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Sample records for photoactive tungsten disulfide

  1. Diameter-dependent wetting of tungsten disulfide nanotubes.

    PubMed

    Goldbart, Ohad; Cohen, Sidney R; Kaplan-Ashiri, Ifat; Glazyrina, Polina; Wagner, H Daniel; Enyashin, Andrey; Tenne, Reshef

    2016-11-29

    The simple process of a liquid wetting a solid surface is controlled by a plethora of factors-surface texture, liquid droplet size and shape, energetics of both liquid and solid surfaces, as well as their interface. Studying these events at the nanoscale provides insights into the molecular basis of wetting. Nanotube wetting studies are particularly challenging due to their unique shape and small size. Nonetheless, the success of nanotubes, particularly inorganic ones, as fillers in composite materials makes it essential to understand how common liquids wet them. Here, we present a comprehensive wetting study of individual tungsten disulfide nanotubes by water. We reveal the nature of interaction at the inert outer wall and show that remarkably high wetting forces are attained on small, open-ended nanotubes due to capillary aspiration into the hollow core. This study provides a theoretical and experimental paradigm for this intricate problem.

  2. Observation of two distinct negative trions in tungsten disulfide monolayers

    SciTech Connect

    Boulesbaa, Abdelaziz; Huang, Bing; Wang, Kai; Lin, Ming-Wei; Mahjouri-Samani, Masoud; Rouleau, Christopher M.; Xiao, Kai; Yoon, Mina; Sumpter, Bobby G.; Puretzky, Alexander A.; Geohegan, David B.

    2015-09-25

    We report on the observation of two distinct photogenerated negative trion states TA and TB in two-dimensional tungsten disulfide (2D-WS2) monolayers. These trions are postulated to emerge from their parent excitons XA and XB, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between TA and TB photoformation, following dissociation of XA and XB through hole trapping at internal or substrate defect sites. While TA arises directly from its parent XA, TB emerges through a different transition accessible only after XB dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T1) and ~1.98 eV (T2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the excitons XA and XB’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level XA using λpump < 2.4 eV forms only trion T1, which implies that the electron that remains

  3. Observation of two distinct negative trions in tungsten disulfide monolayers

    DOE PAGES

    Boulesbaa, Abdelaziz; Huang, Bing; Wang, Kai; ...

    2015-09-25

    We report on the observation of two distinct photogenerated negative trion states TA and TB in two-dimensional tungsten disulfide (2D-WS2) monolayers. These trions are postulated to emerge from their parent excitons XA and XB, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between TA and TB photoformation, following dissociation of XA and XB through hole trapping at internal or substrate defect sites. While TA arises directly from its parent XA, TB emerges through a different transition accessible only after XB dissociates throughmore » a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T1) and ~1.98 eV (T2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the excitons XA and XB’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level XA using λpump < 2.4 eV forms only trion T1, which implies that the electron that remains from the dissociation of exciton XA is involved in the creation of this trion with a binding energy ~ 10 meV with respect to XA. The absorption peak that corresponds to trion T2 appears when λpump > 2.4 eV, which is just

  4. Tungsten disulfide nanotubes reinforced biodegradable polymers for bone tissue engineering.

    PubMed

    Lalwani, Gaurav; Henslee, Allan M; Farshid, Behzad; Parmar, Priyanka; Lin, Liangjun; Qin, Yi-Xian; Kasper, F Kurtis; Mikos, Antonios G; Sitharaman, Balaji

    2013-09-01

    In this study, we have investigated the efficacy of inorganic nanotubes as reinforcing agents to improve the mechanical properties of poly(propylene fumarate) (PPF) composites as a function of nanomaterial loading concentration (0.01-0.2 wt.%). Tungsten disulfide nanotubes (WSNTs) were used as reinforcing agents in the experimental group. Single- and multi-walled carbon nanotubes (SWCNTs and MWCNTs) were used as positive controls, and crosslinked PPF composites were used as the baseline control. Mechanical testing (compression and three-point bending) shows a significant enhancement (up to 28-190%) in the mechanical properties (compressive modulus, compressive yield strength, flexural modulus and flexural yield strength) of WSNT-reinforced PPF nanocomposites compared to the baseline control. In comparison to the positive controls, significant improvements in the mechanical properties of WSNT nanocomposites were also observed at various concentrations. In general, the inorganic nanotubes (WSNTs) showed mechanical reinforcement better than (up to 127%) or equivalent to that of carbon nanotubes (SWCNTs and MWCNTs). Sol fraction analysis showed significant increases in the crosslinking density of PPF in the presence of WSNTs (0.01-0.2 wt.%). Transmission electron microscopy (TEM) analysis on thin sections of crosslinked nanocomposites showed the presence of WSNTs as individual nanotubes in the PPF matrix, whereas SWCNTs and MWCNTs existed as micron-sized aggregates. The trend in the surface area of nanostructures obtained by Brunauer-Emmett-Teller (BET) surface area analysis was SWCNTs>MWCNTs>WSNTs. The BET surface area analysis, TEM analysis and sol fraction analysis results taken together suggest that chemical composition (inorganic vs. carbon nanomaterials), the presence of functional groups (such as sulfide and oxysulfide) and individual dispersion of the nanomaterials in the polymer matrix (absence of aggregation of the reinforcing agent) are the key parameters

  5. Nanoparticles synthesis of tungsten disulfide via AOT-based microemulsions

    SciTech Connect

    Ghoreishi, S.M.; Meshkat, S.S.; Ghiaci, M.; Dadkhah, A.A.

    2012-06-15

    Graphical abstract: A controlled synthesis of WS2 nanoparticles (most probably inorganic fullerene (IF)) via microemulsion was applied for the first time to prepare WS2 (7–12 nm) by acidification of the water cores of the AOT reverse microemulsion. Highlights: ► An innovative reverse microemulsion technique was developed for WS{sub 2} synthesis. ► WS{sub 2} nanoparticles were obtained with narrow size distribution in range of 7–12 nm. ► Operating cost of microemulsion was lower in contrast to quartz reactor method. ► WS{sub 2} morphology could be controlled to obtain highly active and selective catalysts. ► Lower size of WS{sub 2} in this study overcomes the shortcoming of quartz reactor method. -- Abstract: The tungsten disulfide (WS{sub 2}) nanoparticles (most probably inorganic fullerene (IF)) with a narrow size distribution were synthesized by a reverse micelle technique for the first time. The particle size was controlled by varying water-to-surfactant molar ratio (W{sub 0}), aging time and reagent concentration. The synthesized WS{sub 2} nanoparticles were characterized by zetasizer, UV–visible spectrophotometers and transmission electron microscopy (TEM). The WS{sub 2} nanoparticles with particle diameter size of 7–12 nm were obtained via 24 h aging time. The particle size was controlled by changing the aging time and molar ratio of water/surfactant. Doubling W{sub 0} increased the amount and particle size of WS{sub 2} by 22 and 26%, respectively. The effect of aging time in the range of 6–24 h was investigated and the complete disappearance of yellowish color at 24 h resulted in an optically clear solution, which was the indication of WS{sub 2} formation with 100% conversion of reactant ((NH{sub 4}){sub 2}WS{sub 4}) in the batch reactor.

  6. Electron transfer and coupling in graphene-tungsten disulfide van der Waals heterostructures.

    PubMed

    He, Jiaqi; Kumar, Nardeep; Bellus, Matthew Z; Chiu, Hsin-Ying; He, Dawei; Wang, Yongsheng; Zhao, Hui

    2014-11-25

    The newly discovered two-dimensional materials can be used to form atomically thin and sharp van der Waals heterostructures with nearly perfect interface qualities, which can transform the science and technology of semiconductor heterostructures. Owing to the weak van der Waals interlayer coupling, the electronic states of participating materials remain largely unchanged. Hence, emergent properties of these structures rely on two key elements: electron transfer across the interface and interlayer coupling. Here we show, using graphene-tungsten disulfide heterostructures as an example, evidence of ultrafast and highly efficient interlayer electron transfer and strong interlayer coupling and control. We find that photocarriers injected in tungsten disulfide transfer to graphene in 1 ps and with near-unity efficiency. We also demonstrate that optical properties of tungsten disulfide can be effectively tuned by carriers in graphene. These findings illustrate basic processes required for using van der Waals heterostructures in electronics and photonics.

  7. The electronic and optical properties of Tungsten Disulfide under high pressure

    NASA Astrophysics Data System (ADS)

    Shang, Jimin; Chen, Peng; Zhang, Lamei; Zhai, Fengxiao; Cheng, Xuerui

    2016-05-01

    Using first principles calculations, we have investigated the pressure effects on the electronic and optical properties of Tungsten Disulfide. The results show that the lattice out plane is more sensitive to the pressure than that in plane. In addition, the conduction band maximum drops down and the valence band minimum shifts up with respect to the Fermi level, respectively. Semiconductor to metal transition occurs at a critical pressure (∼36 GPa). Moreover, the dielectric function also has an obviously red shift, and the optical absorption can be improved accordingly. Our study supplies a route to optimize the performance of WS2 devices.

  8. High performance field-effect transistor based on multilayer tungsten disulfide.

    PubMed

    Liu, Xue; Hu, Jin; Yue, Chunlei; Della Fera, Nicholas; Ling, Yun; Mao, Zhiqiang; Wei, Jiang

    2014-10-28

    Semiconducting two-dimensional transition metal chalcogenide crystals have been regarded as the promising candidate for the future generation of transistor in modern electronics. However, how to fabricate those crystals into practical devices with acceptable performance still remains as a challenge. Employing tungsten disulfide multilayer thin crystals, we demonstrate that using gold as the only contact metal and choosing appropriate thickness of the crystal, high performance transistor with on/off ratio of 10(8) and mobility up to 234 cm(2) V(-1) s(-1) at room temperature can be realized in a simple device structure. Furthermore, low temperature study revealed that the high performance of our device is caused by the minimized Schottky barrier at the contact and the existence of a shallow impurity level around 80 meV right below the conduction band edge. From the analysis on temperature dependence of field-effect mobility, we conclude that strongly suppressed phonon scattering and relatively low charge impurity density are the key factors leading to the high mobility of our tungsten disulfide devices.

  9. Improvement of Gas-Sensing Performance of Large-Area Tungsten Disulfide Nanosheets by Surface Functionalization.

    PubMed

    Ko, Kyung Yong; Song, Jeong-Gyu; Kim, Youngjun; Choi, Taejin; Shin, Sera; Lee, Chang Wan; Lee, Kyounghoon; Koo, Jahyun; Lee, Hoonkyung; Kim, Jongbaeg; Lee, Taeyoon; Park, Jusang; Kim, Hyungjun

    2016-10-05

    Semiconducting two-dimensional (2D) transition metal dichalcogenides (TMDCs) are promising gas-sensing materials due to their large surface-to-volume ratio. However, their poor gas-sensing performance resulting from the low response, incomplete recovery, and insufficient selectivity hinders the realization of high-performance 2D TMDC gas sensors. Here, we demonstrate the improvement of gas-sensing performance of large-area tungsten disulfide (WS2) nanosheets through surface functionalization using Ag nanowires (NWs). Large-area WS2 nanosheets were synthesized through atomic layer deposition of WO3 followed by sulfurization. The pristine WS2 gas sensors exhibited a significant response to acetone and NO2 but an incomplete recovery in the case of NO2 sensing. After AgNW functionalization, the WS2 gas sensor showed dramatically improved response (667%) and recovery upon NO2 exposure. Our results establish that the proposed method is a promising strategy to improve 2D TMDC gas sensors.

  10. Dual-wavelength passively Q-switched Nd:GYSGG laser by tungsten disulfide saturable absorber.

    PubMed

    Gao, Y J; Zhang, B Y; Song, Q; Wang, G J; Wang, W J; Hong, M H; Dou, R Q; Sun, D L; Zhang, Q L

    2016-06-20

    A dual-wavelength passively Q-switched Nd:GYSGG laser using vacuum evaporating tungsten disulfide (WS2) as a saturable absorber was demonstrated for the first time to the best of our knowledge. The WS2 saturable absorber was prepared simply by evaporating nanometer WS2 powders onto a quartz substrate in a vacuum. By inserting the WS2 saturable absorber into the laser cavity, stable Q-switched laser operation was achieved with a maximum average output power of 367 mW, a pulse repetition rate of 70.7 kHz, the shortest pulse width of 591 ns, and pulse energy of about 1.05 μJ. By vacuum evaporation method, a high-quality WS2 saturable absorber can be produced, and it seems to be a suitable method for fabrication of 2D transition metal dichalcogenides.

  11. Electronic properties of monolayer tungsten disulfide grown by chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Alharbi, Abdullah; Shahrjerdi, Davood

    2016-11-01

    We demonstrate chemical vapor deposition of large monolayer tungsten disulfide (WS2) (>200 μm). Photoluminescence and Raman spectroscopy provide insight into the structural and strain heterogeneity of the flakes. We observe exciton quenching at grain boundaries that originate from the nucleation site at the center of the WS2 flakes. Temperature variable transport measurements of top-gated WS2 transistors show an apparent metal-to-insulator transition. Variable range and thermally activated hopping mechanisms can explain the carrier transport in the insulating phase at low and intermediate temperatures. The devices exhibit room-temperature field-effect electron mobility as high as 48 cm2/V.s. The mobility increases with decreasing temperature and begins to saturate at below 100 °K, possibly due to Coulomb scattering or defects.

  12. Strain-induced phonon shifts in tungsten disulfide nanoplatelets and nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Fang; Kinloch, Ian A.; Wolverson, Daniel; Tenne, Reshef; Zak, Alla; O'Connell, Eoghan; Bangert, Ursel; Young, Robert J.

    2017-03-01

    The relationship between structure and properties has been followed for different nanoscale forms of tungsten disulfide (2H-WS2) namely exfoliated monolayer and few-layer nanoplatelets, and nanotubes. The similarities and differences between these nanostructured materials have been examined using a combination of optical microscopy, scanning and high-resolution transmission electron microscopy and atomic force microscopy. Photoluminescence and Raman spectroscopy have also been used to distinguish between monolayer and few-layer material. Strain induced phonon shifts have been followed from the changes in the positions of the A1g and {{{{E}}}2{{g}}}1 Raman bands during uniaxial deformation. This has been modelled for monolayer using density functional theory with excellent agreement between the measured and predicted behaviour. It has been found that as the number of WS2 layers increases for few-layer crystals or nanotubes, the A1g mode hardens whereas the {{{{E}}}2{{g}}}1 mode softens. This is believed to be due to the A1g mode, which involves out of plane atomic movements, being constrained by the increasing number of WS2 layers whereas easy sliding reduces stress transfer to the individual layers for the {{{{E}}}2{{g}}}1 mode, involving only in-plane vibrations. This finding has enabled the anomalous phonon shift behaviour in earlier pressure measurements on WS2 to be resolved, as well as similar effects in other transition metal dichalcogenides, such as molybdenum disulfide, to be explained.

  13. Highly efficient supercapacitor electrode with two-dimensional tungsten disulfide and reduced graphene oxide hybrid nanosheets

    NASA Astrophysics Data System (ADS)

    Tu, Chao-Chi; Lin, Lu-Yin; Xiao, Bing-Chang; Chen, Yu-Shiang

    2016-07-01

    Two-dimensional (2D) nanostructures with their high surface area and large in-plane conductivity have been regarded as promising materials for supercapacitors (SCs). Tungsten disulfide (WS2) is highly suitable for charge accumulation with its abundant active sites in the interspacing between the 2D structures and the intraspacing of each atomic layer, as well as on the tungsten centers with the charges generated by the Faradaic reactions. This study proposes the preparation of well-constructed WS2/reduced graphene oxide (RGO) nanosheets using a simple molten salt process as the electroactive material for SCs, which presents a high specific capacitance (CF) of 2508.07 F g-1 at the scan rate of 1 mV s-1, because of the synergic effect of WS2 with its large charge-accumulating sites on the 2D planes and RGO with its highly enhanced conductivity and improved connections in the WS2 networks. The excellent cycling stability of 98.6% retention after 5000 cycles charge/discharge process and the Coulombic efficiency close to 100% for the entire measurement are also achieved for the WS2/RGO-based SC electrode. The results suggest the potential for the combination of the 2D metal sulfide and carbon materials as the charge storage material to solve the energy problems and attain a sustainable society.

  14. Fiber-integrated tungsten disulfide saturable absorber (mirror) for pulsed fiber lasers

    NASA Astrophysics Data System (ADS)

    Chen, Hao; Li, Irene Ling; Ruan, Shuangchen; Guo, Tuan; Yan, Peiguang

    2016-08-01

    We propose two schemes for achieving tungsten disulfide (WS2)-based saturable absorber (SA) and saturable absorber mirror (SAM). By utilizing the pulsed laser deposition method, we grow the WS2 film on microfiber to form an evanescent field interaction SA device. Incorporating this SA device into a common ring-cavity erbium-doped fiber (EDF) laser, stably passive mode-locking can be achieved with pulse duration of 395 fs and signal-to-noise ratio of 64 dB. We also produce a fiber tip integrated WS2-SAM by utilizing the magnetron sputtering technique (MST). This new type of SAM combines the WS2 layer as SA and gold mirror as high reflective mirror. By employing the WS2-SAM, we construct the linear-cavity EDF lasers, and achieve passive mode-locking operation with pulse duration of ˜1 ns and SNR of ˜61 dB. We further achieve stably passive Q-switching operation with pulse duration of ˜160 ns and pulse energy of 54.4 nJ. These fiber-integrated SAs and SAMs have merits of compactness and reliability, paving the way for the development of new photonic devices such as SAs for pulsed laser technology.

  15. High-damage-resistant tungsten disulfide saturable absorber mirror for passively Q-switched fiber laser.

    PubMed

    Chen, Hao; Chen, YuShan; Yin, Jinde; Zhang, Xuejun; Guo, Tuan; Yan, Peiguang

    2016-07-25

    In this paper, we demonstrate a high-damage-resistant tungsten disulfide saturable absorber mirror (WS2-SAM) fabricated by magnetron sputtering technique. The WS2-SAM has an all-fiber-integrated configuration and high-damage-resistant merit because the WS2 layer is protected by gold film so as to avoid being oxidized and destroyed at high pump power. Employing the WS2-SAM in an Erbium-doped fiber laser (EDFL) with linear cavity, the stable Q-switching operation is achieved at central wavelength of 1560 nm, with the repetition rates ranging from 29.5 kHz to 367.8 kHz and the pulse duration ranging from 1.269 μs to 154.9 ns. For the condition of the maximum pump power of 600 mW, the WS2-SAM still works stably with an output power of 25.2 mW, pulse energy of 68.5 nJ, and signal-noise-ratio of 42 dB. The proposed WS2-SAM configuration provides a promising solution for advanced pulsed fiber lasers with the characteristics of high damage resistance, high output energy, and wide tunable frequency.

  16. Molybdenum disulfide catalyzed tungsten oxide for on-chip acetone sensing

    NASA Astrophysics Data System (ADS)

    Li, Hong; Ahn, Sung Hoon; Park, Sangwook; Cai, Lili; Zhao, Jiheng; He, Jiajun; Zhou, Minjie; Park, Joonsuk; Zheng, Xiaolin

    2016-09-01

    Acetone sensing is critical for acetone leak detection and holds a great promise for the noninvasive diagnosis of diabetes. It is thus highly desirable to develop a wearable acetone sensor that has low cost, miniature size, sub-ppm detection limit, great selectivity, as well as low operating temperature. In this work, we demonstrate a cost-effective on-chip acetone sensor with excellent sensing performances at 200 °C using molybdenum disulfide (MoS2) catalyzed tungsten oxide (WO3). The WO3 based acetone sensors are first optimized via combined mesoscopic nanostructuring and silicon doping. Under the same testing conditions, our optimized mesoporous silicon doped WO3 [Si:WO3(meso)] sensor shows 2.5 times better sensitivity with ˜1000 times smaller active device area than the state-of-art WO3 based acetone sensor. Next, MoS2 is introduced to catalyze the acetone sensing reactions for Si:WO3(meso), which reduces the operating temperature by 100 °C while retaining its high sensing performances. Our miniaturized acetone sensor may serve as a wearable acetone detector for noninvasive diabetes monitoring or acetone leakage detection. Moreover, our work demonstrates that MoS2 can be a promising nonprecious catalyst for catalytic sensing applications.

  17. All-fiber thulium/holmium-doped mode-locked laser by tungsten disulfide saturable absorber

    NASA Astrophysics Data System (ADS)

    Yu, Hao; Zheng, Xin; Yin, Ke; Cheng, Xiang'ai; Jiang, Tian

    2017-01-01

    A passively mode-locked thulium/holmium-doped fiber laser (THDFL) based on tungsten disulfide (WS2) saturable absorber (SA) was demonstrated. The WS2 nanosheets were prepared by liquid phase exfoliation method and the SA was fabricated by depositing the few-layer WS2 nanosheets on the surface of a fiber taper. The modulation depth, saturable intensity, and non-saturable loss of this SA were measured to be 8.2%, 0.82 GW cm-2, and 29.4%, respectively. Based on this SA, a stable mode-locked laser operated at 1.91 µm was achieved with pulse duration of 825 fs and repetition rate of 15.49 MHz, and signal-to-noise ratio (SNR) of 67 dB. Meanwhile, by increasing the pump power and adjusting the position of polarization controller, harmonic mode-locking operations were obtained. These results showed that the WS2 nanosheet-based SA could be served as a desirable candidate for a short-pulse mode locker at 2 µm wavelength.

  18. Biocompatibility of Tungsten Disulfide Inorganic Nanotubes and Fullerene-Like Nanoparticles with Salivary Gland Cells

    PubMed Central

    Goldman, Elisheva B.; Zak, Alla; Tenne, Reshef; Kartvelishvily, Elena; Levin-Zaidman, Smadar; Neumann, Yoav; Stiubea-Cohen, Raluca; Palmon, Aaron; Hovav, Avi-Hai

    2015-01-01

    Impaired salivary gland (SG) function leading to oral diseases is relatively common with no adequate solution. Previously, tissue engineering of SG had been proposed to overcome this morbidity, however, not yet clinically available. Multiwall inorganic (tungsten disulfide [WS2]) nanotubes (INT-WS2) and fullerene-like nanoparticles (IF-WS2) have many potential medical applications. A yet unexplored venue application is their interaction with SG, and therefore, our aim was to test the biocompatibility of INT/IF-WS2 with the A5 and rat submandibular cells (RSC) SG cells. The cells were cultured and subjected after 1 day to different concentrations of INT-WS2 and were compared to control groups. Growth curves, trypan blue viability test, and carboxyfluorescein succinimidyl ester (CFSE) proliferation assay were obtained. Furthermore, cells morphology and interaction with the nanoparticles were observed by light microscopy, scanning electron microscopy and transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy. The results showed no significant differences in growth curves, proliferation kinetics, and viability between the groups compared. Moreover, no alterations were observed in the cell morphology. Interestingly, TEM images indicated that the nanoparticles are uptaken by the cells and accumulate in cytoplasmic vesicles. These results suggest promising future medical applications for these nanoparticles. PMID:25366879

  19. Mechanistic study of the hydrodesulfurization of methanethiol over tungsten disulfide; a survey of rare earth sulfides for hydrodesulfurization activity

    SciTech Connect

    Dowd, D.Q.

    1985-06-01

    Hydrodesulfurization is a process whereby sulfur bound in organic compounds is removed as hydrogen sulfide, and is important to the control of sulfur dioxide emissions in the combustion of petroleum and coal fuels. It involves the cleavage of carbon sulfur bonds, and is catalyzed by layered disulfides such as molybdenum and tungsten disulfide. The simplest example is the reaction CH/sub 3/SH + H/sub 2/ ..-->.. CH/sub 4/ + H/sub 2/S. The mechanism of even this protypical reaction is unclear. In an effort to clarify it, the kinetics of methanethiol hydrodesulfurization over tungsten disulfide at low pressures was established, with partial pressures of methanethiol and hydrogen varied over a hundred fold. The kinetic order in each reactant was positive when its partial pressure was low negative when its partial pressure was high. The negative order in hydrogen had not been previously seen. The product gases, methane and hydrogen sulfide, each exhibited negative kinetic orders at high partial pressures, zero kinetic orders at low partial pressures. A dual site Langmuir-Hinshelwood type mechanism, which defines one active site as two adjacent edge sulfur vacancies and the second as a neighboring sulfur atom, describes these results quite well. Seventeen rare earth sulfides were surveyed for catalytic activity toward methanethiol hydrodesulfurization. These sulfides included both stoichiometric and nonstoichiometric compositions and four different morphologies. In general, nonconductors were inactive and conductors were active. This correlation extended to the nonstoichiometric ..gamma..-phase sesquisulfides which exhibit both insulating and conducting properties. 96 refs.

  20. Mechanistic study of the hydrodesulfurization of methanethiol over tungsten disulfide. II. A survey of rare earth sulfides for hydrodesulfurization activity

    SciTech Connect

    Dowd, D.Q.

    1985-01-01

    I. Hydrodesulfurization is a process whereby sulfur bound in organic compounds is removed as hydrogen sulfide, and is important to the control of sulfur dioxide emissions in the combustion of petroleum and coal fuels. It involves the cleavage of carbon sulfur bonds, and is catalyzed by layered disulfides such as molybdenum and tungsten disulfide. The simplest example is the reaction CH/sub 3/SH + H/sub 2/ ..-->.. CH/sub 4/ + H/sub 2/S. The mechanism of even this prototypical reaction is unclear. In an effort to clarify it, the kinetics of methanethiol hydro desulfurization over tungsten disulfide at low pressures was established, with partial pressures of methanethiol and hydrogen varied over a hundred fold. The kinetic order in each reactant was positive when its partial pressure was low, negative when its partial pressure was high. The negative order in hydrogen had not been previously seen. The product gases, methane and hydrogen sulfide, each exhibited negative kinetic orders at high partial pressures, zero kinetic orders at low partial pressures. A dual site Langmuir-Hinshelwood type mechanism, which defines one active site as two adjacent edge sulfur vacancies and the second as a neighboring sulfur atom, describes these results quite well. II. Seventeen rare earth sulfides were surveyed for catalytic activity toward methanethiol hydrodesulfurization. These sulfides included both stoichiometric and nonstoichiometric compositions and four different morphologies. In general, nonconductors were inactive and conductors were active. This correlation extended to the nonstoichiometric ..gamma..-phase sesquisulfides which exhibit both insulating and conducting properties.

  1. Tip-Enhanced Raman Scattering Imaging of Two-Dimensional Tungsten Disulfide with Optimized Tip Fabrication Process

    PubMed Central

    Lee, Chanwoo; Kim, Sung Tae; Jeong, Byeong Geun; Yun, Seok Joon; Song, Young Jae; Lee, Young Hee; Park, Doo Jae; Jeong, Mun Seok

    2017-01-01

    We successfully achieve the tip-enhanced nano Raman scattering images of a tungsten disulfide monolayer with optimizing a fabrication method of gold nanotip by controlling the concentration of etchant in an electrochemical etching process. By applying a square-wave voltage supplied from an arbitrary waveform generator to a gold wire, which is immersed in a hydrochloric acid solution diluted with ethanol at various ratios, we find that both the conical angle and radius of curvature of the tip apex can be varied by changing the ratio of hydrochloric acid and ethanol. We also suggest a model to explain the origin of these variations in the tip shape. From the systematic study, we find an optimal condition for achieving the yield of ~60% with the radius of ~34 nm and the cone angle of ~35°. Using representative tips fabricated under the optimal etching condition, we demonstrate the tip-enhanced Raman scattering experiment of tungsten disulfide monolayer grown by a chemical vapor deposition method with a spatial resolution of ~40 nm and a Raman enhancement factor of ~4,760. PMID:28084466

  2. Tip-Enhanced Raman Scattering Imaging of Two-Dimensional Tungsten Disulfide with Optimized Tip Fabrication Process

    NASA Astrophysics Data System (ADS)

    Lee, Chanwoo; Kim, Sung Tae; Jeong, Byeong Geun; Yun, Seok Joon; Song, Young Jae; Lee, Young Hee; Park, Doo Jae; Jeong, Mun Seok

    2017-01-01

    We successfully achieve the tip-enhanced nano Raman scattering images of a tungsten disulfide monolayer with optimizing a fabrication method of gold nanotip by controlling the concentration of etchant in an electrochemical etching process. By applying a square-wave voltage supplied from an arbitrary waveform generator to a gold wire, which is immersed in a hydrochloric acid solution diluted with ethanol at various ratios, we find that both the conical angle and radius of curvature of the tip apex can be varied by changing the ratio of hydrochloric acid and ethanol. We also suggest a model to explain the origin of these variations in the tip shape. From the systematic study, we find an optimal condition for achieving the yield of ~60% with the radius of ~34 nm and the cone angle of ~35°. Using representative tips fabricated under the optimal etching condition, we demonstrate the tip-enhanced Raman scattering experiment of tungsten disulfide monolayer grown by a chemical vapor deposition method with a spatial resolution of ~40 nm and a Raman enhancement factor of ~4,760.

  3. Tungsten

    SciTech Connect

    1996-08-01

    The name tungsten, derived from the Swedish words {open_quotes}tung{close_quotes} and {open_quotes}sten{close_quotes}, meaning heavy stone, was first applied to a tungsten-containing mineral in 1755. The mineral, itself, was subsequently identified by C.W. Scheele in 1781, and named scheelite. Metallic tungsten was first isolated from the mineral wolframite in 1783, and given the German name {open_quotes}wolfram,{close_quotes} which remains an alternative name for the element. Ultimately, the English word, tungsten, became the official name, while W remains the element`s chemical symbol. This article discusses the geology, exploitation, applications, and market overview of tungsten.

  4. Tungsten disulfide nanosheet and exonuclease III co-assisted amplification strategy for highly sensitive fluorescence polarization detection of DNA glycosylase activity.

    PubMed

    Zhao, Jingjin; Ma, Yefei; Kong, Rongmei; Zhang, Liangliang; Yang, Wen; Zhao, Shulin

    2015-08-05

    Herein, we introduced a tungsten disulfide (WS2) nanosheet and exonuclease III (Exo III) co-assisted signal amplification strategy for highly sensitive fluorescent polarization (FP) assay of DNA glycosylase activity. Two DNA glycosylases, uracil-DNA glycosylase (UDG) and human 8-oxoG DNA glycosylase 1 (hOGG1), were tested. A hairpin-structured probe (HP) which contained damaged bases in the stem was used as the substrate. The removal of damaged bases from substrate by DNA glycosylase would lower the melting temperature of HP. The HP was then opened and hybridized with a FAM dye-labeled single strand DNA (DP), generating a duplex with a recessed 3'-terminal of DP. This design facilitated the Exo III-assisted amplification by repeating the hybridization and digestion of DP, liberating numerous FAM fluorophores which could not be adsorbed on WS2 nanosheet. Thus, the final system exhibited a small FP signal. However, in the absence of DNA glycosylases, no hybridization between DP and HP was occurred, hampering the hydrolysis of DP by Exo III. The intact DP was then adsorbed on the surface of WS2 nanosheet that greatly amplified the mass of the labeled-FAM fluorophore, resulting in a large FP value. With the co-assisted amplification strategy, the sensitivity was substantially improved. In addition, this method was applied to detect UDG activity in cell extracts. The study of the inhibition of UDG was also performed. Furthermore, this method is simple in design, easy in implementation, and selective, which holds potential applications in the DNA glycosylase related mechanism research and molecular diagnostics.

  5. Photoactive porous silicon nanopowder.

    PubMed

    Meekins, Benjamin H; Lin, Ya-Cheng; Manser, Joseph S; Manukyan, Khachatur; Mukasyan, Alexander S; Kamat, Prashant V; McGinn, Paul J

    2013-04-24

    Bulk processing of porous silicon nanoparticles (nSi) of 50-300 nm size and surface area of 25-230 m(2)/g has been developed using a combustion synthesis method. nSi exhibits consistent photoresponse to AM 1.5 simulated solar excitation. In confirmation of photoactivity, the films of nSi exhibit prompt bleaching following femtosecond laser pulse excitation resulting from the photoinduced charge separation. Photocurrent generation observed upon AM 1.5 excitation of these films in a photoelectrochemical cell shows strong dependence on the thickness of the intrinsic silica shell that encompasses the nanoparticles and hinders interparticle electron transfer.

  6. Carbon disulfide

    Integrated Risk Information System (IRIS)

    Carbon disulfide ; CASRN 75 - 15 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  7. Tungsten toxicity.

    PubMed

    Witten, Mark L; Sheppard, Paul R; Witten, Brandon L

    2012-04-05

    There is emerging evidence that tungsten has toxic health effects. We summarize the recent tungsten toxicity research in this short review. Tungsten is widely used in many commercial and military applications because it has the second highest melting temperature of any element. Consequently, it is important to elucidate the potential health effects of tungsten.

  8. Protein disulfide engineering.

    PubMed

    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.

  9. TiO2/WO3 photoactive bilayers in the UV-Vis light region

    NASA Astrophysics Data System (ADS)

    Vasilaki, E.; Vernardou, D.; Kenanakis, G.; Vamvakaki, M.; Katsarakis, N.

    2017-04-01

    In this work, photoactive bilayered films consisting of anatase TiO2 and monoclinic WO3 were synthesized by a sol-gel route. Titanium isopropoxide and tungsten hexachloride were used as metal precursors and deposition was achieved by spin-coating on Corning glass substrates. The samples were characterized by X-ray diffraction, photoluminescence, UV-Vis, and Raman spectroscopy, as well as field emission scanning electron microscopy. The prepared immobilized catalysts were tested for their photocatalytic performance by the decolorization of methylene blue in aqueous matrices, under UV-Vis light irradiation. The annealing process influenced the crystallinity of the bilayered films, while the concentration of the tungsten precursor solution and the position of the tungsten trioxide layer further affected their photocatalytic performance. In particular, the photocatalytic performance of the bilayered films was optimized at a concentration of 0.1 M of the WO3 precursor solution, when deposited as an overlying layer on TiO2 by two annealing steps ( 76% methylene blue decolorization in 300 min of irradiation versus 59% in the case of a bare TiO2 film). In general, the coupled layer catalysts exhibited superior photoactivity compared to that of bare TiO2 films with WO3 acting as an electron trap, resulting, therefore, in a more efficient electron-hole separation and inhibiting their recombination.

  10. Carbon Fiber and Tungsten Disulfide Nanoscale Architectures for Armor Applications

    DTIC Science & Technology

    2012-06-01

    ceramic plate is adhered to the ductile layer to improve overall properties , but at the same time the interactions between the materials can also...the material , this difference in propagation speeds directs a series of tensile waves back into the ceramic . These tensile waves often cause the...expected from the bulk [28]. The effect of sintering can be noted by studying the change in surface area of nickel nanoparticles with BET. To

  11. Extraordinary Second Harmonic Generation in tungsten disulfide monolayers.

    PubMed

    Janisch, Corey; Wang, Yuanxi; Ma, Ding; Mehta, Nikhil; Elías, Ana Laura; Perea-López, Néstor; Terrones, Mauricio; Crespi, Vincent; Liu, Zhiwen

    2014-07-02

    We investigate Second Harmonic Generation (SHG) in monolayer WS₂ both deposited on a SiO₂/Si substrate or suspended using transmission electron microscopy grids. We find unusually large second order nonlinear susceptibility, with an estimated value of d(eff) ~ 4.5 nm/V nearly three orders of magnitude larger than other common nonlinear crystals. In order to quantitatively characterize the nonlinear susceptibility of two-dimensional (2D) materials, we have developed a formalism to model SHG based on the Green's function with a 2D nonlinear sheet source. In addition, polarized SHG is demonstrated as a useful method to probe the structural symmetry and crystal orientation of 2D materials. To understand the large second order nonlinear susceptibility of monolayer WS₂, density functional theory based calculation is performed. Our analysis suggests the origin of the large nonlinear susceptibility in resonance enhancement and a large joint density of states, and yields an estimate of the nonlinear susceptibility value d(eff) = 0.77 nm/V for monolayer WS₂, which shows good order-of-magnitude agreement with the experimental result.

  12. 46 CFR 153.1040 - Carbon disulfide.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Carbon disulfide. 153.1040 Section 153.1040 Shipping... § 153.1040 Carbon disulfide. (a) No person may load, carry, or discharge carbon disulfide unless the... charge of a carbon disulfide transfer operation shall ensure that carbon disulfide is discharged only...

  13. 46 CFR 153.1040 - Carbon disulfide.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Carbon disulfide. 153.1040 Section 153.1040 Shipping... § 153.1040 Carbon disulfide. (a) No person may load, carry, or discharge carbon disulfide unless the... charge of a carbon disulfide transfer operation shall ensure that carbon disulfide is discharged only...

  14. 46 CFR 153.1040 - Carbon disulfide.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Carbon disulfide. 153.1040 Section 153.1040 Shipping... § 153.1040 Carbon disulfide. (a) No person may load, carry, or discharge carbon disulfide unless the... charge of a carbon disulfide transfer operation shall ensure that carbon disulfide is discharged only...

  15. 46 CFR 153.1040 - Carbon disulfide.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Carbon disulfide. 153.1040 Section 153.1040 Shipping... § 153.1040 Carbon disulfide. (a) No person may load, carry, or discharge carbon disulfide unless the... charge of a carbon disulfide transfer operation shall ensure that carbon disulfide is discharged only...

  16. 46 CFR 153.1040 - Carbon disulfide.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Carbon disulfide. 153.1040 Section 153.1040 Shipping... § 153.1040 Carbon disulfide. (a) No person may load, carry, or discharge carbon disulfide unless the... charge of a carbon disulfide transfer operation shall ensure that carbon disulfide is discharged only...

  17. Quantification of Thiols and Disulfides

    PubMed Central

    Winther, Jakob R.; Thorpe, Colin

    2013-01-01

    Background Disulfide bond formation is a key posttranslational modification, with implications for structure, function and stability of numerous proteins. While disulfide bond formation is a necessary and essential process for many proteins, it is deleterious and disruptive for others. Cells go to great lengths to regulate thiol-disulfide bond homeostasis, typically with several, apparently redundant, systems working in parallel. Dissecting the extent of oxidation and reduction of disulfides is an ongoing challenge due, in part, to the facility of thiol/disulfide exchange reactions. Scope of the review In the present account, we briefly survey the toolbox available to the experimentalist for the chemical determination of thiols and disulfides. We have chosen to focus on the key chemical aspects of current methodology, together with identifying potential difficulties inherent in their experimental implementation. Major conclusions While many reagents have been described for the measurement and manipulation of the redox status of thiols and disulfides, a number of these methods remain underutilized. The ability to effectively quantify changes in redox conditions in living cells presents a continuing challenge. General Significance Many unresolved questions in the metabolic interconversion of thiols and disulfides remain. For example, while pool sizes of redox pairs and their intracellular distribution are being uncovered, very little is known about the flux in thiol-disulfide exchange pathways. New tools are needed to address this important aspect of cellular metabolism. PMID:23567800

  18. Quantifying Friction Effects of Molybdenum Disulfide, Tungsten Disulfide, Hexagonal Boron Nitride, and Lubalox as Bullet Coating

    DTIC Science & Technology

    2012-07-30

    also claims that these coatings eliminate copper fouling of the barrel. The Swedish ammunition company Norma Precision advertises friction reduction...Lubricant,” US Patent 6036996. [7] Norma , 2011. “ Norma Diamond Line.” http://www.norma.cc/en/Products/Our-Brands/ Norma - Diamond-Line/ Accessed

  19. Thin films of photoactive polymer blends.

    PubMed

    Ruderer, Matthias A; Metwalli, Ezzeldin; Wang, Weinan; Kaune, Gunar; Roth, Stephan V; Müller-Buschbaum, Peter

    2009-03-09

    The morphology inside photoactive blended films of two conjugated homopolymers poly [(1-methoxy)-4-(2-ethylhexyloxy)-p-phenylene-vinylene] (MEH-PPV) and poly(3-hexylthiophene-2,5-diyl) (P3HT) is investigated. For both homopolymers a linear dependence of the installed film thickness from the concentration of the polymer solution used in spin coating is probed. This dependence allows preparation of an efficient series of blended films with constant thickness and different blending ratios. Information about the lateral structure inside the films is gained from grazing incidence small angle X-ray scattering. At the calculated critical blending ratio the smallest lateral separation between adjacent domains is found representing the highest surface contact between both homopolymers in the films. The presence of wetting layers at both interfaces as detected with X-ray reflectivity and atomic force microscopy is promising for photovoltaic applications. UV/Vis spectroscopy complements the structural investigation.

  20. Photoactive devices including porphyrinoids with coordinating additives

    DOEpatents

    Forrest, Stephen R; Zimmerman, Jeramy; Yu, Eric K; Thompson, Mark E; Trinh, Cong; Whited, Matthew; Diev, Vlacheslav

    2015-05-12

    Coordinating additives are included in porphyrinoid-based materials to promote intermolecular organization and improve one or more photoelectric characteristics of the materials. The coordinating additives are selected from fullerene compounds and organic compounds having free electron pairs. Combinations of different coordinating additives can be used to tailor the characteristic properties of such porphyrinoid-based materials, including porphyrin oligomers. Bidentate ligands are one type of coordinating additive that can form coordination bonds with a central metal ion of two different porphyrinoid compounds to promote porphyrinoid alignment and/or pi-stacking. The coordinating additives can shift the absorption spectrum of a photoactive material toward higher wavelengths, increase the external quantum efficiency of the material, or both.

  1. Reactive superhydrophobic surface and its photoinduced disulfide-ene and thiol-ene (bio)functionalization.

    PubMed

    Li, Junsheng; Li, Linxian; Du, Xin; Feng, Wenqian; Welle, Alexander; Trapp, Oliver; Grunze, Michael; Hirtz, Michael; Levkin, Pavel A

    2015-01-14

    Reactive superhydrophobic surfaces are highly promising for biotechnological, analytical, sensor, or diagnostic applications but are difficult to realize due to their chemical inertness. In this communication, we report on a photoactive, inscribable, nonwettable, and transparent surface (PAINTS), prepared by polycondensation of trichlorovinylsilane to form thin transparent reactive porous nanofilament on a solid substrate. The PAINTS shows superhydrophobicity and can be conveniently functionalized with the photoclick thiol-ene reaction. In addition, we show for the first time that the PAINTS bearing vinyl groups can be easily modified with disulfides under UV irradiation. The effect of superhydrophobicity of PAINTS on the formation of high-resolution surface patterns has been investigated. The developed reactive superhydrophobic coating can find applications for surface biofunctionalization using abundant thiol or disulfide bearing biomolecules, such as peptides, proteins, or antibodies.

  2. Method of monitoring photoactive organic molecules in-situ during gas-phase deposition of the photoactive organic molecules

    DOEpatents

    Forrest, Stephen R.; Vartanian, Garen; Rolin, Cedric

    2015-06-23

    A method for in-situ monitoring of gas-phase photoactive organic molecules in real time while depositing a film of the photoactive organic molecules on a substrate in a processing chamber for depositing the film includes irradiating the gas-phase photoactive organic molecules in the processing chamber with a radiation from a radiation source in-situ while depositing the film of the one or more organic materials and measuring the intensity of the resulting photoluminescence emission from the organic material. One or more processing parameters associated with the deposition process can be determined from the photoluminescence intensity data in real time providing useful feedback on the deposition process.

  3. Photoactive molecules for applications in molecular imaging and cell biology.

    PubMed

    Shao, Qing; Xing, Bengang

    2010-08-01

    Photoactive technology has proven successful for non-invasive regulation of biological activities and processes in living cells. With the light-directed generation of biomaterials or signals, mechanisms in cell biology can be investigated at the molecular level with spatial and temporal resolution. In this tutorial review, we aim to introduce the important applications of photoactive molecules for elucidating cell biology on aspects of protein engineering, fluorescence labelling, gene regulation and cell physiological functions.

  4. Photovoltaic device comprising compositionally graded intrinsic photoactive layer

    DOEpatents

    Hoffbauer, Mark A; Williamson, Todd L

    2013-04-30

    Photovoltaic devices and methods of making photovoltaic devices comprising at least one compositionally graded photoactive layer, said method comprising providing a substrate; growing onto the substrate a uniform intrinsic photoactive layer having one surface disposed upon the substrate and an opposing second surface, said intrinsic photoactive layer consisting essentially of In.sub.1-xA.sub.xN,; wherein: i. 0.ltoreq.x.ltoreq.1; ii. A is gallium, aluminum, or combinations thereof; and iii. x is at least 0 on one surface of the intrinsic photoactive layer and is compositionally graded throughout the layer to reach a value of 1 or less on the opposing second surface of the layer; wherein said intrinsic photoactive layer is isothermally grown by means of energetic neutral atom beam lithography and epitaxy at a temperature of 600.degree. C. or less using neutral nitrogen atoms having a kinetic energy of from about 1.0 eV to about 5.0 eV, and wherein the intrinsic photoactive layer is grown at a rate of from about 5 nm/min to about 100 nm/min.

  5. Tungsten Filament Fire

    ERIC Educational Resources Information Center

    Ruiz, Michael J.; Perkins, James

    2016-01-01

    We safely remove the outer glass bulb from an incandescent lamp and burn up the tungsten filament after the glass is removed. This demonstration dramatically illustrates the necessity of a vacuum or inert gas for the environment surrounding the tungsten filament inside the bulb. Our approach has added historical importance since the incandescent…

  6. Tungsten filament fire

    NASA Astrophysics Data System (ADS)

    Ruiz, Michael J.; Perkins, James

    2016-05-01

    We safely remove the outer glass bulb from an incandescent lamp and burn up the tungsten filament after the glass is removed. This demonstration dramatically illustrates the necessity of a vacuum or inert gas for the environment surrounding the tungsten filament inside the bulb. Our approach has added historical importance since the incandescent light bulb is being replaced by compact fluorescent and LED lamps.

  7. KISMET tungsten dispersal experiment

    SciTech Connect

    Wohletz, K.; Kunkle, T.; Hawkins, W.

    1996-12-01

    Results of the KISMET tungsten dispersal experiment indicate a relatively small degree of wall-rock contamination caused by this underground explosive experiment. Designed as an add-on to the KISMET test, which was performed in the U-1a.02 drift of the LYNER facility at Nevada Test Site on 1 March 1995, this experiment involved recovery and analysis of wall-rock samples affected by the high- explosive test. The chemical, high-explosive blast drove tungsten powder, placed around the test package as a plutonium analog, into the surrounding wall- rock alluvium. Sample analyses by an analytical digital electron microscope (ADEM) show tungsten dispersed in the rock as tiny (<10 {mu}m) particles, agglomerates, and coatings on alluvial clasts. Tungsten concentrations, measured by energy dispersive spectral analysis on the ADEM, indicate penetration depths less than 0.1 m and maximum concentrations of 1.5 wt % in the alluvium.

  8. Photodynamic Graphene Quantum Dot: Reduction Condition Regulated Photoactivity and Size Dependent Efficacy.

    PubMed

    Du, Dou; Wang, Kun; Wen, Ya; Li, Yan; Li, Yong Y

    2016-02-10

    Prequenching and selective activation of photosensitizer (PS) are highly desired in photodynamic therapy (PDT) to avoid off-target effect due to nonspecific activation and poor targeting selectivity of PS. In this study, nanographene materials as a unique π-conjugated planar system for electronic transfer were employed as the robust platform for temporarily quenching of PS. Photosensitizer chlorin e6 (Ce6) was integrated onto planar structure of graphene quantum dot (GQD) or graphene oxide (GO) via a reduction cleavable disulfide linker. The formed hybrid nanosystem displayed considerable fluorescence quenching and slight phototoxicity, even under the condition of light irradiation, while the photoactivity of PS could be selectively recovered in the presence of the reducing agent. Compared with graphene oxide system with larger size (around 200 nm), GQD nanosystem exhibited significantly improved tumor accumulation via enhanced permeation and retention effect (EPR effect). The in vivo study demonstrated extremely effective suppression of tumor growth for the group treated with the GQD nanosystem with cleavable linker, revealing the promising application of the presented novel strategy.

  9. Nanoengineering Applied to Tungsten

    DTIC Science & Technology

    2006-05-01

    and R. Z. Valiev ARL-RP- 123 May 2006 A reprint from the Proceedings of the Sixth International Conference on Tungsten, Refractory...Ground, MD 21005-5066 ARL-RP- 123 May 2006 Nanoengineering Applied to Tungsten Q. Wei University of North Carolina-Charlotte B. E...ORGANIZATION REPORT NUMBER ARL-RP- 123 10. SPONSOR/MONITOR’S ACRONYM(S) 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 11. SPONSOR

  10. Plasma deposition of tungsten

    SciTech Connect

    Greenberg, K.E.

    1986-12-01

    Tungsten films were plasma-deposited using an abnormal glow discharge through a mixture of tungsten hexafluoride, hydrogen, and argon. The films adhered well to silicon, silicon dioxide, gallium arsenide, and aluminum substrates placed directly on the discharge cathode. Typical deposition rates were on the order of 160 Angstroms/minute with as-deposited film resistivities of 40 to 70 microohm-cm. The tungsten was analyzed using a number of techniques including x-ray diffraction, scanning electron microscopy, and Auger spectroscopy. Low-resistivity (<10 microohm-cm) films that adhered well to silicon dioxide were obtained with a two-step process utilizing plasma deposition and conventional chemical vapor deposition.

  11. Chemical downstream etching of tungsten

    SciTech Connect

    Blain, M.G.; Jarecki, R.L.; Simonson, R.J.

    1998-07-01

    The downstream etching of tungsten and tungsten oxide has been investigated. Etching of chemical vapor deposited tungsten and e-beam deposited tungsten oxide samples was performed using atomic fluorine generated by a microwave discharge of argon and NF{sub 3}. Etching was found to be highly activated with activation energies approximated to be 6.0{plus_minus}0.5thinspkcal/mol and 5.4{plus_minus}0.4thinspkcal/mol for W and WO{sub 3}, respectively. In the case of F etching of tungsten, the addition of undischarged nitric oxide (NO) directly into the reaction chamber results in the competing effects of catalytic etch rate enhancement and the formation of a nearly stoichiometric WO{sub 3} passivating tungsten oxide film, which ultimately stops the etching process. For F etching of tungsten oxide, the introduction of downstream NO reduces the etch rate. {copyright} {ital 1998 American Vacuum Society.}

  12. Diffusion of tungsten hexafluoride

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of tungsten hexafluoride

  13. Gas tungsten arc welder

    DOEpatents

    Christiansen, D.W.; Brown, W.F.

    A welder for automated closure of fuel pins by a gas tungsten arc process in which a rotating length of cladding is positioned adjacent a welding electrode in a sealed enclosure. An independently movable axial grinder is provided in the enclosure for refurbishing the used electrode between welds.

  14. High purity tungsten targets

    NASA Technical Reports Server (NTRS)

    1975-01-01

    High purity tungsten, which is used for targets in X-ray tubes was considered for space processing. The demand for X-ray tubes was calculated using the growth rates for dental and medical X-ray machines. It is concluded that the cost benefits are uncertain.

  15. Recent progress in photoactive organic field-effect transistors.

    PubMed

    Wakayama, Yutaka; Hayakawa, Ryoma; Seo, Hoon-Seok

    2014-04-01

    Recent progress in photoactive organic field-effect transistors (OFETs) is reviewed. Photoactive OFETs are divided into light-emitting (LE) and light-receiving (LR) OFETs. In the first part, LE-OFETs are reviewed from the viewpoint of the evolution of device structures. Device performances have improved in the last decade with the evolution of device structures from single-layer unipolar to multi-layer ambipolar transistors. In the second part, various kinds of LR-OFETs are featured. These are categorized according to their functionalities: phototransistors, non-volatile optical memories, and photochromism-based transistors. For both, various device configurations are introduced: thin-film based transistors for practical applications, single-crystalline transistors to investigate fundamental physics, nanowires, multi-layers, and vertical transistors based on new concepts.

  16. Recent progress in photoactive organic field-effect transistors

    NASA Astrophysics Data System (ADS)

    Wakayama, Yutaka; Hayakawa, Ryoma; Seo, Hoon-Seok

    2014-04-01

    Recent progress in photoactive organic field-effect transistors (OFETs) is reviewed. Photoactive OFETs are divided into light-emitting (LE) and light-receiving (LR) OFETs. In the first part, LE-OFETs are reviewed from the viewpoint of the evolution of device structures. Device performances have improved in the last decade with the evolution of device structures from single-layer unipolar to multi-layer ambipolar transistors. In the second part, various kinds of LR-OFETs are featured. These are categorized according to their functionalities: phototransistors, non-volatile optical memories, and photochromism-based transistors. For both, various device configurations are introduced: thin-film based transistors for practical applications, single-crystalline transistors to investigate fundamental physics, nanowires, multi-layers, and vertical transistors based on new concepts.

  17. Detection of photoactive siderophore biosynthetic genes in the marine environment.

    PubMed

    Gärdes, Astrid; Triana, Christopher; Amin, Shady A; Green, David H; Romano, Ariel; Trimble, Lyndsay; Carrano, Carl J

    2013-06-01

    Iron is an essential element for oceanic microbial life but its low bioavailability limits microorganisms in large areas of the oceans. To acquire this metal many marine bacteria produce organic chelates that bind and transport iron (siderophores). While it has been hypothesized that the global production of siderophores by heterotrophic bacteria and some cyanobacteria constitutes the bulk of organic ligands binding iron in the ocean because stability constants of siderophores and these organic ligands are similar, and because ligand concentrations rise sharply in response to iron fertilization events, direct evidence for this proposal is lacking. This lack is due to the difficulty in characterizing these ligands due both to their extremely low concentrations and their highly heterogeneous nature. The situation for characterizing photoactive siderophores in situ is more problematic because of their expected short lifetimes in the photic zone. An alternative approach is to make use of high sensitivity molecular technology (qPCR) to search for siderophore biosynthesis genes related to the production of photoactive siderophores. In this way one can access their "biochemical potential" and utilize this information as a proxy for the presence of these siderophores in the marine environment. Here we show, using qPCR primers designed to detect biosynthetic genes for the siderophores vibrioferrin, petrobactin and aerobactin that such genes are widespread and based on their abundance, the "biochemical potential" for photoactive siderophore production is significant. Concurrently we also briefly examine the microbial biodiversity responsible for such production as a function of depth and location across a North Atlantic transect.

  18. Thiol/disulfide homeostasis in asphalt workers.

    PubMed

    Yilmaz, Ömer Hınç; Bal, Ceylan; Neşelioglu, Salim; Büyükşekerci, Murat; Gündüzöz, Meşide; Eren, Funda; Tutkun, Lutfiye; Yilmaz, Fatma Meric

    2016-09-02

    The aim of this study was to investigate thiol/disulfide homeostasis in asphalt workers who are exposed to polycyclic aromatic hydrocarbons occupationally. The study was carried out in 34 nonsmoker asphalt workers. Additionally, 35 healthy nonsmoker volunteers were recruited as control group. Thiol and disulfide concentrations were determined using the novel automated measurement method. Levels of urinary 1-OH-pyrene were analyzed by liquid chromatography. Disulfide/thiol ratio was significantly higher in exposed group (p = .034). Also, a positive correlation was detected between disulfide/thiol ratio and 1-OH-pyrene values (r = .249, p = .036). Thiol/disulfide homeostasis was found to be disturbed in asphalt workers. The novel test used in this study may be useful for evaluating the oxidative status in polycyclic aromatic hydrocarbon (PAH) exposure.

  19. Titania-lanthanum phosphate photoactive and hydrophobic new generation catalyst

    SciTech Connect

    Jyothi, Chembolli K.; Jaimy, Kanakkanmavudi B.; Ghosh, Swapankumar; Sankar, Sasidharan; Smitha, V.S.; Warrier, K.G.K.

    2011-07-15

    Titania-lanthanum phosphate nanocomposites with multifunctional properties have been synthesized by aqueous sol-gel method. The precursor sols with varying TiO{sub 2}:LaPO{sub 4} ratios were applied as thin coating on glass substrates in order to be transparent, hydrophobic, photocatalytically active coatings. The phase compositions of the composite powders were identified by powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). The anatase phase of TiO{sub 2} in TiO{sub 2}-LaPO{sub 4} composite precursors was found to be stable even on annealing at 800 deg. C. The glass substrates, coated with TL1 (TiO{sub 2}-LaPO{sub 4} composition with 1 mol% LaPO{sub 4}) and TL50 (composite precursor containing TiO{sub 2} and LaPO{sub 4} with molar ratio 1:1) sols and annealed at 400 deg. C, produced contact angles of 74 deg. and 92 deg., respectively, though it is only 62 deg. for pure TiO{sub 2} coating. The glass substrates, coated with TL50 sol, produced surfaces with relatively high roughness and uneven morphology. The TL1 material, annealed at 800 deg. C, has shown the highest UV photoactivity with an apparent rate constant, k{sub app}=24x10{sup -3} min{sup -1}, which is over five times higher than that observed with standard Hombikat UV 100 (k{sub app}=4x10{sup -3} min{sup -1}). The photoactivity combined with a moderate contact angle (85.3 deg.) shows that this material has a promise as an efficient self-cleaning precursor. - Graphical abstract: Multifunctional TiO{sub 2}-LaPO{sub 4} composite stabilizes anatase phase with enhanced photocatalytic activity, and moderately higher hydrophobicity is a promising material for self-cleaning application. Highlights: > Titania-lanthanum phosphate nanocomposites were synthesized by aqueous sol-gel method. > Transparent, hydrophobic, photoactive coatings were developed on glass substrates. > The glass substrates, coated with TL1 annealed at 400 deg. C, produced a contact angle of 74 deg

  20. Optical anisotropy of tungsten-doped ReS2 layered crystals

    NASA Astrophysics Data System (ADS)

    Hsu, H. P.; Lin, K. H.; Huang, Y. S.

    2016-12-01

    The optical anisotropy of tungsten-doped rhenium disulfide (ReS2:W) layered crystals have been studied by polarization and temperature dependent piezoreflectance (PzR) spectroscopy from 25 to 300 K. The direct band edge excitonic transitions E1ex feature at E∥b polarization and E2ex feature at E⊥b polarization of tungsten-doped ReS2 layered crystals were determined from a detailed line-shape fit of the PzR spectra. The PzR spectra reveal a slightly blue shifted of excitonic transition with the tungsten incorporation. The angular dependence of the excitonic feature amplitudes agrees with Malus' rule. The parameters that describe the temperature variation of the energies and broadening function of the excitonic transitions are determined and discussed.

  1. Selective formation of tungsten nanowires

    PubMed Central

    2011-01-01

    We report on a process for fabricating self-aligned tungsten (W) nanowires with polycrystalline silicon core. Tungsten nanowires as thin as 10 nm were formed by utilizing polysilicon sidewall transfer technology followed by selective deposition of tungsten by chemical vapor deposition (CVD) using WF6 as the precursor. With selective CVD, the process is self-limiting whereby the tungsten formation is confined to the polysilicon regions; hence, the nanowires are formed without the need for lithography or for additional processing. The fabricated tungsten nanowires were observed to be perfectly aligned, showing 100% selectivity to polysilicon and can be made to be electrically isolated from one another. The electrical conductivity of the nanowires was characterized to determine the effect of its physical dimensions. The conductivity for the tungsten nanowires were found to be 40% higher when compared to doped polysilicon nanowires of similar dimensions. PMID:21970543

  2. Tungsten trioxide as a visible light photocatalyst for volatile organic carbon removal.

    PubMed

    Wicaksana, Yossy; Liu, Sanly; Scott, Jason; Amal, Rose

    2014-10-31

    Tungsten trioxide (WO3) has been demonstrated to possess visible light photoactivity and presents a means of overcoming the UV-light dependence of photocatalysts, such as titanium dioxide. In this study, WO3 nanostructures have been synthesised by a hydrothermal method using sodium tungstate (Na2WO4·2H2O), sulphate precursors and pH as structure-directing agents and parameters, respectively. By altering the concentration of the sulphate precursors and pH, it was shown that different morphologies and phases of WO3 can be achieved. The effect of the morphology of the final WO3 product on the visible light photoactivity of ethylene degradation in the gas phase was investigated. In addition, platinum (Pt) was photodeposited on the WO3 structures with various morphologies to enhance the photocatalytic properties. It was found that the photocatalytic properties of the WO3 samples greatly depend on their morphology, chemical composition and surface modification. WO3 with a cuboid morphology exhibited the highest visible light photoactivity compared to other morphologies, while adding Pt to the surface improved the performance of certain WO3 structures.

  3. Helium bubble bursting in tungsten

    SciTech Connect

    Sefta, Faiza; Juslin, Niklas; Wirth, Brian D.

    2013-12-28

    Molecular dynamics simulations have been used to systematically study the pressure evolution and bursting behavior of sub-surface helium bubbles and the resulting tungsten surface morphology. This study specifically investigates how bubble shape and size, temperature, tungsten surface orientation, and ligament thickness above the bubble influence bubble stability and surface evolution. The tungsten surface is roughened by a combination of adatom “islands,” craters, and pinholes. The present study provides insight into the mechanisms and conditions leading to various tungsten topology changes, which we believe are the initial stages of surface evolution leading to the formation of nanoscale fuzz.

  4. Mineral resource of the month: tungsten

    USGS Publications Warehouse

    Shedd, Kim B.

    2012-01-01

    The article offers information on tungsten. It says that tungsten is a metal found in chemical compounds such as in the scheelite and ore minerals wolframite. It states that tungsten has the highest melting point and it forms a compound as hard as diamond when combined with carbon. It states that tungsten can be used as a substitute for lead in fishing weights, ammunition, and hunting shot. Moreover, China started to export tungsten materials and products instead of tungsten raw materials.

  5. Photocatalytic activity of tungsten-doped TiO2 with hydrothermal treatment under blue light irradiation.

    PubMed

    Putta, Thapanan; Lu, Ming-Chun; Anotai, Jin

    2011-09-01

    Tungsten doping and hydrothermal treatment were found to significantly improve the visible-light photoactivity of TiO(2) synthesized by the sol-gel method. It was observed that TiO(2) doped with a 0.5% W:Ti mole ratio and treated with 4 h of hydrothermal curing showed photoactivity under blue light irradiation equal to 74% of the commercial Degussa P-25 under UV irradiation, i.e., 0.01 mM 2-chlorophenol was completely removed in 120 and 90 min, respectively. Light absorptivity and photocatalytic activity under blue light irradiation were not dependent on the crystallite structure of the TiO(2). The oxidation kinetics under blue light irradiation can be effectively explained by the Langmuir-Hinshelwood model with an apparent reaction rate constant and a Langmuir constant of 3.60 × 10(-4) mM min(-1) and 206.53 mM(-1), respectively.

  6. Photo Control of Protein Function Using Photoactive Yellow Protein.

    PubMed

    Reis, Jakeb M; Woolley, G Andrew

    2016-01-01

    Photoswitchable proteins are becoming increasingly common tools for manipulating cellular processes with high spatial and temporal precision. Photoactive yellow protein (PYP) is a small, water-soluble protein that undergoes a blue light induced change in conformation. It can serve as a scaffold for designing new tools to manipulate biological processes, but with respect to other protein scaffolds it presents some technical challenges. Here, we present practical information on how to overcome these, including how to synthesize the PYP chromophore, how to express and purify PYP, and how to screen for desired activity.

  7. Soft Computing Methods for Disulfide Connectivity Prediction

    PubMed Central

    Márquez-Chamorro, Alfonso E.; Aguilar-Ruiz, Jesús S.

    2015-01-01

    The problem of protein structure prediction (PSP) is one of the main challenges in structural bioinformatics. To tackle this problem, PSP can be divided into several subproblems. One of these subproblems is the prediction of disulfide bonds. The disulfide connectivity prediction problem consists in identifying which nonadjacent cysteines would be cross-linked from all possible candidates. Determining the disulfide bond connectivity between the cysteines of a protein is desirable as a previous step of the 3D PSP, as the protein conformational search space is highly reduced. The most representative soft computing approaches for the disulfide bonds connectivity prediction problem of the last decade are summarized in this paper. Certain aspects, such as the different methodologies based on soft computing approaches (artificial neural network or support vector machine) or features of the algorithms, are used for the classification of these methods. PMID:26523116

  8. Transfer of molybdenum disulfide to various metals

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

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

  9. Identification of Allosteric Disulfides from Prestress Analysis

    PubMed Central

    Zhou, Beifei; Baldus, Ilona B.; Li, Wenjin; Edwards, Scott A.; Gräter, Frauke

    2014-01-01

    Disulfide bonds serve to form physical cross-links between residues in protein structures, thereby stabilizing the protein fold. Apart from this purely structural role, they can also be chemically active, participating in redox reactions, and they may even potentially act as allosteric switches controlling protein functions. Specific types of disulfide bonds have been identified in static protein structures from their distinctive pattern of dihedral bond angles, and the allosteric function of such bonds is purported to be related to the torsional strain they store. Using all-atom molecular-dynamics simulations for ∼700 disulfide bonded proteins, we analyzed the intramolecular mechanical forces in 20 classes of disulfide bonds. We found that two particular classes, the −RHStaple and the −/+RHHook disulfides, are indeed more stressed than other disulfide bonds, but the stress is carried primarily by stretching of the S-S bond and bending of the neighboring bond angles, rather than by dihedral torsion. This stress corresponds to a tension force of magnitude ∼200 pN, which is balanced by repulsive van der Waals interactions between the cysteine Cα atoms. We confirm stretching of the S-S bond to be a general feature of the −RHStaples and the −/+RHHooks by analyzing ∼20,000 static protein structures. Given that forced stretching of S-S bonds is known to accelerate their cleavage, we propose that prestress of allosteric disulfide bonds has the potential to alter the reactivity of a disulfide, thereby allowing us to readily switch between functional states. PMID:25099806

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

    PubMed

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

    2017-02-01

    Transition metal dichalcogenides (TMDs) are becoming significant because of their interesting semiconducting and photonic properties. In particular, TMDs such as molybdenum disulfide (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.

  11. Gleeble Testing of Tungsten Samples

    DTIC Science & Technology

    2013-02-01

    close off porosity left after manufacturing and create a fully dense part. In order to alleviate this problem, rhenium was added to sintered nano...with and without rhenium , to determine a set of processing parameters that could be used during post-processing steps to create fully dense nano...4.2 Tungsten With Rhenium .................................................................................................9 4.3 Commercial Tungsten

  12. Selective oxidation of alcohols using photoactive VO@g-C3N4.

    EPA Science Inventory

    A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.

  13. TUNGSTEN BASE ALLOYS

    DOEpatents

    Schell, D.H.; Sheinberg, H.

    1959-12-15

    A high-density quaternary tungsten-base alloy having high mechanical strength and good machinability composed of about 2 wt.% Ni, 3 wt.% Cu, 5 wt.% Pb, and 90wt.% W is described. This alloy can be formed by the powder metallurgy technique of hot pressing in a graphite die without causing a reaction between charge and the die and without formation of a carbide case on the final compact, thereby enabling re-use of the graphite die. The alloy is formable at hot- pressing temperatures of from about 1200 to about 1350 deg C. In addition, there is little component shrinkage, thereby eliminating the necessity of subsequent extensive surface machining.

  14. Preparation of tungsten oxide

    DOEpatents

    Bulian, Christopher J.; Dye, Robert C.; Son, Steven F.; Jorgensen, Betty S.; Perry, W. Lee

    2009-09-22

    Tungsten trioxide hydrate (WO.sub.3.H.sub.2O) was prepared from a precursor solution of ammonium paratungstate in concentrated aqueous hydrochloric acid. The precursor solution was rapidly added to water, resulting in the crash precipitation of a yellow white powder identified as WO.sub.3.H.sub.2O nanosized platelets by x-ray diffraction and scanning electron microscopy. Annealing of the powder at 200.degree. C. provided cubic phase WO.sub.3 nanopowder, and at 400.degree. C. provided WO.sub.3 nanopowder as a mixture of monoclinic and orthorhombic phases.

  15. Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

    SciTech Connect

    McGrane, Shawn David; Bolme, Cynthia Anne; Greenfield, Margo Torello; Chavez, David E.; Hanson, Susan Kloek; Scharff, Robert Jason

    2016-01-21

    High explosives that are photoactive, i.e., can be initiated with light, offer significant advantages in reduced potential for accidental electrical initiation. In this study, we examined a series of structurally related tetrazine based photoactive high explosive materials to detail their photochemical and photophysical properties. Using photobleaching infrared absorption, we determined quantum yields of photochemistry for nanosecond pulsed excitation at 355 and 532 nm. Changes in mass spectrometry during laser irradiation in vacuum measured the evolution of gaseous products. Fluorescence spectra, quantum yields, and lifetimes were measured to observe radiative channels of energy decay that compete with photochemistry. For the 6 materials studied, quantum yields of photochemistry ranged from <10–5 to 0.03 and quantum yield of fluorescence ranged from <10–3 to 0.33. In all cases, the photoexcitation nonradiatively relaxed primarily to heat, appropriate for supporting photothermal initiation processes. Lastly, the photochemistry observed was dominated by ring scission of the tetrazine, but there was evidence of more extensive multistep reactions as well.

  16. Structure and photoactivity of titania derived from nanotubes and nanofibers.

    PubMed

    Inagaki, Michio; Kondo, Naho; Nonaka, Rie; Ito, Eiki; Toyoda, Masahiro; Sogabe, Kazuo; Tsumura, Tomoki

    2009-01-30

    Photoactivity under UV irradiation for the decomposition of methylene blue in water and for the oxidation of NO gas was studied on titania powders derived from titanate nanotube (TNT) and nanofiber (TNF) by annealing at high temperatures, comparing with granular titania (ST-01). Rate constant for methylene blue decomposition k(MB) increased with increasing annealing temperature above 300 degrees C after the conversion from titanate to tinania. It tended to decrease above 700 degrees C, mainly due to the phase transformation from anatase to rutile. The dependences of k(MB) on full width at half maximum intensity (FWHM) were common for three samples, a sharp maximum at around 0.4 degrees in FWHM, but TNF-derived sample gave much higher maximum than ST-01. Change in fraction of oxidized NO with annealing temperature showed a plateau at around 50% and then decreased abruptly by high temperature annealing. Starting from TNT and TNF has an advantage to form fine particles by annealing above 300 degrees C, giving high photoactivity due to high crystallinity and high adsorptivity particularly for methylene blue.

  17. Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

    DOE PAGES

    McGrane, Shawn David; Bolme, Cynthia Anne; Greenfield, Margo Torello; ...

    2016-01-21

    High explosives that are photoactive, i.e., can be initiated with light, offer significant advantages in reduced potential for accidental electrical initiation. In this study, we examined a series of structurally related tetrazine based photoactive high explosive materials to detail their photochemical and photophysical properties. Using photobleaching infrared absorption, we determined quantum yields of photochemistry for nanosecond pulsed excitation at 355 and 532 nm. Changes in mass spectrometry during laser irradiation in vacuum measured the evolution of gaseous products. Fluorescence spectra, quantum yields, and lifetimes were measured to observe radiative channels of energy decay that compete with photochemistry. For the 6more » materials studied, quantum yields of photochemistry ranged from <10–5 to 0.03 and quantum yield of fluorescence ranged from <10–3 to 0.33. In all cases, the photoexcitation nonradiatively relaxed primarily to heat, appropriate for supporting photothermal initiation processes. Lastly, the photochemistry observed was dominated by ring scission of the tetrazine, but there was evidence of more extensive multistep reactions as well.« less

  18. Infection Mitigation Efficacy of Photoactive Titania on Orthopedic Implant Materials

    PubMed Central

    Azad, Abdul-Majeed; Hershey, Ryan; Aboelzahab, Asem; Goel, Vijay

    2011-01-01

    In order to impede infection and achieve accelerated wound healing in the postorthopaedic surgery patients, a simple and benign procedure for creating nanotubular or nanofibrillar structure of photoactive TiO2 on the surface of Ti plates and wires is described. The nanoscale TiO2 films on titanium were grown by hydrothermal processing in one case and by anodization in the presence of dilute mineral acids under mild and benign conditions in the other. Confocal microscopy results demonstrated at least 50% reduction in the population of E. coli colonies (concentration 2.15 × 107 cells/mL) on TiO2-coated implants upon an IR exposure of up to 30 s; it required ∼20 min of exposure to UV beam for the same effect. These findings suggest the probability of eliminating wound infection during and after orthopedic surgical procedures by brief illumination of photoactive titania films on the implants with an IR beam. PMID:21994891

  19. High-Throughput Preparation of New Photoactive Nanocomposites.

    PubMed

    Conterosito, Eleonora; Benesperi, Iacopo; Toson, Valentina; Saccone, Davide; Barbero, Nadia; Palin, Luca; Barolo, Claudia; Gianotti, Valentina; Milanesio, Marco

    2016-06-08

    New low-cost photoactive hybrid materials based on organic luminescent molecules inserted into hydrotalcite (layered double hydroxides; LDH) were produced, which exploit the high-throughput liquid-assisted grinding (LAG) method. These materials are conceived for applications in dye-sensitized solar cells (DSSCs) as a co-absorbers and in silicon photovoltaic (PV) panels to improve their efficiency as they are able to emit where PV modules show the maximum efficiency. A molecule that shows a large Stokes' shift was designed, synthesized, and intercalated into LDH. Two dyes already used in DSSCs were also intercalated to produce two new nanocomposites. LDH intercalation allows the stability of organic dyes to be improved and their direct use in polymer melt blending. The prepared nanocomposites absorb sunlight from UV to visible and emit from blue to near-IR and thus can be exploited for light-energy management. Finally one nanocomposite was dispersed by melt blending into a poly(methyl methacrylate)-block-poly(n-butyl acrylate) copolymer to obtain a photoactive film.

  20. 49 CFR 173.338 - Tungsten hexafluoride.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Tungsten hexafluoride. 173.338 Section 173.338... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.338 Tungsten hexafluoride. (a) Tungsten... expansion test, must be condemned if removed from tungsten hexafluoride service....

  1. 49 CFR 173.338 - Tungsten hexafluoride.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Tungsten hexafluoride. 173.338 Section 173.338... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.338 Tungsten hexafluoride. (a) Tungsten... expansion test, must be condemned if removed from tungsten hexafluoride service....

  2. 49 CFR 173.338 - Tungsten hexafluoride.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Tungsten hexafluoride. 173.338 Section 173.338... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.338 Tungsten hexafluoride. (a) Tungsten... expansion test, must be condemned if removed from tungsten hexafluoride service. [ 74 FR 16143, Apr. 9,...

  3. 49 CFR 173.338 - Tungsten hexafluoride.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Tungsten hexafluoride. 173.338 Section 173.338... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.338 Tungsten hexafluoride. (a) Tungsten... expansion test, must be condemned if removed from tungsten hexafluoride service....

  4. High strength uranium-tungsten alloy process

    DOEpatents

    Dunn, Paul S.; Sheinberg, Haskell; Hogan, Billy M.; Lewis, Homer D.; Dickinson, James M.

    1990-01-01

    Alloys of uranium and tungsten and a method for making the alloys. The amount of tungsten present in the alloys is from about 4 wt % to about 35 wt %. Tungsten particles are dispersed throughout the uranium and a small amount of tungsten is dissolved in the uranium.

  5. 49 CFR 173.338 - Tungsten hexafluoride.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Tungsten hexafluoride. 173.338 Section 173.338... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.338 Tungsten hexafluoride. (a) Tungsten... expansion test, must be condemned if removed from tungsten hexafluoride service....

  6. High strength uranium-tungsten alloys

    DOEpatents

    Dunn, Paul S.; Sheinberg, Haskell; Hogan, Billy M.; Lewis, Homer D.; Dickinson, James M.

    1991-01-01

    Alloys of uranium and tungsten and a method for making the alloys. The amount of tungsten present in the alloys is from about 4 wt % to about 35 wt %. Tungsten particles are dispersed throughout the uranium and a small amount of tungsten is dissolved in the uranium.

  7. Synthesis of Nanostructured Tungsten and Tungsten - Phases

    NASA Astrophysics Data System (ADS)

    Angastiniotis, Nicos Costa

    Reductive decomposition of spray dried ammonium metatungstate gives rise to nanocrystalline alpha -W (bcc structure) or nanocrystalline beta -W (A15 structure), depending on the specifics of the processing conditions. By controlling the reaction rate of the high surface area alpha-W and beta -W phases with oxygen at low temperatures ( <=300^circC) it is possible to transform both phases to an amorphous tungsten oxide. Furthermore, reduction of the amorphous oxide in hydrogen at <=400 ^circC yields gamma -W (amorphous structure), in which all or nearly all of the oxygen atoms are removed. The high surface area alpha -W and beta-W phases show striking differences in susceptibility to gas-solid reactions. Reaction of beta-W with ammonia at low temperatures (100^circ-300^ circC) results in the formation of an intermediate amorphous delta-WN_ {rm x} phase, which decomposes at higher temperatures (>=650 ^circC) into nanocrystalline rm W_2N_{x} phase. On the other hand, if nitridation is initiated at room temperature and continues as the temperature gradually increases to 300^circC, another amorphous phase (gamma-WN_{ rm x}) is formed. A similar behavior occurs when beta -W is reacted with carbon monoxide at low temperatures, starting at room temperature and continuing as the temperature gradually increases to 300^circC. The resulting amorphous phase delta- rm WC_{x}O_{y } is exceptionally stable. Only upon heating to 800^circC in carbon monoxide does it decompose to rm WC_{x }.. The unusual chemical activity of high surface area beta-W led to speculation concerning its susceptibility to solid-solid reactions, in addition to the gas-solid reactions noted above. Tests on the W -Cu system, in which both elements are mutually insoluble in the solid state, clearly showed that Cu can be diffused into beta-W to form a metastable solid solution. Some diffusional disordering evidently occurs because of the disappearance of the high order peaks of beta-W. However, the disordering

  8. METHOD OF MAKING TUNGSTEN FILAMENTS

    DOEpatents

    Frazer, J.W.

    1962-12-18

    A method of making tungsten filaments is described in which the tungsten is completely free of isotope impurities in the range of masses 234 to 245 for use in mass spectrometers. The filament comprises a tantalum core generally less than 1 mil in diameter having a coating of potassium-free tantalum-diffused tungsten molecularly bonded thereto. In the preferred process of manufacture a short, thin tantalum filament is first mounted between terminal posts mounted in insulated relation through a backing plate. The tungsten is most conveniently vapor plated onto the tantalum by a tungsten carbonyl vapor decomposition method having a critical step because of the tendency of the tantalum to volatilize at the temperature of operntion of the filament. The preferred recipe comprises volatilizing tantalum by resistance henting until the current drops by about 40%, cutting the voltage back to build up the tungsten, and then gradually building the temperature back up to balance the rate of tungsten deposition with the rate of tantalum volatilization. (AEC)

  9. Display of disulfide-rich proteins by complementary DNA display and disulfide shuffling assisted by protein disulfide isomerase.

    PubMed

    Naimuddin, Mohammed; Kubo, Tai

    2011-12-01

    We report an efficient system to produce and display properly folded disulfide-rich proteins facilitated by coupled complementary DNA (cDNA) display and protein disulfide isomerase-assisted folding. The results show that a neurotoxin protein containing four disulfide linkages can be displayed in the folded state. Furthermore, it can be refolded on a solid support that binds efficiently to its natural acetylcholine receptor. Probing the efficiency of the display proteins prepared by these methods provided up to 8-fold higher enrichment by the selective enrichment method compared with cDNA display alone, more than 10-fold higher binding to its receptor by the binding assays, and more than 10-fold higher affinities by affinity measurements. Cotranslational folding was found to have better efficiency than posttranslational refolding between the two investigated methods. We discuss the utilities of efficient display of such proteins in the preparation of superior quality proteins and protein libraries for directed evolution leading to ligand discovery.

  10. Cellular disulfide bond formation in bioactive peptides and proteins.

    PubMed

    Patil, Nitin A; Tailhades, Julien; Hughes, Richard Anthony; Separovic, Frances; Wade, John D; Hossain, Mohammed Akhter

    2015-01-14

    Bioactive peptides play important roles in metabolic regulation and modulation and many are used as therapeutics. These peptides often possess disulfide bonds, which are important for their structure, function and stability. A systematic network of enzymes--a disulfide bond generating enzyme, a disulfide bond donor enzyme and a redox cofactor--that function inside the cell dictates the formation and maintenance of disulfide bonds. The main pathways that catalyze disulfide bond formation in peptides and proteins in prokaryotes and eukaryotes are remarkably similar and share several mechanistic features. This review summarizes the formation of disulfide bonds in peptides and proteins by cellular and recombinant machinery.

  11. RECOVERY OF URANIUM FROM TUNGSTEN

    DOEpatents

    Newnam, K.

    1959-02-01

    A method is presented for the rccovery of uranium which has adhered to tungsten parts in electromagnetic isotope separation apparatus. Such a tungsten article is dissolved electrolytically in 20% NaOH by using the tungsten article as the anode. The resulting solution, containing soluble sodium lungstate and an insoluble slime, is then filtered. The slime residue is ignited successively with sodium nitrate and sodium pyrosulfate and leashed, and the resulting filtrates are combined with the original filtrate. Uranium is then recovered from the combined flltrates by diuranate precipitation.

  12. Tungsten Toxicity in Plants

    PubMed Central

    Adamakis, Ioannis-Dimosthenis S.; Panteris, Emmanuel; Eleftheriou, Eleftherios P.

    2012-01-01

    Tungsten (W) is a rare heavy metal, widely used in a range of industrial, military and household applications due to its unique physical properties. These activities inevitably have accounted for local W accumulation at high concentrations, raising concerns about its effects for living organisms. In plants, W has primarily been used as an inhibitor of the molybdoenzymes, since it antagonizes molybdenum (Mo) for the Mo-cofactor (MoCo) of these enzymes. However, recent advances indicate that, beyond Mo-enzyme inhibition, W has toxic attributes similar with those of other heavy metals. These include hindering of seedling growth, reduction of root and shoot biomass, ultrastructural malformations of cell components, aberration of cell cycle, disruption of the cytoskeleton and deregulation of gene expression related with programmed cell death (PCD). In this article, the recent available information on W toxicity in plants and plant cells is reviewed, and the knowledge gaps and the most pertinent research directions are outlined. PMID:27137642

  13. Tungsten resources of Brazil

    USGS Publications Warehouse

    White, Max Gregg

    1974-01-01

    Brazilian tungsten production, 85 percent of which is exported, comes almost entirely from scheelite-bearing tactites in northeast Brazil, and has reached an annual rate of about 2,000 metric tons (2,200 short tons) of scheelite concentrate with 70 percent WO3. Scheelite ore reserves, located principally in the State of Rio Grande do Norte, are estimated to be as high as 8,300,000 tons (9,100,000 short tons) containing 0.7 percent WO3. Minor deposits (or those about which only minimal information is available) of wolframite, with which some cassiterite is associated, are located in Sao Paulo, Santa Catarina, and Rio Grande do Sul. Both the scheelite and the wolframite deposits are considered . to be late Precambrian A (620 to 900 m.y.) or early Cambrian in age.

  14. The two photocycles of photoactive yellow protein from Rhodobacter sphaeroides.

    PubMed

    Haker, Andrea; Hendriks, Johnny; van Stokkum, Ivo H M; Heberle, Joachim; Hellingwerf, Klaas J; Crielaard, Wim; Gensch, Thomas

    2003-03-07

    The absorption spectrum of the photoactive yellow protein from Rhodobacter sphaeroides (R-PYP) shows two maxima, absorbing at 360 nm (R-PYP(360)) and 446 nm (R-PYP(446)), respectively. Both forms are photoactive and part of a temperature- and pH-dependent equilibrium (Haker, A., Hendriks, J., Gensch, T., Hellingwerf, K. J., and Crielaard, W. (2000) FEBS Lett. 486, 52-56). At 20 degrees C, for PYP characteristic, the 446-nm absorbance band displays a photocycle, in which the depletion of the 446-nm ground state absorption occurs in at least three phases, with time constants of <30 ns, 0.5 micros, and 17 micros. Intermediates with both blue- and red-shifted absorption maxima are transiently formed, before a blue-shifted intermediate (pB(360), lambda(max) = 360 nm) is established. The photocycle is completed with a monophasic recovery of the ground state with a time constant of 2.5 ms. At 7 degrees C these photocycle transitions are slowed down 2- to 3-fold. Upon excitation of R-PYP(360) with a UV-flash (330 +/- 50 nm) a species with a difference absorption maximum at approximately 435 nm is observed that returns to R-PYP(360) on a minute time scale. Recovery can be accelerated by a blue light flash (450 nm). R-PYP(360) and R-PYP(446) differ in their overall protein conformation, as well as in the isomerization and protonation state of the chromophore, as determined with the fluorescent polarity probe Nile Red and Fourier Transform Infrared spectroscopy, respectively.

  15. Photoactive dye enhanced tissue ablation for endoscopic laser prostatectomy

    NASA Astrophysics Data System (ADS)

    Ahn, Minwoo; Nguyen, Trung Hau; Nguyen, Van Phuc; Oh, Junghwan; Kang, Hyun Wook

    2015-02-01

    Laser light has been widely used as a surgical tool to treat benign prostate hyperplasia with high laser power. The purpose of this study was to validate the feasibility of photoactive dye injection to enhance light absorption and eventually to facilitate tissue ablation with low laser power. The experiment was implemented on chicken breast due to minimal optical absorption Amaranth (AR), black dye (BD), hemoglobin powder (HP), and endoscopic marker (EM), were selected and tested in vitro with a customized 532-nm laser system with radiant exposure ranging from 0.9 to 3.9 J/cm2. Light absorbance and ablation threshold were measured with UV-VIS spectrometer and Probit analysis, respectively, and compared to feature the function of the injected dyes. Ablation performance with dye-injection was evaluated in light of radiant exposure, dye concentration, and number of injection. Higher light absorption by injected dyes led to lower ablation threshold as well as more efficient tissue removal in the order of AR, BD, HP, and EM. Regardless of the injected dyes, ablation efficiency principally increased with input parameter. Among the dyes, AR created the highest ablation rate of 44.2+/-0.2 μm/pulse due to higher absorbance and lower ablation threshold. Preliminary tests on canine prostate with a hydraulic injection system demonstrated that 80 W with dye injection yielded comparable ablation efficiency to 120 W with no injection, indicating 33 % reduced laser power with almost equivalent performance. In-depth comprehension on photoactive dye-enhanced tissue ablation can help accomplish efficient and safe laser treatment for BPH with low power application.

  16. Heated die facilitates tungsten forming

    NASA Technical Reports Server (NTRS)

    Chattin, J. H.; Haystrick, J. E.; Laughlin, J. C.; Leidy, R. A.

    1966-01-01

    Tungsten forming in a press brake employs a bottom die assembly with a heating manifold between two water-cooled die sections. The manifold has hydrogen-oxygen burners spaced along its length for even heat during forming.

  17. Disulfide-Functionalized Diblock Copolymer Worm Gels.

    PubMed

    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

  18. Selective Oxidation of Alcohols Using Photoactive VO@g??C3N4

    EPA Pesticide Factsheets

    A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, M. Nadagouda , and R. Varma. Selective oxidation of alcohols using photoactive VO@g-C3N4.. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(3): 1094-1098, (2015).

  19. 46 CFR 153.520 - Special requirements for carbon disulfide.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Special requirements for carbon disulfide. 153.520... Equipment Special Requirements § 153.520 Special requirements for carbon disulfide. A containment system carrying carbon disulfide must meet the following: (a) Each cargo pump must be of the intank type...

  20. 40 CFR 180.467 - Carbon disulfide; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Carbon disulfide; tolerances for... § 180.467 Carbon disulfide; tolerances for residues. Tolerances are established for the nematicide, insecticide, and fungicide carbon disulfide, from the application of sodium tetrathiocarbonate, in or on...

  1. 40 CFR 180.467 - Carbon disulfide; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Carbon disulfide; tolerances for... § 180.467 Carbon disulfide; tolerances for residues. Tolerances are established for the nematicide, insecticide, and fungicide carbon disulfide, from the application of sodium tetrathiocarbonate, in or on...

  2. 46 CFR 153.520 - Special requirements for carbon disulfide.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Special requirements for carbon disulfide. 153.520... Equipment Special Requirements § 153.520 Special requirements for carbon disulfide. A containment system carrying carbon disulfide must meet the following: (a) Each cargo pump must be of the intank type...

  3. 40 CFR 180.467 - Carbon disulfide; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Carbon disulfide; tolerances for... § 180.467 Carbon disulfide; tolerances for residues. Tolerances are established for the nematicide, insecticide, and fungicide carbon disulfide, from the application of sodium tetrathiocarbonate, in or on...

  4. 40 CFR 180.467 - Carbon disulfide; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Carbon disulfide; tolerances for... § 180.467 Carbon disulfide; tolerances for residues. Tolerances are established for the nematicide, insecticide, and fungicide carbon disulfide, from the application of sodium tetrathiocarbonate, in or on...

  5. 40 CFR 180.467 - Carbon disulfide; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Carbon disulfide; tolerances for... § 180.467 Carbon disulfide; tolerances for residues. Tolerances are established for the nematicide, insecticide, and fungicide carbon disulfide, from the application of sodium tetrathiocarbonate, in or on...

  6. 46 CFR 153.520 - Special requirements for carbon disulfide.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Special requirements for carbon disulfide. 153.520... Equipment Special Requirements § 153.520 Special requirements for carbon disulfide. A containment system carrying carbon disulfide must meet the following: (a) Each cargo pump must be of the intank type...

  7. 46 CFR 153.520 - Special requirements for carbon disulfide.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Special requirements for carbon disulfide. 153.520... Equipment Special Requirements § 153.520 Special requirements for carbon disulfide. A containment system carrying carbon disulfide must meet the following: (a) Each cargo pump must be of the intank type...

  8. 21 CFR 524.2101 - Selenium disulfide suspension.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Selenium disulfide suspension. 524.2101 Section... § 524.2101 Selenium disulfide suspension. (a) Specifications. The product contains 0.9-percent weight in weight (w/w) selenium disulfide (1-percent weight in volume (w/v)). (b) Sponsors. See Nos. 000061,...

  9. 21 CFR 524.2101 - Selenium disulfide suspension.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Selenium disulfide suspension. 524.2101 Section... § 524.2101 Selenium disulfide suspension. (a) Specifications. The product contains 0.9-percent weight in weight (w/w) selenium disulfide (1-percent weight in volume (w/v)). (b) Sponsors. See Nos. 000061,...

  10. 21 CFR 524.2101 - Selenium disulfide suspension.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Selenium disulfide suspension. 524.2101 Section... § 524.2101 Selenium disulfide suspension. (a) Specifications. The product contains 0.9-percent weight in weight (w/w) selenium disulfide (1-percent weight in volume (w/v)). (b) Sponsors. See Nos. 000061,...

  11. 21 CFR 524.2101 - Selenium disulfide suspension.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Selenium disulfide suspension. 524.2101 Section... § 524.2101 Selenium disulfide suspension. (a) Specifications. The product contains 0.9-percent weight in weight (w/w) selenium disulfide (1-percent weight in volume (w/v)). (b) Sponsors. See Nos. 000061,...

  12. 21 CFR 524.2101 - Selenium disulfide suspension.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Selenium disulfide suspension. 524.2101 Section... § 524.2101 Selenium disulfide suspension. (a) Specifications. The product contains 0.9-percent weight in weight (w/w) selenium disulfide (1-percent weight in volume (w/v)). (b) Sponsors. See Nos. 000061,...

  13. Polarographic determination of tungsten in rocks

    USGS Publications Warehouse

    Reichen, L.E.

    1954-01-01

    This work was undertaken to develop a simpler and faster method than the classical gravimetric procedure for the determination of tungsten in rocks and ores. A new polarographic wave of tungsten is obtained in a supporting electrolyte of dilute hydrochloric acid containing tartrate ion. This permits the determination of tungsten both rapidly and accurately. No precipitation of the tungsten is necessary, and only the iron need be separated from the tungsten. The accuracy is within the limits of a polarographic procedure; comparison of polarographic and gravimetric results is given. The method reduces appreciably the amount of time ordinarily consumed in determination of tungsten.

  14. Process Of Bonding Copper And Tungsten

    DOEpatents

    Slattery, Kevin T.; Driemeyer, Daniel E.; Davis, John W.

    2000-07-18

    Process for bonding a copper substrate to a tungsten substrate by providing a thin metallic adhesion promoting film bonded to a tungsten substrate and a functionally graded material (FGM) interlayer bonding the thin metallic adhesion promoting film to the copper substrate. The FGM interlayer is formed by sintering a stack of individual copper and tungsten powder blend layers having progressively higher copper content/tungsten content, by volume, ratio values in successive powder blend layers in a lineal direction extending from the tungsten substrate towards the copper substrate. The resulting copper to tungsten joint well accommodates the difference in the coefficient of thermal expansion of the materials.

  15. Preparation and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin films.

    PubMed

    Addamo, Maurizio; Bellardita, Marianna; Di Paola, Agatino; Palmisano, Leonardo

    2006-12-21

    Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions.

  16. Solvothermal synthesis of nickel-tungsten sulfides for 2-propanol dehydration.

    PubMed

    Gómez-Gutiérrez, Claudia M; Luque, P A; Guerra-Rivas, G; López-Sánchez, J A; Armenta, M A; Quintana, J M; Olivas, A

    2015-01-01

    The bimetallic nickel-tungsten catalysts were prepared via solvothermal method. The X-ray Diffractometer (XRD) analysis revealed that the corresponding peaks at 14°, 34°, and 58° were for tungsten disulfide (WS2 ) hexagonal phase. The catalysts displayed different crystalline phase with nickel addition, and as an effect the WS2 surface area decreased from 74.7 to 2.0 m(2) g(--1) . In this sense, high-resolution transmission electron microscopy (HRTEM) showed the layers set in direction (002) with an onion-like morphology, and in the center of the particles there is a large amount of nickel contained with 6-8 layers covering it. The catalytic dehydration of 2-propanol was selective to propene in 100% at 250 °C for the sample with 0.7 of atomic ratio of Ni/Ni + W.

  17. Disulfide Bond Requirements for Active Wnt Ligands*

    PubMed Central

    MacDonald, Bryan T.; Hien, Annie; Zhang, Xinjun; Iranloye, Oladoyin; Virshup, David M.; Waterman, Marian L.; He, Xi

    2014-01-01

    Secreted Wnt lipoproteins are cysteine-rich and lipid-modified morphogens that bind to the Frizzled (FZD) receptor and LDL receptor-related protein 6 (LRP6). Wnt engages FZD through protruding thumb and index finger domains, which are each assembled from paired β strands secured by disulfide bonds and grasp two sides of the FZD ectodomain. The importance of Wnt disulfide bonds has been assumed but uncharacterized. We systematically analyzed cysteines and associated disulfide bonds in the prototypic Wnt3a. Our data show that mutation of any individual cysteine of Wnt3a results in covalent Wnt oligomers through ectopic intermolecular disulfide bond formation and diminishes/abolishes Wnt signaling. Although individual cysteine mutations in the amino part of the saposin-like domain and in the base of the index finger are better tolerated and permit residual Wnt3a secretion/activity, those in the amino terminus, the thumb, and at the tip of the index finger are incompatible with secretion and/or activity. A few select double cysteine mutants based on the disulfide bond pattern restore Wnt secretion/activity. Further, a double cysteine mutation at the index finger tip results in a Wnt3a with normal secretion but minimal FZD binding and dominant negative properties. Our results experimentally validate predictions from the Wnt crystal structure and highlight critical but different roles of the saposin-like and cytokine-like domains, including the thumb and the index finger in Wnt folding/secretion and FZD binding. Finally, we modified existing expression vectors for 19 epitope-tagged human WNT proteins by removal of a tag-supplied ectopic cysteine, thereby generating tagged WNT ligands active in canonical and non-canonical signaling. PMID:24841207

  18. Trion fine structure and coupled spin–valley dynamics in monolayer tungsten disulfide

    PubMed Central

    Plechinger, Gerd; Nagler, Philipp; Arora, Ashish; Schmidt, Robert; Chernikov, Alexey; del Águila, Andrés Granados; Christianen, Peter C.M.; Bratschitsch, Rudolf; Schüller, Christian; Korn, Tobias

    2016-01-01

    Monolayer transition-metal dichalcogenides have recently emerged as possible candidates for valleytronic applications, as the spin and valley pseudospin are directly coupled and stabilized by a large spin splitting. The optical properties of these two-dimensional crystals are dominated by tightly bound electron–hole pairs (excitons) and more complex quasiparticles such as charged excitons (trions). Here we investigate monolayer WS2 samples via photoluminescence and time-resolved Kerr rotation. In photoluminescence and in energy-dependent Kerr rotation measurements, we are able to resolve two different trion states, which we interpret as intravalley and intervalley trions. Using time-resolved Kerr rotation, we observe a rapid initial valley polarization decay for the A exciton and the trion states. Subsequently, we observe a crossover towards exciton–exciton interaction-related dynamics, consistent with the formation and decay of optically dark A excitons. By contrast, resonant excitation of the B exciton transition leads to a very slow decay of the Kerr signal. PMID:27586517

  19. Correlatively Dependent Lattice and Electronic Structural Evolutions in Compressed Monolayer Tungsten Disulfide.

    PubMed

    Han, Bo; Li, Fangfei; Li, Liang; Huang, Xiaoli; Gong, Yuanbo; Fu, Xinpeng; Gao, Hanxue; Zhou, Qiang; Cui, Tian

    2017-03-02

    Transition-metal dichalcogenides (TMDs) are promising materials for optoelectronic devices. Their lattice and electronic structural evolutions under high strain conditions and their relations remain open questions. We exert pressure on WS2 monolayers on different substrates, namely, Si/SiO2 substrate and diamond anvil surface up to ∼25 GPa. Structural distortions in various degree are disclosed based on the emergence of Raman-inactive B mode. Splits of out-of-plane B and A1' modes are only observed on Si/SiO2 substrate due to extra strain imported from volume decrease in Si and corrugation of SiO2 surface, and its photoluminescence (PL) quenches quickly because of decreased K-K transition by conspicuous distortion of Brillouin zone. While diamond anvil surface provides better hydrostatic environment, combined analysis of PL and absorption proves that pressure effectively tunes PL emission energy and enhances Coulomb interactions. Knowledge of these distinct pressure tunable characteristics of monolayer WS2 improves further understanding of structural and optical properties of TMDs.

  20. Increased monolayer domain size and patterned growth of tungsten disulfide through controlling surface energy of substrates

    NASA Astrophysics Data System (ADS)

    Godin, Kyle; Kang, Kyungnam; Fu, Shichen; Yang, Eui-Hyeok

    2016-08-01

    We report a surface energy-controlled low-pressure chemical vapor deposition growth of WS2 monolayers on SiO2 using pre-growth oxygen plasma treatment of substrates, facilitating increased monolayer surface coverage and patterned growth without lithography. Oxygen plasma treatment of the substrate caused an increase in the average domain size of WS2 monolayers by 78%  ±  2% while having a slight reduction in nucleation density, which translates to increased monolayer surface coverage. This substrate effect on growth was exploited to grow patterned WS2 monolayers by patterned plasma treatment on patterned substrates and by patterned source material with resolutions less than 10 µm. Contact angle-based surface energy measurements revealed a dramatic increase in polar surface energy. A growth model was proposed with lowered activation energies for growth and increased surface diffusion length consistent with the range of results observed. WS2 samples grown with and without oxygen plasma were similar high quality monolayers verified through transmission electron microscopy, selected area electron diffraction, atomic force microscopy, Raman, and photoluminescence measurements. This technique enables the production of large-grain size, patterned WS2 without a post-growth lithography process, thereby providing clean surfaces for device applications.

  1. Controllable synthesis of molybdenum tungsten disulfide alloy for vertically composition-controlled multilayer

    PubMed Central

    Song, Jeong-Gyu; Ryu, Gyeong Hee; Lee, Su Jeong; Sim, Sangwan; Lee, Chang Wan; Choi, Taejin; Jung, Hanearl; Kim, Youngjun; Lee, Zonghoon; Myoung, Jae-Min; Dussarrat, Christian; Lansalot-Matras, Clement; Park, Jusang; Choi, Hyunyong; Kim, Hyungjun

    2015-01-01

    The effective synthesis of two-dimensional transition metal dichalcogenides alloy is essential for successful application in electronic and optical devices based on a tunable band gap. Here we show a synthesis process for Mo1−xWxS2 alloy using sulfurization of super-cycle atomic layer deposition Mo1−xWxOy. Various spectroscopic and microscopic results indicate that the synthesized Mo1−xWxS2 alloys have complete mixing of Mo and W atoms and tunable band gap by systematically controlled composition and layer number. Based on this, we synthesize a vertically composition-controlled (VCC) Mo1−xWxS2 multilayer using five continuous super-cycles with different cycle ratios for each super-cycle. Angle-resolved X-ray photoemission spectroscopy, Raman and ultraviolet–visible spectrophotometer results reveal that a VCC Mo1−xWxS2 multilayer has different vertical composition and broadband light absorption with strong interlayer coupling within a VCC Mo1−xWxS2 multilayer. Further, we demonstrate that a VCC Mo1−xWxS2 multilayer photodetector generates three to four times greater photocurrent than MoS2- and WS2-based devices, owing to the broadband light absorption. PMID:26204328

  2. Synthesis and Optical Control of Circular Polarization in monolayer Tungsten Disulfide

    NASA Astrophysics Data System (ADS)

    McCreary, Kathleen; Hanbicki, Aubrey; Jonker, Berend; Currie, Marc; Kioseoglou, George

    The unique electronic band structure in single layer WS2 provides the ability to selectively populate a desired valley by exciting with circularly polarized light. The valley population is reflected through the circular polarization of photoluminescence (PL). We investigate the circularly polarized PL in WS2 monolayers synthesized using chemical vapor deposition (CVD). The resulting polarization is strongly dependent on the sample preparation. As-grown CVD WS2 (still on the growth substrate) exhibits low polarized emission, regardless of laser excitation or laser power. Removing WS2 from the growth substrate and repositioning on the same substrate significantly impacts the optical properties. In transferred films, the excitonic state is optically controlled via high-powered laser exposure such that subsequent PL is solely from either the charged exciton state or the neutral exciton state. Neutral excitonic emission exhibits zero polarization whereas the trion polarization can exceed 25% at room temperature. The removal process may modify the strain, sample-to-substrate distance, and chemical doping in the WS2 monolayer, and work is underway to determine how these factors influence the valley populations. These results demonstrate a new method to control the excitonic state and PL polarization in monolayer WS2. . Supported by core programs at NRL and the NRL Nanoscience Institute, and by the Air Force Office of Scientific Research #AOARD 14IOA018-134141.

  3. Assigning Peptide Disulfide Linkage Pattern Among Regio-Isomers via Methoxy Addition to Disulfide and Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Durand, Kirt L.; Tan, Lei; Stinson, Craig A.; Love-Nkansah, Chasity B.; Ma, Xiaoxiao; Xia, Yu

    2017-02-01

    Pinpointing disulfide linkage pattern is critical in the characterization of proteins and peptides consisting of multiple disulfide bonds. Herein, we report a method based on coupling online disulfide modification and tandem mass spectrometry (MS/MS) to distinguish peptide disulfide regio-isomers. Such a method relies on a new disulfide bond cleavage reaction in solution, involving methanol as a reactant and 254 nm ultraviolet (UV) irradiation. This reaction leads to selective cleavage of a disulfide bond and formation of sulfenic methyl ester (-SOCH3) at one cysteine residue and a thiol (-SH) at the other. Under low energy collision-induced dissociation (CID), cysteine sulfenic methyl ester motif produces a signature methanol loss (-32 Da), allowing its identification from other possible isomeric structures such as S-hydroxylmethyl (-SCH2OH) and methyl sulfoxide (-S(O)-CH3). Since disulfide bond can be selectively cleaved and modified upon methoxy addition, subsequent MS2 CID of the methoxy addition product provides enhanced sequence coverage as demonstrated by the analysis of bovine insulin. More importantly, this reaction does not induce disulfide scrambling, likely due to the fact that radical intermediates are not involved in the process. An approach based on methoxy addition followed by MS3 CID has been developed for assigning disulfide linkage patterns in peptide disulfide regio-isomers. This methodology was successfully applied to characterizing peptide systems having two disulfide bonds and three disulfide linkage isomers: side-by-side, overlapped, and looped-within-a-loop configurations.

  4. Protein stabilization by introduction of cross-strand disulfides.

    PubMed

    Chakraborty, Kausik; Thakurela, Sudhir; Prajapati, Ravindra Singh; Indu, S; Ali, P Shaik Syed; Ramakrishnan, C; Varadarajan, Raghavan

    2005-11-08

    Disulfides cross-link residues in a protein that are separated in primary sequence and stabilize the protein through entropic destabilization of the unfolded state. While the removal of naturally occurring disulfides leads to protein destabilization, introduction of engineered disulfides does not always lead to significant stabilization of a protein. We have analyzed naturally occurring disulfides that span adjacent antiparallel strands of beta sheets (cross-strand disulfides). Cross-strand disulfides have recently been implicated as redox-based conformational switches in proteins such as gp120 and CD4. The propensity of these disulfides to act as conformational switches was postulated on the basis of the hypothesis that this class of disulfide is conformationally strained. In the present analysis, there was no evidence to suggest that cross-strand disulfides are more strained compared to other disulfides as assessed by their torsional energy. It was also observed that these disulfides occur solely at non-hydrogen-bonded (NHB) registered pairs of adjacent antiparallel strands and not at hydrogen-bonded (HB) positions as suggested previously. One of the half-cystines involved in cross-strand disulfide formation often occurs at an edge strand. Experimental confirmation of the stabilizing effects of such disulfides was carried out in Escherichia coli thioredoxin. Four pairs of cross-strand cysteines were introduced, two at HB and two at NHB pairs. Disulfides were formed in all four cases. However, as predicted from our analysis, disulfides at NHB positions resulted in an increase in melting temperature of 7-10 degrees C, while at HB positions there was a corresponding decrease of -7 degrees C. The reduced state of all proteins had similar stability.

  5. Tungsten diffusion in silicon

    SciTech Connect

    De Luca, A.; Texier, M.; Burle, N.; Oison, V.; Pichaud, B.; Portavoce, A.; Grosjean, C.

    2014-01-07

    Two doses (10{sup 13} and 10{sup 15} cm{sup −2}) of tungsten (W) atoms were implanted in different Si(001) wafers in order to study W diffusion in Si. The samples were annealed or oxidized at temperatures between 776 and 960 °C. The diffusion profiles were measured by secondary ion mass spectrometry, and defect formation was studied by transmission electron microscopy and atom probe tomography. W is shown to reduce Si recrystallization after implantation and to exhibit, in the temperature range investigated, a solubility limit close to 0.15%–0.2%, which is higher than the solubility limit of usual metallic impurities in Si. W diffusion exhibits unusual linear diffusion profiles with a maximum concentration always located at the Si surface, slower kinetics than other metals in Si, and promotes vacancy accumulation close to the Si surface, with the formation of hollow cavities in the case of the higher W dose. In addition, Si self-interstitial injection during oxidation is shown to promote W-Si clustering. Taking into account these observations, a diffusion model based on the simultaneous diffusion of interstitial W atoms and W-Si atomic pairs is proposed since usual models used to model diffusion of metallic impurities and dopants in Si cannot reproduce experimental observations.

  6. Fabrication techniques developed for small- diameter, thin-wall tungsten and tungsten alloy tubing

    NASA Technical Reports Server (NTRS)

    Brillhart, D. C.; Burt, W. R.; Karasek, F. J.; Mayfield, R. M.

    1968-01-01

    Report describes methods for the fabrication of tungsten and tungsten alloys into small-diameter, thin-wall tubing of nuclear quality. The tungsten, or tungsten alloy tube blanks are produced by double extrusion. Plug-drawing has emerged as an excellent secondary fabrication technique for the reduction of the overall tube dimensions.

  7. Photo-active collagen systems with controlled triple helix architecture.

    PubMed

    Tronci, Giuseppe; Russell, Stephen J; Wood, David J

    2013-08-14

    The design of photo-active collagen systems is presented as a basis for establishing biomimetic materials with varied network architecture and programmable macroscopic properties. Following in-house isolation of type I collagen, reaction with vinyl-bearing compounds of varied backbone rigidity, i.e. 4-vinylbenzyl chloride (4VBC) and glycidyl methacrylate (GMA), was carried out. TNBS colorimetric assay, (1)H-NMR and ATR-FTIR confirmed covalent and tunable functionalization of collagen lysines. Depending on the type and extent of functionalization, controlled stability and thermal denaturation of triple helices were observed via circular dichroism (CD), whereby the hydrogen-bonding capability of introduced moieties was shown to play a major role. Full gel formation was observed following photo-activation of functionalized collagen solutions. The presence of a covalent network only slightly affected collagen triple helix conformation (as observed by WAXS and ATR-FTIR), confirming the structural organization of functionalized collagen precursors. Photo-activated hydrogels demonstrated an increased denaturation temperature (DSC) with respect to native collagen, suggesting that the formation of the covalent network successfully stabilized collagen triple helices. Moreover, biocompatibility and mechanical competence of obtained hydrogels were successfully demonstrated under physiologically-relevant conditions. These results demonstrate that this novel synthetic approach enabled the formation of biocompatible collagen systems with defined network architecture and programmable macroscopic properties, which can only partially be obtained with current synthetic methods.

  8. The Diatom Staurosirella pinnata for Photoactive Material Production

    PubMed Central

    Prosposito, Paolo; Casalboni, Mauro; Lamastra, Francesca Romana; Nanni, Francesca; Congestri, Roberta

    2016-01-01

    A native isolate of the colonial benthic diatom Staurosirella pinnata was cultivated for biosilica production. The silicified cell walls (frustules) were used as a source of homogeneous and structurally predictable porous biosilica for dye trapping and random laser applications. This was coupled with the extraction of lipids from biomass showing potential to fabricate photoactive composite materials sustainably. The strain was selected for its ease of growth in culture and harvesting. Biosilica and lipids were obtained at the end of growth in indoor photobioreactors. Frustules were structurally characterized microscopically and their chemistry analyzed with Fourier Transform Infrared Spectroscopy. Frustule capacity of binding laser dyes was evaluated on a set of frustules/Rhodamine B (Rho B) solutions and with respect to silicon dioxide and diatomite by Fluorescence Spectroscopy demonstrating a high affinity for the organic dye. The effect of dye trapping property in conveying Rho B emission to frustules, with enhancement of scattering events, was analyzed on Rho B doped polyacrylamide gels filled or not with frustules. Amplified spontaneous emission was recorded at increasing pump power indicating the onset of a random laser effect in frustule filled gels at lower power threshold compared to unfilled matrices. PMID:27828985

  9. Accurate pointing of tungsten welding electrodes

    NASA Technical Reports Server (NTRS)

    Ziegelmeier, P.

    1971-01-01

    Thoriated-tungsten is pointed accurately and quickly by using sodium nitrite. Point produced is smooth and no effort is necessary to hold the tungsten rod concentric. The chemically produced point can be used several times longer than ground points. This method reduces time and cost of preparing tungsten electrodes.

  10. Method of synthesizing tungsten nanoparticles

    SciTech Connect

    Thoma, Steven G; Anderson, Travis M

    2013-02-12

    A method to synthesize tungsten nanoparticles has been developed that enables synthesis of nanometer-scale, monodisperse particles that can be stabilized only by tetrahydrofuran. The method can be used at room temperature, is scalable, and the product concentrated by standard means. Since no additives or stabilizing surfactants are required, this method is particularly well suited for producing tungsten nanoparticles for dispersion in polymers. If complete dispersion is achieved due to the size of the nanoparticles, then the optical properties of the polymer can be largely maintained.

  11. The alkaline earth intercalates of molybdenum disulfide

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

  12. Process Of Bonding Copper And Tungsten

    DOEpatents

    Slattery, Kevin T.; Driemeyer, Daniel E.

    1999-11-23

    Process for bonding a copper substrate to a tungsten substrate by providing a thin metallic adhesion promoting film bonded to a tungsten substrate and a functionally graded material (FGM) interlayer bonding the thin metallic adhesion promoting film to the copper substrate. The FGM interlayer is formed by thermal plasma spraying mixtures of copper powder and tungsten powder in a varied blending ratio such that the blending ratio of the copper powder and the tungsten powder that is fed to a plasma torch is intermittently adjusted to provide progressively higher copper content/tungsten content, by volume, ratio values in the interlayer in a lineal direction extending from the tungsten substrate towards the copper substrate. The resulting copper to tungsten joint well accommodates the difference in the coefficient of thermal expansion of the materials.

  13. Process development for cladding APT tungsten targets

    SciTech Connect

    Horner, M H; Barber, R; Dalder, E

    2000-11-27

    This report describes development of processes for cladding APT Target tungsten components with a thin layer (0.127-mm) of Alloy 718, Alloy 600 or 316L stainless steel alloy. The application requires that the cladding be thermally bonded to the tungsten in order to transfer heat generated in the tungsten volume to a surrounding coolant. High temperature diffusion bonding using the hot isostatic processing (HIP) technique was selected as the method for creating a metallurgical bond between pure tungsten tubes and rods and the cladding materials. Bonding studies using a uniaxially loaded vacuum hot press were conducted in preliminary experiments to determine acceptable time-temperature conditions for diffusion bonding. The results were successfully applied in cladding tungsten rods and tubes with these alloys. Temperatures 800-810 C were suitable for cladding tungsten with Alloy 600 and 316L stainless steel alloy, whereas tungsten was clad with Alloy 718 at 1020 C.

  14. Fabrication of tungsten wire needles

    SciTech Connect

    Roder, A.

    1983-02-01

    Fine point needles for field emissoin are conventionally produced by electrolytically or chemically etching tungsten wire. Points formed in this manner have a typical tip radius of about 0.5 microns and a cone angle of some 30 degrees. The construction of needle matrix detector chambers has created a need for tungsten needles whose specifications are: 20 mil tungsten wire, 1.5 inch total length, 3 mm-long taper (resulting in a cone angle of about 5 degrees), and 25 micron-radius point (similar to that found on sewing needles). In the process described here for producing such needles, tungsten wire, immersed in a NaOH solution and in the presence of an electrode, is connected first to an ac voltage and then to a dc supply, to form a taper and a point on the end of the wire immersed in the solution. The process parameters described here are for needles that will meet the above specifications. Possible variations will be discussed under each approprite heading.

  15. Mineral of the month: tungsten

    USGS Publications Warehouse

    Shedd, Kim B.

    2006-01-01

    Tungsten has the highest melting point of all metals, one of the highest densities and, when combined with carbon, is almost as hard as diamond. These and other properties make it useful in a wide variety of important commercial, industrial and military applications.

  16. Vacuum Gas Tungsten Arc Welding

    NASA Technical Reports Server (NTRS)

    Weeks, J. L.; Todd, D. T.; Wooten, J. R.

    1997-01-01

    A two-year program investigated vacuum gas tungsten arc welding (VGTAW) as a method to modify or improve the weldability of normally difficult-to-weld materials. After a vacuum chamber and GTAW power supply were modified, several difficult-to-weld materials were studied and key parameters developed. Finally, Incoloy 903 weld overlays were produced without microfissures.

  17. GAMMA-RADIOLYSIS OF DISULFIDES IN AQUEOUS SOLUTION. II. D-PENICILLAMINE DISULFIDE,

    DTIC Science & Technology

    The gamma-radiolysis of D- penicillamine disulfide (PenSSPen) in an aqueous solution has been studied under aerated and deaerated conditions. G...values were determined for the following products: penicillamine sulfinic acid (PenSO2H), penicillaminic acid (PenSO3H), beta-hydroxyvaline (PenOH), 2...amino-3-methylbut-3-enoic acid (HOOC.CH(NH2).C(CH3)=CH2), penicillamine (PenSH), penicillamine disulfide-S-monoxide (PenS(O)SPen), valine (PenH

  18. The Dynamic Disulfide Relay of Quiescin Sulfhydryl Oxidase

    PubMed Central

    Alon, Assaf; Grossman, Iris; Gat, Yair; Kodali, Vamsi K.; DiMaio, Frank; Mehlman, Tevie; Haran, Gilad; Baker, David; Thorpe, Colin; Fass, Deborah

    2012-01-01

    Protein stability, assembly, localization, and regulation often depend on formation of disulfide cross-links between cysteine side chains. Enzymes known as sulfhydryl oxidases catalyze de novo disulfide formation and initiate intra- and intermolecular dithiol/disulfide relays to deliver the disulfides to substrate proteins1,2. Quiescin sulfhydryl oxidase (QSOX) is a unique, multi-domain disulfide catalyst that is localized primarily to the Golgi apparatus and secreted fluids3 and has attracted attention due to its over-production in tumors4,5. In addition to its physiological importance, QSOX is a mechanistically intriguing enzyme, encompassing functions typically carried out by a series of proteins in other disulfide formation pathways. How disulfides are relayed through the multiple redox-active sites of QSOX and whether there is a functional benefit to concatenating these sites on a single polypeptide are open questions. We determined the first crystal structure of an intact QSOX enzyme, derived from a trypanosome parasite. Notably, sequential sites in the disulfide relay were found more than 40 Å apart in this structure, too far for direct disulfide transfer. To resolve this puzzle, we trapped and crystallized an intermediate in the disulfide hand-off, which showed a 165° domain rotation relative to the original structure, bringing the two active sites within disulfide bonding distance. The comparable structure of a mammalian QSOX enzyme, also presented herein, reveals additional biochemical features that facilitate disulfide transfer in metazoan orthologs. Finally, we quantified the contribution of concatenation to QSOX activity, providing general lessons for the understanding of multi-domain enzymes and the design of novel catalytic relays. PMID:22801504

  19. Origin of photoactivity of oxygen-deficient TiO{sub 2} under visible light

    SciTech Connect

    Lo, H.-H.; Gopal, Neeruganti O.; Ke, S.-C.

    2009-08-24

    As it is now well established that oxygen vacancies are spontaneously introduced during nitrogen doping of anatase TiO{sub 2}, there is a lively debate on whether nitrogen dopant or oxygen vacancy contributes to the visible light photoactivity of the doped catalyst. We showed that the coordinately unsaturated Ti site is integral to the visible light photoactivity in anatase oxygen-deficient TiO{sub 2} catalyst. Accordingly, oxygen vacancies may contribute to the visible light photoactivities in N-doped TiO{sub 2} and other nonmetallic ion-doped TiO{sub 2} as well. A redox active visible light photocatalyst has been developed based on oxygen-deficient structure in anatase TiO{sub 2}.

  20. Origin of photoactivity of oxygen-deficient TiO2 under visible light

    NASA Astrophysics Data System (ADS)

    Lo, Hsin-Hsi; Gopal, Neeruganti O.; Ke, Shyue-Chu

    2009-08-01

    As it is now well established that oxygen vacancies are spontaneously introduced during nitrogen doping of anatase TiO2, there is a lively debate on whether nitrogen dopant or oxygen vacancy contributes to the visible light photoactivity of the doped catalyst. We showed that the coordinately unsaturated Ti site is integral to the visible light photoactivity in anatase oxygen-deficient TiO2 catalyst. Accordingly, oxygen vacancies may contribute to the visible light photoactivities in N-doped TiO2 and other nonmetallic ion-doped TiO2 as well. A redox active visible light photocatalyst has been developed based on oxygen-deficient structure in anatase TiO2.

  1. All-optical microfluidic circuit for biochemical and cellular analysis powered by photoactive nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Gang L.; Kim, Jaeyoun; Lee, Luke P.

    2006-08-01

    We have invented a novel all-optical-logic microfluidic system which is automatically controlled only by visible or near infrared light with down to submilliwatt power. No electric power supply, no external or MEMS pump, no tubings or connectors, no microfluidic valves, nor surface patterning are required in our system. Our device only consists of a single-layer PDMS microfluidic chip and newly invented photoactive nanoparticles. Our photoactive nanoparticles are capable of converting optical energy to hydrodynamic energy in fluids. The nanoparticle themselves are biocompatible and can be biofunctionalized. Via these photoactive nanoparticles, we used only light to drive, guide, switch and mix liquid in optofluidic logic circuits with desired speeds and directions. We demonstrated the optofluidic controls in transportation of biomolecules and cells.

  2. Characterization and modeling of tungsten source during DIII-D tungsten ring experiments

    NASA Astrophysics Data System (ADS)

    Guterl, J.; Abrams, T.; Elder, D.; Guo, H. Y.

    2016-10-01

    Two tungsten toroidal rings in the DIII-D divertor region were recently exposed to H-mode plasmas. During these experiments, the gross erosion rate of tungsten was spectroscopically monitored for various ELMy H-mode conditions to characterize the tungsten source in the divertor region (see e.g.). However, only a small fraction of tungsten eroded particles eventually exits the divertor region because of the large tungsten local redeposition. Tungsten local redeposition and migration in the vicinity of the tungsten tiles are simulated using the ERO-OEDGE code package to link the effective tungsten source to the measured gross erosion rates between and during ELMs. It is shown that the energy and angular distributions of sputtered tungsten particles strongly affect the ratio of locally redeposited particles and thus the effective tungsten source. Effects of carbon deposition on tungsten tiles between ELMs on the tungsten erosion rate are also discussed. Preliminary studies of divertor screening on long-range tungsten transport in the SOL between ELMs are also presented. Work supported in part by the US Department of Energy under DE-AC05-06OR23100 and DE-FC02-04ER54698.

  3. Assigning Peptide Disulfide Linkage Pattern Among Regio-Isomers via Methoxy Addition to Disulfide and Tandem Mass Spectrometry.

    PubMed

    Durand, Kirt L; Tan, Lei; Stinson, Craig A; Love-Nkansah, Chasity B; Ma, Xiaoxiao; Xia, Yu

    2017-02-13

    Pinpointing disulfide linkage pattern is critical in the characterization of proteins and peptides consisting of multiple disulfide bonds. Herein, we report a method based on coupling online disulfide modification and tandem mass spectrometry (MS/MS) to distinguish peptide disulfide regio-isomers. Such a method relies on a new disulfide bond cleavage reaction in solution, involving methanol as a reactant and 254 nm ultraviolet (UV) irradiation. This reaction leads to selective cleavage of a disulfide bond and formation of sulfenic methyl ester (-SOCH3) at one cysteine residue and a thiol (-SH) at the other. Under low energy collision-induced dissociation (CID), cysteine sulfenic methyl ester motif produces a signature methanol loss (-32 Da), allowing its identification from other possible isomeric structures such as S-hydroxylmethyl (-SCH2OH) and methyl sulfoxide (-S(O)-CH3). Since disulfide bond can be selectively cleaved and modified upon methoxy addition, subsequent MS(2) CID of the methoxy addition product provides enhanced sequence coverage as demonstrated by the analysis of bovine insulin. More importantly, this reaction does not induce disulfide scrambling, likely due to the fact that radical intermediates are not involved in the process. An approach based on methoxy addition followed by MS(3) CID has been developed for assigning disulfide linkage patterns in peptide disulfide regio-isomers. This methodology was successfully applied to characterizing peptide systems having two disulfide bonds and three disulfide linkage isomers: side-by-side, overlapped, and looped-within-a-loop configurations. Graphical Abstract ᅟ.

  4. Carbon disulfide assisted polymerization of benzene.

    PubMed

    Zhou, Mi; Li, Zhanlong; Men, Zhiwei; Gao, Shuqin; Li, Zuowei; Lu, Guohui; Sun, Chenglin

    2012-03-01

    The chemical transformation of benzene (C(6)H(6)) and carbon disulfide (CS(2)) binary solution under high pressure condition is investigated by means of Raman spectroscopy up to 6.8 GPa. On increasing the pressure, all the Raman bands of benzene decrease in intensity, whereas new broad bands start to be observed at 1520 and 1450 cm(-1), indicating that a highly cross-linked polymer is formed. The recovered sample is analyzed through Raman and FT-IR spectroscopy and is identified as a saturated hydrocarbon and element sulfur.

  5. Temperature-controlled neutron reflectometry sample cell suitable for study of photoactive thin films

    SciTech Connect

    Yager, Kevin G.; Tanchak, Oleh M.; Barrett, Christopher J.; Watson, Mike J.; Fritzsche, Helmut

    2006-04-15

    We describe a novel cell design intended for the study of photoactive materials using neutron reflectometry. The cell can maintain sample temperature and control of ambient atmospheric environment. Critically, the cell is built with an optical port, enabling light irradiation or light probing of the sample, simultaneous with neutron reflectivity measurements. The ability to measure neutron reflectivity with simultaneous temperature ramping and/or light illumination presents unique opportunities for measuring photoactive materials. To validate the cell design, we present preliminary results measuring the photoexpansion of thin films of azobenzene polymer.

  6. Tungsten foil laminate for structural divertor applications - Joining of tungsten foils

    NASA Astrophysics Data System (ADS)

    Reiser, Jens; Rieth, Michael; Möslang, Anton; Dafferner, Bernhard; Hoffmann, Jan; Mrotzek, Tobias; Hoffmann, Andreas; Armstrong, D. E. J.; Yi, Xiaoou

    2013-05-01

    This paper is the fourth in our series on tungsten laminates. The aim of this paper is to discuss laminate synthesis, meaning the joining of tungsten foils. It is obvious that the properties of the tungsten laminate strongly depend on the combination of (i) interlayer and (ii) joining technology, as this combination defines (i) the condition of the tungsten foil after joining (as-received or recrystallised) as well as (ii) the characteristics of the interface between the tungsten foil and the interlayer (wettability or diffusion leading to a solid solution or the formation of intermetallics). From the example of tungsten laminates joined by brazing with (i) an eutectic silver copper brazing filler, (ii) copper, (iii) titanium, and (iv) zirconium, the microstructure will be discussed, with special focus on the interface. Based on our assumptions of the mechanism of the extraordinary ductility of tungsten foil we present three syntheses strategies and make recommendations for the synthesis of high temperature tungsten laminates.

  7. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-07-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials.

  8. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    PubMed Central

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  9. Laser cleaning of tungsten ribbon

    NASA Astrophysics Data System (ADS)

    Kumar, Aniruddha; Sonar, V. R.; Das, D. K.; Bhatt, R. B.; Behere, P. G.; Afzal, Mohd.; Kumar, Arun; Nilaya, J. P.; Biswas, D. J.

    2014-07-01

    Removal of a thin oxide layer from a tungsten ribbon was achieved using the fundamental, second and third harmonic radiation from a Q- switched Nd-YAG laser. It was found that beyond the threshold, oxide removal was achieved at all wavelengths for a wide range of fluence values. The removal mechanism of the oxide layer was found to be critically dependent on both wavelength and fluence of the incident radiation and has been identified as ejection or sublimation. The un-cleaned and cleaned surfaces were analyzed by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDS) and atomic force microscopy (AFM). Laser cleaned tungsten ribbons were used in a thermal ionization mass spectrometer (TIMS) to determine isotopic composition of Neodymium atoms.

  10. Does speciation matter for tungsten ecotoxicology?

    PubMed

    Strigul, Nikolay

    2010-09-01

    Tungsten is a widely used transition metal that has not been thoroughly investigated with regards to its ecotoxicological effects. Tungsten anions polymerize in environmental systems as well as under physiological conditions in living organisms. These polymerization/condensation reactions result in the development of several types of stable polyoxoanions. Certain chemical properties (in particular redox and acidic properties) differentiate these polyanions from monotungstates. However, our current state of knowledge on tungsten toxicology, biological and environmental effects is based entirely on experiments where monotungstates were used and assumed by the authors to be the form of tungsten that was present and that produced the observed effect. Recent discoveries indicate that tungsten speciation may be important to ecotoxicology. New results obtained by different research groups demonstrate that polytungstates develop and persist in environmental systems, and that polyoxotungstates are much more toxic than monotungstates. This paper reviews the available toxicological information from the standpoint of tungsten speciation and identifies knowledge gaps and pertinent future research directions.

  11. Tin-tungsten mineralizing processes in tungsten vein deposits: Panasqueira, Portugal

    NASA Astrophysics Data System (ADS)

    Lecumberri-Sanchez, P.; Pinto, F.; Vieira, R.; Wälle, M.; Heinrich, C. A.

    2015-12-01

    Tungsten has a high heat resistance, density and hardness, which makes it widely applied in industry (e.g. steel, tungsten carbides). Tungsten deposits are typically magmatic-hydrothermal systems. Despite the economic significance of tungsten, there are no modern quantitative analytical studies of the fluids responsible for the formation of its highest-grade deposit type (tungsten vein deposits). Panasqueira (Portugal) is a tungsten vein deposit, one of the leading tungsten producers in Europe and one of the best geologically characterized tungsten vein deposits. In this study, compositions of the mineralizing fluids at Panasqueira have been determined through combination of detailed petrography, microthermometric measurements and LA-ICPMS analyses, and geochemical modeling has been used to determine the processes that lead to tungsten mineralization. We characterized the fluids related to the various mineralizing stages in the system: the oxide stage (tin and tungsten mineralization), the sulfide stage (chalcopyrite and sphalerite mineralization) and the carbonate stage. Thus, our results provide information on the properties of fluids related with specific paragenetic stages. Furthermore we used those fluid compositions in combination with host rock mineralogy and chemistry to evaluate which are the controlling factors in the mineralizing process. This study provides the first quantitative analytical data on fluid composition for tungsten vein deposits and evaluates the controlling mineralization processes helping to determine the mechanisms of formation of the Panasqueira tin-tungsten deposit and providing additional geochemical constraints on the local distribution of mineralization.

  12. Converting a Sulfenic Acid Reductase into a Disulfide Bond Isomerase

    PubMed Central

    Chatelle, Claire; Kraemer, Stéphanie; Ren, Guoping; Chmura, Hannah; Marechal, Nils; Boyd, Dana; Roggemans, Caroline; Ke, Na; Riggs, Paul; Bardwell, James

    2015-01-01

    Abstract Aims: Posttranslational formation of disulfide bonds is essential for the folding of many secreted proteins. Formation of disulfide bonds in a protein with more than two cysteines is inherently fraught with error and can result in incorrect disulfide bond pairing and, consequently, misfolded protein. Protein disulfide bond isomerases, such as DsbC of Escherichia coli, can recognize mis-oxidized proteins and shuffle the disulfide bonds of the substrate protein into their native folded state. Results: We have developed a simple blue/white screen that can detect disulfide bond isomerization in vivo, using a mutant alkaline phosphatase (PhoA*) in E. coli. We utilized this screen to isolate mutants of the sulfenic acid reductase (DsbG) that allowed this protein to act as a disulfide bond isomerase. Characterization of the isolated mutants in vivo and in vitro allowed us to identify key amino acid residues responsible for oxidoreductase properties of thioredoxin-like proteins such as DsbC or DsbG. Innovation and Conclusions: Using these key residues, we also identified and characterized interesting environmental homologs of DsbG with novel properties, thus demonstrating the capacity of this screen to discover and elucidate mechanistic details of in vivo disulfide bond isomerization. Antioxid. Redox Signal. 23, 945–957. PMID:26191605

  13. 46 CFR 151.50-41 - Carbon disulfide (carbon bisulfide).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Carbon disulfide (carbon bisulfide). 151.50-41 Section... CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-41 Carbon disulfide (carbon bisulfide). (a) All openings shall be in the top of the tank. (b) Loading lines...

  14. 46 CFR 151.50-41 - Carbon disulfide (carbon bisulfide).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Carbon disulfide (carbon bisulfide). 151.50-41 Section... CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-41 Carbon disulfide (carbon bisulfide). (a) All openings shall be in the top of the tank. (b) Loading lines...

  15. 46 CFR 151.50-41 - Carbon disulfide (carbon bisulfide).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Carbon disulfide (carbon bisulfide). 151.50-41 Section... CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-41 Carbon disulfide (carbon bisulfide). (a) All openings shall be in the top of the tank. (b) Loading lines...

  16. 46 CFR 151.50-41 - Carbon disulfide (carbon bisulfide).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Carbon disulfide (carbon bisulfide). 151.50-41 Section... CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-41 Carbon disulfide (carbon bisulfide). (a) All openings shall be in the top of the tank. (b) Loading lines...

  17. 40 CFR 421.100 - Applicability: Description of the primary tungsten subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary tungsten subcategory. 421.100 Section 421.100 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Primary Tungsten Subcategory § 421.100 Applicability: Description of the primary tungsten... tungsten at primary tungsten facilities....

  18. 40 CFR 421.100 - Applicability: Description of the primary tungsten subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary tungsten subcategory. 421.100 Section 421.100 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Primary Tungsten Subcategory § 421.100 Applicability: Description of the primary tungsten... tungsten at primary tungsten facilities....

  19. 40 CFR 421.100 - Applicability: Description of the primary tungsten subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary tungsten subcategory. 421.100 Section 421.100 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Primary Tungsten Subcategory § 421.100 Applicability: Description of the primary tungsten... tungsten at primary tungsten facilities....

  20. 40 CFR 421.100 - Applicability: Description of the primary tungsten subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary tungsten subcategory. 421.100 Section 421.100 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Primary Tungsten Subcategory § 421.100 Applicability: Description of the primary tungsten... tungsten at primary tungsten facilities....

  1. 40 CFR 421.100 - Applicability: Description of the primary tungsten subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary tungsten subcategory. 421.100 Section 421.100 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Primary Tungsten Subcategory § 421.100 Applicability: Description of the primary tungsten... tungsten at primary tungsten facilities....

  2. Direct observation of disulfide isomerization in a single protein

    NASA Astrophysics Data System (ADS)

    Alegre-Cebollada, Jorge; Kosuri, Pallav; Rivas-Pardo, Jaime Andrés; Fernández, Julio M.

    2011-11-01

    Photochemical uncaging techniques use light to release active molecules from otherwise inert compounds. Here we expand this class of techniques by demonstrating the mechanical uncaging of a reactive species within a single protein. We proved this novel technique by capturing the regiospecific reaction between a thiol and a vicinal disulfide bond. We designed a protein that includes a caged cysteine and a buried disulfide. The mechanical unfolding of this protein in the presence of an external nucleophile frees the single reactive cysteine residue, which now can cleave the target disulfide via a nucleophilic attack on either one of its two sulfur atoms. This produces two different and competing reaction pathways. We used single-molecule force spectroscopy to monitor the cleavage of the disulfides, which extends the polypeptide by a magnitude unambiguously associated with each reaction pathway. This allowed us to measure, for the first time, the kinetics of disulfide-bond isomerization in a protein.

  3. A short history of structure based research on the photocycle of photoactive yellow protein

    PubMed Central

    Schmidt, Marius

    2017-01-01

    The goals of time-resolved macromolecular crystallography are to extract the molecular structures of the reaction intermediates and the reaction dynamics from time-resolved X-ray data alone. To develop the techniques of time-resolved crystallography, biomolecules with special properties are required. The Photoactive Yellow Protein is the most sparkling of these. PMID:28191482

  4. Photoactive terthiophenes: the influence of serum on anti-HIV (human immunodeficiency virus) activities.

    PubMed

    Hudson, J B; Marles, R J; Soucy-Breau, C; Harris, L; Arnason, J T

    1994-12-01

    A number of carboxylic acid derivatives of the photoactive terthiophene, alpha-terthienyl, were found to possess impressive UVA-dependent activity against the human immunodeficiency virus, HIV-1; but only when assayed in the absence of serum, indicating that the latter contained interfering components. Good antiviral activity required a high rate of singlet oxygen production, in accordance with previous observations on thiophenes.

  5. Semiconductor liquid junction photocell having a p-type photoactive electrode

    SciTech Connect

    Heller, A.; Lewerenz, H.J.; Miller, B.

    1982-08-10

    A semiconductor liquid junction photocell has a photovoltaic junction between a p-type photoactive electrode comprising InP or Si and an electrolyte comprising a redox couple selected from the group consisting of V2+/V3+, Nb4+/Nb5+, and Ti3+/Ti4+ produces a stable photocurrent output.

  6. Early events in the disulfide-coupled folding of BPTI.

    PubMed Central

    Bulaj, G.; Goldenberg, D. P.

    1999-01-01

    Recent studies of the refolding of reduced bovine pancreatic trypsin inhibitor (BPTI) have shown that a previously unidentified intermediate with a single disulfide is formed much more rapidly than any other one-disulfide species. This intermediate contains a disulfide that is present in the native protein (between Cys14 and 38), but it is thermodynamically less stable than the other two intermediates with single native disulfides. To characterize the role of the [14-38] intermediate and the factors that favor its formation, detailed kinetic and mutational analyses of the early disulfide-formation steps were carried out. The results of these studies indicate that the formation of [14-38] from the fully reduced protein is favored by both local electrostatic effects, which enhance the reactivities of the Cys14 and 38 thiols, and conformational tendencies that are diminished by the addition of urea and are enhanced at lower temperatures. At 25 degrees C and pH 7.3, approximately 35% of the reduced molecules were found to initially form the 14-38 disulfide, but the majority of these molecules then undergo intramolecular rearrangements to generate non-native disulfides, and subsequently the more stable intermediates with native disulfides. Amino acid replacements, other than those involving Cys residues, were generally found to have only small effects on either the rate of forming [14-38] or its thermodynamic stability, even though many of the same substitutions greatly destabilized the native protein and other disulfide-bonded intermediates. In addition, those replacements that did decrease the steady-state concentration of [14-38] did not adversely affect further folding and disulfide formation. These results suggest that the weak and transient interactions that are often detected in unfolded proteins and early folding intermediates may, in some cases, not persist or promote subsequent folding steps. PMID:10493584

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

    PubMed

    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.

  8. Superconductivity in highly disordered dense carbon disulfide.

    PubMed

    Dias, Ranga P; Yoo, Choong-Shik; Struzhkin, Viktor V; Kim, Minseob; Muramatsu, Takaki; Matsuoka, Takahiro; Ohishi, Yasuo; Sinogeikin, Stanislav

    2013-07-16

    High pressure plays an increasingly important role in both understanding superconductivity and the development of new superconducting materials. New superconductors were found in metallic and metal oxide systems at high pressure. However, because of the filled close-shell configuration, the superconductivity in molecular systems has been limited to charge-transferred salts and metal-doped carbon species with relatively low superconducting transition temperatures. Here, we report the low-temperature superconducting phase observed in diamagnetic carbon disulfide under high pressure. The superconductivity arises from a highly disordered extended state (CS4 phase or phase III[CS4]) at ~6.2 K over a broad pressure range from 50 to 172 GPa. Based on the X-ray scattering data, we suggest that the local structural change from a tetrahedral to an octahedral configuration is responsible for the observed superconductivity.

  9. Advances in rechargeable lithium molybdenum disulfide batteries

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  10. Ultrafast response of monolayer molybdenum disulfide photodetectors

    PubMed Central

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

    2015-01-01

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

  11. Mechanism of SN2 disulfide bond cleavage by phosphorus nucleophiles. Implications for biochemical disulfide reducing agents.

    PubMed

    Dmitrenko, Olga; Thorpe, Colin; Bach, Robert D

    2007-10-26

    The B3LYP variant of DFT has been used to study the mechanism of S-S bond scission in dimethyl disulfide by a phosphorus nucleophile, trimethylphospine (TMP). The reaction is highly endothermic in the gas phase and requires significant external stabilization of the charged products. DFT calculations (B3LYP) were performed with explicit (water molecules added) and implicit solvent corrections (COSMO model). The transition structures for this SN2 displacement reaction in a number of model systems have been located and fully characterized. The reaction barriers calculated with different approaches for different systems are quite close (around 11 kcal/mol). Remarkably, the calculations suggest that the reaction is almost barrierless with respect to the preorganized reaction complex and that most of the activation energy is required to rearrange the disulfide and TMP to its most effective orientation for the SMe group transfer way. Different reactivities of different phosphorus nucleophiles were suggested to be the result of steric effects, as manifested largely by varying amounts of hindrance to solvation of the initial product phosphonium ion. These data indicate that the gas-phase addition of a phosphine to the disulfide moiety will most likely form a phosphonium cation-thiolate anion salt, in the presence of four or more water molecules, that provide sufficient H-bonding stabilization to allow displacement of the thiolate anion, a normal uncomplicated SN2 transition state is to be expected.

  12. Tungsten deposition by hydrogen-atom reaction with tungsten hexafluoride

    SciTech Connect

    Lee, W.W.

    1991-01-01

    Using gaseous hydrogen atoms with WF[sub 6], tungsten atoms can be produced in a gas-phase reaction. The atoms then deposit in a near-room temperature process, which results in the formation of tungsten films. The W atoms (10[sup 10]-10[sup 11]/cm[sup 3]) were measured in situ by atomic absorption spectroscopy during the CVD process. Deposited W films were characterized by Auger electron spectroscopy, Rutherford backscattering, and X-ray diffraction. The surface morphology of the deposited films and filled holes was studied using scanning electron microscopy. The deposited films were highly adherent to different substrates, such as Si, SiO[sub 2], Ti/Si, TiN/Si and Teflon. The reaction mechanism and kinetics were studied. The experimental results indicated that this method has three advantages compared to conventional CVD or PECVD: (1) film growth occurs at low temperatures; (2) deposition takes place in a plasma-free environment; and (3) a low level of impurities results in high-quality adherent films.

  13. Enzyme structure captures four cysteines aligned for disulfide relay

    PubMed Central

    Gat, Yair; Vardi-Kilshtain, Alexandra; Grossman, Iris; Major, Dan Thomas; Fass, Deborah

    2014-01-01

    Thioredoxin superfamily proteins introduce disulfide bonds into substrates, catalyze the removal of disulfides, and operate in electron relays. These functions rely on one or more dithiol/disulfide exchange reactions. The flavoenzyme quiescin sulfhydryl oxidase (QSOX), a catalyst of disulfide bond formation with an interdomain electron transfer step in its catalytic cycle, provides a unique opportunity for exploring the structural environment of enzymatic dithiol/disulfide exchange. Wild-type Rattus norvegicus QSOX1 (RnQSOX1) was crystallized in a conformation that juxtaposes the two redox-active di-cysteine motifs in the enzyme, presenting the entire electron-transfer pathway and proton-transfer participants in their native configurations. As such a state cannot generally be enriched and stabilized for analysis, RnQSOX1 gives unprecedented insight into the functional group environments of the four cysteines involved in dithiol/disulfide exchange and provides the framework for analysis of the energetics of electron transfer in the presence of the bound flavin adenine dinucleotide cofactor. Hybrid quantum mechanics/molecular mechanics (QM/MM) free energy simulations based on the X-ray crystal structure suggest that formation of the interdomain disulfide intermediate is highly favorable and secures the flexible enzyme in a state from which further electron transfer via the flavin can occur. PMID:24888638

  14. Development of Tungsten Based Composites

    DTIC Science & Technology

    1992-02-01

    Rise, 0 C L 4 / /2’ C) r, 1 / 1 1 00 /Pressure in /’ Stress Wave, SPa L 6. 44 // © , " / 1000 10,000 Impact Velocity, Ft/Sec - 4- be phase...and it is not desirable to make the steel and tungsten segments quite so long. Accordingly, it is necessary to make stress wave analyses of bar...stresses, because of wave superposition and bar segment lengths. Wave analyses similar to those presented above may result in higher stresses delivered to

  15. Novel properties of Tungsten ditelluride

    NASA Astrophysics Data System (ADS)

    Liu, Huimei; National Laboratory of Solid State Microstructures, School of Physics, Collaborative Innovation Cent Collaboration

    Tungsten ditelluride has attracted intense research interest due to the recent discovery of its large unsaturated magnetoresistance up to 60 Tesla. By using density functional theory calculations, we qualitatively reproduced the observed spin texture. Since the spin texture would forbid back scatterings that are directly involved in the resistivity, we suggest that the SOC and the related spin and orbital angular momentum textures may play an important role in the anomalously large magnetoresistance of WTe2. Motivated by the presence of a small, sensitive Fermi surface of 5d electronic orbitals, we also boost the electronic properties by applying a high pressure, and introduce superconductivity successfully.

  16. Strengthening mechanisms of tungsten powder reinforced uranium

    SciTech Connect

    Lewis, M.A.K.; Hill, M.A.; Rollett, A.D.; Dunn, P.S.; Mortensen, A.; Massachusetts Inst. of Tech., Cambridge, MA )

    1989-01-01

    Tungsten powder reinforced uranium exhibits a three-fold increase in yield strength due to precipitation hardening. The tungsten-rich interphase precipitates form at moving phase boundaries during slow cooling. Further increases in yield strength, attained with increasing tungsten content, are due to composite strengthening; this is verified by increasing elastic modulus with increasing tungsten content. Age hardening behavior is observed, with strengthening occurring at aging temperatures low in the alpha phase. Aging higher in alpha gives initial strengthening followed by rapid overaging. Beta phase aging results in a very soft structure with precipitates visible optically. Wrought material exhibits significant strain hardening as well as composite strengthening due to elongation of the tungsten particles. 7 refs., 15 figs., 4 tabs.

  17. Steric effects in peptide and protein exchange with activated disulfides.

    PubMed

    Kerr, Jason; Schlosser, Jessica L; Griffin, Donald R; Wong, Darice Y; Kasko, Andrea M

    2013-08-12

    Disulfide exchange is an important bioconjugation tool, enabling chemical modification of peptides and proteins containing free cysteines. We previously reported the synthesis of a macromer bearing an activated disulfide and its incorporation into hydrogels. Despite their ability to diffuse freely into hydrogels, larger proteins were unable to undergo in-gel disulfide exchange. In order to understand this phenomenon, we synthesized four different activated disulfide-bearing model compounds (Mn = 300 Da to 10 kDa) and quantified their rate of disulfide exchange with a small peptide (glutathione), a moderate-sized protein (β-lactoglobulin), and a large protein (bovine serum albumin) in four different pH solutions (6.0, 7.0, 7.4, and 8.0) to mimic biological systems. Rate constants of exchange depend significantly on the size and accessibility of the thiolate. pH also significantly affects the rate of reaction, with the faster reactions occurring at higher pH. Surprisingly, little difference in exchange rates is seen between macromolecular disulfides of varying size (Mn = 2 kDa - 10 kDa), although all undergo exchange more slowly than their small molecule analogue (MW = 300 g/mol). The maximum exchange efficiencies (% disulfides exchanged after 24 h) are not siginificantly affected by thiol size or pH, but somewhat affected by disulfide size. Therefore, while all three factors investigated (pH, disulfide size, and thiolate size) can influence the exchange kinetics and extent of reaction, the size of the thiolate and its accessibility plays the most significant role.

  18. Catalysis of Protein Disulfide Bond Isomerization in a Homogeneous Substrate†

    PubMed Central

    Kersteen, Elizabeth A.; Barrows, Seth R.; Raines, Ronald T.

    2008-01-01

    Protein disulfide isomerase (PDI) catalyzes the rearrangement of nonnative disulfide bonds in the endoplasmic reticulum of eukaryotic cells, a process that often limits the rate at which polypeptide chains fold into a native protein conformation. The mechanism of the reaction catalyzed by PDI is unclear. In assays involving protein substrates, the reaction appears to involve the complete reduction of some or all of its nonnative disulfide bonds followed by oxidation of the resulting dithiols. The substrates in these assays are, however, heterogeneous, which complicates mechanistic analyses. Here, we report the first analysis of disulfide bond isomerization in a homogeneous substrate. Our substrate is based on tachyplesin I, a 17-mer peptide that folds into a _-hairpin stabilized by two disulfide bonds. We describe the chemical synthesis of a variant of tachyplesin I in which its two disulfide bonds are in a nonnative state and side chains near its N-and C-terminus contain a fluorescence donor (tryptophan) and acceptor (N_-dansyllysine). Fluorescence resonance energy transfer from 280 to 465 nm increases by 28-fold upon isomerization of the disulfide bonds into their native state (which has a lower E°_ = -0.313 V than does PDI). We use this continuous assay to analyze catalysis by wild-type human PDI and a variant in which the C-terminal cysteine residue within each Cys—Gly—His—Cys active site is replaced with alanine. We find that wild-type PDI catalyzes the isomerization of the substrate with kcat/KM = 1.7 _ 105 M–1M s–1, which is the largest value yet reported for catalysis of disulfide bond isomerization. The variant, which is a poor catalyst of disulfide bond reduction and dithiol oxidation, retains virtually all of the activity of wild-type PDI in catalysis of disulfide bond isomerization. Thus, the C-terminal cysteine residues play an insignificant role in the isomerization of the disulfide bonds in nonnative tachyplesin I. We conclude that

  19. Chemical shift and coupling constant analysis of dibenzyloxy disulfides

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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 1H NMR, which can shift by over 1.1 ppm 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.

  20. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

  1. Photodecolorization of Rhodamine B on tungsten-doped TiO2/activated carbon under visible-light irradiation.

    PubMed

    Li, Youji; Zhou, Xiaoming; Chen, Wei; Li, Leiyong; Zen, Mengxiong; Qin, Shidong; Sun, Shuguo

    2012-08-15

    Tungsten-doped TiO(2)/activated carbon catalysts have been prepared by a supercritical-pretreatment-assisted sol-gel process. The structural features of the photocatalysts have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV/Vis diffuse-reflectance spectroscopy (DRS), electron dispersive X-ray (EDX), photoluminescence spectroscopy, and Brunauer-Emmett-Teller (BET) analysis. The results revealed that a W-TiO(2) layer was coated on the AC surface, and had higher surface area and smaller crystallite size than TiO(2)/AC obtained by a similar route. The W dopant was responsible for narrowing the band gap of TiO(2) and shifting its optical response from the ultraviolet (UV) to the visible-light region. The photocatalytic performances of the supported catalysts have been evaluated for the degradation of Rhodamine B (RhB) solution under visible-light irradiation. Compared with bulk W-TiO(2), the photoactivity was obviously enhanced when it was coated onto AC. In addition, it was found that the reactivity showed a significant relationship with the amount of W dopant, and the photoactivity order of the catalysts from weak to strong showed good agreement with their PL intensities. The effects of TiO(2) content, tungsten ion content, catalyst amount, pH, and initial RhB concentration have been examined as operational parameters. The photocatalytic reactions followed pseudo-first-order kinetics and are discussed in terms of the Langmuir-Hinshelwood model.

  2. Development of tungsten fibre-reinforced tungsten composites towards their use in DEMO—potassium doped tungsten wire

    NASA Astrophysics Data System (ADS)

    Riesch, J.; Han, Y.; Almanstötter, J.; Coenen, J. W.; Höschen, T.; Jasper, B.; Zhao, P.; Linsmeier, Ch; Neu, R.

    2016-02-01

    For the next step fusion reactor the use of tungsten is inevitable to suppress erosion and allow operation at elevated temperature and high heat loads. Tungsten fibre-reinforced composites overcome the intrinsic brittleness of tungsten and its susceptibility to operation embrittlement and thus allow its use as a structural as well as an armour material. That this concept works in principle has been shown in recent years. In this contribution we present a development approach towards its use in a future fusion reactor. A multilayer approach is needed addressing all composite constituents and manufacturing steps. A huge potential lies in the optimization of the tungsten wire used as fibre. We discuss this aspect and present studies on potassium doped tungsten wire in detail. This wire, utilized in the illumination industry, could be a replacement for the so far used pure tungsten wire due to its superior high temperature properties. In tensile tests the wire showed high strength and ductility up to an annealing temperature of 2200 K. The results show that the use of doped tungsten wire could increase the allowed fabrication temperature and the overall working temperature of the composite itself.

  3. Polycrystalline silicon on tungsten substrates

    NASA Technical Reports Server (NTRS)

    Bevolo, A. J.; Schmidt, F. A.; Shanks, H. R.; Campisi, G. J.

    1979-01-01

    Thin films of electron-beam-vaporized silicon were deposited on fine-grained tungsten substrates under a pressure of about 1 x 10 to the -10th torr. Mass spectra from a quadrupole residual-gas analyzer were used to determine the partial pressure of 13 residual gases during each processing step. During separate silicon depositions, the atomically clean substrates were maintained at various temperatures between 400 and 780 C, and deposition rates were between 20 and 630 A min. Surface contamination and interdiffusion were monitored by in situ Auger electron spectrometry before and after cleaning, deposition, and annealing. Auger depth profiling, X-ray analysis, and SEM in the topographic and channeling modes were utilized to characterize the samples with respect to silicon-metal interface, interdiffusion, silicide formation, and grain size of silicon. The onset of silicide formation was found to occur at approximately 625 C. Above this temperature tungsten silicides were formed at a rate faster than the silicon deposition. Fine-grain silicon films were obtained at lower temperatures.

  4. Fracture behaviour of polycrystalline tungsten

    NASA Astrophysics Data System (ADS)

    Gaganidze, Ermile; Rupp, Daniel; Aktaa, Jarir

    2014-03-01

    Fracture behaviour of round blank polycrystalline tungsten was studied by means of three point bending Fracture-Mechanical (FM) tests at temperatures between RT and 1000 °C and under high vacuum. To study the influence of the anisotropic microstructure on the fracture toughness (FT) and ductile-to-brittle transition (DBT) the specimens were extracted in three different, i.e. longitudinal, radial and circumferential orientations. The FM tests yielded distinctive fracture behaviour for each specimen orientation. The crack propagation was predominantly intergranular for longitudinal orientation up to 600 °C, whereas transgranular cleavage was observed at low test temperatures for radial and circumferentially oriented specimens. At intermediate test temperatures the change of the fracture mode took place for radial and circumferential orientations. Above 800 °C all three specimen types showed large ductile deformation without noticeable crack advancement. For longitudinal specimens the influence of the loading rate on the FT and DBT was studied in the loading rate range between 0.06 and 18 MPa m1/2/s. Though an increase of the FT was observed for the lowest loading rate, no resolvable dependence of the DBT on the loading rate was found partly due to loss of FT validity. A Master Curve approach is proposed to describe FT vs. test temperature data on polycrystalline tungsten. Fracture safe design space was identified by analysis compiled FT data.

  5. 21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide...

  6. 21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide...

  7. 21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide...

  8. 21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide...

  9. 21 CFR 520.1802a - Piperazine-carbon disulfide complex suspension.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Piperazine-carbon disulfide complex suspension... § 520.1802a Piperazine-carbon disulfide complex suspension. (a) Specifications. Each fluid ounce of suspension contains 7.5 grams of piperazine-carbon disulfide complex. The piperazine-carbon disulfide...

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

    NASA Technical Reports Server (NTRS)

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

    1964-01-01

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

  11. 46 CFR 151.50-41 - Carbon disulfide (carbon bisulfide).

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... disulfide (carbon bisulfide). (a) All openings shall be in the top of the tank. (b) Loading lines shall... extending from the tank top to a point near the tank bottom. A blanket of water shall be formed in this...

  12. A Potent, Versatile Disulfide-Reducing Agent from Aspartic Acid

    PubMed Central

    2013-01-01

    Dithiothreitol (DTT) is the standard reagent for reducing disulfide bonds between and within biological molecules. At neutral pH, however, >99% of DTT thiol groups are protonated and thus unreactive. Herein, we report on (2S)-2-amino-1,4-dimercaptobutane (dithiobutylamine or DTBA), a dithiol that can be synthesized from l-aspartic acid in a few high-yielding steps that are amenable to a large-scale process. DTBA has thiol pKa values that are ∼1 unit lower than those of DTT and forms a disulfide with a similar E°′ value. DTBA reduces disulfide bonds in both small molecules and proteins faster than does DTT. The amino group of DTBA enables its isolation by cation-exchange and facilitates its conjugation. These attributes indicate that DTBA is a superior reagent for reducing disulfide bonds in aqueous solution. PMID:22353145

  13. Association of thiol disulfide homeostasis with slow coronary flow.

    PubMed

    Kundi, Harun; Gok, Murat; Cetin, Mustafa; Kiziltunç, Emrullah; Topcuoglu, Canan; Neşelioğlu, Salim; Erel, Ozcan; Ulusoy, Feridun Vasfi

    2016-08-01

    Objective The aim of this study was to investigate the role of thiol disulfide homeostasis in the presence of slow coronary flow. Material and methods In this cross-sectional study, a total of 110 patients who admitted to our hospital between March 2014 and December 2015 were included in the study. There were 65 patients in the slow coronary flow, and 45 patients in the normal flow groups. Results We found significant differences between slow coronary flow and the normal flow groups for thiol disulfide homeostasis, and the results of our study indicated that hsCRP, and thiol disulfide ratio were independently associated with slow coronary flow. Conclusion Our study showed that thiol disulfide homeostasis was significantly and independently related to the presence of slow coronary flow.

  14. Properties of tungsten-rhenium and tungsten-rhenium with hafnium carbide

    NASA Astrophysics Data System (ADS)

    Leonhardt, Todd

    2009-07-01

    Historically, tungsten-25wt.% rhenium alloy has been manufactured into wire for the thermocouple market, but recent demands for high-temperature structural components have forced the development of novel processing techniques for tungsten-rhenium and tungsten-rhenium with hafnium carbide. With a melting temperature of 3,050°C, and a recrystallization temperature near 1,900°C, tungsten-rhenium alloys are being used in aerospace, temperature measuring, and friction stir welding applications. The mechanical properties and microstructures of tungsten-25wt.% rhenium and tungsten-25wt.% rhenium with hafnium carbide are reported at ambient temperature, 1,371°C, and 1,926°C, after processing by three methods: hot isostatic pressing, swaging, and extrusion.

  15. Fabrication and properties of tungsten heavy metal alloys containing 30% to 90% tungsten

    SciTech Connect

    Gurwell, W.E.; Nelson, R.G.; Dudder, G.B.; Davis, N.C.

    1984-09-01

    In 1983, Pacific Northwest Laboratory conducted a survey of tungsten heavy metal alloys having lower-than-normal (<90%) tungsten content. The purpose of the work was to develop tougher, more impact-resistant high-density alloys for applications benefitting from improved mechanical properties. Tungsten heavy metal alloys of 30 to 90% tungsten content were fabricated and their mechanical properties measured. Although ultimate strength was essentially independent of tungsten content, lower tungsten-content alloys had lower yield stress, hardness, and density, and decidedly higher elongations and impact energies. Cold work was effective in raising strength and hardness but detrimental to elongation and impact energies. Precipitation hardening and strain aging raised hardness effectively but had less influence on other mechanical properties. 34 figures, 7 tables.

  16. High strength and density tungsten-uranium alloys

    DOEpatents

    Sheinberg, Haskell

    1993-01-01

    Alloys of tungsten and uranium and a method for making the alloys. The amount of tungsten present in the alloys is from about 55 vol % to about 85 vol %. A porous preform is made by sintering consolidated tungsten powder. The preform is impregnated with molten uranium such that (1) uranium fills the pores of the preform to form uranium in a tungsten matrix or (2) uranium dissolves portions of the preform to form a continuous uranium phase containing tungsten particles.

  17. Photoactive Self-Shaping Hydrogels as Noncontact 3D Macro/Microscopic Photoprinting Platforms.

    PubMed

    Liao, Yue; An, Ning; Wang, Ning; Zhang, Yinyu; Song, Junfei; Zhou, Jinxiong; Liu, Wenguang

    2015-12-01

    A photocleavable terpolymer hydrogel cross-linked with o-nitrobenzyl derivative cross-linker is shown to be capable of self-shaping without losing its physical integrity and robustness due to spontaneous asymmetric swelling of network caused by UV-light-induced gradient cleavage of chemical cross-linkages. The continuum model and finite element method are used to elucidate the curling mechanism underlying. Remarkably, based on the self-changing principle, the photosensitive hydrogels can be developed as photoprinting soft and wet platforms onto which specific 3D characters and images are faithfully duplicated in macro/microscale without contact by UV light irradiation under the cover of customized photomasks. Importantly, a quick response (QR) code is accurately printed on the photoactive hydrogel for the first time. Scanning QR code with a smartphone can quickly connect to a web page. This photoactive hydrogel is promising to be a new printing or recording material.

  18. Fluorinated ethylene propylene copolymer coating for the stability enhancement of electroactive and photoactive systems

    NASA Astrophysics Data System (ADS)

    Zhao, Luping; Neoh, K. G.; Zhang, Yan; Kang, E. T.

    2003-11-01

    The effectiveness of radio frequency sputtered fluorinated ethylene propylene copolymer (FEP) for the stability enhancement of electroactive and photoactive systems was investigated. Two kinds of electroactive polymer systems, polyaniline (PANI) coated low density polyethylene (LDPE) film and PANI-viologen assembly, were tested. In both cases, a sputtered FEP coating of <10 nm in thickness significantly enhanced the electrical stability of the films in water. The enhancement of the electrical stability of the PANI-LDPE film was also achieved in basic aqueous solution of pH up to 12 with a FEP coating of 40-50 nm in thickness. The deposition of a FEP coating on the photoactive viologen system (viologen grafted on LDPE film) prolonged its photochromic effect by inhibiting the diffusion of oxygen, and hence the reoxidation of the highly colored viologen radical cations to the dication state.

  19. Photoactivity and stability of Ag2WO4 for organic degradation in aqueous suspensions

    NASA Astrophysics Data System (ADS)

    Chen, Haihang; Xu, Yiming

    2014-11-01

    Silver tungstate as photocatalyst for water splitting and dye degradation has been reported, but the catalyst stability is not known. In this work, we find that both α- and β-Ag2WO4 are not stable under UV light for the photocatalytic degradation of phenol and azo-dye X3B in aqueous solutions. Comparatively, β-Ag2WO4 was more photoactive, but less stable than α-Ag2WO4. Solid characterization with X-ray diffraction and scanning electron microscope showed that metallic silver particles were produced with the two catalysts, consequently resulting into decrease in the activity for organic degradation. Measurement of photoluminescence revealed that β-Ag2WO4 had a weaker band gap emission and higher portion of structural defects than α-Ag2WO4. A possible mechanism responsible for the observed difference in photoactivity and stability between the two tungstates is proposed.

  20. One-pot Synthesis of Soluble Nanoscale CIGS Photoactive Functional Materials.

    PubMed

    Lin, Ying; Chen, Yu; Feng, Miao; Yan, Aixia; Zhuang, Xiaodong

    2007-12-04

    Promising alternatives for solar energy utilization are thin film technologies involving various new materials. This contribution describes an easy and inexpensive synthetic method that can be used to prepare soluble nanoscale triphenyl phosphine-coordinated CIGS (TPP-CIGS) photoactive functional materials. This complex is stable in the solid state under the irradiation of the ambient light, but its solution becomes a little bit unstable under the illumination of the low intensity laser.

  1. Chiral Hydrogen Bond Environment Providing Unidirectional Rotation in Photoactive Molecular Motors.

    PubMed

    García-Iriepa, Cristina; Marazzi, Marco; Zapata, Felipe; Valentini, Alessio; Sampedro, Diego; Frutos, Luis Manuel

    2013-05-02

    Generation of a chiral hydrogen bond environment in efficient molecular photoswitches is proposed as a novel strategy for the design of photoactive molecular motors. Here, the following strategy is used to design a retinal-based motor presenting singular properties: (i) a single excitation wavelength is needed to complete the unidirectional rotation process (360°); (ii) the absence of any thermal step permits the process to take place at low temperatures; and (iii) the ultrafast process permits high rotational frequencies.

  2. Transfer-Free Growth of Atomically Thin Transition Metal Disulfides Using a Solution Precursor by a Laser Irradiation Process and Their Application in Low-Power Photodetectors.

    PubMed

    Huang, Chi-Chih; Medina, Henry; Chen, Yu-Ze; Su, Teng-Yu; Li, Jian-Guang; Chen, Chia-Wei; Yen, Yu-Ting; Wang, Zhiming M; Chueh, Yu-Lun

    2016-04-13

    Although chemical vapor deposition is the most common method to synthesize transition metal dichalcogenides (TMDs), several obstacles, such as the high annealing temperature restricting the substrates used in the process and the required transfer causing the formation of wrinkles and defects, must be resolved. Here, we present a novel method to grow patternable two-dimensional (2D) transition metal disulfides (MS2) directly underneath a protective coating layer by spin-coating a liquid chalcogen precursor onto the transition metal oxide layer, followed by a laser irradiation annealing process. Two metal sulfides, molybdenum disulfide (MoS2) and tungsten disulfide (WS2), are investigated in this work. Material characterization reveals the diffusion of sulfur into the oxide layer prior to the formation of the MS2. By controlling the sulfur diffusion, we are able to synthesize continuous MS2 layers beneath the top oxide layer, creating a protective coating layer for the newly formed TMD. Air-stable and low-power photosensing devices fabricated on the synthesized 2D WS2 without the need for a further transfer process demonstrate the potential applicability of TMDs generated via a laser irradiation process.

  3. Direct Electrochemical Preparation of Cobalt, Tungsten, and Tungsten Carbide from Cemented Carbide Scrap

    NASA Astrophysics Data System (ADS)

    Xiao, Xiangjun; Xi, Xiaoli; Nie, Zuoren; Zhang, Liwen; Ma, Liwen

    2017-02-01

    A novel process of preparing cobalt, tungsten, and tungsten carbide powders from cemented carbide scrap by molten salt electrolysis has been investigated in this paper. In this experiment, WC-6Co and NaCl-KCl salt were used as sacrificial anode and electrolyte, respectively. The dissolution potential of cobalt and WC was determined by linear sweep voltammetry to be 0 and 0.6 V ( vs Ag/AgCl), respectively. Furthermore, the electrochemical behavior of cobalt and tungsten ions was investigated by a variety of electrochemical techniques. Results of cyclic voltammetry (CV) and square-wave voltammetry show that the cobalt and tungsten ions existed as Co2+ and W2+ on melts, respectively. The effect of applied voltage, electrolysis current, and electrolysis times on the composition of the product was studied. Results showed that pure cobalt powder can be obtained when the electrolysis potential is lower than 0.6 V or during low current and short times. Double-cathode and two-stage electrolysis was utilized for the preparation of cobalt, tungsten carbide, and tungsten powders. Additionally, X-ray diffraction results confirm that the product collected at cathodes 1 and 2 is pure Co and WC, respectively. Pure tungsten powder was obtained after electrolysis of the second part. Scanning electron microscope results show that the diameters of tungsten, tungsten carbide, and cobalt powder are smaller than 100, 200, and 200 nm, respectively.

  4. Properties of tungsten and tungsten disilicide layers on Si(100) substrates

    NASA Astrophysics Data System (ADS)

    Cros, A.; Pierrisnard, R.; Pierre, F.; Layet, J. M.; Meyer, F.

    1989-09-01

    Tungsten layers have been evaporated on Si(100) surfaces under ultra high vacuum conditions. The tungsten is in the α phase. Before the disilicide formation (at ˜ 700°C), a low temperature (400°C) reaction has been observed. Si atoms segregate at the surface and do not form crystalline WSI 2 while the tungsten layer stays in the α phase. It is suggested that this low temperature reaction plays an important role in the roughness and the adhesion properties of the tungsten disilicide subsequently grown.

  5. Tungsten wire for incandescent lamps

    SciTech Connect

    Walter, J.L.; Briant, C.L. )

    1990-09-01

    Tungsten wire for incandescent lamp filaments must operate at high temperatures and for long times. To meet these requirements, the grain morphology of the wire must be controlled to reduce the propensity for grain boundary sliding. The morphology is a function of the distribution of very small pockets of potassium in the wire and the mechanical processing from ingot to wire. The behavior of the filament is directly related to the grain morphology. This paper describes the mechanism by which the potassium is incorporated into and distributed in the ingot. The elongation and spheroidization of the bubbles during hot rolling and swaging is also examined and related to the grain morphology of wire. Some indications of the relationship between grain morphology and filament behavior are also given.

  6. Composition of CVD tungsten silicides

    SciTech Connect

    Hara, T.; Takahashi, H.; Ishizawa, Y.

    1987-05-01

    The composition of tungsten silicide (WSi/sub x/) deposited by chemical vapor deposition on silicon and silicon dioxide substrates was studied. The composition x changed from 2.7 to 2.2 with varying WF/sub 6/ flow rate from 6 to 20 cm/sup 3//min in the deposition on silicon. When annealing was performed at 1000C, the dissociation of excess silicon occurred from the nonstoichiometric silicide in the layer on the silicon. As a result, the composition of each layer, which was different when deposited, tended toward the same composition of around 2.1. This result indicated the formation of near-stoichiometric silicide as a result of annealing.

  7. Dielectronic recombination of tungsten ions

    NASA Astrophysics Data System (ADS)

    Li, Bowen; O'Sullivan, Gerry; Dong, Chenzhong; Chen, Ximeng

    2016-08-01

    Ab initio calculations of dielectronic recombination rate coefficients of Ne-, Pd- and Ag-like tungsten have been performed. Energy levels, radiative transition probabilities and autoionization rates were calculated using the Flexible Atomic Code. The contributions from different channels to the total rate coefficients are discussed. The present calculated rate coefficients are compared with other calculations where available. Excellent agreement has been found for Ne-like W while a large discrepancy was found for Pd-like W, which implies that more ab initio calculations and experimental measurements are badly needed. Further calculations demonstrated that the influence of configuration interaction is small while nonresonant radiative stabilizing (NRS) contribution to doubly excited non-autoionizing states are vital. The data obtained are expected to be useful for modeling plasmas for fusion applications, especially for the ITER community, which makes experimental verification even more essential.

  8. Ion mobility mass spectrometry as a potential tool to assign disulfide bonds arrangements in peptides with multiple disulfide bridges.

    PubMed

    Echterbille, Julien; Quinton, Loïc; Gilles, Nicolas; De Pauw, Edwin

    2013-05-07

    Disulfide bridges play a major role in defining the structural properties of peptides and proteins. However, the determination of the cysteine pairing is still challenging. Peptide sequences are usually achieved using tandem mass spectrometry (MS/MS) spectra of the totally reduced unfolded species, but the cysteine pairing information is lost. On the other hand, MS/MS experiments performed on native folded species show complex spectra composed of nonclassical ions. MS/MS alone does not allow either the cysteine pairing or the full sequence of an unknown peptide to be determined. The major goal of this work is to set up a strategy for the full structural characterization of peptides including disulfide bridges annotation in the sequence. This strategy was developed by combining ion mobility spectrometry (IMS) and collision-induced dissociation (CID). It is assumed that the opening of one S-S bridge in a peptide leads to a structural evolution which results in a modification of IMS drift time. In the presence of multiple S-S bridges, the shift in arrival time will depend on which disulfide(s) has (have) been reduced and on the shape adopted by the generated species. Due to specific fragmentations observed for each species, CID experiments performed after the mobility separation could provide not only information on peptide sequence but also on the localization of the disulfide bridges. To achieve this goal, synthetic peptides containing two disulfides were studied. The openings of the bridges were carried out following different experimental conditions such as reduction, reduction/alkylation, or oxidation. Due to disulfide scrambling highlighted with the reduction approaches, oxidation of S-S bonds into cysteic acids appeared to be the best strategy. Cysteine connectivity was then unambiguously determined for the two peptides, without any disulfide scrambling interference.

  9. Strain aging in tungsten heavy alloys

    SciTech Connect

    Dowding, R.J.; Tauer, K.J. . Materials Technology Lab.)

    1991-01-01

    This paper reports on tungsten heavy alloys which are two-phase mixtures of body center cubic (BCC) tungsten surrounded by a face center cubic (FCC) matrix. The matrix is most often composed of nickel and iron in a ratio of 70:30 but, occasionally, the matrix may also contain cobalt or copper. Nickel, however, is always the primary matrix component. The tungsten heavy alloy is fabricated through powder metallurgy techniques. Elemental powders are blended, pressed to shape, and sintered. Depending upon the tungsten content, the sintering temperatures are usually in the range of 1450{degrees}C to 1525{degrees}C. These temperatures are high enough that, as a result, the matrix is at the liquid phase and the process is known as liquid phase sintering. At the liquid phase temperature, the matrix becomes saturated with tungsten, but this does not change the FCC character of the matrix. The sintering is usually done in a hydrogen atmosphere furnace in order to reduce the oxides on the tungsten powder surfaces and create clean, active surfaces which will enhance the adherence between the tungsten and the matrix. The hydrogen atmosphere also creates the presence of excess dissolved hydrogen in the alloy. It has been shown that the hydrogen degrades the toughness and ductility of the heavy alloy. A post-sintering vacuum heat treatment is generally required to insure that there is no residual hydrogen present. The as-sintered tensile strength of a 90% tungsten, 7% nickel, 3% iron alloy (90W) is in the range of 800 to 940 MPa and can be increased significantly by cold working, usually rolling or swaging. Swaging to reductions in area of 20% can result in tensile strengths of 1250 MPa or more. As the strength increases, the elongation, which may have been 30% or more, decreases to less than 5%.

  10. Tungsten Speciation in Firing Range Soils

    DTIC Science & Technology

    2011-01-01

    32 Figure 8. Microprobe XRF images of normalized iron, tungsten, and calcium fluorescence intensities for a soil collected...measuring the XRF spectrum for 250 μs at each point (2 s at NSLS). Regions of interest were defined for a number of elements, includ- ing tungsten, calcium ...K-range. Nevertheless, iron K-edge XANES is highly effective at identify- ing and quantifying crystalline iron oxides, ferrihydrite, iron silicates

  11. Speciation and Geochemistry of Tungsten in Soil

    DTIC Science & Technology

    2006-11-01

    sodium tungstate dihydrate was purchased from Sigma Aldrich (St. Louis, MO) and Alfa Aesar (Ward Hill, MA), respectively. Single element and mixed...yielding an amorphous tungsten oxide (WO3) coating. This coating rapidly dissolves to yield the tungstate anion (WO42-), which can migrate in...well characterized. Tungsten exists in most environmental matrices as the soluble and mobile tungstate anion, which can polymerize with itself and

  12. Visualization of Gas Tungsten Arc Weld Pools

    DTIC Science & Technology

    1991-09-01

    flow visualization of Gas Tungsten Arc weld pools for HY-80 steel is presented using a pulsed laser light source and a conventional night~vision...visualization of Gas Tungsten Arc weld pools for HY-80 steel is presented using a pulsed laser light source and a conventional night-vision image-intensifier...effects of electromagnetic stirring on GTA welds in austenitic stainless steel . Changes in shape and solidification structure of welds observed

  13. International strategic mineral issues summary report: tungsten

    USGS Publications Warehouse

    Werner, Antony B.T.; Sinclair, W. David; Amey, Earle B.

    1998-01-01

    In 1995, China and the former Soviet Union accounted for over three-fourths of the world's mine production of tungsten. China alone produced about two-thirds of world output. Given its vast resources, China will likely maintain its prominent role in world tungsten supply. By the year 2020, changes in supply patterns are likely to result from declining output from individual deposits in Australia, Austria, and Portugal and the opening of new mines in Canada, China, and the United Kingdom.

  14. Tungsten targets the tumor microenvironment to enhance breast cancer metastasis.

    PubMed

    Bolt, Alicia M; Sabourin, Valérie; Molina, Manuel Flores; Police, Alice M; Negro Silva, Luis Fernando; Plourde, Dany; Lemaire, Maryse; Ursini-Siegel, Josie; Mann, Koren K

    2015-01-01

    The number of individuals exposed to high levels of tungsten is increasing, yet there is limited knowledge of the potential human health risks. Recently, a cohort of breast cancer patients was left with tungsten in their breasts following testing of a tungsten-based shield during intraoperative radiotherapy. While monitoring tungsten levels in the blood and urine of these patients, we utilized the 66Cl4 cell model, in vitro and in mice to study the effects of tungsten exposure on mammary tumor growth and metastasis. We still detect tungsten in the urine of patients' years after surgery (mean urinary tungsten concentration at least 20 months post-surgery = 1.76 ng/ml), even in those who have opted for mastectomy, indicating that tungsten does not remain in the breast. In addition, standard chelation therapy was ineffective at mobilizing tungsten. In the mouse model, tungsten slightly delayed primary tumor growth, but significantly enhanced lung metastasis. In vitro, tungsten did not enhance 66Cl4 proliferation or invasion, suggesting that tungsten was not directly acting on 66Cl4 primary tumor cells to enhance invasion. In contrast, tungsten changed the tumor microenvironment, enhancing parameters known to be important for cell invasion and metastasis including activated fibroblasts, matrix metalloproteinases, and myeloid-derived suppressor cells. We show, for the first time, that tungsten enhances metastasis in an animal model of breast cancer by targeting the microenvironment. Importantly, all these tumor microenvironmental changes are associated with a poor prognosis in humans.

  15. Tungsten Targets the Tumor Microenvironment to Enhance Breast Cancer Metastasis

    PubMed Central

    Bolt, Alicia M.; Sabourin, Valérie; Molina, Manuel Flores; Police, Alice M.; Negro Silva, Luis Fernando; Plourde, Dany; Lemaire, Maryse; Ursini-Siegel, Josie; Mann, Koren K.

    2015-01-01

    The number of individuals exposed to high levels of tungsten is increasing, yet there is limited knowledge of the potential human health risks. Recently, a cohort of breast cancer patients was left with tungsten in their breasts following testing of a tungsten-based shield during intraoperative radiotherapy. While monitoring tungsten levels in the blood and urine of these patients, we utilized the 66Cl4 cell model, in vitro and in mice to study the effects of tungsten exposure on mammary tumor growth and metastasis. We still detect tungsten in the urine of patients’ years after surgery (mean urinary tungsten concentration at least 20 months post-surgery = 1.76 ng/ml), even in those who have opted for mastectomy, indicating that tungsten does not remain in the breast. In addition, standard chelation therapy was ineffective at mobilizing tungsten. In the mouse model, tungsten slightly delayed primary tumor growth, but significantly enhanced lung metastasis. In vitro, tungsten did not enhance 66Cl4 proliferation or invasion, suggesting that tungsten was not directly acting on 66Cl4 primary tumor cells to enhance invasion. In contrast, tungsten changed the tumor microenvironment, enhancing parameters known to be important for cell invasion and metastasis including activated fibroblasts, matrix metalloproteinases, and myeloid-derived suppressor cells. We show, for the first time, that tungsten enhances metastasis in an animal model of breast cancer by targeting the microenvironment. Importantly, all these tumor microenvironmental changes are associated with a poor prognosis in humans. PMID:25324207

  16. Assessment of disulfide and hinge modifications in monoclonal antibodies.

    PubMed

    Moritz, Bernd; Stracke, Jan Olaf

    2016-12-16

    During the last years there was a substantial increase in the use of antibodies and related proteins as therapeutics. The emphasis of the pharmaceutical industry is on IgG1, IgG2, and IgG4 antibodies, which are therefore in the focus of this article. In order to ensure appropriate quality control of such biopharmaceuticals, deep understanding of their chemical degradation pathways and the resulting impact on potency, pharmacokinetics, and safety is required. Criticality of modifications may be specific for individual antibodies and has to be assessed for each molecule. However, some modifications of conserved structure elements occur in all or at least most IgGs. In these cases, criticality assessment may be applicable to related molecules or molecule formats. The relatively low dissociation energy of disulfide bonds and the high flexibility of the hinge region frequently lead to modifications and cleavages. Therefore, the hinge region and disulfide bonds require specific consideration during quality assessment of mAbs. In this review, available literature knowledge on underlying chemical reaction pathways of modifications, analytical methods for quantification and criticality are discussed. The hinge region is prone to cleavage and is involved in pathways that lead to thioether bond formation, cysteine racemization, and iso-Asp (Asp, aspartic acid) formation. Disulfide or sulfhydryl groups were found to be prone to reductive cleavage, trisulfide formation, cysteinylation, glutathionylation, disulfide bridging to further light chains, and disulfide scrambling. With regard to potency, disulfide cleavage, hinge cleavage, disulfide bridging to further light chains, and cysteinylation were found to influence antigen binding and fragment crystallizable (Fc) effector functionalities. Renal clearance of small fragments may be faster, whereas clearance of larger fragments appears to depend on their neonatal Fc receptor (FcRn) functionality, which in turn may be impeded by

  17. Ordered mesoporous tungsten suboxide counter electrode for highly efficient iodine-free electrolyte-based dye-sensitized solar cells.

    PubMed

    Jeong, Inyoung; Jo, Changshin; Anthonysamy, Arockiam; Kim, Jung-Min; Kang, Eunae; Hwang, Jongkook; Ramasamy, Easwaramoorthi; Rhee, Shi-Woo; Kim, Jin Kon; Ha, Kyoung-Su; Jun, Ki-Won; Lee, Jinwoo

    2013-02-01

    A disulfide/thiolate (T(2)/T(-)) redox-couple electrolyte, which is a promising iodine-free electrolyte owing to its transparent and noncorrosive properties, requires alternative counter-electrode materials because conventional Pt shows poor catalytic activity in such an electrolyte. Herein, ordered mesoporous tungsten suboxide (m-WO(3-x)), synthesized by using KIT-6 silica as a hard template followed by a partial reduction, is used as a catalyst for a counter electrode in T(2)/T(-)-electrolyte-based dye-sensitized solar cells (DSCs). The mesoporous tungsten suboxide, which possesses interconnected pores of 4 and 20 nm, provides a large surface area and efficient electrolyte penetration into the m-WO(3-x) pores. In addition to the advantages conferred by the mesoporous structure, partial reduction of tungsten oxide creates oxygen vacancies that can function as active catalytic sites, which causes a high electrical conductivity because of intervalence charge transfer between the W(5+) and W(6+) ions. m-WO(3-x) shows a superior photovoltaic performance (79 % improvement in the power conversion efficiency) over Pt in the T(2)/T(-) electrolyte. The superior catalytic activity of m-WO(3-x) is investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Tafel polarization curve analysis.

  18. Semienzymatic cyclization of disulfide-rich peptides using Sortase A.

    PubMed

    Jia, Xinying; Kwon, Soohyun; Wang, Ching-I Anderson; Huang, Yen-Hua; Chan, Lai Y; Tan, Chia Chia; Rosengren, K Johan; Mulvenna, Jason P; Schroeder, Christina I; Craik, David J

    2014-03-07

    Disulfide-rich cyclic peptides have generated great interest in the development of peptide-based therapeutics due to their exceptional stability toward chemical, enzymatic, or thermal attack. In particular, they have been used as scaffolds onto which bioactive epitopes can be grafted to take advantage of the favorable biophysical properties of disulfide-rich cyclic peptides. To date, the most commonly used method for the head-to-tail cyclization of peptides has been native chemical ligation. In recent years, however, enzyme-mediated cyclization has become a promising new technology due to its efficiency, safety, and cost-effectiveness. Sortase A (SrtA) is a bacterial enzyme with transpeptidase activity. It recognizes a C-terminal penta-amino acid motif, LPXTG, and cleaves the amide bond between Thr and Gly to form a thioacyl-linked intermediate. This intermediate undergoes nucleophilic attack by an N-terminal poly-Gly sequence to form an amide bond between the Thr and N-terminal Gly. Here, we demonstrate that sortase A can successfully be used to cyclize a variety of small disulfide-rich peptides, including the cyclotide kalata B1, α-conotoxin Vc1.1, and sunflower trypsin inhibitor 1. These peptides range in size from 14 to 29 amino acids and contain three, two, or one disulfide bond, respectively, within their head-to-tail cyclic backbones. Our findings provide proof of concept for the potential broad applicability of enzymatic cyclization of disulfide-rich peptides with therapeutic potential.

  19. Disulfide Bridges: Bringing Together Frustrated Structure in a Bioactive Peptide.

    PubMed

    Zhang, Yi; Schulten, Klaus; Gruebele, Martin; Bansal, Paramjit S; Wilson, David; Daly, Norelle L

    2016-04-26

    Disulfide bridges are commonly found covalent bonds that are usually believed to maintain structural stability of proteins. Here, we investigate the influence of disulfide bridges on protein dynamics through molecular dynamics simulations on the cysteine-rich trypsin inhibitor MCoTI-II with three disulfide bridges. Correlation analysis of the reduced cyclic peptide shows that two of the three disulfide distances (Cys(11)-Cys(23) and Cys(17)-Cys(29)) are anticorrelated within ∼1 μs of bridge formation or dissolution: when the peptide is in nativelike structures and one of the distances shortens to allow bond formation, the other tends to lengthen. Simulations over longer timescales, when the denatured state is less structured, do not show the anticorrelation. We propose that the native state contains structural elements that frustrate one another's folding, and that the two bridges are critical for snapping the frustrated native structure into place. In contrast, the Cys(4)-Cys(21) bridge is predicted to form together with either of the other two bridges. Indeed, experimental chromatography and nuclear magnetic resonance data show that an engineered peptide with the Cys(4)-Cys(21) bridge deleted can still fold into its near-native structure even in its noncyclic form, confirming the lesser role of the Cys(4)-Cys(21) bridge. The results highlight the importance of disulfide bridges in a small bioactive peptide to bring together frustrated structure in addition to maintaining protein structural stability.

  20. Thiol/disulfide redox states in signaling and sensing

    PubMed Central

    Go, Young-Mi; Jones, Dean P.

    2015-01-01

    Rapid advances in redox systems biology are creating new opportunities to understand complexities of human disease and contributions of environmental exposures. New understanding of thiol-disulfide systems have occurred during the past decade as a consequence of the discoveries that thiol and disulfide systems are maintained in kinetically controlled steady-states displaced from thermodynamic equilibrium, that a widely distributed family of NADPH oxidases produces oxidants that function in cell signaling, and that a family of peroxiredoxins utilize thioredoxin as a reductant to complement the well-studied glutathione antioxidant system for peroxide elimination and redox regulation. This review focuses on thiol/disulfide redox state in biologic systems and the knowledge base available to support development of integrated redox systems biology models to better understand the function and dysfunction of thiol-disulfide redox systems. In particular, central principles have emerged concerning redox compartmentalization and utility of thiol/disulfide redox measures as indicators of physiologic function. Advances in redox proteomics show that, in addition to functioning in protein active sites and cell signaling, cysteine residues also serve as redox sensors to integrate biologic functions. These advances provide a framework for translation of redox systems biology concepts to practical use in understanding and treating human disease. Biological responses to cadmium, a widespread environmental agent, are used to illustrate the utility of these advances to the understanding of complex pleiotropic toxicities. PMID:23356510

  1. Atomic scale calculations of tungsten surface binding energy and beryllium-induced tungsten sputtering

    NASA Astrophysics Data System (ADS)

    Yang, Xue; Hassanein, Ahmed

    2014-02-01

    Tungsten surface binding energy is calculated using classical molecular dynamic simulations with three many-body potentials. We present the consistency in tungsten sputtering yield by beryllium bombardment between molecular dynamic LAMMPS code and binary collision approximation ITMC code using the new surface binding energy (11.75 eV). The commonly used heat of sublimation value (8.68 eV) could lead to overestimated sputtering yield results. The analysis of the sputtered tungsten angular distributions show that molecular dynamic accurately reproduced the [1 1 1] most prominent preferential ejection directions in bcc tungsten, while the distinct shapes by typical MC codes such as ITMC code is caused by the treatment of amorphous target. The ITMC calculated emitted tungsten energy profile matches the Thompson energy spectrum, while the molecular dynamic results generally follow the Falcone energy spectrum.

  2. A mechanism for selectivity loss during tungsten CVD

    SciTech Connect

    Creighton, J.R.

    1989-01-01

    The authors have investigated possible mechanisms for the loss of selectivity (i.e., deposition on silicon dioxide) during tungsten CVD by reduction of tungsten hexafluoride and found strong evidence that selectivity loss is initiated by desorption of tungsten subfluorides formed by the reaction of WF/sub 6/ with metallic tungsten surfaces. Adsorption and disproportionation of the tungsten subfluorides on the silicon dioxide surface produces a reactive state of tungsten that can lead directly to selectivity loss. The key feature of the experimental setup is the ability to independently heat a tungsten foil and a nearby oxide-covered silicon sample in the presence of tungsten hexafluoride. With the tungsten foil at 600/sup 0/C and the SiO/sub 2//Si sample at --30/sup 0/C under a WF/sub 6/ ambient, a tungsten subfluoride was found to deposit on the SiO/sub 2/ surface. Auger electron spectroscopy was used to measure a F/W ratio of 3.7 +- 0.5. Heating this tungsten subfluoride overlayer resulted in disporportionation to yield gas-phase WF/sub 6/ and metallic tungsten which remained on the surface. With the tungsten foil at 600/sup 0/C and the SiO/sub 2//Si sample at 300/sup 0/C in the presence of WF/sub 6/, metallic tungsten deposited directly on the SiO/sub 2/ without stopping at the subfluoride adsorption step. The net effect of this tungsten subfluoride desorption-disproportionation mechanism is the transport of tungsten from tungsten surfaces to silicon dioxide surfaces as well as other regions in the deposition chamber. Extrapolated rates for this process are high enough to explain the magnitude of the selectivity loss seen at normal CVD temperatures.

  3. Structural basis of protein disulfide bond generation in the cell.

    PubMed

    Inaba, Kenji

    2010-09-01

    The formation of protein disulfide bonds is an oxidative reaction that is crucial for the folding and maturation of many secreted and membrane proteins. Both prokaryotic and eukaryotic cells possess various disulfide oxidoreductases and redox-active cofactors to accelerate this oxidative reaction in a correct manner. Crystal or solution structures have been solved for some of the oxidoreductases in the past 10 years, leading to remarkable progress in the field of thiol-based redox cell biology. Consequently, structural and mechanistic similarities in the disulfide bond formation pathways have been uncovered. This review highlights the molecular basis of the elaborate oxidative systems operating in the Escherichia coli periplasm, the endoplasmic reticulum lumen and the mitochondrial intermembrane space. The accumulated knowledge provides important insights into how protein and redox homeostasis are maintained in the cell.

  4. A molybdenum disulfide/carbon nanotube heterogeneous complementary inverter.

    PubMed

    Huang, Jun; Somu, Sivasubramanian; Busnaina, Ahmed

    2012-08-24

    We report a simple, bottom-up/top-down approach for integrating drastically different nanoscale building blocks to form a heterogeneous complementary inverter circuit based on layered molybdenum disulfide and carbon nanotube (CNT) bundles. The fabricated CNT/MoS(2) inverter is composed of n-type molybdenum disulfide (MOS(2)) and p-type CNT transistors, with a high voltage gain of 1.3. The CNT channels are fabricated using directed assembly while the layered molybdenum disulfide channels are fabricated by mechanical exfoliation. This bottom-up fabrication approach for integrating various nanoscale elements with unique characteristics provides an alternative cost-effective methodology to complementary metal-oxide-semiconductors, laying the foundation for the realization of high performance logic circuits.

  5. From structure to redox: the diverse functional roles of disulfides and implications in disease

    PubMed Central

    Bechtel, Tyler J.; Weerapana, Eranthie

    2017-01-01

    This review provides a comprehensive overview of the functional roles of disulfide bonds and their relevance to human disease. The critical roles of disulfide bonds in protein structure stabilization and redox regulation of protein activity are addressed. Disulfide bonds are essential to the structural stability of many proteins within the secretory pathway and can exist as intramolecular or inter-domain disulfides. The proper formation of these bonds often relies on folding chaperones and oxidases such as members of the protein disulfide isomerase (PDI) family. Many of the PDI family members catalyze disulfide-bond formation, reduction and isomerization through redox-active disulfides and perturbed PDI activity is characteristic of carcinomas and neurodegenerative diseases. In addition to catalytic function in oxidoreductases, redox-active disulfides are also found on a diverse array of cellular proteins and act to regulate protein activity and localization in response to oxidative changes in the local environment. These redox-active disulfides are either dynamic intramolecular protein disulfides or mixed disulfides with small-molecule thiols generating glutathionylation and cysteinylation adducts. The oxidation and reduction of redox-active disulfides are mediated by cellular reactive oxygen species and activity of reductases, such as glutaredoxin and thioredoxin. Dysregulation of cellular redox conditions and resulting changes in mixed disulfide formation are directly linked to diseases such as cardiovascular disease and Parkinson’s disease. PMID:28044432

  6. Bandgap- and local field-dependent photoactivity of Ag/black phosphorus nanohybrids

    DOE PAGES

    Lei, Wanying; Zhang, Tingting; Liu, Ping; ...

    2016-10-18

    Black phosphorus (BP) is the most exciting post-graphene layered nanomaterial that serendipitously bridges the 2D materials gap between semimetallic graphene and large bandgap transition-metal dichalcogenides in terms of high charge-carrier mobility and tunable direct bandgap, yet research into BP-based solar to chemical energy conversion is still in its infancy. Herein, a novel hybrid photocatalyst with Ag nanoparticles supported on BP nanosheets is prepared using a chemical reduction approach. Spin-polarized density functional theory (DFT) calculations show that Ag nanoparticles are stabilized on BP by covalent bonds at the Ag/BP interface and Ag–Ag interactions. In the visible-light photocatalysis of rhodamine B bymore » Ag/BP plasmonic nanohybrids, a significant rise in photoactivity compared with pristine BP nanosheets is observed either by decreasing BP layer thickness or increasing Ag particle size, with the greatest enhancement being up to ~20-fold. By virtue of finite-difference time domain (FDTD) simulations and photocurrent measurements, we give insights into the enhanced photocatalytic performance of Ag/BP nanohybrids, including the effects of BP layer thickness and Ag particle size. In comparison with BP, Ag/BP nanohybrids present intense local field amplification at the perimeter of Ag NPs, which is increased by either decreasing the BP layer thickness from multiple to few layers or increasing the Ag particle size from 20 to 40 nm. Additionally, when the BP layer thickness is decreased from multiple to few layers, the bandgap becomes favorable to generate more strongly oxidative holes in the proximity of the Ag/BP interface to enhance photoactivity. Our findings illustrate a synergy between locally enhanced electric fields and BP bandgap, in which BP layer thickness and Ag particle size can be independently tuned to enhance photoactivity. Lastly, this study may open a new avenue for further exploiting BP-based plasmonic nanostructures in

  7. Bandgap- and local field-dependent photoactivity of Ag/black phosphorus nanohybrids

    SciTech Connect

    Lei, Wanying; Zhang, Tingting; Liu, Ping; Rodriguez, Jose A.; Liu, Gang; Liu, Minghua

    2016-10-18

    Black phosphorus (BP) is the most exciting post-graphene layered nanomaterial that serendipitously bridges the 2D materials gap between semimetallic graphene and large bandgap transition-metal dichalcogenides in terms of high charge-carrier mobility and tunable direct bandgap, yet research into BP-based solar to chemical energy conversion is still in its infancy. Herein, a novel hybrid photocatalyst with Ag nanoparticles supported on BP nanosheets is prepared using a chemical reduction approach. Spin-polarized density functional theory (DFT) calculations show that Ag nanoparticles are stabilized on BP by covalent bonds at the Ag/BP interface and Ag–Ag interactions. In the visible-light photocatalysis of rhodamine B by Ag/BP plasmonic nanohybrids, a significant rise in photoactivity compared with pristine BP nanosheets is observed either by decreasing BP layer thickness or increasing Ag particle size, with the greatest enhancement being up to ~20-fold. By virtue of finite-difference time domain (FDTD) simulations and photocurrent measurements, we give insights into the enhanced photocatalytic performance of Ag/BP nanohybrids, including the effects of BP layer thickness and Ag particle size. In comparison with BP, Ag/BP nanohybrids present intense local field amplification at the perimeter of Ag NPs, which is increased by either decreasing the BP layer thickness from multiple to few layers or increasing the Ag particle size from 20 to 40 nm. Additionally, when the BP layer thickness is decreased from multiple to few layers, the bandgap becomes favorable to generate more strongly oxidative holes in the proximity of the Ag/BP interface to enhance photoactivity. Our findings illustrate a synergy between locally enhanced electric fields and BP bandgap, in which BP layer thickness and Ag particle size can be independently tuned to enhance photoactivity. Lastly, this study may open a new avenue for further exploiting BP-based plasmonic nanostructures in photocatalysis

  8. Disulfide-rich macrocyclic peptides as templates in drug design.

    PubMed

    Northfield, Susan E; Wang, Conan K; Schroeder, Christina I; Durek, Thomas; Kan, Meng-Wei; Swedberg, Joakim E; Craik, David J

    2014-04-22

    Recently disulfide-rich head-to-tail cyclic peptides have attracted the interest of medicinal chemists owing to their exceptional thermal, chemical and enzymatic stability brought about by their constrained structures. Here we review current trends in the field of peptide-based pharmaceuticals and describe naturally occurring cyclic disulfide-rich peptide scaffolds, discussing their pharmaceutically attractive properties and benefits. We describe how we can utilise these stable frameworks to graft and/or engineer pharmaceutically interesting epitopes to increase their selectivity and bioactivity, opening up new possibilities for addressing 'difficult' pharmaceutical targets.

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

    SciTech Connect

    Pagel, Mark D.

    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.

  10. Synthesis of Neoglycoconjugates by the Desulfurative Rearrangement of Allylic Disulfides

    PubMed Central

    Crich, David; Yang, Fan

    2009-01-01

    Two series of neoglucosyl donors are prepared based on connection of the allylic disulfide motif to the anomeric center via either a simple O-glycosyl linkage or N-glycosyl amide unit. Conjugation of both sets of donors to cysteine in peptides is demonstrated through classical disulfide exchange followed by the phosphine-mediated desulfurative allylic rearrangement resulting in neoglycopeptides characterized by a simple thioether spacer. The conjugation reaction functions in the absence of protecting groups on both the neoglycosyl donor and peptide in aqueous media at room temperature. PMID:18729514

  11. Ultrasonic drawing of tungsten wire for incandescent lamps production.

    PubMed

    Mordyuk, B N; Mordyuk, V S; Buryak, V V

    2004-04-01

    An influence of ultrasonic treatment (drawing) on structure, high temperature durability, evaporation and creep behaviours of tungsten single crystal and wires were investigated. A relation of tungsten wires properties with dislocation distribution was determined.

  12. Some Tungsten Oxidation-Reduction Chemistry: A Paint Pot Titration.

    ERIC Educational Resources Information Center

    Pickering, Miles; Monts, David L.

    1982-01-01

    Reports an oxidation-reduction experiment using tungsten, somewhat analogous to the classical student experiment involving oxidation-reduction of vanadium. Includes experimental procedures, results, and toxicity/cost of tungsten compounds. (Author/JN)

  13. Growth of tungsten oxide on carbon nanowalls templates

    SciTech Connect

    Wang, Hua; Su, Yan; Chen, Shuo; Quan, Xie

    2013-03-15

    Highlights: ► Tungsten oxide deposited on carbon nanowalls by hot filament chemical vapor deposition technique. ► This composite has two-dimensional uniform morphology with a crystalline structure of monoclinic tungsten trioxide. ► Surface photoelectric voltage measurements show that this product has photoresponse properties. - Abstract: In the present work we present a simple approach for coupling tungsten oxide with carbon nanowalls. The two-dimensional carbon nanowalls with open boundaries were grown using plasma enhanced hot filament chemical vapor deposition, and the subsequent tungsten oxide growth was performed in the same equipment by direct heating of a tungsten filament. The tungsten oxide coating is found to have uniform morphology with a crystalline structure of monoclinic tungsten trioxide. Surface photoelectric voltage measurements show that this product has photoresponse properties. The method of synthesis described here provides an operable route to the production of two-dimensional tungsten oxide nanocomposites.

  14. Evaporites and strata-bound tungsten mineralization

    SciTech Connect

    Ririe, G.T. )

    1989-02-01

    Discoidal gypsum crystal cavities occur in quartzites that host varying amounts of strata-bound scheelite mineralization near Halls Creek in Western Australia. The host quartzites have been regionally metamorphosed to greenschist facies and are contained within a Middle Proterozoic sequence that includes pelites, mafic and felsic volcanics, and volcaniclastic rocks. Textural, fluid inclusion, and oxygen isotope data indicate that scheelite was present in the host quartzites prior to regional metamorphism. The presence of crystal cavities after gypsum in the quartzites implies an evaporitic origin for this sequence. The continental-sabkha playa basins of the Mojave Desert, California, are suggested to be possible modern analogs-e.g., Searles Lake, where the tungsten content is up to 70 ppm WO{sub 3} in brines and 118 ppm in muds, and exceeds the amount of tungsten in all known deposits in the United States. Metamorphism of a continental evaporitic sequence containing tungsten could produce an assemblage of rocks very similar to those reported from several stratabound tungsten deposits. Some of these, such as at Halls Creek, may be related to original accumulations of tungsten in nonmarine evaporitic environments.

  15. Time-resolved serial crystallography captures high-resolution intermediates of photoactive yellow protein

    SciTech Connect

    Tenboer, Jason; Basu, Shibom; Zatsepin, Nadia; Pande, Kanupriya; Milathianaki, Despina; Frank, Matthias; Hunter, Mark; Boutet, Sebastien; Williams, Garth J.; Koglin, Jason E.; Oberthuer, Dominik; Heymann, Michael; Kupitz, Christopher; Conrad, Chelsie; Coe, Jesse; Roy-Chowdhury, Shatabdi; Weierstall, Uwe; James, Daniel; Wang, Dingjie; Grant, Thomas; Barty, Anton; Yefanov, Oleksandr; Scales, Jennifer; Gati, Cornelius; Seuring, Carolin; Srajer, Vukica; Henning, Robert; Schwander, Peter; Fromme, Raimund; Ourmazd, Abbas; Moffat, Keith; Van Thor, Jasper J.; Spence, John C. H.; Fromme, Petra; Chapman, Henry N.; Schmidt, Marius

    2014-12-05

    We report that serial femtosecond crystallography using ultrashort pulses from X-ray Free Electron Lasers (XFELs) offers the possibility to study light-triggered dynamics of biomolecules. Using microcrystals of the blue light photoreceptor, photoactive yellow protein, as a model system, we present high resolution, time-resolved difference electron density maps of excellent quality with strong features, which allow the determination of structures of reaction intermediates to 1.6 Å resolution. These results open the way to the study of reversible and non-reversible biological reactions on time scales as short as femtoseconds under conditions which maximize the extent of reaction initiation throughout the crystal.

  16. Singlet oxygen generation by photoactive polymeric microparticles with enhanced aqueous compatibility.

    PubMed

    Fabregat, Víctor; Burguete, M Isabel; Galindo, Francisco; Luis, Santiago V

    2014-10-01

    Two new photoactive materials compatible with environmentally friendly solvents (water and methanol) have been synthesized and characterized. They are comprised of a porous matrix of polystyrene and divinylbenzene with bound Rose Bengal and additional pendant groups added to increase the hydrophilicity (ethylenediamine and γ-gluconolactone). The new polymers are efficient photocatalysts capable of generating singlet oxygen after irradiation with visible light. Photochemical oxygenations of 9,10-anthracenedipropionic acid and 2-furoic acid have been carried out. The measured conversions indicate that the new supported photosensitizers are more effective than the parent hydrophobic polymer.

  17. Synthesis of Photoactive Materials by Sonication: Application in Photocatalysis and Solar Cells.

    PubMed

    Colmenares, Juan C; Kuna, Ewelina; Lisowski, Paweł

    2016-10-01

    In recent years, a good number of methods have become available for the preparation of an important group of photoactive materials for applications in photocatalysis and solar cells. Nevertheless, the benefits derived from preparing those materials through unconventional approaches are very attractive from the green chemistry point of view. This critical review work is focused on sonication as one of these promising new synthetic procedures that allow control over size, morphology, nanostructure and tuning of catalytic properties. Ultrasound-based procedures offer a facile, versatile synthetic tool for the preparation of light-activated materials often inaccessible through conventional methods.

  18. Fabrication and evaluation of chemically vapor deposited tungsten heat pipe

    NASA Technical Reports Server (NTRS)

    Bacigalupi, R. J.

    1972-01-01

    A network of lithium-filled tungsten heat pipes is considered as a method of heat extraction from high temperature nuclear reactors. The need for material purity and shape versatility in these applications dictates the use of chemically vapor deposited (CVD) tungsten. Adaptability of CVD tungsten to complex heat pipe designs is shown. Deposition and welding techniques are described. Operation of two lithium-filled CVD tungsten heat pipes above 1800 K is discussed.

  19. Process for the recovery of tungsten in a pure form from tungsten-containing materials

    SciTech Connect

    Fruchter, M.; Moscovici, A.

    1986-12-16

    A process is described for the recovery of tungsten from tungsten-containing materials which comprises the steps of (i) admixing the tungsten-containing material with a melt at a temperature of between 680/sup 0/C and 750/sup 0/C. The melt consists of a salt selected from the group consisting of sodium nitrate, sodium nitrite and mixtures thereof in a substantially stoichiometrical amount to the tungsten constituent of the tungsten-containing material. This is done to disintegrate the tungsten-containing material and to form sodium tungstate, cooling the melt, and leaching the cooled melt with water to obtain an aqueous solution of sodium tungstate; (ii) admixing a solution of calcium chloride with the aqueous solution of sodium tungstate at a temperature of between 40/sup 0/C and 95/sup 0/C to form a calcium tungstate precipitate and separating the calcium tungstate; (iii) admixing the calcium tungstate with a preheated concentrated hydrochloric acid solution to form a tungstic acid precipitate and a CaCl/sub 2/ solution having a concentration of between 80 g/l and 180 g/l free HCl and separating the tungstic acid precipitate and obtaining tungstic acid which is substantially free of calcium ions, and (iv) calcining the tungstic acid to convert it to tungstic oxide and reducing the tungstic oxide to form metallic tungsten.

  20. Gas-driven permeation of deuterium through tungsten and tungsten alloys

    SciTech Connect

    Buchenauer, Dean A.; Karnesky, Richard A.; Fang, Zhigang Zak; Ren, Chai; Oya, Yasuhisa; Otsuka, Teppei; Yamauchi, Yuji; Whaley, Josh A.

    2016-03-25

    Here, to address the transport and trapping of hydrogen isotopes, several permeation experiments are being pursued at both Sandia National Laboratories (deuterium gas-driven permeation) and Idaho National Laboratories (tritium gas- and plasma-driven tritium permeation). These experiments are in part a collaboration between the US and Japan to study the performance of tungsten at divertor relevant temperatures (PHENIX). Here we report on the development of a high temperature (≤1150 °C) gas-driven permeation cell and initial measurements of deuterium permeation in several types of tungsten: high purity tungsten foil, ITER-grade tungsten (grains oriented through the membrane), and dispersoid-strengthened ultra-fine grain (UFG) tungsten being developed in the US. Experiments were performed at 500–1000 °C and 0.1–1.0 atm D2 pressure. Permeation through ITER-grade tungsten was similar to earlier W experiments by Frauenfelder (1968–69) and Zaharakov (1973). Data from the UFG alloy indicates marginally higher permeability (< 10×) at lower temperatures, but the permeability converges to that of the ITER tungsten at 1000 °C. The permeation cell uses only ceramic and graphite materials in the hot zone to reduce the possibility for oxidation of the sample membrane. Sealing pressure is applied externally, thereby allowing for elevation of the temperature for brittle membranes above the ductile-to-brittle transition temperature.

  1. Raman scattering from rapid thermally annealed tungsten silicide

    NASA Technical Reports Server (NTRS)

    Kumar, Sandeep; Dasgupta, Samhita; Jackson, Howard E.; Boyd, Joseph T.

    1987-01-01

    Raman scattering as a technique for studying the formation of tungsten silicide is presented. The tungsten silicide films have been formed by rapid thermal annealing of thin tungsten films sputter deposited on silicon substrates. The Raman data are interpreted by using data from resistivity measurements, Auger and Rutherford backscattering measurements, and scanning electron microscopy.

  2. 40 CFR 721.10168 - Cesium tungsten oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cesium tungsten oxide. 721.10168... Substances § 721.10168 Cesium tungsten oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cesium tungsten oxide (PMN P-08-275; CAS No....

  3. 40 CFR 721.10168 - Cesium tungsten oxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Cesium tungsten oxide. 721.10168... Substances § 721.10168 Cesium tungsten oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cesium tungsten oxide (PMN P-08-275; CAS No....

  4. 40 CFR 721.10168 - Cesium tungsten oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Cesium tungsten oxide. 721.10168... Substances § 721.10168 Cesium tungsten oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cesium tungsten oxide (PMN P-08-275; CAS No....

  5. 40 CFR 721.10168 - Cesium tungsten oxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Cesium tungsten oxide. 721.10168... Substances § 721.10168 Cesium tungsten oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cesium tungsten oxide (PMN P-08-275; CAS No....

  6. 40 CFR 721.10168 - Cesium tungsten oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cesium tungsten oxide. 721.10168... Substances § 721.10168 Cesium tungsten oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cesium tungsten oxide (PMN P-08-275; CAS No....

  7. TPV Systems with Solar Powered Tungsten Emitters

    SciTech Connect

    Vlasov, A. S.; Khvostikov, V. P.; Khvostikova, O. A.; Gazaryan, P. Y.; Sorokina, S. V.; Andreev, V. M.

    2007-02-22

    A solar TPV generator development and characterization are presented. A double stage sunlight concentrator ensures 4600x concentration ratio. TPV modules based on tungsten emitters and GaSb cells were designed, fabricated and tested at indoor and outdoor conditions. The performance of tungsten emitter under concentrated solar radiation was analyzed. Emitter temperatures in the range of 1400-2000 K were measured, depending on the emitter size. The light distribution in the module has been characterized, 1x1 cm GaSb TPV cells were fabricated with the use of the Zn-diffusion and LPE technologies. The cell efficiency of 19% under illumination by a tungsten emitter (27% under spectra cut-off at {lambda} > 1820 nm) heated up to 1900-2000 K had been derived from experimentally measured PV parameters. The series connection of PV cells was ensured by the use of BeO ceramics. The possibilities of system performance improvement are discussed.

  8. Element 74, the Wolfram Versus Tungsten Controversy

    SciTech Connect

    Holden,N.E.

    2008-08-11

    Two and a quarter centuries ago, a heavy mineral ore was found which was thought to contain a new chemical element called heavy stone (or tungsten in Swedish). A few years later, the metal was separated from its oxide and the new element (Z=74) was called wolfram. Over the years since that time, both the names wolfram and tungsten were attached to this element in various countries. Sixty years ago, IUPAC chose wolfram as the official name for the element. A few years later, under pressure from the press in the USA, the alternative name tungsten was also allowed by IUPAC. Now the original, official name 'wolfram' has been deleted by IUPAC as one of the two alternate names for the element. The history of this controversy is described here.

  9. Superhard Diamond/tungsten Carbide Nanocomposites

    SciTech Connect

    Z Lin; J Zhang; B Li; L Wang; H Mao; R Hemley; Y Zhao

    2011-12-31

    We investigated the processing conditions of diamond/tungsten carbide (WC) composites using in situ synchrotron x-ray diffraction (XRD) and reactive sintering techniques at high pressure and high temperatures. The as-synthesized composites were characterized by synchrotron XRD, scanning electron microscopy, high-resolution transmission electron microscopy, and indentation hardness measurements. Through tuning of the reaction temperature and time, we produced fully reacted, well-sintered, and nanostructured diamond composites with Vickers hardness of about 55 GPa and the grain size of WC binding matrix smaller than 50 nm. A specific set of orientation relationships between WC and tungsten is identified to gain microstructural insight into the reaction mechanism between diamond and tungsten.

  10. Characterization of plasma coated tungsten heavy alloy

    SciTech Connect

    Bose, A.; Kapoor, D.; Lankford, J. Jr.; Nicholls, A.E.

    1996-06-01

    The detrimental environmental impact of Depleted Uranium-based penetrators have led to tremendous development efforts in the area of tungsten heavy alloy based penetrators. One line of investigation involves the coating of tungsten heavy alloys with materials that are prone to shear localization. Plasma spraying of Inconel 718 and 4340 steel have been used to deposit dense coatings on tungsten heavy alloy substrates. The aim of the investigation was to characterize the coating primarily in terms of its microstructure and a special push-out test. The paper describes the results of the push-out tests and analyzes some of the possible failure mechanisms by carrying out microstructural characterization of the failed rings obtained from the push out tests.

  11. 21 CFR 520.1802c - Piperazine-carbon disulfide complex with phenothiazine suspension.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Piperazine-carbon disulfide complex with... ANIMAL DRUGS § 520.1802c Piperazine-carbon disulfide complex with phenothiazine suspension. (a) Specifications. Each fluid ounce contains 5 grams of piperazine-carbon disulfide complex and 0.83 gram...

  12. 21 CFR 520.1802b - Piperazine-carbon disulfide complex boluses.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Piperazine-carbon disulfide complex boluses. 520....1802b Piperazine-carbon disulfide complex boluses. (a) Specifications. Each bolus contains 20 grams of piperazine-carbon disulfide complex. (b) Sponsor. See 000009 in § 510.600(c) of this chapter. (c)...

  13. 21 CFR 520.1802c - Piperazine-carbon disulfide complex with phenothiazine suspension.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Piperazine-carbon disulfide complex with... ANIMAL DRUGS § 520.1802c Piperazine-carbon disulfide complex with phenothiazine suspension. (a) Specifications. Each fluid ounce contains 5 grams of piperazine-carbon disulfide complex and 0.83 gram...

  14. 21 CFR 520.1802b - Piperazine-carbon disulfide complex boluses.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Piperazine-carbon disulfide complex boluses. 520....1802b Piperazine-carbon disulfide complex boluses. (a) Specifications. Each bolus contains 20 grams of piperazine-carbon disulfide complex. (b) Sponsor. See 000009 in § 510.600(c) of this chapter. (c)...

  15. 21 CFR 520.1802c - Piperazine-carbon disulfide complex with phenothiazine suspension.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Piperazine-carbon disulfide complex with... ANIMAL DRUGS § 520.1802c Piperazine-carbon disulfide complex with phenothiazine suspension. (a) Specifications. Each fluid ounce contains 5 grams of piperazine-carbon disulfide complex and 0.83 gram...

  16. 21 CFR 520.1802b - Piperazine-carbon disulfide complex boluses.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Piperazine-carbon disulfide complex boluses. 520....1802b Piperazine-carbon disulfide complex boluses. (a) Specifications. Each bolus contains 20 grams of piperazine-carbon disulfide complex. (b) Sponsor. See 000009 in § 510.600(c) of this chapter. (c)...

  17. 21 CFR 520.1802c - Piperazine-carbon disulfide complex with phenothiazine suspension.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Piperazine-carbon disulfide complex with... ANIMAL DRUGS § 520.1802c Piperazine-carbon disulfide complex with phenothiazine suspension. (a) Specifications. Each fluid ounce contains 5 grams of piperazine-carbon disulfide complex and 0.83 gram...

  18. 21 CFR 520.1802c - Piperazine-carbon disulfide complex with phenothiazine suspension.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Piperazine-carbon disulfide complex with... ANIMAL DRUGS § 520.1802c Piperazine-carbon disulfide complex with phenothiazine suspension. (a) Specifications. Each fluid ounce contains 5 grams of piperazine-carbon disulfide complex and 0.83 gram...

  19. 21 CFR 520.1802b - Piperazine-carbon disulfide complex boluses.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Piperazine-carbon disulfide complex boluses. 520....1802b Piperazine-carbon disulfide complex boluses. (a) Specifications. Each bolus contains 20 grams of piperazine-carbon disulfide complex. (b) Sponsor. See 000009 in § 510.600(c) of this chapter. (c)...

  20. 21 CFR 520.1802b - Piperazine-carbon disulfide complex boluses.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Piperazine-carbon disulfide complex boluses. 520....1802b Piperazine-carbon disulfide complex boluses. (a) Specifications. Each bolus contains 20 grams of piperazine-carbon disulfide complex. (b) Sponsor. See 000009 in § 510.600(c) of this chapter. (c)...

  1. Comparison of Self-Assembled Monolayers on Gold: Coadsorption of Thiols and Disulfides

    DTIC Science & Technology

    1989-02-15

    self-assembled monolayers of thiols and disulfides. Previous studies by Dubois et alt t of the adsorption of dimethyl disulfide and methanethiol on...with an activation energy of desorption of 28 kcal/mol of disulfide, but the methanethiol was only physisorbed on the gold surface and desorbed intact

  2. Photoresponsive azo-doped aerosil/7CB nematic nanocomposites: the effect from concentration of the azobenzene photoactive agent

    NASA Astrophysics Data System (ADS)

    Hadjichristov, G. B.; Marinov, Y. G.; Petrov, A. G.; Prasad, S. K.

    2017-01-01

    We studied nanomaterials composed from 3 wt.% aerosil nanospheres and the room-temperature nematic liquid crystal 4-n-heptyl cyanobiphenyl (7CB), as doped with the photoactive liquid crystal 4-(4'-ethoxyphenylazo)phenyl hexanoate (EPH). The molecules of the azobenzene photoactive agent EPH were included at concentration ranging from 1 wt.% to 10 wt.%. The object of our interest is the effect of the EPH amount on the photosensitized electro-optical properties of thin films of aerosil/7CB/EPH nematic nanocomposites.

  3. Equipment simulation of selective tungsten deposition

    SciTech Connect

    Werner, C.; Ulacia, J.I.; Hopfmann, C.; Flynn, P. )

    1992-02-01

    This paper presents the numerical modeling of a cold wall reactor for selective tungsten chemical vapor deposition. In a two dimensional simulation the mass and heat transfer equations were solved considering the five chemical species H{sub 2}, WF{sub 6}, HF, WF{sub x}, and SiF{sub y}. Detailed models for multicomponent diffusion and for the autocatalytic tungsten nucleation process were implemented. Model results are in good agreement with experimental findings. The simulations are used to study the impact of reactor design on selectivity.

  4. Measured emissivities of uranium and tungsten plasmas.

    NASA Technical Reports Server (NTRS)

    Miller, M. H.

    1971-01-01

    Uranium and tungsten absorption coefficients between 2,500-8500 A were measured as functions of thermodynamic variables. A gas-driven shock tube was used to obtain plasma temperatures, heavy metal partial pressures, and total pressures in the ranges 7,000-12,000 K, 0.02-1.0 atm, and 3.0-48 atm, respectively. Emission and absorption data were recorded both photographically and photoelectrically. The spectral distributions, thermal dependence and line-to-continuum ratios of the uranium and tungsten radiation differ distinctly. The uranium data are compared with theoretical predictions and with results from other experiments.

  5. Localized cell stimulation by nitric oxide using a photoactive porous coordination polymer platform

    PubMed Central

    Diring, Stéphane; Wang, Dan Ohtan; Kim, Chiwon; Kondo, Mio; Chen, Yong; Kitagawa, Susumu; Kamei, Ken-ichiro; Furukawa, Shuhei

    2013-01-01

    Functional cellular substrates for localized cell stimulation by small molecules provide an opportunity to control and monitor cell signalling networks chemically in time and space. However, despite improvements in the controlled delivery of bioactive compounds, the precise localization of gaseous biomolecules at the single-cell level remains challenging. Here we target nitric oxide, a crucial signalling molecule with site-specific and concentration-dependent activities, and we report a synthetic strategy for developing spatiotemporally controllable nitric oxide-releasing platforms based on photoactive porous coordination polymers. By organizing molecules with poor reactivity into polymer structures, we observe increased photoreactivity and adjustable release using light irradiation. We embed photoactive polymer crystals in a biocompatible matrix and achieve precisely controlled nitric oxide delivery at the cellular level via localized two-photon laser activation. The biological relevance of the exogenous nitric oxide produced by this strategy is evidenced by an intracellular change in calcium concentration, mediated by nitric oxide-responsive plasma membrane channel proteins. PMID:24158008

  6. Characteristics of titanium dioxide microdispersions with different photo-activity suitable for sunscreen formulations.

    PubMed

    Kubáč, L; Akrman, J; Kejlová, K; Bendová, H; Klánová, K; Hladíková, Z; Pikal, P; Kovaříková, L; Kašparová, L; Jírová, D

    2015-03-15

    The aim of the study was the comparison of photo-activity of three types of titanium dioxide (TiO2) micro-dispersions intended for use as UV filters for cosmetic sunscreen products. The dispersions were also investigated with regard to their influence on the stability of photo-protective systems in cosmetic emulsions, their skin penetration/absorption and their photo-toxicity for humans and skin bacterial flora. All the tested micro-dispersions of rutile TiO2 type (agglomerates with diameter 120-150 nm), with primary particle size lower than 100 nm, demonstrated no phototoxic effect and insignificant antimicrobial behaviour. On the other hand, TiO2 with insufficient deactivation of photo-activity had significant negative impact on the stability of other organic UV filters and therefore on the stability of declared UV protective factors (SPF, UVA-PF). The study demonstrated that the level of deactivation of TiO2 is one of the highly important factors for evaluation of UV filters used as sunscreens.

  7. Multifunctional Single-Phase Photocatalysts: Extended Near Infrared Photoactivity and Reliable Magnetic Recyclability

    PubMed Central

    Li, Xiaoning; Zhu, Zhu; Li, Feng; Huang, Yan; Hu, Xiang; Huang, Haoliang; Peng, Ranran; Zhai, XiaoFang; Fu, Zhengping; Lu, Yalin

    2015-01-01

    A practical photocatalyst should be able to integrate together various functions including the extended solar conversion, a feasible and economic recyclability, and above the room temperature operation potential, et al., in order to fulfill the spreading application needs in nowadays. In this report, a multifunctional single-phase photocatalyst which possesses a high photoactivity extended into the near infrared region, an easy magnetic recyclability and the high temperature stability was developed by doping Co into a new layer-structured Bi7Fe3Ti3O21 material. Light absorption and photocatalytic activity of the resulted Bi7Fe3-xCoxTi3O21 photocatalyst were extended to the long wavelength as far as 800 nm. Its strong ferromagnetism above the room temperature enables the nanopowders fully recyclable in viscous solutions simply with a magnet bar in an experimental demonstration. Furthermore, such photoactivity and magnetic recyclability were heavily tested under high-temperature and high-viscosity conditions, which was intended to simulate the actual industrial environments. This work brings the bright light to a full availability of a new multifunctional photocatalyst, via integrating the much enhanced ferromagnetic, ferroelectric, optoelectronic properties, most importantly, into a single-phase structure. PMID:26503907

  8. Thermal Annealing Effect on Poly(3-hexylthiophene): Fullerene:Copper-Phthalocyanine Ternary Photoactive Layer

    PubMed Central

    Derouiche, H.; Mohamed, A. B.

    2013-01-01

    We have fabricated poly(3-hexylthiophene) (P3HT)/copper phthalocyanine (CuPc)/fullerene (C60) ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT/PSS) photoanode and a bathocuproine (BCP)/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM) and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the I-V characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc0.5:C600.5/BCP/Al and ITO/PEDOT:PSS/P3HT0.3:CuPc0.3:C600.4/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation. PMID:23766722

  9. Understanding the adsorptive and photoactivity properties of Ag-graphene oxide nanocomposites.

    PubMed

    Martínez-Orozco, R D; Rosu, H C; Lee, Soo-Wohn; Rodríguez-González, V

    2013-12-15

    Nanocomposites of graphene oxide (GO) and silver nanoparticles (AgNPs) were synthetized using a practical photochemical silver functionalization. Their photocatalytic activities were evaluated with two dyes, Rhodamine B and Indigo Carmine, under visible-light irradiation. The prepared nanocomposites were characterized by HRTEM, FESEM, XRD, Raman, FTIR and UV-vis absorption spectroscopy. These nanocomposites present new defect domains of sp(3) type in combination with several graphitic functional groups that act as nucleation sites for anchoring AgNPs, while the sp(2)-sp(3) edge defects domains of GO generate the photoactivity. Furthermore, their photocatalytic performances are governed by their large adsorption capacity, and strong interaction with dye chromophores. A comprehensive photocatalytic way underlying the importance of adsorption is suggested to explain the low visible-light responsive photoactivity of the AgNPs-GO nanocomposites and the possible binding-site saturation. Then, the usage of H2SO4 allows the production of ionic species and helps to confirm the strong adsorption of both dyes. The ability to synthesize AgNPs-GO nanocomposites with extensive adsorptive capacity is certainly of interest for the efficient removal of hazardous materials.

  10. n-Type reduced graphene oxide field-effect transistors (FETs) from photoactive metal oxides.

    PubMed

    Yoo, Heejoun; Kim, Youngmin; Lee, Junghyun; Lee, Hyemi; Yoon, Yeoheung; Kim, Giyoun; Lee, Hyoyoung

    2012-04-16

    Graphene is of considerable interest as a next-generation semiconductor material to serve as a possible substitute for silicon. For real device applications with complete circuits, effective n-type graphene field effect transistors (FETs) capable of operating even under atmospheric conditions are necessary. In this study, we investigated n-type reduced graphene oxide (rGO) FETs of photoactive metal oxides, such as TiO(2) and ZnO. These metal oxide doped FETs showed slight n-type electric properties without irradiation. Under UV light these photoactive materials readily generated electrons and holes, and the generated electrons easily transferred to graphene channels. As a result, the graphene FET showed strong n-type electric behavior and its drain current was increased. These n-doping effects showed saturation curves and slowly returned back to their original state in darkness. Finally, the n-type rGO FET was also highly stable in air due to the use of highly resistant metal oxides and robust graphene as a channel.

  11. Photoactive transparent nano-crystalline glass-ceramic for remazole red dye degradation

    SciTech Connect

    Gad-Allah, Tarek A.; Margha, Fatma H.

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► Preparation and characterization of novel transparent nanocrystalline glass-ceramic. ► Precipitation of photoactive phases by using controlled heat-treatment. ► Conservation of transparency along with photoactivity. ► Using the prepared nanocrystalline glass-ceramic in water purification. -- Abstract: Transparent glass ceramic material was prepared from alkali-borosilicate glass containing titania by proper heat treatment scheme. The prepared samples were characterized using differential thermal analysis, X-ray diffraction, transmission electron microscope, selected area electron diffraction and UV–visible spectroscopy. The applied heat treatment program allowed the crystallization of nano-crystalline anatase, rutile, barium titanate, titanium borate and silicate phases while maintaining the transparency. The precipitated nano-crystalline anatase and rutile phases were responsible for the observed high photocatalytic activity of the prepared samples. Samples of 24.29 and 32.39 TiO{sub 2} wt% showed better efficiency for the decolorization of remazole red dye compared with commercial-TiO{sub 2} used in preparation of glass-ceramic. The reuse of prepared glass-ceramic photocatalyst with nearly same efficiency for different times was also proved.

  12. Thermal annealing effect on poly(3-hexylthiophene): fullerene:copper-phthalocyanine ternary photoactive layer.

    PubMed

    Derouiche, H; Mohamed, A B

    2013-01-01

    We have fabricated poly(3-hexylthiophene) (P3HT)/copper phthalocyanine (CuPc)/fullerene (C60) ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT/PSS) photoanode and a bathocuproine (BCP)/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM) and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the I-V characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc₀.₅:C60₀.₅/BCP/Al and ITO/PEDOT:PSS/P3HT₀.₃:CuPc₀.₃:C60₀.₄/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation.

  13. Design of photoactive ruthenium complexes to study electron transfer and proton pumping in cytochrome oxidase.

    PubMed

    Durham, Bill; Millett, Francis

    2012-04-01

    This review describes the development and application of photoactive ruthenium complexes to study electron transfer and proton pumping reactions in cytochrome c oxidase (CcO). CcO uses four electrons from Cc to reduce O(2) to two waters, and pumps four protons across the membrane. The electron transfer reactions in cytochrome oxidase are very rapid, and cannot be resolved by stopped-flow mixing techniques. Methods have been developed to covalently attach a photoactive tris(bipyridine)ruthenium group [Ru(II)] to Cc to form Ru-39-Cc. Photoexcitation of Ru(II) to the excited state Ru(II*), a strong reductant, leads to rapid electron transfer to the ferric heme group in Cc, followed by electron transfer to Cu(A) in CcO with a rate constant of 60,000s(-1). Ruthenium kinetics and mutagenesis studies have been used to define the domain for the interaction between Cc and CcO. New ruthenium dimers have also been developed to rapidly inject electrons into Cu(A) of CcO with yields as high as 60%, allowing measurement of the kinetics of electron transfer and proton release at each step in the oxygen reduction mechanism.

  14. Echistatin disulfide bridges: selective reduction and linkage assignment.

    PubMed Central

    Gray, W. R.

    1993-01-01

    Echistatin is the smallest member of the disintegrin family of snake venom proteins, containing four disulfides in a peptide chain of 49 residues. Partial assignment of disulfides has been made previously by NMR and chemical approaches. A full assignment was made by a newly developed chemical approach, using partial reduction with tris-(2-carboxyethyl)-phosphine at acid pH. Reduction proceeded in a stepwise manner at pH 3, and the intermediates were isolated by high performance liquid chromatography. Alkylation of free thiols, followed by sequencer analysis, enabled all four bridges to be identified: (1) at 20 degrees C a single bridge linking Cys 2-Cys 11 was broken, giving a relatively stable intermediate; (2) with further treatment at 41 degrees C the bridges Cys 7-Cys 32 and Cys 8-Cys 37 became accessible to the reagent and were reduced at approx. equal rates; (3) the two bicyclic peptides produced in this manner were less stable and could be reduced at 20 degrees C to a peptide that retains a single bridge linking Cys 20-Cys 39; and (4) the monocyclic peptide can be reduced to the linear molecule at 20 degrees C. Some disulfide exchange occurred during alkylation of the bicyclic intermediates, but results unambiguously show the pattern to be [2-11; 7-32; 8-37; 20-39]. A comparison is made with kistrin, a longer disintegrin whose disulfide structure has been proposed from NMR analysis. PMID:8251946

  15. Response of soil organisms to dimethyl disulfide fumigation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    After the commonly used soil fumigant methyl bromide (MeBr) was phased out in the United States, alternatives to MeBr such as dimethyl disulfide (DMDS) which is known to have broad pest control spectrum, is increasingly used. However, effectiveness of DMDS has been mainly investigated to study targe...

  16. Synthesis of unsymmetric disulfides as potential antiradiation drugs

    SciTech Connect

    Womble, S.W.

    1988-01-01

    This research involved the synthesis of unsymmetric disulfides which contain the radioprotective compound cysteamine attached to a biologically active molecule via a disulfide linkage. This study involved the synthesis of unsymmetric disulfides of cysteamine with amino acids, amino acid esters, steroidal thiols, glutathione, and other known radio-protective compounds which were submitted for biological evaluation. It is hoped that by attaching a known radioprotective compound to a molecule such as an amino acid or steroid we may obtain an enhanced concentration of the radioprotective substance in the target areas within the cell. The use of steroidal thiols coupled to cysteamine may result in the protection of the central nervous system for which there is no known radioprotective agent available. In the second part of this work a synthesis of a thiol containing polymer was developed which would give a highly functionalized product. This thiol containing polymer can be utilized in a solid phase synthesis scheme for the preparation of unsymmetric disulfides free of side products.

  17. Topology of the disulfide bonds in the antiviral lectin scytovirin

    PubMed Central

    Moulaei, Tinoush; Stuchlik, Olga; Reed, Matthew; Yuan, Weirong; Pohl, Jan; Lu, Wuyuan; Haugh-Krumpe, Lauren; O'Keefe, Barry R; Wlodawer, Alexander

    2010-01-01

    The antiviral lectin scytovirin (SVN) contains a total of five disulfide bonds in two structurally similar domains. Previous reports provided contradictory results on the disulfide pairing in each individual domain, and we have now re-examined the disulfide topology. N-terminal sequencing and mass spectrometry were used to analyze proteolytic fragments of native SVN obtained at acidic pH, yielding the assignment as Cys7–Cys55, Cys20–Cys32, Cys26–Cys38, Cys68–Cys80, and Cys74–Cys86. We also analyzed the N-terminal domain of SVN (SD1, residues 1–48) prepared by expression/oxidative folding of the recombinant protein and by chemical synthesis. The disulfide pairing in the chemically synthesized SD1 was forced into predetermined topologies: SD1A (Cys20–Cys26, Cys32–Cys38) or SD1B (Cys20–Cys32, Cys26–Cys38). The topology of native SVN was found to be in agreement with the SD1B and the one determined for the recombinant SD1 domain. Although the two synthetic forms of SD1 were distinct when subjected to chromatography, their antiviral properties were indistinguishable, having low nM activity against HIV. Tryptic fragments, the “cystine clusters” [Cys20–Cys32/Cys26–Cys38; SD1] and [Cys68–Cys80/Cys74–C-86; SD2], were found to undergo rapid disulfide interchange at pH 8. This interchange resulted in accumulation of artifactual fragments in alkaline pH digests that are structurally unrelated to the original topology, providing a rational explanation for the differences between the topology reported herein and the one reported earlier (Bokesh et al., Biochemistry 2003;42:2578–2584). Our observations emphasize the fact that proteins such as SVN, with disulfide bonds in close proximity, require considerable precautions when being fragmented for the purpose of disulfide assignment. PMID:20572021

  18. Semienzymatic Cyclization of Disulfide-rich Peptides Using Sortase A*

    PubMed Central

    Jia, Xinying; Kwon, Soohyun; Wang, Ching-I Anderson; Huang, Yen-Hua; Chan, Lai Y.; Tan, Chia Chia; Rosengren, K. Johan; Mulvenna, Jason P.; Schroeder, Christina I.; Craik, David J.

    2014-01-01

    Disulfide-rich cyclic peptides have generated great interest in the development of peptide-based therapeutics due to their exceptional stability toward chemical, enzymatic, or thermal attack. In particular, they have been used as scaffolds onto which bioactive epitopes can be grafted to take advantage of the favorable biophysical properties of disulfide-rich cyclic peptides. To date, the most commonly used method for the head-to-tail cyclization of peptides has been native chemical ligation. In recent years, however, enzyme-mediated cyclization has become a promising new technology due to its efficiency, safety, and cost-effectiveness. Sortase A (SrtA) is a bacterial enzyme with transpeptidase activity. It recognizes a C-terminal penta-amino acid motif, LPXTG, and cleaves the amide bond between Thr and Gly to form a thioacyl-linked intermediate. This intermediate undergoes nucleophilic attack by an N-terminal poly-Gly sequence to form an amide bond between the Thr and N-terminal Gly. Here, we demonstrate that sortase A can successfully be used to cyclize a variety of small disulfide-rich peptides, including the cyclotide kalata B1, α-conotoxin Vc1.1, and sunflower trypsin inhibitor 1. These peptides range in size from 14 to 29 amino acids and contain three, two, or one disulfide bond, respectively, within their head-to-tail cyclic backbones. Our findings provide proof of concept for the potential broad applicability of enzymatic cyclization of disulfide-rich peptides with therapeutic potential. PMID:24425873

  19. Influence of tungsten content, swaging, and grain size on the viscoplastic response of tungsten heavy alloys

    SciTech Connect

    Ramesh, K.T.

    1992-12-31

    The response of tungsten-nickel-iron (W-Ni-Fe) alloys to high rates of deformation has been investigated using compression and torsional Kolsky bars. The influence of tungsten content, swaging, and grain size on the dynamic behavior of commercially available alloys has been examined, The results indicate that the flow stresses sustained by these materials have a distinct dependence on strain rate, over a range from 10(exp {minus}4)/sec to 7 x 10(exp 3)/sec. The rate sensitivity itself appears to be influenced by tungsten content and degree of prior swaging, but appears to be almost independent of tungsten grain size. Metallographic analyses and microhardness measurements were performed to study the microstructural evolution with increasing strain at high rates. Adiabatic shear localization has been observed in high-rate shearing tests; relatively narrow shear bands are formed, followed immediately by catastrophic fracture.

  20. Visible emission spectroscopy of highly charged tungsten ions in LHD: II. Evaluation of tungsten ion temperature

    NASA Astrophysics Data System (ADS)

    Fujii, K.; Takahashi, Y.; Nakai, Y.; Kato, D.; Goto, M.; Morita, S.; Hasuo, M.; Experiment Group2, LHD

    2015-12-01

    We demonstrated a polarization-resolved high resolution spectroscopy of a visible emission line of highly charged tungsten ions (λ0 = 668.899 nm, Shinohara et al Phys. Scr. 90 125402) for the large helical device (LHD) plasma, where the tungsten ions were introduced by a pellet injection. Its spectral profile shows broadening and polarization dependence, which are attributed to the Doppler and Zeeman effects, respectively. The tungsten ion temperature was evaluated for the first time from the broadening of visible the emission line, with its emission location determined by the Abel inversion of the chord-integrated emission intensities observed with multiple chords. The tungsten ion temperature was found to be close to the helium-like argon ion temperature, which is used as an ion temperature monitor in LHD.

  1. Electrical Properties of Tungsten Filaments and Films Fabricated by the Reduction of Tungsten Hexafluoride by Silicon.

    NASA Astrophysics Data System (ADS)

    Feinerman, Alan Dov

    1987-12-01

    A novel method of photolithography has been developed for fabricating ultrathin tungsten filaments and films. It is based on the selective deposition of tungsten via low pressure chemical vapor deposition on undoped polycrystalline silicon. Tungsten filaments have been fabricated with heights from 93nm down to 5nm, and with lengths from 10 to 350mu. Tungsten films from 3 to 49nm were simultaneously fabricated on the same silicon wafer. The self-limiting thickness of the deposited tungsten layer, and the amount of encroachment of tungsten into the silicon/silicon dioxide interface is affected by the surface treatment used immediately prior to the tungsten deposition. Various plasma and wet chemical treatments have been studied. A quick etch of the polycrystalline silicon in a dilute mixture of HF in HNO_ {3} acid minimizes encroachment. Encroachment is maximized by etching in CF_{4} /O_{2} plasma. Both treatments are isotropic etches of silicon. The resistance of the filaments and films has been measured from.05 to 400K and in magnetic fields up to 5 tesla. The filaments and films have a superconducting transition temperature (T_{rm c}) between.7 and 4.1K, and a critical field larger than 5 tesla. The superconducting transitions are very broad, possibly due to a distribution of grain sizes and strain. The high values obtained for T_ {rm c} and the x-ray diffraction studies suggest that the tungsten deposits in both alpha and beta phases. The broad superconducting transition suppresses localization and electron-electron interactions effects. The temperature dependence of the resistance between 30 and 400K is different for films and filaments. The filaments and films were deposited simultaneously and there should be no dimensionality effects in this temperature range.

  2. Thermal cycling and high power density hydrogen ion beam irradiation of tungsten layers on tungsten substrate

    NASA Astrophysics Data System (ADS)

    Airapetov, A. A.; Begrambekov, L. B.; Gretskaya, I. Yu; Grunin, A. V.; Dyachenko, M. Yu; Puntakov, N. A.; Sadovskiy, Ya A.

    2016-09-01

    Tungsten layers with iron impurity were deposited on tungsten substrates modeling re-deposited layers in a fusion device. The samples were tested by thermocycling and hydrogen ion beam tests. Thermocycling revealed globule formation on the surface. The size of the globules depended on iron impurity content in the coating deposited. Pore formation was observed which in some cases lead to exfoliation of the coatings. Hydrogen ion irradiation lead to formation of blisters on the coating and finally its exfoliation.

  3. First examples of oxidizing secondary alcohols to ketones in the presence of the disulfide functional group: synthesis of novel diketone disulfides.

    PubMed

    Fang, X; Bandarage, U K; Wang, T; Schroeder, J D; Garvey, D S

    2001-06-01

    The disulfide functionality is present in a number of organic compounds of interest in the fields of both chemistry and biology. Because the disulfide group is known to be highly susceptible to further oxidation by a wide range of agents, performing a chemoselective oxidation without further oxidizing the disulfide moiety poses a synthetic challenge. Reported herein are the first examples of such a chemoselective oxidation in which a series of novel secondary alcohol disulfides 2a-f have been converted to the corresponding symmetrical diketones 3a-f utilizing a modified Swern oxidation.

  4. Examination of the effect of increasing the number of intra-disulfide amino functional groups on the performance of small molecule cyclic polyamine disulfide vectors.

    PubMed

    Drake, Christopher R; Aissaoui, Abderrahim; Argyros, Orestis; Thanou, Maya; Steinke, Joachim H G; Miller, Andrew D

    2013-10-10

    Establishing structure-activity relationships is vital if the efficacy of non-viral vectors is to match that of their viral counter-parts. Recently, we reported on the ability of a series of small molecule, cyclic polyamine disulfides to condense and cage plasmid DNA (pDNA) by a process of thermodynamically controlled templated polymerization, leading to a series of corresponding pDNA-polyplex nanoparticles able to mediate high levels of transfection with no associated cytotoxicities. The leading cyclic polyamine disulfide was shown to be the spermine tetra-amine disulfide (TetraN-3,4,3). Herein we report on the significantly more challenging syntheses of cyclic disulfides with longer polyamine motifs. Two new cyclic polyamine disulfides, based on hexa- and octa-amine inserts, were prepared and their transfection efficacies and cytotoxicities compared with our previously reported cyclic tri- and tetra-amine disulfides. The new cyclic hexa- and octa-amine disulfides prove more effective at transfection in vitro, especially of lung epithelial A549 cell line. By contrast, our original cyclic tetra-amine disulfide remains the most efficient agent for the transfection of lung epithelial cells in vivo following intra-nasal administration. Hypothetical mechanistic reasons are presented to explain this outcome. Our data in toto support the concept of shorter cyclic polyamine disulfides as preferred agents for polycation-mediated controlled condensation and functional delivery of pDNA to lung epithelial cells in vivo.

  5. Visible light photoinactivation of bacteria by tungsten oxide nanostructures formed on a tungsten foil

    NASA Astrophysics Data System (ADS)

    Ghasempour, Fariba; Azimirad, Rouhollah; Amini, Abbas; Akhavan, Omid

    2015-05-01

    Antibacterial activity of tungsten oxide nanorods/microrods were studied against Escherichia coli bacteria under visible light irradiation and in dark. A two-step annealing process at temperatures up to 390 °C and 400-800 °C was applied to synthesize the tungsten oxide nanorods/microrods on tungsten foils using KOH as a catalyst. Annealing the foils at 400 °C in the presence of catalyst resulted in formation of tungsten oxide nanorods (with diameters of 50-90 nm and crystalline phase of WO3) on surface of tungsten foils. By increasing the annealing temperature up to 800 °C, tungsten oxide microrods with K2W6O19 crystalline phase were formed on the foils. The WO3 nanorods showed a strong antibacterial property under visible light irradiation, corresponding to >92% bacterial inactivation within 24 h irradiation at room temperature, while the K2W6O19 microrods formed at 800 °C could inactivate only ∼45% of the bacteria at the same conditions.

  6. Plasma-enhanced etching of tungsten, tungsten silicide, and molybdenum in chlorine-containing discharges

    SciTech Connect

    Fischl, D.S.

    1988-01-01

    Thin films of tungsten, tungsten silicide, and molybdenum were etched both within and downstream from Cl{sub 2} discharges. Without a discharge, molecular chlorine did not etch the films. Experimental conditions ranged from 0.1 to 1.0 Torr pressure, 30 to 180{degree}C electrode temperature, 0.2 to 1.0 W/cm{sup 2} power density, and 3 to 200 sccm flow rate. In-discharge etch rates varied from 10 to 90 nm/min for tungsten (W), 10 to 450 nm/min for tungsten silicide (WSi{sub x}), and 1 to 8 nm/min for molybdenum (Mo). Small additions of BCl{sub 3}, during W and WSi{sub x} etching, significantly increased the etch rates and improved the reproducibility. When samples were positioned downstream from a Cl{sub 2} discharge, etching proceeded solely by chemical reaction of the film with chlorine atoms. Downstream and in-plasma tungsten etch rates were approximately equal at 110{degree}C, but the chlorine atom etch rate dropped more rapidly than the in-plasma etch rate as temperature decreased. In contrast, molybdenum etched faster by atoms alone than in the plasma, although atom etching was not observed below 100{degree}C. Reactions of tungsten with a modulated beam of chlorine atoms and molecules were also studied.

  7. Gas-driven permeation of deuterium through tungsten and tungsten alloys

    DOE PAGES

    Buchenauer, Dean A.; Karnesky, Richard A.; Fang, Zhigang Zak; ...

    2016-03-25

    Here, to address the transport and trapping of hydrogen isotopes, several permeation experiments are being pursued at both Sandia National Laboratories (deuterium gas-driven permeation) and Idaho National Laboratories (tritium gas- and plasma-driven tritium permeation). These experiments are in part a collaboration between the US and Japan to study the performance of tungsten at divertor relevant temperatures (PHENIX). Here we report on the development of a high temperature (≤1150 °C) gas-driven permeation cell and initial measurements of deuterium permeation in several types of tungsten: high purity tungsten foil, ITER-grade tungsten (grains oriented through the membrane), and dispersoid-strengthened ultra-fine grain (UFG) tungstenmore » being developed in the US. Experiments were performed at 500–1000 °C and 0.1–1.0 atm D2 pressure. Permeation through ITER-grade tungsten was similar to earlier W experiments by Frauenfelder (1968–69) and Zaharakov (1973). Data from the UFG alloy indicates marginally higher permeability (< 10×) at lower temperatures, but the permeability converges to that of the ITER tungsten at 1000 °C. The permeation cell uses only ceramic and graphite materials in the hot zone to reduce the possibility for oxidation of the sample membrane. Sealing pressure is applied externally, thereby allowing for elevation of the temperature for brittle membranes above the ductile-to-brittle transition temperature.« less

  8. Electrospark doping of steel with tungsten

    SciTech Connect

    Denisova, Yulia Shugurov, Vladimir; Seksenalina, Malika; Ivanova, Olga Ikonnikova, Irina; Kunitsyna, Tatyana Vlasov, Victor; Klopotov, Anatoliy; Ivanov, Yuriy

    2016-01-15

    The paper is devoted to the numerical modeling of thermal processes and the analysis of the structure and properties of the surface layer of carbon steel subjected to electrospark doping with tungsten. The problem of finding the temperature field in the system film (tungsten) / substrate (iron) is reduced to the solution of the heat conductivity equation. A one-dimensional case of heating and cooling of a plate with the thickness d has been considered. Calculations of temperature fields formed in the system film / substrate synthesized using methods of electrospark doping have been carried out as a part of one-dimensional approximation. Calculations have been performed to select the mode of the subsequent treatment of the system film / substrate with a high-intensity pulsed electron beam. Authors revealed the conditions of irradiation allowing implementing processes of steel doping with tungsten. A thermodynamic analysis of phase transformations taking place during doping of iron with tungsten in equilibrium conditions has been performed. The studies have been carried out on the surface layer of the substrate modified using the method of electrospark doping. The results showed the formation in the surface layer of a structure with a highly developed relief and increased strength properties.

  9. Gas tungsten arc welder with electrode grinder

    DOEpatents

    Christiansen, David W.; Brown, William F.

    1984-01-01

    A welder for automated closure of fuel pins by a gas tungsten arc process in which a rotating length of cladding is positioned adjacent a welding electrode in a sealed enclosure. An independently movable axial grinder is provided in the enclosure for refurbishing the used electrode between welds.

  10. Joining of Tungsten Armor Using Functional Gradients

    SciTech Connect

    John Scott O'Dell

    2006-12-31

    The joining of low thermal expansion armor materials such as tungsten to high thermal expansion heat sink materials has been a major problem in plasma facing component (PFC) development. Conventional planar bonding techniques have been unable to withstand the high thermal induced stresses resulting from fabrication and high heat flux testing. During this investigation, innovative functional gradient joints produced using vacuum plasma spray forming techniques have been developed for joining tungsten armor to copper alloy heat sinks. A model was developed to select the optimum gradient architecture. Based on the modeling effort, a 2mm copper rich gradient was selected. Vacuum plasma pray parameters and procedures were then developed to produce the functional gradient joint. Using these techniques, dual cooling channel, medium scale mockups (32mm wide x 400mm length) were produced with vacuum plasma spray formed tungsten armor. The thickness of the tungsten armor was up to 5mm thick. No evidence of debonding at the interface between the heat sink and the vacuum plasma sprayed material was observed.

  11. Processing and alloying of tungsten heavy alloys

    SciTech Connect

    Bose, A.; Dowding, R.J.

    1993-12-31

    Tungsten heavy alloys are two-phase metal matrix composites with a unique combination of density, strength, and ductility. They are processed by liquid-phase sintering of mixed elemental powders. The final microstructure consists of a contiguous network of nearly pure tungsten grains embedded in a matrix of a ductile W-Ni-Fe alloy. Due to the unique property combination of the material, they are used extensively as kinetic energy penetrators, radiation shields. counterbalances, and a number of other applications in the defense industry. The properties of these alloys are extremely sensitive to the processing conditions. Porosity levels as low as 1% can drastically degrade the properties of these alloys. During processing, care must be taken to reduce or prevent incomplete densification, hydrogen embrittlement, impurity segregation to the grain boundaries, solidification shrinkage induced porosity, and in situ formation of pores due to the sintering atmosphere. This paper will discuss some of the key processing issues for obtaining tungsten heavy alloys with good properties. High strength tungsten heavy alloys are usually fabricated by swaging and aging the conventional as-sintered material. The influence of this on the shear localization tendency of a W-Ni-Co alloy will also be demonstrated. Recent developments have shown that the addition of certain refractory metals partially replacing tungsten can significantly improve the strength of the conventional heavy alloys. This development becomes significant due to the recent interest in near net shaping techniques such as powder injection moldings. The role of suitable alloying additions to the classic W-Ni-Fe based heavy alloys and their processing techniques will also be discussed in this paper.

  12. Magnetic Fe@g-C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes

    EPA Science Inventory

    A photoactive catalyst, Fe@g-C3N4, has been developed for the hydrogenation of alkenes and alkynes using hydrazine hydrate as a source of hydrogen. The magnetically separable Fe@g-C3N4 eliminates the use of high pressure hydrogenation and the reaction can be accomplished using vi...

  13. Virus Capsids as Targeted Nanoscale Delivery Vessels of Photoactive Compounds for Site-Specific Photodynamic Therapy

    NASA Astrophysics Data System (ADS)

    Cohen, Brian A.

    The research presented in this work details the use of a viral capsid as an addressable delivery vessel of photoactive compounds for use in photodynamic therapy. Photodynamic therapy is a treatment that involves the interaction of light with a photosensitizing molecule to create singlet oxygen, a reactive oxygen species. Overproduction of singlet oxygen in cells can cause oxidative damage leading to cytotoxicity and eventually cell death. Challenges with the current generation of FDA-approved photosensitizers for photodynamic therapy primarily stem from their lack of tissue specificity. This work describes the packaging of photoactive cationic porphyrins inside the MS2 bacteriophage capsid, followed by external modification of the capsid with cancer cell-targeting G-quadruplex DNA aptamers to generate a tumor-specific photosensitizing agent. First, a cationic porphyrin is loaded into the capsids via nucleotide-driven packaging, a process that involves charge interaction between the porphyrin and the RNA inside the capsid. Results show that over 250 porphyrin molecules associate with the RNA within each MS2 capsid. Removal of RNA from the capsid severely inhibits the packaging of the cationic porphyrins. Porphyrin-virus constructs were then shown to photogenerate singlet oxygen, and cytotoxicity in non-targeted photodynamic treatment experiments. Next, each porphyrin-loaded capsid is externally modified with approximately 60 targeting DNA aptamers by employing a heterobifunctional crosslinking agent. The targeting aptamer is known to bind the protein nucleolin, a ubiquitous protein that is overexpressed on the cell surface by many cancer cell types. MCF-7 human breast carcinoma cells and MCF-10A human mammary epithelial cells were selected as an in vitro model for breast cancer and normal tissue, respectively. Fluorescently tagged virus-aptamer constructs are shown to selectively target MCF-7 cells versus MCF-10A cells. Finally, results are shown in which porphyrin

  14. Preparation of photoactive polymers and postmodification via nitroxide trapping under UV irradiation.

    PubMed

    Mardyukov, Artur; Studer, Armido

    2013-01-11

    New types of photoactive homo and block copolymers bearing α-hydroxyalkylphenylketone (2-hydroxy-2-methyl-1-phenylpropan-1-one) moieties as backbone substituents are prepared using nitroxide-mediated radical polymerization (NMP). Such polymers can be readily activated via the Norrish-type I photoreaction to give polymeric acyl radicals. Photolysis in the presence of a persistent nitroxide, which serves as a C- radical trapping reagent, leads to chemically modified polymers conjugated with nitroxide moieties. The number-average molecular weight (M(n)) of the prepolymers and the chemically modified polymers was determined by gel permeation chromatography (GPC). Structures were further confirmed by NMR spectroscopy and by attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy.

  15. Design and application of carbon nanomaterials for photoactive and charge transport layers in organic solar cells

    NASA Astrophysics Data System (ADS)

    Jin, Sunghwan; Jun, Gwang Hoon; Jeon, Seokwoo; Hong, Soon Hyung

    2016-04-01

    Commercialization of organic solar cell (OSC) has faltered due to their low power conversion efficiency (PCE) compared to inorganic solar cell. Low electrical conductivity, low charge mobility, and short-range light absorption of most organic materials limit the PCE of OSCs. Carbon nanomaterials, especially carbon nanotubes (CNTs) and graphenes, are of great interest for use in OSC applications due to their high electrical conductivity, mobility, and unique optical properties for enhancing the performance of OSCs. In this review, recent progress toward the integration of carbon nanomaterials into OSCs is described. The role of carbon nanomaterials and strategies for their integration into various layers of OSCs, including the photoactive layer and charge transport layer, are discussed. Based on these, we also discuss the prospects of carbon nanomaterials for specific OSC layers to maximize the PCE.

  16. Design and application of carbon nanomaterials for photoactive and charge transport layers in organic solar cells.

    PubMed

    Jin, Sunghwan; Jun, Gwang Hoon; Jeon, Seokwoo; Hong, Soon Hyung

    2016-01-01

    Commercialization of organic solar cell (OSC) has faltered due to their low power conversion efficiency (PCE) compared to inorganic solar cell. Low electrical conductivity, low charge mobility, and short-range light absorption of most organic materials limit the PCE of OSCs. Carbon nanomaterials, especially carbon nanotubes (CNTs) and graphenes, are of great interest for use in OSC applications due to their high electrical conductivity, mobility, and unique optical properties for enhancing the performance of OSCs. In this review, recent progress toward the integration of carbon nanomaterials into OSCs is described. The role of carbon nanomaterials and strategies for their integration into various layers of OSCs, including the photoactive layer and charge transport layer, are discussed. Based on these, we also discuss the prospects of carbon nanomaterials for specific OSC layers to maximize the PCE.

  17. Plasmon enhanced broadband optical absorption in ultrathin silicon nanobowl array for photoactive devices applications

    SciTech Connect

    Sun, Rui-Nan; Peng, Kui-Qing Hu, Bo; Hu, Ya; Zhang, Fu-Qiang; Lee, Shuit-Tong

    2015-07-06

    Both photonic and plasmonic nanostructures are key optical components of photoactive devices for light harvesting, enabling solar cells with significant thickness reduction, and light detectors capable of detecting photons with sub-band gap energies. In this work, we study the plasmon enhanced broadband light absorption and electrical properties of silicon nanobowl (SiNB) arrays. The SiNB-metal photonic-plasmonic nanostructure-based devices exhibited superior light-harvesting ability across a wide range of wavelengths up to the infrared regime well below the band edge of Si due to effective optical coupling between the SiNB array and incident sunlight, as well as electric field intensity enhancement around metal nanoparticles due to localized surface plasmon resonance. The photonic-plasmonic nanostructure is expected to result in infrared-light detectors and high-efficiency solar cells by extending light-harvesting to infrared frequencies.

  18. Structural Determinats Underlying Photoprotection in the Photoactive Orange Carotenoid Protein of Cyanobacteria

    SciTech Connect

    Wilson, Adjele; Kinney, James N.; Zwart, Petrus H.; Punginelli, Claire; D'Haene, Sandrine; Perreau, Francois; Klein, Michael G.; Kirilovsky, Diana; Kerfeld, Cheryl

    2010-04-01

    The photoprotective processes of photosynthetic organisms involve the dissipation of excess absorbed light energy as heat. Photoprotection in cyanobacteria is mechanistically distinct from that in plants; it involves the Orange Carotenoid Protein (OCP), a water-soluble protein containing a single carotenoid. The OCP is a new member of the family of blue light photoactive proteins; blue-green light triggers the OCP-mediated photoprotective response. Here we report structural and functional characterization of the wildtype and two mutant forms of the OCP, from the model organism Synechocystis PCC6803. The structural analysis provides highresolution detail of the carotenoidprotein interactions that underlie the optical properties of the OCP, unique among carotenoid-proteins in binding a single pigment per polypeptide chain. Collectively, these data implicate several key amino acids in the function of the OCP and reveal that the photoconversion and photoprotective responses of the OCP to blue-green light can be decoupled.

  19. Fabrication of carbohydrate microarrays on a poly(2-hydroxyethyl methacrylate)-based photoactive substrate.

    PubMed

    Sundhoro, Madanodaya; Wang, Hui; Boiko, Scott T; Chen, Xuan; Jayawardena, H Surangi N; Park, JaeHyeung; Yan, Mingdi

    2016-01-21

    We report the fabrication of carbohydrate microarrays on a photoactive polymer, poly(HEMA-co-HEMA-PFPA), synthesized by RAFT copolymerization of 2-hydroxyethyl methacrylate (HEMA) and perfluorophenyl azide (PFPA)-derivatized HEMA (HEMA-PFPA). PFPA allows the covalent immobilization of carbohydrates whereas the HEMA polymer provides an antifouling surface, thus the microarrays can be used directly without pretreating the array with a blocking agent. The microarrays were prepared by spin-coating the polymer followed by printing the carbohydrates. Subsequent irradiation simultaneously immobilized the carbohydrates and crosslinked the polymer matrix. The obtained 3D carbohydrate microarrays showed enhanced fluorescence signals upon treating with a fluorescent lectin in comparison with a 2D microarray. The signals were acquired at a lower lectin concentration and a shorter incubation time. When treated with E. coli bacteria, the carbohydrate microarray showed results that were consistent with their binding patterns.

  20. Plasmon enhanced broadband optical absorption in ultrathin silicon nanobowl array for photoactive devices applications

    NASA Astrophysics Data System (ADS)

    Sun, Rui-Nan; Peng, Kui-Qing; Hu, Bo; Hu, Ya; Zhang, Fu-Qiang; Lee, Shuit-Tong

    2015-07-01

    Both photonic and plasmonic nanostructures are key optical components of photoactive devices for light harvesting, enabling solar cells with significant thickness reduction, and light detectors capable of detecting photons with sub-band gap energies. In this work, we study the plasmon enhanced broadband light absorption and electrical properties of silicon nanobowl (SiNB) arrays. The SiNB-metal photonic-plasmonic nanostructure-based devices exhibited superior light-harvesting ability across a wide range of wavelengths up to the infrared regime well below the band edge of Si due to effective optical coupling between the SiNB array and incident sunlight, as well as electric field intensity enhancement around metal nanoparticles due to localized surface plasmon resonance. The photonic-plasmonic nanostructure is expected to result in infrared-light detectors and high-efficiency solar cells by extending light-harvesting to infrared frequencies.

  1. Development of Advanced Oxide Dispersion Strengthened Tungsten Heavy Alloy for Penetrator Application

    DTIC Science & Technology

    2005-09-30

    preparation, sintering, cyclic heat-treatment, swaging , and annealing processes, on microstructures and static/dynamic mechanical properties of ODS tungsten ... tungsten / tungsten contiguity. The swaging and annealing processes of ODS tungsten heavy alloy increase the tensile strength with decreasing the...Final Report for 2nd Year Contract of AOARD 034032 Development of Advanced Oxide Dispersion Strengthened Tungsten Heavy Alloy for

  2. Investigation of the compatibility of tungsten and high temperature sodium

    NASA Astrophysics Data System (ADS)

    Xu, Yong-Li; Long, Bin; Xu, Yuan-Chao; Li, Hua-Qing

    2005-08-01

    The compatibility of rotary swaged tungsten and sodium was investigated at 500, 600, 700 °C, and also at 600 °C of polished tungsten. The weight loss curves for the two kinds of W-specimens appear significantly different, however their weight losses approach constant values after testing for 400 h. The asymptotic change in sodium containing 30 μg/g oxygen at 600 °C are about 2.3 and 0.8 mg/cm 2 from 400 to 1500 h, respectively for the rotary swaging tungsten and the polishing tungsten. The corrosion products at the surfaces of two kinds of W-specimens after testing in high temperature sodium are different. The grains show significant growth after testing of both kinds of tungsten. The fracture stress of the rotary swaged tungsten at room temperature decreases considerably after testing with the effect slightly increasing with temperature from 500, 600 to 700 °C. A much smaller decrease of fracture stress is observed for polished tungsten at 600 °C, which already before testing has much smaller value. The micro-morphologies of the fracture surface indicate brittle inter-granular fracture in both kinds of tungsten. Embrittlement becomes much more notable for rotary swaged tungsten, while inter- and trans-granular fracture modes appear after corrosion tests in high temperature sodium for both kinds of tungsten.

  3. Pressure-time profile of multiply shocked carbon disulfide

    NASA Astrophysics Data System (ADS)

    Sutherland, G. T.; Gupta, Y. M.; Bellamy, P. M.

    1986-02-01

    An experimental method was developed to measure the pressure-time profile of a liquid in a reverberation of multiple-shock experiment. Profiles, with peak pressures to 30 kbars, were measured for carbon disulfide using shorted quartz gauges (25.4 mm diameter by 3.15 mm thick); these gauges formed the back surfaces of cells which contained the carbon disulfide. Sapphire plates were used both as impactors and as the front surfaces of the cell. Up to six pressure steps were clearly observed in the quartz-gauge output. Measured pressure-time profiles were compared to profiles calculated with available equations of state. The experiments agreed well with profiles predicted with an equation of state proposed by Sheffield (1983). Calibration experiments were performed to characterize both the initial current response and the subsequent current ramping of the shorted quartz gauges used in this study.

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

    PubMed

    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

    2015-12-21

    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.

  5. Scorpion venom peptides with no disulfide bridges: a review.

    PubMed

    Almaaytah, Ammar; Albalas, Qosay

    2014-01-01

    Scorpion venoms are rich sources of biologically active peptides that are classified into disulfide-bridged peptides (DBPs) and non-disulfide-bridged peptides (NDBPs). DBPs are the main scorpion venom components responsible for the neurotoxic effects observed during scorpion envenomation as they usually target membrane bound ion channels of excitable and non-excitable cells. Several hundred DBPs have been identified and functionally characterized in the past two decades. The NDBPs represent a novel group of molecules that have gained great interest only recently due to their high diversity both in their primary structures and bioactivities. This review provides an overview of scorpion NDBPs focusing on their therapeutic applications, modes of discovery, mechanisms of NDBPs genetic diversity and structural properties. It also provides a simple classification for NDBPs that could be adopted and applied to other NDBPs identified in future studies.

  6. Disulfide isoforms of recombinant glia maturation factor beta.

    PubMed

    Zaheer, A; Lim, R

    1990-09-14

    Recombinant human glia maturation factor beta (r-hGMF-beta) is a single-chain polypeptide (141 amino acid residues) containing three cysteines, at positions 7, 86 and 95. Nascent r-hGMF-beta exists in the reduced state and has no biological activity. The protein can be activated through oxidative refolding by incubation with a mixture of reduced and oxidized glutathione. Reverse-phase HPLC analysis of the refolded r-hGMF-beta shows the presence of four peaks, corresponding to the reduced form plus three newly generated intrachain disulfide-containing isoforms predicted from the number of cysteine residues. Only one isoform shows biological activity when tested for growth suppression on C6 glioma cells. We infer from the HPLC elution pattern that the active form contains the disulfide bridge Cys86-Cys95.

  7. Moderate temperature sodium cells. I - Transition metal disulfide cathodes

    NASA Technical Reports Server (NTRS)

    Abraham, K. M.; Pitts, L.; Schiff, R.

    1980-01-01

    TiS2, VS2, and Nb(1.1)S2 transition metal disulfides were evaluated as cathode materials for a moderate temperature rechargeable Na cell operating at 130 C. The 1st discharge of TiS2 results in a capacity of 0.85 eq/mole; approximately half of the Na in the 1st phase spanning the Na range from zero to 0.30 and almost all the Na in the 2nd phase spanning the 0.37 to 0.80 range are rechargeable. VS2 intercalates up to one mole of Na/mole of VS2 in the 1st discharge; the resulting Na(x)VS2 ternary consists of 3 phases in the 3 ranges of Na from zero to 1. Niobium disulfide undergoes a phase change in the 1st discharge; the average rechargeable capacity in extended cycling of this cathode is 0.50 eq/mole.

  8. High hemoglobin mixed disulfide content in hemolysates from stressed shark.

    PubMed

    Dafré, A L; Reischl, E

    1990-01-01

    1. Hemolysate from heavily stressed smooth hammerhead shark, Sphyrna zygaena, shows three electrophoretic components, SZ I, SZ II and SZ III, whose relative concentrations are 36.4 +/- 6.8, 36.4 +/- 5.0 and 20.8 +/- 5.7%, respectively. After reduction with DTE only SZ I remained. 2. SZ I reacted with glutathione disulfide reconstitute SZ II and SZ III. 3. Non-reduced, DTE-reduced, and denatured hemoglobin were found to have 2.0 +/- 0.4, 3.7 +/- 0.6, and 9.4 +/- 0.7-SH groups, respectively. 4. Erythrocyte non-protein--SH (NPSH), including glutathione present as mixed disulfide with SZ II and SZ III, is 1.7 NPSH/Hb.

  9. Rose bengal in poly(2-hydroxyethyl methacrylate) thin films: self-quenching by photoactive energy traps

    NASA Astrophysics Data System (ADS)

    Ezquerra Riega, Sergio D.; Rodríguez, Hernán B.; San Román, Enrique

    2017-03-01

    The effect of dye concentration on the fluorescence,ΦF, and singlet molecular oxygen,ΦΔ, quantum yields of rose bengal loaded poly(2-hydroxyethyl methacrylate) thin films (∼200 nm thick) was investigated, with the aim of understanding the effect of molecular interactions on the photophysical properties of dyes in crowded constrained environments. Films were characterized by absorption and fluorescence spectroscopy, singlet molecular oxygen (1O2) production was quantified using a chemical monitor, and the triplet decay was determined by laser flash-photolysis. For the monomeric dilute dye, ΦF = 0.05 ± 0.01 and ΦΔ = 0.76 ± 0.14. The effect of humidity and the photostability of the dye were also investigated. Spectral changes in absorption and fluorescence in excess of 0.05 M and concentration self-quenching after 0.01 M are interpreted in the context of a quenching radius model. Calculations of energy migration and trapping rates were performed assuming random distribution of the dye. Best fits of fluorescence quantum yields with concentration are obtained in the whole concentration range with a quenching radius r Q = 1.5 nm, in the order of molecular dimensions. Agreement is obtained only if dimeric traps are considered photoactive, with an observed fluorescence quantum yield ratio ΦF,trap/ΦF,monomer ≈ 0.35. Fluorescent traps are capable of yielding triplet states and 1O2. Results show that the excited state generation efficiency, calculated as the product between the absorption factor and the fluorescence quantum yield, is maximized at around 0.15 M, a very high concentration for random dye distributions. Relevant information for the design of photoactive dyed coatings is provided.

  10. Rose bengal in poly(2-hydroxyethyl methacrylate) thin films: self-quenching by photoactive energy traps.

    PubMed

    Ezquerra Riega, Sergio D; Rodríguez, Hernán B; San Román, Enrique

    2017-03-09

    The effect of dye concentration on the fluorescence,ΦF, and singlet molecular oxygen,ΦΔ, quantum yields of rose bengal loaded poly(2-hydroxyethyl methacrylate) thin films (∼200 nm thick) was investigated, with the aim of understanding the effect of molecular interactions on the photophysical properties of dyes in crowded constrained environments. Films were characterized by absorption and fluorescence spectroscopy, singlet molecular oxygen ((1)O2) production was quantified using a chemical monitor, and the triplet decay was determined by laser flash-photolysis. For the monomeric dilute dye, ΦF = 0.05 ± 0.01 and ΦΔ = 0.76 ± 0.14. The effect of humidity and the photostability of the dye were also investigated. Spectral changes in absorption and fluorescence in excess of 0.05 M and concentration self-quenching after 0.01 M are interpreted in the context of a quenching radius model. Calculations of energy migration and trapping rates were performed assuming random distribution of the dye. Best fits of fluorescence quantum yields with concentration are obtained in the whole concentration range with a quenching radius r Q = 1.5 nm, in the order of molecular dimensions. Agreement is obtained only if dimeric traps are considered photoactive, with an observed fluorescence quantum yield ratio ΦF,trap/ΦF,monomer ≈ 0.35. Fluorescent traps are capable of yielding triplet states and (1)O2. Results show that the excited state generation efficiency, calculated as the product between the absorption factor and the fluorescence quantum yield, is maximized at around 0.15 M, a very high concentration for random dye distributions. Relevant information for the design of photoactive dyed coatings is provided.

  11. Potential Impacts from Using Photoactive Roads as AN Air Quality Mitigation Strategy

    NASA Astrophysics Data System (ADS)

    Toro, C.; Jobson, B. T.; Shen, S.; Chung, S. H.; Haselbach, L.

    2013-12-01

    Mobile sources are major contributors to photochemical air pollution in urban areas. It has been proposed that the use of TiO2 coated roadways ('photoactive roads') could be an effective approach to reduce mobile source emissions by oxidizing NOx and VOC emissions at the roadway surface. However, studies have shown that formation of HONO and aldehydes can occur from some TiO2 treated surfaces during the photocatalytic oxidation of NOx and VOC, respectively. By changing the NOx-to-VOC ratio and generating photolabile HOx radical precursors, photoactive roads may enhance ozone formation rates in urban areas. In this work we present results that quantify NOx and VOC loss rates onto TiO2 treated asphalt and concrete samples, as well as HONO and aldehydes yields that result from the photocatalytic process. The treatment used a commercially available product. These objectives are relevant considering that the quantification of pollutant loss rates and yields of byproducts have not been determined for asphalt and that in the US more than 90% of the roadway surface is made of this material. Surface reaction probabilities (γ) and byproduct yields were determined using a CSTR photochemical chamber under varying conditions of water vapor and UV-A light intensity. Our results indicate that asphalt surfaces have a significantly higher molar yield of HONO compared to concrete surfaces with similar TiO2 loading. Concrete surfaces have reaction probabilities with NO one order of magnitude higher than asphalt samples. Fresh asphalt samples showed negligible photocatalytic activity, presumably due to absorption of TiO2 into the bitumen substrate. Laboratory-prepared asphalt samples with a higher degree of exposed aggregates showed increased HONO molar yields when compared to real-road asphalt samples, whose HONO molar yield was ~1%. Preliminary results for aldehydes formation showed similar molar yields between aged asphalt and concrete, even though aged asphalt samples had twice

  12. Photoactive layer-by-layer films of cellulose phosphate and titanium dioxide containing phosphotungstic acid

    NASA Astrophysics Data System (ADS)

    Ullah, Sajjad; Acuña, José Javier Sáez; Pasa, André Avelino; Bilmes, Sara A.; Vela, Maria Elena; Benitez, Guillermo; Rodrigues-Filho, Ubirajara Pereira

    2013-07-01

    A versatile layer-by-layer (LbL) procedure for the preparation of highly dispersed, adherent and porous multilayer films of TiO2 nanoparticles (NPs) and phosphotungstic acid (HPW) on a variety of substrates at room temperature was developed based on the use of cellulose phosphate (CP) as an efficient and non-conventional polyelectrolyte. UV/vis absorption spectroscopy confirmed the linear and regular growth of the films with the number of immersion cycles and a strong adsorption ability of CP towards TiO2 NPs. FTIR spectroscopy showed that HPW binds to the surface of TiO2 through the oxygen atom at the corner of the Keggin structure. XPS results showed that the interaction between TiO2 and CP is through Ti-O-P linkage. A model is proposed for the TiO2-HPW interaction based on XPS and FTIR results. FEG/SEM study of the surface morphology revealed a porous film structure with a homogenous distribution of the TiO2 NPs induced by CP. HRTEM studies showed that the resulting composite films consist of crystalline anatase and rutile phases and poly-nano-crystalline HPW with a semi-crystalline TiO2-HPW interface. These CP/TiO2 and CP/TiO2/HPW LbL films showed good photoactivity against both saturated and unsaturated species, for instance, stearic acid (SA), crystal violet (CV) and methylene blue (MB) under UV irradiation. The CP/HPW films formed on bacterial cellulose (BC) showed good photochromic response which is enhanced in presence of TiO2 due to an interfacial electron transfer from TiO2 to HPW. This simple and environmentally safe method can be used to form coatings on a variety of surfaces with photoactive TiO2 and TiO2/HPW films.

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

    NASA Astrophysics Data System (ADS)

    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

  14. Performance and Safety Characteristics of Lithium-molybdenum Disulfide Cells

    NASA Technical Reports Server (NTRS)

    Stiles, J. A.

    1984-01-01

    The lithium-molybdenum disulfide system offers attractive characteristics including high rate capability, successful operation up to 75 C, a very low self-discharge rate, a good cycle life and safety characteristics which compare favorably to those of other lithium cells. Moreover, the materials and manufacturing costs for the system is effectively controlled, so the cells should ultimately be competitive with currently marketed rechargeable cells.

  15. Oxidation of kinetically trapped thiols by protein disulfide isomerase.

    PubMed

    Walker, K W; Gilbert, H F

    1995-10-17

    The formation of a stabilized structure during oxidative protein folding can severely retard disulfide formation if the structure must be disrupted to gain access to buried cysteines. These kinetic traps can slow protein folding and disulfide bond formation to the extent that unassisted folding is too slow to be kinetically competent in the cell. Protein disulfide isomerase (PDI) facilitates the oxidation of a kinetically trapped state of RTEM-1 beta-lactamase in which two cysteines that form the single disulfide bond in the native protein are buried and approximately 500-fold less reactive than exposed cysteines. Under second-order conditions, PDI-dependent oxidation of reduced, folded beta-lactamase is 500-fold faster than GSSG-dependent oxidation. The rate difference observed between PDI and GSSG can be accounted for by the 520-fold higher kinetic reactivity of PDI as an oxidant. Noncovalent interactions between PDI (35 microM) and beta-lactamase increase the reactivity or unfolding of beta-lactamase in the steady-state by less than 3-fold. At high concentrations of PDI or alkylating agents, the reaction of beta-lactamase cysteines approaches a constant rate, limited by the spontaneous unfolding of the protein (kunfold = 0.024 +/- 0.005 min-1). PDI does not substantially increase the rate of beta-lactamase unfolding; however, once beta-lactamase spontaneously unfolds, PDI at concentrations greater than 44 +/- 4 microM, oxidizes the unfolded substrate before it can refold (kfold = 1.5 +/- 0.2 min-1).(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Vanadium nitride functionalization and denitrogenation by carbon disulfide and dioxide.

    PubMed

    Brask, Justin K; Durà-Vilà, Víctor; Diaconescu, Paula L; Cummins, Christopher C

    2002-04-21

    A dramatic difference in behavior is observed for the dithiocarbamate and carbamate complexes [Ar(But)N]3V(NCE2)Na(THF)2(E = S or O, respectively), prepared from the corresponding nitride species ([Ar(But)N]3V identical to NNa)2 by way of a nucleophilic addition reaction involving carbon disulfide or dioxide, and is rationalized with the aid of DFT calculations.

  17. Selective Gas-Phase Ion/Ion Reactions: Enabling Disulfide Mapping via Oxidation and Cleavage of Disulfide Bonds in Intermolecularly-Linked Polypeptide Ions.

    PubMed

    Pilo, Alice L; McLuckey, Scott A

    2016-09-20

    The selective gas-phase oxidation of disulfide bonds to their thiosulfinate form using ion/ion reactions and subsequent cleavage is demonstrated here. Oxidizing reagent anions are observed to attach to all polypeptides, regardless of amino acid composition. Direct proton transfer yielding a charge-reduced peptide is also frequently observed. Activation of the ion/ion complex between an oxidizing reagent anion and a disulfide-containing peptide cation results in oxygen transfer from the reagent anion to the peptide cation to form the [M+H+O](+) species. This thiosulfinate derivative can undergo one of several rearrangements that result in cleavage of the disulfide bond. Species containing an intermolecular disulfide bond undergo separation of the two chains upon activation. Further activation can be used to generate more sequence information from each chain. These oxidation ion/ion reactions have been used to illustrate the identification of S-glutathionylated and S-cysteinylated peptides, in which low molecular weight thiols are attached to cysteine residues in peptides via disulfide bonds. The oxidation chemistry effectively labels peptide ions with readily oxidized groups, such as disulfide bonds. This enables a screening approach for the identification of disulfide-linked peptides in a disulfide mapping application involving enzymatic digestion. The mixtures of ions generated by tryptic and peptic digestions of lysozyme and insulin, respectively, without prior separation or isolation were subjected both to oxidation and proton transfer ion/ion chemistry to illustrate the identification of peptides in the mixtures with readily oxidized groups.

  18. Femtosecond fiber laser additive manufacturing of tungsten

    NASA Astrophysics Data System (ADS)

    Bai, Shuang; Liu, Jian; Yang, Pei; Zhai, Meiyu; Huang, Huan; Yang, Lih-Mei

    2016-04-01

    Additive manufacturing (AM) is promising to produce complex shaped components, including metals and alloys, to meet requirements from different industries such as aerospace, defense and biomedicines. Current laser AM uses CW lasers and very few publications have been reported for using pulsed lasers (esp. ultrafast lasers). In this paper, additive manufacturing of Tungsten materials is investigated by using femtosecond (fs) fiber lasers. Various processing conditions are studied, which leads to desired characteristics in terms of morphology, porosity, hardness, microstructural and mechanical properties of the processed components. Fully dense Tungsten part with refined grain and increased hardness was obtained and compared with parts made with different pulse widths and CW laser. The results are evidenced that the fs laser based AM provides more dimensions to modify mechanical properties with controlled heating, rapid melting and cooling rates compared with a CW or long pulsed laser. This can greatly benefit to the make of complicated structures and materials that could not be achieved before.

  19. Bend ductility of tungsten heavy alloys

    SciTech Connect

    Gurwell, W.E.; Garnich, M.R.; Dudder, G.B.; Lavender, C.A.

    1992-11-01

    A bend ductility test is used to indicate the formability of tungsten heavy alloys sheet. The primary test bends a notchless Charpy impact specimen to a bend angle of approximately 100C. This can be augmented by a bend-completion test. Finite element modeling as well as strain-gaged bend specimens elucidate the strain distribution in the specimen as a function of material thickness and bend angle. The bend ductilities of 70%W, 807.W and 90%W alloys are characterized. As expected, decreasing thickness or tungsten content enhances bend ductility. Oxidation is not detrimental; therefore, controlled atmosphere is not required for cooling. The potentially detrimental effects of mechanical working (e.g., rolling, roller-leveling, grit blasting, and peening) and machining (e.g., cutting and sanding) are illustrated.

  20. Ultrasonic ranking of toughness of tungsten carbide

    NASA Technical Reports Server (NTRS)

    Vary, A.; Hull, D. R.

    1983-01-01

    The feasibility of using ultrasonic attenuation measurements to rank tungsten carbide alloys according to their fracture toughness was demonstrated. Six samples of cobalt-cemented tungsten carbide (WC-Co) were examined. These varied in cobalt content from approximately 2 to 16 weight percent. The toughness generally increased with increasing cobalt content. Toughness was first determined by the Palmqvist and short rod fracture toughness tests. Subsequently, ultrasonic attenuation measurements were correlated with both these mechanical test methods. It is shown that there is a strong increase in ultrasonic attenuation corresponding to increased toughness of the WC-Co alloys. A correlation between attenuation and toughness exists for a wide range of ultrasonic frequencies. However, the best correlation for the WC-Co alloys occurs when the attenuation coefficient measured in the vicinity of 100 megahertz is compared with toughness as determined by the Palmqvist technique.

  1. Dissecting the Machinery That Introduces Disulfide Bonds in Pseudomonas aeruginosa

    PubMed Central

    Arts, Isabelle S.; Ball, Geneviève; Leverrier, Pauline; Garvis, Steven; Nicolaes, Valérie; Vertommen, Didier; Ize, Bérengère; Tamu Dufe, Veronica; Messens, Joris; Voulhoux, Romé; Collet, Jean-François

    2013-01-01

    ABSTRACT Disulfide bond formation is required for the folding of many bacterial virulence factors. However, whereas the Escherichia coli disulfide bond-forming system is well characterized, not much is known on the pathways that oxidatively fold proteins in pathogenic bacteria. Here, we report the detailed unraveling of the pathway that introduces disulfide bonds in the periplasm of the human pathogen Pseudomonas aeruginosa. The genome of P. aeruginosa uniquely encodes two DsbA proteins (P. aeruginosa DsbA1 [PaDsbA1] and PaDsbA2) and two DsbB proteins (PaDsbB1 and PaDsbB2). We found that PaDsbA1, the primary donor of disulfide bonds to secreted proteins, is maintained oxidized in vivo by both PaDsbB1 and PaDsbB2. In vitro reconstitution of the pathway confirms that both PaDsbB1 and PaDsbB2 shuttle electrons from PaDsbA1 to membrane-bound quinones. Accordingly, deletion of both P. aeruginosa dsbB1 (PadsbB1) and PadsbB2 is required to prevent the folding of several P. aeruginosa virulence factors and to lead to a significant decrease in pathogenicity. Using a high-throughput proteomic approach, we also analyzed the impact of PadsbA1 deletion on the global periplasmic proteome of P. aeruginosa, which allowed us to identify more than 20 new potential substrates of this major oxidoreductase. Finally, we report the biochemical and structural characterization of PaDsbA2, a highly oxidizing oxidoreductase, which seems to be expressed under specific conditions. By fully dissecting the machinery that introduces disulfide bonds in P. aeruginosa, our work opens the way to the design of novel antibacterial molecules able to disarm this pathogen by preventing the proper assembly of its arsenal of virulence factors. PMID:24327342

  2. Modeling of Nano-Tungsten Sintering Data

    DTIC Science & Technology

    2011-04-01

    penetration as that of depleted uranium -3/4% titanium penetrators. This type of behavior produces superior penetration performance (3). For the...Depleted Uranium Replacement Program (DURP), the source of tungsten powder feed stock with a low (~1%) concentration of oxygen was the Chongyi Zhangyuan...then spray dried to remove the solvent . A compact of the powder is formed either by cold iso-static pressing or die pressing. Next, the compact is

  3. Thermal positron interactions with alkali covered tungsten

    NASA Astrophysics Data System (ADS)

    Yamashita, Takashi; Iida, Shimpei; Terabe, Hiroki; Nagashima, Yasuyuki

    2016-11-01

    The branching ratios of positron reemission, positronium emission, positronium negative ion emission and capture to the surface state for thermalized positrons at polycrystalline tungsten surfaces coated with Na, K and Cs have been measured. The data shows that the ratios depend on the coverage of the alkali-metal coating. The fraction of the emitted positronium increases with the coverage of the coating up to 90%.

  4. Mobility, Geochemistry, and Speciation of Tungsten

    DTIC Science & Technology

    2008-12-01

    deionized water used had a resistivity of 18.3 MΩ . cm. Sodium carbonate, sodium polytungstate, and sodium tungstate dihydrate was purchased from Sigma... tungstate anion, although polymerization to form poly- and heteropoly- tungstates has been shown to occur. The current study investigates tungsten...are found in a variety of minerals, which can dissolve to yield the tungstate in most common environmental matrices (Seiler, Stollenwerk, and

  5. Plasma-enhanced chemical vapor deposition of tungsten films

    NASA Astrophysics Data System (ADS)

    Chu, J. K.; Tang, C. C.; Hess, D. W.

    1982-07-01

    High-purity films of tungsten are deposited from tungsten hexafluoride and hydrogen using plasma-enhanced deposition (PED). At 400 °C deposition temperature, resistivities of ˜40 μΩ cm are attained. After annealing at 1100 °C, the resistivity falls to ˜7 μΩ cm. Below 400 °C, the as-deposited film stress is <6×109 dynes/cm2. Tensile, unlike tungsten, molybdenum films deposited by PED displayed high resistivities.

  6. Ballistic performance of oriented columnar-grained tungsten polycrystals

    SciTech Connect

    Leonard, W.; Magness, L.S.; Dowding, R.J.; Trogolo, J.; Chung, M.; Kapoor, D.

    1996-06-01

    Prior ballistic tests have demonstrated that the crystallographic orientation of a single crystal tungsten penetrator with respect to the penetrator axis influences penetration performance. The difference in penetration performance is attributed to anisotropy of the flow and failure of the monocrystalline tungsten penetrators during the penetration of the armor target. In preliminary ballistic experiments, the performance and deformation behaviors of polycrystalline tungsten penetrators having columnar grains oriented in the [100], [110], or [111] crystallographic directions were explored.

  7. Growth rate modeling for selective tungsten LPCVD

    NASA Astrophysics Data System (ADS)

    Wolf, H.; Streiter, R.; Schulz, S. E.; Gessner, T.

    1995-10-01

    Selective chemical vapor deposition of tungsten plugs on sputtered tungsten was performed in a single-wafer cold-wall reactor using silane (SiH 4) and tungsten hexafluoride (WF 6). Extensive SEM measurements of film thickness were carried out to study the dependence of growth rates on various process conditions, wafer loading, and via dimensions. The results have been interpreted by numerical calculations based on a simulation model which is also presented. Both continuum fluid dynamics and the ballistic line-of-sight approach are used for transport modeling. The reaction rate is described by an empirical rate expression using coefficients fitted from experimental data. In the range 0.2 < p( SiH 4) /p( WF 6) < 0.75 , the reaction order was determined as 1.55 and -0.55 with respect to SiH 4 and WF 6, respectively. For higher partial pressure ratios the second-order rate dependence on p(SiH 4) and the minus first-order dependence on p(WF 6) were confirmed.

  8. Controlled nanostructuration of polycrystalline tungsten thin films

    SciTech Connect

    Girault, B.; Eyidi, D.; Goudeau, P.; Guerin, P.; Bourhis, E. Le; Renault, P.-O.; Sauvage, T.

    2013-05-07

    Nanostructured tungsten thin films have been obtained by ion beam sputtering technique stopping periodically the growing. The total thickness was maintained constant while nanostructure control was obtained using different stopping periods in order to induce film stratification. The effect of tungsten sublayers' thicknesses on film composition, residual stresses, and crystalline texture evolution has been established. Our study reveals that tungsten crystallizes in both stable {alpha}- and metastable {beta}-phases and that volume proportions evolve with deposited sublayers' thicknesses. {alpha}-W phase shows original fiber texture development with two major preferential crystallographic orientations, namely, {alpha}-W<110> and unexpectedly {alpha}-W<111> texture components. The partial pressure of oxygen and presence of carbon have been identified as critical parameters for the growth of metastable {beta}-W phase. Moreover, the texture development of {alpha}-W phase with two texture components is shown to be the result of a competition between crystallographic planes energy minimization and crystallographic orientation channeling effect maximization. Controlled grain size can be achieved for the {alpha}-W phase structure over 3 nm stratification step. Below, the {beta}-W phase structure becomes predominant.

  9. The tungsten divertor experiment at ASDEX Upgrade

    NASA Astrophysics Data System (ADS)

    Neu, R.; Asmussen, K.; Krieger, K.; Thoma, A.; Bosch, H.-S.; Deschka, S.; Dux, R.; Engelhardt, W.; García-Rosales, C.; Gruber, O.; Herrmann, A.; Kallenbach, A.; Kaufmann, M.; Mertens, V.; Ryter, F.; Rohde, V.; Roth, J.; Sokoll, M.; Stäbler, A.; Suttrop, W.; Weinlich, M.; Zohm, H.; Alexander, M.; Becker, G.; Behler, K.; Behringer, K.; Behrisch, R.; Bergmann, A.; Bessenrodt-Weberpals, M.; Brambilla, M.; Brinkschulte, H.; Büchl, K.; Carlson, A.; Chodura, R.; Coster, D.; Cupido, L.; de Blank, H. J.; de Peña Hempel, S.; Drube, R.; Fahrbach, H.-U.; Feist, J.-H.; Feneberg, W.; Fiedler, S.; Franzen, P.; Fuchs, J. C.; Fußmann, G.; Gafert, J.; Gehre, O.; Gernhardt, J.; Haas, G.; Herppich, G.; Herrmann, W.; Hirsch, S.; Hoek, M.; Hoenen, F.; Hofmeister, F.; Hohenöcker, H.; Jacobi, D.; Junker, W.; Kardaun, O.; Kass, T.; Kollotzek, H.; Köppendörfer, W.; Kurzan, B.; Lackner, K.; Lang, P. T.; Lang, R. S.; Laux, M.; Lengyel, L. L.; Leuterer, F.; Manso, M. E.; Maraschek, M.; Mast, K.-F.; McCarthy, P.; Meisel, D.; Merkel, R.; Müller, H. W.; Münich, M.; Murmann, H.; Napiontek, B.; Neu, G.; Neuhauser, J.; Niethammer, M.; Noterdaeme, J.-M.; Pasch, E.; Pautasso, G.; Peeters, A. G.; Pereverzev, G.; Pitcher, C. S.; Poschenrieder, W.; Raupp, G.; Reinmüller, K.; Riedl, R.; Röhr, H.; Salzmann, H.; Sandmann, W.; Schilling, H.-B.; Schlögl, D.; Schneider, H.; Schneider, R.; Schneider, W.; Schramm, G.; Schweinzer, J.; Scott, B. D.; Seidel, U.; Serra, F.; Speth, E.; Silva, A.; Steuer, K.-H.; Stober, J.; Streibl, B.; Treutterer, W.; Troppmann, M.; Tsois, N.; Ulrich, M.; Varela, P.; Verbeek, H.; Verplancke, Ph; Vollmer, O.; Wedler, H.; Wenzel, U.; Wesner, F.; Wolf, R.; Wunderlich, R.; Zasche, D.; Zehetbauer, T.; Zehrfeld, H.-P.

    1996-12-01

    Tungsten-coated tiles, manufactured by plasma spray on graphite, were mounted in the divertor of the ASDEX Upgrade tokamak and cover almost 90% of the surface facing the plasma in the strike zone. Over 600 plasma discharges have been performed to date, around 300 of which were auxiliary heated with heating powers up to 10 MW. The production of tungsten in the divertor was monitored by a W I line at 400.8 nm. In the plasma centre an array of spectral lines at 5 nm emitted by ionization states around W XXX was measured. From the intensity of these lines the W content was derived. Under normal discharge conditions W-concentrations around 0741-3335/38/12A/013/img12 or even lower were found. The influence on the main plasma parameters was found to be negligible. The maximum concentrations observed decrease with increasing heating power. In several low power discharges accumulation of tungsten occurred and the temperature profile was flattened. The concentrations of the intrinsic impurities carbon and oxygen were comparable to the discharges with the graphite divertor. Furthermore, the density and the 0741-3335/38/12A/013/img13 limits remained unchanged and no negative influence on the energy confinement or on the H-mode threshold was found. Discharges with neon radiative cooling showed the same behaviour as in the graphite divertor case.

  10. Microstructure and properties of CVD tungsten carbide from tungsten hexafluoride and dimethyl ether

    SciTech Connect

    Skaf, D.W.; Warner, A.W.; Dollahon, N.R.; Fargo, G.H. )

    1994-12-01

    Tungsten carbide was deposited from tungsten hexafluoride, dimethyl ether, and hydrogen using a horizontal, cold-wall reactor. The effects of substrate temperature, reactor pressure, and reagent ratio on the coating growth rate, morphology, composition, and microhardness were studied. Under most conditions, the solid deposit was primarily W[sub 3]C with minor amounts of W. The tungsten carbide growth rate data fit an Arrhenius rate expression for temperatures from 425 to 550 C and had an activation energy of 24 kcal/mol at 70 mmHg total pressure and a WF[sub 6]/DME ratio of 6.3. A variety of surface morphologies and microstructures were observed. The microhardness of the coated substrates increased with coating thickness to a maximum value of 2,400 kg/mm[sup 2].

  11. Secondary electron emission from plasma-generated nanostructured tungsten fuzz

    NASA Astrophysics Data System (ADS)

    Patino, M.; Raitses, Y.; Wirz, R.

    2016-11-01

    Recently, several researchers [e.g., Yang et al., Sci. Rep. 5, 10959 (2015)] have shown that tungsten fuzz can grow on a hot tungsten surface under bombardment by energetic helium ions in different plasma discharges and applications, including magnetic fusion devices with plasma facing tungsten components. This work reports the direct measurements of the total effective secondary electron emission (SEE) from tungsten fuzz. Using dedicated material surface diagnostics and in-situ characterization, we find two important results: (1) SEE values for tungsten fuzz are 40%-63% lower than for smooth tungsten and (2) the SEE values for tungsten fuzz are independent of the angle of the incident electron. The reduction in SEE from tungsten fuzz is most pronounced at high incident angles, which has important implications for many plasma devices since in a negative-going sheath the potential structure leads to relatively high incident angles for the electrons at the plasma confining walls. Overall, low SEE will create a relatively higher sheath potential difference that reduces plasma electron energy loss to the confining wall. Thus, the presence or self-generation in a plasma of a low SEE surface such as tungsten fuzz can be desirable for improved performance of many plasma devices.

  12. Reactive deposition of tungsten and titanium carbides by induction plasma

    NASA Astrophysics Data System (ADS)

    Jiang, X. L.; Gitzhofer, F.; Boulos, M. I.; Tiwari, R.

    1995-05-01

    A study is reported on the use of induction plasma technology for the preparation of dense free-standing deposits of tungsten carbide and titanium carbide from metallic powders and methane. Phase analysis by X-ray diffraction indicates that primary carburization of the particles takes place in-flight giving rise to the formation of W2C and TiC(1 - x). Secondary carburization occurs in the deposits resulting in the formation of tungsten and titanium carbides. Microstructures revealed by optical and scanning electron microscopy show uniform small grains of the carbides. The reactive plasma spray-formed tungsten carbide shows transgranular fracture, while pure tungsten deposits show intergranular fracture.

  13. Tungsten-induced carcinogenesis in human bronchial epithelial cells

    PubMed Central

    Laulicht, Freda; Brocato, Jason; Cartularo, Laura; Vaughan, Joshua; Wu, Feng; Kluz, Thomas; Sun, Hong; Oksuz, Betul Akgol; Shen, Steven; Paena, Massimilano; Medici, Serenella; Zoroddu, Maria Antonietta; Costa, Max

    2015-01-01

    Metals such as arsenic, cadmium, beryllium, and nickel are known human carcinogens; however, other transition metals, such as tungsten (W), remain relatively uninvestigated with regard to their potential carcinogenic activity. Tungsten production for industrial and military applications has almost doubled over the past decade and continues to increase. Here, for the first time, we demonstrate tungsten’s ability to induce carcinogenic related endpoints including cell transformation, increased migration, xenograft growth in nude mice, and the activation of multiple cancer related pathways in transformed clones as determined by RNA seq. Human bronchial epithelial cell line (Beas-2B) exposed to tungsten developed carcinogenic properties. In a soft agar assay, tungsten-treated cells formed more colonies than controls and the tungsten-transformed clones formed tumors in nude mice. RNA-sequencing data revealed that the tungsten-transformed clones altered the expression of many cancer-associated genes when compared to control clones. Genes involved in lung cancer, leukemia, and general cancer genes were deregulated by tungsten. Taken together, our data shows the carcinogenic potential of tungsten. Further tests are needed, including in vivo and human studies, in order to validate tungsten as a carcinogen to humans. PMID:26164860

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

    SciTech Connect

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

    1984-11-13

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

  15. Secondary electron emission from plasma-generated nanostructured tungsten fuzz

    SciTech Connect

    Patino, M.; Raitses, Y.; Wirz, R.

    2016-11-14

    Recently, several researchers (e.g., Q. Yang, Y.-W. You, L. Liu, H. Fan, W. Ni, D. Liu, C. S. Liu, G. Benstetter, and Y. Wang, Scientific Reports 5, 10959 (2015)) have shown that tungsten fuzz can grow on a hot tungsten surface under bombardment by energetic helium ions in different plasma discharges and applications, including magnetic fusion devices with plasma facing tungsten components. This work reports direct measurements of the total effective secondary electron emission (SEE) from tungsten fuzz. Using dedicated material surface diagnostics and in-situ characterization, we find two important results: (1) SEE values for tungsten fuzz are 40-63% lower than for smooth tungsten and (2) the SEE values for tungsten fuzz are independent of the angle of the incident electron. The reduction in SEE from tungsten fuzz is most pronounced at high incident angles, which has important implications for many plasma devices since in a negative-going sheath the potential structure leads to relatively high incident angles for the electrons at the plasma confining walls. Overall, low SEE will create a relatively higher sheath potential difference that reduces plasma electron energy loss to the confining wall. Thus the presence or self-generation in a plasma of a low SEE surface such as tungsten fuzz can be desirable for improved performance of many plasma devices.:7px

  16. Secondary electron emission from plasma-generated nanostructured tungsten fuzz

    DOE PAGES

    Patino, M.; Raitses, Y.; Wirz, R.

    2016-11-14

    Recently, several researchers (e.g., Q. Yang, Y.-W. You, L. Liu, H. Fan, W. Ni, D. Liu, C. S. Liu, G. Benstetter, and Y. Wang, Scientific Reports 5, 10959 (2015)) have shown that tungsten fuzz can grow on a hot tungsten surface under bombardment by energetic helium ions in different plasma discharges and applications, including magnetic fusion devices with plasma facing tungsten components. This work reports direct measurements of the total effective secondary electron emission (SEE) from tungsten fuzz. Using dedicated material surface diagnostics and in-situ characterization, we find two important results: (1) SEE values for tungsten fuzz are 40-63% lowermore » than for smooth tungsten and (2) the SEE values for tungsten fuzz are independent of the angle of the incident electron. The reduction in SEE from tungsten fuzz is most pronounced at high incident angles, which has important implications for many plasma devices since in a negative-going sheath the potential structure leads to relatively high incident angles for the electrons at the plasma confining walls. Overall, low SEE will create a relatively higher sheath potential difference that reduces plasma electron energy loss to the confining wall. Thus the presence or self-generation in a plasma of a low SEE surface such as tungsten fuzz can be desirable for improved performance of many plasma devices.:7px« less

  17. Radical induced disulfide bond cleavage within peptides via ultraviolet irradiation of an electrospray plume.

    PubMed

    Stinson, Craig A; Xia, Yu

    2013-05-21

    Radical induced disulfide bond cleavage in peptides was demonstrated by ultraviolet (UV) radiation of the electrospray ionization (ESI) plume using a low pressure mercury (LP-Hg) lamp. Tandem mass spectrometry and accurate mass measurements confirmed that the primary reaction products were due to disulfide bond cleavage to form thiol (-SH) and sulfinyl radical (-SO˙). Mechanistic studies showed that the 185 nm emission from a LP-Hg lamp was responsible for UV photolysis of atmospheric O2, which further initiated secondary radical formation and subsequent disulfide bond cleavage by radical attack. The radical induced disulfide bond cleavage was found to be analytically useful in providing rich sequence information for naturally occurring peptides containing intrachain disulfide bonds. The utility of this method was also demonstrated for facile disulfide peptide identification and characterization from protein digests.

  18. Do Vicinal Disulfide Bridges Mediate Functionally Important Redox Transformations in Proteins?

    PubMed Central

    de Araujo, Aline Dantas; Herzig, Volker; Windley, Monique J.; Dziemborowicz, Sławomir; Mobli, Mehdi; Nicholson, Graham M.

    2013-01-01

    Abstract Vicinal disulfide bridges, in which a disulfide bond is formed between adjacent cysteine residues, constitute an unusual but expanding class of potential allosteric disulfides. Although vicinal disulfide rings (VDRs) are relatively uncommon, they have proven to be functionally critical in almost all proteins in which they have been discovered. However, it has proved difficult to test whether these sterically constrained disulfides participate in functionally important redox transformations. We demonstrate that chemical replacement of VDRs with dicarba or diselenide bridges can be used to assess whether VDRs function as allosteric disulfides. Our approach leads to the hypothesis that not all VDRs participate in functionally important redox reactions. Antioxid. Redox Signal. 19, 1976–1980. PMID:23646911

  19. Toxicologic evaluation of tungsten: 28-day inhalation study of tungsten blue oxide in rats.

    PubMed

    Rajendran, Narayanan; Hu, Shu-Chieh; Sullivan, Dennis; Muzzio, Miguel; Detrisac, Carol J; Venezia, Carmen

    2012-12-01

    The toxicity and toxicokinetics of tungsten blue oxide (TBO) were examined. TBO is an intermediate in the production of tungsten powder, and has shown the potential to cause cellular damage in in vitro studies. However, in vivo evidence seems to indicate a lack of adverse effects. The present study was undertaken to address the dearth of longer-term inhalation toxicity studies of tungsten oxides by investigating the biological responses induced by TBO when administered via nose-only inhalation to rats at levels of 0.08, 0.325, and 0.65 mg TBO/L of air for 6 h/day for 28 consecutive days, followed by a 14-day recovery period. Inhaled TBO was absorbed systemically and blood levels of tungsten increased as inhaled concentration increased. Among the tissues analyzed for tungsten levels, lung, femur and kidney showed increased levels, with lung at least an order of magnitude greater than kidney or femur. By exposure day 14, tungsten concentration in tissues had reached steady-state. Increased lung weight was noted for both terminal and recovery animals and was attributed to deposition of TBO in the lungs, inducing a macrophage influx. Microscopic evaluation of tissues revealed a dose-related increase in alveolar pigmented macrophages, alveolar foreign material and individual alveolar foamy macrophages in lung. After a recovery period there was a slight reduction in the incidence and severity of histopathological findings. Based on the absence of other adverse effects, the increased lung weights and the microscopic findings were interpreted as nonadverse response to exposure and were not considered a specific reaction to TBO.

  20. A visible light-sensitive tungsten carbide/tungsten trioxde composite photocatalyst

    SciTech Connect

    Kim, Young-ho; Irie, Hiroshi; Hashimoto, Kazuhito

    2008-05-05

    A photocatalyst composed of tungsten carbide (WC) and tungsten oxide (WO{sub 3}) has been prepared by the mechanical mixing of each powder. Its photocatalytic activity was evaluated by the gaseous isopropyl alcohol decomposition process. The photocatalyst showed high visible light photocatalytic activity with a quantum efficiency of 3.2% for 400-530 nm light. The photocatalytic mechanism was explained by means of enhanced oxygen reduction reaction due to WC, which may serve as a multielectron reduction catalyst, as well as the photogeneration of holes in the valence band of WO{sub 3}.

  1. Boron carbide coating deposition on tungsten and testing of tungsten layers and coating under intense plasma load

    SciTech Connect

    Airapetov, A. A.; Begrambekov, L. B.; Buzhinskiy, O. I.; Grunin, A. V.; Gordeev, A. A.; Zakharov, A. M.; Kalachev, A. M.; Sadovskiy, Ya. A.; Shigin, P. A.

    2015-12-15

    A device intended for boron carbide coating deposition and material testing under high heat loads is presented. A boron carbide coating 5 μm thick was deposited on the tungsten substrate. These samples were subjected to thermocycling loads in the temperature range of 400–1500°C. Tungsten layers deposited on tungsten substrates were tested in similar conditions. Results of the surface analysis are presented.

  2. Disulfides as cyanide antidotes: evidence for a new in vivo oxidative pathway for cyanide detoxification.

    PubMed

    Zottola, Mark A; Beigel, Keith; Soni, Sunil-Datta; Lawrence, Richard

    2009-12-01

    It is known that cyanide is converted to thiocyanate in the presence of the enzyme rhodanese. The enzyme is activated by sulfur transfer from an appropriate sulfur donor. The activated enzyme then binds cyanide and transfers the sulfur atom to cyanide to form thiocyanate. This project began as an exploration of the ability of disulfides to act as sulfur donors in the rhodanese-mediated detoxification of cyanide. To our surprise, and contrary to expectations based on efficacy studies in vivo, our in vitro results showed that disulfides are rather poor sulfur donors. The transfer of a sulfur atom from a disulfide to the enzyme must occur via cleavage of a carbon-sulfur bond either of the original disulfide or in a mixed disulfide arising from the reaction of rhodanese with the original disulfide. Extending the reaction time and addition of chloride anion (a nucleophile) did not significantly change the results of the experiment. Using ultrasound as a means of accelerating bond cleavage also had a minimal effect. Those results ruled out cleavage of the carbon-sulfur bond in the original disulfide but did not preclude formation of a mixed disulfide. S-Methyl methylthiosulfonate (MTSO) was used to determine whether a mixed disulfide, if formed, would result in transfer of a sulfur atom to rhodanese. While no thiocyanate was formed in the reaction between cyanide and rhodanese exposed to MTSO, NMR analysis revealed that MTSO reacted directly with cyanide anion to form methyl thiocyanate. This result reveals the body's possible use of oxidized disulfides as a first line of defense against cyanide intoxication. The oxidation of disulfides to the corresponding thiosulfinate or thiosulfonate will result in facilitating their reaction with other nucleophiles. The reaction of an oxidized disulfide with a sulfur nucleophile from glutathione could be a plausible origin for the cyanide metabolite 2-aminothiazoline-4-carboxylic acid.

  3. Method for removal of asphaltene depositions with amine-activated disulfide oil

    SciTech Connect

    Sharp, S.P.

    1983-04-12

    A method for treating and removing unwanted asphaltene deposits from oil and gas wells, surface equipment, flow lines, and pore spaces of oil-baring formations comprises treatment with an amine -activated aliphatic disulfide oil as an asphaltene solvent. In a preferred aspect, the aliphatic disulfide oil is a dialkyl disulfide oil and is activated by the addition of 10 weight percent of diethylamine. In a specific use, the activated disulfide oil is used to remove asphaltene deposits from an oilbearing formation and a producing well penetrating the formation.

  4. Imaging disulfide dinitroxides at 250 MHz to monitor thiol redox status.

    PubMed

    Elajaili, Hanan; Biller, Joshua R; Rosen, Gerald M; Kao, Joseph P Y; Tseytlin, Mark; Buchanan, Laura A; Rinard, George A; Quine, Richard W; McPeak, Joseph; Shi, Yilin; Eaton, Sandra S; Eaton, Gareth R

    2015-11-01

    Measurement of thiol-disulfide redox status is crucial for characterization of tumor physiology. The electron paramagnetic resonance (EPR) spectra of disulfide-linked dinitroxides are readily distinguished from those of the corresponding monoradicals that are formed by cleavage of the disulfide linkage by free thiols. EPR spectra can thus be used to monitor the rate of cleavage and the thiol redox status. EPR spectra of (1)H,(14)N- and (2)H,(15)N-disulfide dinitroxides and the corresponding monoradicals resulting from cleavage by glutathione have been characterized at 250 MHz, 1.04 GHz, and 9 GHz and imaged by rapid-scan EPR at 250 MHz.

  5. Steps in reductive activation of the disulfide-generating enzyme Ero1p

    PubMed Central

    Heldman, Nimrod; Vonshak, Ohad; Sevier, Carolyn S; Vitu, Elvira; Mehlman, Tevie; Fass, Deborah

    2010-01-01

    Ero1p is the primary catalyst of disulfide bond formation in the yeast endoplasmic reticulum (ER). Ero1p contains a pair of essential disulfide bonds that participate directly in the electron transfer pathway from substrate thiol groups to oxygen. Remarkably, elimination of certain other Ero1p disulfides by mutation enhances enzyme activity. In particular, the C150A/C295A Ero1p mutant exhibits increased thiol oxidation in vitro and in vivo and interferes with redox homeostasis in yeast cells by hyperoxidizing the ER. Inhibitory disulfides of Ero1p are thus important for enzyme regulation. To visualize the differences between de-regulated and wild-type Ero1p, we determined the crystal structure of Ero1p C150A/C295A. The structure revealed local changes compared to the wild-type enzyme around the sites of mutation, but no conformational transitions within 25 Å of the active site were observed. To determine how the C150—C295 disulfide nonetheless participates in redox regulation of Ero1p, we analyzed using mass spectrometry the changes in Ero1p disulfide connectivity as a function of time after encounter with reducing substrates. We found that the C150—C295 disulfide sets a physiologically appropriate threshold for enzyme activation by guarding a key neighboring disulfide from reduction. This study illustrates the diverse and interconnected roles that disulfides can play in redox regulation of protein activity. PMID:20669236

  6. Radiation inactivation of ricin occurs with transfer of destructive energy across a disulfide bridge

    SciTech Connect

    Haigler, H.T.; Woodbury, D.J.; Kempner, E.S.

    1985-08-01

    The ionizing radiation sensitivity of ricin, a disulfide-linked heterodimeric protein, was studied as a model to determine the ability of disulfide bonds to transmit destructive energy. The radiation-dependent loss of A chain enzymatic activity after irradiation of either intact ricin or ricin in which the interchain disulfide bond was disrupted gave target sizes corresponding to the molecular size of dimeric ricin or monomeric A chain, respectively. These results clearly show that a disulfide bond can transmit destructive energy between protein subunits.

  7. Thiol-disulfide exchange in peptides derived from human growth hormone.

    PubMed

    Chandrasekhar, Saradha; Epling, Daniel E; Sophocleous, Andreas M; Topp, Elizabeth M

    2014-04-01

    Disulfide bonds stabilize proteins by cross-linking distant regions into a compact three-dimensional structure. They can also participate in hydrolytic and oxidative pathways to form nonnative disulfide bonds and other reactive species. Such covalent modifications can contribute to protein aggregation. Here, we present experimental data for the mechanism of thiol-disulfide exchange in tryptic peptides derived from human growth hormone in aqueous solution. Reaction kinetics was monitored to investigate the effect of pH (6.0-10.0), temperature (4-50°C), oxidation suppressants [ethylenediaminetetraacetic acid (EDTA) and N2 sparging], and peptide secondary structure (amide cyclized vs. open form). The concentrations of free thiol containing peptides, scrambled disulfides, and native disulfide-linked peptides generated via thiol-disulfide exchange and oxidation reactions were determined using reverse-phase HPLC and liquid chromatography-mass spectrometry. Concentration versus time data were fitted to a mathematical model using nonlinear least squares regression analysis. At all pH values, the model was able to fit the data with R(2) ≥ 0.95. Excluding oxidation suppressants (EDTA and N2 sparging) resulted in an increase in the formation of scrambled disulfides via oxidative pathways but did not influence the intrinsic rate of thiol-disulfide exchange. In addition, peptide secondary structure was found to influence the rate of thiol-disulfide exchange.

  8. Magnetic Fe@g??C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes

    EPA Pesticide Factsheets

    A photoactive catalyst, Fe@g-C3N4, has been developed for the hydrogenation of alkenes and alkynes using hydrazine hydrate as a source of hydrogen. The magnetically separable Fe@g-C3N4 eliminates the use of high pressure hydrogenation, and the reaction can be accomplished using visible light without the need for external sources of energy.This dataset is associated with the following publication:Baig, N., S. Verma, R. Varma , and M. Nadagouda. Magnetic Fe@g-C3N4: A Photoactive Catalyst for the Hydrogenation of Alkenes and Alkynes. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(3): 1661-1664, (2016).

  9. Photoactive bile salts with critical micellar concentration in the micromolar range.

    PubMed

    Gomez-Mendoza, Miguel; Marin, M Luisa; Miranda, Miguel A

    2016-05-14

    The aggregation behavior of bile salts is strongly dependent on the number of hydroxyl groups. Thus, cholic acid (CA), with three hydroxyls, starts forming aggregates at 15 mM, while deoxycholic, chenodeoxycholic or ursodeoxycholic acids, with two hydroxyls, start aggregating at 5-10 mM; for lithocholic acid, with only one hydroxyl group, aggregation is observed at lower concentration (2-3 mM). Here, the singular self-assembling properties of dansyl and naproxen derivatives of CA (3β-Dns-CA and 3β-NPX-CA, respectively) have been demonstrated on the basis of their photoactive properties. Thus, the emission spectra of 3β-Dns-CA registered at increasing concentrations (25-140 μM) showed a remarkable non-linear enhancement in the emission intensity accompanied by a hypsochromic shift of the maximum and up to a three-fold increase in the singlet lifetime. The inflection point at around 50-70 μM pointed to the formation of unprecedented assemblies at such low concentrations. In the case of 3β-NPX-CA, when the NPX relative triplet lifetime was plotted against concentration, a marked increase (up to two-fold) was observed at 40-70 μM, indicating the formation of new 3β-NPX-CA assemblies at ca. 50 μM. Additional evidence supporting the formation of new 3β-Dns-CA or 3β-NPX-CA assemblies at 40-70 μM was obtained from singlet excited state quenching experiments using iodide. Moreover, to address the potential formation of hybrid assemblies, 1 : 1 mixtures of 3β-Dns-CA and 3β-NPX-CA (2-60 μM, total concentration) were subjected to steady-state fluorescence experiments, and their behavior was compared to that of the pure photoactive derivatives. A lower increase in the emission was observed for 3β-NPX-CA in the mixture, while a huge increase was experienced by 3β-Dns-CA in the same concentration range (up to 60 μM total). A partial intermolecular energy transfer from NPX to Dns, consistent with their reported singlet energies, was revealed, pointing to the

  10. Controlled fabrication of photoactive copper oxide-cobalt oxide nanowire heterostructures for efficient phenol photodegradation.

    PubMed

    Shi, Wenwu; Chopra, Nitin

    2012-10-24

    Fabrication of oxide nanowire heterostructures with controlled morphology, interface, and phase purity is critical for high-efficiency and low-cost photocatalysis. Here, we have studied the formation of copper oxide-cobalt nanowire heterostructures by sputtering and subsequent air annealing to result in cobalt oxide (Co(3)O(4))-coated CuO nanowires. This approach allowed fabrication of standing nanowire heterostructures with tunable compositions and morphologies. The vertically standing CuO nanowires were synthesized in a thermal growth method. The shell growth kinetics of Co and Co(3)O(4) on CuO nanowires, morphological evolution of the shell, and nanowire self-shadowing effects were found to be strongly dependent on sputtering duration, air-annealing conditions, and alignment of CuO nanowires. Finite element method (FEM) analysis indicated that alignment and stiffness of CuO-Co nanowire heterostructures greatly influenced the nanomechanical aspects such as von Mises equivalent stress distribution and bending of nanowire heterostructures during the Co deposition process. This fundamental knowledge was critical for the morphological control of Co and Co(3)O(4) on CuO nanowires with desired interfaces and a uniform coating. Band gap energies and phenol photodegradation capability of CuO-Co(3)O(4) nanowire heterostructures were studied as a function of Co(3)O(4) morphology. Multiple absorption edges and band gap tailings were observed for these heterostructures, indicating photoactivity from visible to UV range. A polycrystalline Co(3)O(4) shell on CuO nanowires showed the best photodegradation performance (efficiency ~50-90%) in a low-powered UV or visible light illumination with a sacrificial agent (H(2)O(2)). An anomalously high efficiency (~67.5%) observed under visible light without sacrificial agent for CuO nanowires coated with thin (∼5.6 nm) Co(3)O(4) shell and nanoparticles was especially interesting. Such photoactive heterostructures demonstrate unique

  11. Theoretical study of the thermal decomposition of dimethyl disulfide.

    PubMed

    Vandeputte, Aäron G; Reyniers, Marie-Françoise; Marin, Guy B

    2010-10-07

    Despite its use in a wide variety of industrially important thermochemical processes, little is known about the thermal decomposition mechanism of dimethyl disulfide (DMDS). To obtain more insight, the radical decomposition mechanism of DMDS is studied theoretically and a kinetic model is developed accounting for the formation of all the decomposition products observed in the experimental studies available in literature. Thermochemical data and rate coefficients are obtained using the high-level CBS-QB3 composite method. Among five methods tested (BMK/6-311G(2d,d,p), MPW1PW91/6-311G(2d,d,p), G3, G3B3, and CBS-QB3), the CBS-QB3 method was found to reproduce most accurately the experimental standard enthalpies of formation for a set of 17 small organosulfur compounds and the bond dissociation energies for a set of 10 sulfur bonds. Enthalpies of formation were predicted within 4 kJ mol(-1) while the mean absolute deviation on the bond dissociation enthalpies amounts to 7 kJ mol(-1). From the theoretical study, a new reaction path is identified for the formation of carbon disulfide via dithiirane (CH(2)S(2)). A reaction mechanism was constructed containing 36 reactions among 25 species accounting for the formation of all the decomposition products reported in literature. High-pressure limit rate coefficients for the 36 reactions in the reaction mechanism are presented. The kinetic model is able to grasp the experimental observations. With the recombination of thiyl radicals treated as being in the low-pressure limit, the experimentally reported first-order rate coefficients for the decomposition of DMDS are reproduced within 1 order of magnitude, while the observed product selectivities of most compounds are reproduced satisfactory. Simulations indicate that at high conversions most of the carbon disulfide forms according to the newly identified reaction path involving the formation of dithiirane.

  12. Diaryl Disulfides as Novel Stabilizers of Tumor Suppressor Pdcd4

    PubMed Central

    Schmid, Tobias; Blees, Johanna S.; Bajer, Magdalena M.; Wild, Janine; Pescatori, Luca; Cuzzucoli Crucitti, Giuliana; Scipione, Luigi; Costi, Roberta; Henrich, Curtis J.; Brüne, Bernhard; Colburn, Nancy H.; Di Santo, Roberto

    2016-01-01

    The translation inhibitor and tumor suppressor Pdcd4 was reported to be lost in various tumors and put forward as prognostic marker in tumorigenesis. Decreased Pdcd4 protein stability due to PI3K-mTOR-p70S6K1 dependent phosphorylation of Pdcd4 followed by β-TrCP1-mediated ubiquitination, and proteasomal destruction of the protein was characterized as a major mechanism contributing to the loss of Pdcd4 expression in tumors. In an attempt to identify stabilizers of Pdcd4, we used a luciferase-based high-throughput compatible cellular assay to monitor phosphorylation-dependent proteasomal degradation of Pdcd4 in response to mitogen stimulation. Following a screen of approximately 2000 compounds, we identified 1,2-bis(4-chlorophenyl)disulfide as a novel Pdcd4 stabilizer. To determine an initial structure-activity relationship, we used 3 additional compounds, synthesized according to previous reports, and 2 commercially available compounds for further testing, in which either the linker between the aryls was modified (compounds 2–4) or the chlorine residues were replaced by groups with different electronic properties (compounds 5 and 6). We observed that those compounds with alterations in the sulfide linker completely lost the Pdcd4 stabilizing potential. In contrast, modifications in the chlorine residues showed only minor effects on the Pdcd4 stabilizing activity. A reporter with a mutated phospho-degron verified the specificity of the compounds for stabilizing the Pdcd4 reporter. Interestingly, the active diaryl disulfides inhibited proliferation and viability at concentrations where they stabilized Pdcd4, suggesting that Pdcd4 stabilization might contribute to the anti-proliferative properties. Finally, computational modelling indicated that the flexibility of the disulfide linker might be necessary to exert the biological functions of the compounds, as the inactive compound appeared to be energetically more restricted. PMID:26982744

  13. Ultrafast Optical Microscopy of Single Monolayer Molybdenum Disulfide Flakes

    SciTech Connect

    Seo, Minah; Yamaguchi, Hisato; Mohite, Aditya D.; Boubanga-Tombet, Stephane; Blancon, Jean-Christophe; Najmaei, Sina; Ajayan, Pulickel M.; Lou, Jun; Taylor, Antoinette J.; Prasankumar, Rohit P.

    2016-02-15

    We performed ultrafast optical microscopy on single flakes of atomically thin CVD-grown molybdenum disulfide, using non-degenerate femtosecond pump-probe spectroscopy to excite and probe carriers above and below the indirect and direct band gaps. These measurements reveal the influence of layer thickness on carrier dynamics when probing near the band gap. Furthermore, fluence-dependent measurements indicate that carrier relaxation is primarily influenced by surface-related defect and trap states after above-bandgap photoexcitation. Furthermore, the ability to probe femtosecond carrier dynamics in individual flakes can thus give much insight into light-matter interactions in these two-dimensional nanosystems.

  14. A 65 Ah rechargeable lithium molybdenum disulfide battery

    NASA Technical Reports Server (NTRS)

    Brandt, K.

    1986-01-01

    A rechargeable lithium molybdenum disulfide battery which has a number of superior performance characteristics which includes a high energy density, a high power density, and a long charge retention time was developed. The first cell sizes developed included a C size cell and an AA size cell. Over the last two years, a project to demonstrate the feasibility of the scale up to this technology to a BC size cell with 65 Ah capacity was undertaken. The objective was to develop, build, and test a .6 kWh storage battery consisting of 6 BC cells in series.

  15. Ultrafast Optical Microscopy of Single Monolayer Molybdenum Disulfide Flakes

    PubMed Central

    Seo, Minah; Yamaguchi, Hisato; Mohite, Aditya D.; Boubanga-Tombet, Stephane; Blancon, Jean-Christophe; Najmaei, Sina; Ajayan, Pulickel M.; Lou, Jun; Taylor, Antoinette J.; Prasankumar, Rohit P.

    2016-01-01

    We have performed ultrafast optical microscopy on single flakes of atomically thin CVD-grown molybdenum disulfide, using non-degenerate femtosecond pump-probe spectroscopy to excite and probe carriers above and below the indirect and direct band gaps. These measurements reveal the influence of layer thickness on carrier dynamics when probing near the band gap. Furthermore, fluence-dependent measurements indicate that carrier relaxation is primarily influenced by surface-related defect and trap states after above-bandgap photoexcitation. The ability to probe femtosecond carrier dynamics in individual flakes can thus give much insight into light-matter interactions in these two-dimensional nanosystems. PMID:26876194

  16. Improving the visible light photoactivity of In2S3-graphene nanocomposite via a simple surface charge modification approach.

    PubMed

    Yang, Min-Quan; Weng, Bo; Xu, Yi-Jun

    2013-08-20

    We report an efficient and easily accessible self-assembly route to synthesize In2S3-GR nanocomposites via electrostatic interaction of positively charged In2S3 nanoparticles with negatively charged graphene oxide (GO) followed by a hydrothermal process for reduction of GO to graphene (GR). The as-synthesized In2S3-GR nanocomposites exhibit much higher visible light photocatalytic activity toward selective reduction of nitroaromatic compounds in water than bare In2S3 nanoparticles and In2S3-GR-H that is obtained from the simple "hard" integration of GR nanosheets with solid In2S3 nanoparticles without modification of surface charge. On the basis of the joint characterizations and structure-photoactivity correlation it is disclosed that the enhanced photocatalytic performance of In2S3-GR is mainly ascribed to the more efficient interfacial contact between In2S3 and the GR nanosheets than In2S3-GR-H, which would amplify the use of electron conductivity and mobility of GR to improve the lifetime and transfer of photogenerated charge carriers more efficiently and thus boost the photoactivity more effectively. This work highlights the significant effect of preparation methods on the photoactivity of GR-semiconductor nanocomposites. It is expected that such a simple electrostatic self-assembly strategy could aid to rationally fabricate more efficient GR-semiconductor nanocomposites with improved interfacial contact and photocatalytic performance toward various photocatalytic selective transformations.

  17. Solid-state chemistry route for supported tungsten and tungsten carbide nanoparticles

    SciTech Connect

    Hugot, N.; Desforges, A.; Fontana, S.; Mareche, J.F.; Herold, C.; Albiniak, A.

    2012-10-15

    Nanoparticles of tungsten and tungsten carbide have been prepared using solid-state chemistry methods. After the vapor phase impregnation of a tungsten hexachloride precursor on a carbon support, a temperature-programmed reduction/carburization was performed. Several parameters were investigated and the evolution of obtained samples was followed by XRD and TEM. The optimization of the reaction parameters led to the preparation of W, W{sub 2}C and WC particles well dispersed on the support. WC phase however could not be obtained alone with less than 10 nm mean size. This could be explained by the carburization mechanism and the carbon diffusion on the support. - Graphical abstract: Bright field picture of carbon-supported WC nanoparticles dispersed on the surface of the sample 1223 K in 10% CH{sub 4}/90% H{sub 2}. Highlights: Black-Right-Pointing-Pointer We aimed at the preparation of supported nanoparticulate tungsten derivatives. Black-Right-Pointing-Pointer Several parameters were investigated. Black-Right-Pointing-Pointer The evolution of obtained samples was followed by XRD and TEM. Black-Right-Pointing-Pointer The optimal preparation led to W, W{sub 2}C and WC particles dispersed on the support.

  18. Presence of Tungsten-Containing Fibers in Tungsten Refining and Manufacturing Processes

    PubMed Central

    Mckernan, John L.; Toraason, Mark A.; Fernback, Joseph E.; Petersen, Martin R.

    2009-01-01

    In tungsten refining and manufacturing processes, a series of tungsten oxides are typically formed as intermediates in the production of tungsten powder. The present study was conducted to characterize airborne tungsten-containing fiber dimensions, elemental composition and concentrations in the US tungsten refining and manufacturing industry. During the course of normal employee work activities, seven personal breathing zone and 62 area air samples were collected and analyzed using National Institute for Occupational Safety and Health (NIOSH) fiber sampling and counting methods to determine dimensions, composition and airborne concentrations of fibers. Mixed models were used to identify relationships between potential determinants and airborne fiber concentrations. Results from transmission electron microscopy analyses indicated that airborne fibers with length >0.5 μm, diameter >0.01 μm and aspect ratios ≥3:1 were present on 35 of the 69 air samples collected. Overall, the airborne fibers detected had a geometric mean length ≈3 μm and diameter ≈0.3 μm. Ninety-seven percent of the airborne fibers identified were in the thoracic fraction (i.e. aerodynamic diameter ≤ 10 μm). Energy dispersive X-ray spectrometry results indicated that airborne fibers prior to the carburization process consisted primarily of tungsten and oxygen, with other elements being detected in trace quantities. Based on NIOSH fiber counting ‘B’ rules (length > 5 μm, diameter < 3 μm and aspect ratio ≥ 5:1), airborne fiber concentrations ranged from below the limit of detection to 0.085 fibers cm−3, with calcining being associated with the highest airborne concentrations. The mixed model procedure indicated that process temperature had a marginally significant relationship to airborne fiber concentration. This finding was expected since heated processes such as calcining created the highest airborne fiber concentrations. The finding of airborne tungsten-containing fibers in

  19. Calibration and Temperature Profile of a Tungsten Filament Lamp

    ERIC Educational Resources Information Center

    de Izarra, Charles; Gitton, Jean-Michel

    2010-01-01

    The goal of this work proposed for undergraduate students and teachers is the calibration of a tungsten filament lamp from electric measurements that are both simple and precise, allowing to determine the temperature of tungsten filament as a function of the current intensity. This calibration procedure was first applied to a conventional filament…

  20. Fabrication of large tungsten structures by chemical vapor deposition

    NASA Technical Reports Server (NTRS)

    Kahle, V. E.; Lewis, W. J.; Stubbs, V. R.

    1971-01-01

    Process is accomplished by reducing tungsten hexafluoride with hydrogen. Metallic tungsten of essentially 100 percent purity and density is produced and built up as dense deposit on heated mandrel assembly. Process variations are building up, sealing or bonding refractory metals at temperatures below transition temperatures of base metal substrates.

  1. Processing of tungsten scrap into powders by electroerosion disintegration

    SciTech Connect

    Fominskii, L.P.; Leuchuk, M.V.; Myuller, A.S.; Tarabrina, V.P.

    1985-04-01

    Utilization of tungsten and tungsten alloy swarf and other waste and also of rejected and worn parts is a matter of great importance in view of the shortage of this metal. The authors examine the electroerosion (EE) disintegration of tungsten in water as a means of utilizing swarf and other loose waste. Unlike chemical methods, EE disintegration ensures ecological purity since there are no effluent waters or toxic discharges. Swarf and trimmings of rods of diameters up to 20 mm obtained after the lathe-turning of tungsten bars sintered from PVN and PVV tungsten powders were disintegrated in water at room temperature between tungsten electrodes. The phase composition of the powder was studied using FeK /SUB alpha/ radiation, by x-ray diffraction methods in a DRON-2 diffractometer with a graphite monochromator on the secondary beam. When tungsten is heated to boiling during EE disintegration, the impurities present in it can evaporate and burn out. Thus, tungsten powder produced by EE disintegration can be purer than the starting metal.

  2. Tungsten Deposition on Graphite using Plasma Enhanced Chemical Vapour Deposition.

    NASA Astrophysics Data System (ADS)

    Sharma, Uttam; Chauhan, Sachin S.; Sharma, Jayshree; Sanyasi, A. K.; Ghosh, J.; Choudhary, K. K.; Ghosh, S. K.

    2016-10-01

    The tokamak concept is the frontrunner for achieving controlled thermonuclear reaction on earth, an environment friendly way to solve future energy crisis. Although much progress has been made in controlling the heated fusion plasmas (temperature ∼ 150 million degrees) in tokamaks, technological issues related to plasma wall interaction topic still need focused attention. In future, reactor grade tokamak operational scenarios, the reactor wall and target plates are expected to experience a heat load of 10 MW/m2 and even more during the unfortunate events of ELM's and disruptions. Tungsten remains a suitable choice for the wall and target plates. It can withstand high temperatures, its ductile to brittle temperature is fairly low and it has low sputtering yield and low fuel retention capabilities. However, it is difficult to machine tungsten and hence usages of tungsten coated surfaces are mostly desirable. To produce tungsten coated graphite tiles for the above-mentioned purpose, a coating reactor has been designed, developed and made operational at the SVITS, Indore. Tungsten coating on graphite has been attempted and successfully carried out by using radio frequency induced plasma enhanced chemical vapour deposition (rf -PECVD) for the first time in India. Tungsten hexa-fluoride has been used as a pre-cursor gas. Energy Dispersive X-ray spectroscopy (EDS) clearly showed the presence of tungsten coating on the graphite samples. This paper presents the details of successful operation and achievement of tungsten coating in the reactor at SVITS.

  3. Microstructure and tensile properties of tungsten at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Shen, Tielong; Dai, Yong; Lee, Yongjoong

    2016-01-01

    In order to support the development of the 5 MW spallation target for the European Spallation Source, the effect of fabrication process on microstructure, ductile-to-brittle transition temperature (DBTT), tensile and fracture behaviour of powder-metallurgy pure tungsten materials has been investigated. A hot-rolled (HR) tungsten piece of 12 mm thickness and a hot-forged (HF) piece of about 80 mm thickness were used to simulate the thin and thick blocks in the target. The two tungsten pieces were characterized with metallography analysis, hardness measurement and tensile testing. The HR piece exhibits an anisotropic grain structure with an average size of about 330 × 140 × 40 μm in rolling, long transverse and short transverse (thickness) directions. The HF piece possesses a bimodal grain structure with about 310 × 170 × 70 μm grain size in deformed part and about 25 μm sized grains remained from sintering process. Hardness (HV0.2) of the HR piece is slightly greater than that of the HF one. The ductility of the HR tungsten specimens is greater than that of the HF tungsten. For the HF tungsten piece, specimens with small grains in gauge section manifest lower ductility but higher strength. The DBTT evaluated from the tensile results is 250-300 °C for the HR tungsten and about 350 °C for the HF tungsten.

  4. Measurement of the Properties of Tungsten at High Temperatures

    NASA Technical Reports Server (NTRS)

    Margrave, J. L.

    1985-01-01

    The thermophysical properties of tungsten and other materials were measured using containerless techniques. Levitation of liquid silver, gallium and tungsten were studied. The studies of liquid aluminum are almost complete and are expected to derive new, reliable properties for liquid aluminum.

  5. Gas Tungsten Arc Welding. Welding Module 6. Instructor's Guide.

    ERIC Educational Resources Information Center

    Missouri Univ., Columbia. Instructional Materials Lab.

    This guide is intended to assist vocational educators in teaching a three-unit module in gas tungsten arc welding. The module has been designed to be totally integrated with Missouri's Vocational Instruction Management System. The basic principles involved in gas tungsten arc welding, supplies, and applications are covered. The materials included…

  6. The Effect of Tensile Stress on the Conformational Free Energy Landscape of Disulfide Bonds

    PubMed Central

    Anjukandi, Padmesh; Dopieralski, Przemyslaw; Ribas–Arino, Jordi; Marx, Dominik

    2014-01-01

    Disulfide bridges are no longer considered to merely stabilize protein structure, but are increasingly recognized to play a functional role in many regulatory biomolecular processes. Recent studies have uncovered that the redox activity of native disulfides depends on their C–C–S–S dihedrals, and . Moreover, the interplay of chemical reactivity and mechanical stress of disulfide switches has been recently elucidated using force–clamp spectroscopy and computer simulation. The and angles have been found to change from conformations that are open to nucleophilic attack to sterically hindered, so–called closed states upon exerting tensile stress. In view of the growing evidence of the importance of C–C–S–S dihedrals in tuning the reactivity of disulfides, here we present a systematic study of the conformational diversity of disulfides as a function of tensile stress. With the help of force-clamp metadynamics simulations, we show that tensile stress brings about a large stabilization of the closed conformers, thereby giving rise to drastic changes in the conformational free energy landscape of disulfides. Statistical analysis shows that native TDi, DO and interchain Ig protein disulfides prefer open conformations, whereas the intrachain disulfide bridges in Ig proteins favor closed conformations. Correlating mechanical stress with the distance between the two –carbons of the disulfide moiety reveals that the strain of intrachain Ig protein disulfides corresponds to a mechanical activation of about 100 pN. Such mechanical activation leads to a severalfold increase of the rate of the elementary redox reaction step. All these findings constitute a step forward towards achieving a full understanding of functional disulfides. PMID:25286308

  7. The Cyanobacterial Photoactive Orange Carotenoid Protein Is an Excellent Singlet Oxygen Quencher[C][W

    PubMed Central

    Sedoud, Arezki; López-Igual, Rocío; ur Rehman, Ateeq; Wilson, Adjélé; Perreau, François; Boulay, Clémence; Vass, Imre; Krieger-Liszkay, Anja; Kirilovsky, Diana

    2014-01-01

    Cyanobacteria have developed a photoprotective mechanism that decreases the energy arriving at the photosynthetic reaction centers under high-light conditions. The photoactive orange carotenoid protein (OCP) is essential in this mechanism as a light sensor and energy quencher. When OCP is photoactivated by strong blue-green light, it is able to dissipate excess energy as heat by interacting with phycobilisomes. As a consequence, charge separation and recombination leading to the formation of singlet oxygen diminishes. Here, we demonstrate that OCP has another essential role. We observed that OCP also protects Synechocystis cells from strong orange-red light, a condition in which OCP is not photoactivated. We first showed that this photoprotection is related to a decrease of singlet oxygen concentration due to OCP action. Then, we demonstrated that, in vitro, OCP is a very good singlet oxygen quencher. By contrast, another carotenoid protein having a high similarity with the N-terminal domain of OCP is not more efficient as a singlet oxygen quencher than a protein without carotenoid. Although OCP is a soluble protein, it is able to quench the singlet oxygen generated in the thylakoid membranes. Thus, OCP has dual and complementary photoprotective functions as an energy quencher and a singlet oxygen quencher. PMID:24748041

  8. Preparation and characterization of photoactive antimicrobial graphitic carbon nitride (g-C3N4) films.

    PubMed

    Thurston, John H; Hunter, Necia M; Cornell, Kenneth A

    Photoactive films derived from nanostructured samples of metal-free, intermediate band gap semiconductor graphitic carbon nitride (ns-g-C3N4) have been synthesized and characterized for their particle properties and antimicrobial activity. Physical characterization reveals that these materials are composed of discrete nanoparticles whose dimensions range from 200 nm to 700 nm. Investigation of the photochemical reactivity of ns-g-C3N4 using coumarin-3-carboxylic acid (3-CCA) indicates that this material produces reactive oxygen species (ROS) under visible radiation. When irradiated with 0.31J visible light, ns-g-C3N4-based materials reduced the viability of both gram-negative Escherichia coli O157:H7 and gram-positive Staphylococcus aureus by approximately 50%. Nearly complete inactivation of both strains of microorganisms was achieved upon administration of a 0.62J dose of visible radiation. Importantly, no biocidal activity was observed for non-irradiated samples, indicating that the g-C3N4-derived films are not inherently toxic in the absence of visible light. The results of this study suggest that materials and, by extention, films and coatings derived from g-C3N4 may present a novel route for controlling pathogenic microorganisms on surfaces in the environment, and could be useful in reducing incidents of hospital-acquired infections.

  9. Contrasting the Excited-State Dynamics of the Photoactive Yellow Protein Chromophore: Protein versus Solvent Environments

    PubMed Central

    Vengris, Mikas; van der Horst, Michael A.; Zgrablić, Goran; van Stokkum, Ivo H. M.; Haacke, Stefan; Chergui, Majed; Hellingwerf, Klaas J.; van Grondelle, Rienk; Larsen, Delmar S.

    2004-01-01

    Wavelength- and time-resolved fluorescence experiments have been performed on the photoactive yellow protein, the E46Q mutant, the hybrids of these proteins containing a nonisomerizing “locked” chromophore, and the native and locked chromophores in aqueous solution. The ultrafast dynamics of these six systems is compared and spectral signatures of isomerization and solvation are discussed. We find that the ultrafast red-shifting of fluorescence is associated mostly with solvation dynamics, whereas isomerization manifests itself as quenching of fluorescence. The observed multiexponential quenching of the protein samples differs from the single-exponential lifetimes of the chromophores in solution. The locked chromophore in the protein environment decays faster than in solution. This is due to additional channels of excited-state energy dissipation via the covalent and hydrogen bonds with the protein environment. The observed large dispersion of quenching timescales observed in the protein samples that contain the native pigment favors both an inhomogeneous model and an excited-state barrier for isomerization. PMID:15345563

  10. Multiscale Approach to the Determination of the Photoactive Yellow Protein Signaling State Ensemble

    PubMed Central

    A. Rohrdanz, Mary; Zheng, Wenwei; Lambeth, Bradley; Vreede, Jocelyne; Clementi, Cecilia

    2014-01-01

    The nature of the optical cycle of photoactive yellow protein (PYP) makes its elucidation challenging for both experiment and theory. The long transition times render conventional simulation methods ineffective, and yet the short signaling-state lifetime makes experimental data difficult to obtain and interpret. Here, through an innovative combination of computational methods, a prediction and analysis of the biological signaling state of PYP is presented. Coarse-grained modeling and locally scaled diffusion map are first used to obtain a rough bird's-eye view of the free energy landscape of photo-activated PYP. Then all-atom reconstruction, followed by an enhanced sampling scheme; diffusion map-directed-molecular dynamics are used to focus in on the signaling-state region of configuration space and obtain an ensemble of signaling state structures. To the best of our knowledge, this is the first time an all-atom reconstruction from a coarse grained model has been performed in a relatively unexplored region of molecular configuration space. We compare our signaling state prediction with previous computational and more recent experimental results, and the comparison is favorable, which validates the method presented. This approach provides additional insight to understand the PYP photo cycle, and can be applied to other systems for which more direct methods are impractical. PMID:25356903

  11. Predicting the reaction coordinates of millisecond light-induced conformational changes in photoactive yellow protein

    PubMed Central

    Vreede, Jocelyne; Juraszek, Jarek; Bolhuis, Peter G.

    2010-01-01

    Understanding the dynamics of large-scale conformational changes in proteins still poses a challenge for molecular simulations. We employ transition path sampling of explicit solvent molecular dynamics trajectories to obtain atomistic insight in the reaction network of the millisecond timescale partial unfolding transition in the photocycle of the bacterial sensor photoactive yellow protein. Likelihood maximization analysis predicts the best model for the reaction coordinates of each substep as well as tentative transition states, without further simulation. We find that the unfolding of the α-helical region 43–51 is followed by sequential solvent exposure of both Glu46 and the chromophore. Which of these two residues is exposed first is correlated with the presence of a salt bridge that is part of the N-terminal domain. Additional molecular dynamics simulations indicate that the exposure of the chromophore does not result in a productive pathway. We discuss several possibilities for experimental validation of these predictions. Our results open the way for studying millisecond conformational changes in other medium-sized (signaling) proteins. PMID:20133754

  12. Efficient tool to calculate two-dimensional optical spectra for photoactive molecular complexes

    NASA Astrophysics Data System (ADS)

    Duan, Hong-Guang; Dijkstra, Arend G.; Nalbach, Peter; Thorwart, Michael

    2015-10-01

    We combine the coherent modified Redfield theory (CMRT) with the equation of motion-phase matching approach (PMA) to calculate two-dimensional photon-echo spectra for photoactive molecular complexes with an intermediate strength of the coupling to their environment. Both techniques are highly efficient, yet they involve approximations at different levels. By explicitly comparing with the numerically exact quasiadiabatic path integral approach, we show for the Fenna-Matthews-Olson complex that the CMRT describes the decay rates in the population dynamics well, but final stationary populations and the oscillation frequencies differ slightly. In addition, we use the combined CMRT+PMA to calculate two-dimensional photon-echo spectra for a simple dimer model. We find excellent agreement with the exact path integral calculations at short waiting times where the dynamics is still coherent. For long waiting times, differences occur due to different final stationary states, specifically for strong system-bath coupling. For weak to intermediate system-bath couplings, which is most important for natural photosynthetic complexes, the combined CMRT+PMA gives reasonable results with acceptable computational efforts.

  13. Effect of niobium on the structure and photoactivity of anatase (TiO2) nanoparticles.

    PubMed

    Hirano, Masanori; Matsushima, Kazumasa

    2006-03-01

    Anatase-type TiO2 nanoparticles doped with 0-30 mol% niobium were directly formed from precursor solutions of TiOSO4 and NbCl5 under mild hydrothermal conditions at 120-180 degrees C for 5 h using the hydrolysis of urea. When the niobium content increased from 0 to 30 mol%, the crystallite size of anatase increased from 8.5 to 19 nm. The band gap of anatase was slightly decreased by making solid solutions with niobium. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution after maintained in the dark or under UV-light irradiation. To form anatase-type solid solutions by doping 5-15 mol% niobium into TiO2 was effective for improvement of the photoactivity of TiO2. The photocatalytic activity (the photooxidation rate) and the adsorption amount of MB for the sample containing 15 mol% niobium became more than approximately nine times and six times as much as those of the hydrothermal anatase-type pure TiO2, respectively.

  14. Photoactive TiO2 coatings obtained by Plasma Electrolytic Oxidation in refrigerated electrolytes

    NASA Astrophysics Data System (ADS)

    Franz, Silvia; Perego, Daniele; Marchese, Ottavia; Lucotti, Andrea; Bestetti, Massimiliano

    2016-11-01

    The effect of synthesis conditions on the properties of nanoporous TiO2 coatings obtained by PEO in refrigerated electrolytes have been investigated. Linear sweep voltammetry was carried out on the TiO2 coatings, in dark and under UV-C irradiation, in order to assess the photoelectrochemical behavior of samples. The largest photocurrents (0.18 mA/cm2) were measured on TiO2 coatings obtained by PEO in refrigerated aqueous solutions. UV-vis spectra revealed that lowering the processing temperature from 20 to -3.5 °C induced a blue-shift of the absorption band of the TiO2 coatings from 3.05 to 3.42 eV. The main advantage of PEO in refrigerated aqueous solutions over current approaches, based on anodic oxidation and thermal treatments, is that the synthesis of photoactive TiO2 coatings can be carried out in a relatively easy, quick and reproducible way, without annealing pre- and post-treatments. Furthermore, by controlling the solution temperature in PEO process, the photocurrent of the resulting TiO2 coating reaches quite high values.

  15. Ultrafast carbonyl motion of the photoactive yellow protein chromophore probed by femtosecond circular dichroism.

    PubMed

    Mendonça, Lucille; Hache, François; Changenet-Barret, Pascale; Plaza, Pascal; Chosrowjan, Haik; Taniguchi, Seiji; Imamoto, Yasushi

    2013-10-02

    Motions of the trans-p-coumaric acid carbonyl group following the photoexcitation of the R52Q mutant of photoactive yellow protein (PYP) are investigated, for the first time, by ultrafast time-resolved circular dichroism (TRCD) spectroscopy. TRCD is monitored in the near-ultraviolet, over a time scale of 10 ps. Immediately after excitation, TRCD is found to exhibit a large negative peak, which decays within a few picoseconds. A quantitative analysis of the signals shows that, upon excitation, the carbonyl group undergoes a fast (≪0.8 ps) and unidirectional flipping motion in the excited state with an angle of ca. 17-53°. For the subset of proteins that do not enter the signaling photocycle, TRCD provides strong evidence that the carbonyl group moves back to its initial position, leading to the formation of a nonreactive ground-state intermediate of trans conformation. The initial ground state is then restored within ca. 3 ps. Comparative study of R52Q and wild-type PYP provides direct evidence that the absence of Arg52 has no effect on the conformational changes of the chromophore during those steps.

  16. Multiscale approach to the determination of the photoactive yellow protein signaling state ensemble.

    PubMed

    A Rohrdanz, Mary; Zheng, Wenwei; Lambeth, Bradley; Vreede, Jocelyne; Clementi, Cecilia

    2014-10-01

    The nature of the optical cycle of photoactive yellow protein (PYP) makes its elucidation challenging for both experiment and theory. The long transition times render conventional simulation methods ineffective, and yet the short signaling-state lifetime makes experimental data difficult to obtain and interpret. Here, through an innovative combination of computational methods, a prediction and analysis of the biological signaling state of PYP is presented. Coarse-grained modeling and locally scaled diffusion map are first used to obtain a rough bird's-eye view of the free energy landscape of photo-activated PYP. Then all-atom reconstruction, followed by an enhanced sampling scheme; diffusion map-directed-molecular dynamics are used to focus in on the signaling-state region of configuration space and obtain an ensemble of signaling state structures. To the best of our knowledge, this is the first time an all-atom reconstruction from a coarse grained model has been performed in a relatively unexplored region of molecular configuration space. We compare our signaling state prediction with previous computational and more recent experimental results, and the comparison is favorable, which validates the method presented. This approach provides additional insight to understand the PYP photo cycle, and can be applied to other systems for which more direct methods are impractical.

  17. Fabrication of photoactive heterostructures based on quantum dots decorated with Au nanoparticles

    PubMed Central

    Fanizza, Elisabetta; Urso, Carmine; Iacobazzi, R. Maria; Depalo, Nicoletta; Corricelli, Michela; Panniello, Annamaria; Agostiano, Angela; Denora, Nunzio; Laquintana, Valentino; Striccoli, Marinella; Curri, M. Lucia

    2016-01-01

    Abstract Silica based multifunctional heterostructures, exhibiting near infrared (NIR) absorption (650–1200 nm) and luminescence in the visible region, represent innovative nanosystems useful for diagnostic or theranostic applications. Herein, colloidal synthetic procedures are applied to design a photoactive multifunctional nanosystem. Luminescent silica (SiO2) coated quantum dots (QDs) have been used as versatile nanoplatforms to assemble on their surface gold (Au) seeds, further grown into Au spackled structures. The synthesized nanostructures combine the QD emission in the visible region, and, concomitantly, the distinctive NIR absorption of Au nanodomains. The possibility of having multiple QDs in a single heterostructure, the SiO2 shell thickness, and the extent of Au deposition onto SiO2 surface have been carefully controlled. The work shows that a single QD entrapped in 16 nm thick SiO2 shell, coated with Au speckles, represents the most suitable geometry to preserve the QD emission in the visible region and to generate NIR absorption from metal NPs. The resulting architectures present a biomedical potential as an effective optical multimodal probes and as promising therapeutic agents due to the Au NP mediated photothermal effect. PMID:27877861

  18. The growing family of photoactive yellow proteins and their presumed functional roles.

    PubMed

    Meyer, T E; Kyndt, J A; Memmi, S; Moser, T; Colón-Acevedo, B; Devreese, B; Van Beeumen, J J

    2012-10-01

    For several years following the discovery and characterization of the first PYP, from Halorhodospira halophila, it was thought that this photoactive protein was quite unique, notwithstanding the isolation of two additional examples in rapid succession. Mainly because of genomic and metagenomic analyses, we have now learned that more than 140 PYP genes occur in a wide variety of bacteria and metabolic niches although the protein has not been isolated in most cases. The amino acid sequences and physical properties permit their organization into at least seven groups that are also likely to be functionally distinct. Based upon action spectra and the wavelength of maximum absorbance, it was speculated nearly 20 years ago but never proven that Hr. halophila PYP was involved in phototaxis. Nevertheless, in only one instance has the functional role and interaction partner for a PYP been experimentally proven, in Rs. centenum Ppr. Genetic context is one of several types of evidence indicating that PYP is potentially involved in a number of diverse functional roles. The interaction with other sensors to modulate their activity stands out as the single most prominent role for PYP. In this review, we have attempted to summarize the evidence for the functional roles and interaction partners for some 26 of the 35 named species of PYP, which should be considered the basis for further focused molecular and biochemical research.

  19. pH Dependence of the Photoactive Yellow Protein Photocycle Investigated by Time-Resolved Crystallography

    PubMed Central

    Tripathi, Shailesh; Šrajer, Vukica; Purwar, Namrta; Henning, Robert; Schmidt, Marius

    2012-01-01

    Visualizing the three-dimensional structures of a protein during its biological activity is key to understanding its mechanism. In general, protein structure and function are pH-dependent. Changing the pH provides new insights into the mechanisms that are involved in protein activity. Photoactive yellow protein (PYP) is a signaling protein that serves as an ideal model for time-dependent studies on light-activated proteins. Its photocycle is studied extensively under different pH conditions. However, the structures of the intermediates remain unknown until time-resolved crystallography is employed. With the newest beamline developments, a comprehensive time series of Laue data can now be collected from a single protein crystal. This allows us to vary the pH. Here we present the first structure, to our knowledge, of a short-lived protein-inhibitor complex formed in the pB state of the PYP photocycle at pH 4. A water molecule that is transiently stabilized in the chromophore active site prevents the relaxation of the chromophore back to the trans configuration. As a result, the dark-state recovery is slowed down dramatically. At pH 9, PYP stops cycling through the pB state altogether. The electrostatic environment in the chromophore-binding site is the likely reason for this altered kinetics at different pH values. PMID:22339869

  20. Visualizing reaction pathways in photoactive yellow protein from nanoseconds to seconds

    PubMed Central

    Ihee, Hyotcherl; Rajagopal, Sudarshan; Šrajer, Vukica; Pahl, Reinhard; Anderson, Spencer; Schmidt, Marius; Schotte, Friedrich; Anfinrud, Philip A.; Wulff, Michael; Moffat, Keith

    2005-01-01

    Determining 3D intermediate structures during the biological action of proteins in real time under ambient conditions is essential for understanding how proteins function. Here we use time-resolved Laue crystallography to extract short-lived intermediate structures and thereby unveil signal transduction in the blue light photoreceptor photoactive yellow protein (PYP) from Halorhodospira halophila. By analyzing a comprehensive set of Laue data during the PYP photocycle (forty-seven time points from one nanosecond to one second), we track all atoms in PYP during its photocycle and directly observe how absorption of a blue light photon by its p-coumaric acid chromophore triggers a reversible photocycle. We identify a complex chemical mechanism characterized by five distinct structural intermediates. Structural changes at the chromophore in the early, red-shifted intermediates are transduced to the exterior of the protein in the late, blue-shifted intermediates through an initial “volume-conserving” isomerization of the chromophore and the progressive disruption of hydrogen bonds between the chromophore and its surrounding binding pocket. These results yield a comprehensive view of the PYP photocycle when seen in the light of previous biophysical studies on the system. PMID:15870207

  1. pH Dependence of the Photoactive Yellow Protein Photocycle Investigated by Time-Resolved Crystallography

    SciTech Connect

    Tripathi, Shailesh; Šrajer, Vukica; Purwar, Namrta; Henning, Robert; Schmidt, Marius

    2012-05-24

    Visualizing the three-dimensional structures of a protein during its biological activity is key to understanding its mechanism. In general, protein structure and function are pH-dependent. Changing the pH provides new insights into the mechanisms that are involved in protein activity. Photoactive yellow protein (PYP) is a signaling protein that serves as an ideal model for time-dependent studies on light-activated proteins. Its photocycle is studied extensively under different pH conditions. However, the structures of the intermediates remain unknown until time-resolved crystallography is employed. With the newest beamline developments, a comprehensive time series of Laue data can now be collected from a single protein crystal. This allows us to vary the pH. Here we present the first structure, to our knowledge, of a short-lived protein-inhibitor complex formed in the pB state of the PYP photocycle at pH 4. A water molecule that is transiently stabilized in the chromophore active site prevents the relaxation of the chromophore back to the trans configuration. As a result, the dark-state recovery is slowed down dramatically. At pH 9, PYP stops cycling through the pB state altogether. The electrostatic environment in the chromophore-binding site is the likely reason for this altered kinetics at different pH values.

  2. Photoactive composite films prepared from mixtures of polystyrene microgel dispersions and poly(3-hexylthiophene) solutions.

    PubMed

    Chen, Mu; Cui, Zhengxing; Edmondson, Steve; Hodson, Nigel; Zhou, Mi; Yan, Junfeng; O'Brien, Paul; Saunders, Brian R

    2015-11-14

    Whilst polystyrene microgels belong to the oldest family of microgel particles, their behaviours when deposited onto substrates or prepared as composites have received little attention. Because polystyrene microgels are solvent-swellable, and inherently colloidally stable, they are well suited to form composites with conjugated polymers. Here, we investigate the morphology and light absorption properties of spin coated composite films prepared from mixed dispersions of polystyrene microgels and poly(3-hexylthiophene) (P3HT) for the first time. We compare the morphologies of the composite films to spin coated microgel films. The films were studied using optical microscopy, SEM, AFM, wide-angle X-ray diffraction and UV-visible spectroscopy. The films contained flattened microgel particles with an aspect ratio of ∼10. Microgel islands containing hexagonally close packed particles were evident for both the pure microgel and microgel/P3HT composite films. The latter were electrically conducting. The composite film morphology was dependent on the microgel and P3HT concentration used for film preparation and a morphology phase diagram was constructed. The P3HT phase acted as an electrically conducting cement and increased the robustness of the films to solvent washing. The composite films were photoactive due to the P3HT component. The absorbance for the films was tuneable and increased linearly with both microgel and P3HT concentration. The results of the study should apply to other organic swellable microgel/conjugated polymer combinations and may lead to new colloidal composites for future optoelectronic applications.

  3. Conversion of light-energy into molecular strain in the photocycle of the photoactive yellow protein.

    PubMed

    Gamiz-Hernandez, Ana P; Kaila, Ville R I

    2016-01-28

    The Photoactive Yellow Protein (PYP) is a light-driven photoreceptor, responsible for the phototaxis of halophilic bacteria. Recently, a new short-lived intermediate (pR0) was characterized in the PYP photocycle using combined time-resolved X-ray crystallography and density functional theory calculations. The pR0 species was identified as a highly contorted cis-intermediate, which is stabilized by hydrogen bonds with protein residues. Here we show by hybrid quantum mechanics/classical mechanics (QM/MM) molecular dynamics simulations, and first-principles calculations of optical properties, that the optical shifts in the early steps of the PYP photocycle originate from the conversion of light energy into molecular strain, stored in the pR0 state, and its relaxation in subsequent reaction steps. Our calculations quantitatively reproduce experimental data, which enables us to identify molecular origins of the optical shifts. Our combined approach suggests that the short-lived pR0 intermediate stores ∼1/3 of the photon energy as molecular strain, thus providing the thermodynamic driving force for later conformational changes in the protein.

  4. Influence of annealing and blending of photoactive polymers on their crystalline structure.

    PubMed

    Ruderer, Matthias A; Prams, Stefan M; Rawolle, Monika; Zhong, Qi; Perlich, Jan; Roth, Stephan V; Müller-Buschbaum, Peter

    2010-12-02

    Thin photoactive polymer films of poly(3-octylthiophene-2,5-diyl) (P3OT) and poly(2,5-di(hexyloxy)cyanoterephthalylidene) (CN-PPV) are investigated. With X-ray reflectivity measurements, a linear concentration-thickness dependence is found for both polymers and the molecular weight of CN-PPV is determined from this concentration-thickness dependence. Based on the molecular weights, the critical blending ratio is determined. Grazing incidence wide-angle X-ray scattering (GIWAXS) is used to probe the crystallinity of thin films and to determine characteristic length scales of the crystalline structure. Moreover, the orientation of the crystalline parts regarding the substrate of both the homopolymer and the blended films is probed with GIWAXS. Temperature annealing is found to improve the crystallization for both homopolymers. In addition, reorientation of the predominant crystalline structures takes place. Blending both polymers reduces or even suppresses the crystallization during spin coating as well as temperature annealing. Absorption measurements complement the structural investigations.

  5. Legionella pneumophila utilizes a single-player disulfide-bond oxidoreductase system to manage disulfide bond formation and isomerization.

    PubMed

    Kpadeh, Zegbeh Z; Day, Shandra R; Mills, Brandy W; Hoffman, Paul S

    2015-03-01

    Legionella pneumophila uses a single homodimeric disulfide bond (DSB) oxidoreductase DsbA2 to catalyze extracytoplasmic protein folding and to correct DSB errors through protein-disulfide isomerase (PDI) activity. In Escherichia coli, these functions are separated to avoid futile cycling. In L. pneumophila, DsbA2 is maintained as a mixture of disulfides (S-S) and free thiols (SH), but when expressed in E. coli, only the SH form is observed. We provide evidence to suggest that structural differences in DsbB oxidases (LpDsbB1 and LpDsbB2) and DsbD reductases (LpDsbD1 and LpDsbD2) (compared with E. coli) permit bifunctional activities without creating a futile cycle. LpdsbB1 and LpdsbB2 partially complemented an EcdsbB mutant while neither LpdsbD1 nor LpdsbD2 complemented an EcdsbD mutant unless DsbA2 was also expressed. When the dsb genes of E. coli were replaced with those of L. pneumophila, motility was restored and DsbA2 was present as a mixture of redox forms. A dominant-negative approach to interfere with DsbA2 function in L. pneumophila determined that DSB oxidase activity was necessary for intracellular multiplication and assembly/function of the Dot/Icm Type IVb secretion system. Our studies show that a single-player system may escape the futile cycle trap by limiting transfer of reducing equivalents from LpDsbDs to DsbA2.

  6. Tungsten fiber reinforced superalloys: A status review

    NASA Technical Reports Server (NTRS)

    Petrasek, D. W.; Signorelli, R. A.

    1981-01-01

    Improved performance of heat engines is largely dependent upon maximum cycle temperatures. Tungsten fiber reinforced superalloys (TFRS) are the first of a family of high temperature composites that offer the potential for significantly raising hot component operating temperatures and thus leading to improved heat engine performance. This status review of TFRS research emphasizes the promising property data developed to date, the status of TFRS composite airfoil fabrication technology, and the areas requiring more attention to assure their applicability to hot section components of aircraft gas turbine engines.

  7. Electrical properties of complex tungsten bronze ceramics

    NASA Astrophysics Data System (ADS)

    Padhee, R.; Das, Piyush R.

    2014-09-01

    This paper highlights the electrical properties of two new complex tungsten bronze ceramics (K2Pb2Eu2W2Ti4Nb4O30 and K2Pb2Pr2W2Ti4Nb4O30) which were prepared by high temperature mixed oxide method. Variation of impedance parameters with temperature (27-500 °C) and frequency (1 kHz to 5 MHz) shows the grain and grain boundary effects in the samples. The variation of dielectric parameters with frequency is also studied. The ac conductivity variation with temperature clearly exhibits that the materials have thermally activated transport properties of Arrhenius type.

  8. Double phase conjugation in tungsten bronze crystals.

    PubMed

    Sharp, E J; Clark Iii, W W; Miller, M J; Wood, G L; Monson, B; Salamo, G J; Neurgaonkar, R R

    1990-02-20

    In this paper we report a new method for double phase conjugation particularly suited to the tungsten bronze crystal strontium barium niobate. It has also been observed to produce conjugate waves in BaTiO(3) and BSKNN. This new arrangement is called the bridge conjugator because the two beams enter opposing [100] crystal faces and fan together to form a bridge without reflection off a crystal face. Our measurements indicate that the bridge conjugator is competitive with previously reported double phase conjugate mirrors in reflectivity, response time, ease of alignment, and fidelity.

  9. Xenon-Ion Drilling of Tungsten Films

    NASA Technical Reports Server (NTRS)

    Garner, C. E.

    1986-01-01

    High-velocity xenon ions used to drill holes of controlled size and distribution through tungsten layer that sheaths surface of controlled-porosity dispenser cathode of traveling wave-tube electron emitter. Controlled-porosity dispenser cathode employs barium/calcium/ aluminum oxide mixture that migrates through pores in cathode surface, thus coating it and reducing its work function. Rapid, precise drilling technique applied to films of other metals and used in other applications where micron-scale holes required. Method requires only few hours, as opposed to tens of hours by prior methods.

  10. Low temperature photoresponse of monolayer tungsten disulphide

    SciTech Connect

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

    2014-11-01

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

  11. Atomic tungsten for ultrafast hard X-ray generation.

    PubMed

    Shan, Fang; Couch, Vernon A; Guo, Ting

    2005-05-19

    High-resolution X-ray absorption measurements (with an accuracy of +/-0.3 eV) of ZnSO(4) (aq) were performed with ultrafast selected energy X-ray absorption spectroscopy (USEXAS) using a laser-driven tungsten target X-ray source. The results were used to determine the absolute spectral positions of characteristic emission lines. By comparing these positions to those predicted for the line emission from tungsten of different oxidation states using the Dirac-Fock formula, the tungsten species responsible for ultrafast hard X-ray generation were found to be tungsten atoms. This finding provides the first direct evidence to support the mechanism of X-ray generation via high-energy electrons interacting with tungsten atoms in the solid target.

  12. Dynamics of small mobile helium clusters near tungsten surfaces

    NASA Astrophysics Data System (ADS)

    Hu, Lin; Hammond, Karl D.; Wirth, Brian D.; Maroudas, Dimitrios

    2014-08-01

    We report the results of a systematic atomic-scale analysis of the dynamics of small mobile helium clusters in tungsten, near tungsten surfaces. These helium clusters are attracted to tungsten surfaces due to an elastic interaction force that drives surface segregation. As the clusters migrate toward the surface, trap mutation and cluster dissociation are activated at rates higher than in the bulk. These kinetic processes are responsible for important structural, morphological, and compositional features in plasma-exposed tungsten, including surface adatoms, near-surface immobile helium-vacancy complexes, and retained helium content. Detailed results are presented for di-helium and tri-helium clusters near low-Miller-index tungsten surfaces.

  13. Tungsten recycling in the United States in 2000

    USGS Publications Warehouse

    Shedd, Kim B.

    2011-01-01

    This report, which is one of a series of reports on metals recycling, defines and quantifies the flow of tungsten-bearing materials in the United States from imports and stock releases through consumption and disposition in 2000, with particular emphasis on the recycling of industrial scrap (new scrap) and used products (old scrap). Because of tungsten's many diverse uses, numerous types of scrap were available for recycling by a wide variety of processes. In 2000, an estimated 46 percent of U.S. tungsten supply was derived from scrap. The ratio of tungsten consumed from new scrap to that consumed from old scrap was estimated to be 20:80. Of all the tungsten in old scrap available for recycling, an estimated 66 percent was either consumed in the United States or exported to be recycled.

  14. Diversity of the Epsilonproteobacteria Dsb (disulfide bond) systems.

    PubMed

    Bocian-Ostrzycka, Katarzyna M; Grzeszczuk, Magdalena J; Dziewit, Lukasz; Jagusztyn-Krynicka, Elżbieta K

    2015-01-01

    The bacterial proteins of the Dsb family-important components of the post-translational 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.

  15. Methods of measuring Protein Disulfide Isomerase activity: a critical overview

    NASA Astrophysics Data System (ADS)

    Watanabe, Monica; Laurindo, Francisco; Fernandes, Denise

    2014-09-01

    Protein disulfide isomerase is an essential redox chaperone from the endoplasmic reticulum (ER) and is responsible for correct disulfide bond formation in nascent proteins. PDI is also found in other cellular locations in the cell, particularly the cell surface. Overall, PDI contributes to ER and global cell redox homeostasis and signaling. The knowledge about PDI structure and function progressed substantially based on in vitro studies using recombinant PDI and chimeric proteins. In these experimental scenarios, PDI reductase and chaperone activities are readily approachable. In contrast, assays to measure PDI isomerase activity, the hallmark of PDI family, are more complex. Assessment of PDI roles in cells and tissues mainly relies on gain- or loss-of-function studies. However, there is limited information regarding correlation of experimental readouts with the distinct types of PDI activities. In this mini-review, we evaluate the main methods described for measuring the different kinds of PDI activity: thiol reductase, thiol oxidase, thiol isomerase and chaperone. We emphasize the need to use appropriate controls and the role of critical interferents (e.g., detergent, presence of reducing agents). We also discuss the translation of results from in vitro studies with purified recombinant PDI to cellular and tissue samples, with critical comments on the interpretation of results.

  16. An experimental study of the influence of oxygen on silicide formation with tungsten deposited from tungsten hexafluoride

    NASA Astrophysics Data System (ADS)

    Zhang, S.-L.; Smith, U.; Buchta, R.; Östling, M.

    1991-01-01

    Tungsten disilicide (WSi2) was formed by annealing tungsten films deposited by low-pressure chemical vapor deposition on <100>-silicon substrates. The influence of oxygen on the silicidation rate was studied. Si wafers with different oxygen content in the form of Czochralski, float-zone, and epitaxial wafers were used. Oxygen was also ion implanted into either the silicon substrate or the as-deposited tungsten film. The Rutherford backscattering technique was used to follow the progress of the silicidation. The silicidation rate was found to be dependent on the oxygen content of the Si substrates. The rate was lowest for Czochralski substrates and highest for float-zone substrates. Secondary ion mass spectroscopy was used to study the oxygen and fluorine profiles in the films prior to and after silicidation. Growth of WSi2 was found to be retarded concurrently with a pile-up of fluorine at the tungsten side of the W/WSi2 interface and a gettering of oxygen from the annealing atmosphere at the interface. Growth of WSi2 was then transferred to the tungsten surface. Oxygen implantation into silicon and tungsten, respectively, reduced the rate of silicide formation. Oxygen implantation into tungsten altered the distribution of fluorine and suppressed WSi2 growth at the tungsten surface. The observations led to a conceptual model, which ascribes the retardation in the growth of the inner WSi2 to a``poisoning'' effect caused by the increase of oxygen and fluorine levels at the interface.

  17. Copper-mediated stereospecific C-H oxidative sulfenylation of terminal alkenes with disulfides.

    PubMed

    Tu, Hai-Yong; Hu, Bo-Lun; Deng, Chen-Liang; Zhang, Xing-Guo

    2015-11-04

    A copper and iodine-mediated C-H oxidative sulfenylation of olefins with diaryl disulfides has been developed for the stereospecific synthesis of vinyl thioether. With the combination of Cu(OTf)2 and I2, a variety of terminal alkenes underwent oxidative coupling reaction with various diaryl disulfides successfully to afford the corresponding E-vinyl sulfides in moderate to good yields.

  18. 21 CFR 520.1802 - Piperazine-carbon disulfide complex oral dosage forms.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Piperazine-carbon disulfide complex oral dosage forms. 520.1802 Section 520.1802 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... § 520.1802 Piperazine-carbon disulfide complex oral dosage forms....

  19. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  20. 21 CFR 520.1802 - Piperazine-carbon disulfide complex oral dosage forms.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Piperazine-carbon disulfide complex oral dosage forms. 520.1802 Section 520.1802 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... § 520.1802 Piperazine-carbon disulfide complex oral dosage forms....

  1. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  2. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  3. 21 CFR 520.1802 - Piperazine-carbon disulfide complex oral dosage forms.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Piperazine-carbon disulfide complex oral dosage forms. 520.1802 Section 520.1802 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... § 520.1802 Piperazine-carbon disulfide complex oral dosage forms....

  4. 21 CFR 520.1802 - Piperazine-carbon disulfide complex oral dosage forms.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Piperazine-carbon disulfide complex oral dosage forms. 520.1802 Section 520.1802 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... § 520.1802 Piperazine-carbon disulfide complex oral dosage forms....

  5. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  6. 46 CFR 151.50-40 - Additional requirements for carbon disulfide (carbon bisulfide) and ethyl ether.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Additional requirements for carbon disulfide (carbon... Special Requirements § 151.50-40 Additional requirements for carbon disulfide (carbon bisulfide) and ethyl... waterways at the loading and unloading points. (f) The special requirements of § 151.50-41 for...

  7. 21 CFR 520.1802 - Piperazine-carbon disulfide complex oral dosage forms.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Piperazine-carbon disulfide complex oral dosage forms. 520.1802 Section 520.1802 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... § 520.1802 Piperazine-carbon disulfide complex oral dosage forms....

  8. Regulation of interleukin-4 signaling by extracellular reduction of intramolecular disulfides

    SciTech Connect

    Curbo, Sophie; Gaudin, Raphael; Carlsten, Mattias; Malmberg, Karl-Johan; Troye-Blomberg, Marita; Ahlborg, Niklas; Karlsson, Anna; Johansson, Magnus; Lundberg, Mathias

    2009-12-25

    Interleukin-4 (IL-4) contains three structurally important intramolecular disulfides that are required for the bioactivity of the cytokine. We show that the cell surface of HeLa cells and endotoxin-activated monocytes can reduce IL-4 intramolecular disulfides in the extracellular space and inhibit binding of IL-4 to the IL-4R{alpha} receptor. IL-4 disulfides were in vitro reduced by thioredoxin 1 (Trx1) and protein disulfide isomerase (PDI). Reduction of IL-4 disulfides by the cell surface of HeLa cells was inhibited by auranofin, an inhibitor of thioredoxin reductase that is an electron donor to both Trx1 and PDI. Both Trx1 and PDI have been shown to be located at the cell surface and our data suggests that these enzymes are involved in catalyzing reduction of IL-4 disulfides. The pro-drug N-acetylcysteine (NAC) that promotes T-helper type 1 responses was also shown to mediate the reduction of IL-4 disulfides. Our data provides evidence for a novel redox dependent pathway for regulation of cytokine activity by extracellular reduction of intramolecular disulfides at the cell surface by members of the thioredoxin enzyme family.

  9. Gamma-Radiolysis of Cysteine-Cysteamine Disulfide in Aqueous Solution,

    DTIC Science & Technology

    Gamma-radiolysis of a mixed disulfide, cysteine- cysteamine disulfide, in unbuffered aqueous solution (0.3 mM) was investigated in the presence and...absence of oxygen. The principal products were the thiols (cysteine and cysteamine ), the corresponding sulfinic and sulfonic acids, the symmetrical

  10. Modeling of Tungsten Thermal Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Kim, Byunghoon; Akiyama, Yasunobu; Imaishi, Nobuyuki; Park, Heung-Chul

    1999-05-01

    Low-pressure chemical vapor deposition (LPCVD) of tungsten (W)film on silicon (Si) substrate was performed by reducting hexafluoride(WF6) with hydrogen. This CVD system is known for its nonlineardependence of growth rate on WF6 concentration. This study adopted asimple surface-reaction model which assumes that the precursor, i.e.,WF6, in the gas phase adsorbs on solid surfaces and then the adsorbedWF6 molecule is converted into tungsten solid film. The two kineticparameters involved in the model are derived from the experimentalresults. The solidification rate constant (ks) is equal to the growthrate at very high WF6 concentrations. The adsorption rate constant(ka) is derived from profile analyses of films grown in microtrenchesunder very low WF6 concentrations by applying the conventional MonteCarlo simulation code, which is valid for linear surface-reactionsystems. In the temperature range of 623 to 823 K, ka and ks haveactivation energies of 82 kJmol-1, 66.1 kJmol-1, respectively. A newlyproposed Monte Carlo simulation for nonlinear reaction systems, incombination with the two kinetic parameters, can quantitativelypredict the shape of film in microtrenches for a wide range oftemperatures and WF6 concentrations.

  11. Concentration dependent hydrogen diffusion in tungsten

    NASA Astrophysics Data System (ADS)

    Ahlgren, T.; Bukonte, L.

    2016-10-01

    The diffusion of hydrogen in tungsten is studied as a function of temperature, hydrogen concentration and pressure using Molecular Dynamics technique. A new analysis method to determine diffusion coefficients that accounts for the random oscillation of atoms around the equilibrium position is presented. The results indicate that the hydrogen migration barrier of 0.25 eV should be used instead of the presently recommended value of 0.39 eV. This conclusion is supported by both experiments and density functional theory calculations. Moreover, the migration volume at the saddle point for H in W is found to be positive: ΔVm ≈ 0.488 Å3, leading to a decrease in the diffusivity at high pressures. At high H concentrations, a dramatic reduction in the diffusion coefficient is observed, due to site blocking and the repulsive H-H interaction. The results of this study indicates that high flux hydrogen irradiation leads to much higher H concentrations in tungsten than expected.

  12. Transport analysis of tungsten impurity in ITER

    NASA Astrophysics Data System (ADS)

    Murakami, Y.; Amano, T.; Shimizu, K.; Shimada, M.

    2003-03-01

    The radial distribution of tungsten impurity in ITER is calculated by using the 1.5D transport code TOTAL coupled with NCLASS, which can solve the neo-classical impurity flux considering arbitrary aspect ratio and collisionality. An impurity screening effect is observed when the density profile is flat and the line radiation power is smaller than in the case without impurity transport by a factor of 2. It is shown that 90 MW of line radiation power is possible without significant degradation of plasma performance ( HH98( y,2) ˜1) when the fusion power is 700 MW (fusion gain Q=10). The allowable tungsten density is about 7×10 15/m 3, which is 0.01% of the electron density and the increase of the effective ionic charge Zeff is about 0.39. In this case, the total radiation power is more than half of the total heating power 210 MW, and power to the divertor region is less than 100 MW. This operation regime gives an opportunity for high fusion power operation in ITER with acceptable divertor conditions. Simulations for the case with an internal transport barrier (ITB) are also performed and it is found that impurity shielding by an ITB is possible with density profile control.

  13. Tungsten - Yttrium Based Nuclear Structural Materials

    NASA Astrophysics Data System (ADS)

    Ramana, Chintalapalle; Chessa, Jack; Martinenz, Gustavo

    2013-04-01

    The challenging problem currently facing the nuclear science community in this 21st century is design and development of novel structural materials, which will have an impact on the next-generation nuclear reactors. The materials available at present include reduced activation ferritic/martensitic steels, dispersion strengthened reduced activation ferritic steels, and vanadium- or tungsten-based alloys. These materials exhibit one or more specific problems, which are either intrinsic or caused by reactors. This work is focussed towards tungsten-yttrium (W-Y) based alloys and oxide ceramics, which can be utilized in nuclear applications. The goal is to derive a fundamental scientific understanding of W-Y-based materials. In collaboration with University of Califonia -- Davis, the project is designated to demonstrate the W-Y based alloys, ceramics and composites with enhanced physical, mechanical, thermo-chemical properties and higher radiation resistance. Efforts are focussed on understanding the microstructure, manipulating materials behavior under charged-particle and neutron irradiation, and create a knowledge database of defects, elemental diffusion/segregation, and defect trapping along grain boundaries and interfaces. Preliminary results will be discussed.

  14. High temperature annealing of ion irradiated tungsten

    DOE PAGES

    Ferroni, Francesco; Yi, Xiaoou; Arakawa, Kazuto; ...

    2015-03-21

    In this study, transmission electron microscopy of high temperature annealing of pure tungsten irradiated by self-ions was conducted to elucidate microstructural and defect evolution in temperature ranges relevant to fusion reactor applications (500–1200°C). Bulk isochronal and isothermal annealing of ion irradiated pure tungsten (2 MeV W+ ions, 500°C, 1014 W+/cm2) with temperatures of 800, 950, 1100 and 1400°C, from 0.5 to 8 h, was followed by ex situ characterization of defect size, number density, Burgers vector and nature. Loops with diameters larger than 2–3 nm were considered for detailed analysis, among which all loops had View the MathML source andmore » were predominantly of interstitial nature. In situ annealing experiments from 300 up to 1200°C were also carried out, including dynamic temperature ramp-ups. These confirmed an acceleration of loop loss above 900°C. At different temperatures within this range, dislocations exhibited behaviour such as initial isolated loop hopping followed by large-scale rearrangements into loop chains, coalescence and finally line–loop interactions and widespread absorption by free-surfaces at increasing temperatures. An activation energy for the annealing of dislocation length was obtained, finding Ea=1.34±0.2 eV for the 700–1100°C range.« less

  15. Vaccum Gas Tungsten Arc Welding, phase 1

    NASA Technical Reports Server (NTRS)

    Weeks, J. L.; Krotz, P. D.; Todd, D. T.; Liaw, Y. K.

    1995-01-01

    This two year program will investigate Vacuum Gas Tungsten Arc Welding (VGTAW) as a method to modify or improve the weldability of normally difficult-to-weld materials. VGTAW appears to offer a significant improvement in weldability because of the clean environment and lower heat input needed. The overall objective of the program is to develop the VGTAW technology and implement it into a manufacturing environment that will result in lower cost, better quality and higher reliability aerospace components for the space shuttle and other NASA space systems. Phase 1 of this program was aimed at demonstrating the process's ability to weld normally difficult-to-weld materials. Phase 2 will focus on further evaluation, a hardware demonstration and a plan to implement VGTAW technology into a manufacturing environment. During Phase 1, the following tasks were performed: (1) Task 11000 Facility Modification - an existing vacuum chamber was modified and adapted to a GTAW power supply; (2) Task 12000 Materials Selection - four difficult-to-weld materials typically used in the construction of aerospace hardware were chosen for study; (3) Task 13000 VGTAW Experiments - welding experiments were conducted under vacuum using the hollow tungsten electrode and evaluation. As a result of this effort, two materials, NARloy Z and Incoloy 903, were downselected for further characterization in Phase 2; and (4) Task 13100 Aluminum-Lithium Weld Studies - this task was added to the original work statement to investigate the effects of vacuum welding and weld pool vibration on aluminum-lithium alloys.

  16. High temperature annealing of ion irradiated tungsten

    SciTech Connect

    Ferroni, Francesco; Yi, Xiaoou; Fitzgerald, Steven P.; Edmondson, Philip D.; Roberts, Steve G.

    2015-03-21

    In this study, transmission electron microscopy of high temperature annealing of pure tungsten irradiated by self-ions was conducted to elucidate microstructural and defect evolution in temperature ranges relevant to fusion reactor applications (500–1200°C). Bulk isochronal and isothermal annealing of ion irradiated pure tungsten (2 MeV W+ ions, 500°C, 1014 W+/cm2) with temperatures of 800, 950, 1100 and 1400°C, from 0.5 to 8 h, was followed by ex situ characterization of defect size, number density, Burgers vector and nature. Loops with diameters larger than 2–3 nm were considered for detailed analysis, among which all loops had View the MathML source and were predominantly of interstitial nature. In situ annealing experiments from 300 up to 1200°C were also carried out, including dynamic temperature ramp-ups. These confirmed an acceleration of loop loss above 900°C. At different temperatures within this range, dislocations exhibited behaviour such as initial isolated loop hopping followed by large-scale rearrangements into loop chains, coalescence and finally line–loop interactions and widespread absorption by free-surfaces at increasing temperatures. An activation energy for the annealing of dislocation length was obtained, finding Ea=1.34±0.2 eV for the 700–1100°C range.

  17. Fuzzy tungsten in a magnetron sputtering device

    NASA Astrophysics Data System (ADS)

    Petty, T. J.; Khan, A.; Heil, T.; Bradley, J. W.

    2016-11-01

    Helium ion induced tungsten nanostructure (tungsten fuzz) has been studied in a magnetron sputtering device. Three parameters were varied, the fluence from 3.4 × 1023-3.0 × 1024 m-2, the He ion energy from 25 to 70 eV, and the surface temperature from 900 to 1200 K. For each sample, SEM images were captured, and measurements of the fuzz layer thickness, surface roughness, reflectivity, and average structure widths are provided. A cross-over point from pre-fuzz to fully formed fuzz is found at 2.4 ± 0.4 × 1024 m-2, and a temperature of 1080 ± 60 K. No significant change was observed in the energy sweep. The fuzz is compared to low fluence fuzz created in the PISCES-A linear plasma device. Magnetron fuzz is less uniform than fuzz created by PISCES-A and with generally larger structure widths. The thicknesses of the magnetron samples follow the original Φ1/2 relation as opposed to the incubation fluence fit.

  18. Overview of the regulation of disulfide bond formation in Peptide and protein folding.

    PubMed

    Hidaka, Yuji

    2014-04-01

    Disulfide bonds play a critical role in the maintenance of the native conformation of proteins under thermodynamic control. In general, disulfide bond formation is associated with protein folding, and this restricts the formation of folding intermediates such as misbridged disulfide isomers or kinetically trapped conformations, which provide important information related to how proteins fold into their native conformation. Therefore, numerous studies have focused on the structural analysis of folding intermediates in vitro. However, isolating or trapping folding intermediates, as well as the entire proteins, including mutant proteins, is not an easy task. Several chemical methods have recently been developed for examining peptide and protein folding and for producing, e.g., intact, post-translationally modified, or kinetically trapped proteins, or proteins with misbridged disulfide bonds. This overview introduces chemical methods for regulating the formation of disulfide bonds of peptides and proteins in the context of the thermodynamic and kinetic control of peptide and protein folding.

  19. Air oxidation method employed for the disulfide bond formation of natural and synthetic peptides.

    PubMed

    Calce, Enrica; Vitale, Rosa Maria; Scaloni, Andrea; Amodeo, Pietro; De Luca, Stefania

    2015-08-01

    Among the available protocols, chemically driven approaches to oxidize cysteine may not be required for molecules that, under the native-like conditions, naturally fold in conformations ensuring an effective pairing of the right disulfide bridge pattern. In this contest, we successfully prepared the distinctin, a natural heterodimeric peptide, and some synthetic cyclic peptides that are inhibitors of the CXCR4 receptor. In the first case, the air oxidation reaction allowed to connect two peptide chains via disulfide bridge, while in the second case allowed the cyclization of rationally designed peptides by an intramolecular disulfide bridge. Computational approaches helped to either drive de-novo design or suggest structural modifications and optimal oxidization protocols for disulfide-containing molecules. They are able to both predict and to rationalize the propensity of molecules to spontaneously fold in suitable conformations to achieve the right disulfide bridges.

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

    PubMed

    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.

  1. Au nanostructure-decorated TiO2 nanowires exhibiting photoactivity across entire UV-visible region for photoelectrochemical water splitting.

    PubMed

    Pu, Ying-Chih; Wang, Gongming; Chang, Kao-Der; Ling, Yichuan; Lin, Yin-Kai; Fitzmorris, Bob C; Liu, Chia-Ming; Lu, Xihong; Tong, Yexiang; Zhang, Jin Z; Hsu, Yung-Jung; Li, Yat

    2013-08-14

    Here we demonstrate that the photoactivity of Au-decorated TiO2 electrodes for photoelectrochemical water oxidation can be effectively enhanced in the entire UV-visible region from 300 to 800 nm by manipulating the shape of the decorated Au nanostructures. The samples were prepared by carefully depositing Au nanoparticles (NPs), Au nanorods (NRs), and a mixture of Au NPs and NRs on the surface of TiO2 nanowire arrays. As compared with bare TiO2, Au NP-decorated TiO2 nanowire electrodes exhibited significantly enhanced photoactivity in both the UV and visible regions. For Au NR-decorated TiO2 electrodes, the photoactivity enhancement was, however, observed in the visible region only, with the largest photocurrent generation achieved at 710 nm. Significantly, TiO2 nanowires deposited with a mixture of Au NPs and NRs showed enhanced photoactivity in the entire UV-visible region. Monochromatic incident photon-to-electron conversion efficiency measurements indicated that excitation of surface plasmon resonance of Au is responsible for the enhanced photoactivity of Au nanostructure-decorated TiO2 nanowires. Photovoltage experiment showed that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was attributable to the effective surface passivation of Au NPs. Furthermore, 3D finite-difference time domain simulation was performed to investigate the electrical field amplification at the interface between Au nanostructures and TiO2 upon SPR excitation. The results suggested that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was partially due to the increased optical absorption of TiO2 associated with SPR electrical field amplification. The current study could provide a new paradigm for designing plasmonic metal/semiconductor composite systems to effectively harvest the entire UV-visible light for solar fuel production.

  2. 40 CFR 440.60 - Applicability; description of the tungsten ore subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... tungsten ore subcategory. 440.60 Section 440.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Tungsten Ore Subcategory § 440.60 Applicability; description of the tungsten ore subcategory. The provisions of this subpart F are applicable to discharges from (a) mines that produce tungsten ore and...

  3. 40 CFR 440.60 - Applicability; description of the tungsten ore subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... tungsten ore subcategory. 440.60 Section 440.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Tungsten Ore Subcategory § 440.60 Applicability; description of the tungsten ore subcategory. The provisions of this subpart F are applicable to discharges from (a) mines that produce tungsten ore and...

  4. 40 CFR 440.60 - Applicability; description of the tungsten ore subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... tungsten ore subcategory. 440.60 Section 440.60 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Tungsten Ore Subcategory § 440.60 Applicability; description of the tungsten ore subcategory. The provisions of this subpart F are applicable to discharges from (a) mines that produce tungsten ore and...

  5. Molecular Bases of Cyclic and Specific Disulfide Interchange between Human ERO1α Protein and Protein-disulfide Isomerase (PDI)*

    PubMed Central

    Masui, Shoji; Vavassori, Stefano; Fagioli, Claudio; Sitia, Roberto; Inaba, Kenji

    2011-01-01

    In the endoplasmic reticulum (ER) of human cells, ERO1α and protein-disulfide isomerase (PDI) constitute one of the major electron flow pathways that catalyze oxidative folding of secretory proteins. Specific and limited PDI oxidation by ERO1α is essential to avoid ER hyperoxidation. To investigate how ERO1α oxidizes PDI selectively among more than 20 ER-resident PDI family member proteins, we performed docking simulations and systematic biochemical analyses. Our findings reveal that a protruding β-hairpin of ERO1α specifically interacts with the hydrophobic pocket present in the redox-inactive PDI b′-domain through the stacks between their aromatic residues, leading to preferred oxidation of the C-terminal PDI a′-domain. ERO1α associated preferentially with reduced PDI, explaining the stepwise disulfide shuttle mechanism, first from ERO1α to PDI and then from oxidized PDI to an unfolded polypeptide bound to its hydrophobic pocket. The interaction of ERO1α with ERp44, another PDI family member protein, was also analyzed. Notably, ERO1α-dependent PDI oxidation was inhibited by a hyperactive ERp44 mutant that lacks the C-terminal tail concealing the substrate-binding hydrophobic regions. The potential ability of ERp44 to inhibit ERO1α activity may suggest its physiological role in ER redox and protein homeostasis. PMID:21398518

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

    NASA Astrophysics Data System (ADS)

    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. Intradomain Confinement of Disulfides in the Folding of Two Consecutive Modules of the LDL Receptor

    PubMed Central

    Martínez-Oliván, Juan; Fraga, Hugo; Arias-Moreno, Xabier; Ventura, Salvador; Sancho, Javier

    2015-01-01

    The LDL receptor internalizes circulating LDL and VLDL particles for degradation. Its extracellular binding domain contains ten (seven LA and three EGF) cysteine-rich modules, each bearing three disulfide bonds. Despite the enormous number of disulfide combinations possible, LDLR oxidative folding leads to a single native species with 30 unique intradomain disulfides. Previous folding studies of the LDLR have shown that non native disulfides are initially formed that lead to compact species. Accordingly, the folding of the LDLR has been described as a "coordinated nonvectorial” reaction, and it has been proposed that early compaction funnels the reaction toward the native structure. Here we analyze the oxidative folding of LA4 and LA5, the modules critical for ApoE binding, isolated and in the LA45 tandem. Compared to LA5, LA4 folding is slow and inefficient, resembling that of LA5 disease-linked mutants. Without Ca++, it leads to a mixture of many two-disulfide scrambled species and, with Ca++, to the native form plus two three-disulfide intermediates. The folding of the LA45 tandem seems to recapitulate that of the individual repeats. Importantly, although the folding of the LA45 tandem takes place through formation of scrambled isomers, no interdomain disulfides are detected, i.e. the two adjacent modules fold independently without the assistance of interdomain covalent interactions. Reduction of incredibly large disulfide combinatorial spaces, such as that in the LDLR, by intradomain confinement of disulfide bond formation might be also essential for the efficient folding of other homologous disulfide-rich receptors. PMID:26168158

  8. Cell-free synthesis system suitable for disulfide-containing proteins

    SciTech Connect

    Matsuda, Takayoshi; Watanabe, Satoru; Kigawa, Takanori

    2013-02-08

    Highlights: ► Cell-free synthesis system suitable for disulfide-containing proteins is proposed. ► Disulfide bond formation was facilitated by the use of glutathione buffer. ► DsbC catalyzed the efficient shuffling of incorrectly formed disulfide bonds. ► Milligram quantities of functional {sup 15}N-labeled BPTI and lysozyme C were obtained. ► Synthesized proteins were both catalytically functional and properly folded. -- Abstract: Many important therapeutic targets are secreted proteins with multiple disulfide bonds, such as antibodies, cytokines, hormones, and proteases. The preparation of these proteins for structural and functional analyses using cell-based expression systems still suffers from several issues, such as inefficiency, low yield, and difficulty in stable-isotope labeling. The cell-free (or in vitro) protein synthesis system has become a useful protein production method. The openness of the cell-free system allows direct control of the reaction environment to promote protein folding, making it well suited for the synthesis of disulfide-containing proteins. In this study, we developed the Escherichia coli (E. coli) cell lysate-based cell-free synthesis system for disulfide-containing proteins, which can produce sufficient amounts of functional proteins for NMR analyses. Disulfide bond formation was facilitated by the use of glutathione buffer. In addition, disulfide isomerase, DsbC, catalyzed the efficient shuffling of incorrectly formed disulfide bonds during the protein synthesis reaction. We successfully synthesized milligram quantities of functional {sup 15}N-labeled higher eukaryotic proteins, bovine pancreatic trypsin inhibitor (BPTI) and human lysozyme C (LYZ). The NMR spectra and functional analyses indicated that the synthesized proteins are both catalytically functional and properly folded. Thus, the cell-free system is useful for the synthesis of disulfide-containing proteins for structural and functional analyses.

  9. Measurement of uptake and release of tritium by tungsten

    SciTech Connect

    Nakayama, M.; Torikai, Y.; Saito, M.; Penzhorn, R.D.; Isobe, K.; Yamanishi, T.; Kurishita, H.

    2015-03-15

    Tungsten is currently contemplated as plasma facing material for the divertor of future fusion machines. In this paper the uptake of tritium by tungsten and its release behavior have been investigated. Tungsten samples have been annealed at various temperatures and loaded at also different temperatures with deuterium containing 7.2 % tritium at a pressure of 1.2 kPa. A specific system was designed to assess the release of tritiated water and molecular tritium by the samples. Due to the rather low solubility of hydrogen isotopes in tungsten it is particularly important to be aware of the presence of hydrogen traps or thin oxide films. As shown in this work, traps or oxide films may affect the retention capability of tungsten and lead to significantly modified release properties. It became clear that there were capture sites that had different thermal stability and different capture intensity in tungsten after polishing, or oxide films that were grown on the surface of tungsten and had barrier effects.

  10. Microstructural influences on the dynamic response of tungsten heavy alloys

    SciTech Connect

    Ramesh, K.T.; Coates, R.S.

    1992-09-01

    The influence of tungsten content, swaging, and grain size on the dynamic behavior of commercially available tungsten-nickel-iron (W-Ni-Fe) alloys has been examined using the compression Kolsky bar. The observed flow stresses increase with increasing tungsten content and with degree of swaging but are essentially independent of grain size for these compressive deformations. Further, the flow stresses sustained by these materials have a distinct dependence on strain rate, in that the flow stress increases by at least 20 pct over a range from 10(exp {minus}4)/s to 7 x 10(exp 3)/s. The rate sensitivity itself increases with increasing tungsten content. The rate sensitivity of the alloy with the highest tungsten content (97 pct W) appears to be essentially the same as that of pure polycrystalline tungsten. In addition to showing greater strain hardening, the unswaged alloy also shows a much higher rate dependence than the swaged alloys, with the flow stress almost doubling when the rate of deformation increases from quasistatic to 5 x 1O(exp 3)/s. The rate-hardening mechanism within the composite appears to be essentially that associated with the tungsten grains; however, the matrix contribution is significant in the case of an unswaged alloy.

  11. Structural changes in the photoactive site of proteorhodopsin during the primary photoreaction.

    PubMed

    Bergo, Vladislav; Amsden, Jason J; Spudich, Elena N; Spudich, John L; Rothschild, Kenneth J

    2004-07-20

    Proteorhodopsin (PR), found in marine gamma-proteobacteria, is a newly discovered light-driven proton pump similar to bacteriorhodopsin (BR). Because of the widespread distribution of proteobacteria in the worldwide oceanic waters, this pigment may contribute significantly to the global solar energy input in the biosphere. We examined structural changes that occur during the primary photoreaction (PR --> K) of wild-type pigment and two mutants using low-temperature FTIR difference spectroscopy. Several vibrations detected in the 3500-3700 cm(-1) region are assigned on the basis of H(2)O --> H(2)(18)O exchange to the perturbation of one or more internal water molecules. Substitution of the negatively charged Schiff base counterion, Asp97, with the neutral asparagine caused a downshift of the ethylenic (C=C) and Schiff base (C=N) stretching modes, in agreement with the 27 nm red shift of the visible lambda(max). However, this replacement did not alter the normal all-trans to 13-cis isomerization of the chromophore or the environment of the detected water molecule(s). In contrast, substitution of Asn230, which is in a position to interact with the Schiff base, with Ala induces a 5 nm red shift of the visible lambda(max) and alters the PR chromophore structure, its isomerization to K, and the environment of the detected internal water molecules. The combination of FTIR and site-directed mutagenesis establishes that both Asp97 and Asn230 are perturbed during the primary phototransition. The environment of Asn230 is further altered during the thermal decay of K. These results suggest that significant differences exist in the conformational changes which occur in the photoactive sites of proteorhodopsin and bacteriorhodopsin during the primary photoreaction.

  12. On the Involvement of Single-Bond Rotation in the Primary Photochemistry of Photoactive Yellow Protein

    PubMed Central

    Stahl, Andreas D.; Hospes, Marijke; Singhal, Kushagra; van Stokkum, Ivo; van Grondelle, Rienk; Groot, Marie Louise; Hellingwerf, Klaas J.

    2011-01-01

    Prior experimental observations, as well as theoretical considerations, have led to the proposal that C4-C7 single-bond rotation may play an important role in the primary photochemistry of photoactive yellow protein (PYP). We therefore synthesized an analog of this protein's 4-hydroxy-cinnamic acid chromophore, (5-hydroxy indan-(1E)-ylidene)acetic acid, in which rotation across the C4-C7 single bond has been locked with an ethane bridge, and we reconstituted the apo form of the wild-type protein and its R52A derivative with this chromophore analog. In PYP reconstituted with the rotation-locked chromophore, 1), absorption spectra of ground and intermediate states are slightly blue-shifted; 2), the quantum yield of photochemistry is ∼60% reduced; 3), the excited-state dynamics of the chromophore are accelerated; and 4), dynamics of the thermal recovery reaction of the protein are accelerated. A significant finding was that the yield of the transient ground-state intermediate in the early phase of the photocycle was considerably higher in the rotation-locked samples than in the corresponding samples reconstituted with p-coumaric acid. In contrast to theoretical predictions, the initial photocycle dynamics of PYP were observed to be not affected by the charge of the amino acid residue at position 52, which was varied by 1), varying the pH of the sample between 5 and 10; and 2), site-directed mutagenesis to construct R52A. These results imply that C4-C7 single-bond rotation in PYP is not an alternative to C7=C8 double-bond rotation, in case the nearby positive charge of R52 is absent, but rather facilitates, presumably with a compensatory movement, the physiological Z/E isomerization of the blue-light-absorbing chromophore. PMID:21889456

  13. How Robust are Semiconductor Nanorods? Investigating the Stability and Chemical Decomposition Pathways of Photoactive Nanocrystals

    SciTech Connect

    Reichert, Malinda D; Lin, Chia-Cheng; Vela, Javier

    2014-07-08

    Anisotropic II–VI semiconductor nanostructures are important photoactive materials for various energy conversion and optical applications. However, aside from the many available surface chemistry studies and from their ubiquitous photodegradation under continuous illumination, the general chemical reactivity and thermal stability (phase and shape transformations) of these materials are poorly understood. Using CdSe and CdS nanorods as model systems, we have investigated the behavior of II–VI semiconductor nanorods against various conditions of extreme chemical and physical stress (acids, bases, oxidants, reductants, and heat). CdSe nanorods react rapidly with acids, becoming oxidized to Se or SeO2. In contrast, CdSe nanorods remain mostly unreactive when treated with bases or strong oxidants, although bases do partially etch the tips of the nanorods (along their axis). Roasting (heating in air) of CdSe nanorods results in rock-salt CdO, but neither CdSe nor CdO is easily reduced by hydrogen (H2). Another reductant, n-BuLi, reduces CdSe nanorods to metallic Cd. Variable temperature X-ray diffraction experiments show that axial annealing and selective axial melting of the nanorods precede particle coalescence. Furthermore, thermal analysis shows that the axial melting of II–VI nanorods is a ligand-dependent process. In agreement with chemical reactivity and thermal stability observations, silica-coating experiments show that the sharpest (most curved) II–VI surfaces are most active against heterogeneous nucleation of a silica shell. These results provide valuable insights into the fate and possible ways to enhance the stability and improve the use of II–VI semiconductor nanostructures in the fields of optics, magnetism, and energy conversion.

  14. Hierarchical Organization of Organic Dyes and Protein Cages into Photoactive Crystals.

    PubMed

    Mikkilä, Joona; Anaya-Plaza, Eduardo; Liljeström, Ville; Caston, Jose R; Torres, Tomas; Escosura, Andrés de la; Kostiainen, Mauri A

    2016-01-26

    Phthalocyanines (Pc) are non-natural organic dyes with wide and deep impact in materials science, based on their intense absorption at the near-infrared (NIR), long-lived fluorescence and high singlet oxygen ((1)O2) quantum yields. However, Pcs tend to stack in buffer solutions, losing their ability to generate singlet oxygen, which limits their scope of application. Furthermore, Pcs are challenging to organize in crystalline structures. Protein cages, on the other hand, are very promising biological building blocks that can be used to organize different materials into crystalline nanostructures. Here, we combine both kinds of components into photoactive biohybrid crystals. Toward this end, a hierarchical organization process has been designed in which (a) a supramolecular complex is formed between octacationic zinc Pc (1) and a tetraanionic pyrene (2) derivatives, driven by electrostatic and π-π interactions, and (b) the resulting tetracationic complex acts as a molecular glue that binds to the outer surface anionic patches of the apoferritin (aFt) protein cage, inducing cocrystallization. The obtained ternary face-centered cubic (fcc) packed cocrystals, with diameters up to 100 μm, retain the optical properties of the pristine dye molecules, such as fluorescence at 695 nm and efficient light-induced (1)O2 production. Considering that (1)O2 is utilized in important technologies such as photodynamic therapy (PDT), water treatments, diagnostic arrays and as an oxidant in organic synthesis, our results demonstrate a powerful methodology to create functional biohybrid systems with unprecedented long-range order. This approach should greatly aid the development of nanotechnology and biomedicine.

  15. Low-temperature Fourier transform infrared spectroscopy of photoactive yellow protein.

    PubMed

    Imamoto, Y; Shirahige, Y; Tokunaga, F; Kinoshita, T; Yoshihara, K; Kataoka, M

    2001-07-31

    The photocycle intermediates of photoactive yellow protein (PYP) were characterized by low-temperature Fourier transform infrared spectroscopy. The difference FTIR spectra of PYP(B), PYP(H), PYP(L), and PYP(M) minus PYP were measured under the irradiation condition determined by UV-visible spectroscopy. Although the chromophore bands of PYP(B) were weak, intense sharp bands complementary to the 1163-cm(-1) band of PYP, which show the chromophore is deprotonated, were observed at 1168-1169 cm(-1) for PYP(H) and PYP(L), indicating that the proton at Glu46 is not transferred before formation of PYP(M). Free trans-p-coumaric acid had a 1294-cm(-1) band, which was shifted to 1288 cm(-1) in the cis form. All the difference FTIR spectra obtained had the pair of bands corresponding to them, indicating that all the intermediates have the chromophore in the cis configuration. The characteristic vibrational modes at 1020-960 cm(-1) distinguished the intermediates. Because these modes were shifted by deuterium-labeling at the ethylene bond of the chromophore while labeling at the phenol part had no effect, they were attributed to the ethylene bond region. Hence, structural differences among the intermediates are present in this region. Bands at about 1730 cm(-1), which show that Glu46 is protonated, were observed for all intermediates except for PYP(M). Because the frequency of this mode was constant in PYP(B), PYP(H), and PYP(L), the environment of Glu46 is conserved in these intermediates. The photocycle of PYP would therefore proceed by changing the structure of the twisted ethylene bond of the chromophore.

  16. Signal to noise considerations for single crystal femtosecond time resolved crystallography of the Photoactive Yellow Protein.

    PubMed

    van Thor, Jasper J; Warren, Mark M; Lincoln, Craig N; Chollet, Matthieu; Lemke, Henrik Till; Fritz, David M; Schmidt, Marius; Tenboer, Jason; Ren, Zhong; Srajer, Vukica; Moffat, Keith; Graber, Tim

    2014-01-01

    Femtosecond time resolved pump-probe protein X-ray crystallography requires highly accurate measurements of the photoinduced structure factor amplitude differences. In the case of femtosecond photolysis of single P63 crystals of the Photoactive Yellow Protein, it is shown that photochemical dynamics place a considerable restraint on the achievable time resolution due to the requirement to stretch and add second order dispersion in order to generate threshold concentration levels in the interaction region. Here, we report on using a 'quasi-cw' approach to use the rotation method with monochromatic radiation and 2 eV bandwidth at 9.465 keV at the Linac Coherent Light Source operated in SASE mode. A source of significant Bragg reflection intensity noise is identified from the combination of mode structure and jitter with very small mosaic spread of the crystals and very low convergence of the XFEL source. The accuracy with which the three dimensional reflection is approximated by the 'quasi-cw' rotation method with the pulsed source is modelled from the experimentally collected X-ray pulse intensities together with the measured rocking curves. This model is extended to predict merging statistics for recently demonstrated self seeded mode generated pulse train with improved stability, in addition to extrapolating to single crystal experiments with increased mosaic spread. The results show that the noise level can be adequately modelled in this manner, indicating that the large intensity fluctuations dominate the merged signal-to-noise (I/σI) value. Furthermore, these results predict that using the self seeded mode together with more mosaic crystals, sufficient accuracy may be obtained in order to resolve typical photoinduced structure factor amplitude differences, as taken from representative synchrotron results.

  17. Carbon nanotubes and tungsten oxide nanorods: Synthesis and applications

    NASA Astrophysics Data System (ADS)

    Xiao, Bing

    Synthesis and applications of two types of one-dimensional nanomaterials, carbon nanotubes (CNTs) and tungsten oxide nanorods, are investigated in this dissertation. Multi-walled CNTs have been successfully synthesized using two types of chemical vapor deposition (CVD) methods: microwave plasma enhanced CVD and atmospheric pressure thermal CVD. CNTs and their synthesis processes are characterized with various analysis techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and optical emission spectroscopy. Ultra-thin and high quality multi-walled CNTs are discovered in CNT films produced by MPCVD, which exhibit good field emission performance that is found to be dependent on the synthesis conditions, like the growth time and CH4/H2 flow ratio. CNTs grown by thermal CVD have similar field emission performance. Based on silicon surface micromachining techniques and thermal CVD method, a self-aligned method has been developed to fabricate CNT based gated field emitter arrays (FEAs) which demonstrate low turn-on voltage and good emission current. Tungsten oxide nanorods have been synthesized on various tungsten substrates via thermal annealing in argon at atmospheric pressure. Nanorod growth mechanism is proposed based on thermal oxidation of tungsten in gas ambient with a very low partial pressure of oxygen as well as the self-catalytic effect on tungsten surface. The lattice structure and composition of the tungsten oxide nanorods are observed and analyzed using high resolution TEM, selected area electron diffraction (SAD), and energy dispersive X-ray spectroscopy (EDXS). The analysis results reveal that the lattice structure of the tungsten oxide nanorods is closest to that of the monoclinic WO3 crystal. Tungsten oxide nanorods have been successfully grown on tungsten tips for use in scanning tunneling microscope (STM) as probes which readily produce atomic resolution images on sample surface. Nanorod

  18. Temporal Variability of Tungsten and Cobalt in Fallon, Nevada

    PubMed Central

    Sheppard, Paul R.; Speakman, Robert J.; Ridenour, Gary; Witten, Mark L.

    2007-01-01

    Background Since 1997, Fallon, Nevada, has experienced a cluster of childhood leukemia that has been declared “one of the most unique clusters of childhood cancer ever reported.” Multiple environmental studies have shown airborne tungsten and cobalt to be elevated within Fallon, but the question remains: Have these metals changed through time in correspondence with the onset of the leukemia cluster? Methods We used dendrochemistry, the study of element concentrations through time in tree rings, in Fallon to assess temporal variability of airborne tungsten and cobalt since the late 1980s. The techniques used in Fallon were also tested in a different town (Sweet Home, OR) that has airborne tungsten from a known source. Results The Sweet Home test case confirms the accuracy of dendrochemistry for showing temporal variability of environmental tungsten. Given that dendrochemistry works for tungsten, tree-ring chemistry shows that tungsten increased in Fallon relative to nearby comparison towns beginning by the mid-1990s, slightly before the onset of the cluster, and cobalt has been high throughout the last ~ 15 years. Other metals do not show trends through time in Fallon. Discussion Results in Fallon suggest a temporal correspondence between the onset of excessive childhood leukemia and elevated levels of tungsten and cobalt. Although environmental data alone cannot directly link childhood leukemia with exposure to metals, research by others has shown that combined exposure to tungsten and cobalt can be carcinogenic to humans. Conclusion Continued biomedical research is warranted to directly test for linkage between childhood leukemia and tungsten and cobalt. PMID:17520058

  19. Preparation and electrocatalytic activity of tungsten carbide and titania nanocomposite

    SciTech Connect

    Hu, Sujuan; Shi, Binbin; Yao, Guoxing; Li, Guohua; Ma, Chunan

    2011-10-15

    Graphical abstract: The electrocatalytic activity of tungsten carbide and titania nanocomposite is related to the structure, crystal phase and chemical components of the nanocomposite, and is also affected by the property of electrolyte. A synergistic effect exists between tungsten carbide and titania of the composite. Highlights: {yields} Electrocatalytic activity of tungsten carbide and titania nanocomposite with core-shell structure. {yields} Activity is related to the structure, crystal phase and chemical component of the nanocomposite. {yields} The property of electrolyte affects the electrocatalytic activity. {yields} A synergistic effect exists between tungsten carbide and titania of the composite. -- Abstract: Tungsten carbide and titania nanocomposite was prepared by combining a reduced-carbonized approach with a mechanochemical approach. The samples were characterized by X-ray diffraction, transmission electron microscope under scanning mode and X-ray energy dispersion spectrum. The results show that the crystal phases of the samples are composed of anatase, rutile, nonstoichiometry titanium oxide, monotungsten carbide, bitungsten carbide and nonstoichiometry tungsten carbide, and they can be controlled by adjusting the parameters of the reduced-carbonized approach; tungsten carbide particles decorate on the surface of titania support, the diameter of tungsten carbide particle is smaller than 20 nm and that of titania is around 100 nm; the chemical components of the samples are Ti, O, W and C. The electrocatalytic activity of the samples was measured by a cyclic voltammetry with three electrodes. The results indicate that the electrocatalytic activities of the samples are related to their crystal phases and the property of electrolyte in aqueous solution. A synergistic effect between titania and tungsten carbide is reported for the first time.

  20. Mechanism for chemical-vapor deposition of tungsten on silicon from tungsten hexafluoride

    SciTech Connect

    Yarmoff, J.A.; McFeely, F.R.

    1988-06-01

    The mechanism for the growth of tungsten films on silicon substrates with the use of low-pressure chemical-vapor deposition from WF/sub 6/ was studied with soft-x-ray photoemission by growing films in situ. The dissociative chemisorption of WF/sub 6/ on Si(111) was found to be complete, even at room temperature. The reaction is self-poisoning at room temperature, however, as the fluorine liberated from WF/sub 6/ ties up the active Si sites responsible for the dissociation. The mechanism for continued growth of tungsten films at elevated temperature was determined to proceed via Si diffusion through the layer towards the surface. Post-fluorination of these films via XeF/sub 2/ was employed as a means for illustrating their morphology.

  1. Mechanism for chemical-vapor deposition of tungsten on silicon from tungsten hexafluoride

    NASA Astrophysics Data System (ADS)

    Yarmoff, Jory A.; McFeely, F. Read

    1988-06-01

    The mechanism for the growth of tungsten films on silicon substrates with the use of low-pressure chemical-vapor deposition from WF6 was studied with soft-x-ray photoemission by growing films in situ. The dissociative chemisorption of WF6 on Si(111) was found to be complete, even at room temperature. The reaction is self-poisoning at room temperature, however, as the fluorine liberated from WF6 ties up the active Si sites responsible for the dissociation. The mechanism for continued growth of tungsten films at elevated temperature was determined to proceed via Si diffusion through the layer towards the surface. Post-fluorination of these films via XeF2 was employed as a means for illustrating their morphology.

  2. Temperature-dependent morphology of chemical vapor grown molybdenum disulfide

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoyin; Wang, Yantao; Zhou, Jiadong; Liu, Zheng

    2017-04-01

    Monolayered molybdenum disulfide (MoS2) is a 2D direct band gap semiconductor with promising potential applications. In this work, we observed the temperature dependency of the morphologies of MoS2 monolayers from chemical vapor deposition. At a low growing temperature below 850 °C, MoS2 flakes tend to be trianglular in shape. At 850–950 °C, hexagonal MoS2 flakes can be observed. While at a temperature over 950 °C, MoS2 flakes can form rectangular shapes. Complementary characterizations have been made to these samples. We also proposed a mechanism for such temperature-dependent shape evolution based on thermodynamic simulation.

  3. Peptide Bond Formation in Water Mediated by Carbon Disulfide.

    PubMed

    Leman, Luke J; Huang, Zheng-Zheng; Ghadiri, M Reza

    2015-09-01

    Demonstrating plausible nonenzymatic polymerization mechanisms for prebiotic monomers represents a fundamental goal in prebiotic chemistry. While a great deal is now known about the potentially prebiotic synthesis of amino acids, our understanding of abiogenic polymerization processes to form polypeptides is less well developed. Here, we show that carbon disulfide (CS2), a component of volcanic emission and sulfide mineral weathering, and a widely used synthetic reagent and solvent, promotes peptide bond formation in modest yields (up to ∼20%) from α-amino acids under mild aqueous conditions. Exposure of a variety of α-amino acids to CS2 initially yields aminoacyl dithiocarbamates, which in turn generate reactive 2-thiono-5-oxazolidone intermediates, the thio analogues of N-carboxyanhydrides. Along with peptides, thiourea and thiohydantoin species are produced. Amino acid stereochemistry was preserved in the formation of peptides. Our findings reveal that CS2 could contribute to peptide bond formation, and possibly other condensation reactions, in abiogenic settings.

  4. Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

    PubMed Central

    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

  5. High Performance Molybdenum Disulfide Amorphous Silicon Heterojunction Photodetector

    PubMed Central

    Esmaeili-Rad, Mohammad R.; Salahuddin, Sayeef

    2013-01-01

    One important use of layered semiconductors such as molybdenum disulfide (MoS2) could be in making novel heterojunction devices leading to functionalities unachievable using conventional semiconductors. Here we demonstrate a metal-semiconductor-metal heterojunction photodetector, made of MoS2 and amorphous silicon (a-Si), with rise and fall times of about 0.3 ms. The transient response does not show persistent (residual) photoconductivity, unlike conventional a-Si devices where it may last 3–5 ms, thus making this heterojunction roughly 10X faster. A photoresponsivity of 210 mA/W is measured at green light, the wavelength used in commercial imaging systems, which is 2−4X larger than that of a-Si and best reported MoS2 devices. The device could find applications in large area electronics, such as biomedical imaging, where a fast response is critical. PMID:23907598

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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.

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

    SciTech Connect

    Amara, Kiran Kumar; Chu, Leiqiang; Kumar, Rajeev; Toh, Minglin; Eda, Goki

    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.

  8. ALS-linked protein disulfide isomerase variants cause motor dysfunction.

    PubMed

    Woehlbier, Ute; Colombo, Alicia; Saaranen, Mirva J; Pérez, Viviana; Ojeda, Jorge; Bustos, Fernando J; Andreu, Catherine I; Torres, Mauricio; Valenzuela, Vicente; Medinas, Danilo B; Rozas, Pablo; Vidal, Rene L; Lopez-Gonzalez, Rodrigo; Salameh, Johnny; Fernandez-Collemann, Sara; Muñoz, Natalia; Matus, Soledad; Armisen, Ricardo; Sagredo, Alfredo; Palma, Karina; Irrazabal, Thergiory; Almeida, Sandra; Gonzalez-Perez, Paloma; Campero, Mario; Gao, Fen-Biao; Henny, Pablo; van Zundert, Brigitte; Ruddock, Lloyd W; Concha, Miguel L; Henriquez, Juan P; Brown, Robert H; Hetz, Claudio

    2016-04-15

    Disturbance of endoplasmic reticulum (ER) proteostasis is a common feature of amyotrophic lateral sclerosis (ALS). Protein disulfide isomerases (PDIs) areERfoldases identified as possibleALSbiomarkers, as well as neuroprotective factors. However, no functional studies have addressed their impact on the disease process. Here, we functionally characterized fourALS-linked mutations recently identified in two majorPDIgenes,PDIA1 andPDIA3/ERp57. Phenotypic screening in zebrafish revealed that the expression of thesePDIvariants induce motor defects associated with a disruption of motoneuron connectivity. Similarly, the expression of mutantPDIs impaired dendritic outgrowth in motoneuron cell culture models. Cellular and biochemical studies identified distinct molecular defects underlying the pathogenicity of thesePDImutants. Finally, targetingERp57 in the nervous system led to severe motor dysfunction in mice associated with a loss of neuromuscular synapses. This study identifiesERproteostasis imbalance as a risk factor forALS, driving initial stages of the disease.

  9. Intercalation Pseudocapacitance of Exfoliated Molybdenum Disulfide for Ultrafast Energy Storage

    DOE PAGES

    Yoo, Hyun Deog; Li, Yifei; Liang, Yanliang; ...

    2016-05-23

    In this study, we report intercalation pseudocapacitance of 250 F g-1 for exfoliated molybdenum disulfide (MoS2) in non-aqueous electrolytes that contain lithium ions. The exfoliated MoS2 shows surface-limited reaction kinetics with high rate capability up to 3 min of charge or discharge. The intercalation pseudocapacitance originates from the extremely fast kinetics due to the enhanced ionic and electronic transport enabled by the slightly expanded layer structure as well as the metallic 1T-phase. The exfoliated MoS2 could be also used in a Li-Mg-ion hybrid capacitor, which shows full cell specific capacitance of 240 F g-1.

  10. Intercalation Pseudocapacitance of Exfoliated Molybdenum Disulfide for Ultrafast Energy Storage

    SciTech Connect

    Yoo, Hyun Deog; Li, Yifei; Liang, Yanliang; Lan, Yucheng; Wang, Feng; Yao, Yan

    2016-05-23

    In this study, we report intercalation pseudocapacitance of 250 F g-1 for exfoliated molybdenum disulfide (MoS2) in non-aqueous electrolytes that contain lithium ions. The exfoliated MoS2 shows surface-limited reaction kinetics with high rate capability up to 3 min of charge or discharge. The intercalation pseudocapacitance originates from the extremely fast kinetics due to the enhanced ionic and electronic transport enabled by the slightly expanded layer structure as well as the metallic 1T-phase. The exfoliated MoS2 could be also used in a Li-Mg-ion hybrid capacitor, which shows full cell specific capacitance of 240 F g-1.

  11. Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation.

    PubMed

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

    2016-10-21

    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.

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

    NASA Astrophysics Data System (ADS)

    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 (<1.0 mg mL-1) using synthetic 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 (<1.0 mg mL-1) using synthetic 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

  13. Thermal expansion method for lining tantalum alloy tubing with tungsten

    NASA Technical Reports Server (NTRS)

    Watson, G. K.; Whittenberger, J. D.; Mattson, W. F.

    1973-01-01

    A differential-thermal expansion method was developed to line T-111 (tantalum - 8 percent tungsten - 2 percent hafnium) tubing with a tungsten diffusion barrier as part of a fuel element fabrication study for a space power nuclear reactor concept. This method uses a steel mandrel, which has a larger thermal expansion than T-111, to force the tungsten against the inside of the T-111 tube. Variables investigated include lining temperature, initial assembly gas size, and tube length. Linear integrity increased with increasing lining temperature and decreasing gap size. The method should have more general applicability where cylinders must be lined with a thin layer of a second material.

  14. Mechanisms of selectivity loss during tungsten CVD (chemical vapor deposition)

    SciTech Connect

    Creighton, J.R.

    1990-01-01

    The tungsten subfluoride mechanism as well as other proposed mechanisms of selectivity loss are reviewed. To further demonstrate the viability of the tungsten subfluoride mechanism, we have extended the measurement of the tungsten subfluoride production rate down to 450{degree}C. We also report results from some preliminary experiments designed to identify the selectivity loss mechanism when elemental silicon is available for reaction. Comments regarding the origins of the insulator effect and selectivity loss for silane reduction are offered. 23 refs., 2 figs.

  15. Electrode potentials of tungsten in fused alkali chlorides

    NASA Astrophysics Data System (ADS)

    Ivanov, A. B.; Volkovich, V. A.; Poskryakov, D. A.; Vasin, B. D.; Griffiths, T. R.

    2016-09-01

    Anodic dissolution of tungsten was studied at 823-1173 K in the melts based on NaCl-CsCl, NaCl-KCl-CsCl and LiCl-KCl-CsCl eutectic mixtures. The process results in the formation of W(IV) ions. Prolonged contact with silica results in oxidation W(IV) ions and decreasing tungsten concentration in the electrolyte due to formation of volatile higher oxidation state chloro- and oxychloro-species. Tungsten electrode potentials were measured in NaCl-CsCl and NaCl-KCl-CsCl based melts using potentiometry.

  16. Chemically assisted ion beam etching of polycrystalline and (100)tungsten

    NASA Technical Reports Server (NTRS)

    Garner, Charles

    1987-01-01

    A chemically assisted ion-beam etching technique is described which employs an ion beam from an electron-bombardment ion source and a directed flux of ClF3 neutrals. This technique enables the etching of tungsten foils and films in excess of 40 microns thick with good anisotropy and pattern definition over areas of 30 sq mm, and with a high degree of selectivity. (100) tungsten foils etched with this process exhibit preferred-orientation etching, while polycrystalline tungsten films exhibit high etch rates. This technique can be used to pattern the dispenser cathode surfaces serving as electron emitters in traveling-wave tubes to a controlled porosity.

  17. A facile one-step electrochemical strategy of doping iron, nitrogen, and fluorine into titania nanotube arrays with enhanced visible light photoactivity.

    PubMed

    Hua, Zulin; Dai, Zhangyan; Bai, Xue; Ye, Zhengfang; Gu, Haixin; Huang, Xin

    2015-08-15

    Highly ordered iron, nitrogen, and fluorine tri-doped TiO2 (Fe, (N, F)-TiO2) nanotube arrays were successfully synthesized by a facile one-step electrochemical method in an NH4F electrolyte containing Fe ions. The morphology, structure, composition, and photoelectrochemical property of the as-prepared nanotube arrays were characterized by various methods. The photoactivities of the samples were evaluated by the degradation of phenol in an aqueous solution under visible light. Tri-doped TiO2 showed higher photoactivities than undoped TiO2 under visible light. The optimum Fe(3+) doping amount at 0.005M exhibited the highest photoactivity and exceeded that of undoped TiO2 by a factor of 20 times under visible light. The formation of N 2p level near the valence band (VB) contributed to visible light absorption. Doping fluorine and appropriate Fe(3+) ions reduced the photogenerated electrons-holes recombination rate and enhanced visible light photoactivity. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) results indicated the presence of synergistic effects in Fe, N, and F tri-doped TiO2, which enhanced visible light photoactivity. The Fe, (N, F)-TiO2 photocatalyst exhibited high stability.

  18. Protein disulfide isomerase is essential for viability in Saccharomyces cerevisiae.

    PubMed

    Farquhar, R; Honey, N; Murant, S J; Bossier, P; Schultz, L; Montgomery, D; Ellis, R W; Freedman, R B; Tuite, M F

    1991-12-01

    Protein disulfide isomerase (PDI) is an enzyme involved in the catalysis of disulfide bond formation in secretory and cell-surface proteins. Using an oligodeoxyribonucleotide designed to detect the conserved 'thioredoxin-like' active site of vertebrate PDIs, we have isolated a gene encoding PDI from the lower eukaryote, Saccharomyces cerevisiae. The nucleotide sequence and deduced open reading frame of the cloned gene predict a 530-amino-acid (aa) protein of Mr 59,082 and a pI of 4.1, physical properties characteristic of mammalian PDIs. Furthermore, the aa sequence shows 30-32% identity with mammalian and avian PDI sequences and has a very similar overall organisation, namely the presence of two approx. 100-aa segments, each of which is repeated, with the most significant homologies to mammalian and avian PDIs being in the regions (a, a') that contain the conserved 'thioredoxin-like' active site. The N-terminal region has the characteristics of a cleavable secretory signal sequence and the C-terminal four aa (-His-Asp-Glu-Leu) are consistent with the protein being a component of the S. cerevisiae endoplasmic reticulum. Transformants carrying multiple copies of this gene (designated PDI1) have tenfold higher levels of PDI activity and overproduce a protein of the predicted Mr. The PDI1 gene is unique in the yeast genome and encodes a single 1.8-kb transcript that is not found in stationary phase cells. Disruption of the PDI1 gene is haplo-lethal indicating that the product of this gene is essential for viability.

  19. Density-functional studies of tungsten trioxide, tungsten bronzes, and related systems

    NASA Astrophysics Data System (ADS)

    Ingham, B.; Hendy, S. C.; Chong, S. V.; Tallon, J. L.

    2005-08-01

    Tungsten trioxide adopts a variety of structures which can be intercalated with charged species to alter the electronic properties, thus forming “tungsten bronzes.” Similar effects are observed upon removing oxygen from WO3 . We present a computational study of cubic and hexagonal alkali bronzes and examine the effects on cell size and band structure as the size of the intercalated ion is increased. With the exception of hydrogen (which is predicted to be unstable as an intercalate), the behavior of the bronzes are relatively consistent. NaWO3 is the most stable of the cubic systems, although in the hexagonal system the larger ions are more stable. The band structures are identical, with the intercalated atom donating its single electron to the tungsten 5d valence band. A study of fractional doping in the NaxWO3 system (0⩽x⩽1) showed a linear variation in cell parameter and a systematic shift in the Fermi level into the conduction band. In the oxygen-deficient WO3-x system the Fermi level undergoes a sudden jump into the conduction band at around x=0.2 . Lastly, three compounds of a layered WO4•α,ω -diaminoalkane hybrid series were studied and found to be insulating, with features in the band structure similar to those of the parent WO3 compound that relate well to experimental UV-visible spectroscopy results.

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

    SciTech Connect

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

    2016-02-01

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

  1. Tensile behavior of tungsten and tungsten-alloy wires from 1300 to 1600 K

    NASA Technical Reports Server (NTRS)

    Hee, Man Yun

    1988-01-01

    The tensile behavior of a 200-micrometer-diameter tungsten lamp (218CS-W), tungsten + 1.0 atomic percent (a/o) thoria (ST300-W), and tungsten + 0.4 a/o hafnium carbide (WHfC) wires was determined over the temperature range 1300 t0 1600 K at strain rates of 3.3 X 10 to the -2 to 3.3 X 10 to the -5/sec. Although most tests were conducted on as-drawn materials, one series of tests was undertaken on ST300-W wires in four different conditions: as-drawn and vacuum-annealed at 1535 K for 1 hr, with and without electroplating. Whereas heat treatment had no effect on tensile properties, electropolishing significantly increased both the proportional limit and ductility, but not the ultimate tensile strength. Comparison of the behavior of the three alloys indicates that the HfC-dispersed material possesses superior tensile properties. Theoretical calculations indicate that the strength/ductility advantage of WHfC is due to the resistance to recrystallization imparted by the dispersoid.

  2. Unit-cell intergrowth of pyrochlore and hexagonal tungsten bronze structures in secondary tungsten minerals

    SciTech Connect

    Grey, Ian E. . E-mail: ian.grey@csiro.au; Birch, William D.; Bougerol, Catherine

    2006-12-15

    Structural relations between secondary tungsten minerals with general composition A{sub x}[(W,Fe)(O,OH){sub 3}]{sub .y}H{sub 2}O are described. Phyllotungstite (A=predominantly Ca) is hexagonal, a=7.31(3)A, c=19.55(1)A, space group P6{sub 3}/mmc. Pittongite, a new secondary tungsten mineral from a wolframite deposit near Pittong in Victoria, southeastern Australia (A=predominantly Na) is hexagonal, a=7.286(1)A, c=50.49(1)A, space group P-6m2. The structures of both minerals can be described as unit-cell scale intergrowths of (111){sub py} pyrochlore slabs with pairs of hexagonal tungsten bronze (HTB) layers. In phyllotungstite, the (111){sub py} blocks have the same thickness, 6A, whereas pittongite contains pyrochlore blocks of two different thicknesses, 6 and 12A. The structures can alternatively be described in terms of chemical twinning of the pyrochlore structure on (111){sub py} oxygen planes. At the chemical twin planes, pairs of HTB layers are corner connected as in hexagonal WO{sub 3}.

  3. Human β-defensin 4 with non-native disulfide bridges exhibit antimicrobial activity.

    PubMed

    Sharma, Himanshu; Nagaraj, Ramakrishnan

    2015-01-01

    Human defensins play multiple roles in innate immunity including direct antimicrobial killing and immunomodulatory activity. They have three disulfide bridges which contribute to the stability of three anti-parallel β-strands. The exact role of disulfide bridges and canonical β-structure in the antimicrobial action is not yet fully understood. In this study, we have explored the antimicrobial activity of human β-defensin 4 (HBD4) analogs that differ in the number and connectivity of disulfide bridges. The cysteine framework was similar to the disulfide bridges present in μ-conotoxins, an unrelated class of peptide toxins. All the analogs possessed enhanced antimicrobial potency as compared to native HBD4. Among the analogs, the single disulfide bridged peptide showed maximum potency. However, there were no marked differences in the secondary structure of the analogs. Subtle variations were observed in the localization and membrane interaction of the analogs with bacteria and Candida albicans, suggesting a role for disulfide bridges in modulating their antimicrobial action. All analogs accumulated in the cytosol where they can bind to anionic molecules such as nucleic acids which would affect several cellular processes leading to cell death. Our study strongly suggests that native disulfide bridges or the canonical β-strands in defensins have not evolved for maximal activity but they play important roles in determining their antimicrobial potency.

  4. Thermodynamic and mechanical effects of disulfide bonds in CXCLl7 chemokine

    NASA Astrophysics Data System (ADS)

    Singer, Christopher

    Chemokines are a family of signaling proteins mainly responsible for the chemotaxis of leukocytes, where their biological activity is modulated by their oligomerization state. Here, the dynamics and thermodynamic stability are characterized in monomer and homodimer structures of CXCL7, one of the most abundant platelet chemokines. The effects of dimerization and disulfide bond formation are investigated using computational methods that include molecular dynamics (MD) simulations and the Distance Constraint Model (DCM). A consistent picture emerges for the effect of dimerization and role of the Cys5-Cys31 and Cys7- Cys47 disulfide bonds. Surprisingly, neither disulfide bond is critical for maintaining structural stability in the monomer or dimer, although the monomer is destabilized more than the dimer upon removal of disulfide bonds. Instead, it is found that disulfide bonds influence the native state dynamics as well as modulates the relative stability between monomer and dimer. The combined analysis elucidates how CXCL7 is mechanically stable as a monomer, and how upon dimerization flexibly correlated motions are induced between the 30s and 50s loop within each monomer and across the dimer interface. Interestingly, the greatest gain in flexibility upon dimerization occurs when both disulfide bonds are present in each domain, and the homodimer is least stable relative to its two monomers. These results suggest the highly conserved disulfide bonds in chemokines facilitate a structural mechanism for distinguishing functional characteristics between monomer and dimer.

  5. An in vivo pathway for disulfide bond isomerization in Escherichia coli.

    PubMed

    Rietsch, A; Belin, D; Martin, N; Beckwith, J

    1996-11-12

    Biochemical studies have shown that the periplasmic protein disulfide oxidoreductase DsbC can isomerize aberrant disulfide bonds. Here we present the first evidence for an in vivo role of DsbC in disulfide bond isomerization. Furthermore, our data suggest that the enzymes DsbA and DsbC play distinct roles in the cell in disulfide bond formation and isomerization, respectively. We have shown that mutants in dsbC display a defect in disulfide bond formation specific for proteins with multiple disulfide bonds. The defect can be complemented by the addition of reduced dithiothreitol to the medium, suggesting that absence of DsbC results in accumulation of misoxidized proteins. Mutations in the dipZ and trxA genes have similar phenotypes. We propose that DipZ, a cytoplasmic membrane protein with a thioredoxin-like domain, and thioredoxin, the product of the trxA gene, are components of a pathway for maintaining DsbC active as a protein disulfide bond isomerase.

  6. Simple plate-based, parallel synthesis of disulfide fragments using the CuAAC click reaction.

    PubMed

    Turner, David M; Tom, Christopher T M B; Renslo, Adam R

    2014-12-08

    Disulfide exchange screening is a site-directed approach to fragment-based lead discovery that requires a bespoke library of disulfide-containing fragments. Previously, we described a simple one-pot, two-step synthesis of disulfide fragments from amine- or acid-bearing starting materials. Here, we describe the synthesis of disulfide fragments that bear a 1,4-substituted-1,2,3-triazole linkage between disulfide and molecular diversity element. This work establishes the compatibility of copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry with a one-pot, two-step reaction sequence that can be readily parallelized. We performed 96 reactions in a single deep-well microtiter plate, employing 48 alkynes and two different azide linker reagents. From this effort, a total of 81 triazole-containing disulfide fragments were obtained in useful isolated yields. Thus, CuAAC chemistry offers an experimentally convenient method to rapidly prepare disulfide fragments that are structurally distinct from fragments accessed via amide, sulfonamide, or isocyanate chemistries.

  7. Disulfide Trapping for Modeling and Structure Determination of Receptor:Chemokine Complexes

    PubMed Central

    Kufareva, Irina; Gustavsson, Martin; Holden, Lauren G.; Qin, Ling; Zheng, Yi; Handel, Tracy M.

    2016-01-01

    Despite the recent breakthrough advances in GPCR crystallography, structure determination of protein-protein complexes involving chemokine receptors and their endogenous chemokine ligands remains challenging. Here we describe disulfide trapping, a methodology for generating irreversible covalent binary protein complexes from unbound protein partners by introducing two cysteine residues, one per interaction partner, at selected positions within their interaction interface. Disulfide trapping can serve at least two distinct purposes: (i) stabilization of the complex to assist structural studies, and/or (ii) determination of pairwise residue proximities to guide molecular modeling. Methods for characterization of disulfide-trapped complexes are described and evaluated in terms of throughput, sensitivity, and specificity towards the most energetically favorable cross-links. Due to abundance of native disulfide bonds at receptor:chemokine interfaces, disulfide trapping of their complexes can be associated with intramolecular disulfide shuffling and result in misfolding of the component proteins; because of this, evidence from several experiments is typically needed to firmly establish a positive disulfide crosslink. An optimal pipeline that maximizes throughput and minimizes time and costs by early triage of unsuccessful candidate constructs is proposed. PMID:26921956

  8. Evaluation of protein disulfide conversion in vitro using a continuous flow dialysis system.

    PubMed

    Jiang, Xinzhao Grace; Wang, Tian; Kaltenbrunner, Oliver; Chen, Kenneth; Flynn, Gregory C; Huang, Gang

    2013-01-15

    Recombinant therapeutic proteins are heterogeneous due to chemical and physical modifications. Understanding the impact of these modifications on drug safety and efficacy is critical for optimal process development and for setting reasonable specification limits. In this study, we describe the development of an in vitro continuous flow dialysis system to evaluate potential in vivo behavior of thiol adducted species and incorrectly disulfide bonded species of therapeutic proteins. The system is capable of maintaining the low-level cysteine concentrations found in human blood. Liabilities of cysteamine adducted species, incorrectly disulfide bonded species, and the correctly disulfide bonded form of an Fc-fusion protein were studied using this system. Results showed that 90% of the cysteamine adduct converted into the correctly disulfide bonded form and incorrectly disulfide bonded species in approximately 4 h under physiological conditions. Approximately 50% of incorrectly disulfide bonded species converted into the correctly bonded form in 2 days. These results provide valuable information on potential in vivo stability of the cysteamine adduct, incorrectly disulfide bonded species, and the correctly bonded form of the Fc-fusion protein. These are important considerations when evaluating the criticality of product quality attributes.

  9. Rhenium alloying of tungsten heavy alloys

    SciTech Connect

    German, R.M.; Bose, A.; Jerman, G.

    1989-01-01

    Alloying experiments were performed using rhenium additions to a classic 90 mass % tungsten heavy alloy. The mixed-powder system was liquid phase sintered to full density at 1500 C in 60 min The rhenium-modified alloys exhibited a smaller grain size, higher hardness, higher strength, and lower ductility than the unalloyed system. For an alloy with a composition of 84W-6Re-8Ni-2Fe, the sintered density was 17, 4 Mg/m{sup 3} with a yield strength of 815 MPa, tensile strength of 1180 MPa, and elongation to failure of 13%. This property combination results from the aggregate effects of grain size reduction and solid solution hardening due to rhenium. In the unalloyed system these properties require post-sintering swaging and aging; thus, alloying with rhenium is most attractive for applications where net shaping is desired, such as by powder injection molding.

  10. A Study of Tungsten-Technetium Alloys

    NASA Technical Reports Server (NTRS)

    Maltz, J. W.

    1965-01-01

    Technetium is a sister element to rhenium and has many properties that are similar to rhenium. It is predicted that technetium will have about the same effects on tungsten as rhenium in regard to increase in workability, lowered ductile to brittle transition temperature, and improved ductility. The objectives of the current work are to recover technetium from fission product wastes at Hanford Atomic Products Operation and reduce to purified metal; prepare W-Tc alloys containing up to 50 atomic% Tc; fabricate the alloy ingots to sheet stock, assessing the effect of technetium on workability; and perform metallurgical and mechanical properties evaluation of the fabricated alloys. Previous reports have described the separation and purification of 800 g of technetium metal powder, melting of technetium and W-Tc alloys, and some initial observation of the alloy material.

  11. Laser irradiation of carbon-tungsten materials

    NASA Astrophysics Data System (ADS)

    Marcu, A.; Avotina, L.; Marin, A.; Lungu, C. P.; Grigorescu, C. E. A.; Demitri, N.; Ursescu, D.; Porosnicu, C.; Osiceanu, P.; Kizane, G.; Grigoriu, C.

    2014-09-01

    Carbon-tungsten layers deposited on graphite by thermionic vacuum arc (TVA) were directly irradiated with a femtosecond terawatt laser. The morphological and structural changes produced in the irradiated area by different numbers of pulses were systematically explored, both along the spots and in their depths. Although micro-Raman and Synchrotron-x-ray diffraction investigations have shown no carbide formation, they have shown the unexpected presence of embedded nano-diamonds in the areas irradiated with high fluencies. Scanning electron microscopy images show a cumulative effect of the laser pulses on the morphology through the ablation process. The micro-Raman spatial mapping signalled an increased percentage of sp3 carbon bonding in the areas irradiated with laser fluencies around the ablation threshold. In-depth x-ray photoelectron spectroscopy investigations suggested a weak cumulative effect on the percentage increase of the sp2-sp3 transitions with the number of laser pulses just for nanometric layer thicknesses.

  12. Magneto photoluminescence measurements of tungsten disulphide monolayers

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  13. Tungsten-doped thin film materials

    DOEpatents

    Xiang, Xiao-Dong; Chang, Hauyee; Gao, Chen; Takeuchi, Ichiro; Schultz, Peter G.

    2003-12-09

    A dielectric thin film material for high frequency use, including use as a capacitor, and having a low dielectric loss factor is provided, the film comprising a composition of tungsten-doped barium strontium titanate of the general formula (Ba.sub.x Sr.sub.1-x)TiO.sub.3, where X is between about 0.5 and about 1.0. Also provided is a method for making a dielectric thin film of the general formula (Ba.sub.x Sr.sub.1-x)TiO.sub.3 and doped with W, where X is between about 0.5 and about 1.0, a substrate is provided, TiO.sub.2, the W dopant, Ba, and optionally Sr are deposited on the substrate, and the substrate containing TiO.sub.2, the W dopant, Ba, and optionally Sr is heated to form a low loss dielectric thin film.

  14. Thermomechanical processing of tungsten-copper composites

    SciTech Connect

    Ohriner, E.K.; Bryskin, B.

    1996-05-01

    A tungsten-40 wt% Cu composite was consolidated by liquid-phase sintering and further processed to full density by a number of deformation methods. Fully dense materials were obtained by hot extrusion or cold rolling of the W-Cu composite. Subsequent processing by cold rolling, cold swaging, or hot swaging did not produce large changes in the aspect ratio of the W particles. The materials develop high hardness with small grain sizes of 5 {mu}m or less. The work-hardening, recrystallization, and grain growth of the material are characterized, and the hardness and tensile properties are related to processing parameters. Wire with tensile strengths up to 1120 MPa were produced. Further improvements in properties are anticipated with optimized processing parameters.

  15. Enhanced toughness and stable crack propagation in a novel tungsten fibre-reinforced tungsten composite produced by chemical vapour infiltration

    NASA Astrophysics Data System (ADS)

    Riesch, J.; Höschen, T.; Linsmeier, Ch; Wurster, S.; You, J.-H.

    2014-04-01

    Tungsten is a promising candidate for the plasma-facing components of a future fusion reactor, but its use is strongly restricted by its inherent brittleness. An innovative concept to overcome this problem is tungsten fibre-reinforced tungsten composite. In this paper we present the first mechanical test of such a composite material using a sample containing multiple fibres. The in situ fracture experiment was performed in a scanning electron microscope for close observation of the propagating crack. Stable crack propagation accompanied with rising load bearing capacity is observed. The fracture toughness is estimated using the test results and the surface observation.

  16. Light-induced disulfide dimerization of recoverin under ex vivo and in vivo conditions.

    PubMed

    Zernii, Evgeni Yu; Nazipova, Aliya A; Gancharova, Olga S; Kazakov, Alexey S; Serebryakova, Marina V; Zinchenko, Dmitry V; Tikhomirova, Natalya K; Senin, Ivan I; Philippov, Pavel P; Permyakov, Eugene A; Permyakov, Sergei E

    2015-06-01

    Despite vast knowledge of the molecular mechanisms underlying photochemical damage of photoreceptors, linked to progression of age-related macular degeneration, information on specific protein targets of the light-induced oxidative stress is scarce. Here, we demonstrate that prolonged intense illumination (halogen bulb, 1500 lx, 1-5 h) of mammalian eyes under ex vivo (cow) or in vivo (rabbit) conditions induces disulfide dimerization of recoverin, a Ca(2+)-dependent inhibitor of rhodopsin kinase. Western blotting and mass spectrometry analysis of retinal extracts reveals illumination time-dependent accumulation of disulfide homodimers of recoverin and its higher order disulfide cross-linked species, including a minor fraction of mixed disulfides with intracellular proteins (tubulins, etc.). Meanwhile, monomeric bovine recoverin remains mostly reduced. These effects are accompanied by accumulation of disulfide homodimers of visual arrestin. Histological studies demonstrate that the light-induced oxidation of recoverin and arrestin occurs in intact retina (illumination for 2 h), while illumination for 5 h is associated with damage of the photoreceptor layer. A comparison of ex vivo levels of disulfide homodimers of bovine recoverin with redox dependence of its in vitro thiol-disulfide equilibrium (glutathione redox pair) gives the lowest estimate of redox potential in rod outer segments under illumination from -160 to -155 mV. Chemical crosslinking and dynamic light scattering data demonstrate an increased propensity of disulfide dimer of bovine recoverin to multimerization/aggregation. Overall, the oxidative stress caused by the prolonged intense illumination of retina might affect rhodopsin desensitization via concerted disulfide dimerization of recoverin and arrestin. The developed herein models of eye illumination are useful for studies of the light-induced thiol oxidation of visual proteins.

  17. Characterization of disulfide bonds by planned digestion and tandem mass spectrometry.

    PubMed

    Na, Seungjin; Paek, Eunok; Choi, Jong-Soon; Kim, Duwoon; Lee, Seung Jae; Kwon, Joseph

    2015-04-01

    The identification of disulfide bonds provides critical information regarding the structure and function of a protein and is a key aspect in understanding signaling cascades in biological systems. Recent proteomic approaches using digestion enzymes have facilitated the characterization of disulfide-bonds and/or oxidized products from cysteine residues, although these methods have limitations in the application of MS/MS. For example, protein digestion to obtain the native form of disulfide bonds results in short lengths of amino acids, which can cause ambiguous MS/MS analysis due to false positive identifications. In this study we propose a new approach, termed planned digestion, to obtain sufficient amino acid lengths after cleavage for proteomic approaches. Application of the DBond software to planned digestion of specific proteins accurately identified disulfide-linked peptides. RNase A was used as a model protein in this study because the disulfide bonds of this protein have been well characterized. Application of this approach to peptides digested with Asp-N/C (chemical digestion) and trypsin under acid hydrolysis conditions identified the four native disulfide bonds of RNase A. Missed cleavages introduced by trypsin treatment for only 3 hours generated sufficient lengths of amino acids for identification of the disulfide bonds. Analysis using MS/MS successfully showed additional fragmentation patterns that are cleavage products of S-S and C-S bonds of disulfide-linkage peptides. These fragmentation patterns generate thioaldehydes, persulfide, and dehydroalanine. This approach of planned digestion with missed cleavages using the DBond algorithm could be applied to other proteins to determine their disulfide linkage and the oxidation patterns of cysteine residues.

  18. Fluoride compounds of tungsten with bridging deprotonated diols

    SciTech Connect

    Kokunov, Yu.V.; Bochkareva, V.A.; Buslaev, Yu.A.

    1987-05-01

    The reactions of tungsten hexafluoride with ethylene glycol, 1,2- and 1,3-propanediol, and 2,3-butanediol have been studied by /sup 19/F NMR. As a result, dimeric, trimeric, and tetrameric compounds with four or five fluoride atoms in which the tungsten atoms are joined to one another by deprotonated moieties of the diols, and each metal atom is bonded to the other metal atoms by means of only one such group, were obtained. Dimeric compounds, in which the two tungsten atoms are joined by two bridging deprotonated moieties of the diols in a stabilized gauche conformation, are obtained at an appropriate concentration of the diols. When the diol:WF/sub 6/ ratio is increased, monomeric octahedral compounds of tungsten with three fluorine atoms form. The parameters of the /sup 19/F NMR spectra of the compounds obtained have been determined.

  19. Refractory metals welded or brazed with tungsten inert gas equipment

    NASA Technical Reports Server (NTRS)

    Wisner, J. P.

    1965-01-01

    Appropriate brazing metals and temperatures facilitate the welding or brazing of base metals with tungsten inert gas equipment. The highest quality bond is obtained when TIG welding is performed in an inert atmosphere.

  20. A Compact Gas/Tungsten-Arc Welding Torch

    NASA Technical Reports Server (NTRS)

    Morgen, Gene E.

    1991-01-01

    Compact gas/tungsten-arc welding torch delivers 100-A current, yet used in confined spaces inaccessible to even smallest commercially available torch. Despite its extremely small size, torch contains all usual components and delivers high current.

  1. OBJECT KINETIC MONTE CARLO SIMULATIONS OF CASCADE ANNEALING IN TUNGSTEN

    SciTech Connect

    Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.; Roche, Kenneth J.; Kurtz, Richard J.; Wirth, Brian D.

    2014-03-31

    The objective of this work is to study the annealing of primary cascade damage created by primary knock-on atoms (PKAs) of various energies, at various temperatures in bulk tungsten using the object kinetic Monte Carlo (OKMC) method.

  2. Tungsten-nickel-cobalt alloy and method of producing same

    DOEpatents

    Dickinson, James M.; Riley, Robert E.

    1977-03-15

    An improved tungsten alloy having a tungsten content of approximately 95 weight percent, a nickel content of about 3 weight percent, and the balance being cobalt of about 2 weight percent is described. A method for producing said tungsten-nickel-cobalt alloy is further described and comprises (a) coating the tungsten particles with a nickel-cobalt alloy, (b) pressing the coated particles into a compact shape, (c) heating said compact in hydrogen to a temperature in the range of 1400.degree. C and holding at this elevated temperature for a period of about 2 hours, (d) increasing this elevated temperature to about 1500.degree. C and holding for 1 hour at this temperature, (e) cooling to about 1200.degree. C and replacing the hydrogen atmosphere with an inert argon atmosphere while maintaining this elevated temperature for a period of about 1/2 hour, and (f) cooling the resulting alloy to room temperature in this argon atmosphere.

  3. Processes of carbon disulfide degradation under the action of a pulsed corona discharge

    NASA Astrophysics Data System (ADS)

    Kuznetsov, D. L.; Filatov, I. E.; Uvarin, V. V.

    2016-08-01

    Experiments on decomposition of carbon disulfide CS2 in air under the action of a pulsed nanosecond corona discharge have been carried out. The energetic efficiency of the degradation amounted to 290-340 g (kW h)-1, which is significantly higher than with the use of a corona discharge at a constant voltage. The main degradation products are sulfur dioxide SO2, carbonyl sulfide COS, sulfuric acid, and carbon dioxide. Processes occurring in pulsed corona discharge plasma and leading to carbon disulfide degradation are considered. Different methods of air purification from carbon disulfide are compared.

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

    PubMed

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

    2016-11-21

    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 Review, we present the chemical design, advantages and limitations of the disulfide rebridging reagents, while summarizing their relevance for synthetic customization of functional protein bioconjugates, as well as the resultant impact and advancement for biomedical applications.

  5. Combined use of ion mobility and collision-induced dissociation to investigate the opening of disulfide bridges by electron-transfer dissociation in peptides bearing two disulfide bonds.

    PubMed

    Massonnet, Philippe; Upert, Gregory; Smargiasso, Nicolas; Gilles, Nicolas; Quinton, Loïc; De Pauw, Edwin

    2015-01-01

    Disulfide bonds are post-translational modifications (PTMs) often found in peptides and proteins. They increase their stability toward enzymatic degradations and provide the structure and (consequently) the activity of such folded proteins. The characterization of disulfide patterns, i.e., the cysteine connectivity, is crucial to achieve a global picture of the active conformation of the protein of interest. Electron-transfer dissociation (ETD) constitutes a valuable tool to cleave the disulfide bonds in the gas phase, avoiding chemical reduction/alkylation in solution. To characterize the cysteine pairing, the present work proposes (i) to reduce by ETD one of the two disulfide bridges of model peptides, resulting in the opening of the cyclic structures, (ii) to separate the generated species by ion mobility, and (iii) to characterize the species using collision-induced dissociation (CID). Results of this strategy applied to several peptides show different behaviors depending on the connectivity. The loss of SH· radical species, observed for all the peptides, confirms the cleavage of the disulfides during the ETD process.

  6. Identifying the presence of a disulfide linkage in peptides by the selective elimination of hydrogen disulfide from collisionally activated alkali and alkaline earth metal complexes.

    PubMed

    Kim, Hugh I; Beauchamp, J L

    2008-01-30

    We report a new method for identifying disulfide linkages in peptides using mass spectrometry. This is accomplished by collisional activation of singly charged cationic alkali and alkaline earth metal complexes, which results in the highly selective elimination of hydrogen disulfide (H2S2). Complexes of peptides possessing disulfide bonds with sodium and alkaline earth metal are generated using electrospray ionization (ESI). Isolation followed by collision induced dissociation (CID) of singly charged peptide complexes results in selective elimination of H2S2 to leave newly formed dehydroalanine residues in the peptide. Further activation of the product yields sequence information in the region previously short circuited by the disulfide bond. For example, singly charged magnesium and calcium ion bound complexes of [Lys8]-vasopressin exhibit selective elimination of H2S2 via low-energy CID. Further isolation of the product followed by CID yields major b- and z-type fragments revealing the peptide sequence in the region between the newly formed dehydroalanine residues. Numerous model peptides provide mechanistic details for the selective elimination of H2S2. The process is initiated starting with a metal stabilized enolate anion at Cys, followed by cleavage of the S-C bond. An examination of the peptic digest of insulin provides an example of the application of the selective elimination of H2S2 for the identification of peptides with disulfide linkages. The energetics and mechanisms of H2S2 elimination from model compounds are investigated using density functional theory (DFT) calculations.

  7. Reactivity of disulfide bonds is markedly affected by structure and environment: implications for protein modification and stability

    PubMed Central

    Karimi, Maryam; Ignasiak, Marta T.; Chan, Bun; Croft, Anna K.; Radom, Leo; Schiesser, Carl H.; Pattison, David I.; Davies, Michael J.

    2016-01-01

    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 that selected disulfides react extremely rapidly, with a variation of 104 in rate constants. Five-membered ring disulfides are particularly reactive compared with acyclic (linear) disulfides or six-membered rings. Particular disulfides in proteins also show enhanced reactivity. This variation occurs 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 of efficient scavengers and high-stability proteins. These data are consistent with selective oxidative damage to particular disulfides, including those in some proteins. PMID:27941824

  8. Reactivity of disulfide bonds is markedly affected by structure and environment: implications for protein modification and stability

    NASA Astrophysics Data System (ADS)

    Karimi, Maryam; Ignasiak, Marta T.; Chan, Bun; Croft, Anna K.; Radom, Leo; Schiesser, Carl H.; Pattison, David I.; Davies, Michael J.

    2016-12-01

    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 that selected disulfides react extremely rapidly, with a variation of 104 in rate constants. Five-membered ring disulfides are particularly reactive compared with acyclic (linear) disulfides or six-membered rings. Particular disulfides in proteins also show enhanced reactivity. This variation occurs 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 of efficient scavengers and high-stability proteins. These data are consistent with selective oxidative damage to particular disulfides, including those in some proteins.

  9. Reactivity of disulfide bonds is markedly affected by structure and environment: implications for protein modification and stability.

    PubMed

    Karimi, Maryam; Ignasiak, Marta T; Chan, Bun; Croft, Anna K; Radom, Leo; Schiesser, Carl H; Pattison, David I; Davies, Michael J

    2016-12-12

    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 that selected disulfides react extremely rapidly, with a variation of 10(4) in rate constants. Five-membered ring disulfides are particularly reactive compared with acyclic (linear) disulfides or six-membered rings. Particular disulfides in proteins also show enhanced reactivity. This variation occurs 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 of efficient scavengers and high-stability proteins. These data are consistent with selective oxidative damage to particular disulfides, including those in some proteins.

  10. Processing effects on the mechanical properties of tungsten heavy alloys

    NASA Technical Reports Server (NTRS)

    Kishi, Toshihito; German, R. M.

    1990-01-01

    Tungsten heavy alloys exhibit significant mechanical property sensitivities to the fabrication variables. These sensitivities are illustrated in this examination of vacuum sintering and the effects of composition, sintering temperature, and sintering time on the mechanical properties of tungsten heavy alloys. Measurements were conducted to assess the density, strength, hardness, and elongation dependencies. A detrimental aspect of vacuum sintering is matrix phase evaporation, although vacuum sintering does eliminate the need for postsintering heat treatments.

  11. Ductile tungsten-nickel-alloy and method for manufacturing same

    DOEpatents

    Ludwig, Robert L.

    1978-01-01

    The tensile elongation of a tungsten-nickel-iron alloy containing essentially 95 weight percent reprocessed tungsten, 3.5 weight percent nickel, and 1.5 weight percent iron is increased from a value of less than about 1 percent up to about 23 percent by the addition of less than 0.5 weight percent of a reactive metal consisting of niobium and zirconium.

  12. Coated Tungsten Powders for Advanced Ordnance Applications, Phase 2, SBIR.

    DTIC Science & Technology

    1992-05-01

    eds., Vapor Devosition (John Wiley & Sons, New York, 1966). 26. D. Kunii and 0. Levenspiel , Fluidization Engineering (John Wiley & Sons, New York, 1966...SUBJECT TERMS (Continue on reverse if necessary and identify by block number) FIELD GROUP SUB-GROUP Tungsten powder, Composites, Chemical vapor deposition...optimized and characterized a fluidized-bed chemical vapor deposition (CVD) process for depositing nickel and iron onto tungsten particles for

  13. Tryptophan fluorescence monitors structural changes accompanying signalling state formation in the photocycle of photoactive yellow protein.

    PubMed

    Gensch, Thomas; Hendriks, Johnny; Hellingwerf, Klaas J

    2004-06-01

    Photoactive yellow protein, a small, water-soluble blue-light absorbing photoreceptor protein from Ectothiorhodospira(Halorhodospira)[space]halophila has a structure with two hydrophobic cores, of which the main one houses its light-sensitive chromophore (p-coumaric acid), separated by a central [small beta]-sheet. This photoreceptor protein contains a single tryptophan residue (W119) that is situated at the interface between the central beta-sheet and its N-terminal cap. The fluorescence properties of W119 in the dark state pG (lambda(max)= 328 nm; Phi(fl)= 0.01; nearly pH-independent) are typical for a buried tryptophan in a hydrophobic environment with significant quenching by nearby amino acid residues. Signalling state formation leads to pH-dependent fluorescence changes: At pH values <6.5 the fluorescence emission increases, with a minor blue shift of the emission maximum. Above this pH, the emission maximum of the tryptophan shifts considerably to the red, whereas its total intensity decreases. These results further support the contention that signalling state formation in PYP leads to significant changes in the structure of this protein, even at sites that are at a considerable distance from the chromophore. The nature of these changes in pB, however, depend upon the pH imposed upon the protein: At slightly alkaline pH, which presumably is closest to the pH to which this protein is exposed in vivo, these changes lead to an exposure of the part of the central beta-sheet harbouring W119. At slightly acidic pH the polarity of the environment of W119 is hardly affected by the formation of the signalling state but the quenching of its fluorescence emission, possibly by nearby amino acids, is reduced. On the other hand, its accessibility for quenching by small molecules in the solution is enhanced at acidic and alkaline pH in the signalling state (pB) compared to the dark state (pG). This latter observation points towards a more flexible structure of the N

  14. Transient low-barrier hydrogen bond in the photoactive state of green fluorescent protein.

    PubMed

    Nadal-Ferret, Marc; Gelabert, Ricard; Moreno, Miquel; Lluch, José M

    2015-12-14

    In this paper, we have analyzed the feasibility of spontaneous proton transfer in GFP at the Franck-Condon region directly after photoexcitation. Computation of a sizeable portion of the potential energy surface at the Franck-Condon region of A the structure shows the process of proton transfer to be unfavorable by 3 kcal mol(-1) in S1 if no further structural relaxation is permitted. The ground vibrational state is found to lie above the potential energy barrier of the proton transfer in both S0 and S1. Expectation values of the geometry reveal that the proton shared between the chromophore and W22, and the proton shared between Ser205 and Glu222 are very close to the center of the respective hydrogen bonds, giving support to the claim that the first transient intermediate detected after photoexcitation (I0*) has characteristics similar to those of a low-barrier hydrogen bond [Di Donato et al., Phys. Chem. Chem. Phys., 2012, 13, 16295]. A quantum dynamical calculation of the evolution in the excited state shows an even larger probability of finding those two protons close to the center compared to in the ground state, but no formation of the proton-transferred product is observed. A QM/MM photoactive state geometry optimization, initiated using a configuration obtained by taking the A minimum and moving the protons to the product side, yields a minimum energy structure with the protons transferred and in which the His148 residue is substantially closer to the now anionic chromophore. These results indicate that: (1) proton transfer is not possible if structural relaxation of the surroundings of the chromophore is prevented; (2) protons H1 and H3 especially are found very close to the point halfway between the donor and acceptor after photoexcitation when the zero-point energy is considered; (3) a geometrical parameter exists (the His148-Cro distance) under which the structure with the protons transferred is not a minimum, and that, if included, should lead to the

  15. Role of a helix B lysine residue in the photoactive site in channelrhodopsins.

    PubMed

    Li, Hai; Govorunova, Elena G; Sineshchekov, Oleg A; Spudich, John L

    2014-04-15

    In most studied microbial rhodopsins two conserved carboxylic acid residues (the homologs of Asp-85 and Asp-212 in bacteriorhodopsin) and an arginine residue (the homolog of Arg-82) form a complex counterion to the protonated retinylidene Schiff base, and neutralization of the negatively charged carboxylates causes red shifts of the absorption maximum. In contrast, the corresponding neutralizing mutations in some relatively low-efficiency channelrhodopsins (ChRs) result in blue shifts. These ChRs do not contain a lysine residue in the second helix, conserved in higher efficiency ChRs (Lys-132 in the crystallized ChR chimera). By action spectroscopy of photoinduced channel currents in HEK293 cells and absorption spectroscopy of detergent-purified pigments, we found that in tested ChRs the Lys-132 homolog controls the direction of spectral shifts in the mutants of the photoactive site carboxylic acid residues. Analysis of double mutants shows that red spectral shifts occur when this Lys is present, whether naturally or by mutagenesis, and blue shifts occur when it is replaced with a neutral residue. A neutralizing mutation of the Lys-132 homolog alone caused a red spectral shift in high-efficiency ChRs, whereas its introduction into low-efficiency ChR1 from Chlamydomonas augustae (CaChR1) caused a blue shift. Taking into account that the effective charge of the carboxylic acid residues is a key factor in microbial rhodopsin spectral tuning, these findings suggest that the Lys-132 homolog modulates their pKa values. On the other hand, mutation of the Arg-82 homolog that fulfills this role in bacteriorhodopsin caused minimal spectral changes in the tested ChRs. Titration revealed that the pKa of the Asp-85 homolog in CaChR1 lies in the alkaline region unlike in most studied microbial rhodopsins, but is substantially decreased by introduction of a Lys-132 homolog or neutralizing mutation of the Asp-212 homolog. In the three ChRs tested the Lys-132 homolog also alters

  16. Electrodeposited ZnO with squaraine sentisizers as photoactive anode of DSCs

    NASA Astrophysics Data System (ADS)

    Venditti, Iole; Barbero, Nadia; Vittoria Russo, Maria; Di Carlo, Aldo; Decker, Franco; Fratoddi, Ilaria; Barolo, Claudia; Dini, Danilo

    2014-03-01

    The adsorption behavior of two symmetrical indolenine-based squaraines, indicated with VG1-C2 and VG1-C10, sensitizing electrodeposited mesoporous zinc oxide (ZnO), was studied and compared with that of di-tetrabutylammonium cis-bis(isothiocyanato) bis(2,2‧-bipyridyl-4,4‧-dicarboxylato) ruthenium (II) (N719). The choice of squaraines as metal-free dye-sensitizers was motivated by their far-red NIR sensitivity with respect to the traditional Ru complex-based dyes, the ease of their preparation and their higher molar extinction coefficient. The electrochemically grown ZnO here described were porous due to the high volume yield of electrodeposition (about 104 cm3 of ZnO per unit charge of electrolysis). In the present analysis the process of sensitization of TiO2 with the same set of dyes and the performance of the corresponding DSCs were also considered for sake of comparison. VG1-C2 sensitizer proved to be particularly effective electron injector in ZnO electrodes giving larger photocurrents in VG1-C2-sensitized ZnO with respect to TiO2. The latter system presented higher kinetic stability of the photoinjected charges as evidenced by the larger photovoltages of TiO2-based DSCs with respect to ZnO-based devices with the same sensitizer. The long alkyl substituents in squaraine VG1-C10 inhibit electron injection in ZnO and a specific effect of electrical passivation of the ZnO surface introduced by the bulky apolar groups was claimed. Overall efficiencies in the order of 1% were measured with the ZnO-based DSCs under AM 1.5 solar simulator when the photoactive area and the thickness of ZnO films were 0.5 cm2 and 2 μm, respectively. These results on ZnO-based DSCs with the oxide prepared at temperatures below 260 °C are particularly interesting considering the relatively large area and small thickness of the related electrodes, which makes them in principle useful for application in weakly absorbing devices utilizing flexible substrates.

  17. Using CO to NOX Ratios to Understand the Impact of Photoactive Roadways on Urban Atmospheric Chemistry and their Efficiency in Mitigating Air Pollution

    NASA Astrophysics Data System (ADS)

    Toro, C.; Jobson, B. T.; Haselbach, L.; Shen, S.

    2015-12-01

    Photoactive roadways and the incorporation of diverse photocatalytic surfaces into the built environment have been proposed as a strategy to improve air quality in urban areas. Laboratory studies show that surfaces treated with TiO2 are efficient in removing nitrogen oxides (NOX). Nonetheless, measurements under ambient conditions capable of isolating the impact of the photoactive surface are scarce. Previous work by our group demonstrated that CO remains stable during the timescale where NOX removal is detected, and thus can be used as a tracer. The work presented herein focuses on outdoor tests comparing CO to NOX ratios (CO/NOX) before and after interacting with photoactive pavement materials. The samples were placed in a Teflon chamber receiving a controlled flow of ambient air supplemented with a constant addition of CO and NO calibration gases. Experiments started before sunrise and continued until sunset to understand the variation due to changing UV levels. CO and NOx were monitored at the input and output of the chamber; O3 was monitored at the input. Preliminary results with asphalt roadway samples indicate that while the input CO/NOX remains constant during the day, the output CO/NOX shows a maximum during early morning and subsequently decreases to a steady value throughout the afternoon. Our previous laboratory work indicates that NO2 removal by photoactive asphalt is smaller than that of NO. We hypothesize that the decrease in the CO/NOx ratio after early morning hours is caused by 1) the enhancement in O3 concentrations as the atmospheric photochemistry increases resulting in more NO2 entering the chamber and 2) NO2 released during photocatalytic NO removal process. Therefore, as the NO2/NO increases, the efficiency of photoactive process decreases indicating that the potential benefit from photoactive roads would likely be driven by a balance between UV levels and local photochemistry.

  18. Effect of deuterium retention upon sputtering yield of tungsten by deuterons

    NASA Astrophysics Data System (ADS)

    Kenmotsu, T.; Ono, T.; Wada, M.

    2011-08-01

    Sputtering yields of tungsten from tungsten containing deuterium (D2) and tungsten containing carbon (C) atoms bombarded by deuterium and carbon atoms are calculated with a Monte Carlo code ACAT. The ACAT results have shown that the tungsten sputtering yields are changed by carbon retention in tungsten. The tungsten sputtering yield by deuterium bombardment around the sputtering threshold for pure tungsten have been enlarged by two mechanisms; one is the reduction in sputtering threshold due to smaller surface binding energy, the other is the enhanced development of collision cascade. As the carbon bombarding energy exceeds 200-300 eV, the sputtering yields for tungsten retaining deuterium and carbon become smaller due to the reduction in density of tungsten target atoms.

  19. Alternative processing methods for tungsten-base composite materials

    SciTech Connect

    Ohriner, E.K.; Sikka, V.K.

    1996-06-01

    Tungsten composite materials contain large amounts of tungsten distributed in a continuous matrix phase. Current commercial materials include the tungsten-nickel-iron with cobalt replacing some or all of the iron, and also tungsten-copper materials. Typically, these are fabricated by liquid-phase sintering of blended powders. Liquid-phase sintering offers the advantages of low processing costs, established technology, and generally attractive mechanical properties. However, liquid-phase sintering is restricted to a very limited number of matrix alloying elements and a limited range of tungsten and alloying compositions. In the past few years, there has been interest in a wider range of matrix materials that offer the potential for superior composite properties. These must be processed by solid-state processes and at sufficiently low temperatures to avoid undesired reactions between the tungsten and the matrix phase. These processes, in order of decreasing process temperature requirements, include hot isostatic pressing (HEPing), hot extrusion, and dynamic compaction. The HIPing and hot extrusion processes have also been used to improve mechanical properties of conventional liquid-phase-sintered materials. The results of laboratory-scale investigations of solid-state consolidation of a variety of matrix materials, including titanium, hafnium, nickel aluminide, and steels are reviewed. The potential advantages and disadvantages of each of the possible alternative consolidation processes are identified. Post consolidation processing to control microstructure and macrostructure is discussed, including novel methods of controlling microstructure alignment.

  20. Alternative processing methods for tungsten-base composite materials

    SciTech Connect

    Ohriner, E.K.; Sikka, V.K.

    1995-12-31

    Tungsten composite materials contain large amounts of tungsten distributed in a continuous matrix phase. Current commercial materials include the tungsten-nickel-iron with cobalt replacing some or all of the iron, and also tungsten-copper materials. Typically, these are fabricated by liquid-phase sintering of blended powders. Liquid-phase sintering offers the advantages of low processing costs, established technology, and generally attractive mechanical properties. However, liquid-phase sintering is restricted to a very limited number of matrix alloying elements and a limited range of tungsten and alloying compositions. In the past few years, there has been interest in a wider range of matrix materials that offer the potential for superior composite properties. These must be processed by solid-state processes and at sufficiently low temperatures to avoid undesired reactions between the tungsten and the matrix phase. These processes, in order of decreasing process temperature requirements, include hot-isostatic pressing (HIPing), hot extrusion, and dynamic compaction. The HIPing and hot extrusion processes have also been used to improve mechanical properties of conventional liquid-phase-sintered materials. Results of laboratory-scale investigations of solid-state consolidation of a variety of matrix materials, including titanium, hafnium, nickel aluminide, and steels are reviewed. The potential advantages and disadvantages of each of the possible alternative consolidation processes are identified. Postconsolidation processing to control microstructure and macrostructure is discussed, including novel methods of controlling microstructure alignment.