protas, Bridget; Padmanahban, Vasantha; Diamond, Michael P; Puscheck, Elizabeth; Daly, Douglas; Paneth, Nigel; Wirth, Julia J

    2010-01-01

    To explore associations between exposure to metals and male reproductive hormone levels. Cross-sectional epidemiology study with adjustment for potential confounders. University Medical Center. Men recruited through two infertility clinics in Michigan. Metal concentrations and reproductive hormone levels were measured in blood samples collected from 219 men. Serum FSH, LH, inhibin B, T, and sex hormone-binding globulin levels. Cadmium, copper, and lead were all significantly or suggestively positively associated with T when modeled individually, findings that are consistent with limited previous human and animal studies. Conversely, molybdenum was associated with reduced T. A significant inverse trend between molybdenum and T remained when additionally considering other metals in the model, and a positive association between T and zinc was also found. Finally, in exploratory analysis there was evidence for an interaction between molybdenum and zinc, whereby high molybdenum was associated with a 37% reduction in T (relative to the population median level) among men with low zinc. Although reductions in T and reproductive toxicity after molybdenum exposure have been previously demonstrated in animal studies, more research is needed to determine whether molybdenum poses a risk to human reproductive health. Copyright 2010 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

  2. Environmental exposure to metals and male reproductive hormones: Circulating testosterone is inversely associated with blood molybdenum

    Science.gov (United States)

    Meeker, John D.; Rossano, Mary G.; Protas, Bridget; Padmanabhan, Vasantha; Diamond, Michael P.; Puscheck, Elizabeth; Daly, Douglas; Paneth, Nigel; Wirth, Julia J.

    2010-01-01

    Study Objective To explore associations between exposure to metals and male reproductive hormone levels. Design Cross-sectional epidemiology study with adjustment for potential confounders. Setting Metal concentrations and reproductive hormone levels were measured in blood samples collected from 219 men. Patients: Men recruited through two Michigan, USA infertility clinics. Interventions None Main Outcome Measures Serum FSH, LH, inhibin B, testosterone, and SHBG. Results Cadmium, copper and lead were all significantly or suggestively positively associated with testosterone when modeled individually (p-values = 0.1, 0.03, and 0.07, respectively), findings that are consistent with limited previous human and animal studies. Conversely, molybdenum was associated with reduced testosterone (p-value for trend = 0.001). A significant inverse trend between molybdenum and testosterone remained when additionally considering other metals in the model, where a positive association between testosterone and zinc was also found. Finally, in exploratory analysis there was evidence for an interaction between molybdenum and zinc, where high molybdenum was associated with a 37% reduction in testosterone (relative to the population median level) among men with low zinc. Conclusions While reductions in testosterone and reproductive toxicity following molybdenum exposure have been previously demonstrated in animal studies, more research is needed to determine whether molybdenum poses a risk to human reproductive health. PMID:18990371

  3. Magnetic composites based on metallic nickel and molybdenum carbide: A potential material for pollutants removal

    Energy Technology Data Exchange (ETDEWEB)

    Mambrini, Raquel V.; Fonseca, Thales L. [Departamento de Quimica, Universidade Federal de Minas Gerais, Belo Horizonte, MG 31270-901 (Brazil); Dias, Anderson [Departamento de Quimica, Universidade Federal de Ouro Preto, Ouro Preto, MG 35400-000 (Brazil); Oliveira, Luiz C.A.; Araujo, Maria Helena [Departamento de Quimica, Universidade Federal de Minas Gerais, Belo Horizonte, MG 31270-901 (Brazil); Moura, Flavia C.C., E-mail: flaviamoura@ufmg.br [Departamento de Quimica, Universidade Federal de Minas Gerais, Belo Horizonte, MG 31270-901 (Brazil)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer New magnetic molybdenum carbide composites can be prepared by CVD from ethanol. Black-Right-Pointing-Pointer Magnetic molybdenum carbide shows promising results for pollutants removal. Black-Right-Pointing-Pointer The carbide composites can be easily recovered magnetically and reused. - Abstract: New magnetic composites based on metallic nickel and molybdenum carbide, Ni/Mo{sub 2}C, have been produced via catalytic chemical vapor deposition from ethanol. Scanning electron microscopy, thermal analysis, Raman spectroscopy and X-ray diffraction studies suggest that the CVD process occurs in a single step. This process involves the reduction of NiMo oxides at different temperatures (700, 800 and 900 Degree-Sign C) with catalytic deposition of carbon from ethanol producing molybdenum carbide on Ni surface. In the absence of molybdenum the formation of Ni/C was observed. The magnetic molybdenum carbide was successfully used as pollutants removal by adsorption of sulfur and nitrogen compounds from liquid fuels and model dyes such as methylene blue and indigo carmine. The dibenzothiofene adsorption process over Ni/Mo{sub 2}C reached approximately 20 mg g{sup -1}, notably higher than other materials described in the literature and also removed almost all methylene blue dye. The great advantage of these carbide composites is that they may be easily recovered magnetically and reused.

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

    Science.gov (United States)

    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. In this study, development of a novel thermoplastic bio-based composite with excellent antimicrobial surface properties is investigated. To the best of our knowledge, this is the first report to evaluate the antimicrobial properties of molybdenum trioxide embedded into a cellulose acetate as biopolymer matrix. The developed composites might step up to innovative applications used in modern medical and public environments. © 2016 The Society for Applied Microbiology.

  5. Different dynamics and pathway of disulfide bonds reduction of two human defensins, a molecular dynamics simulation study.

    Science.gov (United States)

    Zhang, Liqun

    2017-04-01

    Human defensins are a class of antimicrobial peptides that are crucial components of the innate immune system. Both human α defensin type 5 (HD5) and human β defensin type 3 (hBD-3) have 6 cysteine residues which form 3 pairs of disulfide bonds in oxidizing condition. Disulfide bond linking is important to the protein structure stabilization, and the disulfide bond linking and breaking order have been shown to influence protein function. In this project, microsecond long molecular dynamics simulations were performed to study the structure and dynamics of HD5 and hBD-3 wildtype and analogs which have all 3 disulfide bonds released in reducing condition. The structure of hBD-3 was found to be more dynamic and flexible than HD5, based on RMSD, RMSF, and radius of gyration calculations. The disulfide bridge breaking order of HD5 and hBD-3 in reducing condition was predicted by two kinds of methods, which gave consistent results. It was found that the disulfide bonds breaking pathways for HD5 and hBD-3 are very different. The breaking of disulfide bonds can influence the dimer interface by making the dimer structure less stable for both kinds of defensin. In order to understand the difference in dynamics and disulfide bond breaking pathway, hydrophilic and hydrophobic accessible surface areas (ASA), buried surface area between cysteine pairs, entropy of cysteine pairs, and internal energy were calculated. Comparing to the wildtype, hBD-3 analog is more hydrophobic, while HD5 is more hydrophilic. For hBD-3, the disulfide breaking is mainly entropy driven, while other factors such as the solvation effects may take the major role in controlling HD5 disulfide breaking pathway. Proteins 2017; 85:665-681. © 2016 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  6. Purification of correctly oxidized MHC class I heavy-chain molecules under denaturing conditions: A novel strategy exploiting disulfide assisted protein folding

    DEFF Research Database (Denmark)

    Ferré, Henrik; Ruffet, E.; Blicher, T.

    2003-01-01

    disulfide bonding are formed under non-reducing denaturing conditions and separated from scrambled disulfide bond forms by hydrophobic interaction chromatography. In the second step, rapid refolding of the oxidized heavy chains is afforded by disulfide bond-assisted folding in the presence of beta(2...

  7. Purification of correctly oxidized MHC class I heavy-chain molecules under denaturing conditions: a novel strategy exploiting disulfide assisted protein folding

    DEFF Research Database (Denmark)

    Ferré, Henrik; Ruffet, Emmanuel; Blicher, Thomas

    2003-01-01

    with correct disulfide bonding are formed under non-reducing denaturing conditions and separated from scrambled disulfide bond forms by hydrophobic interaction chromatography. In the second step, rapid refolding of the oxidized heavy chains is afforded by disulfide bond-assisted folding in the presence of beta...

  8. Stabilization of cyclohexanone monooxygenase by a computationally designed disulfide bond spanning only one residue

    NARCIS (Netherlands)

    Beek, Hugo L. van; Wijma, Hein J.; Fromont, Lucie; Janssen, Dick B.; Fraaije, Marco W.

    2014-01-01

    Enzyme stability is an important parameter in biocatalytic applications, and there is a strong need for efficient methods to generate robust enzymes. We investigated whether stabilizing disulfide bonds can be computationally designed based on a model structure. In our approach, unlike in previous

  9. X-ray absorption studies of organo-disulfide redox cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Skotheim, T.A. (Moltech Corp., Stony Brook, NY (United States)); Yang, X.Q.; Xue, K.H.; Lee, H.S.; McBreen, J. (Brookhaven National Lab., Upton, NY (United States)); Lu, F. (Kentucky Univ., Lexington, KY (United States))

    1991-01-01

    We have measured the near-edge x-ray absorption fine structure (NEXAFS) spectra of the K-edge of sulfur in organo-disulfide redox polymeric electrodes in both charged and discharged states. The formation and scission of S-S bonding during the charge-discharge cycle were observed through NEXAFS spectroscopy. 4 refs., 2 figs.

  10. Accurate disulfide-bonding network predictions improve ab initio structure prediction of cysteine-rich proteins.

    Science.gov (United States)

    Yang, Jing; He, Bao-Ji; Jang, Richard; Zhang, Yang; Shen, Hong-Bin

    2015-12-01

    Cysteine-rich proteins cover many important families in nature but there are currently no methods specifically designed for modeling the structure of these proteins. The accuracy of disulfide connectivity pattern prediction, particularly for the proteins of higher-order connections, e.g., >3 bonds, is too low to effectively assist structure assembly simulations. We propose a new hierarchical order reduction protocol called Cyscon for disulfide-bonding prediction. The most confident disulfide bonds are first identified and bonding prediction is then focused on the remaining cysteine residues based on SVR training. Compared with purely machine learning-based approaches, Cyscon improved the average accuracy of connectivity pattern prediction by 21.9%. For proteins with more than 5 disulfide bonds, Cyscon improved the accuracy by 585% on the benchmark set of PDBCYS. When applied to 158 non-redundant cysteine-rich proteins, Cyscon predictions helped increase (or decrease) the TM-score (or RMSD) of the ab initio QUARK modeling by 12.1% (or 14.4%). This result demonstrates a new avenue to improve the ab initio structure modeling for cysteine-rich proteins. http://www.csbio.sjtu.edu.cn/bioinf/Cyscon/ zhng@umich.edu or hbshen@sjtu.edu.cn. Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  11. Decontamination of Oils Contaminated with Polychlorinated Biphenyls and Dibenzyl Disulfide Using Polar Aprotic Solvents

    Czech Academy of Sciences Publication Activity Database

    Kaštánek, František; Matějková, Martina; Spáčilová, Lucie; Maléterová, Ywetta; Kaštánek, P.; Šolcová, Olga

    2015-01-01

    Roč. 4, č. 2 (2015), s. 41-48 ISSN 2319-5967 R&D Projects: GA TA ČR(CZ) TA04020151 Institutional support: RVO:67985858 Keywords : corrosive sulfur * dibenzyl disulfide * polar aprotic solvents Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.ijesit.com/Volume%204/Issue%202/IJESIT201502_06.pdf

  12. Differential expression of disulfide reductase enzymes in a free-living platyhelminth (Dugesia dorotocephala.

    Directory of Open Access Journals (Sweden)

    Alberto Guevara-Flores

    Full Text Available A search of the disulfide reductase activities expressed in the adult stage of the free-living platyhelminth Dugesia dorotocephala was carried out. Using GSSG or DTNB as substrates, it was possible to obtain a purified fraction containing both GSSG and DTNB reductase activities. Through the purification procedure, both disulfide reductase activities were obtained in the same chromatographic peak. By mass spectrometry analysis of peptide fragments obtained after tryptic digestion of the purified fraction, the presence of glutathione reductase (GR, thioredoxin-glutathione reductase (TGR, and a putative thioredoxin reductase (TrxR was detected. Using the gold compound auranofin to selectively inhibit the GSSG reductase activity of TGR, it was found that barely 5% of the total GR activity in the D. dorotocephala extract can be assigned to GR. Such strategy did allow us to determine the kinetic parameters for both GR and TGR. Although It was not possible to discriminate DTNB reductase activity due to TrxR from that of TGR, a chromatofocusing experiment with a D. dorotocephala extract resulted in the obtention of a minor protein fraction enriched in TrxR, strongly suggesting its presence as a functional protein. Thus, unlike its parasitic counterparts, in the free-living platyhelminth lineage the three disulfide reductases are present as functional proteins, albeit TGR is still the major disulfide reductase involved in the reduction of both Trx and GSSG. This fact suggests the development of TGR in parasitic flatworms was not linked to a parasitic mode of life.

  13. Protein disulfide isomerase of Toxoplasma gondii is targeted by mucosal IgA antibodies in humans

    NARCIS (Netherlands)

    Meek, Bob; Back, Jaap Willem; Klaren, Vincent N. A.; Speijer, Dave; Peek, Ron

    2002-01-01

    Mass spectrometric analysis identified a 49 kDa antigen from Toxoplasma gondii as protein disulfide isomerase (PDI). This antigen is generally recognized by IgA in tears of healthy humans. We determined the complete open reading frame and expressed PDI recombinantly. Recombinant PDI was recognized

  14. Differential Labeling of Free and Disulfide-Bound Thiol Functions in Proteins

    NARCIS (Netherlands)

    Seiwert, B.; Hayen, H.; Karst, U.

    2008-01-01

    A method for the simultaneous determination of the number of free cysteine groups and disulfide-bound cysteine groups in proteins has been developed based on the sequential labeling of free and bound thiol functionalities with two ferrocene-based maleimide reagents. Liquid

  15. Selective removal of heavy metal ions by disulfide linked polymer networks

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Dongah [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark); Lee, Joo Sung [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Patel, Hasmukh A. [Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States); Jakobsen, Mogens H. [Department of Micro and Nano technology, Technical University of Denmark, Ørsteds Plads, 345B, 2800 Kgs. Lyngby (Denmark); Hwang, Yuhoon [Department of Environmental Engineering, Seoul National University of Science and Technology, 232 Gongreung-ro, Nowon-gu, Seoul 01811 (Korea, Republic of); Yavuz, Cafer T. [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Hansen, Hans Chr. Bruun [Department of Plant and Environmental Sciences, University of Copenhagen, Frederiksberg, Thorvaldsensvej 40, 1871 Frederiksberg C (Denmark); Andersen, Henrik R., E-mail: henrik@ndersen.net [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark)

    2017-06-15

    Highlights: • Disulfide/thiol polymer networks are promising as sorbent for heavy metals. • Rapid sorption and high Langmuir affinity constant (a{sub L}) for stormwater treatment. • Selective sorption for copper, cadmium, and zinc in the presence of calcium. • Reusability likely due to structure stability of disulfide linked polymer networks. - Abstract: Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions–copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

  16. Fluorometric polyethyleneglycol-peptide hybrid substrates for quantitative assay of protein disulfide isomerase

    DEFF Research Database (Denmark)

    Christiansen, Camilla; St Hilaire, Phaedria M; Winther, Jakob R.

    2004-01-01

    of an intramolecular disulfide bond between fluorophore-containing and quencher-containing peptide segments results in a redox-dependent fluorescence signal. We find a model compound of this type to be a highly sensitive substrate for PDI both in oxidation and in reduction assays under steady state conditions...

  17. Identification of Thioredoxin Target Disulfides Using Isotope-Coded Affinity Tags

    DEFF Research Database (Denmark)

    Hägglund, Per; Bunkenborg, Jakob; Maeda, Kenji

    2014-01-01

    extracts is described. The procedure utilizes the isotope-coded affinity tag (ICAT) reagents containing a thiol reactive iodoacetamide group and a biotin affinity tag to target peptides containing reduced cysteine residues. The identification of substrates for Trx and the extent of target disulfide...

  18. Increased Functional Half-life of Fibroblast Growth Factor-1 by Recovering a Vestigial Disulfide Bond

    Directory of Open Access Journals (Sweden)

    Jihun Lee

    2010-12-01

    Full Text Available The fibroblast growth factor (FGF family of proteins contains an absolutely conserved Cys residue at position 83 that is present as a buried free cysteine. We have previously shown that mutation of the structurally adjacent residue, Ala66, to cysteine results in the formation of a stabilizing disulfide bond in FGF-1. This result suggests that the conserved free cysteine residue at position 83 in the FGF family of proteins represents a vestigial half-cystine. Here, we characterize the functional half-life and mitogenic activity of the oxidized form of the Ala66Cys mutation to identify the effect of the recovered vestigial disulfide bond between Cys83 and Cys66 upon the cellular function of FGF-1. The results show that the mitogenic activity of this mutant is significantly increased and that its functional half-life is greatly extended. These favorable effects are conferred by the formation of a disulfide bond that simultaneously increases thermodynamic stability of the protein and removes a reactive buried thiol at position 83. Recovering this vestigial disulfide by introducing a cysteine at position 66 is a potentially useful protein engineering strategy to improve the functional half-life of other FGF family members.

  19. Per-2,3-O-alkylated beta-cyclodextrin duplexes connected with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Tatar, Ameneh; Grishina, Anastasia; Buděšínský, Miloš; Kraus, Tomáš

    2017-01-01

    Roč. 29, č. 1 (2017), s. 40-48 ISSN 1061-0278 R&D Projects: GA MŠk LD12019 Grant - others:COST(XE) CM1005 Institutional support: RVO:61388963 Keywords : cyclodextrin s * inclusion complexes * disulfide bonds Subject RIV: CC - Organic Chemistry Impact factor: 1.264, year: 2016

  20. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Science.gov (United States)

    2010-10-01

    ... bisulfide) and ethyl ether. 151.50-40 Section 151.50-40 Shipping COAST GUARD, DEPARTMENT OF HOMELAND... ether. (a) The provisions of this section are applicable if specifically referenced in the Special... disulfide (carbon bisulfide) and § 151.50-42 for ethyl ether shall also be observed. ...

  1. Identification of intra- and intermolecular disulfide bridges in the multidrug resistance transporter ABCG2

    DEFF Research Database (Denmark)

    Henriksen, Ulla Birk; Fog, Jacob U; Litman, Thomas

    2005-01-01

    ABCG2 is an ATP binding cassette (ABC) half-transporter that plays a key role in multidrug resistance to chemotherapy. ABCG2 is believed to be a functional homodimer that has been proposed to be linked by disulfide bridges. We have investigated the structural and functional role of the only three...

  2. Model building of disulfide bonds in proteins with known three-dimensional structure

    NARCIS (Netherlands)

    Hazes, Bart; Dijkstra, Bauke W.

    1988-01-01

    As an aid in the selection of sites in a protein where a disulfide bond might be engineered, a computer program has been developed. The algorithm starts with the generation of Cβ positions from the N, Cα and C atom coordinates available from a three-dimensional model. A first set of residue pairs

  3. Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide

    NARCIS (Netherlands)

    Verkruijsse, H.D.; Brandsma, L.

    1987-01-01

    Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide. Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in high yields. Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained

  4. The use of polydisulfides and copolymeric disulfides in the Li/PEO/SRPE battery system

    Energy Technology Data Exchange (ETDEWEB)

    Doeff, M.M.; Lerner, M.M.; Visco, S.J.; DeJonghe, L.C. (Lawrence Berkeley Lab., CA (United States))

    1982-08-01

    This paper reports that solid redox polymerization electrodes (SRPEs) have recently been used successfully as cathodes in lithium solid polymer electrolyte batteries. SRPEs contain organopolydisulfides (SRS) as the electroactive material; upon cell discharge these materials are reductively depolymerized via scission of the disulfide linkages to di- or trithiolate salts. The thiolate slats are reoxidized to the polymeric disulfides when the cell is recharged. Organopolydisulfides are easily synthesized via a one-step process, are inexpensive, and exhibit high performance levels in batteries. A characteristic unique to the ability to combine the desirable features of several compounds by copolymerization. The discharge characteristics of several different polymeric and copolymeric disulfides are presented in this paper. In general aliphatic organopoly-disulfides exhibit a flat discharge potential of about 2 V vs. Li, while other have higher cell voltages. The low equivalent weight and the high utilization of thick cathodes of-(SCH[sub 2]CH[sub 2]S)[sub n](X8) translate into high energy densities for lithium polymer electrolytes cells.

  5. Characterization of a foldase, protein disulfide isomerase A, in the protein secretory pathway of Aspergillus niger

    NARCIS (Netherlands)

    Ngiam, C.; Jeenes, D.J.; Punt, P.J.; Hondel, C.A.M.J.J. van den; Archer, D.B.

    2000-01-01

    Protein disulfide isomerase (PDI) is important in assisting the folding and maturation of secretory proteins in eukaryotes. A gene, pdiA, encoding PDIA was previously isolated from Aspergillus niger, and we report its functional characterization here. Functional analysis of PDIA showed that it

  6. Disulfide bonds in egg-white riboflavin-binding protein. Chemical reduction studies.

    Science.gov (United States)

    Kozik, A

    1982-01-01

    All eight disulfide bonds in the apo-form of egg white riboflavin-binding protein were easily reduced by 2-mercaptoethanol and dithiothreitol. These bonds exhibited nearly the same reactivity, thus they appeared to be exposed in the native structure, or 'superficial'. The cleavage of protein disulfides resulted in a loss of riboflavin-binding capacity. A correlation between these two related processes, analysed by kinetic and statistical methods, suggested a single bond to be essential for binding of riboflavin by the apoprotein. In the riboflavin-apoprotein complex the disulfides were rather poorly reducible but they still constituted a single reactivity class. The essential bond was not protected against modification, suggesting it was located out of the riboflavin-binding site. A postulated subunit structure of riboflavin-binding protein was not confirmed. The cleavage of disulfides caused some aggregation of the protein molecules. Only dimers and high polymers were formed, the former being relatively stable. Hydrophobic forces were probably involved in the formation of dimers.

  7. Exploring the folding pathway of green fluorescent protein through disulfide engineering.

    Science.gov (United States)

    Pitman, Derek J; Banerjee, Shounak; Macari, Stephen J; Castaldi, Christopher A; Crone, Donna E; Bystroff, Christopher

    2015-03-01

    We have introduced two disulfide crosslinks into the loop regions on opposite ends of the beta barrel in superfolder green fluorescent protein (GFP) in order to better understand the nature of its folding pathway. When the disulfide on the side opposite the N/C-termini is formed, folding is 2× faster, unfolding is 2000× slower, and the protein is stabilized by 16 kJ/mol. But when the disulfide bond on the side of the termini is formed we see little change in the kinetics and stability. The stabilization upon combining the two crosslinks is approximately additive. When the kinetic effects are broken down into multiple phases, we observe Hammond behavior in the upward shift of the kinetic m-value of unfolding. We use these results in conjunction with structural analysis to assign folding intermediates to two parallel folding pathways. The data are consistent with a view that the two fastest transition states of folding are "barrel closing" steps. The slower of the two phases passes through an intermediate with the barrel opening occurring between strands 7 and 8, while the faster phase opens between 9 and 4. We conclude that disulfide crosslink-induced perturbations in kinetics are useful for mapping the protein folding pathway. © 2014 The Protein Society.

  8. Dissecting molecular interactions involved in recognition of target disulfides by the barley thioredoxin system

    DEFF Research Database (Denmark)

    Björnberg, Olof; Maeda, Kenji; Svensson, Birte

    2012-01-01

    Thioredoxin reduces disulfide bonds, thus regulating activities of target proteins in various biological systems, e.g., inactivation of inhibitors of starch hydrolases and proteases in germinating plant seeds. In the three-dimensional structure of a complex with barley α-amylase/subtilisin...

  9. Soil biotic and abiotic responses to dimethyl disulfide spot drip fumigation in established grape vines

    Science.gov (United States)

    Dimethyl disulfide (DMDS) is a soil fumigant used in agricultural systems as an alternative to methyl bromide (MeBr) for the control of soilborne pests and pathogens. However, fumigants including DMDS that have broad biocidal activity can affect both target and non-target organisms in soil. Many bio...

  10. Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

    Energy Technology Data Exchange (ETDEWEB)

    Spink, D.

    1990-09-21

    Hexanuclear molybdenum clusters with mixed chloride and sulfide bridging ligands were prepared by reacting {alpha}-MoCl{sub 2} with sodium hydrosulfide in the presence of sodium butoxide. The resulting species, Mo{sub 6}Cl{sub (8-x)}S{sub x}{center dot}npy(x {congruent} 3.6, n {congruent} 4, py = pyridine), was pyrophoric and insoluble. The mixed sulfide chloride cluster species Mo{sub 6}S{sub 4}Cl{sub 4}{center dot}6OPEt{sub 3} and Mo{sub 6}S{sub {approximately}5}Cl{sub {approximately}3}{center dot}6PEt{sub 3} and Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} were isolated and characterized. Phosphorus-31 nuclear magnetic resonance, electron paramagnetic resonance, and UV/visible spectra were obtained for each fraction. The completely sulfided cluster, Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3}, was prepared similarly and used in various experiments as a possible precursor to Chevrel phase materials of the type Mo{sub 6}S{sub 8}or M{sub n}Mo{sub 6}S{sub 8}. With the goal of removing all of the triethylphosphine ligands, Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} was reacted with the transition metal carbonyls molybdenum hexacarbonyl and dicobalt octacarbonyl. Reaction on the molecular sulfide cluster with copper(I) chloride in toluene gave a completely insoluble product. The reaction of Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} with propylene sulfide gave a product whose infrared spectra showed only very weak peaks associated with coordinated triethylphosphine. The elemental analysis of this product fit the formula Mo{sub 6}S{sub 8}{center dot}5SPEt{sub 3}. Reactivity of the outer ligands of the Mo{sub 6}S{sub 8}{center dot}npy and Mo{sub 6}S{sub 8}{center dot}(6{minus}x)PrNH{sub x} clusters were investigated. Crystalline Mo{sub 6}S{sub 8}{center dot}6THT was recovered from the reaction of the n-propylamine derivative with THT. A crystal structure determination was done. 87 refs., 12 fig., 15 tabs.

  11. The investigation of molybdenum migration in aqueous media landscape of the Khibiny massif to develop environmental activities

    Directory of Open Access Journals (Sweden)

    Sulimenko L.P.

    2015-06-01

    Full Text Available Relations of natural and technogenic factors at forming of molybdenum making streams in superficial and underground waters in the Khibiny massif have been studied. The priority sources of receipt of molybdenum in water objects have been considered. Taking into account hydrogeochemistrical properties of molybdenum the terms of strategy of decline of its negative influence on superficial currents in the conditions of productive mining complex activity have been defined

  12. A Method for the Calculation of Lattice Energies of Complex Crystals with Application to the Oxides of Molybdenum

    Science.gov (United States)

    Chaney, William S.

    1961-01-01

    A theoretical study has been made of molybdenum dioxide and molybdenum trioxide in order to extend the knowledge of factors Involved in the oxidation of molybdenum. New methods were developed for calculating the lattice energies based on electrostatic valence theory, and the coulombic, polarization, Van der Waals, and repulsion energie's were calculated. The crystal structure was examined and structure details were correlated with lattice energy.

  13. Dissecting the role of disulfide bonds on the amyloid formation of insulin

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yang; Gong, Hao [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Sun, Yue [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Yan, Juan; Cheng, Biao; Zhang, Xin [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Huang, Jing [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Yu, Mengying; Guo, Yu [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Zheng, Ling, E-mail: lzheng217@hotmail.com [College of Life Sciences, Wuhan University, Wuhan 430072 (China); Huang, Kun, E-mail: kunhuang2008@hotmail.com [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Centre for Biomedicine Research, Wuhan Institutes of Biotechnology, Wuhan 430070 (China)

    2012-06-29

    Highlights: Black-Right-Pointing-Pointer We dissect how individual disulfide bond affects the amyloidogenicity of insulin. Black-Right-Pointing-Pointer A controlled reduction system for insulin is established in this study. Black-Right-Pointing-Pointer Disulfide breakage is associated with unfolding and increased amyloidogenicity. Black-Right-Pointing-Pointer Breakage of A6-A11 is associated with significantly increased cytotoxicity. Black-Right-Pointing-Pointer Analogs without A6-A11 have a higher potency to form high order toxic oligomers. -- Abstract: Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6 > INS-3 > INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7

  14. Determination of molybdenum in various materials by normal-phase liquid chromatography using N-benzoyl-N-phenylhydroxylamine

    Energy Technology Data Exchange (ETDEWEB)

    Bagur, Gracia; Sanchez-Vinas, Mercedes; Gazquez, Domingo [Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada (Spain)

    1995-06-20

    A normal-phase liquid chromatographic method for the selective determination of molybdenum with N-benzoyl-N-phenylhydroxylamine is described. The molybdenum(VI) complex was preconcentrated by extraction into chloroform and injected onto a nitrile column for chromatography. The mobile phase was a 0.075 M solution of reagent in chloroform (stabilized with amylene). The detection limit for molybdenum by the proposed method was 0.88 ng for a phase volume ratio of 20:1 (aqueous to organic). Molybdenum has been determined in several samples with satisfactory accuracy and precision.

  15. Identification of a disulfide bridge important for transport function of SNAT4 neutral amino acid transporter.

    Directory of Open Access Journals (Sweden)

    Rugmani Padmanabhan Iyer

    Full Text Available SNAT4 is a member of system N/A amino acid transport family that primarily expresses in liver and muscles and mediates the transport of L-alanine. However, little is known about the structure and function of the SNAT family of transporters. In this study, we showed a dose-dependent inhibition in transporter activity of SNAT4 with the treatment of reducing agents, dithiothreitol (DTT and Tris(2-carboxyethylphosphine (TCEP, indicating the possible involvement of disulfide bridge(s. Mutation of residue Cys-232, and the two highly conserved residues Cys-249 and Cys-321, compromised the transport function of SNAT4. However, this reduction was not caused by the decrease of SNAT4 on the cell surface since the cysteine-null mutant generated by replacing all five cysteines with alanine was equally capable of being expressed on the cell surface as wild-type SNAT4. Interestingly, by retaining two cysteine residues, 249 and 321, a significant level of L-alanine uptake was restored, indicating the possible formation of disulfide bond between these two conserved residues. Biotinylation crosslinking of free thiol groups with MTSEA-biotin provided direct evidence for the existence of a disulfide bridge between Cys-249 and Cys-321. Moreover, in the presence of DTT or TCEP, transport activity of the mutant retaining Cys-249 and Cys-321 was reduced in a dose-dependent manner and this reduction is gradually recovered with increased concentration of H2O2. Disruption of the disulfide bridge also decreased the transport of L-arginine, but to a lesser degree than that of L-alanine. Together, these results suggest that cysteine residues 249 and 321 form a disulfide bridge, which plays an important role in substrate transport but has no effect on trafficking of SNAT4 to the cell surface.

  16. Mapping of disulfide bonds within the amino-terminal extracellular domain of the inhibitory glycine receptor.

    Science.gov (United States)

    Vogel, Nicolas; Kluck, Christoph J; Melzer, Nima; Schwarzinger, Stephan; Breitinger, Ulrike; Seeber, Silke; Becker, Cord-Michael

    2009-12-25

    The strychnine-sensitive glycine receptor (GlyR) is a ligand-gated chloride channel and a member of the superfamily of cysteine loop (Cys-loop) neurotransmitter receptors, which also comprises the nicotinic acetylcholine receptor (nAChR). Within the extracellular domain (ECD), the eponymous Cys-loop harbors two conserved cysteines, assumed to be linked by a superfamily-specific disulfide bond. The GlyR ECD carries three additional cysteine residues, two are predicted to form a second, GlyR-specific bond. The configuration of none of the cysteines of GlyR, however, had been determined directly. Based on a crystal structure of the nAChRalpha1 ECD, we generated a model of the human GlyRalpha1 where close proximity of the respective cysteines was consistent with the formation of both the Cys-loop and the GlyR-specific disulfide bonds. To identify native disulfide bonds, the GlyRalpha1 ECD was heterologously expressed and refolded under oxidative conditions. By matrix-assisted laser desorption ionization time-of-flight mass spectrometry, we detected tryptic fragments of the ECD indicative of disulfide bond formation for both pairs of cysteines, as proposed by modeling. The identity of tryptic fragments was confirmed using chemical modification of cysteine and lysine residues. As evident from circular dichroism spectroscopy, mutagenesis of single cysteines did not impair refolding of the ECD in vitro, whereas it led to partial or complete intracellular retention and consequently to a loss of function of full-length GlyR subunits in human embryonic kidney 293 cells. Our results indicate that the GlyR ECD forms both a Cys-loop and a GlyR-specific disulfide bond. In addition, cysteine residues appear to be important for protein maturation in vivo.

  17. Dissecting the role of disulfide bonds on the amyloid formation of insulin.

    Science.gov (United States)

    Li, Yang; Gong, Hao; Sun, Yue; Yan, Juan; Cheng, Biao; Zhang, Xin; Huang, Jing; Yu, Mengying; Guo, Yu; Zheng, Ling; Huang, Kun

    2012-06-29

    Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6>INS-3>INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7-B7 induced more unfolding of the insulin structure and a higher amyloidogenicity than breakage of A6-A11, but breakage of A6-A11 caused a significant cytotoxicity increase and a higher potency to form high order toxic oligomers. Copyright © 2012 Elsevier Inc. All rights reserved.

  18. Molybdenum isotope behaviour in groundwaters and terrestrial hydrothermal systems, Iceland

    Science.gov (United States)

    Neely, Rebecca A.; Gislason, Sigurdur R.; Ólafsson, Magnus; McCoy-West, Alex J.; Pearce, Christopher R.; Burton, Kevin W.

    2018-03-01

    Molybdenum (Mo) isotopes have proved useful in the reconstruction of paleoredox conditions. Their application generally relies upon a simplified model of ocean inputs in which rivers dominate Mo fluxes to the oceans and hydrothermal fluids are considered to be a minor contribution. To date, however, little attention has been paid to the extent of Mo isotope variation of hydrothermal waters, or to the potential effect of direct groundwater discharge to the oceans. Here we present Mo isotope data for two Icelandic groundwater systems (Mývatn and Þeistareykir) that are both influenced by hydrothermal processes. Relative to NIST 3134 = +0.25‰, the cold (Icelandic rivers. In contrast, waters that are hydrothermally influenced (>10 °C) possess isotopically heavy δ98/95MoHYDROTHERMAL values of +0.25‰ to +2.06‰ (n = 18) with the possibility that the high temperature endmembers are even heavier. Although the mechanisms driving this fractionation remain unresolved, the incongruent dissolution of the host basalt and both the dissolution and precipitation of sulfides are considered. Regardless of the processes driving these variations, the δ98Mo data presented in this study indicate that groundwater and hydrothermal waters have the potential to modify ocean budget calculations.

  19. SAXS study of molybdenum irradiated with helium ions

    Science.gov (United States)

    Osamura, Kozo; Suzuki, Hideo

    1983-01-01

    Defects produced by helium ion irradiation have been investigated by means of small-angle X-ray scattering (SAXS) measurements, transmission electron microscope (TEM) and scanning electron microscope (SEM) observations. He + ions with projectile energy of 2 MeV were implanted in thin high-purity molybdenum foils with dose rates of 7-56 μA cm -2 up to total doses of 0.43-3.46 × 10 18 ions cm -2. The critical fluence producing blisters and the blister skin thickness were measured to be about 0.5 × 10 18 ions cm t-2 and 2.8 ± 0.4 μm, respectively, from SEM observations. Two types of bubbles were observed by TEM. The angular dependence of SAXS intensity was explained by the superposition of three Gaussian-shaped scattering curves, suggesting three different types of irradiation defects. Type II, which had a dimension of 4-7 nm, was identified with polygonal bubbles observed by TEM. This type appeared beyond the critical dose of 0.6 × 10 18 ions cm -2. Type III, which had a dimension of 0.6-2.7 nm, was identified with finer bubbles observed by TEM and distinguishable from type II. The SAXS results have been applied to evaluate quantitatively the kinetics of formation of these bubbles.

  20. Assessing the standard Molybdenum projector augmented wave VASP potentials

    Energy Technology Data Exchange (ETDEWEB)

    Mattsson, Ann E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Multi-Scale Science

    2014-07-01

    Density Functional Theory (DFT) based Equation of State (EOS) construction is a prominent part of Sandia’s capabilities to support engineering sciences. This capability is based on augmenting experimental data with information gained from computational investigations, especially in those parts of the phase space where experimental data is hard, dangerous, or expensive to obtain. A key part of the success of the Sandia approach is the fundamental science work supporting the computational capability. Not only does this work enhance the capability to perform highly accurate calculations but it also provides crucial insight into the limitations of the computational tools, providing high confidence in the results even where results cannot be, or have not yet been, validated by experimental data. This report concerns the key ingredient of projector augmented-wave (PAW) potentials for use in pseudo-potential computational codes. Using the tools discussed in SAND2012-7389 we assess the standard Vienna Ab-initio Simulation Package (VASP) PAWs for Molybdenum.

  1. Iron binary and ternary coatings with molybdenum and tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Yar-Mukhamedova, Gulmira, E-mail: gulmira-alma-ata@mail.ru [Institute Experimental and Theoretical Physics Al-Farabi Kazakh National University, 050038, Al-Farabi av., 71, Almaty (Kazakhstan); Ved, Maryna; Sakhnenko, Nikolay; Karakurkchi, Anna; Yermolenko, Iryna [National Technical University “Kharkov Polytechnic Institute”, Kharkov (Ukraine)

    2016-10-15

    Highlights: • High quality coatings of double Fe-Mo and ternary Fe-Mo-W electrolytic alloys can be produced both in a dc and a pulsed mode. • Application of unipolar pulsed current allows receiving an increased content of the alloying components and their more uniform distribution over the surface. • It is established that Fe-Mo and Fe-Mo-W coatings have an amorphous structure and exhibit improved corrosion resistance and microhardness as compared with the steel substrate due to the inclusion molybdenum and tungsten. - Abstract: Electrodeposition of Fe-Mo-W and Fe-Mo layers from a citrate solution containing iron(III) on steel and iron substrates is compared. The utilization of iron(III) compounds significantly improved the electrolyte stability eliminating side anodic redox reactions. The influence of concentration ratios and electrodeposition mode on quality, chemical composition, and functional properties of the alloys is determined. It has been found that alloys deposited in pulse mode have more uniform surface morphology and chemical composition and contain less impurities. Improvement in physical and mechanical properties as well as corrosion resistance of Fe-Mo and Fe-Mo-W deposits when compared with main alloy forming metals is driven by alloying components chemical passivity as well as by alloys amorphous structure. Indicated deposits can be considered promising materials in surface hardening technologies and repair of worn out items.

  2. Hydrogen reduction of molybdenum oxide at room temperature

    Science.gov (United States)

    Borgschulte, Andreas; Sambalova, Olga; Delmelle, Renaud; Jenatsch, Sandra; Hany, Roland; Nüesch, Frank

    2017-01-01

    The color changes in chemo- and photochromic MoO3 used in sensors and in organic photovoltaic (OPV) cells can be traced back to intercalated hydrogen atoms stemming either from gaseous hydrogen dissociated at catalytic surfaces or from photocatalytically split water. In applications, the reversibility of the process is of utmost importance, and deterioration of the layer functionality due to side reactions is a critical challenge. Using the membrane approach for high-pressure XPS, we are able to follow the hydrogen reduction of MoO3 thin films using atomic hydrogen in a water free environment. Hydrogen intercalates into MoO3 forming HxMoO3, which slowly decomposes into MoO2 +1/2 H2O as evidenced by the fast reduction of Mo6+ into Mo5+ states and slow but simultaneous formation of Mo4+ states. We measure the decrease in oxygen/metal ratio in the thin film explaining the limited reversibility of hydrogen sensors based on transition metal oxides. The results also enlighten the recent debate on the mechanism of the high temperature hydrogen reduction of bulk molybdenum oxide. The specific mechanism is a result of the balance between the reduction by hydrogen and water formation, desorption of water as well as nucleation and growth of new phases.

  3. Photodecomposition of Molybdenum andTungsten Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Thamer A. Alwani

    2009-01-01

    Full Text Available The photodecomposition of four different colored organometallic molybdenum and tungsten carbonyl complexes, i.e. [Mo(CO52LA] (complex I, [(Mo(CO3(bipy2LB] (complex II, [(W(CO3(tmen2LB] (complex III and [Mo(CO2LC]2 (complex I V where LA 2-phenyl-1,3-indandionebis(2-methyl anilines, LB 2-phenyl-1,3-indandione bis (4-hydroxy anilines and LCbis (2-hydroxo-benzalydine benzidine ion have been performed at 365 nm in chloroform at 25 °C under oxygen atmosphere. The absorbance spectrum of these complexes has been recorded with the time of irradiation in order to examine the kinetics of photodecomposition. The rate of the photodecomposition process was investigated and the relative values of the rate constants of dissociation (Kd for the first-order reaction are tabulated. The apparent rate constant of photodecomposition was found to be (8.33-11.50 × 10-5 s-1.

  4. Preparation and characterization of DC sputtered molybdenum thin films

    Directory of Open Access Journals (Sweden)

    Abd El-Hady B. Kashyout

    2011-03-01

    Full Text Available Molybdenum (Mo thin films have been deposited on soda-lime glass substrates using a DC magnetron sputtering system. Their electrical resistivity, and their morphological, structural and adhesive properties have been examined with respect to the deposition power, deposition time and substrate temperature. The electrical resistivity of the Mo films could be reduced by increasing any of the above parameters. Within the range of the investigated deposition parameters, the films showed a mono-crystalline nature with a preferred orientation along the (1 1 0 plane. The Mo films adhesion to the soda-lime glass could be improved by increasing the substrate temperature. At a deposition power of 200 W, deposition time of 20 min and substrate temperature of 450 °C, Mo thin film exhibiting mono-crystalline structure with thickness equal to 450 nm and electrical resistivity equal to 1.85 × 10−4 Ω cm was obtained.

  5. EUV nanosecond laser ablation of silicon carbide, tungsten and molybdenum

    Science.gov (United States)

    Frolov, Oleksandr; Kolacek, Karel; Schmidt, Jiri; Straus, Jaroslav; Choukourov, Andrei; Kasuya, Koichi

    2015-09-01

    In this paper we present results of study interaction of nanosecond EUV laser pulses at wavelength of 46.9 nm with silicon carbide (SiC), tungsten (W) and molybdenum (Mo). As a source of laser radiation was used discharge-plasma driver CAPEX (CAPillary EXperiment) based on high current capillary discharge in argon. The laser beam is focused with a spherical Si/Sc multilayer-coated mirror on samples. Experimental study has been performed with 1, 5, 10, 20 and 50 laser pulses ablation of SiC, W and Mo at various fluence values. Firstly, sample surface modification in the nanosecond time scale have been registered by optical microscope. And the secondly, laser beam footprints on the samples have been analyzed by atomic-force microscope (AFM). This work supported by the Czech Science Foundation under Contract GA14-29772S and by the Grant Agency of the Ministry of Education, Youth and Sports of the Czech Republic under Contract LG13029.

  6. Speciation of aluminium, arsenic and molybdenum in excessively limed lakes

    Energy Technology Data Exchange (ETDEWEB)

    Sjoestedt, Carin, E-mail: carinsj@kth.se [Department of Land and Water Resources Engineering, KTH (Royal Institute of Technology), Teknikringen 76, SE-100 44 Stockholm (Sweden); Waellstedt, Teresia [Department of Aquatic Sciences and Assessment, SLU (Swedish University of Agricultural Sciences), P.O. Box 7050, SE-750 07 Uppsala (Sweden); Gustafsson, Jon Petter [Department of Land and Water Resources Engineering, KTH (Royal Institute of Technology), Teknikringen 76, SE-100 44 Stockholm (Sweden); Borg, Hans [Department of Applied Environmental Science, SU (Stockholm University), SE-106 91 Stockholm (Sweden)

    2009-09-01

    The possible existence of the potentially toxic oxyanions of Al (Al(OH){sub 4}{sup -}), As (HAsO{sub 4}{sup 2-}), and Mo (MoO{sub 4}{sup 2-}) was examined in excessively limed lakes. In-situ dialysis (MWCO 1 kDa) was performed in the surface and bottom waters of two excessively limed lakes (pH 7.1-7.7) and one acidic lake (pH {approx} 5.4). The dialysable metal concentrations were compared to the equilibrium distribution of species as calculated with the geochemical code Visual MINTEQ incorporating the CD-MUSIC and Stockholm Humic models for complexation onto colloidal ferrihydrite and dissolved organic matter. Arsenic and molybdenum in the excessively limed lakes were to a large extent present in the dialysable fraction (> 79% and > 92% respectively). They were calculated to exist as free or adsorbed oxyanions. Most of the Al was observed to reside in the colloidal fraction (51-82%). In agreement with this, model predictions indicated aluminium to be present mostly as colloids or bound to dissolved organic matter. Only a small fraction was modelled as Al(OH){sub 4}{sup -} ions. In most cases, modelled values were in agreement with the dialysis results. The free concentrations of the three oxyanions were mostly low compared to toxic levels.

  7. Carbon nanotube synthesis via the catalytic chemical vapor deposition of methane in the presence of iron, molybdenum, and iron-molybdenum alloy thin layer catalysts

    Science.gov (United States)

    Yahyazadeh, Arash; Khoshandam, Behnam

    In this study, we documented the catalytic chemical vapor deposition synthesis of carbon nanotubes (CNTs) using ferrocene and molybdenum hexacarbonyl as catalyst nanoparticle precursors and methane as a nontoxic and economical carbon source for the first time. Field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, wavelength dispersive X-ray spectrometry and transmission electron microscopy of the thin layer catalyst as a simple and cost effective catalyst preparation after methane decomposition reaction, along with Fourier transform infrared spectroscopy and Raman spectroscopy confirmed the growth of CNTs, from bimetallic nanoparticles, which are converted into iron-molybdenum alloy nanoparticles at 700 °C for pretreatment by hydrogen after chemical vapor deposition of thin layers. An investigation of the weight percentages of the chemical elements present in the CNTs synthesized from iron-molybdenum catalyst using quartz sheet substrate at 750 °C, confirmed a significant carbon yield of 75.4% which represents high catalyst activity. Additionally, multi-walled carbon nanotubes (∼16-55 nm in diameter and 1.2 μm in length) were observed in the iron-molybdenum alloy sample after methane decomposition reaction at 750 °C for 35 min. To show the role of iron and molybdenum coated on silicon substrate as two thin layer catalysts, samples were considered for CNTs growth (diameter ∼47-69 nm) at 800 °C and 830 °C, respectively. Moreover, the effect of hydrogen pretreatment was evaluated in terms of active metal coating properly. The best graphitic structure due to Raman spectroscopy outcomes (ID/IG ratio) was obtained for iron coated on a quartz sheet, which was estimated at 0.8505. Thermogravimetric analysis proved the thermal stability of the synthesized CNTs using iron thin-layer catalyst up to 350 °C.

  8. Synthesis, Dynamic Combinatorial Chemistry, and PCR Amplification of 3'-5' and 3'-6' Disulfide-linked Oligonucleotides

    DEFF Research Database (Denmark)

    Hansen, Dennis Jul; Manuguerra, Ilenia; Kjelstrup, Michael Brøndum

    2014-01-01

    Disulfide dithymidines linked 3'-5' or 3'-6' were synthesized and incorporated into oligonucleotides through a combined phosphotriester and phosphoramidite solid-phase oligonucleotide synthesis approach. The disulfide links are cleaved and formed reversibly in the presence of thiols...... and oligonucleotides. This link was shown to be sequence-adaptive in response to given templates in the presence of mercaptoethanol. The artificial 3'-5' and 3'-6' disulfide link was tolerated by polymerases in the polymerase chain reaction (PCR). By using sequencing analysis, we show that single mutations frequently...

  9. An extracellular disulfide bond forming protein (DsbF) from Mycobacterium tuberculosis: Structural, biochemical and gene expression analysis

    OpenAIRE

    Chim, Nicholas; Riley, Robert; The, Juliana; Im, Soyeon; Segelke, Brent; Lekin, Tim; Yu, Minmin; Hung, Li Wei; Terwilliger, Tom; Whitelegge, Julian P.; Goulding, Celia W.

    2010-01-01

    Disulfide bond forming (Dsb) proteins ensure correct folding and disulfide bond formation of secreted proteins. Previously, we showed that Mycobacterium tuberculosis DsbE (Mtb DsbE, Rv2878c) aids in vitro oxidative folding of proteins. Here we present structural, biochemical and gene expression analyses of another putative Mtb secreted disulfide bond isomerase protein homologous to Mtb DsbE, Mtb DsbF (Rv1677). The X-ray crystal structure of Mtb DsbF reveals a conserved thioredoxin fold althou...

  10. Coelenterate Cnidae Capsules: Disulfide Linkages Revealed by Silver Cytochemistry and Their Differential Responses to Thiol Reagents.

    Science.gov (United States)

    Goldberg, W M; Taylor, G T

    1997-02-01

    The sulfur cytochemistry of cnidae from the Portuguese man-of-war Physalia physalis, the scyphozoan Cassiopeia xamachana, and the black coral Cirrhipathes luetkeni was evaluated on the basis of electron microscopy, X-ray microanalysis, amino acid analysis, and response to disulfide reducing agents. The cnidae examined included large and small holotrichous isorhizas in P. physalis, another small isorhiza in C. xamachana, and both spirocysts and microbasic mastigophore nematocysts in C. leutkeni. A strong reaction with methenamine-silver reagent was characteristic of all cnidae capsules, but the pattern and extent of that argentophilia was dependent upon the type of cnida and its state of maturity. The large isorhizas of P. physalis reacted primarily in the outermost capsule layers, but in C. xamachana isorhizas, silver stained the entire capsule with the exception of the outermost region. The small isorhizas of P. physalis and the mastigophore capsules of C. leutkeni stained throughout, whereas the spirocyst capsules were outlined by silver, clearly delineating the inner and outer layers. All of these reactions were abolished with alkylation, but only after treatment with disulfide reducing agents; alkylation alone diminished silver staining only slightly, indicating that the argentophilic response was due primarily to disulfide linkages. The cystine content of these cnidae varied from 4.1 to 4.7 mole percent for a given species, but amino acid analyses did not separate components of the cnidom. Cnidae, both within and among species, exhibited differential responses to the disulfide reducing agent dithiothreitol (DTT). Isolated, unfixed, large isorhizas of P. physalis discharged and appeared to dissolve rapidly in the presence of this reagent, whereas small isorhizas from both P. physalis and C. xamachana discharged, but dissolved slowly if at all. The discharge and solution responses of the capsule coincided with the complete development of the tubule. Cnidae

  11. The metal content of molybdenum-mineralizing fluids

    Science.gov (United States)

    Lerchbaumer, L.; Audétat, A.

    2012-04-01

    Molybdenum can be found in porphyry-type systems as well as in hydrothermal veins and breccias associated with granite systems. Up to now our knowledge on the metal content of fluids forming molybdenum ore deposits has been very limited. The only data available so far are from the porphyry Mo deposit at Questa, New Mexico, and from the Cave Peak porphyry Mo-Nb deposit in Texas. We have studied early, intermediate-density fluid inclusions in quartz crystals from miarolitic cavities in the Drammen and Glitrevann granites (Norway) and the Treasure Mountain Dome (Colorado/USA) to obtain more information about the bulk composition of magmatic-hydrothermal fluids exsolved from these plutons. The Treasure Mountain Dome contains weak Mo mineralization and is an apophysis of the Alma Batholith that produced also the famous Climax and Henderson porphyry Mo deposits; the Glitrevann granite hosts a sub-economic Mo stockwork, and the Drammen Granite contains numerous vein-type Mo mineralizations. As a preliminary result, based on analyses of fluid inclusions using optical microscopy, microthermometry, Raman spectroscopy, and LA-ICP-MS we conclude that the primordial fluid of the Drammen granite was of high acidity and carried certain amounts of metals at conditions of 650°C and 1.3-1.5 kbar. The total elemental budget is: 3 wt% Na, 1.8 wt% K, 0.5 wt% S, 0.4 wt% Fe, 0.3 wt% Cu, 0.2 wt% Mn, 40 ppm Mo, 800 ppm Zn, 600 ppm Rb, 300 ppm Cs, 180 ppm Pb, 150 ppm As, 40 ppm W, 15 ppm Bi, and minor amounts of Ag, Sn, and Ce. Striking is the fact, that all the metal concentrations show little variability except the one of Cu. In view of recent studies (Lerchbaumer & Audétat, 2011) showing that the Cu-values in quartz-hosted fluid inclusions are not always representative of the primary fluid and in fact can be too high, we want to check if this could be the case for the Cu-values measured in the samples from Norway and Colorado. The alteration of the original Cu-concentrations stems from

  12. 40 CFR 440.100 - Applicability; description of the copper, lead, zinc, gold, silver, and molybdenum ores subcategory.

    Science.gov (United States)

    2010-07-01

    ... any combination of these ores; (3) Mines and mills that use dump, heap, in-situ leach, or vat-leach... 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...

  13. On-Line Electrochemical Reduction of Disulfide Bonds: Improved FTICR-CID and -ETD Coverage of Oxytocin and Hepcidin

    Science.gov (United States)

    Nicolardi, Simone; Giera, Martin; Kooijman, Pieter; Kraj, Agnieszka; Chervet, Jean-Pierre; Deelder, André M.; van der Burgt, Yuri E. M.

    2013-12-01

    Particularly in the field of middle- and top-down peptide and protein analysis, disulfide bridges can severely hinder fragmentation and thus impede sequence analysis (coverage). Here we present an on-line/electrochemistry/ESI-FTICR-MS approach, which was applied to the analysis of the primary structure of oxytocin, containing one disulfide bridge, and of hepcidin, containing four disulfide bridges. The presented workflow provided up to 80 % (on-line) conversion of disulfide bonds in both peptides. With minimal sample preparation, such reduction resulted in a higher number of peptide backbone cleavages upon CID or ETD fragmentation, and thus yielded improved sequence coverage. The cycle times, including electrode recovery, were rapid and, therefore, might very well be coupled with liquid chromatography for protein or peptide separation, which has great potential for high-throughput analysis.

  14. Identification of disulfide bonds in protein proteolytic degradation products using de novo-protein unique sequence tags approach.

    Science.gov (United States)

    Shen, Yufeng; Tolić, Nikola; Purvine, Samuel O; Smith, Richard D

    2010-08-06

    Disulfide bonds are a form of post-translational modification that often determines protein structure(s) and function(s). In this work, we report a mass spectrometry method for identification of disulfides in degradation products of proteins, specifically endogenous peptides in the human blood plasma peptidome. LC-Fourier transform tandem mass spectrometry (FT MS/MS) was used for acquiring mass spectra that were de novo sequenced and then searched against the IPI human protein database. Through the use of unique sequence tags (UStags), we unambiguously correlated the spectra to specific database proteins. Examination of the UStags' prefix and/or suffix sequences that contain cysteine(s) in conjunction with sequences of the UStags-specified database proteins is shown to enable the unambigious determination of disulfide bonds. Using this method, we identified the intermolecular and intramolecular disulfides in human blood plasma peptidome peptides that have molecular weights of up to approximately 10 kDa.

  15. Molybdenum oxide nanocolloids prepared by an external field-assisted laser ablation in water

    Science.gov (United States)

    Spadaro, Salvatore; Bonsignore, Martina; Fazio, Enza; Cimino, Francesco; Speciale, Antonio; Trombetta, Domenico; Barreca, Francesco; Saija, Antonina; Neri, Fortunato

    2018-01-01

    he synthesis of extremely stable molybdenum oxide nanocolloids by pulsed laser ablation was studied. This green technique ensures the formation of contaminant-free nanostructures and the absence of by-products. A focused picosecond pulsed laser beam was used to ablate a solid molybdenum target immersed in deionized water. Molybdenum oxide nearly spherical nanoparticles with dimensions within few nanometers (20-100 nm) are synthesized when the ablation processes were carried out, in water, at room temperature and 80°C. The application of an external electric field during the ablation process induces a nanostructures reorganization, as indicated by Scanning-Transmission Electron Microscopy images analysis. The ablation products were also characterized by some spectroscopic techniques: conventional UV-vis optical absorption, atomic absorption, dynamic light scattering, micro-Raman and X-ray photoelectron spectroscopies. Finally, NIH/3T3 mouse fibroblasts were used to evaluate cell viability by the sulforhodamine B assay

  16. Molybdenum oxide nanocolloids prepared by an external field-assisted laser ablation in water

    Directory of Open Access Journals (Sweden)

    Spadaro Salvatore

    2018-01-01

    Full Text Available he synthesis of extremely stable molybdenum oxide nanocolloids by pulsed laser ablation was studied. This green technique ensures the formation of contaminant-free nanostructures and the absence of by-products. A focused picosecond pulsed laser beam was used to ablate a solid molybdenum target immersed in deionized water. Molybdenum oxide nearly spherical nanoparticles with dimensions within few nanometers (20-100 nm are synthesized when the ablation processes were carried out, in water, at room temperature and 80°C. The application of an external electric field during the ablation process induces a nanostructures reorganization, as indicated by Scanning-Transmission Electron Microscopy images analysis. The ablation products were also characterized by some spectroscopic techniques: conventional UV-vis optical absorption, atomic absorption, dynamic light scattering, micro-Raman and X-ray photoelectron spectroscopies. Finally, NIH/3T3 mouse fibroblasts were used to evaluate cell viability by the sulforhodamine B assay

  17. Silver and Molybdenum Codoped TiO2: Visible Light Active Photocatalyst for Photoelectrochemical Applications

    Science.gov (United States)

    Gul, Sahar Ramin; Khan, Matiullah; Yi, Zeng; Wu, Bo; Fawad, U.

    2017-11-01

    To improve the photoelectrochemical properties of TiO2, an approach of codoping is introduced to simultaneously tailor the band gap and control the life time of photoexcited electron-hole pairs. Molybdenum doping is used to extend the optical absorption of TiO2 while silver inclusion in the molybdenum-doped TiO2 network improves the separation between the photogenerated carriers leading to improved photodegradation response. X-ray photoelectron spectroscopy (XPS) confirmed the existence of dopant atoms in the bulk lattice and the codoped sample exhibits enhanced photodegradation performance compared to monodoped samples. With less structure modifications and stable structure, the silver molybdenum codoped TiO2 highly improve the wide functionalities of TiO2 in photoelectrochemical applications.

  18. DFT study of the molybdenum-catalyzed deoxydehydration of vicinal diols.

    Science.gov (United States)

    Lupp, Daniel; Christensen, Niels Johan; Dethlefsen, Johannes R; Fristrup, Peter

    2015-02-16

    The mechanism of the molybdenum-catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an Mo(VI) oxo complex, oxidative cleavage of the diol resulting in an Mo(IV) complex, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum-catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding of the mechanism should expedite future optimization of molybdenum-catalyzed biomass transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. DFT Study of the Molybdenum-Catalyzed Deoxydehydration of Vicinal Diols

    DEFF Research Database (Denmark)

    Lupp, Daniel; Christensen, Niels Johan; Dethlefsen, Johannes Rytter

    2015-01-01

    The mechanism of the molybdenum-catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an MoVI oxo complex, oxidative cleavage of the diol resulting in an MoIV complex, and extru......The mechanism of the molybdenum-catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an MoVI oxo complex, oxidative cleavage of the diol resulting in an MoIV complex......, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum- catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding...

  20. Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli

    Directory of Open Access Journals (Sweden)

    Hatahet Feras

    2010-09-01

    Full Text Available Abstract Background The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Results Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3 pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Conclusions Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory.

  1. Increasing Tumor Accessibility with Conjugatable Disulfide-Bridged Tumor-Penetrating Peptides for Cancer Diagnosis and Treatment

    OpenAIRE

    Venkata Ramana Kotamraju; Shweta Sharma; Poornima Kolhar; Lilach Agemy; James Pavlovich; Erkki Ruoslahti

    2016-01-01

    Tumor-homing peptides with tissue-penetrating properties increase the efficacy of targeted cancer therapy by delivering an anticancer agent to the tumor interior. LyP-1 (CGNKRTRGC) and iRGD (CRGDKGPDC) are founding members of this class of peptides. The presence of the cysteines forming the cyclizing disulfide bond complicates conjugation of these peptides with other molecules, such as drugs. Here, we report the synthesis of conjugatable disulfide-bridged peptides and their conjugation to bio...

  2. A Strategy for Production of Correctly Folded Disulfide-Rich Peptides in the Periplasm of E. coli.

    Science.gov (United States)

    Saez, Natalie J; Cristofori-Armstrong, Ben; Anangi, Raveendra; King, Glenn F

    2017-01-01

    Recombinant expression of disulfide-reticulated peptides and proteins is often challenging. We describe a method that exploits the periplasmic disulfide-bond forming machinery of Escherichia coli and combines this with a cleavable, solubility-enhancing fusion tag to obtain higher yields of correctly folded target protein than is achievable via cytoplasmic expression. The protocols provided herein cover all aspects of this approach, from vector construction and transformation to purification of the cleaved target protein and subsequent quality control.

  3. Determination of Disulfide Bond Connectivity of Cysteine-rich Peptide IpTx{sub a}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chul Won; Kim, Jim Il [Chonnam National Univ., Gwangju (Korea, Republic of); Sato, Kazuki [Fukuoka Women' s Univ., Fukuoka (Japan)

    2013-06-15

    Cysteine-rich peptides stabilized by intramolecular disulfide bonds have often been isolated from venoms of microbes, animals and plants. These peptides typically have much higher stability and improved biopharmaceutical properties compared to their linear counterparts. Therefore the correct disulfide bond formation of small proteins and peptides has been extensively studied for a better understanding of their folding mechanism and achieving efficient generation of the naturally occurring biologically active product. Imperatoxin A (IpTx{sub a}), a peptide toxin containing 6 cysteine residues, was isolated from the venom of scorpion Pandinus imperator, selectively binds the ryanodine receptors and activates Ca{sup 2+} release from sarcoplasmic reticulum (SR). IpTx{sub a} increases the binding of ryanodine to ryanodine receptors (RyRs) and encourages reconstituted single channel to induce subconductance states.

  4. MLKL forms disulfide bond-dependent amyloid-like polymers to induce necroptosis.

    Science.gov (United States)

    Liu, Shuzhen; Liu, Hua; Johnston, Andrea; Hanna-Addams, Sarah; Reynoso, Eduardo; Xiang, Yougui; Wang, Zhigao

    2017-09-05

    Mixed-lineage kinase domain-like protein (MLKL) is essential for TNF-α-induced necroptosis. How MLKL promotes cell death is still under debate. Here we report that MLKL forms SDS-resistant, disulfide bond-dependent polymers during necroptosis in both human and mouse cells. MLKL polymers are independent of receptor-interacting protein kinase 1 and 3 (RIPK1/RIPK3) fibers. Large MLKL polymers are more than 2 million Da and are resistant to proteinase K digestion. MLKL polymers are fibers 5 nm in diameter under electron microscopy. Furthermore, the recombinant N-terminal domain of MLKL forms amyloid-like fibers and binds Congo red dye. MLKL mutants that cannot form polymers also fail to induce necroptosis efficiently. Finally, the compound necrosulfonamide conjugates cysteine 86 of human MLKL and blocks MLKL polymer formation and subsequent cell death. These results demonstrate that disulfide bond-dependent, amyloid-like MLKL polymers are necessary and sufficient to induce necroptosis.

  5. Rational design of a fusion protein to exhibit disulfide-mediated logic gate behavior.

    Science.gov (United States)

    Choi, Jay H; Ostermeier, Marc

    2015-04-17

    Synthetic cellular logic gates are primarily built from gene circuits owing to their inherent modularity. Single proteins can also possess logic gate functions and offer the potential to be simpler, quicker, and less dependent on cellular resources than gene circuits. However, the design of protein logic gates that are modular and integrate with other cellular components is a considerable challenge. As a step toward addressing this challenge, we describe the design, construction, and characterization of AND, ORN, and YES logic gates built by introducing disulfide bonds into RG13, a fusion of maltose binding protein and TEM-1 β-lactamase for which maltose is an allosteric activator of enzyme activity. We rationally designed these disulfide bonds to manipulate RG13's allosteric regulation mechanism such that the gating had maltose and reducing agents as input signals, and the gates could be toggled between different gating functions using redox agents, although some gates performed suboptimally.

  6. Conversion of a disulfide bond into a thioacetal group during echinomycin biosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hotta, Kinya; Keegan, Ronan M.; Ranganathan, Soumya; Fang, Minyi; Bibby, Jaclyn; Winn, Martyn D.; Sato, Michio; Lian, Mingzhu; Watanabe, Kenji; Rigden, Daniel J.; Kim, Chu-Young (Liverpool); (Daresbury); (NU Singapore); (Shizuoka); (RAL)

    2013-12-02

    Echinomycin is a nonribosomal depsipeptide natural product with a range of interesting bioactivities that make it an important target for drug discovery and development. It contains a thioacetal bridge, a unique chemical motif derived from the disulfide bond of its precursor antibiotic triostin A by the action of an S-adenosyl-L-methionine-dependent methyltransferase, Ecm18. The crystal structure of Ecm18 in complex with its reaction products S-adenosyl-L-homocysteine and echinomycin was determined at 1.50 Å resolution. Phasing was achieved using a new molecular replacement package called AMPLE, which automatically derives search models from structure predictions based on ab initio protein modelling. Structural analysis indicates that a combination of proximity effects, medium effects, and catalysis by strain drives the unique transformation of the disulfide bond into the thioacetal linkage.

  7. REACTION PRODUCTS AND CORROSION OF MOLYBDENUM ELECTRODE IN GLASS MELT CONTAINING ANTIMONY OXIDES AND SODIUM SULFATE

    Directory of Open Access Journals (Sweden)

    JIŘÍ MATĚJ

    2012-09-01

    Full Text Available The products on the interface of a molybdenum electrode and glass melt were investigated primarily at 1400°C in three model glass melts without ingredients, with 1 % Sb2O3 and with 1 % Sb2O3 and 0.5 % SO3 (wt. %, both under and without load by alternating current. Corrosion of the molybdenum electrode in glass melt without AC load is higher by one order of magnitude if antimony oxides are present. The corrosion continues to increase if sulfate is present in addition to antimony oxides. Isolated antimony droplets largely occur on the electrode-glass melt interface, and numerous droplets are also dissipated in the surrounding glass if only antimony oxides are present in the glass melt. A comparatively continuous layer of antimony occurs on the interface if SO3 is also present, antimony being always in contact with molybdenum sulfide. Almost no antimony droplets are dissipated in the glass melt. The total amount of precipitated antimony also increases. The presence of sulfide on the interface likely facilitates antimony precipitation. The reaction of molybdenum with antimony oxides is inhibited in sites covered by an antimony layer. The composition of sulfide layers formed at 1400°C approximates that of Mo2S3. At 1100°C, the sulfide composition approximates that of MoS4. Corrosion multiplies in the glass melt without additions through the effect of AC current, most molybdenum being separated in the form of metallic particles. Corrosion also increases in the glass melt containing antimony oxides. This is due to increased corrosion in the neighborhood of the separated antimony droplets. This mechanism also results in the loosening of molybdenum particles. The amount of precipitated antimony also increases through the effect of the AC current. AC exerts no appreciable effect on either corrosion, the character of the electrode-glass interface, or antimony precipitation in the glass melt containing SO3.

  8. Catalytic determination of molybdenum by means of the sodium perborate/bromide/ascorbic acid Landolt reaction using potentiometric measurements

    Energy Technology Data Exchange (ETDEWEB)

    Shraydeh, B.F. (An-Najah National Univ., Nablus (Israel)) Svehla, G. (University College, Cork (Ireland))

    1992-06-01

    Molybdenum is considered to be an important element in agriculture for its presence in soil is essential for the fixation of nitrogen by certain plants. If the Molybdenum concentration exceeds a certain limit then it can be detrimental and harmful to grazing animals. A new catalytic method for the determination of 0.1-10 ppm molybdenum is described. Molybdenum catalyzes the perborate - bromide ascorbic acid Landolt reaction at pH 3.64. The rate is monitored by potentiometry. A calibration graph is based on the ratio of the reaction times for the blank and the sample, (t(o)/t(c)), plotted against the concentration of molybdenum. Optimal conditions for the determination are discussed. Also the effect of various ions and interferences are described.

  9. Disulfide stress-induced aluminium toxicity: molecular insights through genome-wide screening of Saccharomyces cerevisiae.

    Science.gov (United States)

    Tun, Nay M; O'Doherty, Patrick J; Perrone, Gabriel G; Bailey, Trevor D; Kersaitis, Cindy; Wu, Ming J

    2013-08-01

    Formation of non-native disulfide bonds within or between proteins can lead to protein misfolding and disruption to cellular metabolism. Such a process is defined as disulfide stress. A marked effect of disulfide stress in cells is the elevated accumulation of the intracellular aluminium ion (Al(3+)) accompanied by increased cytotoxicity. To gain an in-depth understanding of the underlying molecular mechanism for disulfide stress-induced aluminium toxicity, the complete set of Saccharomyces cerevisiae deletion mutants (5047) was screened in this study simultaneously with a combination of the two stressors, diamide and Al(3+). The combined treatment of a benign concentration of diamide (0.8 mM) with a sublethal concentration of aluminium sulfate (0.4 mM) revealed 494 sensitive deletion mutants, distinct from those found when either of the single stressors (0.8 mM diamide or 0.4 mM aluminium sulfate) was used. Hierarchical clustering and functional analyses of the 494 mutants sensitive to the dual stressors indicated a significant enrichment in the genes involved in cell wall homeostasis, signaling cascades, secretory transport machinery and detoxification. The results highlight the process of maintaining cell wall integrity as the central response to the combined exposure of diamide and Al(3+), which is mediated by the signaling pathways and transcription activation via Rlm1p and Swi6p for biosynthesis of the essential cell wall components such as glucan and chitin. Sensitivity of mutants associated with endoplasmic reticulum (ER), vesicle and vacuole functions demonstrates that secretory machinery is essential for surviving the stress conditions, probably due to their roles in transporting polysaccharides to the cell wall and detoxification of accumulated Al(3+). Finally, the phenotype of 100 previously uncharacterized genes against the dual stressors will contribute to their eventual functional annotation.

  10. drFrnE Represents a Hitherto Unknown Class of Eubacterial Cytoplasmic Disulfide Oxido-Reductases.

    Science.gov (United States)

    Bihani, Subhash C; Panicker, Lata; Rajpurohit, Yogendra S; Misra, Hari S; Kumar, Vinay

    2017-10-16

    Living cells employ thioredoxin and glutaredoxin disulfide oxido-reductases to protect thiol groups in intracellular proteins. FrnE protein of Deinococcus radiodurans (drFrnE) is a disulfide oxido-reductase that is induced in response to Cd(2+) exposure and is involved in cadmium and radiation tolerance. The aim of this study is to probe structure, function, and cellular localization of FrnE class of proteins. Here, we show drFrnE as a novel cytoplasmic oxido-reductase that could be functional in eubacteria under conditions where thioredoxin/glutaredoxin systems are inhibited or absent. Crystal structure analysis of drFrnE reveals thioredoxin fold with an alpha helical insertion domain and a unique, flexible, and functionally important C-terminal tail. The C-tail harbors a novel 239-CX4C-244 motif that interacts with the active site 22-CXXC-25 motif. Crystal structures with different active site redox states, including mixed disulfide (Cys22-Cys244), are reported here. The biochemical data show that 239-CX4C-244 motif channels electrons to the active site cysteines. drFrnE is more stable in the oxidized form, compared with the reduced form, supporting its role as a disulfide reductase. Using bioinformatics analysis and fluorescence microscopy, we show cytoplasmic localization of drFrnE. We have found "true" orthologs of drFrnE in several eubacterial phyla and, interestingly, all these groups apparently lack a functional glutaredoxin system. Innovation and Conclusion: We show that drFrnE represents a new class of hitherto unknown intracellular oxido-reductases that are abundantly present in eubacteria. Unlike other well-known oxido-reductases, FrnE harbors an additional dithiol motif that acts as a conduit to channel electrons to the active site during catalytic turnover. Antioxid. Redox Signal. 00, 000-000.

  11. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators

    OpenAIRE

    Akam, Eman A.; Chang, Tsuhen M.; Astashkin, Andrei V.; Tomat, Elisa

    2014-01-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is acti...

  12. An intercomparison of aircraft instrumentation for tropospheric measurements of carbonyl sulfide, hydrogen sulfide, and carbon disulfide

    OpenAIRE

    Gregory, Gerald L; Douglas D. Davis; Thornton, Donald C; James E. Johnson; Bandy, Alan R.; Saltzman, Eric S.; Andreae, Meinrat O.; Barrick, John D

    1993-01-01

    This paper reports results of NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements for carbonyl sulfide (COS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were intercompared. Instrumentation included a gas chromatograph using flame photometric detection (COS, H2S, and CS2), a gas chromatograph using mass spectrometric detection (COS and CS2), a gas chromatograph using fluorination and subsequent SF6 detection via electron capture (COS and CS2)...

  13. Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide.

    Science.gov (United States)

    Cuevasanta, Ernesto; Lange, Mike; Bonanata, Jenner; Coitiño, E Laura; Ferrer-Sueta, Gerardo; Filipovic, Milos R; Alvarez, Beatriz

    2015-11-06

    Hydrogen sulfide (H2S) is increasingly recognized to modulate physiological processes in mammals through mechanisms that are currently under scrutiny. H2S is not able to react with reduced thiols (RSH). However, H2S, more precisely HS(-), is able to react with oxidized thiol derivatives. We performed a systematic study of the reactivity of HS(-) toward symmetric low molecular weight disulfides (RSSR) and mixed albumin (HSA) disulfides. Correlations with thiol acidity and computational modeling showed that the reaction occurs through a concerted mechanism. Comparison with analogous reactions of thiolates indicated that the intrinsic reactivity of HS(-) is 1 order of magnitude lower than that of thiolates. In addition, H2S is able to react with sulfenic acids (RSOH). The rate constant of the reaction of H2S with the sulfenic acid formed in HSA was determined. Both reactions of H2S with disulfides and sulfenic acids yield persulfides (RSSH), recently identified post-translational modifications. The formation of this derivative in HSA was determined, and the rate constants of its reactions with a reporter disulfide and with peroxynitrite revealed that persulfides are better nucleophiles than thiols, which is consistent with the α effect. Experiments with cells in culture showed that treatment with hydrogen peroxide enhanced the formation of persulfides. Biological implications are discussed. Our results give light on the mechanisms of persulfide formation and provide quantitative evidence for the high nucleophilicity of these novel derivatives, setting the stage for understanding the contribution of the reactions of H2S with oxidized thiol derivatives to H2S effector processes. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  14. Insights into the role of the unusual disulfide bond in copper-zinc superoxide dismutase.

    Science.gov (United States)

    Sea, Kevin; Sohn, Se Hui; Durazo, Armando; Sheng, Yuewei; Shaw, Bryan F; Cao, Xiaohang; Taylor, Alexander B; Whitson, Lisa J; Holloway, Stephen P; Hart, P John; Cabelli, Diane E; Gralla, Edith Butler; Valentine, Joan Selverstone

    2015-01-23

    The functional and structural significance of the intrasubunit disulfide bond in copper-zinc superoxide dismutase (SOD1) was studied by characterizing mutant forms of human SOD1 (hSOD) and yeast SOD1 lacking the disulfide bond. We determined x-ray crystal structures of metal-bound and metal-deficient hC57S SOD1. C57S hSOD1 isolated from yeast contained four zinc ions per protein dimer and was structurally very similar to wild type. The addition of copper to this four-zinc protein gave properly reconstituted 2Cu,2Zn C57S hSOD, and its spectroscopic properties indicated that the coordination geometry of the copper was remarkably similar to that of holo wild type hSOD1. In contrast, the addition of copper and zinc ions to apo C57S human SOD1 failed to give proper reconstitution. Using pulse radiolysis, we determined SOD activities of yeast and human SOD1s lacking disulfide bonds and found that they were enzymatically active at ∼10% of the wild type rate. These results are contrary to earlier reports that the intrasubunit disulfide bonds in SOD1 are essential for SOD activity. Kinetic studies revealed further that the yeast mutant SOD1 had less ionic attraction for superoxide, possibly explaining the lower rates. Saccharomyces cerevisiae cells lacking the sod1 gene do not grow aerobically in the absence of lysine, but expression of C57S SOD1 increased growth to 30-50% of the growth of cells expressing wild type SOD1, supporting that C57S SOD1 retained a significant amount of activity. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  15. Effects of acute and chronic exercise on disulfide-linked growth hormone variants.

    Science.gov (United States)

    Pierce, Joseph R; Tuckow, Alexander P; Alemany, Joseph A; Rarick, Kevin R; Staab, Jeffery S; Harman, Everett A; Nindl, Bradley C

    2009-03-01

    To test the hypothesis that the appearance of disulfide-linked growth hormone (GH) aggregates during and after an acute resistance exercise test (ARET) in men could be influenced by chronic physical training. Fourteen men (28 +/- 1 yr) underwent two different 8-wk physical training programs designed to improve military performance. Before and after chronic training, subjects performed an ARET (six sets of 10 repetition-maximum squat) and had venous blood drawn pre-, mid-, and post-ARET (0, 15, and 30 min postexercise). To determine whether GH molecules were disulfide-linked, serum samples were chemically reduced via glutathione (GSH). Serum immunoreactive GH (IRGH) and immunofunctional GH (IFGH) concentrations were determined using two specific immunoassays, in nonreduced (-GSH) and reduced (+GSH) states. Data were analyzed using repeated-measures ANOVA. No differences were observed in the GH responses of the two training programs; therefore, training group data were combined for analysis. GSH reduction increased the mean GH signal (-GSH: 1.4 +/- 0.3 microg x L(-1) vs +GSH: 1.7 +/- 0.3 microg x L(-1); P physical training had no effect on the ARET-induced GH response. Acute resistance exercise leads to the appearance of disulfide-linked IRGH aggregates, and this response does not appear to be affected by 8 wk of chronic physical training. The physiological significance of increased proportions of disulfide-linked GH aggregates postexercise remains uncertain; however, structural alterations in GH moieties after acute exercise may represent important regulatory steps in mediating GH biological activity at selected target tissues.

  16. {sup 13}C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Mitsuhiro [Kumamoto University, Department of Structural BioImaging, Faculty of Life Sciences (Japan); Miyanoiri, Yohei [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan); Terauchi, Tsutomu [Tokyo Metropolitan University, Graduate School of Science and Engineering (Japan); Kainosho, Masatsune, E-mail: kainosho@tmu.ac.jp [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan)

    2016-09-15

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14–Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D {sup 13}C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically {sup 13}C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14–Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m{sub c14} and m{sub c38}). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for {sup 13}C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m{sub c38} isomerization, the {sup 1}H-{sup 13}C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  17. Neutron in-beam Moessbauer spectroscopic study of iron disulfide at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Kubo, M. K. [International Christian University, College of Liberal Arts (Japan); Kobayashi, Y., E-mail: kyoshio@riken.jp [RIKEN (Japan); Nonaka, H.; Yamada, Y. [Science University of Tokyo, Department of Chemistry (Japan); Sakai, Y. [Daido Institute of Technology (Japan); Shoji, H. [Tokyo Metropolitan University, Graduate School of Science (Japan); Matsue, H. [Japan Atomic Energy Research Institute (Japan)

    2005-11-15

    An in-beam emission Moessbauer spectrum of {sup 57}Fe arising from the {sup 56}Fe(n, {gamma}) {sup 57}Fe reaction in iron disulfide at room temperature was measured with a parallel plate avalanche counter. It was clearly observed that the nuclear reaction and the following process lead to the production of a new chemical species of iron different from the parent compound.

  18. Neutron in-beam Moessbauer spectroscopy of iron disulfide at 298 and 78 K

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Y., E-mail: kyoshio@riken.jp [RIKEN (Japan); Yamada, Y. [Tokyo University of Science, Department of Chemistry (Japan); Tsuruoka, Y.; Kubo, M. K. [International Christian University (Japan); Shoji, H. [Tokyo Metropolitan University, Graduate School of Science (Japan); Watanabe, Y. [Saint-Gobain K. K., Crystal Division (Japan); Takayama, T.; Sakai, Y. [Daido Institute of Technology (Japan); Sato, W.; Shinohara, A. [Osaka University, Graduate School of Science (Japan); Segawa, M.; Matsue, H. [Japan Atomic Energy Agency (Japan)

    2008-11-15

    Emission Moessbauer spectra of {sup 57}Fe arising from the {sup 56}Fe(n, {gamma}){sup 57}Fe reaction in two crystal forms of iron disulfide were measured at room temperature and liquid nitrogen temperature. Both forms exhibited two doublets assignable to the parent material and the new species produced by the nuclear reaction. At low temperature three doublets explained the spectra obtained. Production of thermally unstable species after the neutron capture reaction was suggested.

  19. Recent contributions in the field of the recombinant expression of disulfide bonded proteins in bacteria

    OpenAIRE

    de Marco, Ario

    2012-01-01

    Abstract The production of heterologous disulfide bonded proteins in bacteria remains a biotechnological challenge. A rapid literature survey results in the identification of some interesting proposals, such as the option of producing functional proteins in the cytoplasm in the presence of sulfhydryl oxidases and isomerases. Furthermore, an ever-increasing number of applications refers to recombinant proteins displayed at the bacterial surface. Time will tell whether these developments will l...

  20. Recent contributions in the field of the recombinant expression of disulfide bonded proteins in bacteria

    Directory of Open Access Journals (Sweden)

    de Marco Ario

    2012-09-01

    Full Text Available Abstract The production of heterologous disulfide bonded proteins in bacteria remains a biotechnological challenge. A rapid literature survey results in the identification of some interesting proposals, such as the option of producing functional proteins in the cytoplasm in the presence of sulfhydryl oxidases and isomerases. Furthermore, an ever-increasing number of applications refers to recombinant proteins displayed at the bacterial surface. Time will tell whether these developments will lead to universally accepted laboratory protocols.

  1. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir

    2017-04-06

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  2. Spectrographic analysis of uranium-molybdenum alloys; Analisis espectrografico de aleaciones uranio-molibdeno

    Energy Technology Data Exchange (ETDEWEB)

    Roca, M.

    1967-07-01

    A spectrographic method of analysis has been developed for uranium-molybdenum alloys containing up to 10 % Mo. The carrier distillation technique, with gallium oxide and graphite as carriers, is used for the semiquantitative determination of Al, Cr, Fe, Ni and Si, involving the conversion of the samples into oxides. As a consequence of the study of the influence of the molybdenum on the line intensities, it is useful to prepare only one set of standards with 0,6 % MoO{sub 3}. Total burning excitation is used for calcium, employing two sets of standards with 0,6 and 7.5 MoO{sub 3}. (Author) 5 refs.

  3. Nanostructures obtained from a mechanically alloyed and heat treated molybdenum carbide

    Energy Technology Data Exchange (ETDEWEB)

    Diaz Barriga Arceo, L. [Programa de Ingenieria Molecular, I.M.P. Lazaro Cardenas 152, C.P. 07730 D.F. Mexico (Mexico) and ESIQIE-UPALM, IPN Apdo Postal 118-395, C.P. 07051 D.F. Mexico (Mexico)]. E-mail: luchell@yahoo.com; Orozco, E. [Instituto de Fisica UNAM, Apdo Postal 20-364, C.P. 01000 D.F. Mexico (Mexico)]. E-mail: eorozco@fisica.unam.mx; Mendoza-Leon, H. [ESIQIE-UPALM, IPN Apdo Postal 118-395, C.P. 07051 D.F. Mexico (Mexico)]. E-mail: luchell@yahoo.com; Palacios Gonzalez, E. [Programa de Ingenieria Molecular, I.M.P. Lazaro Cardenas 152, C.P. 07730 D.F. Mexico (Mexico)]. E-mail: epalacio@imp.mx; Leyte Guerrero, F. [Programa de Ingenieria Molecular, I.M.P. Lazaro Cardenas 152, C.P. 07730 D.F. Mexico (Mexico)]. E-mail: fleyte@imp.mx; Garibay Febles, V. [Programa de Ingenieria Molecular, I.M.P. Lazaro Cardenas 152, C.P. 07730 D.F. Mexico (Mexico)]. E-mail: vgaribay@imp.mx

    2007-05-31

    Mechanical alloying was used to prepare molybdenum carbide. Microstructural characterization of samples was performed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. Molybdenum carbide was heated at 800 {sup o}C for 15 min in order to produce carbon nanotubes. Nanoparticles of about 50-140 nm in diameter and nanotubes with diameters of about 70-260 nm and 0.18-0.3 {mu}m in length were obtained after heating at 800 {sup o}C, by means of this process.

  4. Mixing of electronic states in molybdenum complexes involved in nitrogen activation

    Energy Technology Data Exchange (ETDEWEB)

    Stranger, Robert [Department of Chemistry, Australian National University, Canberra ACT 0200 (Australia); School of Chemistry, University of Tasmania, Private Bag 75, Hobart TAS 7001 (Australia); Yates, Brian F. [Department of Chemistry, Australian National University, Canberra ACT 0200 (Australia); School of Chemistry, University of Tasmania, Private Bag 75, Hobart TAS 7001 (Australia)], E-mail: Brian.Yates@utas.edu.au

    2006-05-09

    The mechanism for nitrogen activation by molybdenum complexes is a complicated one, involving as it does the coupling of a quartet molybdenum reactant with a singlet nitrogen molecule, passing via a series of quartet and doublet encounter complexes to a triplet intermediate, with the subsequent spin crossing to the singlet surface which then leads via a singlet transition state to the final pair of singlet products. We have investigated in detail a variety of levels of theory to describe the crossing of these electronic surfaces and have calculated both lower-bound and actual minimum energy crossing points for the key spin inversion processes.

  5. Supported Molybdenum Catalysts for the Deoxydehydration of 1,4-Anhydroerythritol into 2,5-Dihydrofuran.

    Science.gov (United States)

    Sandbrink, Lennart; Beckerle, Klaus; Meiners, Isabell; Liffmann, Rebecca; Rahimi, Khosrow; Okuda, Jun; Palkovits, Regina

    2017-04-10

    Efficient deoxygenation strategies are crucial for the valorization of renewable feedstocks. Deoxydehydration (DODH) enables the direct transformation of two adjacent hydroxyl groups into a double bond. Supported molybdenum-based catalysts were utilized for the first time in DODH. MoOx /TiO2 showed superior catalytic activity compared to common molybdenum salts. The catalyst efficiently converted 1,4-anhydroerythritol into 2,5-dihydrofuran in the presence of 3-octanol as reducing agent, showing high reproducibility and stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The membrane-proximal intermolecular disulfide bonds in glycoprotein Ib influence receptor binding to von Willebrand factor.

    Science.gov (United States)

    Mo, X; Luo, S-Z; Munday, A D; Sun, W; Berndt, M C; López, J A; Dong, J-F; Li, R

    2008-10-01

    In the platelet glycoprotein (GP)Ib-IX complex, the binding site for its ligand von Willebrand factor (VWF) is restricted to the N-terminal domain of the GPIbalpha subunit. How the other subunits in the complex, GPIbbeta and GPIX, regulate the GPIbalpha-VWF interaction is not clear. As GPIbalpha connects with two GPIbbeta subunits via disulfide bonds, we tested whether these intersubunit covalent links were important to the proper VWF-binding activity of the GPIb-IX complex by characterizing the structure and VWF-binding activity of a mutant GPIb-IX complex that lacked the GPIbalpha-GPIbbeta disulfide bonds. Mutating both Cys484 and Cys485 of GPIbalpha to serine prevents GPIbalpha from forming covalent disulfide bonds with GPIbbeta, while maintaining the integrity of the complex in the membrane. The mutations cause two GPIbbeta subunits to form a disulfide bond between themselves. As compared to Chinese hamster ovary (CHO) cells stably expressing the wild-type GPIb-IX complex at a comparable level, CHO cells stably expressing the mutant GPIb-IX complex bind to significantly less soluble VWF in the presence of ristocetin and roll on the immobilized VWF under flow at a higher velocity. The disulfide bonds between GPIbalpha and GPIbbeta are necessary for optimal GPIbalpha binding to VWF. The structural plasticity around the disulfide bonds may also help to shed light on the inside-out mechanism underlying GPIbbeta modulation of VWF binding.

  7. New Oxidative Stress Markers Useful in the Diagnosis of Acute Appendicitis in Children: Thiol/Disulfide Homeostasis and the Asymmetric Dimethylarginine Level.

    Science.gov (United States)

    Elmas, Bahri; Yildiz, Turan; Yazar, Hayrullah; İlçe, Zekeriya; Bal, Ceylan; Özbek, Betül; Yürümez, Yusuf

    2017-11-14

    The aim of this study was to evaluate 2 new oxidative stress markers, thiol/disulfide homeostasis status and the asymmetric dimethylarginine (ADMA) level, in children with acute appendicitis (AA) and to evaluate their diagnostic utility. This case-control study included 45 patients with AA and 35 healthy children. Age, sex, white blood cell count, neutrophil-to-lymphocyte ratio, high-sensitivity C-reactive protein (hs-CRP) level, ultrasonographic findings, thiol/disulfide homeostasis parameters (native and total thiol levels, native thiol/total thiol ratios [antioxidant parameters], and disulfide, disulfide/native thiol, and disulfide/total thiol ratios [oxidant parameters]), and the ADMA level were compared between the 2 groups. The native and total thiol levels, and the native thiol/total thiol ratio, were significantly lower, and the disulfide level and disulfide/native thiol and disulfide/total thiol ratios significantly higher, in the AA compared with the control group (all P level was significantly higher in a perforated versus nonperforated subgroup of AA patients, but the thiol/disulfide homeostasis parameters did not differ significantly between the two subgroups. In addition, the hs-CRP level and appendiceal wall thickness were higher in the perforated subgroup. The thiol/disulfide antioxidant parameters and ADMA level correlated negatively with the white blood cell count, the neutrophil-to-lymphocyte ratio, and the hs-CRP level, in the AA group, but correlated positively with oxidant parameters. The sensitivity and specificity of the disulfide/native thiol and disulfide/total thiol ratios were high when used to diagnose AA, whereas the sensitivity of the ADMA level was high when used to diagnose perforated appendicitis. Thiol/disulfide homeostasis and the ADMA level, together with certain other parameters, may be useful biomarkers of AA in children.

  8. INACTIVATION OF SEXUAL AGGLUTINATION IN HANSENULA WINGEI AND SACCHAROMYCES KLUYVERI BY DISULFIDE-CLEAVING AGENTS

    Science.gov (United States)

    Taylor, Neil W.

    1964-01-01

    Taylor, Neil W. (Northern Regional Research Laboratory, Peoria, Ill.). Inactivation of sexual agglutination in Hansenula wingei and Saccharomyces kluyveri by disulfide-cleaving agents. J. Bacteriol. 88:929–936. 1964.—Mating types of both Hansenula wingei and Saccharomyces kluyveri can be activated to produce uniformly strong sexual agglutination by treatments with various solvents, such as 8 m LiBr. The strongly agglutinative mating-type preparations were irreversibly inactivated for sexual agglutination by various chemical treatments. Type 5 of H. wingei was inactivated by disulfide-cleaving reagents, but type 21 of H. wingei was not. Type 3 of S. kluyveri was more sensitive than type 26 of S. kluyveri to inactivation by disulfide-cleaving reagents. Comparison of sensitivities to these and other treatments, plus a moderately strong cross-agglutination between type 3 and type 21, indicated that the sexually agglutinative elements on type 3 are similar to type 5, and those of type 21 are similar to those of type 26. Inactivation-rate experiments showed a loss of agglutinative ability according to a sigmoid decrement with time for both types 5 and 21. The apparent extent of inactivation depended markedly on agglutination test conditions. Results of these experiments were interpreted to indicate tentatively, first, that the agglutinative elements of both types of a species are proteins and, second, that several agglutinating linkages are formed between any two cells in sexual agglutination. PMID:14219056

  9. Protein disulfide-isomerase interacts with a substrate protein at all stages along its folding pathway.

    Directory of Open Access Journals (Sweden)

    Alistair G Irvine

    Full Text Available In contrast to molecular chaperones that couple protein folding to ATP hydrolysis, protein disulfide-isomerase (PDI catalyzes protein folding coupled to formation of disulfide bonds (oxidative folding. However, we do not know how PDI distinguishes folded, partly-folded and unfolded protein substrates. As a model intermediate in an oxidative folding pathway, we prepared a two-disulfide mutant of basic pancreatic trypsin inhibitor (BPTI and showed by NMR that it is partly-folded and highly dynamic. NMR studies show that it binds to PDI at the same site that binds peptide ligands, with rapid binding and dissociation kinetics; surface plasmon resonance shows its interaction with PDI has a Kd of ca. 10(-5 M. For comparison, we characterized the interactions of PDI with native BPTI and fully-unfolded BPTI. Interestingly, PDI does bind native BPTI, but binding is quantitatively weaker than with partly-folded and unfolded BPTI. Hence PDI recognizes and binds substrates via permanently or transiently unfolded regions. This is the first study of PDI's interaction with a partly-folded protein, and the first to analyze this folding catalyst's changing interactions with substrates along an oxidative folding pathway. We have identified key features that make PDI an effective catalyst of oxidative protein folding - differential affinity, rapid ligand exchange and conformational flexibility.

  10. Protein disulfide-isomerase - a trigger of tissue factor-dependent thrombosis.

    Science.gov (United States)

    Kiouptsi, Klytaimnistra; Reinhardt, Christoph

    2016-01-01

    The plasmatic coagulation system is tightly controlled by natural anticoagulant mechanisms, preventing thrombosis to ensure the supply of tissues with oxygen and nutrients without provoking susceptibility to bleeding diatheses. The membrane receptor tissue factor (TF) is the principal initiator of coagulation, forming a high affinity complex with coagulation factor VIIa, thus catalyzing quantitative formation of the coagulation factor Xa. While it has been well-established that the TF-VIIa complex is efficiently blocked by factor Xa associated with tissue factor pathway inhibitor (TFPI), it was uncovered during the last decade that TF contains an intramolecular allosteric disulfide, which is prone to reduction and is crucial for TF's procoagulant and prothrombotic function. The compromised integrity of the allosteric TF disulfide pair Cys186/Cys209 was demonstrated to be responsible for the cryptic nature of TF procoagulant activity on monocytes and other cell types as well as in mouse thrombosis models. Cell surface associated protein disulfide-isomerases (PDI) were identified as activators of cryptic tissue factor. Here, we review this current concept of TF de-encryption by PDI oxidoreductases that have become interesting targets for the development of new antithrombotic treatment strategies.

  11. Molecular weight-dependent genetic information transfer with disulfide-linked polyethylenimine-based nonviral vectors.

    Science.gov (United States)

    Parhiz, Hamideh; Hashemi, Maryam; Hatefi, Arash; Shier, Wayne Thomas; Farzad, Sara Amel; Ramezani, Mohammad

    2013-07-01

    One strategy for improving gene vector properties of polyethylenimine is to facilitate individual transfection mechanism steps. This study investigates (i) improving transfection efficiency by attaching peptide nuclear localization signals (nuclear localization signals: SV40 large T antigen nuclear localization signal or C-terminus of histone H1) to polyethylenimine (10 kDa) and (ii) using disulfide linkages, which are expected to be stable during polyplex formation, but cleaved inside cells giving improved gene release. Nuclear localization signal-containing polyplexes exhibited low cytotoxicity, whereas transfection efficiency with high molecular weight plasmid DNA increased up to 3.6 times that of underivatized polyethylenimine in Neuro2A cells at higher molar ratio of polyethylenimine-nitrogen to DNA-phosphate (N/P) ratios. However, with luciferase-specific low molecular weight small interfering RNA in Neuro2A/EGFPLuc cells, nuclear localization signal-containing polyplexes with disulfide linkages caused substantial cytotoxicity at N/P ratios >15 and no consistent significant reduction in luciferase expression. Possible explanations for molecular weight-dependent differences in genetic information transfer by polyplexes containing disulfide-linked nuclear localization signals are discussed.

  12. Disulfide bonds are necessary for structure and activity in Aspergillus ficuum phytase.

    Science.gov (United States)

    Ullah, A H; Mullaney, E J

    1996-10-14

    The function of disulfide bonds in Aspergillus ficuum phytase was elucidated by unfolding studies, using guanidinium hydrochloride (Gu.HCl) as denaturant. Although the enzyme is totally inactivated by 0.8 M Gu.HCl, at pH 5.0, the active conformation is instantaneously restored by 0.6 M Gu.HCl, at pH 5.0. Conditions which would permit refolding of phytase are completely negated by 10 mM beta-mercaptoethanol and causes its catalytic demise at pH 7.5. Assay of free thiols using Ellman's reagent indicates that none of the thiols in the ten cysteines in phytase are free; five disulfide bonds were predicted for the enzyme. Sequence comparison of mold phytases and yeast acid phosphatases indicates four conserved cysteines. Thus, disulfide bonds play an important role in the folding of fungal phytase; any perturbation of the process of its formation causes an altered three-dimensional structure that is inconsistent with catalytic activity.

  13. TXNDC5, a Newly Discovered Disulfide Isomerase with a Key Role in Cell Physiology and Pathology

    Science.gov (United States)

    Horna-Terrón, Elena; Pradilla-Dieste, Alberto; Sánchez-de-Diego, Cristina; Osada, Jesús

    2014-01-01

    Thioredoxin domain-containing 5 (TXNDC5) is a member of the protein disulfide isomerase family, acting as a chaperone of endoplasmic reticulum under not fully characterized conditions As a result, TXNDC5 interacts with many cell proteins, contributing to their proper folding and correct formation of disulfide bonds through its thioredoxin domains. Moreover, it can also work as an electron transfer reaction, recovering the functional isoform of other protein disulfide isomerases, replacing reduced glutathione in its role. Finally, it also acts as a cellular adapter, interacting with the N-terminal domain of adiponectin receptor. As can be inferred from all these functions, TXNDC5 plays an important role in cell physiology; therefore, dysregulation of its expression is associated with oxidative stress, cell ageing and a large range of pathologies such as arthritis, cancer, diabetes, neurodegenerative diseases, vitiligo and virus infections. Its implication in all these important diseases has made TXNDC5 a susceptible biomarker or even a potential pharmacological target. PMID:25526565

  14. Biocompatible thermoresponsive PEGMA nanoparticles crosslinked with cleavable disulfide-based crosslinker for dual drug release.

    Science.gov (United States)

    Ulasan, Mehmet; Yavuz, Emine; Bagriacik, Emin Umit; Cengeloglu, Yunus; Yavuz, Mustafa Selman

    2015-01-01

    Smart materials have been attracting much attention because of their stimuli responsive nature. We have synthesized biocompatible thermoresponsive crosslinked poly(ethylene glycol) methyl ether methacrylate (PEGMA)-co-vinyl pyrrolidone nanoparticles (PEGMA NPs) using disulfide-based crosslinker by surfactant-free emulsion polymerization method. Particle characterization studies were carried out by dynamic light scattering, and scanning electron microscopy. Polymerization kinetics, effect of crosslinker and initiator concentrations on both average hydrodynamic diameter and polydispersity index were investigated. Hydrodynamic diameters of thermoresponsive PEGMA NPs were decreased from 210 nm to 90 nm upon heating over the lowest critical solution temperature (LCST). Disulfide crosslinked PEGMA NPs were demonstrated as a dual delivery system. Rhodamine B, a model of small-sized drug molecule, and poly(ethylene glycol) (PEG)-alizarin yellow, a model of large drug molecule, were loaded into PEGMA NPs where LCST of these NPs was tuned to 37°C, the body temperature. The rhodamine B was released from PEGMA NPs upon heating to 39°C. Then, PEG-alizarin content was released by subsequent degradation of nanoparticles using dithiothreitol (DTT), which reduces disulfide bonds to thiols. Furthermore, cytotoxicity studies of PEGMA NPs were carried out in 3T3 cells, which resulted in no toxic effect on the cells. © 2014 Wiley Periodicals, Inc.

  15. Two-dimensional metallic tantalum disulfide as a hydrogen evolution catalyst.

    Science.gov (United States)

    Shi, Jianping; Wang, Xina; Zhang, Shuai; Xiao, Lingfeng; Huan, Yahuan; Gong, Yue; Zhang, Zhepeng; Li, Yuanchang; Zhou, Xiebo; Hong, Min; Fang, Qiyi; Zhang, Qing; Liu, Xinfeng; Gu, Lin; Liu, Zhongfan; Zhang, Yanfeng

    2017-10-16

    Two-dimensional metallic transition metal dichalcogenides are emerging as prototypes for uncovering fundamental physical phenomena, such as superconductivity and charge-density waves, as well as for engineering-related applications. However, the batch production of such envisioned transition metal dichalcogenides remains challenging, which has hindered the aforementioned explorations. Herein, we fabricate thickness-tunable tantalum disulfide flakes and centimetre-sized ultrathin films on an electrode material of gold foil via a facile chemical vapour deposition route. Through temperature-dependent Raman characterization, we observe the transition from nearly commensurate to commensurate charge-density wave phases with our ultrathin tantalum disulfide flakes. We have obtained high hydrogen evolution reaction efficiency with the as-grown tantalum disulfide flakes directly synthesized on gold foils comparable to traditional platinum catalysts. This work could promote further efforts for exploring new efficient catalysts in the large materials family of metallic transition metal dichalcogenides, as well as exploiting their applications towards more versatile applications.Metallic transition metal dichalcogenides are important materials for catalysis, but scalable and controllable preparation methods are scarce. Here, the authors synthesize 2H-TaS2 as centimetre-scale films of tunable thickness and show they are an efficient catalyst for hydrogen evolution.

  16. Resolution of Disulfide Heterogeneity in Nogo Receptor 1 Fusion Proteins by Molecular Engineering

    Energy Technology Data Exchange (ETDEWEB)

    P Weinreb; D Wen; F Qian; C Wildes; E Garber; L Walus; M Jung; J Wang; J Relton; et al.

    2011-12-31

    NgRI (Nogo-66 receptor) is part of a signalling complex that inhibits axon regeneration in the central nervous system. Truncated soluble versions of NgRI have been used successfully to promote axon regeneration in animal models of spinal-cord injury, raising interest in this protein as a potential therapeutic target. The LRR (leucine-rich repeat) regions in NgRI are flanked by N- and C-terminal disulfide-containing 'cap' domains (LRRNT and LRRCT respectively). In the present work we show that, although functionally active, the NgRI(310)-Fc fusion protein contains mislinked and heterogeneous disulfide patterns in the LRRCT domain, and we report the generation of a series of variant molecules specifically designed to prevent this heterogeneity. Using these variants we explored the effects of modifying the NgRI truncation site or the spacing between the NgRI and Fc domains, or replacing cysteines within the NgRI or IgG hinge regions. One variant, which incorporates replacements of Cys{sup 266} and Cys{sup 309} with alanine residues, completely eliminated disulfide scrambling while maintaining functional in vitro and in vivo efficacy. This modified NgRI-Fc molecule represents a significantly improved candidate for further pharmaceutical development, and may serve as a useful model for the optimization of other IgG fusion proteins made from LRR proteins.

  17. Structure of the Noncatalytic Domains and Global Fold of the Protein Disulfide Isomerase ERp72

    Energy Technology Data Exchange (ETDEWEB)

    Kozlov, G.; Määttänen, P; Schrag, J; Hura, G; Gabrielli, L; Cygler, M; Thomas, D; Gehring, K

    2009-01-01

    Protein disulfide isomerases are a family of proteins that catalyze the oxidation and isomerization of disulfide bonds in newly synthesized proteins in the endoplasmic reticulum. The family includes general enzymes such as PDI that recognize unfolded proteins, and others that are selective for specific classes of proteins. Here, we report the X-ray crystal structure of central non-catalytic domains of a specific isomerase, ERp72 (also called CaBP2 and protein disulfide-isomerase A4) from Rattus norvegicus. The structure reveals strong similarity to ERp57, a PDI-family member that interacts with the lectin-like chaperones calnexin and calreticulin but, unexpectedly, ERp72 does not interact with calnexin as shown by isothermal titration calorimetry and nuclear magnetic resonance (NMR) spectroscopy. Small-angle X-ray scattering (SAXS) of ERp72 was used to develop models of the full-length protein using both rigid body refinement and ab initio simulated annealing of dummy atoms. The two methods show excellent agreement and define the relative positions of the five thioredoxin-like domains of ERp72 and potential substrate or chaperone binding sites.

  18. The intracellular delivery of plasmid DNA using cationic reducible carbon nanotube - Disulfide conjugates of polyethylenimine.

    Science.gov (United States)

    Nia, Azadeh Hashem; Eshghi, Hossein; Abnous, Kalil; Ramezani, Mohammad

    2017-03-30

    A series of polyethylenimine conjugates of single-walled carbon nanotube (PEI-SWNT) containing bioreducible disulfide bonds was synthesized and evaluated for their transfection efficiency. Different molecular weights of polyethylenimine (PEI) were thiolated with different mole ratio of 2-iminothiolane (2-IT). Single-walled carbon nanotube (SWNT) was first carboxylated and then three different cysteine-functionalized SWNT formulations were synthesized via introduced linkers: a) carbonyl group b) spermidine c) 1,8-diamino 3,6-dioxo octane. The final nanocarriers were fabricated upon conjugation of thiolated PEIs and thiolated SWNT via oxidative disulfide bond formation. All PEI-disulfide-SWNT conjugates were capable of DNA condensation and showed improved viability and transfection efficiency compared to PEI itself. Transfection efficiencies were up to 1500 times greater than PEI 25kDa (C/P=0.8). The results of this study suggest that the synthesized formulations based on SWNT-CO-Cysteine and PEI 1.8kDa were the most efficient carriers. Considering the decreased cytotoxicity and higher transfection levels, the conjugates bear the potential for effective delivery of genetic materials. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Overcoming residual frustration in domain-swapping: the roles of disulfide bonds in dimerization and aggregation.

    Science.gov (United States)

    Cho, Samuel S; Levy, Yaakov; Onuchic, José N; Wolynes, Peter G

    2005-06-01

    The prevalence of domain-swapping in nature is a manifestation of the principle of minimal frustration in that the interactions designed by evolution to stabilize the protein are also involved in this mode of binding. We previously demonstrated that the Symmetrized-Go potential accurately predicts the experimentally observed domain-swapped structure of Eps8 based solely on the structure of the monomer. There can be, however, multiple modes of domain-swapping, reflecting a higher level of frustration, which is a consequence of symmetry. The human prion and cyanovirin-N are too frustrated to form unique domain-swapped structures on the basis of the Symmetrized-Go potential. However, supplementing the completely symmetric model with intermolecular and intramolecular disulfide bonds in the prion and cyanovirin-N proteins, respectively, yielded unique domain-swapped structures with a remarkable similarity to the experimentally observed ones. These results suggest that the disulfide bonds may sometimes be critical in overcoming the intrinsic frustration of the symmetrized energy landscapes for domain-swapping. We also discuss the implications of intermolecular disulfide bonds in the formation of mammalian prion aggregates.

  20. Solid-phase reducing agents as alternative for reducing disulfide bonds in proteins.

    Science.gov (United States)

    Grazú, Valeria; Ovsejevi, Karen; Cuadra, Karina; Betancor, Lorena; Manta, Carmen; Batista-Viera, Francisco

    2003-07-01

    Disulfide reduction of Kluyveromyces lactis and Aspergillus oryzae beta-galactosidases and beta-lactoglobulin was assessed. Reduction was performed using one of two thiol-containing agents: dithiothreitol (DTT) or thiopropyl-agarose with a high degree of substitution (1000 micromol of SH groups/g of dried gel). Both reductants allowed an increase of three- (for K. lactis beta-galactosidase) and fourfold (for A. oryzae beta-galactosidase) in the initial content of SH groups in the lactases. Nearly sevenfold fewer micromoles of SH groups per milligram of protein were needed to perform the reduction of K. lactis beta-galactosidase with thiopropyl-agarose than for the same reduction with DTT. However, for A. oryzae beta-galactosidase, nearly twice as many micromoles of SH groups per milligram of protein were needed with thiopropylagarose than with DTT. Disulfide bonds in beta-lactoglobulin were not accessible to thiopropyl-agarose, since this reduction was only possible in the presence of 6 M urea. These results proved that highly substituted thiopropyl-agarose is as good a reducing agent as DTT, for the reduction of disulfide bonds in proteins. Moreover, excess reducing agent was very simply separated from the reduced protein by filtration, making it easier to control the reaction and providing reduced protein solutions free of reductant. All these advantages substantially cut down the time required and therefore the cost of the overall process.