WorldWideScience

Sample records for catalyzed reporter deposition

  1. In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition

    DEFF Research Database (Denmark)

    Kofoed, Michael Vedel; Stief, Peter; Poulsen, Morten; Schramm, Andreas

    In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition   Michael V.W. Kofoed, Peter Stief, Morten Poulsen, and Andreas Schramm Department of Biological Sciences, Microbiology, University of Aarhus, Denmark Denitrification, the sequential...... and catalyzed fluorescent reporter deposition (CARD-FISH). The general feasibility of the approach was first tested with pure cultures of Pseudomonas stutzeri and various denitrifying and nitrate-reducing isolates. Detailed studies of probe specificity and hybridization conditions using Clone-FISH of...

  2. Catalyzed Reporter Deposition-Fluorescence In Situ Hybridization Allows for Enrichment-Independent Detection of Microcolony-Forming Soil Bacteria

    OpenAIRE

    Ferrari, Belinda C.; Tujula, Niina; Stoner, Kate; Kjelleberg, Staffan

    2006-01-01

    Advances in the growth of hitherto unculturable soil bacteria have emphasized the requirement for rapid bacterial identification methods. Due to the slow-growing strategy of microcolony-forming soil bacteria, successful fluorescence in situ hybridization (FISH) requires an rRNA enrichment step for visualization. In this study, catalyzed reporter deposition (CARD)-FISH was employed as an alternative method to rRNA enhancement and was found to be superior to conventional FISH for the detection ...

  3. Hydrogen dilution effect on microstructure of Si thin film grown by catalyzer enhanced chemical vapor deposition

    International Nuclear Information System (INIS)

    The effect of hydrogen dilution on microstructure of in situ polycrystalline Si (poly-Si) films grown by catalyzer-enhanced chemical vapor deposition (CECVD) has been investigated by using transmission electron microscopy (TEM) and transmission electron diffraction (TED) analysis. It was shown that the increase of the hydrogen dilution ratio resulted in transition of microstructure of Si thin film from amorphous to polycrystalline in CECVD at low substrate temperature (∼80 deg. C). These results indicate that the CECVD technique is a promising candidate to grow high-quality in situ polycrystalline Si films on glass or a flexible substrate for low-temperature poly-Si (LTPS) and flexible displays

  4. Hydrogen dilution effect on microstructure of Si thin film grown by catalyzer enhanced chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Han-Ki [School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology (KIT), 1 Yangho-dong, Gumi, Gyeongbuk, 730-701 (Korea, Republic of)]. E-mail: hkkim@kumoh.ac.kr

    2006-12-15

    The effect of hydrogen dilution on microstructure of in situ polycrystalline Si (poly-Si) films grown by catalyzer-enhanced chemical vapor deposition (CECVD) has been investigated by using transmission electron microscopy (TEM) and transmission electron diffraction (TED) analysis. It was shown that the increase of the hydrogen dilution ratio resulted in transition of microstructure of Si thin film from amorphous to polycrystalline in CECVD at low substrate temperature ({approx}80 deg. C). These results indicate that the CECVD technique is a promising candidate to grow high-quality in situ polycrystalline Si films on glass or a flexible substrate for low-temperature poly-Si (LTPS) and flexible displays.

  5. Supercritical Fluid Atomic Layer Deposition: Base-Catalyzed Deposition of SiO2.

    Science.gov (United States)

    Kalan, Roghi E; McCool, Benjamin A; Tripp, Carl P

    2016-07-19

    An in situ FTIR thin film technique was used to study the sequential atomic layer deposition (ALD) reactions of SiCl4, tetraethyl orthosilicate (TEOS) precursors, and water on nonporous silica powder using supercritical CO2 (sc-CO2) as the solvent. The IR work on nonporous powders was used to identify the reaction sequence for using a sc-CO2-based ALD to tune the pore size of a mesoporous silica. The IR studies showed that only trace adsorption of SiCl4 occurred on the silica, and this was due to the desiccating power of sc-CO2 to remove the adsorbed water from the surface. This was overcome by employing a three-step reaction scheme involving a first step of adsorption of triethylamine (TEA), followed by SiCl4 and then H2O. For TEOS, a three-step reaction sequence using TEA, TEOS, and then water offered no advantage, as the TEOS simply displaced the TEA from the silica surface. A two-step reaction involving the addition of TEOS followed by H2O in a second step did lead to silica film growth. However, higher growth rates were obtained when using a mixture of TEOS/TEA in the first step. The hydrolysis of the adsorbed TEOS was also much slower than that of the adsorbed SiCl4, and this was overcome by using a mixture of water/TEA during the second step. While the three-step process with SiCl4 showed a higher linear growth rate than obtained with two-step process using TEOS/TEA, its use was not practical, as the HCl generated led to corrosion of our sc-CO2 delivery system. However, when applying the two-step ALD reaction using TEOS on an MCM-41 powder, a 0.21 nm decrease in pore diameter was obtained after the first ALD cycle whereas further ALD cycles did not lead to further pore size reduction. This was attributed to the difficulty in removal of the H2O in the pores after the first cycle. PMID:27338186

  6. A novel Ag catalyzation process using swelling impregnation method for electroless Ni deposition on Kevlar® fiber

    Science.gov (United States)

    Pang, Hongwei; Bai, Ruicheng; Shao, Qinsi; Gao, Yufang; Li, Aijun; Tang, Zhiyong

    2015-12-01

    A novel Ag catalyzation process using swelling impregnation pretreatment method was developed for electroless nickel (EN) deposition on Kevlar fiber. Firstly, the fiber was immersed into an aqueous dimethylsulfoxide (DMSO) solution of silver nitrate to impart silver nitrate into the inner part of the fiber near the surface. Subsequently silver nitrate was reduced to metal silver nanoparticles on the fiber surface by treatment with aqueous solution of sodium borohydride. After electroless plating, a dense and homogeneous nickel coating was obtained on the fiber surface. The silver nanoparticles formed at the fiber surface functioned as a catalyst for electroless deposition as well as an anchor for the plated layer. The study also revealed that the incorporation of surfactant sodium dodecyl sulfate (SDS) in electroless nickel plating bath can enhance the adhesion strength of EN layer with the fiber surface and minimize the surface roughness of the EN coating. The Ni plated Kevlar fiber possessed excellent corrosion resistance and high tensile strength.

  7. Fabrication of highly ultramicroporous carbon nanofoams by SF6-catalyzed laser-induced chemical vapor deposition

    Science.gov (United States)

    Hattori, Yoshiyuki; Shuhara, Ai; Kondo, Atsushi; Utsumi, Shigenori; Tanaka, Hideki; Ohba, Tomonori; Kanoh, Hirofumi; Takahashi, Kunimitsu; Vallejos-Burgos, Fernando; Kaneko, Katsumi

    2016-05-01

    We have developed a laser-induced chemical vapor deposition (LCVD) method for preparing nanocarbons with the aid of SF6. This method would offer advantages for the production of aggregates of nanoscale foams (nanofoams) at high rates. Pyrolysis of the as-grown nanofoams induced the high surface area (1120 m2 g-1) and significantly enhanced the adsorption of supercritical H2 (16.6 mg g-1 at 77 K and 0.1 MPa). We also showed that the pyrolized nanofoams have highly ultramicroporous structures. The pyrolized nanofoams would be superior to highly microporous nanocarbons for the adsorption of supercritical gases.

  8. Palladium deposits spontaneously grown on nickel foam for electro-catalyzing methanol oxidation: Effect of precursors

    Science.gov (United States)

    Niu, Xiangheng; Zhao, Hongli; Lan, Minbo

    2016-02-01

    Methanol, a high-energy substance, is widely used for green fuel cells. However, the sluggish electrochemical methanol oxidation reaction (MOR) on state-of-the-art catalysts still requires for exploring high-performance and low-cost materials to further promote the reaction kinetics at low overpotentials. Here we carried out the first electrocatalytic comparison study of two Ni foam-supported Pd nanomaterials (Pd-2-Ni and Pd-4-Ni, respectively), obtained through the spontaneous galvanic replacement of Ni with different palladic precursors ([PdCl4]2- and [PdCl6]2-, respectively), toward MOR. With replacement, Pd deposits with discrepant arrangements and coverages were grown on the porous Ni support. Compared to commercial Pd/C, both Pd-2-Ni and Pd-4-Ni exhibited better mass activity and catalytic durability for MOR in alkaline media. More interestingly, different palladic precursors made a significant effect on the catalytic performance of the Ni foam-supported Pd deposits. In Pd-4-Ni, the 2:1 stoichiometric replacement of Ni with [PdCl6]2- enabled the incompact arrangement of Pd structures, with more exposure of Ni atoms adjoined to Pd atoms on the catalytic interface compared to Pd-2-Ni. As a result, with the favorable Ni-neighbor-Pd regime and the higher utilization efficiency of Pd atoms, the synthesized Pd-4-Ni catalyst provided a mass activity of approximately 1.5 times higher than Pd-2-Ni toward MOR.

  9. Ultrasensitive electrochemical immunosensor employing glucose oxidase catalyzed deposition of gold nanoparticles for signal amplification.

    Science.gov (United States)

    Zhang, Jie; Pearce, Mark C; Ting, Boon Ping; Ying, Jackie Y

    2011-09-15

    This paper describes a novel enzymatic amplification strategy for ultrasensitive electrochemical immunosensing. This approach utilizes glucose oxidase for the enzymatic deposition of gold nanoparticles onto an indium tin oxide (ITO) electrode surface using a novel gold developer solution consisting of 20 mM of glucose, 20 mM of NaSCN, 0.5 M of p-benzoquinone (PBQ) and 1 mM of AuCl(4)(-) dissolved in 0.1 M of pH 7.5 phosphate buffer solution. The amount of gold deposited was quantified electrochemically by monitoring the reduction of gold oxide in an aqueous solution of 0.5 M of H(2)SO(4), which was correlated to the amount of antigens in the solution. The effectiveness of this strategy was demonstrated experimentally through the construction of an immunosensor for the detection of mouse IgG using a sandwich immunoassay in a linear dynamic range of 5 pg/ml to 50 ng/ml. A good mean apparent recovery in the range of 88-102% was obtained over the entire linear dynamic range of the sensor response in the serum samples. This suggested that the immunosensor would be useful for the testing of proteins in real clinical samples. PMID:21782410

  10. Sub-femtomolar electrochemical detection of DNA using surface circular strand-replacement polymerization and gold nanoparticle catalyzed silver deposition for signal amplification.

    Science.gov (United States)

    Gao, Fenglei; Zhu, Zhu; Lei, Jianping; Geng, Yao; Ju, Huangxian

    2013-01-15

    A highly sensitive method was developed for detection of target DNA. This method combined circular strand-displacement polymerization (CSRP) with silver enhancement to achieve dual signal amplification. After molecular beacon (MB) hybridized with target DNA, the reporter gold nanoparticle (Au NPs) was attached to an electrode surface by hybridization between Au NP labeled primer and stem part of the MB to initiate a polymerization of DNA strand, which led to the release of target and another polymerization cycle. Thus the CSRP produced the multiplication of target-related reporter Au NPs on the surface. The Au NPs then catalyzed silver deposition for subsequent stripping analysis of silver. The dual signal amplification offered a dramatic enhancement of the stripping response. This signal could discriminate perfect matched target DNA from 1-base mismatch DNA. The dynamic range of the sequence-specific DNA detection was from 10(-16) to 10(-12)mol L(-1) with a detection limit down to sub-femtomolar level. This proposed method exhibited an efficient amplification performance, and would open new opportunities for sensitive detection of other biorecognition events. PMID:22883748

  11. Energy-deposition studies. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Vroom, D.A.

    1976-08-31

    Studies on energy deposition in materials by high energy radiation based on excitation measurements and measurements of secondary electron emission from the ionization process are reported. The experimental apparatus used for studying excitation in low-energy electron collisions with hydrogen and deuterium is described. Differential angular distribution measurements of photoelectrons emitted from water vapor and nitric oxide are reported. Also, electron impact secondary electron differential cross sections are presented for hydrogen, methane, acetylene, ethylene, ethane, propane, and butane at 1, 2.5, 5, 7.5, and 10 keV. (WHK)

  12. Particle deposition in granular media: Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Tien, Chi

    1987-01-01

    This paper discusses topics on particle deposition in granular media. The six topics discussed are: experimental determination of initial collection efficiency in granular beds - an assessment of the effect of instrument sensitivity and the extent of particle bounce-off; deposition of polydispersed aerosols in granular media; in situ observation of aerosol deposition in a two-dimensional model filter; solid velocity in cross-flow granular moving bed; aerosol deposition in granular moving bed; and aerosol deposition in a magnetically stabilized fluidized bed. (LSP)

  13. Boron deposition from fused salts. Final report

    International Nuclear Information System (INIS)

    A partial evaluation of the feasibility of a process to electrodeposit pure coherent coatings of elemental boron from molten fluorides has been performed. The deposit produced was powdery and acicular, unless the fluoride melt was purified to have very low oxygen concentration. When the oxygen activity was reduced in the melt by addition of crystalline elemental boron, dense, amorphous boron deposit was produced. The boron deposits produced had cracks but were otherwise pure and dense and ranged up to 0.35 mm thick. Information derived during this project suggests that similar deposits might be obtained crack-free up to 1.00 mm thick by process modifications and improvements

  14. Investigation of parameters critical to muon-catalyzed fusion: Annual performance report, 1986-1987

    International Nuclear Information System (INIS)

    It has been demonstrated (in conjunction with our colleagues) that muon catalysis cycling rates increase rapidly with increasing deuterium-tritium gas temperatures and densities. Furthermore, muon-capture losses are significantly smaller than predicted before the experiments began, although recent theoretical work narrows the gap between theory and observation. As a result of these effects, it was possible to achieve muon-catalyzed fusion yields of 150 fusions/muon (average). The fusion energy thereby released, nearly 3 GeV/muon, significantly exceeds theoretical expectations, and still higher yields are expected. Therefore, the limits of muon-catalyzed fusion are being explored to provide answers to questions regarding energy applications of muon-catalyzed fusion

  15. MOCVD Growth of High-Quality and Density-Tunable GaAs Nanowires on ITO Catalyzed by Au Nanoparticles Deposited by Centrifugation.

    Science.gov (United States)

    Wu, Dan; Tang, Xiaohong; Yoon, Ho Sup; Wang, Kai; Olivier, Aurelien; Li, Xianqiang

    2015-12-01

    High-quality and density-tunable GaAs nanowires (NWs) are directly grown on indium tin oxide (ITO) using Au nanoparticles (NPs) as catalysts by metal organic chemical vapor deposition (MOCVD). Au catalysts were deposited on ITO glass substrate using a centrifugal method. Compared with the droplet-only method, high-area density Au NPs were uniformly distributed on ITO. Tunable area density was realized through variation of the centrifugation time, and the highest area densities were obtained as high as 490 and 120 NP/μm(2) for 10- and 20-nm diameters of Au NPs, respectively. Based on the vapor-liquid-solid growth mechanism, the growth rates of GaAs NWs at 430 °C were 18.2 and 21.5 nm/s for the highest area density obtained of 10- and 20-nm Au NP-catalyzed NWs. The growth rate of the GaAs NWs was reduced with the increase of the NW density due to the competition of precursor materials. High crystal quality of the NWs was also obtained with no observable planar defects. 10-nm Au NP-induced NWs exhibit wurtzite structure whereas zinc-blende is observed for 20-nm NW samples. Controllable density and high crystal quality of the GaAs NWs on ITO demonstrate their potential application in hybrid a solar cell. PMID:26487507

  16. Oxidation and reduction of copper and iron species in steam generator deposits - Effects of hydrazine, carbohydrazide and catalyzed hydrazine

    International Nuclear Information System (INIS)

    It has long been suspected that oxidation and reduction of secondary side deposits in PWR steam generators have a significant influence on the onset of intergranular attack and stress corrosion cracking (IGA/SCC) of mill annealed Alloy 600 steam generator tubes. It is believed that these same processes could affect the possible future occurrence of IGA/SCC of thermally treated Alloy 600 and Alloy 690 tubes that are in newer steam generators. The working hypothesis for describing the influence of oxides on accelerated tube degradation is that deposits formed during normal operation are oxidized during lay-up. During subsequent operation, these oxidized species accelerate tube degradation by raising the electrochemical potential. (authors)

  17. Rapid Deposition of Extensin during the Elicitation of Grapevine Callus Cultures Is Specifically Catalyzed by a 40-Kilodalton Peroxidase1

    Science.gov (United States)

    Jackson, Phil A.P.; Galinha, Carla I.R.; Pereira, Cristina S.; Fortunato, Ana; Soares, Nelson C.; Amâncio, Sara B.Q.; Ricardo, Cândido P. Pinto

    2001-01-01

    Elicitation or peroxide stimulation of grape (Vitis vinifera L. cv Touriga) vine callus cultures results in the rapid and selective in situ insolubilization of an abundant and ionically bound cell wall protein-denominated GvP1. Surface-enhanced laser desorption/ionization/time of flight-mass spectrometry analysis, the amino acid composition, and the N-terminal sequence of purified GvP1 identified it as an 89.9-kD extensin. Analysis of cell walls following the in situ insolubilization of GvP1 indicates large and specific increases in the major amino acids of GvP1 as compared with the amino acids present in salt-eluted cell walls. We calculate that following deposition, covalently bound GvP1 contributes up to 4% to 5% of the cell wall dry weight. The deposition of GvP1 in situ requires peroxide and endogenous peroxidase activity. Isoelectric focusing of saline eluates of callus revealed only a few basic peroxidases that were all isolated or purified to electrophoretic homogeneity. In vitro and in situ assays of extensin cross-linking activity using GvP1 and peroxidases showed that a 40-kD peroxidase cross-linked GvP1 within minutes, whereas other grapevine peroxidases had no significant activity with GvP1. Internal peptide sequences indicated this extensin peroxidase (EP) is a member of the class III peroxidases. We conclude that we have identified and purified an EP from grapevine callus that is responsible for the catalysis of GvP1 deposition in situ during elicitation. Our results suggest that GvP1 and this EP play an important combined role in grapevine cell wall defense. PMID:11706187

  18. Techniques for freeing deposited canisters. Final report

    International Nuclear Information System (INIS)

    Four different techniques for removal of the bentonite buffer around a deposited canister have been identified, studied and evaluated: mechanical, hydrodynamical, thermal, and electrical techniques. Different techniques to determine the position of the canister in the buffer have also been studied: mechanical, electromagnetic, thermal and acoustic techniques. The mechanical techniques studied are full-face boring, milling and core-drilling. It is expected that the bentonite can be machined relatively easily. It is assessed that cooling by means of flushing water over the outer surfaces of the tools is not feasible in view of the tendency of bentonite to form a gel. The mechanical techniques are characterized by the potential of damaging the canister, a high degree of complexity, and high requirements of energy/power input. The generated byproduct is solid and cannot be removed by means of flushing. Removal is assessed to be simplest in conjunction with full-face boring and most difficult when coredrilling is applied. The hydrodynamical techniques comprise high-pressure hydrodynamic techniques, where pressures above and below 100 bar, and low pressure hydrodynamical techniques (< 10 bar) are separated. At pressures above 100 bar, a water jet with a diameter of approximately a millimetre cuts through the material. If desired, sand can be added to the jet. At pressures below 100 bar the jet has a diameter of one or a few centimetres. The liquid contains a few percent of salt, which is essential for the efficiency of the process. The flushing is important not only because it removes the modified bentonite but also because it frees previously unaffected bentonite and thereby makes it accessible to chemical modification. All of the hydrodynamical techniques are applicable for freeing the end surface as well as the mantle surface. The degree of complexity and the requirement on energy/power decrease with a decrease in pressure. A significant potential for damaging the

  19. Growth and process modeling studies of nickel-catalyzed metalorganic chemical vapor deposition of GaN nanowires

    Science.gov (United States)

    Burke, Robert A.; Lamborn, Daniel R.; Weng, Xiaojun; Redwing, Joan M.

    2009-06-01

    A combination of experimental and computational fluid dynamics-based reactor modeling studies were utilized to study the effects of process conditions on GaN nanowire growth by metalorganic chemical vapor deposition (MOCVD) in an isothermal tube reactor. The GaN nanowires were synthesized on (0 0 0 1) sapphire substrates using nickel thin films as a catalyst. GaN nanowire growth was observed over a furnace temperature range of 800-900 °C at V/III ratios ranging from 33 to 67 and was found to be strongly dependent on the position of the substrate relative to the group III inlet tube. The modeling studies revealed that nanowire growth consistently occurred in a region in the reactor where the GaN thin-film deposition rate was reduced and the gas phase consisted primarily of intermediate species produced by the reaction and decomposition of trimethylgallium-ammonia adduct compounds. The GaN nanowires exhibited a predominant [1 1 2¯ 0] growth direction. Photoluminescence measurements revealed an increase in the GaN near-band edge emission intensity and a reduction in the deep-level yellow luminescence with increasing growth temperature and V/III ratio.

  20. Muon-catalyzed fusion experiment target and detector system. Preliminary design report

    International Nuclear Information System (INIS)

    We present detailed plans for the target and particle detector systems for the muon-catalyzed fusion experiment. Requirements imposed on the target vessel by experimental conditions and safety considerations are delineated. Preliminary designs for the target vessel capsule and secondary containment vessel have been developed which meet these requirements. In addition, the particle detection system is outlined, including associated fast electronics and on-line data acquisition. Computer programs developed to study the target and detector system designs are described

  1. A report of fatal cervical throtrast deposition

    International Nuclear Information System (INIS)

    A case of fatal Thorotrastoma seen by a 67-year-old male was reported. The patient received a right carotid angiography in 1943 for the investigation of a gunshot wound during the war. Extravasation of Thorotrast was notified by the physician and a small induration remained. In 1976, the induration increased in size occupying the whole of the right lateral cervical area. This was accompanied with bouts of clonic seizure, loss of consciousness and lower cranial nerve palsies. In June, 1980, A sudden increase of the mass, high fever with general malaise, and permanent lower cranial nerve palsies led the patient seek administration to the University Hospital. His general condition kept detereorating with two attacks of severe hemoptysis and the patient deceased. Necropsy revealed a large Thorotrast granuloma, containing amorphous mass of residual Thorotrast, extending from the cranial base down to the mediastinum. Two perforations, which led to the fatal hemoptysis, were identified at the hypopharynx and tracheocarina. Both the right brachiocephalic artery and innominate vein were occluded and the right carotid artery was constricted to a narrow cleft. A bibliographical review of Thorotrast granuloma was also included. (author)

  2. Investigation of parameters critical to muon-catalyzed fusion: Performance report, May 19-August 31, 1987: [Final technical report

    International Nuclear Information System (INIS)

    We have demonstrated (in conjunction with our colleagues) that muon catalysis cycling rates increase rapidly with increasing deuterium-tritium gas temperatures and densities. Furthermore, muon-capture losses are significantly smaller than predicted before the experiments began, although recent theoretical work narrows the gap between theory and observation. As a result of these effects, we have been able to achieve muon-catalyzed fusion yields of 150 fusions/muon (average). The fusion energy thereby released, nearly 3 GeV/muon, significantly exceeds theoretical expectations, and still higher yields are expected. Therefore, we are exploring the limits of muon-catalyzed fusion, to provide answers to questions regarding energy applications of muon-catalyzed fusion

  3. Ag-deposited silica-coated Fe3O4 magnetic nanoparticles catalyzed reduction of p-nitrophenol

    International Nuclear Information System (INIS)

    In this paper, a novel approach was successfully developed for advanced catalyst Ag-deposited silica-coated Fe3O4 magnetic nanoparticles, which possess a silica coated magnetic core and growth active silver nanoparticles on the outer shell using n-butylamine as the reductant of AgNO3 in ethanol. The as-synthesized nanoparticles have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectra (FT-IR), vibration sample magnetometer (VSM), and have been exploited as a solid phase catalyst for the reduction of p-nitrophenol in the presence of NaBH4 by UV-vis spectrophotometry. The obtained products exhibited monodisperse and bifunctional with high magnetization and excellent catalytic activity towards p-nitrophenol reduction. As a result, the as-obtained nanoparticles showed high performance in catalytic reduction of p-nitrophenol to p-aminophenol with conversion of 95% within 14 min in the presence of an excess amount of NaBH4, convenient magnetic separability, as well as remained activity after recycled more than 6 times. The Fe3O4-SiO2-Ag functional nanostructure could hold great promise for various catalytic reactions.

  4. Acidic deposition: State of science and technology. Report 4. The regional acid deposition model and engineering model. Final report

    International Nuclear Information System (INIS)

    The report describes the Regional Acid Deposition Model (RADM), a constantly evolving system of computational models that describe the major physical and chemical processes involved in acid deposition on a regional scale. RADM was developed by the Acid Deposition Modeling Project (ADMP), established at the National Center for Atmospheric Research (NCAR) in 1983 to design, develop, and implement a comprehensive modeling system suitable for assessment studies to be conducted as part of the National Acid Precipitation Assessment Program (NAPAP). The project was based at NCAR until 1987, when it moved to the Atmospheric Sciences Research Center (ASRC) of the State University of New York (SUNY) at Albany as the focus of its work moved into model testing and application. The ADMP team developed the RADM system, performed preliminary evaluation, transferred the system to the Environmental Protection Agency (EPA), and participated in NAPAP studies designed to test RADM and develop applications for the model

  5. ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES: CLEAN DIESEL TECHNOLOGIES FUEL-BORNE CATALYST WITH MITSUI/PUREARTH CATALYZED WIRE MESH FILTER

    Science.gov (United States)

    The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with Mitsui/PUREarth Catalyzed Wire Mesh Filter manufactured by Clean Diesel Technologies, Inc. The technology is a platinum/cerium fuel-borne catalyst in commerci...

  6. Self-Catalyzed Growth and Characterization of In(As)P Nanowires on InP(111)B Using Metal-Organic Chemical Vapor Deposition

    Science.gov (United States)

    Park, Jeung Hun; Pozuelo, Marta; Setiawan, Bunga P. D.; Chung, Choong-Heui

    2016-04-01

    We report the growth of vertical -oriented InAs x P1- x (0.11 ≤ x ≤ 0.27) nanowires via metal-organic chemical vapor deposition in the presence of indium droplets as catalysts on InP(111)B substrates at 375 °C. Trimethylindium, tertiarybutylphosphine, and tertiarybutylarsine are used as the precursors, corresponding to P/In and As/In molar ratios of 29 and 0.01, respectively. The as-grown nanowire growth morphologies, crystallinity, composition, and optical characteristics are determined using a combination of scanning and transmission electron microscopies, electron diffraction, and X-ray photoelectron, energy dispersive X-ray, and Raman spectroscopies. We find that the InAs x P1- x nanowires are tapered with narrow tops, wider bases, and In-rich In-As alloy tips, characteristic of vapor-liquid-solid process. The wires exhibit a mixture of zinc blende and wurtzite crystal structures and a high density of structural defects such as stacking faults and twins. Our results suggest that the incorporation of As into InP wires decreases with increasing substrate temperature. The Raman spectra obtained from the In(As)P nanowires reveal a red-shift and lower intensity of longitudinal optical mode relative to both InP nanowires and InP(111)B bulk, due to the incorporation of As into the InP matrix.

  7. Self-Catalyzed Growth and Characterization of In(As)P Nanowires on InP(111)B Using Metal-Organic Chemical Vapor Deposition.

    Science.gov (United States)

    Park, Jeung Hun; Pozuelo, Marta; Setiawan, Bunga P D; Chung, Choong-Heui

    2016-12-01

    We report the growth of vertical -oriented InAs x P1-x (0.11 ≤ x ≤ 0.27) nanowires via metal-organic chemical vapor deposition in the presence of indium droplets as catalysts on InP(111)B substrates at 375 °C. Trimethylindium, tertiarybutylphosphine, and tertiarybutylarsine are used as the precursors, corresponding to P/In and As/In molar ratios of 29 and 0.01, respectively. The as-grown nanowire growth morphologies, crystallinity, composition, and optical characteristics are determined using a combination of scanning and transmission electron microscopies, electron diffraction, and X-ray photoelectron, energy dispersive X-ray, and Raman spectroscopies. We find that the InAs x P1-x nanowires are tapered with narrow tops, wider bases, and In-rich In-As alloy tips, characteristic of vapor-liquid-solid process. The wires exhibit a mixture of zinc blende and wurtzite crystal structures and a high density of structural defects such as stacking faults and twins. Our results suggest that the incorporation of As into InP wires decreases with increasing substrate temperature. The Raman spectra obtained from the In(As)P nanowires reveal a red-shift and lower intensity of longitudinal optical mode relative to both InP nanowires and InP(111)B bulk, due to the incorporation of As into the InP matrix. PMID:27094822

  8. Regional aerosol deposition in human upper airways. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Swift, D.L.

    1997-11-01

    During the award period, a number of studies have been carried out related to the overall objective of the project which is to elucidate important factors which influence the upper airway deposition and dose of particles in the size range 0.5 nm - 10 {mu}m, such as particle size, breathing conditions, age, airway geometry, and mode of breathing. These studies are listed below. (1) A high voltage electrospray system was constructed to generate polydispersed 1-10 {mu}m diameter di-ethylhexyl sebacate aerosol for particle deposition studies in nasal casts and in human subjects. (2) The effect of nostril dimensions, nasal passage geometry, and nasal resistance on particle deposition efficiency in forty healthy, nonsmoking adults at a constant flowrate were studied. (3) The effect of nostril dimensions, nasal passage dimensions and nasal resistance on the percentage of particle deposition in the anterior 3 cm of the nasal passage of spontaneously breathing humans were studied. (4) The region of deposition of monodispersed aerosols were studied using replicate casts. (5) Ultrafine aerosol deposition using simulated breath holding path and natural path was compared. (6) An experimental technique was proposed and tested to measure the oral deposition of inhaled ultrafine particles. (7) We have calculated the total deposition fraction of ultrafine aerosols from 5 to 200 n in the extrathoracic airways and in the lung. (8) The deposition fraction of radon progeny in the head airways was studied using several head airway models.

  9. Acidic deposition: State of science and technology. Report 11. Historical changes in surface-water acid-base chemistry in response to acidic deposition. Final report

    International Nuclear Information System (INIS)

    The objectives of the analyses reported in the State of Science report are to: identify the lake and stream populations in the United States that have experienced chronic changes in biologically significant constituents of surface water chemistry (e.g. pH, Al) in response to acidic deposition; quantify biologically meaningful historical changes in chronic surface water chemistry associated with acidic deposition, with emphasis on ANC, pH, and Al; estimate the proportion of lakes nor acidic that were not acidic in pre-industrial times; estimate the proportional response of each of the major chemical constituents that have changed in response to acidic deposition using a subset of statistically selected Adirondack lakes for which paleolimnological reconstructions of pre-industrial surface water chemistry have been performed; evaluate and improve, where appropriate and feasible, empirical models of predicting changes in ANC; and evaluate the response of seepage lakes to acidic deposition

  10. Measurements of dry-deposition parameters for the California acid-deposition monitoring program. Final report

    International Nuclear Information System (INIS)

    The State of California monitors the concentrations of acidic gases and particles at 10 sites throughout the state. Seven sites represent urban areas (South Coast Air Basin - three sites, San Francisco Bay Area, Bakersfield, Santa Barbara, and Sacramento) and three represent forested areas (Sequoia National Park, Yosemite National Park, and Gasquet). Several sites are collocated with monitoring instruments for other air quality and forest response networks. Continuous monitors for the dry deposition network collect hourly average values for ozone, wind speed, wind direction, atmospheric stability, temperature, dew point, time of wetness, and solar radiation. A newly-designed gas/particle sampler collects daytime (6 a.m. to 6 p.m.) and nighttime (6 p.m. to 6 a.m.) samples every sixth day for sulfur dioxide, ammonia, nitrogen dioxide, and nitric acid. Particles are collected on the same day/night schedule in PM(10) and PM(2.5) size ranges, and are analyzed for mass, sulfate, nitrate, chloride, ammonium, sodium, magnesium, potassium, and calcium ions. The sampling schedule follows the regulatory schedule adopted by the EPA and ARB for suspended particulate matter. Wet deposition data are collected at or nearby the dry deposition stations. The first year of the monitoring program included installation of the network, training of technicians, acquisition and validation of data, and transfer of the sampling and analysis technology to Air Resources Board operating divisions. Data have been validated and stored for the period May, 1988 through September, 1989

  11. Kinetic Studies of Iron Deposition Catalyzed by Recombinant Human Liver Heavy, and Light Ferritins and Azotobacter Vinelandii Bacterioferritin Using O2 and H2O2 as Oxidants

    Science.gov (United States)

    Bunker, Jared; Lowry, Thomas; Davis, Garrett; Zhang, Bo; Brosnahan, David; Lindsay, Stuart; Costen, Robert; Choi, Sang; Arosio, Paolo; Watt, Gerald D.

    2005-01-01

    The discrepancy between predicted and measured H2O2 formation during iron deposition with recombinant heavy human liver ferritin (rHF) was attributed to reaction with the iron protein complex [Biochemistry 40 (2001) 10832-10838]. This proposal was examined by stopped-flow kinetic studies and analysis for H2O2 production using (1) rHF, and Azotobacter vinelandii bacterial ferritin (AvBF), each containing 24 identical subunits with ferroxidase centers; (2) site-altered rHF mutants with functional and dysfunctional ferroxidase centers; and (3) rccombinant human liver light ferritin (rLF), containing 110 ferroxidase center. For rHF, nearly identical pseudo-first-order rate constants of 0.18 per second at pH 7.5 were measured for Fe(2+) oxidation by both O2 and H2O2, but for rLF, the rate with O2 was 200-fold slower than that for H2O2 (k-0.22 per second). A Fe(2+)/O2 stoichiometry near 2.4 was measured for rHF and its site altered forms, suggesting formation of H2O2. Direct measurements revealed no H2O2 free in solution 0.5-10 min after all Fe(2+) was oxidized at pH 6.5 or 7.5. These results are consistent with initial H2O2 formation, which rapidly reacts in a secondary reaction with unidentified solution components. Using measured rate constants for rHF, simulations showed that steady-state H2O2 concentrations peaked at 14 pM at approx. 600 ms and decreased to zero at 10-30 s. rLF did not produce measurable H2O2 but apparently conducted the secondary reaction with H2O2. Fe(2+)/O2 values of 4.0 were measured for AvBF. Stopped-flow measurements with AvBF showed that both H2O2 and O2 react at the same rate (k=0.34 per second), that is faster than the reactions with rHF. Simulations suggest that AvBF reduces O2 directly to H2O without intermediate H2O2 formation.

  12. Study on the role of filament temperature on growth of indium-catalyzed silicon nanowires by the hot-wire chemical vapor deposition technique

    Energy Technology Data Exchange (ETDEWEB)

    Chong, Su Kong, E-mail: sukong1985@yahoo.com.my [Low Dimensional Materials Research Centre, Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia); Goh, Boon Tong [Low Dimensional Materials Research Centre, Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia); Dee, Chang Fu [Institute of Microengineering and Nanoelectronics (IMEN), Universiti Kebangsaan Malaysia (UKM), Bangi, Selangor (Malaysia); Rahman, Saadah Abdul [Low Dimensional Materials Research Centre, Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2012-08-15

    Silicon nanowires (SiNWs) were synthesized from indium catalysts on the Si(111) substrate using the hot-wire chemical vapor deposition technique. A tungsten filament with purity of 99.95% was employed for both the evaporation of an indium wire as catalyst and the decomposition of the precursor gas silane diluted in hydrogen. In this study, we investigated the role of the filament temperature (T{sub f}) on the growth and structural properties of the SiNWs. A threshold T{sub f} for the successive growth of the SiNWs via a vapor-liquid-solid process was observed at T{sub f} between 1400 and 1500 Degree-Sign C. For T{sub f} of 1400 Degree-Sign C and below, only a layer of Si shell cladding was formed on the indium core. An increase in T{sub f} above the threshold resulted in a significant increase in the number density and the aspect ratio of the SiNWs. X-ray diffraction and micro-Raman measurements indicated an enhancement in crystallinity of the SiNWs with the increase in T{sub f}. Fourier transform infrared analysis showed an enhancement in the presence of Si-O and Si-H related bonds with the increase in T{sub f}. The Si-O bond is mostly originated from the native oxide layer of SiNWs, while Si-H bond suggests that Si-H{sub x} species were responsible for the growth. -- Highlights: Black-Right-Pointing-Pointer Threshold filament temperature for successive growth of SiNWs is between 1400-1500 Degree-Sign C. Black-Right-Pointing-Pointer Catalytic effect of indium particles is enhanced by removes their native oxide layer. Black-Right-Pointing-Pointer Growth rate of SiNWs is related to the desorption rate of Si radicals. Black-Right-Pointing-Pointer Increase in filament temperature can improve the crystallinity of the SiNWs.

  13. Superacid Catalyzed Depolymerization and Conversion of Coals. Final Technical Report. [HF:BF{sub 2}/H{sub 2}

    Science.gov (United States)

    Olah, G.

    1980-01-01

    We were interested in applying superacid catalyzed cleavage-depolymerization and ionic hydrogenation low temperature conversion of coal to liquid hydrocarbon, as well as obtaining information about the reactions involved and the structure of intermediates of the coal liquefaction process. In order to show the feasibility of our proposed research we have carried out preliminary investigation in these areas. Preceding our work there was no practical application of a superacid system to coal liquefaction. We carried out an extensive study of the potential of the HF:BF{sub 3}/H{sub 2} system for coal hydroliquefaction. Under varying conditions of reactant ratio, reaction time and temperature, we were able to obtain over 95% pyridine extractible product by treating coal in HF:BF{sub 3}:H{sub 2} system at approx. 100 degrees C for 4 hours. The coal to acid ratio was 1:5 and FB{sub 3} at 900 psi and H{sub 2} at 500 psi were used. These are extremely encouraging results in that the conditions used are drastically milder than those used in any known process, such as Exxon donor solvent and related processes. The cyclohexane extractibility of the treated coal was as high as 27% and the yield of liquid distillate at 400 degrees C/5 x 10{sup -3}/sup torr/ was approx. 30%. The infrared spectrum of product coal, extracts and distillates were distinctly different from the starting coal and show a significant increase in the amount of saturates. The {sup 1}H NMR spectrum of cyclohexane extract of the treated coal shows essentially all aliphatic photons. The spectra of other treated coal extracts show increased amounts and types of aliphatic protons as well as significant amounts of protons bound to unsaturated sites. This again indicates that the HF-BF{sub 3} system is depolymerizing the coal to small fragments which are soluble in non-polar solvents.

  14. Iron Deposition in Duodenal Mucosa; A Review and Report of Three Cases in Pediatric Age Group

    Directory of Open Access Journals (Sweden)

    Farzaneh Moatamed

    2011-06-01

    Full Text Available Background:Ferrous sulfate drops are routinely used in Iran in infants older than 6 months of age. Effect of ferrous sulfate drops in preventive or therapeutic doses on gastrointestinal mucosa of infants is not studied as yet. Upper gastrointestinal complications due to acute iron poisoning are well known in this age group. In this article, we reviewed published articles on iron deposition in upper gastro-intestinal tract and also introduce clinical, endoscopic and histological findings in three cases with iron deposition in duodenal mucosa. Cases Presentation:We encountered three cases of iron deposition in duodenal mucosa among about 8000 biopsies during a 10 year period which is a very low incidence despite routine use of iron supplement in children above 6 months of age in this country. One of our cases suffered from steatorrhea and another from failure to thrive, which raises concern about effects of iron deposition in small intestine. Conclusion:The clinical significance and effects of iron deposition in pediatric age group is yet to be elucidated. Iron deposition as a solitary finding is not reported in duodenal biopsies of infants as yet. Since iron supplement is widely used in this age group, it is justified to consider its deposition and possible effects on absorption.

  15. Examination of the relationship between audit committee characteristics and financial reporting quality of Nigerian deposit banks

    OpenAIRE

    Fodio Inuwa MUSA; Foluke Omolayo OLORUNTOBA; Victor Chiedu OBA

    2014-01-01

    This study investigates the effects of audit committee characteristics on the quality of financial reporting by deposit banks in Nigeria. The study employs a multivariate regression analysis to assess the aggregate and individual effect of certain audit committee characteristics on financial reporting of sample banks. The study documents a positive relationship between audit committee independence and quality of financial reporting. Findings also revealed that audit committee expertise has po...

  16. The source term experiments project deposition sample characterization: Interim report

    International Nuclear Information System (INIS)

    A series of four experiments aimed at characterizing the radiological source term associated with postulated severe light water reactor accidents has been conducted at Argonne National Laboratory's TREAT Facility. The experiments were designed to provide dta regarding the physicochemical properties, near the point of origin, of the biologically important volatile fission products released early in such accidents. The experimental vehicles were equipped to capture representative fission products released from fuel rods undergoing severe cladding degradation in a steam environment. Test conditions of pressure, fuel heatup rate, and steam flow were selected to simulate conditions predicted for hypothetical reactor accident sequences. One of the main components of the experimental vehicle's aerosol characterization system, common to all four tests, was a sample tree. It served to suspend coupons composed of a variety of materials, some typical of reactor structures, into the fission-product-laden steam flow. These coupons collected particulates and condensing vapors. Coupons frome ach of the four tests have been examined using scanning electron microscopy and associated energy dispersive x-ray analysis. The results of these initial sample examinations are presented. They are preceeded by a brief description of the test series and the experimental vehicle. Also included is a discussion of planned posttest examinations of other aerosol characterization system components and the test fuel as well as further examinations of the sample tree coupons. Results of the additional examinations thermal-hydraulic data, and interpretation of the information for each test will be included in future reports

  17. Study of elimination of vapor atom deposition. Final report

    International Nuclear Information System (INIS)

    The major objective of this study was to define and evaluate methods by which an optical system could be protected from performance degradation arising from exposure to a beam of heavy metal atoms. The optical system is coupled to a chamber in which the metal atoms are being produced and processed. The coupling aperture is the source of the contaminating metal atom beam, which, if un-attenuated, would degrade the system performance in an unacceptably short period of time. It was agreed early in the program to concentrate on a gaseous scattering technique, with a stated objective of metal beam flux reduction of about 106. Additional constraints require that the scattering gas must not effuse back into the main process chamber at such a rate that it has significant effect on the vacuum level in the chamber, which is of the order of 10-6 torr; finally, the path length between the main chamber and the optical system must not be increased unduly. This report summarizes the analyses that were performed under the program. Section 2 presents a summary review, while the details of the analyses are described in Section 3. Recommendations leading toward final system design are given in Section 4. Finally, an appendix contains a description and printout of a program that was developed and used to facilitate the evaluation of system performance parametrically. 6 refs., 9 figs

  18. Routine estimation and reporting of dry deposition for the U.S.A. Dry-Deposition Network

    International Nuclear Information System (INIS)

    A National Dry Deposition Network (NDDN) was established in the United States during 1986 to document the magnitude, spatial variability, and trends in dry deposition of ozone and acidic particles and gases. Currently, the network consists of 50 stations: 41 in the eastern United States and 9 in the western United States. Dry deposition is not measured directly in the NDDN, but is estimated by an inferential approach, i.e., fluxes are calculated as the product of measured ambient concentration and modeled deposition velocity. The temporal resolution for the dry deposition calculations is weekly. Chemical species include ozone, sulfate, nitrate, ammonium, sulfur dioxide and nitric acid. Preliminary dry deposition calculations yielded the following observations: (1) calculated values of dry deposition for colocated sites are in good agreement suggesting good network precision, and (2) spatial patterns of SO2 and HNO3 dry deposition are consistent with emission patterns

  19. ChtVis-Tomato, a genetic reporter for in vivo visualization of chitin deposition in Drosophila.

    Science.gov (United States)

    Sobala, Lukasz F; Wang, Ying; Adler, Paul N

    2015-11-15

    Chitin is a polymer of N-acetylglucosamine that is abundant and widely found in the biological world. It is an important constituent of the cuticular exoskeleton that plays a key role in the insect life cycle. To date, the study of chitin deposition during cuticle formation has been limited by the lack of a method to detect it in living organisms. To overcome this limitation, we have developed ChtVis-Tomato, an in vivo reporter for chitin in Drosophila. ChtVis-Tomato encodes a fusion protein that contains an apical secretion signal, a chitin-binding domain (CBD), a fluorescent protein and a cleavage site to release it from the plasma membrane. The chitin reporter allowed us to study chitin deposition in time lapse experiments and by using it we have identified unexpected deposits of chitin fibers in Drosophila pupae. ChtVis-Tomato should facilitate future studies on chitin in Drosophila and other insects. PMID:26395478

  20. Final report on LDRD project: Low-cost Pd-catalyzed metallization technology for rapid prototyping of electronic substrates and devices

    Energy Technology Data Exchange (ETDEWEB)

    Chen, K.S.; Morgan, W.P.; Zich, J.L.

    1998-02-01

    A low-cost, thermally-activated, palladium-catalyzed metallization process was developed for rapid prototyping of polymeric electronic substrates and devices. The process was successfully applied in producing adhesiveless copper/polyimide laminates with high peel strengths and thick copper coating; copper/polyimide laminates are widely used in fabricating interconnects such as printed wiring boards (PWBs) and flexible circuits. Also successfully metallized using this low-cost metallization process were: (1) scaled-down models of radar-and-communication antenna and waveguide; (2) scaled-down model of pulsed-power-accelerator electrode; (3) three-dimensional micro-porous, open-cell vitreous carbon foams. Moreover, additive patterned metallization was successfully achieved by selectively printing or plotting the catalyst ink only on areas where metallization is desired, and by uniform thermal activation. Additive patterned metallization eliminates the time-consuming, costly and environmentally-unfriendly etching process that is routinely carried out in conventional subtractive patterned metallization. A metallization process via ultraviolet (UV) irradiation activation was also demonstrated. In this process palladium-catalyst solution is first uniformly coated onto the substrate. A masking pattern is used to cover the areas where metallization is not wanted. UV irradiation is applied uniformly to activate the palladium catalyst and to cure the polymer carrier in areas that are not covered by the mask. Metal is then deposited by electroless plating only or by a combination of electroless and electrolytic plating. This UV-activation technique is particularly useful in additive fine-line patterned metallization. Lastly, computer models for electrolytic and electroless plating processes were developed to provide guidance in plating-process design.

  1. Linking deposit morphology and clogging in subsurface remediation: Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Mays, David C. [University of Colorado Denver

    2013-12-11

    Groundwater is a crucial resource for water supply, especially in arid and semiarid areas of the United States west of the 100th meridian. Accordingly, remediation of contaminated groundwater is an important application of science and technology, particularly for the U.S. Department of Energy (DOE), which oversees a number of groundwater remediation sites from Cold War era mining. Groundwater remediation is complex, because it depends on identifying, locating, and treating contaminants in the subsurface, where remediation reactions depend on interacting geological, hydrological, geochemical, and microbiological factors. Within this context, permeability is a fundamental concept, because it controls the rates and pathways of groundwater flow. Colloid science is intimately related to permeability, because when colloids are present (particles with equivalent diameters between 1 nanometer and 10 micrometers), changes in hydrological or geochemical conditions can trigger a detrimental reduction in permeability called clogging. Accordingly, clogging is a major concern in groundwater remediation. Several lines of evidence suggest that clogging by colloids depends on (1) colloid deposition, and (2) deposit morphology, that is, the structure of colloid deposits, which can be quantified as a fractal dimension. This report describes research, performed under a 2-year, exploratory grant from the DOE’s Subsurface Biogeochemical Research (SBR) program. This research employed a novel laboratory technique to simultaneously measure flow, colloid deposition, deposit morphology, and permeability in a flow cell, and also collected field samples from wells at the DOE’s Old Rifle remediation site. Field results indicate that suspended solids at the Old Rifle site have fractal structures. Laboratory results indicate that clogging is associated with colloid deposits with smaller fractal dimensions, in accordance with previous studies on initially clean granular media. Preliminary

  2. Geology and recognition criteria for uranium deposits of the quartz-pebble conglomerate type. Final report

    International Nuclear Information System (INIS)

    This report is concerned with Precambrian uraniferous conglomerates. This class of deposit has been estimated to contain between approximately 16 and 35 percent of the global uranium reserve in two rather small areas, one in Canada, the other in South Africa. Similar conglomerates, which are often gold-bearing, are, however, rather widespread, being found in parts of most Precambrian shield areas. Data have been synthesized on the geologic habitat and character of this deposit type. The primary objective has been to provide the most relevant geologic observations in a structural fashion to allow resource studies and exploration to focus on the most prospective targets in the shortest possible time

  3. Geology and recognition criteria for uranium deposits of the quartz-pebble conglomerate type. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Button, A.; Adams, S.S.

    1981-03-01

    This report is concerned with Precambrian uraniferous conglomerates. This class of deposit has been estimated to contain between approximately 16 and 35 percent of the global uranium reserve in two rather small areas, one in Canada, the other in South Africa. Similar conglomerates, which are often gold-bearing, are, however, rather widespread, being found in parts of most Precambrian shield areas. Data have been synthesized on the geologic habitat and character of this deposit type. The primary objective has been to provide the most relevant geologic observations in a structural fashion to allow resource studies and exploration to focus on the most prospective targets in the shortest possible time.

  4. Muon Catalyzed Fusion

    Science.gov (United States)

    Armour, Edward A.G.

    2007-01-01

    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  5. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether

    OpenAIRE

    Andrews, Ian P.; Kwon, Ohyun

    2008-01-01

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethy...

  6. International Standard Problem 40 - Aerosol Deposition and Resuspension. Final Comparison Report

    International Nuclear Information System (INIS)

    -October 1997 and the deadline for submission of the results of this second phase was the end of January 1998. A first draft of this comparison report was produced in March 1998, followed by a workshop in Ispra in mid-March. Two errors in the supplied data had been detected and were communicated to the participants in this workshop, one concerning the steam flow rate in the deposition phase of the exercise and the other the size distribution of the resuspended aerosols in the resuspension phase. The decision whether or not to re-do their calculations was left to the each ISP participant and the deadline for the submission of new results, with these or other modifications relative to the previous ones, was the end of May 1998. These new calculations, having been performed in open conditions, are presented separately in this report. The final draft of the comparison report was distribute in June 1998, followed by a final workshop in Ispra the same month. This report is divided into six main sections, one concerning the experimental set-up and results, two each for the deposition and resuspension phases of the International Standard Problem (blind and open calculations), and one on general conclusions and recommendations. According to the opinion of the ISP participants, the results in the two sections on the deposition and resuspension exercises are listed by computer code and, for each code, by organisation. The calculations submitted by the Joint Research Centre are included together with the others. Although the JRC staff who performed the calculations did not have access to the experimental results before submitting their results, their knowledge of the facility puts their calculations in a separate class

  7. Visual Hallucinations and Amyloid Deposition in Parkinson's Disease Dementia: A Case Report.

    Science.gov (United States)

    Um, Yoo Hyun; Kim, Tae-Won; Jeong, Jong-Hyun; Seo, Ho-Jun; Han, Jin-Hee; Hong, Seung-Chul; Jung, Won-Sang; Choi, Woo Hee; Lee, Chang-Uk; Lim, Hyun Kook

    2016-05-01

    Parkinson's disease dementia (PDD) is notorious for its debilitating clinical course and high mortality rates. Consequently, various attempts to investigate predictors of cognitive decline in Parkinson's disease (PD) have been made. Here we report a case of a 75-year-old female patient with PD who visited the clinic with complaints of recurrent visual hallucinations and cognitive decline, whose symptoms were ameliorated by the titration of rivastigmine. Imaging results showed pronounced diffuse cortical amyloid deposition evidenced by 18F-florbetaben amyloid positron emission tomography (PET) imaging. This observation suggests that pronounced amyloid deposition and visual hallucinations in PD patients could be clinically significant predictors of cognitive decline in PD patients. Future research should concentrate on accumulating more evidence for possible predictors of cognitive decline and their association with PD pathology that can enable an early intervention and standardized treatment in PDD patients. PMID:27247605

  8. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...

  9. Geology and recognition criteria for roll-type uranium deposits in continental sandstones. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Harshman, E.N.; Adams, S.S.

    1981-01-01

    The study of roll-type deposits during the past 20 years, since the first description of a deposit in the United States, has developed general concepts of ore formation which are accepted widely and are compatible with available data. If this were not the case the concepts would not have endured and could not have been so successfully applied to exploration using the relations of altered-unaltered sandstone. The comparative simplicity of the model, and the ease with which it has been applied to exploration have, oddly enough, probably inhibited detailed studies of ore districts that would have provided data now needed for refinement of ore controls for exploration and resource assessment programs. The most thorough study of a roll-type district was that of the Shirley Basin which is drawn on heavily in this report. The general concept of roll-type formation provides a strong basis for the development of geological observations and guides, or recognition criteria, for resource studies and exploration. Indeed, industry has been developing and using them for 20 years. As the objective of this study was to identify the most useful recognition criteria and develop a method for their systematic use in resource studies and exploration, the study is best summarized by reference to the important geological observations about roll-type deposits.

  10. Geology and recognition criteria for roll-type uranium deposits in continental sandstones. Final report

    International Nuclear Information System (INIS)

    The study of roll-type deposits during the past 20 years, since the first description of a deposit in the United States, has developed general concepts of ore formation which are accepted widely and are compatible with available data. If this were not the case the concepts would not have endured and could not have been so successfully applied to exploration using the relations of altered-unaltered sandstone. The comparative simplicity of the model, and the ease with which it has been applied to exploration have, oddly enough, probably inhibited detailed studies of ore districts that would have provided data now needed for refinement of ore controls for exploration and resource assessment programs. The most thorough study of a roll-type district was that of the Shirley Basin which is drawn on heavily in this report. The general concept of roll-type formation provides a strong basis for the development of geological observations and guides, or recognition criteria, for resource studies and exploration. Indeed, industry has been developing and using them for 20 years. As the objective of this study was to identify the most useful recognition criteria and develop a method for their systematic use in resource studies and exploration, the study is best summarized by reference to the important geological observations about roll-type deposits

  11. Uptake kinetics and biodistribution of 14C-d-luciferin - a radiolabeled substrate for the firefly luciferase catalyzed bioluminescence reaction: impact on bioluminescence based reporter gene imaging

    International Nuclear Information System (INIS)

    Firefly luciferase catalyzes the oxidative decarboxylation of d-luciferin to oxyluciferin in the presence of cofactors, producing bioluminescence. This reaction is used in optical bioluminescence-based molecular imaging approaches to detect the expression of the firefly luciferase reporter gene. Biokinetics and distribution of the substrate most likely have a significant impact on levels of light signal and therefore need to be investigated. Benzene ring 14C(U)-labeled d-luciferin was utilized. Cell uptake and efflux assays, murine biodistribution, autoradiography and CCD-camera based optical bioluminescence imaging were carried out to examine the in vitro and in vivo characteristics of the tracer in cell culture and in living mice respectively. Radiolabeled and unlabeled d-luciferin revealed comparable levels of light emission when incubated with equivalent amounts of the firefly luciferase enzyme. Cell uptake assays in pCMV-luciferase-transfected cells showed slow trapping of the tracer and relatively low uptake values (up to 22.9-fold higher in firefly luciferase gene-transfected vs. nontransfected cells, p=0.0002). Biodistribution studies in living mice after tail-vein injection of 14C-d-luciferin demonstrated inhomogeneous tracer distribution with early predominant high radioactivity levels in kidneys (10.6% injected dose [ID]/g) and liver (11.9% ID/g), followed at later time points by the bladder (up to 81.3% ID/g) and small intestine (6.5% ID/g), reflecting the elimination routes of the tracer. Kinetics and uptake levels profoundly differed when using alternate injection routes (intravenous versus intraperitoneal). No clear trapping of 14C-d-luciferin in firefly luciferase-expressing tissues could be observed in vivo. The data obtained with 14C-d-luciferin provide insights into the dynamics of d-luciferin cell uptake, intracellular accumulation, and efflux. Results of the biodistribution and autoradiographic studies should be useful for optimizing and

  12. The mechanisms of platinum-catalyzed silicon nanowire growth

    International Nuclear Information System (INIS)

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire. (paper)

  13. The mechanisms of platinum-catalyzed silicon nanowire growth

    Science.gov (United States)

    Hibst, N.; Knittel, P.; Biskupek, J.; Kranz, C.; Mizaikoff, B.; Strehle, S.

    2016-02-01

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire.

  14. Palladium-Catalyzed Amination of Bromoanthancene

    Institute of Scientific and Technical Information of China (English)

    YU Ming-Xin; CHEN Xiao-Hang; CHENG Chien-Hong

    2003-01-01

    @@ Triarylamines are an important class of compounds, because they have been used as the hole-transport layer in electroluminescent devices. [1] New palladium catalyzed methods to form arylamines have emerged recently from Hartwing and Bucchwald . [2,3] Our group have investigated unusual diboration of allenes catalyzed by palladium complex and organic iodides. [4] Here we will report that arylamines react with bromoanthrancene (or dibromoanthancene) to afford triarylamines in the presence of Ligand-palladium complex. The structures of products were de termined by 1H NMR, 13C NMR, 13C (DEPT), IR and MS (HREI and EI) spectra.

  15. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  16. Quarterly Report: Microchannel-Assisted Nanomaterial Deposition Technology for Photovoltaic Material Production

    Energy Technology Data Exchange (ETDEWEB)

    Palo, Daniel R.

    2011-04-26

    Quarterly report to ITP for Nanomanufacturing program. Report covers FY11 Q2. The primary objective of this project is to develop a nanomanufacturing process which will reduce the manufacturing energy, environmental discharge, and production cost associated with current nano-scale thin-film photovoltaic (PV) manufacturing approaches. The secondary objective is to use a derivative of this nanomanufacturing process to enable greener, more efficient manufacturing of higher efficiency quantum dot-based photovoltaic cells now under development. The work is to develop and demonstrate a scalable (pilot) microreactor-assisted nanomaterial processing platform for the production, purification, functionalization, and solution deposition of nanomaterials for photovoltaic applications. The high level task duration is shown. Phase I consists of a pilot platform for Gen II PV films along with parallel efforts aimed at Gen III PV quantum dot materials. Status of each task is described.

  17. Postglacial volcanic deposits at Glacier Peak, Washington, and potential hazards from future eruptions; a preliminary report

    Science.gov (United States)

    Beget, J.E.

    1982-01-01

    Eruptions and other geologic events at Glacier Peak volcano in northern Washington have repeatedly affected areas near the volcano as well as areas far downwind and downstream. This report describes the evidence of this activity preserved in deposits on the west and east flanks of the volcano. On the west side of Glacier Peak the oldest postglacial deposit is a large, clayey mudflow which traveled at least 35 km down the White Chuck River valley sometime after 14,000 years ago. Subsequent large explosive eruptions produced lahars and at least 10 pyroclastic-flow deposits, including a semiwelded vitric tuff in the White Chuck River valley. These deposits, known collectively as the White Chuck assemblage, form a valley fill which is locally preserved as far as 100 km downstream from the volcano in the Stillaguamish River valley. At least some of the assemblage is about 11,670-11,500 radiocarbon years old. A small clayey lahar, containing reworked blocks of the vitric tuff, subsequently traveled at least 15 km down the White Chuck River. This lahar is overlain by lake sediments containing charred wood which is about 5,500 years old. A 150-m-thick assemblage of pyroclastic-flow deposits and lahars, called the Kennedy Creek assemblage, is in part about 5,500-5,100 radiocarbon years old. Lithic lahars from this assemblage extend at least 100 km downstream in the Skagit River drainage. The younger lahar assemblages, each containing at least three lahars and reaching at least 18 km downstream from Glacier Peak in the White Chuck River valley, are about 2,800 and 1,800 years old, respectively. These are postdated by a lahar containing abundant oxyhornblende dacite, which extends at least 30 km to the Sauk River. A still younger lahar assemblage that contains at least five lahars, and that also extends at least 30 km to the Sauk River, is older than a mature forest growing on its surface. At least one lahar and a flood deposit form a low terrace at the confluence of the

  18. Tritium catalyzed deuterium tokamaks

    International Nuclear Information System (INIS)

    A preliminary assessment of the promise of the Tritium Catalyzed Deuterium (TCD) tokamak power reactors relative to that of deuterium-tritium (D-T) and catalyzed deuterium (Cat-D) tokamaks is undertaken. The TCD mode of operation is arrived at by converting the 3He from the D(D,n)3He reaction into tritium, by neutron capture in the blanket; the tritium thus produced is fed into the plasma. There are three main parts to the assessment: blanket study, reactor design and economic analysis and an assessment of the prospects for improvements in the performance of TCD reactors (and in the promise of the TCD mode of operation, in general)

  19. Kinase-Catalyzed Biotinylation

    OpenAIRE

    Senevirathne, Chamara; Green, Keith D.; Pflum, Mary Kay H.

    2012-01-01

    Kinase-catalyzed protein phosphorylation plays an essential role in a variety of biological processes. Methods to detect phosphoproteins and phosphopeptides in cellular mixtures will aid in cell biological and signaling research. Our laboratory recently discovered the utility of γ-modified ATP analogues as tools for studying phosphorylation. Specifically, ATP-biotin can be used for labeling and visualizing phosphoproteins from cell lysates. Because the biotin tag is suitable for protein detec...

  20. [Paste deposition and chip bonding process development]. IBM, Endicott tenth quarterly report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-05-01

    The scope of Endicott activity during this quarter includes: paste deposition process development and chip bonding process development. It was discovered that small voids exist in the photobumps. These are typically at the base of the bump and are believed to have always been present. Although the reliability test results have been positive and no failure is attributed to voids, the process development work during the last quarter has focused on understanding how these form and how to reduce them. High feed pressure, slow nozzle speed and lower viscosity reduce void formation. Nozzle design changes have been identified. One change will increase the shearing of the paste during feed, thus reducing the viscosity, a second change will allow higher feed pressures. Chip bonding process development has focused on correlating bonding results between the IBM in-house chip bonder made by Research Devices, Inc. and the Universal development bond tool. Two variables have been identified that correlate with poor bond results. The report describes more detail of the activity during the tenth quarter for paste deposition and chip bonding in each of these areas.

  1. Removal of asphaltene and paraffin deposits using micellar solutions and fused reactions. Final report, 1995--1997

    Energy Technology Data Exchange (ETDEWEB)

    Chang, C.L.; Nalwaya, V.; Singh, P.; Fogler, H.S.

    1998-05-01

    Chemical treatments of paraffin and asphaltene deposition by means of cleaning fluids were carried out in this research project. Research focused on the characterization of asphaltene and paraffin materials and dissolution of asphaltene and paraffin deposits using surfactant/micellar fluids developed early in the project. The key parameters controlling the dissolution rate were identified and the process of asphaltene/paraffin dissolution were examined using microscopic apparatus. Numerical modeling was also carried out to understand the dissolution of paraffin deposits. The results show that fused chemical reaction systems are a promising way of removing paraffin deposits in subsea pipelines. The fused system may be in the form of alternate pulses, emulsions systems or encapsulated catalyst systems. Fused reaction systems, in fact, are extremely cost-effective--less than 10% of the cost of replacing entire sections of the blocked pipeline. The results presented in this report can have a real impact on the petroleum industry and the National Oil Program, if it is realized that the remediation technologies developed here can substantially delay abandonment (due to asphaltene/paraffin plugging) of domestic petroleum resources. The report also sheds new light on the nature and properties of asphaltenes and paraffin deposits which will ultimately help the scientific and research community to develop effective methods in eliminating asphaltene/paraffin deposition problems. It must also be realized that asphaltene remediation technologies developed and presented in this report are a real alternative to aromatic cleaning fluids currently used by the petroleum industry.

  2. The Iron-Catalyzed Oxidation of Hydrazine by Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Karraker, D.G.

    2001-07-17

    To assess the importance of iron to hydrazine stability, the study of hydrazine oxidation by nitric acid has been extended to investigate the iron-catalyzed oxidation. This report describes those results.

  3. Heterocycles via intramolecular platinum-catalyzed propargylic substitution

    OpenAIRE

    Liang, Qiren; De Brabander, Jef K

    2011-01-01

    We report a Pt(II)-catalyzed cyclization of nucleophile-tethered propargylic acetates yielding substituted heterocycles containing multiple heteroatoms including morpholines, dioxanes and sulfamates with high cis-selectivity.

  4. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.

    2012-06-29

    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  5. Amino Acids Catalyzed Direct Aldol Reactions in Aqueous Micelles

    Institute of Scientific and Technical Information of China (English)

    PENG Yi-Yuan; WANG Qi; DING Qiu-Ping; HE Jia-Qi; CHENG Jin-Pei

    2003-01-01

    @@ Since the discovery of its roles as a good small-organic-molecule catalyst in intramolecular aldol reactions, pro line has drawn considerable attention in synthetic chemistry due to its similarity to the type-Ⅰ aldolases. Recently,List and others have reported some new direct asymmetric intermolecular reactions catalyzed by proline, including aldol, Mannich, Michael, and other analogous reactions. Except for two recent examples, [1,2] proline catalyzed aldol reactions in aqueous micelles have not been reported, nor have other amino acids as organocatalysts in directly catalyzing aldol reaction been reported. Herein we wish to present our recent results regarding environmentally be nign direct aldol reactions catalyzed by amino acids including proline, histidine and arginine in aqueous media.

  6. SUPERSENSITIVE IN SITU HYBRIDIZATION BY TYRAMIDE SIGNAL AMPLIFICATION AND NANOGOLD SILVER STAINING: THE CONTRIBUTION OF AUTOMETALLOGRAPHY AND CATALYZED REPORTER DEPOSITION TO THE REJUVENATION OF IN SITU HYBRIDIZATION.

    Energy Technology Data Exchange (ETDEWEB)

    TUBBS,R.R.PETTAY,J.GROGAN,T.CHEUNG,A.L.M.POWELL,R.D.HAINFELD,J.HAUSER-KRONBERGER,C.HACKER,G.W.

    2002-04-17

    It is peculiar that in situ hybridization (ISH), a technique with many similarities to immunohistochemistry (IHC), has not enjoyed the phenomenal growth in both basic research and clinical applications as has its sister technique IHC. Since the late 1970s, when immunoperoxidase techniques began to be applied to routine diagnostic material and to numerous research applications, there has been a natural evolution of the IHC procedure. Namely, only a few primary antibodies were available commercially at the onset, and only one indirect and the peroxidase-antiperoxidase (PAP) technique detection systems were in place. With the advent of avidin-biotin detection systems and monoclonal antibodies, and a viable commercial market, extraordinary growth of the procedure's applications in clinical research and diagnostic pathology occurred during the subsequent two decades. Today, IHC is automated and widely used for research purposes and, to a large extent, has become a routine diagnostic ''special stain'' in most clinical laboratories. During the same period, ISH enjoyed very little growth in both research and diagnostic applications. What has accounted for this lack of maturation of the technique? The success of IHC is part of the reason measuring a gene's encoded protein routinely and inexpensively, particularly as automation evolved, rendered IHC a more viable choice in many instances. Inherent comparative sensitivity of the procedures has also clearly been a factor. Unfortunately, the chromogenic procedures in place are often insufficiently sensitive to detect the relatively low amounts of DNA and RNA levels at which the clinical utility is to be found.

  7. Hydrogen evolution catalyzed by cobaloximes.

    Science.gov (United States)

    Dempsey, Jillian L; Brunschwig, Bruce S; Winkler, Jay R; Gray, Harry B

    2009-12-21

    Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H(2)O, CO(2)) to energy-rich ones (O(2), (CH(2)O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the "Holy Grail" of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H(2). In this Account, we report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co(II)-diglyoxime generates a Co(I) species that reacts with a proton source to produce a Co(III)-hydride. Then, in a homolytic pathway, two Co(III)-hydrides react in a bimolecular step to eliminate H(2). Alternatively, in a heterolytic pathway, protonation of the Co(III)-hydride produces H(2) and Co(III). A thermodynamic analysis of H(2) evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co(I)-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H(2) evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co(III)-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H(2) evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co(III)-hydrides. PMID:19928840

  8. Characterization and quantification of deposits build up and removal in straw suspension fired boilers. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Arendt Jensen, Peter; Wedel, S.; Jappe Frandsen, F.; Dam-Johansen, K.; Shafique Bashir, M. [Technical Univ. of Denmark. CHEC Research Centre, Kgs. Lyngby (Denmark); Wadenback, J.; Thaaning Pedersen, S. [Vattenfall A/S, Copenhagen (Denmark)

    2013-07-15

    This project deals with ash deposit formation in suspension fired biomass power plant boilers. The project has been conducted in a tight collaboration between Vattenfall and the CHEC Research Centre at DTU Department of Chemical Engineering. A large part of the project has been performed by conducting advanced probe measurements at the Amagervaerkets Vattenfall owed boilers. It was the objective of the project to provide an improved understanding of ash deposit formation and removal in biomass suspension fired boilers. The project have provided a large amount of knowledge on the following issues: 1) The influence of local boiler conditions on deposit formation in suspension fired boilers using wood or co-firing straw and wood, 2) quantification of deposit removal in biomass suspension firing boilers with regards both to natural shedding and soot blower induced shedding, 3) established relations of the properties of fuel ash, fly ash and deposits, 4) use of coal ash to remedy biomass ash induced boiler deposit problems. (Author)

  9. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    time and in combination with other social processes establish more aligned and standardized environmental performance between countries. However, examples of the introduction of environmental management suggests that EMS’ only plays a minor role in developing the actual environmental objectives......This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved...... they are implemented in and how the changing context is reflected in the environmental objectives that are established and prioritised. Our argument is, that the ability of the standard to achieve an impact is dependant on the constitution of ’coherent’ environmental issues in the context, where the management system...

  10. Regional aerosol deposition in human upper airways: Progress report, June 1, 1988--February 28, 1989

    International Nuclear Information System (INIS)

    The objective of this research program is to elucidate important factors which influence overall and local deposition of aerosols in the human airways above the trachea, including nasal airways, oral passage, pharynx and larynx. The intent is to develop information which can be used for exposure models for radon from unattached radon progeny (/approximately/1nm) up to 10 μm. Special emphasis is upon flow rate and airway dimensions as influenced by age and respiratory condition, as no experimental data presently exist for age-related deposition. Because of ethical and practical considerations associated with measuring aerosol deposition in children and difficulties of measuring local deposition in vivo, our experimental approach is to construct faithful replicate models of the airways for several ages of humans in which detailed studies of deposition can be carried out with well-characterized aerosols. Initial studies of overall deposition of ultrafine aerosols in an adult model have been carried out using replicate nasal passage models provided from this laboratory. These studies demonstrate a significant deposition percent for particle sizes approaching that of unattached radon progeny (40--50%), decreasing as particle size approaches 0.1 μm. Studies of the effect of flow rate indicate that higher deposition percent is realized at lower flow rate over the range from 4--60 lmin-1

  11. Quantitative measurement of aerosol deposition on skin, hair and clothing for dosimetric assessment. Final report

    International Nuclear Information System (INIS)

    In the past, very little thought has been given to the processes and implications of deposition of potentially hazardous aerosol directly onto humans. This state of unpreparedness is unsatisfactory and suitable protocols have been developed and validated for tracer experiments to investigate the deposition and subsequent fate of contaminant aerosol on skin, hair and clothing. The main technique applied involves the release and subsequent deposition on volunteers in test rooms of particles of different sizes labelled with neutron activatable rare earth tracers. Experiments indicate that the deposition velocity to skin increases linearly with the particle size. A wind tunnel experiment simulating outdoor conditions showed a dependence on skin deposition velocity of wind speed, indicating that outdoor deposition velocities may be great. Both in vivo and in vitro experiments were conducted, and the influence of various factors, such as surface type, air flow, heating and electrostatics were examined. The dynamics of particle removal from human skin were studied by fluorescence scanning. This technique was also applied to estimate the fraction of aerosol dust transferred to skin by contact with a contaminated surface. The various parameters determined were applied to establish a model for calculation of radiation doses received from deposition of airborne radioactive aerosol on human body surfaces. It was found that the gamma doses from deposition on skin may be expected to be of the same order of magnitude as the gamma doses received over the first year from contamination on outdoor surfaces. According to the calculations, beta doses from skin deposition to individuals in areas of Russia, where dry deposition of Chernobyl fallout led to very high levels of contamination, may have amounted to several Sievert and may thus be responsible for a significant cancer risk. (au)

  12. Quantitative measurement of aerosol deposition on skin, hair and clothing for dosimetric assessment. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Fogh, C.L.; Byrne, M.A.; Andersson, K.G.; Bell, K.F.; Roed, J.; Goddard, A.J.H.; Vollmair, D.V.; Hotchkiss, S.A.M

    1999-06-01

    In the past, very little thought has been given to the processes and implications of deposition of potentially hazardous aerosol directly onto humans. This state of unpreparedness is unsatisfactory and suitable protocols have been developed and validated for tracer experiments to investigate the deposition and subsequent fate of contaminant aerosol on skin, hair and clothing. The main technique applied involves the release and subsequent deposition on volunteers in test rooms of particles of different sizes labelled with neutron activatable rare earth tracers. Experiments indicate that the deposition velocity to skin increases linearly with the particle size. A wind tunnel experiment simulating outdoor conditions showed a dependence on skin deposition velocity of wind speed, indicating that outdoor deposition velocities may be great. Both in vivo and in vitro experiments were conducted, and the influence of various factors, such as surface type, air flow, heating and electrostatics were examined. The dynamics of particle removal from human skin were studied by fluorescence scanning. This technique was also applied to estimate the fraction of aerosol dust transferred to skin by contact with a contaminated surface. The various parameters determined were applied to establish a model for calculation of radiation doses received from deposition of airborne radioactive aerosol on human body surfaces. It was found that the gamma doses from deposition on skin may be expected to be of the same order of magnitude as the gamma doses received over the first year from contamination on outdoor surfaces. According to the calculations, beta doses from skin deposition to individuals in areas of Russia, where dry deposition of Chernobyl fallout led to very high levels of contamination, may have amounted to several Sievert and may thus be responsible for a significant cancer risk. (au)

  13. Base-Catalyzed Depolymerization of Lignin with Heterogeneous Catalysts: Cooperative Research and Development Final Report, CRADA Number CRD-13-513

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2015-08-04

    We will synthesize and screen solid catalysts for the depolymerization of lignin to monomeric and oligomeric oxygenated species, which could be fractionated and integrated into refinery intermediate streams for selective upgrading, or catalytically upgraded to fuels and chemicals. This work will primarily focus on the synthesis and application of layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for depolymerization of lignin model compounds and softwood lignin. LDHs have been shown in our group to offer good supports and catalysts to promote base-catalyzed depolymerization of lignin model compounds and in preliminary experiments for the depolymerization of lignin from an Organosolv process. We will also include additional catalyst supports such as silica, alumina, and carbon as identified in ongoing and past efforts at NREL. This work will consist of two tasks. Overall, this work will be synergistic with ongoing efforts at NREL, funded by the DOE Biomass Program, on the development of catalysts for lignin depolymerization in the context of biochemical and thermochemical conversion of corn stover and other biomass feedstocks to advanced fuels and chemicals.

  14. Geology and recognition criteria for uraniferous humate deposits, Grants Uranium Region, New Mexico. Final report

    International Nuclear Information System (INIS)

    The geology of the uraniferous humate uranium deposits of the Grants Uranium Region, northwestern New Mexico, is summarized. The most important conclusions of this study are enumerated. Although the geologic characteristics of the uraniferous humate deposits of the Grants Uranium Region are obviously not common in the world, neither are they bizarre or coincidental. The source of the uranium in the deposits of the Grants Uranium Region is not known with certainty. The depositional environment of the host sediments was apparently the mid and distal portions of a wet alluvial fan system. The influence of structural control on the location and accumulation of the host sediments is now supported by considerable data. The host sediments possess numerous important characteristics which influenced the formation of uraniferous humate deposits. Ilmenite-magnetite distribution within potential host sandstones is believed to be the simplest and most useful regional alteration pattern related to this type of uranium deposit. A method is presented for organizing geologic observations into what is referred to as recognition criteria. The potential of the United States for new districts similar to the Grants Uranium Region is judged to be low based upon presently available geologic information. Continuing studies on uraniferous humate deposits are desirable in three particular areas

  15. Geology and recognition criteria for uraniferous humate deposits, Grants Uranium Region, New Mexico. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Adams, S.S.; Saucier, A.E.

    1981-01-01

    The geology of the uraniferous humate uranium deposits of the Grants Uranium Region, northwestern New Mexico, is summarized. The most important conclusions of this study are enumerated. Although the geologic characteristics of the uraniferous humate deposits of the Grants Uranium Region are obviously not common in the world, neither are they bizarre or coincidental. The source of the uranium in the deposits of the Grants Uranium Region is not known with certainty. The depositional environment of the host sediments was apparently the mid and distal portions of a wet alluvial fan system. The influence of structural control on the location and accumulation of the host sediments is now supported by considerable data. The host sediments possess numerous important characteristics which influenced the formation of uraniferous humate deposits. Ilmenite-magnetite distribution within potential host sandstones is believed to be the simplest and most useful regional alteration pattern related to this type of uranium deposit. A method is presented for organizing geologic observations into what is referred to as recognition criteria. The potential of the United States for new districts similar to the Grants Uranium Region is judged to be low based upon presently available geologic information. Continuing studies on uraniferous humate deposits are desirable in three particular areas.

  16. Palladium-Catalyzed Environmentally Benign Acylation.

    Science.gov (United States)

    Suchand, Basuli; Satyanarayana, Gedu

    2016-08-01

    Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp(2) C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone. PMID:27377566

  17. Geology and recognition criteria for veinlike uranium deposits of the lower to middle Proterozoic unconformity and strata-related types. Final report

    International Nuclear Information System (INIS)

    The discovery of the Rabbit Lake deposit, Saskatchewan, in 1968 and the East Alligator Rivers district, Northern Territory, Australia, in 1970 established the Lower-Middle Proterozoic veinlike-type deposits as one of the major types of uranium deposits. The term veinlike is used in order to distinguish it from the classical magmatic-hydrothermal vein or veintype deposits. The veinlike deposits account for between a quarter and a third of the Western World's proven uranium reserves. Lower-Middle Proterozoic veinlike deposits, as discussed in this report include several subtypes of deposits, which have some significantly different geologic characteristics. These various subtypes appear to have formed from various combinations of geologic processes ranging from synsedimentary uranium precipitation through some combination of diagenesis, metamorphism, metasomatism, weathering, and deep burial diagenesis. Some of the deposit subtypes are based on only one or two incompletely described examples; hence, even the classification presented in this report may be expected to change. Geologic characteristics of the deposits differ significantly between most districts and in some cases even between deposits within districts. Emphasis in this report is placed on deposit descriptions and the interpretations of the observers

  18. Geology and recognition criteria for veinlike uranium deposits of the lower to middle Proterozoic unconformity and strata-related types. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Dahlkamp, F.J.; Adams, S.S.

    1981-01-01

    The discovery of the Rabbit Lake deposit, Saskatchewan, in 1968 and the East Alligator Rivers district, Northern Territory, Australia, in 1970 established the Lower-Middle Proterozoic veinlike-type deposits as one of the major types of uranium deposits. The term veinlike is used in order to distinguish it from the classical magmatic-hydrothermal vein or veintype deposits. The veinlike deposits account for between a quarter and a third of the Western World's proven uranium reserves. Lower-Middle Proterozoic veinlike deposits, as discussed in this report include several subtypes of deposits, which have some significantly different geologic characteristics. These various subtypes appear to have formed from various combinations of geologic processes ranging from synsedimentary uranium precipitation through some combination of diagenesis, metamorphism, metasomatism, weathering, and deep burial diagenesis. Some of the deposit subtypes are based on only one or two incompletely described examples; hence, even the classification presented in this report may be expected to change. Geologic characteristics of the deposits differ significantly between most districts and in some cases even between deposits within districts. Emphasis in this report is placed on deposit descriptions and the interpretations of the observers.

  19. Dependence of silicon carbide coating properties on deposition parameters: preliminary report

    International Nuclear Information System (INIS)

    Fuel particles for the High-Temperature Gas-Cooled Reactor (HTGR) contain a layer of pyrolytic silicon carbide, which acts as a pressure vessel and provides containment of metallic fission products. The silicon carbide (SiC) is deposited by the thermal decomposition of methyltrichlorosilane (CH3SiCl3 or MTS) in an excess of hydrogen. The purpose of the current study is to determine how the deposition variables affect the structure and properties of the SiC layer

  20. Literature survey and documentation on organic solid deposition problem. Status report

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Ting-Horng

    1993-12-01

    Organic solid deposition is often a major problem in petroleum production and processing. Recently, this problem has attracted more attention because operating costs have become more critical to the profit of oil production. Also, in miscible gas flooding, asphaltene deposition often occurs in the wellbore region after gas breakthrough and causes plugging. The organic deposition problem is particularly serious in offshore oil production. Cooling of crude oil when it flows through long-distance pipelines under sea water may cause organic deposition in the pipeline and result in plugging. NIPER`s Gas EOR Research Project has been devoted to the study of the organic solid deposition problem for three years. NIPER has received many requests for technical support. Recently, the DeepStar project committee on thermo-technology development and standardization has asked NIPER to provide them with NIPER`s expertise and experience. To assist the oil industry, NIPER is preparing a state-of-the-art review on the technical development for the organic deposition problem. In the first quarter, this project has completed a literature survey and documentation. total of 258 publications (114 for wax, 124 for asphaltene, and 20 for related subjects) were collected and categorized. This literature survey was focused on the two subjects: wax and asphaltene. The subjects of bitumen, asphalt, and heavy oil are not included. Also, the collected publications are mostly related to production problems.

  1. Ossifying tendinitis of the rotator cuff after arthroscopic excision of calcium deposits: report of two cases and literature review

    OpenAIRE

    Merolla, Giovanni; Dave, Arpit C.; Paladini, Paolo; Campi, Fabrizio; Porcellini, Giuseppe

    2014-01-01

    Ossifying tendinitis (OT) is a type of heterotopic ossification, characterized by deposition of hydroxyapatite crystals in a histologic pattern of mature lamellar bone. It is usually associated with surgical intervention or trauma and is more commonly seen in Achilles or distal biceps tendons, and also in the gluteus maximus tendon. To our knowledge, there is no description of OT as a complication of calcifying tendinitis of the rotator cuff. In this report, we describe two cases in which the...

  2. Case report 364: Massive calcium pyrophosphate dihydrate crystal deposition disorder (MCPDD) involving thumb

    International Nuclear Information System (INIS)

    In summary, the case is presented of a 46-year-old man who developed stiffness and pain in his right thumb. Radiological study showed calcific deposits around the first metacarpophalangeal joint, which grew in extent and amount considerably over a two year period. The diagnosis of massive calcium pyrophosphate dihydrate crystal deposition disease (MCPDD) was established both by biopsy and operation. The surgical procedure was performed to remove the calcific mass after pressure on a digital nerve resulted in loss of sensation over the ulnar aspect of the thumb and flareups of swelling, pain and erythema, had developed at the first M-P joint. (orig./HP)

  3. Case report 364: Massive calcium pyrophosphate dihydrate crystal deposition disorder (MCPDD) involving thumb

    Energy Technology Data Exchange (ETDEWEB)

    El-Khoury, G.Y.; Smoker, W.R.K.; Foucar, E.; Blair, W.F.; Malvitz, T.A.; Strottmann, M.P.

    1986-05-01

    In summary, the case is presented of a 46-year-old man who developed stiffness and pain in his right thumb. Radiological study showed calcific deposits around the first metacarpophalangeal joint, which grew in extent and amount considerably over a two year period. The diagnosis of massive calcium pyrophosphate dihydrate crystal deposition disease (MCPDD) was established both by biopsy and operation. The surgical procedure was performed to remove the calcific mass after pressure on a digital nerve resulted in loss of sensation over the ulnar aspect of the thumb and flareups of swelling, pain and erythema, had developed at the first M-P joint.

  4. Bias and precision of selected analytes reported by the National Atmospheric Deposition Program and National Trends Network, 1984

    Science.gov (United States)

    Brooks, M.H.; Schroder, L.J.; Willoughby, T.C.

    1987-01-01

    The U.S. Geological Survey operated a blind audit sample program during 1974 to test the effects of the sample handling and shipping procedures used by the National Atmospheric Deposition Program and National Trends Network on the quality of wet deposition data produced by the combined networks. Blind audit samples, which were dilutions of standard reference water samples, were submitted by network site operators to the central analytical laboratory disguised as actual wet deposition samples. Results from the analyses of blind audit samples were used to calculate estimates of analyte bias associated with all network wet deposition samples analyzed in 1984 and to estimate analyte precision. Concentration differences between double blind samples that were submitted to the central analytical laboratory and separate analyses of aliquots of those blind audit samples that had not undergone network sample handling and shipping were used to calculate analyte masses that apparently were added to each blind audit sample by routine network handling and shipping procedures. These calculated masses indicated statistically significant biases for magnesium, sodium , potassium, chloride, and sulfate. Median calculated masses were 41.4 micrograms (ug) for calcium, 14.9 ug for magnesium, 23.3 ug for sodium, 0.7 ug for potassium, 16.5 ug for chloride and 55.3 ug for sulfate. Analyte precision was estimated using two different sets of replicate measures performed by the central analytical laboratory. Estimated standard deviations were similar to those previously reported. (Author 's abstract)

  5. Pulsed DC deposition of near-frictionless carbon. Final CRADA report.

    Energy Technology Data Exchange (ETDEWEB)

    Fenske, G.; Energy Systems

    2005-06-30

    Near-Frictionless Carbon (NFC) coatings, CemeCon, Inc. arranged for the loan of a Pinnacle Plus pulsed DC power supply with ancillary support equipment and appropriate sputter targets for the deposition of CemeCon's graded Cr-based bond coat. A process engineer from CemeCon AG also came to Argonne to install and operate the new power supply, and work with ANL scientists on process development. By any measure, these results are extremely encouraging. It has now been established that NFC coatings can be deposited in the CemeCon CC800/9sx unit using pulsed DC to generate the plasma, and further that the DLC3000 bond coat technology can be used with PACVD coatings. In terms of process variables, it should be possible to increase the deposition rate by increasing either or both the deposition pressure and/or the pulsed bias voltage without adversely affecting the coating quality. Other structural characterization may be performed on the coatings, including fluctuation microscopy, ultraviolet Raman spectroscopy, and near-edge x-ray absorption fine structure spectroscopy.

  6. Quaternary allostratigraphy of surficial deposit map units at Yucca Mountain, Nevada: A progress report

    International Nuclear Information System (INIS)

    Surficial geologic mapping at Yucca Mountain, Nevada, is relevant to site characterization studies of paleoclimate, tectonics, erosion, flood hazards, and water infiltration. Alluvial, colluvial, and eolian allostratigraphic map units are defined on the basis of age-related surface characteristics and soil development, as well as lithology and sedimentology indicative of provenance and depositional mode. In gravelly alluvial units, which include interbedded debris flows, the authors observe a useful qualitative correlation between surface and soil properties. Map units of estimated middle Pleistocene age typically have a well-developed, varnished desert pavement, and minimal erosional and preserved depositional microrelief, associated with a soil with a reddened Bt horizon and stage 3 carbonate and silica morphology. Older units have greater erosional relief, an eroded argillic horizon and stage 4 carbonate morphology, whereas younger units have greater preservation of depositional morphology, but lack well-developed pavements, rock varnish, and Bt and Kqm soil horizons. Trench and gully-wall exposures show that alluvial, colluvial and eolian dominated surface units are underlain by multiple buried soils separating sedimentologically similar deposits; this stratigraphy increases the potential for understanding the long-term Quaternary paleoenvironmental history of Yucca Mountain. Age estimates for allostratigraphic units, presently based on uranium-trend dating and regional correlation using soil development, will be further constrained by ongoing dating studies that include tephra identification, uranium-series disequilibrium, and thermoluminescence methods

  7. Energy-deposition studies. Summary report for the period ending August 31, 1973

    Energy Technology Data Exchange (ETDEWEB)

    Vroom, D.A.

    1973-05-29

    A detailed description of the experimental programs undertaken is given together with the results that have been obtained. The main research accomplishments and apparatus built are described, and the present state of knowledge in the field of energy deposition by fast particles is given.

  8. Deposition and Characterization of Improved Hydrogen Getter Materials - Report on FY 14-15 Activities

    Energy Technology Data Exchange (ETDEWEB)

    Hubbard, Kevin Mark [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Sandoval, Cynthia Wathen [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-10-15

    The goals of this work have been two-fold. First, to perform an initial, quantitative, optimization of getter performance, with the primary variables being DEB/Pd ratio and UV power. Second, to simplify the deposition process to make it more compatible with the DOE production environment.

  9. Technical committee meeting on aerosol formation, vapour deposits and sodium vapour trapping. Summary report

    International Nuclear Information System (INIS)

    The papers presented at the LMFBR meeting on aerosol formation covered the following four main topics: theoretical studies on aerosol behaviour and comparison with experimental results; techniques for measurement of aerosols; techniques for trapping sodium vapour and aerosols in gas circuits; design of components having to cope with aerosol deposits. The resulting summaries, conclusions and recommendations which were were agreed upon are presented

  10. Intractable membranous lupus nephritis showing selective improvement of subepithelial deposits with tacrolimus therapy: a case report.

    Science.gov (United States)

    Nonaka, Kanae; Ubara, Yoshifumi; Suwabe, Tatsuya; Takaichi, Kenmei; Oohashi, Kenichi

    2013-08-01

    A 37-year-old female patient was admitted for evaluation of nephrotic proteinuria refractory to prednisolone and other immunosuppressants in 2004. On admission, urinary protein loss was 16 g/d. Anti-ds DNA antibody was positive and hypocomplementemia was detected. Renal biopsy revealed membranous lupus nephritis. Because 5 cyclophosphamide pulse therapies did not have an effect, tacrolimus was started at 3 mg daily. Proteinuria decreased to 4.8 g/d after 5 months and was antids DNA antibody remained positive and hypocomplementemia persisted. Repeat renal biopsy revealed thinning of the glomerular capillary walls and disappearance of subepithelial electron-dense deposits. However, the subendothelial and mesangial deposits were unchanged. In this patient, proteinuria refractory to various immunosuppressants including cyclosporine A improved after administration of tacrolimus, and selective disappearance of subepithelial deposits was seen histologically. This is the first histological evidence that tacrolimus therapy may cause removal of subepithelial deposits, which are separated from the circulation by the glomerular basement membrane. This finding is supported by experimental data that tacrolimus selectively block the binding of FK-binding protein 12 to transient receptor potential-cation channel 6, resulting in normalization of affected podocytes. PMID:22541676

  11. Zinc oxide catalyzed growth of single-walled carbon nanotubes

    International Nuclear Information System (INIS)

    We demonstrate that zinc oxide can catalyze the growth of single-walled carbon nanotubes (SWNTs) with high efficiency by a chemical vapor deposition process. The zinc oxide nanocatalysts, prepared using a diblock copolymer templating method and characterized by atomic force microscopy (AFM), were uniformly spaced over a large deposition area with an average diameter of 1.7 nm and narrow size distribution. Dense and uniform SWNTs films with high quality were obtained by using a zinc oxide catalyst, as characterized by scanning electron microscopy (SEM), Raman spectroscopy, AFM, and high-resolution transmission electron microscopy (HRTEM).

  12. Ligand Intermediates in Metal-Catalyzed Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gladysz, John A.

    1999-07-31

    The longest-running goal of this project has been the synthesis, isolation, and physical chemical characterization of homogeneous transition metal complexes containing ligand types believed to be intermediates in the metal-catalyzed conversion of CO/H{sub 2}, CO{sub 2}, CH{sub 4}, and similar raw materials to organic fuels, feedstocks, etc. In the current project period, complexes that contain unusual new types of C{sub x}(carbide) and C{sub x}O{sub y} (carbon oxide) ligands have been emphasized. A new program in homogeneous fluorous phase catalysis has been launched as described in the final report.

  13. Probabilistic accident consequence uncertainty analysis: Dispersion and deposition uncertainty assessment, main report

    Energy Technology Data Exchange (ETDEWEB)

    Harper, F.T.; Young, M.L.; Miller, L.A. [Sandia National Labs., Albuquerque, NM (United States); Hora, S.C. [Univ. of Hawaii, Hilo, HI (United States); Lui, C.H. [Nuclear Regulatory Commission, Washington, DC (United States); Goossens, L.H.J.; Cooke, R.M. [Delft Univ. of Technology (Netherlands); Paesler-Sauer, J. [Research Center, Karlsruhe (Germany); Helton, J.C. [and others

    1995-01-01

    The development of two new probabilistic accident consequence codes, MACCS and COSYMA, was completed in 1990. These codes estimate the risks presented by nuclear installations based on postulated frequencies and magnitudes of potential accidents. In 1991, the US Nuclear Regulatory Commission (NRC) and the Commission of the European Communities (CEC) began a joint uncertainty analysis of the two codes. The ultimate objective of the joint effort was to develop credible and traceable uncertainty distributions for the input variables of the codes. Expert elicitation was identified as the best technology available for developing a library of uncertainty distributions for the selected consequence parameters. The study was formulated jointly and was limited to the current code models and to physical quantities that could be measured in experiments. Experts developed their distributions independently. To validate the distributions generated for the wet deposition input variables, samples were taken from these distributions and propagated through the wet deposition code model. Resulting distributions closely replicated the aggregated elicited wet deposition distributions. To validate the distributions generated for the dispersion code input variables, samples from the distributions and propagated through the Gaussian plume model (GPM) implemented in the MACCS and COSYMA codes. Project teams from the NRC and CEC cooperated successfully to develop and implement a unified process for the elaboration of uncertainty distributions on consequence code input parameters. Formal expert judgment elicitation proved valuable for synthesizing the best available information. Distributions on measurable atmospheric dispersion and deposition parameters were successfully elicited from experts involved in the many phenomenological areas of consequence analysis. This volume is the first of a three-volume document describing the project.

  14. Probabilistic accident consequence uncertainty analysis: Dispersion and deposition uncertainty assessment, main report

    International Nuclear Information System (INIS)

    The development of two new probabilistic accident consequence codes, MACCS and COSYMA, was completed in 1990. These codes estimate the risks presented by nuclear installations based on postulated frequencies and magnitudes of potential accidents. In 1991, the US Nuclear Regulatory Commission (NRC) and the Commission of the European Communities (CEC) began a joint uncertainty analysis of the two codes. The ultimate objective of the joint effort was to develop credible and traceable uncertainty distributions for the input variables of the codes. Expert elicitation was identified as the best technology available for developing a library of uncertainty distributions for the selected consequence parameters. The study was formulated jointly and was limited to the current code models and to physical quantities that could be measured in experiments. Experts developed their distributions independently. To validate the distributions generated for the wet deposition input variables, samples were taken from these distributions and propagated through the wet deposition code model. Resulting distributions closely replicated the aggregated elicited wet deposition distributions. To validate the distributions generated for the dispersion code input variables, samples from the distributions and propagated through the Gaussian plume model (GPM) implemented in the MACCS and COSYMA codes. Project teams from the NRC and CEC cooperated successfully to develop and implement a unified process for the elaboration of uncertainty distributions on consequence code input parameters. Formal expert judgment elicitation proved valuable for synthesizing the best available information. Distributions on measurable atmospheric dispersion and deposition parameters were successfully elicited from experts involved in the many phenomenological areas of consequence analysis. This volume is the first of a three-volume document describing the project

  15. Decision model for assessment of sandstone uranium deposits. National Uranium Resource Evaluation. Final report

    International Nuclear Information System (INIS)

    The main objective of the National Uranium Resource Evaluation (NURE) program is an estimation of the uranium resources of the United States. To achieve this objective, a geologic evaluation and resource assessment program was initiated using NTMS 20 quadrangles as the basic work unit. The evaluation activity commences with data collection within th 20 quadrangles in order to identify and delineate geologic environments that are favorable for the occurrence of uranium deposits. A favorable environment is depicted as a geologic setting that has the potential for containing at least 100 tons of U3O8 in rocks whose uranium grade exceeds 100 ppM. Geologic field reconnaissance, hydrochemical and stream sediment reconnaissance, aerial radiometric and magnetic surveys, and logging are the principal means by which favorable environments are identified. The principal investigator of each evaluation team is required to classify a favorable environments according to a preliminary classification of uranium occurrences and favorable environments. Based on this information the uranium potential in each quadrangle is estimated. The scope of this study is limited to development of an assessment procedure and a Bayesian decision model for estimating the endowed area A/sub e/ for three sandstone type uranium deposits: Wyoming roll-type, South Texas roll-type, and Uravan/Salt Wash tabular type deposits

  16. Quantitative measurement of aerosol deposition on skin, hair and clothing for dosimetric assessment. Final report

    DEFF Research Database (Denmark)

    Fogh, C.L.; Byrne, M.A.; Andersson, Kasper Grann;

    1999-01-01

    In the past, very little thought has been given to the processes and implications of deposition of potentially hazardous aerosol directly onto humans. This state of unpreparedness is unsatisfactory and suitable protocols have been developed and validatedfor tracer experiments to investigate the...... influence of various factors, such as surface type, air flow, heating and electrostatics were examined. Thedynamics of particle removal from human skin were studied by fluorescence scanning. This technique was also applied to estimate the fraction of aerosol dust transferred to skin by contact with a...

  17. PEER D2.2 Final report on the provision of usage data and manuscript deposit procedures for publishers and repository managers

    OpenAIRE

    Bayer-Schur, Barbara; Bretel, Foudil; Bulatovic, Natasa; Harangi, Gabriella; Horstmann, Wolfram; Kleinfercher, Friederike; Koning, Rianne; Kuciukas, Vilius; Mühlhölzer, Marianna; Peters, Dale; Romary, Laurent; Schirrwagen, Jochen; Vanderfeesten, Maurice

    2009-01-01

    The Draft report on the provision of usage data and manuscript deposit procedures for publishers and repository managers, deliverable 2.1, set out to establish a workflow for depositing stage-2 outputs in and harvesting log files from repositories to enable the research envisaged in the PEER project. As that report preceded the tendering process whereby the respective research teams were selected, a number of issues were flagged for attention, particularly of the Usage research team, in WP5 a...

  18. External quality assurance project report for the National Atmospheric Deposition Program’s National Trends Network and Mercury Deposition Network, 2013–14

    Science.gov (United States)

    Wetherbee, Gregory A.; Martin, RoseAnn

    2016-01-01

    The U.S. Geological Survey Branch of Quality Systems operated five distinct programs to provide external quality assurance monitoring for the National Atmospheric Deposition Program’s (NADP) National Trends Network and Mercury Deposition Network during 2013–14. The National Trends Network programs include (1) a field audit program to evaluate sample contamination and stability, (2) an interlaboratory comparison program to evaluate analytical laboratory performance, and (3) a colocated sampler program to evaluate bias from precipitation sampler upgrades. The Mercury Deposition Network programs include the (4) system blank program and (5) an interlaboratory comparison program. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends for chemical constituents in wet deposition.

  19. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  20. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  1. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  2. Interstitial Pregnancy Resulting in a Viable Infant Coexistent with Massive Perivillous Fibrin Deposition: A Case Report and Literature Review

    Directory of Open Access Journals (Sweden)

    Yusuke Tanaka

    2014-05-01

    Full Text Available Objective - The objective of this report is to describe a rare case of interstitial pregnancy ultimately resulting in a viable infant coexistent with massive perivillous fibrin deposition (MPFD. Study Design - This study is a case report and literature review. Results - A 35-year-old female patient underwent cesarean section at 32 weeks of gestation due to fetal growth restriction (FGR and breech presentation. During the operation, a diagnosis of interstitial pregnancy was established. There was no evidence of placental separation. We decided to complete surgery without removal of the placenta and waited until the placenta delivered spontaneously. The conservative management was successful, and the patient was discharged on postoperative day 13. The pathologic examination showed MPFD. Conclusion - If interstitial pregnancies are not diagnosed at an early gestational age, it can result in a viable fetus, but such pregnancies may be associated with FGR or placenta accreta.

  3. Iodine-catalyzed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, J.T.; Duffield, J.E.; Davidson, M.G. (Amoco Oil Company, Naperville, IL (USA). Research and Development Dept.)

    Coals of two different ranks were liquefied in high yields using catalytic quantities of elemental iodine or iodine compounds. Iodine monochloride was found to be especially effective for enhancing both coal conversion and product quality. It appears that enhancement in coal conversion is due to the unique ability of iodine to catalyze radical-induced bond scission and hydrogen addition to the coal macromolecule or coal-derived free radicals. The starting iodine can be fully accounted for in the reaction products as both organic-bound and water-soluble forms. Unconverted coal and the heavy product fractions contain the majority of the organic-bound iodine. The results of iodine-catalyzed coal reactions emphasize the need for efficient hydrogen atom transfer along with bond scission to achieve high conversion and product quality. 22 refs., 12 tabs.

  4. Biginelli reaction catalyzed by copper nanoparticles.

    Directory of Open Access Journals (Sweden)

    Manika Dewan

    Full Text Available We recently reported a novel synthesis of copper nanoparticles from copper sulphate utilizing the charge-compensatory effect of ionic liquid [bmim]BF(4 and ethylene glycol. The nanoparticles were characterized and found to be stable for one year. Here we hypothesize that the stabilized nanoparticles should be able to catalyze one-pot multicomponent organic reactions. We show that the nanoparticles catalyzed Biginelli reaction at room temperature to give the product 3,4-dihydopyrimidinone (>90% yield in ~15 minutes from aldehydes, β-diketoester (ethylacetoacetate and urea (or thiourea. . Remarkably, such high yields and rapid kinetics was found to be independent of the electronic density on the reactant aryl-aldehyde. This was probably because even the surface-active particles reacted faster in the presence of ionic liquid as compared to conventional methods. The heterocyclic dihydropyrimidinones (DHPMs and their derivatives are widely used in natural and synthetic organic chemistry due to their wide spectrum of biological and therapeutic properties (resulting from their antibacterial, antiviral, antitumor and anti-inflammatory activities. Our method has an easy work-up procedure and the nanoparticles could be recycled with minimal loss of efficiency.

  5. Palladium-Catalyzed Arylation of Fluoroalkylamines

    Science.gov (United States)

    Brusoe, Andrew T.; Hartwig, John F.

    2015-01-01

    We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

  6. Fundamental studies of the mechanisms of slag deposit formation: Studies on initiation, growth and sintering in the formation of utility boiler deposits: Topical technical report

    Energy Technology Data Exchange (ETDEWEB)

    Tangsathitkulchai, M.; Austin, L.G.

    1986-03-01

    Three laboratory-scale devices were utilized to investigate the mechanisms of the initiation, growth and sintering process involved in the formation of boiler deposits. Sticking apparatus investigations were conducted to study deposit initiation by comparing the adhesion behavior of the ash drops on four types of steel-based heat exchanger materials under the conditions found in a utility boiler and an entrained slagging gasifier. In addition, the adhesion behavior of the ash drops on a reduced steel surface were investigated. All the ash drops studied in this investigation were produced from bituminous coals.

  7. Particle deposition in human and canine tracheobronchial casts: Annual progress report

    International Nuclear Information System (INIS)

    This work measures deposition patterns and efficiencies of aerosols within realistic, physical models of the tracheobronchial airways of humans and experimental animals over a range of particle sizes from 0.01 to 1.0 μm, for a variety of respiratory modes and rates. Full morphometric and flow distribution measurements were completed on casts of human and canine tracheobronchial airways, which extend from just below the larynx to airways 1 mm in diameter. They show basic similarities in the distribution of airflow, but also species differences which must be considered. The distribution of airflow was measured for minute volumes equivalent to 6, 11, 17 and 22 L min-1 for the human and 3, 6, 8 and 11 L min-1 for the canine for both constant and pulsatile inspiratory flow. Inertance was found to carry more of the flow to airways of the lower lobes at higher flow rates. Basic differences in airway branching pattern result in a more distinct change in airflow distribution as flow rate changes for the canine cast as compared with the human cast. These differences will contribute to differing patterns of mass transfer of inhaled particles in central airways of the two species. 8 refs., 2 figs., 5 tabs

  8. Processes of energy deposition by heavy-particle and electron impact. Final progress report

    International Nuclear Information System (INIS)

    Progress is reported in three areas of reasearch during the present period: K-shell ionization in high energy collisions of heavy ions with light target atoms using the sudden (Magnus) approximation, K-L level matching phenomena associated with K-shell vacancy production in heavy-ion collisions, and studies of low energy collisions of electrons with molecules using semi-classical perturbation theory. A brief discussion of each of these activities is given

  9. Metastatic Pulmonary Adenocarcinoma Deposit Arising Within a Cutaneous Basal Cell Carcinoma: A Case Report

    OpenAIRE

    Carey, Elinor; Jones, Simon D; Griffiths, Paul; Baxter, Prue

    2011-01-01

    Skin metastases are rare complications of internal malignancies, and most commonly arise from primary lung carcinoma (Brownstein and Helwig in Arch Dermatol 105:82–68, 1972). Metastatic cutaneous lesions have not previously been documented to arise within other skin tumours. We report our experience of a solitary pulmonary adenocarcinoma metastasis that arose within a pre-existing basal cell carcinoma in a patient with undiagnosed lung cancer. Immunohistochemistry was invaluable in confirming...

  10. Result of UT verification test for stainless steel through weld deposit. 2nd report

    International Nuclear Information System (INIS)

    Japanese code for ultrasonic testing in-service inspection, named JEAC 4207, allows inspection through weld metal, in case that some factors, such as weld crown or other structures, disturb scanning. The applicability of through weld metal inspection had been reported with BWR piping. This paper will be technical basis of applicability of through weld metal inspection for PWR piping, which is thicker and has factor hardens inspection. The data successfully shows the capability for detection and sizing by through weld metal inspection. (author)

  11. Theoretical survey of muon catalyzed fusion

    International Nuclear Information System (INIS)

    The main steps in the muon-catalyzed d-t fusion cycle are given in this report. Most of the stages are very fast, and therefore do not contribute significantly to the cycling time. Thus at liquid H2 densities (/phi/ = 1 in the standard convention) the time for stopping the negative muon, its subsequent capture and deexcitation to the ground state is estimated to be /approximately/ 10/sup/minus/11/ sec.1 The muon spends essentially all of its time in either the (dμ) ground state, waiting for transfer to a (tμ) ground state to occur, or in the (tμ) ground state, writing for molecular formation to occur. Following the formation of this ''mesomolecule'' (actually a muonic molecular ion), deexcitation and fusion are again fast. Then the muon is (usually) liberated to go around again. We will discuss these steps in some detail. 5 refs., 3 figs

  12. External quality-assurance project report for the National Atmospheric Deposition Program/National Trends Network and Mercury Deposition Network, 2009-2010

    Science.gov (United States)

    Wetherbee, Gregory A.; Martin, RoseAnn; Rhodes, Mark F.; Chesney, Tanya A.

    2014-01-01

    The U.S. Geological Survey operated six distinct programs to provide external quality-assurance monitoring for the National Atmospheric Deposition Program/National Trends Network (NTN) and Mercury Deposition Network (MDN) during 2009–2010. The field-audit program assessed the effects of onsite exposure, sample handling, and shipping on the chemistry of NTN samples; a system-blank program assessed the same effects for MDN. Two interlaboratory-comparison programs assessed the bias and variability of the chemical analysis data from the Central Analytical Laboratory (CAL) and Mercury (Hg) Analytical Laboratory (HAL). The blind-audit program was also implemented for the MDN to evaluate analytical bias in total Hg concentration data produced by the HAL. The co-located-sampler program was used to identify and quantify potential shifts in NADP data resulting from replacement of original network instrumentation with new electronic recording rain gages (E-gages) and precipitation collectors that use optical sensors. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends of chemical constituents in wet deposition across the United States. Results also suggest that retrofit of the NADP networks with the new precipitation collectors could cause –8 to +14 percent shifts in NADP annual precipitation-weighted mean concentrations and total deposition values for ammonium, nitrate, sulfate, and hydrogen ion, and larger shifts (+13 to +74 percent) for calcium, magnesium, sodium, potassium, and chloride. The prototype N-CON Systems bucket collector is more efficient in the catch of precipitation in winter than Aerochem Metrics Model 301 collector, especially for light snowfall.

  13. Stau-catalyzed Nuclear Fusion

    OpenAIRE

    Hamaguchi, K.; Hatsuda, T.(Theoretical Research Division, Nishina Center, RIKEN, Saitama, 351-0198, Japan); Yanagida, T. T.

    2006-01-01

    We point out that the stau may play a role of a catalyst for nuclear fusions if the stau is a long-lived particle as in the scenario of gravitino dark matter. In this letter, we consider d d fusion under the influence of stau where the fusion is enhanced because of a short distance between the two deuterons. We find that one chain of the d d fusion may release an energy of O(10) GeV per stau. We discuss problems of making the stau-catalyzed nuclear fusion of practical use with the present tec...

  14. Gold-catalyzed naphthalene functionalization

    OpenAIRE

    Iván Rivilla; M. Mar Díaz-Requejo; Pedro J. Pérez

    2011-01-01

    The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, M = Cu, 1a; M = Au, 1b), in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethyl)phenyl), catalyze the transfer of carbene groups: C(R)CO2Et (R = H, Me) from N2C(R)CO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either f...

  15. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  16. CRADA Final Report: Properties of Vacuum Deposited Thin Films of Lithium Phosphorous Oxynitride (Lipon) with an Expanded Composition Range

    Energy Technology Data Exchange (ETDEWEB)

    Dudney, N.J.

    2003-12-29

    Thin films of an amorphous, solid-state, lithium electrolyte, referred to as ''Lipon'', were first synthesized and characterized at ORNL in 1991. This material is typically prepared by magnetron sputtering in a nitrogen plasma, which allows nitrogen atoms to substitute for part of the oxygen ions of Li{sub 3}PO{sub 4}. Lipon is the key component in the successful fabrication of ORNL's rechargeable thin film microbatteries. Cymbet and several other US Companies have licensed this technology for commercialization. Optimizing the properties of the Lipon material, particularly the lithium ion conductivity, is extremely important, yet only a limited range of compositions had been explored prior to this program. The goal of this CRADA was to develop new methods to prepare Lipon over an extended composition range and to determine if the film properties might be significantly improved beyond those previously reported by incorporating a larger N component into the film. Cymbet and ORNL investigated different deposition processes for the Lipon thin films. Cymbet's advanced deposition process not only achieved a higher deposition rate, but also permitted independent control the O and N flux to the surface of the growing film. ORNL experimented with several modified sputtering techniques and found that by using sectored sputter targets, composed of Li{sub 3}PO{sub 4} and Li{sub 3}N ceramic disks, thin Lipon films could be produced over an expanded composition range. The resulting Lipon films were characterized by electrical impedance, infrared spectroscopy, and several complementary analytical techniques to determine the composition. When additional N plus Li are incorporated into the Lipon film, the lithium conductivity was generally degraded. However, the addition of N accompanied by a slight loss of Li gave an increase in the conductivity. Although the improvement in the conductivity was only very modest and was a disappointing conclusion of

  17. The Palmottu Analogue Project, Progress Report 1993. The behaviour of natural radionuclides in and around uranium deposits, Nr. 7

    International Nuclear Information System (INIS)

    The report gives a summary of the results of investigations carried out in 1993 at the Palmottu natural analogue study site, which comprises a small U-Th mineralization in Nummi-Pusula, southwestern Finland. Additionally, the report includes several separate articles dealing with various aspects of the Palmottu Analogue Project: (1) 3-dimensional model of fracture zones, (2) redox chemistry of uranium in groundwater, (3) humic substances in groundwater, (4) uranium mineralogy, (5) importance of selective extractions in uranium migration studies, (6) modelling of matrix diffusion, and (7) uranium in surficial deposits. The Palmottu Analogue Project aims at a more profound understanding of radionuclide transport processes in fractured crystalline bedrock. The essential factors controlling transport are groundwater flow and interaction between water and rock. Accordingly, the study includes (1) structural interpretations partly based on geophysical measurements, (2) hydrological studies including hydraulic drill-hole measurements, (3) flow modelling, (4) hydrogeochemical characterization of groundwater, uranium chemistry and colloid chemistry, (5) mineralogical studies, (6) geochemical interpretation and modelling, (7) studies on mobilization and retardation of uranium, and (8) modelling of uranium series data. Paleohydrogeological aspects are of special interest, due to the anticipated future glaciation of the Fennoscandian Shield. Surficial sediments and waters are studied to gain information on postglacial migration in the overburden. (orig.)

  18. U.S. Geological Survey external quality-assurance project report to the National Atmospheric Deposition Program / National Trends Network and Mercury Deposition Network, 2007-08

    Science.gov (United States)

    Wetherbee, Gregory A.; Latysh, Natalie E.; Chesney, Tanya A.

    2010-01-01

    The U.S. Geological Survey (USGS) used six distinct programs to provide external quality-assurance monitoring for the National Atmospheric Deposition Program / National Trends Network (NTN) and Mercury Deposition Network (MDN) during 2007-08. The field-audit program assessed the effects of onsite exposure, sample handling, and shipping on the chemistry of NTN samples, and a system-blank program assessed the same effects for MDN. Two interlaboratory-comparison programs assessed the bias and variability of the chemical analysis data from the Central Analytical Laboratory (CAL), Mercury (Hg) Analytical Laboratory (HAL), and 12 other participating laboratories. A blind-audit program was also implemented for the MDN to evaluate analytical bias in HAL total Hg concentration data. A co-located-sampler program was used to identify and quantify potential shifts in NADP data resulting from replacement of original network instrumentation with new electronic recording rain gages (E-gages) and prototype precipitation collectors. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends of chemical constituents in wet deposition across the U.S. NADP data-quality objectives continued to be achieved during 2007-08. Results also indicate that retrofit of the NADP networks with the new E-gages is not likely to create step-function type shifts in NADP precipitation-depth records, except for sites where annual precipitation depth is dominated by snow because the E-gages tend to catch more snow than the original NADP rain gages. Evaluation of prototype precipitation collectors revealed no difference in sample volumes and analyte concentrations between the original NADP collectors and modified, deep-bucket collectors, but the Yankee Environmental Systems, Inc. (YES) collector obtained samples of significantly higher volumes and analyte concentrations than the standard NADP collector.

  19. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand;

    2015-01-01

    these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed...

  20. The glycosyltransferase involved in thurandacin biosynthesis catalyzes both O- and S-glycosylation

    OpenAIRE

    Wang, Huan; Oman, Trent J.; Zhang, Ran; Garcia De Gonzalo, Chantal V.; Zhang, Qi; van der Donk, Wilfred A.

    2013-01-01

    The S-glycosyltransferase SunS is a recently discovered enzyme that selectively catalyzes the conjugation of carbohydrates to the cysteine thiol of proteins. This study reports the discovery of a second S-glycosyltransferase, ThuS, and shows that ThuS catalyzes both S-glycosylation of the thiol of cysteine and O-glycosylation of the hydroxyl group of serine in peptide substrates. ThuS-catalyzed S-glycosylation is more efficient than O-glycosylation and the enzyme demonstrates high tolerance w...

  1. Monoclonal Gammopathy of Undetermined Significance with Amyloid Deposition in the Lung and Non-Amyloid Eosinophilic Deposition in the Brain: A Case Report

    Directory of Open Access Journals (Sweden)

    Francois Abi-Fadel

    2010-01-01

    Full Text Available Background. Monoclonal gammopathy of undetermined significance (MGUS is rarely complicated by amyloidosis. Case. A 66-year-old white male presented to the emergency room (ER after an unwitnessed fall and change in mental status. Patient was awake and alert but not oriented. There was no focal deficit on neurological exam. Past medical history (PMH included hypertension, hypercholesterolemia, aortic valve replacement (nonmetallic, incomplete heart block controlled by a pacemaker and IgG- IgA type Monoclonal Gammopathy of Undetermined Significance. The MGUS was diagnosed 9 months ago on serum protein electrophoresis (SPEP as patient was referred to the outpatient clinic for hyperglobulinemia on routine blood work. In ER, a head-computed tomography (CT revealed multiple parenchymal hemorrhagic lesions suspicious for metastases. A CT chest, abdomen and pelvis revealed numerous ground-glass and solid nodules in the lungs. Lower extremity duplex and transesophageal echocardiogram were negative. Serial blood cultures and serologies for cryptococcus and histoplasmosis, antineutrophil cytoplasmic antibody (ANCA, antinuclear antibody (ANA, rheumatoid factor (RF, cryoglobulin, and antiglomerular basement membrane (anti-GBM antibodies were all negative. CT guided lung biopsy was positive for Thioflavin T amyloid deposits. Brain biopsy was positive for eosinophilic material (similar to the lungs but negative for Thioflavin T stain. The patient's clinical status continued to deteriorate with cold cyanotic fingers developing on day 12 and a health care acquired pneumonia, respiratory failure, and fungemia on day 18. On day 29, family withdrew life support and denied any autopsies. Conclusion. Described is an atypical course of MGUS complicated by amyloidosis of the lung and nonamyloid eosinophilic deposition in the brain. As MGUS might be complicated by diseases such as amyloidosis and multiple myeloma, a scheduled follow-up of these patients is always

  2. Catalyzed electrolytic plutonium oxide dissolution

    International Nuclear Information System (INIS)

    Catalyzed electrolytic plutonium oxide dissolution (CEPOD) was first demonstrated at Pacific Northwest Laboratory (PNL) in early 1974 in work funded by the Exxon Corporation. The work, aimed at dissolution of Pu-containing residues remaining after the dissolution of spent mixed-oxide reactor fuels, was first publicly disclosed in 1981. The process dissolves PuO2 in an anolyte containing small (catalytic) amounts of elements that form kinetically fast, strongly oxidizing ions. These are continuously regenerated at the anode. Catalysts used, in their oxidized form, include Ag2+, Ce4+, Co3+, and AmO22+. This paper reviews the chemistry involved in CEPOD and the results of its application to the dissolution of the Pu content of a variety of PuO2-containing materials such as off-standard oxide, fuels dissolution residues, incinerator ash, contaminated soils, and other scraps or wastes. Results are presented for both laboratory-scale and plant-scale dissolves

  3. Gold-catalyzed naphthalene functionalization

    Directory of Open Access Journals (Sweden)

    Iván Rivilla

    2011-05-01

    Full Text Available The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenylimidazol-2-ylidene, M = Cu, 1a; M = Au, 1b, in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethylphenyl, catalyze the transfer of carbene groups: C(RCO2Et (R = H, Me from N2C(RCO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed.

  4. DNA-Catalyzed Hydrolysis of Esters and Aromatic Amides

    OpenAIRE

    Brandsen, Benjamin M.; Hesser, Anthony R.; Castner, Marissa A.; Chandra, Madhavaiah; Silverman, Scott K.

    2013-01-01

    We previously reported that DNA catalysts (deoxyribozymes) can hydrolyze DNA phosphodiester linkages, but DNA-catalyzed amide bond hydrolysis has been elusive. Here we used in vitro selection to identify DNA catalysts that hydrolyze ester linkages as well as DNA catalysts that hydrolyze aromatic amides, for which the leaving group is an aniline moiety. The aromatic amide-hydrolyzing deoxyribozymes were examined using linear free energy relationship analysis. The hydrolysis reaction is unaffec...

  5. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    Science.gov (United States)

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  6. Copper-catalyzed stereoselective conjugate addition of alkylboranes to alkynoates

    Science.gov (United States)

    Wakamatsu, Takamichi; Nagao, Kazunori

    2015-01-01

    Summary A copper-catalyzed conjugate addition of alkylboron compounds (alkyl-9-BBN, prepared by hydroboration of alkenes with 9-BBN-H) to alkynoates to form β-disubstituted acrylates is reported. The addition occurred in a formal syn-hydroalkylation mode. The syn stereoselectivity was excellent regardless of the substrate structure. A variety of functional groups were compatible with the conjugate addition. PMID:26734092

  7. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    Directory of Open Access Journals (Sweden)

    Bijay Shrestha

    2015-12-01

    Full Text Available We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1 as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields.

  8. Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

    Science.gov (United States)

    Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

    2015-06-22

    We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. PMID:25959033

  9. Synthesis of Aryldifluoroamides by Copper-Catalyzed Cross-Coupling.

    Science.gov (United States)

    Arlow, Sophie I; Hartwig, John F

    2016-03-24

    A copper-catalyzed coupling of aryl, heteroaryl, and vinyl iodides with α-silyldifluoroamides is reported. The reaction forms α,α-difluoro-α-aryl amides from electron-rich, electron-poor, and sterically hindered aryl iodides in high yield and tolerates a variety of functional groups. The aryldifluoroamide products can be transformed further to provide access to a diverse array of difluoroalkylarenes, including compounds of potential biological interest. PMID:26929068

  10. Cost-risk analysis of protective actions for a low-level deposition of radionuclides. Contract report (final)

    International Nuclear Information System (INIS)

    This report summarizes the results of a cost-effectiveness analysis of protective actions following a low-level deposition of radionuclides. The media contaminated were land, property, water supplies, persons, and biota. The end products of the investigation of such phase are dose and costs associated with dose reduction techniques. The mechanisms by which radionuclides may be taken up by humans were modelled, and control technologies (protective actions) which result in a reduction in the dose were defined. With the exception of Phase VI, the consequences were expressed as the 100-year collective dose commitment equivalent, in person-rem. In Phase VI, the dose calculated was the dose equivalent, also expressin in person-rem. The dose commitment is defined as the sum of all doses to individuals over the entire time period that radioactive material persists in the environment in a state available for interaction with humans. There are two time periods involved, (1) the intake period, during which radionuclides are taken up by humans, in this study taken to be 100 years, and (2) the time interval over which the dose rate is integrated, which was seventy years. The collective dose commitment is obtained by integrating the individual dose commitments over the affected population

  11. Effects of Ni catalyzer on growth velocity and morphology of SiC nano-fibers

    Institute of Scientific and Technical Information of China (English)

    XU Xian-feng; XIAO Peng; XIONG Xiang; HUANG Bai-yun

    2009-01-01

    Composite felts reinforced by both SiC nano-fibers (SiC-NFs) and carbon fibers were prepared at 1 273 K using Ni granules as catalyzers with different deposition time. SiC-NFs were deposited on the surface of the carbon fibers in situ by catalytic chemical vapor deposition(CCVD). The phase, microstructure and morphology of the fibers after electroplating and deposition were characterized by XRD, SEM and TEM. The results show that the SiC-NFs produced by CCVD are composed of single crystal of β-SiC. It is found that smaller nano-granules are more active as catalyzers. The resulting SiC-NFs appear more spindle-like and have a more homogeneous dispersion. The mass change of the samples before and after deposition shows that using more Ni granules results in a faster growth velocity of SiC-NFs. With the same electroplating time, the growth velocity of the SiC-NFs first increases and then decreases. At around 4 h, it reaches the maximum growth velocity, and it becomes nearly constant at around 8 h. After 8 h, the stable growth velocity of the electroplated Ni samples is faster than that of the conventional sample produced without catalyzers, because the SiC-NFs can improve the specific surface area and the activity of the surface.

  12. Simulation of the geochemical interactions in a natural CO2 deposit: the example of Springerville - Saint-Johns (USA). Final report

    International Nuclear Information System (INIS)

    The aim of the study is a better understanding of the geochemical operating of natural analogues by the simulation of scenario representative of the evolution of site since the arrival of CO2 still today. This exercise concerns the Springerville site. Simulation tests with the PHREEQC code have been realized. This final report presents in the first part how the data are collected on a natural CO2, then a bibliographic synthesis on the observed impacts of the CO2 on a deposit. The fourth part is the simulation of the geochemical interactions in the natural CO2 deposit of Springerville. (A.L.B.)

  13. Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts. M.S. Thesis. Final Report, Jan. 1981 - Jul. 1982

    Science.gov (United States)

    Manning, M. P.; Reid, R. C.; Sophonpanich, C.

    1982-01-01

    The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

  14. Using Simple Donors to Drive the Equilibria of Glycosyltransferase-Catalyzed Reactions

    OpenAIRE

    Gantt, Richard W.; Peltier-Pain, Pauline; Cournoyer, William J.; Thorson, Jon S.

    2011-01-01

    We report the ability of simple glycoside donors to drastically shift the equilibria of glycosyltransferase-catalyzed reactions, transforming NDP-sugar formation from an endo- to an exothermic process. To demonstrate the utility of this thermodynamic adaptability, we highlight the glycosyltransferase-catalyzed synthesis of 22 sugar nucleotides from simple aromatic sugar donors as well as the corresponding in situ formation of sugar nucleotides as a driving force in context of glycosyltransfer...

  15. Geology and recognition criteria for sandstone uranium deposits in mixed fluvial-shallow marine sedimentary sequences, South Texas. Final report

    International Nuclear Information System (INIS)

    Uranium deposits in the South Texas Uranium Region are classical roll-type deposits that formed at the margin of tongues of altered sandstone by the encroachment of oxidizing, uraniferous solutions into reduced aquifers containing pyrite and, in a few cases, carbonaceous plant material. Many of the uranium deposits in South Texas are dissimilar from the roll fronts of the Wyoming basins. The host sands for many of the deposits contain essentially no carbonaceous plant material, only abundant disseminated pyrite. Many of the deposits do not occur at the margin of altered (ferric oxide-bearing) sandstone tongues but rather occur entirely within reduced, pyurite-bearing sandstone. The abundance of pyrite within the sands probably reflects the introduction of H2S up along faults from hydrocarbon accumulations at depth. Such introductions before ore formation prepared the sands for roll-front development, whereas post-ore introductions produced re-reduction of portions of the altered tongue, leaving the deposit suspended in reduced sandstone. Evidence from three deposits suggests that ore formation was not accompanied by the introduction of significant amounts of H2S

  16. Geology and recognition criteria for sandstone uranium deposits in mixed fluvial-shallow marine sedimentary sequences, South Texas. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Adams, S.S.; Smith, R.B.

    1981-01-01

    Uranium deposits in the South Texas Uranium Region are classical roll-type deposits that formed at the margin of tongues of altered sandstone by the encroachment of oxidizing, uraniferous solutions into reduced aquifers containing pyrite and, in a few cases, carbonaceous plant material. Many of the uranium deposits in South Texas are dissimilar from the roll fronts of the Wyoming basins. The host sands for many of the deposits contain essentially no carbonaceous plant material, only abundant disseminated pyrite. Many of the deposits do not occur at the margin of altered (ferric oxide-bearing) sandstone tongues but rather occur entirely within reduced, pyurite-bearing sandstone. The abundance of pyrite within the sands probably reflects the introduction of H/sub 2/S up along faults from hydrocarbon accumulations at depth. Such introductions before ore formation prepared the sands for roll-front development, whereas post-ore introductions produced re-reduction of portions of the altered tongue, leaving the deposit suspended in reduced sandstone. Evidence from three deposits suggests that ore formation was not accompanied by the introduction of significant amounts of H/sub 2/S.

  17. Emissions, transport, deposition and effects of base cations in relation to acidification. Report from the UNECE LRTAP workshop in Gothenburg November 2003

    Energy Technology Data Exchange (ETDEWEB)

    Westling, Olle; Loevblad, Gun (eds.)

    2004-06-01

    The workshop on base cation deposition took place in Gothenburg on 26-28 November 2003. It was an official workshop of the Co-operative Programme for Monitoring and Evaluation of the Long Range Transboundary Air Pollution, EMEP and Working Group on Effects under the UNECE/CLRTAP. The workshop report summarises the state-of-knowledge of emissions, dispersion and deposition of base cations over Europe. The workshop evaluated in particular the knowledge with respect to mapping the base cation deposition over Europe as a basis for the application of dynamic models in the coming air pollution abatement strategies in Europe. The knowledge reflects the present situation, historical development and prospects for the coming 10-20 years.

  18. Cytochrome c catalyzes the in vitro synthesis of arachidonoyl glycine

    International Nuclear Information System (INIS)

    Long chain fatty acyl glycines are an emerging class of biologically active molecules that occur naturally and produce a wide array of physiological effects. Their biosynthetic pathway, however, remains unknown. Here we report that cytochrome c catalyzes the synthesis of N-arachidonoyl glycine (NAGly) from arachidonoyl coenzyme A and glycine in the presence of hydrogen peroxide. The identity of the NAGly product was verified by isotope labeling and mass analysis. Other heme-containing proteins, hemoglobin and myoglobin, were considerably less effective in generating arachidonoyl glycine as compared to cytochrome c. The reaction catalyzed by cytochrome c in vitro points to its potential role in the formation of NAGly and other long chain fatty acyl glycines in vivo

  19. A Complete Reporting of MCNP6 Validation Results for Electron Energy Deposition in Single-Layer Extended Media for Source Energies <= 1-MeV

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hughes, Henry Grady [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-04

    In this paper, we expand on previous validation work by Dixon and Hughes. That is, we present a more complete suite of validation results with respect to to the well-known Lockwood energy deposition experiment. Lockwood et al. measured energy deposition in materials including beryllium, carbon, aluminum, iron, copper, molybdenum, tantalum, and uranium, for both single- and multi-layer 1-D geometries. Source configurations included mono-energetic, mono-directional electron beams with energies of 0.05-MeV, 0.1-MeV, 0.3- MeV, 0.5-MeV, and 1-MeV, in both normal and off-normal angles of incidence. These experiments are particularly valuable for validating electron transport codes, because they are closely represented by simulating pencil beams incident on 1-D semi-infinite slabs with and without material interfaces. Herein, we include total energy deposition and energy deposition profiles for the single-layer experiments reported by Lockwood et al. (a more complete multi-layer validation will follow in another report).

  20. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    The viability of a symbiotic combination of Muon Catalyzed Fusion (μCF) and high density generation processes has been investigated. The muon catalyzed fusion reaction rates are formulated in the temperature and density range found under moderate compressive conditions. Simplified energy gain and power balance calculations indicate that significant energy gain occurs only if standard type deuterium-tritium (dt) fusion is ignited. A computer simulation of the hydrodynamics and fusion kinetics of a spherical deuterium-tritium pellet implosion including muons is performed. Using the muon catalyzed fusion reaction rates formulated and under ideal conditions, the pellet ignites (and thus has a significant energy gain) only if the initial muon concentration is approximately 1017 cm-3. The muons need to be delivered to the pellet within a very short-time (≅ 1 ns). The muon pulse required in order to make the high density and temperature muon catalyzed fusion scheme viable is beyond the present technology for muon production. (orig.)

  1. Palladium-Catalyzed Carbonylation and Arylation Reactions

    OpenAIRE

    Sävmarker, Jonas

    2012-01-01

    Palladium-catalyzed reactions have found widespread use in contemporary organic chemistry due to their impressive range of functional group tolerance and high chemo- and regioselectivity. The pioneering contributions to the development of the Pd-catalyzed C-C bond forming cross-coupling reaction were rewarded with the Nobel Prize in Chemistry in 2010. Today, this is a rapidly growing field, and the development of novel methods, as well as the theoretical understanding of the various processes...

  2. Palladium-catalyzed coupling reactions of tetrafluoroethylene with arylzinc compounds.

    Science.gov (United States)

    Ohashi, Masato; Kambara, Tadashi; Hatanaka, Tsubasa; Saijo, Hiroki; Doi, Ryohei; Ogoshi, Sensuke

    2011-03-16

    Organofluorine compounds are widely used in all aspects of the chemical industry. Although tetrafluoroethylene (TFE) is an example of an economical bulk organofluorine feedstock, the use of TFE is mostly limited to the production of poly(tetrafluoroethylene) and copolymers with other alkenes. Furthermore, no catalytic transformation of TFE that involves carbon-fluorine bond activation has been reported to date. We herein report the first example of a palladium-catalyzed coupling reaction of TFE with arylzinc reagents in the presence of lithium iodide, giving α,β,β-trifluorostyrene derivatives in excellent yields. PMID:21322557

  3. Depósito multifocal de grasa en hígado: Reporte de un caso Liver multifocal fat deposition: Case report

    Directory of Open Access Journals (Sweden)

    Federico Pasardi

    2009-03-01

    Full Text Available Describir los hallazgos radiológicos distintivos en ultrasonido (US, tomografía computada (TC y resonancia magnética (RM del depósito multifocal de grasa en hígado y su importancia en el diagnóstico diferencial en pacientes con antecedente neoplásico. Se reporta el caso de una paciente femenina de 66 años de edad, operada de cáncer de mama 2 años atrás, que en controles ecográficos de rutina muestra múltiples imágenes nodulares hiperecogénicas hepáticas de reciente aparición. La paciente fue estudiada con TC, RM e histo-patológicamente, confirmándose la naturaleza grasa de las imágenes nodulares. La esteatosis hepática se trata de una patología bastante frecuente, bien caracterizada por los métodos de imágenes. Presenta patrones de depósito diferentes, siendo necesario en algunos casos para el diagnóstico de certeza la toma de biopsia del tejido afectado, que, en nuestro caso, fue realizada con guía ecográfica.To describe the distinctive imaging findings in ultrasound (US, computed tomography (CT and magnetic resonance imaging (MRI of liver multifocal fat deposition and its importance in the differential diagnosis in patients with neoplasic antecedents. The authors reported a 66 years old female patient, who had surgery for breast cancer two years ago, and presents in routine US multiple liver nodular hiperecogenic images from recent diagnosis. The patient was studied with CT, MRI and histo-pathology confirmed fatty liver disease. Fatty liver disease is a frequent pathology, well characterized with imaging, that presents different patterns, being necessary biopsy for final diagnosis, that in our patient was performed under US guidance.

  4. State-of-the-art for evaluating the potential effects of erosion and deposition on a radioactive waste repository. Final report

    Energy Technology Data Exchange (ETDEWEB)

    1980-07-16

    The potential impact of future geologic processes on the integrity of a deep, high-level radioactive-waste repository is evaluated. The following study identifies the potential consequences of surface erosion and deposition on sub-surface repository containment characteristics and assesses the ability to measure and predict quantitatively the rates and corresponding extent of these processes in the long term. Numerous studies of the magnitudes and rates of surficial erosion and deposition that have been used to determine the minimum allowable depth for a geologic repository (300 m - NRC Code of Federal Regulations, Part 60.122, Draft 10) are cited in this report. Measurement and interpretation of potential rates and extent of surficial processes in these studies involved considerable uncertainty, and the implications of this uncertainty on presently proposed repository siting criteria are addressed herein. Important concepts that should be considered when developing siting criteria to protect against deleterious effects arising from future erosion or deposition are highlighted. Erosion agents that could affect deep repositories are distinguished in this report so that their individual and combined impacts may be examined. This approach is recommended when evaluating potential repository sites in diverse environments that are susceptible to different agents of erosion. In contrast, agents of sedimentation are not differentiated in this report because of their relatively minor impact on a deep repository.

  5. State-of-the-art for evaluating the potential effects of erosion and deposition on a radioactive waste repository. Final report

    International Nuclear Information System (INIS)

    The potential impact of future geologic processes on the integrity of a deep, high-level radioactive-waste repository is evaluated. The following study identifies the potential consequences of surface erosion and deposition on sub-surface repository containment characteristics and assesses the ability to measure and predict quantitatively the rates and corresponding extent of these processes in the long term. Numerous studies of the magnitudes and rates of surficial erosion and deposition that have been used to determine the minimum allowable depth for a geologic repository (300 m - NRC Code of Federal Regulations, Part 60.122, Draft 10) are cited in this report. Measurement and interpretation of potential rates and extent of surficial processes in these studies involved considerable uncertainty, and the implications of this uncertainty on presently proposed repository siting criteria are addressed herein. Important concepts that should be considered when developing siting criteria to protect against deleterious effects arising from future erosion or deposition are highlighted. Erosion agents that could affect deep repositories are distinguished in this report so that their individual and combined impacts may be examined. This approach is recommended when evaluating potential repository sites in diverse environments that are susceptible to different agents of erosion. In contrast, agents of sedimentation are not differentiated in this report because of their relatively minor impact on a deep repository

  6. Cell-surface acceleration of urokinase-catalyzed receptor cleavage

    DEFF Research Database (Denmark)

    Høyer-Hansen, G; Ploug, M; Behrendt, N;

    1997-01-01

    or indirectly mediated by uPA itself. In a soluble system, uPA can cleave purified uPAR, but the low efficiency of this reaction has raised doubts as to whether uPA is directly responsible for uPAR cleavage on the cells. We now report that uPA-catalyzed cleavage of uPAR on the cell surface is...... strongly favored relative to the reaction in solution. The time course of uPA-catalyzed cleavage of cell-bound uPAR was studied using U937 cells stimulated with phorbol 12-myristate 13-acetate. Only 30 min was required for 10 nM uPA to cleave 50% of the cell-bound uPAR. This uPA-catalyzed cleavage reaction...... was inhibited by a prior incubation of the cells with uPA inactivated by diisopropyl fluorophosphate, demonstrating a requirement for specific receptor binding of the active uPA to obtain the high-efficiency cleavage of cell-bound uPAR. Furthermore, amino-terminal sequence analysis revealed that u...

  7. Production of edible carbohydrates from formaldehyde in a spacecraft. pH variations in the calcium hydroxide catalyzed formose reaction. Final Report, 1 Jul. 1973 - 30 Jun. 1974. M.S. Thesis

    Science.gov (United States)

    Weiss, A. H.; Kohler, J. T.; John, T.

    1974-01-01

    The study of the calcium hydroxide catalyzed condensation of formaldehyde was extended to a batch reactor system. Decreases in pH were observed, often in the acid regime, when using this basic catalyst. This observation was shown to be similar to results obtained by others using less basic catalysts in the batch mode. The relative rates of these reactions are different in a batch reactor than in a continuous stirred tank reactor. This difference in relative rates is due to the fact that at any degree of advancement in the batch system, the products have a history of previous products, pH, and dissolved catalyst. The relative rate differences can be expected to yield a different nature of product sugars for the two types of reactors.

  8. Chemical vapor deposition. 1975-1978 (citations from the NTIS Data Base). Report for 1975-78

    Energy Technology Data Exchange (ETDEWEB)

    Cavagnaro, D.M.

    1980-07-01

    This bibliography discusses chemical vapor deposition of carbon, carbides, ceramics, metals, and glasses. Applications of this process include coatings, semiconducting films, laser materials, solar cells, composite fabrication, and nuclear reactor material fabrication. The physical, mechanical, and chemical properties of these coatings are covered. (This updated bibliography contains 246 citations, none of which are new entries to the previous edition.)

  9. Chemical vapor deposition. 1979-June 1980 (citations from the NTIS Data Base). Report for 1979-June 1980

    Energy Technology Data Exchange (ETDEWEB)

    Cavagnaro, D.M.

    1980-07-01

    Research on chemical vapor deposition of carbon, carbides, ceramics, metals, and glasses are cited. Applications of this process include optical coatings, semiconducting films, laser materials, solar cells, composite fabrication, and nuclear reactor material fabrication. The physical, mechanical, and chemical properties of these coatings are covered. (This updated bibliography contains 64 citations, 50 of which are new entries to the previous edition.)

  10. Precision and bias of selected analytes reported by the National Atmospheric Deposition Program and National Trends Network, 1983; and January 1980 through September 1984

    Science.gov (United States)

    Schroder, L.J.; Bricker, A.W.; Willoughby, T.C.

    1985-01-01

    Blind-audit samples with known analyte concentrations have been prepared by the U.S. Geological Survey and distributed to the National Atmospheric Deposition Program 's Central Analytical Laboratory. The difference between the National Atmospheric Deposition Program and National Trends Network reported analyte concentrations and known analyte concentrations have been calculated, and the bias has been determined. Calcium, magnesium , sodium, and chloride were biased at the 99-percent confidence limit; potassium and sulfate were unbiased at the 99-percent confidence limit, for 1983 results. Relative-percent differences between the measured and known analyte concentration for calcium , magnesium, sodium, potassium, chloride, and sulfate have been calculated for 1983. The median relative percent difference for calcium was 17.0; magnesium was 6.4; sodium was 10.8; potassium was 6.4; chloride was 17.2; and sulfate was -5.3. These relative percent differences should be used to correct the 1983 data before user-analysis of the data. Variances have been calculated for calcium, magnesium, sodium, potassium, chloride, and sulfate determinations. These variances should be applicable to natural-sample analyte concentrations reported by the National Atmospheric Deposition Program and National Trends Network for calendar year 1983. (USGS)

  11. Kinetic Parameters for the Noncatalyzed and Enzyme-Catalyzed Mutarotation of Glucose Using a Blood Glucometer

    Science.gov (United States)

    Hardee, John R.; Delgado, Bryan; Jones, Wray

    2011-01-01

    The kinetic parameters for the conversion of alpha-D-glucose to beta-D-glucose were measured using a blood glucometer. The reaction order, rate constant, and Arrhenius activation energy are reported for the noncatalyzed reaction and turnover number and Michaelis constant are reported for the reaction catalyzed by porcine kidney mutarotase. The…

  12. The vapour phase deposition of boron on titanium by the reaction between gaseous boron trichloride and titanium metal. Final report

    International Nuclear Information System (INIS)

    The reaction, between boron trichloride vapour and titanium has been investigated in the temperature range 200 - 1350 deg. C. It has been found that an initial reaction leads to the formation of titanium tetrachloride and the deposition of boron on titanium, but that except for reactions between 900 and 1000 deg. C, the system is complicated by the formation of lower titanium chlorides due to secondary reactions between the titanium and titanium tetrachloride

  13. Ruthenium-Catalyzed meta-Selective C—H Bromination

    Science.gov (United States)

    Teskey, Christopher J; Lui, Andrew Y W; Greaney, Michael F

    2015-01-01

    The first example of a transition-metal-catalyzed, meta-selective C–H bromination procedure is reported. In the presence of catalytic [{Ru(p-cymene)Cl2}2], tetrabutylammonium tribromide can be used to functionalize the meta C–H bond of 2-phenylpyridine derivatives, thus affording difficult to access products which are highly predisposed to further derivatization. We demonstrate this utility with one-pot bromination/arylation and bromination/alkenylation procedures to deliver meta-arylated and meta-alkenylated products, respectively, in a single step. PMID:26288217

  14. Ruthenium-Catalyzed meta-Selective C—H Bromination

    OpenAIRE

    Teskey, Christopher J; Lui, Andrew Y W; Greaney, Michael F.

    2015-01-01

    The first example of a transition-metal-catalyzed, meta-selective C–H bromination procedure is reported. In the presence of catalytic [{Ru(p-cymene)Cl2}2], tetrabutylammonium tribromide can be used to functionalize the meta C–H bond of 2-phenylpyridine derivatives, thus affording difficult to access products which are highly predisposed to further derivatization. We demonstrate this utility with one-pot bromination/arylation and bromination/alkenylation procedures to deliver meta-arylated and...

  15. Iron-Catalyzed Hydroboration: Unlocking Reactivity through Ligand Modulation.

    Science.gov (United States)

    Espinal-Viguri, Maialen; Woof, Callum R; Webster, Ruth L

    2016-08-01

    Iron-catalyzed hydroboration (HB) of alkenes and alkynes is reported. A simple change in ligand structure leads to an extensive change in catalyst activity. Reactions proceed efficiently over a wide range of challenging substrates including activated, unactivated and sterically encumbered motifs. Conditions are mild and do not require the use of reducing agents or other additives. Large excesses of borating reagent are not required, allowing control of chemo- and regioselectivity in the presence of multiple double bonds. Mechanistic insight reveals that the reaction is likely to proceed via a highly reactive iron hydride intermediate. PMID:27321704

  16. Detekce mikroorganismů v půdě a miocénním sedimentu metodou CARD-FISH (Catalyzed Reporter Deposition - Fluorescence in situ Hybridization)

    Czech Academy of Sciences Publication Activity Database

    Dohnalová, Ludmila; Kasalický, Vojtěch; Chroňáková, Alica; Krištůfek, Václav

    Bratislava: Československá spoločnosť mikrobiologická, 2009, s. 149-157. ISBN 978-80-970269-9-8. [Mikrobiológia vody 2009. Poprad (SK), 30.09.2009-02.10.2009] R&D Projects: GA MŠk LC06066; GA AV ČR IAA600660605; GA ČR GA206/09/1642; GA ČR GA526/09/1570 Institutional research plan: CEZ:AV0Z60660521; CEZ:AV0Z60170517 Keywords : detection of microorganisms * soil sediment * CARD-FISH method Subject RIV: EH - Ecology, Behaviour

  17. Attractor Explosions and Catalyzed Vacuum Decay

    Energy Technology Data Exchange (ETDEWEB)

    Green, Daniel; Silverstein, Eva; Starr, David

    2006-05-05

    We present a mechanism for catalyzed vacuum bubble production obtained by combining moduli stabilization with a generalized attractor phenomenon in which moduli are sourced by compact objects. This leads straightforwardly to a class of examples in which the Hawking decay process for black holes unveils a bubble of a different vacuum from the ambient one, generalizing the new endpoint for Hawking evaporation discovered recently by Horowitz. Catalyzed vacuum bubble production can occur for both charged and uncharged bodies, including Schwarzschild black holes for which massive particles produced in the Hawking process can trigger vacuum decay. We briefly discuss applications of this process to the population and stability of metastable vacua.

  18. Deposition of 7Be and 137Cs in Sweden 2001 - 2008. With Radionuclides in ground level air in Sweden. Yearly report 2008

    International Nuclear Information System (INIS)

    Deposition of 7Be and 137Cs for four stations in Sweden are reported for the period 2001- 2008. For 7Be a correlation with total precipitation is seen. For 137Cs there is no correlation with precipitation and no correlation with surface air concentrations of 137Cs. The overall levels of 137Cs fallout is higher in areas that were largely affected by the Chernobyl fallout in 1986. The 137Cs deposition seen in the Gaevle area are mostly due to resuspension of this 137Cs fallout, but for other areas the total yearly deposition and resuspension are down to pre Chernobyl levels. Filtering of ground level air is performed continuously at six different locations in Sweden: Kiruna, Umeaa, Gaevle, Kista, Visby and Ljungbyhed. The filters are pressed into weekly samples and the contents of different radionuclides are measured by gamma spectroscopy. Precipitation is also collected at four of the stations: Kiruna, Gaevle, Kista and Ljungbyhed, the samples are ashed and the contents of radionuclides are measured. The levels of Be-7 and Cs-137 during 2008 in air and precipitation are presented for the different stations. Other anthropogenic radionuclides detected, if any, are also presented

  19. A quality-assurance assessment for constituents reported by the National Atmospheric Deposition Program and the National Trends Network

    Science.gov (United States)

    See, R.B.; Schroder, L.J.; Willoughby, T.C.

    1989-01-01

    A continuing quality-assurance program has been operated by the U.S. Geographical Survey to evaluate any bias introduced by routine handling, shipping, and laboratory analyses of wet-deposition samples collected in the National Atmospheric Deposition Program (NADP) and National Trends Network (NTN). Blind-audit samples having a variety of constituent concentrations and values were selected. Only blind-audit samples with constituent concentrations and values less than the 95th-percentile concentration for natural wet-deposition samples were included in the analysis. Of the major ions, there was a significant increase of Ca2+, Mg2+, K+ SO42+ and Cl- in samples handled according to standard protocols and shipped in NADP/NTN sample-collection buckets. For 1979-1987, graphs of smoothed data showing the estimated contaminations in blind-audit samples indicate a decrease in the median concentration and ranges of Ca2+, Mg2+ and SO42- contamination of blind-audit samples shipped in sample-collection buckets. Part of the contamination detected in blind-audit samples can be attributed to contact with the sample-collection bucket and lid; however, additional sources also seem to contaminate the blind-audit sample. Apparent decreases in the magnitude and range of sample contamination may be caused by differences in sample-collection bucket- and lid-washing procedures by the NADP/NTN Central Analytical Laboratory. Although the degree of bias is minimal for most constituents, summaries of the NADP/NTN data base may contain overestimates of Ca2+, Mg2+, Na-, K+, SO42- and Cl- concentrations, and underestimates of H+ concentrations.

  20. Biosensor Applications of MAPLE Deposited Lipase

    Directory of Open Access Journals (Sweden)

    Valeria Califano

    2014-10-01

    Full Text Available Matrix Assisted Pulsed Laser Evaporation (MAPLE is a thin film deposition technique derived from Pulsed Laser Deposition (PLD for deposition of delicate (polymers, complex biological molecules, etc. materials in undamaged form. The main difference of MAPLE technique with respect to PLD is the target: it is a frozen solution or suspension of the (guest molecules to be deposited in a volatile substance (matrix. Since laser beam energy is mainly absorbed by the matrix, damages to the delicate guest molecules are avoided, or at least reduced. Lipase, an enzyme catalyzing reactions borne by triglycerides, has been used in biosensors for detection of β-hydroxyacid esters and triglycerides in blood serum. Enzymes immobilization on a substrate is therefore required. In this paper we show that it is possible, using MAPLE technique, to deposit lipase on a substrate, as shown by AFM observation, preserving its conformational structure, as shown by FTIR analysis.

  1. Pinacol Coupling Reactions Catalyzed by Active Zinc

    Institute of Scientific and Technical Information of China (English)

    Hui ZHAO; Wei DENG; Qing Xiang GUO

    2005-01-01

    Pinacol coupling reactions catalyzed by active zinc revealed high activity and extensive suitability. The efficiency of the reaction was improved apparently owing to decreasing reductive potential of zinc. In addition, the results indicated that the zinc activity has a direct relation to the coupling reactivity compared to untreated zinc or other general active zinc.

  2. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C...

  3. Sulfilimimines in metal-catalyzed redox reactions

    Czech Academy of Sciences Publication Activity Database

    Voltrová, Svatava; Šrogl, Jiří

    Praha : -, 2009. s. 593-593. ISBN 978-80-02-02160-5. [ESOC 2009. European Symposium on Organic Chemistry /16./. 12.07.2009-16.07.2009, Praha] Institutional research plan: CEZ:AV0Z40550506 Keywords : sulfilimines * metal catalyzed oxidations * benzoisothiazolone Subject RIV: CC - Organic Chemistry

  4. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.

    2005-01-01

    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  5. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    Science.gov (United States)

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.

    2008-09-16

    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  6. Preliminary Report of the AMS analysis of tsunami deposits in Tohoku -- Japan -- 18th to the 21st Century

    CERN Document Server

    Wassmer, P; Hart, D E; Hiraishi, T; Azuma, R; Koenig, B; Trautmann, M

    2015-01-01

    Sedimentary records of tsunamis are a precious tool to assess the occurrence of past events, as attested by an abundant literature, which has seen a particular 'boom' in the aftermath of the 2004 Indian Ocean tsunami and the 2011 Tohoku tsunami. Despite an extensive literature, there is very little to no understanding of the role that the changing coastal environment is playing on the record of a tsunami, and for a given location, it is still unclear whether the largest tsunamis leave the largest amount of deposits. To research this question, the present study took place in Japan, in the Tohoku Region at Agawa-pond, because the pond act as a sediment trap. Using a sediment-slicer, a 1 m thick deposit was retrieved, from which 4 tsunami sequences were identified, including the latest 2011 tsunami. Using a series of sedimentary proxies: the AMS (Anisotropy of Magnetic Susceptibility), grain size analysis, quartz morphoscopy (morphology and surface characteristics) and the analysis of microfossils, disparities b...

  7. Large-scale concentration and deposition maps for the Netherlands. Report on 2012; Grootschalige concentratie- en depositiekaarten Nederland. Rapportage 2012

    Energy Technology Data Exchange (ETDEWEB)

    Velders, G.J.M.; Aben, J.M.M.; Jimmink, B.A.; Geilenkirchen, G.P.; Van der Swaluw, E.; De Vries, W.J.; Wesseling, J.; Van Zanten, M.C.

    2012-06-15

    RIVM (National Institute for Public Health and the Environment) presents new concentration maps for the Netherlands, for eight air pollutants, including nitrogen dioxide and particulate matter, for the period up to 2030. New deposition maps for nitrogen are also presented. These maps are produced annually and show a combined image of the air quality and level of deposition in the Netherlands. They are used in the national air quality collaboration programme (NSL) and in the programmatic approach to nitrogen (PAS) of the Dutch Ministry of Infrastructure and the Environment and the Ministry of Economic Affairs, Agriculture and Innovation. The maps are based both on measurements and model calculations. They have legal status and are considered a touchstone for new infrastructural projects [Dutch] Het RIVM presenteert de nieuwe kaarten waarin de concentraties van acht luchtverontreinigende stoffen (onder andere stikstofdioxide en fijn stof) in Nederland tot 2030 staan weergegeven. Hetzelfde geldt voor de mate waarin stikstof op de bodem neerslaat. Deze kaarten worden jaarlijks gemaakt en geven een beeld van de luchtkwaliteit en de neerslag van stikstof op de bodem in Nederland. Ze worden gebruikt in het Nationaal Samenwerkingsprogramma Luchtkwaliteit (NSL) en de Programmatische Aanpak Stikstof (PAS) van de ministeries van Infrastructuur en Milieu (IenM) en Economische Zaken, Landbouw en Innovatie (ELI). De kaarten hebben een wettelijke status en gelden als toetssteen voor ruimtelijke ordeningsplannen. Ze zijn gemaakt op basis van metingen en modelberekeningen.

  8. Acidic deposition: State of science and technology. Report 10. Watershed and lake processes affecting surface-water acid-base chemistry. Final report

    International Nuclear Information System (INIS)

    The acid-base chemistry of surface waters is governed by the amount and chemistry of deposition and by the biogeochemical reactions that generate acidity or acid neutralizing capacity (ANC) along the hydrologic pathways that water follows through watersheds to streams and lakes. The amount of precipitation and it chemical loading depend on the area's climate and physiography, on it proximity to natural or industrial gaseous or particulate sources, and on local or regional air movements. Vegetation interacts with the atmosphere to enhance both wet and dry deposition of chemicals to a greater or lesser extent, depending on vegetation type. Vegetation naturally acidifies the environment in humid regions through processes of excess base cation uptake and generation of organic acids associated with many biological processes. Natural acid production and atmospheric deposition of acidic materials drive the acidification process. The lake or stream NAC represents a balance between the acidity-and ANC-generating processes that occur along different flow paths in the watershed and the relative importance of each flow path

  9. Kinetics of aggregation growth with competition between catalyzed birth and catalyzed death

    International Nuclear Information System (INIS)

    An aggregation growth model of three species A, B and C with the competition between catalyzed birth and catalyzed death is proposed. Irreversible aggregation occurs between any two aggregates of the like species with the constant rate kernels In(n = 1,2,3). Meanwhile, a monomer birth of an A species aggregate of size k occurs under the catalysis of a B species aggregate of size j with the catalyzed birth rate kernel K(k,j) = Kkjv and a monomer death of an A species aggregate of size k occurs under the catalysis of a C species aggregate of size j with the catalyzed death rate kernel L(k,j)=Lkjv, where v is a parameter reflecting the dependence of the catalysis reaction rates of birth and death on the size of catalyst aggregate. The kinetic evolution behaviours of the three species are investigated by the rate equation approach based on the mean-field theory. The form of the aggregate size distribution of A species ak(t) is found to be dependent crucially on the competition between the catalyzed birth and death of A species, as well as the irreversible aggregation processes of the three species: (1) In the v k(t) satisfies the conventional scaling form; (2) In the v ≥ 0 case, the competition between the catalyzed birth and death dominates the process. When the catalyzed birth controls the process, ak(t) takes the conventional or generalized scaling form. While the catalyzed death controls the process, the scaling description of the aggregate size distribution breaks down completely

  10. National uranium resource evaluation. Geology and recognition criteria for sandstone uranium deposits of the salt wash type, Colorado Plateau Province. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Thamm, J.K.; Kovschak, A.A. Jr.; Adams, S.S.

    1981-01-01

    The uranium-vanadium deposits of the Salt Wash Member of the Morrison Formation in the Colorado Plateau are similar to sandstone uranium deposits elsewhere in the USA. The differences between Salt Wash deposits and other sandstone uranium deposits are also significant. The Salt Wash deposits are unique among sandstone deposits in that they are dominantly vanadium deposits with accessory uranium. The Salt Wash ores generally occur entirely within reduced sandstone, without adjacent tongues of oxidized sandstone. They are more like the deposits of Grants, which similarly occur in reduced sandstones. Recent studies of the Grants deposits have identified alteration assemblages which are asymmetrically distributed about the deposits and provide a basis for a genetic model for those deposits. The alteration types recognized by Shawe in the Slick Rock district may provide similar constraints on ore formation when expanded to broader areas and more complete chemical analyses.

  11. National uranium resource evaluation. Geology and recognition criteria for sandstone uranium deposits of the salt wash type, Colorado Plateau Province. Final report

    International Nuclear Information System (INIS)

    The uranium-vanadium deposits of the Salt Wash Member of the Morrison Formation in the Colorado Plateau are similar to sandstone uranium deposits elsewhere in the USA. The differences between Salt Wash deposits and other sandstone uranium deposits are also significant. The Salt Wash deposits are unique among sandstone deposits in that they are dominantly vanadium deposits with accessory uranium. The Salt Wash ores generally occur entirely within reduced sandstone, without adjacent tongues of oxidized sandstone. They are more like the deposits of Grants, which similarly occur in reduced sandstones. Recent studies of the Grants deposits have identified alteration assemblages which are asymmetrically distributed about the deposits and provide a basis for a genetic model for those deposits. The alteration types recognized by Shawe in the Slick Rock district may provide similar constraints on ore formation when expanded to broader areas and more complete chemical analyses

  12. Synthesis of Biaryls through Nickel-Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-Nitrogen Bond Cleavage.

    Science.gov (United States)

    Shi, Shicheng; Meng, Guangrong; Szostak, Michal

    2016-06-01

    The first Ni-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of widely occurring biaryl compounds through N-C amide bond activation is reported. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents on both coupling partners. The reaction constitutes the first example of the Ni-catalyzed generation of aryl electrophiles from bench-stable amides with potential applications for a broad range of organometallic reactions. PMID:27101428

  13. Final report of a coordinated research project on development of protocols for corrosion and deposit evaluation in large diameter pipes by radiography

    International Nuclear Information System (INIS)

    The International Atomic Energy Agency promotes Non-Destructive Testing (NDT) methodology and technology under its technical cooperation and research programs. Many developing Member States (MS) have established NDT groups which are active in training and certification of NDT specialists and in provision of services to industries. The reliability and safety of industrial equipment especially in petroleum, petrochemical and chemical industries, in power stations, desalination plants and urban gas installations are substantially influenced by degradation processes such as corrosion, erosion, deposits and blocking of pipes which might cause fire, leaks, reduced production or unpredictable and costly shutdowns due to repair and replacement. The condition of critical components in these industries can be monitored by the proper use of non destructive inspection methods even while the plant is in operation, thus making possible the planning of component replacements, repairs, deposit removal and shutdowns. Preventive and corrective maintenance averts the environment and the public from excessive risk of industrial disasters. One of the most important parameters in piping or pipelines to be monitored and measured is the loss of wall thickness due to corrosion. Radiography is an effective method of determining this loss. Radiography is also the method of choice to determine the amount of accumulated deposits and offers the advantage of being able to inspect the pipe without costly removal of insulation material often in harsh plant environment conditions (high temperature, elevated pressure, for example). Tangential radiography and Double Wall (density measurement) techniques are used. The principle of corrosion measurement or monitoring using tangential, film-based radiography is already known. Much of past experience, however, is limited to qualitative determination of internal defects; there are no standardized and universally recognized protocols, recommended practices

  14. An interpretation of differences between field and laboratory pH values reported by the national atmospheric deposition program/national trends network monitoring program

    Science.gov (United States)

    Bigelow, D.S.; Sisterson, D.L.; Schroder, L.J.

    1989-01-01

    Differences between field and laboratory pH values reported by the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) monitoring program from 1984 through 1986 are investigated. Median differences in hydrogen ion concentration between laboratory and field pH determinations at sites averaged -4.6 ??equiv/L in natural precipitation samples on an annual basis. The median difference found in external quality assurance samples analyzed during the same time period was -11 ??equiv/L. The results suggest a systematic bias in pH values reported by the NADP/NTN network. The bias appears to have a fixed component of approximately -7 ??equiv/L, which can be attributed to the sampling bucket and lid, and a seasonal and regional component that ranges from +4 to -22 ??equiv/L at the 10th and 90th percentiles. Differences were found to be independent of sample pH and sample volume. The magnitude of the bias has implications for the interpretation of previously published pH and hydrogen ion concentration and deposition values in the western United States.

  15. Enumeration and characterization of microorganisms associated with the uranium ore deposit at Cigar Lake, Canada. Informal report

    International Nuclear Information System (INIS)

    The high-grade uranium deposit at Cigar Lake, Canada, is being investigated as a natural analog for the disposal of nuclear fuel waste. Geochemical aspects of the site have been studied in detail, but the microbial ecology has not been fully investigated. Microbial populations in an ore sample and in groundwater samples from the vicinity of the ore zone were examined to determine their effect on uranium mobility. Counts of the total number of bacteria and of respiring bacteria were obtained by direct microscopy, and the viable aerobic and anaerobic bacteria were assessed as colony forming units (CFUs) by the dilution plating technique. In addition, the population distribution of denitrifiers, fermenters, iron- and sulfur-oxidizers, iron- and sulfate-reducers, and methanogens was determined by the most probable number (MPN) technique

  16. Gold-Catalyzed Direct Arylation

    OpenAIRE

    Ball, L. T.; Lloyd-jones, G. C.; Russell, C. A.

    2012-01-01

    Biaryls (two directly connected aromatic rings, Ar1-Ar2) are common motifs in pharmaceuticals, agrochemicals, and organic materials. Current methods for establishing the Ar1-Ar2 bond are dominated by the cross-coupling of aryl halides (Ar1-X) with aryl metallics (Ar2-M). We report that, in the presence of 1 to 2 mole percent of a gold catalyst and a mild oxidant, a wide range of arenes (Ar1-H) undergo site-selective arylation by arylsilanes (Ar2-SiMe3) to generate biaryls (Ar1-Ar2), with litt...

  17. Mild Palladium-Catalyzed Cyanation of (Hetero)aryl Halides and Triflates in Aqueous Media

    OpenAIRE

    Cohen, Daniel T.; Buchwald, Stephen L.

    2015-01-01

    A mild, efficient, and low-temperature palladium-catalyzed cyanation of (hetero)aryl halides and triflates is reported. Previous palladium-catalyzed cyanations of (hetero)aryl halides have required higher temperatures to achieve good catalytic activity. This current reaction allows the cyanation of a general scope of (hetero)aryl halides and triflates at 2–5 mol % catalyst loadings with temperatures ranging from rt to 40 °C. This mild method was applied to the synthesis of lersivirine, a reve...

  18. An Iridium-Catalyzed Reductive Approach to Nitrones from N-Hydroxyamides.

    Science.gov (United States)

    Katahara, Seiya; Kobayashi, Shoichiro; Fujita, Kanami; Matsumoto, Tsutomu; Sato, Takaaki; Chida, Noritaka

    2016-04-27

    An Ir-catalyzed reductive formation of functionalized nitrones from N-hydroxyamides was reported. The reaction took place through two types of iridium-catalyzed reactions including dehydrosilylation and hydrosilylation. The method showed high chemoselectivity in the presence of sensitive functional groups, such as methyl esters, and was successfully applied to the synthesis of cyclic and macrocyclic nitrones, which are known to be challenging compounds to access by conventional methods. (1)H NMR studies strongly supported generation of an N-siloxyamide and an N,O-acetal as the actual intermediates. PMID:27071479

  19. Muon catalyzed fusion experiments in thin films and slow negative muon production

    International Nuclear Information System (INIS)

    Muon-catalyzed fusion has been studied in many ways for energy production, however, it has several other applications, for example, an intense fusion neutron source can be produced by the muon-catalyzed fusion in a high density deuterium-tritium mixture. Moreover, intense slow negative muons can also be generated from the successive liberation of -10 keV muons in the muon-catalyzed reaction. Before reaching this hypothetical goal of intense slow negative muon production, a new experimental technique must be developed first to perform muon-catalyzed fusion studies in thin solid hydrogen isotope mixtures at very low temperature to determine the feasibility of this method. Because of the difficulties in handling tritium, the experiment in pure deuterium solid films was adopted. The main objective is to optimize the deuterium layer thickness to maximize slow negative muon emission from the surface. The principle, the experimental method, the experimental setup and the results of muonic hydrogen Kα X-ray, fusion protons and slow negative muon detection, and the Monte Carlo simulation of muon-catalyzed fusion kinetics are reported. Two different contributions to the total fusion yield were observed. (K.I.)

  20. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill

    2013-01-16

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  1. Highly Diastereo- and Enantioselective CuH-Catalyzed Synthesis of 2,3-Disubstituted Indolines

    OpenAIRE

    Ascic, Erhad; Buchwald, Stephen L.

    2015-01-01

    A diastereo- and enantioselective CuH-catalyzed method for the preparation of highly functionalized indolines is reported. The mild reaction conditions and high degree of functional group compatibility as demonstrated with substrates bearing heterocycles, olefins, and substituted aromatic groups, renders this technique highly valuable for the synthesis of a variety of cis-2,3-disubstituted indolines in high yield and enantioeselectivity.

  2. ParA resolvase catalyzes site-specific excision of DNA from the Arabidopsis genome

    Science.gov (United States)

    The small serine resolvase ParA from bacterial plasmids RK2 and RP4 catalyzes the recombination of two identical 133 bp recombination sites known as MRS. Previously, we reported that ParA is active in the fission yeast Schizosaccharomyces pombe. In this work, the parA recombinase gene was placed un...

  3. Large acceleration of α-chymotrypsin-catalyzed dipeptide formation by 18-crown-6 in organic solvents

    NARCIS (Netherlands)

    Unen, van Dirk-Jan; Engbersen, Johan F.J.; Reinhoudt, David N.

    1998-01-01

    The effects of 18-crown-6 on the synthesis of peptides catalyzed by α-chymotrypsin are reported. Lyophilization of the enzyme in the presence of 50 equivalents of 18-crown-6 results in a 425-fold enhanced activity when the reaction between the 2-chloroethylester of N-acetyl-L-phenylalanine and L-phe

  4. Copper-Catalyzed Diastereoselective Arylation of Tryptophan Derivatives: Total Synthesis of (+)-Naseseazines A and B

    OpenAIRE

    Kieffer, Madeleine E.; Chuang, Kangway V.; Reisman, Sarah E.

    2013-01-01

    A copper-catalyzed arylation of tryptophan derivatives is reported. The reaction proceeds with high site- and diastereoselectivity to provide aryl pyrroloindoline products in one step from simple starting materials. The utility of this transformation is highlighted in the five-step syntheses of the natural products (+)-naseseazine A and B.

  5. Syntheses of Calix[4]Pyrroles by Amberlyst-15 Catalyzed Cyclocondensations of Pyrrole with Selected Ketones

    Directory of Open Access Journals (Sweden)

    Tanuja Bisht

    2007-11-01

    Full Text Available A facile and efficient protocol is reported for the synthesis of calix[4]pyrrolesand N-confused calix[4]pyrroles in moderate to excellent yields by reaction of dialkyl orcycloalkyl ketones with pyrrole catalyzed by reusable AmberlystTM-15 under eco-friendlyconditions.

  6. Synthesis of a novel chemotype via sequential metal-catalyzed cycloisomerizations

    Directory of Open Access Journals (Sweden)

    Bo Leng

    2012-08-01

    Full Text Available Sequential cycloisomerizations of diynyl o-benzaldehyde substrates to access novel polycyclic cyclopropanes are reported. The reaction sequence involves initial Cu(I-mediated cycloisomerization/nucleophilic addition to an isochromene followed by diastereoselective Pt(II-catalyzed enyne cycloisomerization.

  7. Palladium-catalyzed carbonylative sonogashira coupling of aryl bromides using near stoichiometric carbon monoxide

    DEFF Research Database (Denmark)

    Neumann, Karoline T.; Laursen, Simon R.; Lindhardt, Anders T.;

    2014-01-01

    A general procedure for the palladium-catalyzed carbonylative Sonogashira coupling of aryl bromides is reported, using near stoichiometric amounts of carbon monoxide. The method allows a broad substrate scope in moderate to excellent yields. The formed alkynone motive serves as a platform for...

  8. Rhodium and copper-catalyzed asymmetric conjugate addition of alkenyl nucleophiles.

    Science.gov (United States)

    Müller, Daniel; Alexakis, Alexandre

    2012-12-25

    Since the initial reports in the mid-90s, metal catalyzed asymmetric conjugate addition (ACA) reactions evolved as an important tool for the synthetic chemist. Most of the research efforts have been done in the field of rhodium and copper catalyzed ACA reactions employing aryl and alkyl nucleophiles. Despite the great synthetic value of the double bond, the addition of alkenyl nucleophiles remains insufficiently explored. In this account, an overview of the developments in the field of rhodium and copper catalyzed ACA reactions with organometallic alkenyl reagents (B, Mg, Al, Si, Zr, Sn) will be provided. The account is intended to give a comprehensive overview of all the existing methods. However, in many cases only selected examples are displayed in order to facilitate comparison of different ligands and methodologies. PMID:23096501

  9. The Palmottu natural analogue project. Progress report 1995. The behaviour of natural radionuclides in and around uranium deposits, Nr. 9

    International Nuclear Information System (INIS)

    Natural analogue studies at Palmottu (in Finland) have concentrated on characterising the general geological, hydrogeological and radiochemical setting of the uranium mineralisation. Since 1992 a research program focusing on the hydrogeological characterisation of potential flow routes has been in progress, and the basis for a constrained flow system has already been identified. Sophisticated studies have also been performed on groundwater redox chemistry and matrix diffusion processes. The report consists of an introduction to the activities carried out in 1995 followed by topical summaries documented by the principal investigators in charge of each activity. The following summaries are included in the report (1) Hydrogeological studies at Palmottu, (2) Modelling of groundwater flow, (3) TV-logging of boreholes, (4) Mineralogical and petrological studies, (5) Radionuclide migration studies and (6) Humic substances. Full technical and scientific results are documented in appropriate topical reports and publications referred to in this Progress Report. (46 refs., 10 figs., 4 tabs.)

  10. Parameters critical to muon-catalyzed fusion

    International Nuclear Information System (INIS)

    We have demonstrated that muon catalysis cycling rates increase rapidly with increasing deuterium-tritium gas temperatures and densities. Furthermore, muon-capture losses are significantly smaller than predicted before the experiments. There remains a significant gap between observation and theoretical expectation for the muon-alpha sticking probability in dense d-t mixtures. We have been able to achieve muon-catalyzed yields of 150 fusion/muon (average). While the fusion energy thereby released significantly exceeds expectations, enhancements by nearly a factor of twenty would be needed to realize energy applications for a pure (non-hybrid) muon-catalyzed fusion reactor. The process could be useful in tritium-breeding schemes. We have also explored a new form of cold nuclear fusion which occurs when hydrogen isotopes are loaded into metals. 22 refs., 10 figs

  11. Cold fusion catalyzed by muons and electrons

    International Nuclear Information System (INIS)

    Two alternative methods have been suggested to produce fusion power at low temperature. The first, muon catalyzed fusion or MCF, uses muons to spontaneously catalyze fusion through the muon mesomolecule formation. Unfortunately, this method fails to generate enough fusion energy to supply the muons, by a factor of about ten. The physics of MCF is discussed, and a possible approach to increasing the number of MCF fusions generated by each muon is mentioned. The second method, which has become known as ''Cold Fusion,'' involves catalysis by electrons in electrolytic cells. The physics of this process, if it exists, is more mysterious than MCF. However, it now appears to be an artifact, the claims for its reality resting largely on experimental errors occurring in rather delicate experiments. However, a very low level of such fusion claimed by Jones may be real. Experiments in cold fusion will also be discussed

  12. Acid-catalyzed kinetics of indium tin oxide etching

    International Nuclear Information System (INIS)

    We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species

  13. Acid base catalyzed transesterification kinetics of waste cooking oil

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Siddharth; Sharma, M.P.; Rajvanshi, Shalini [Alternate Hydro Energy Centre, Indian Institute of Technology, Roorkee (India)

    2011-01-15

    The present study reports the results of kinetics study of acid base catalyzed two step transesterification process of waste cooking oil, carried out at pre-determined optimum temperature of 65 C and 50 C for esterification and transesterification process respectively under the optimum condition of methanol to oil ratio of 3:7 (v/v), catalyst concentration 1%(w/w) for H{sub 2}SO{sub 4} and NaOH and 400 rpm of stirring. The optimum temperature was determined based on the yield of ME at different temperature. Simply, the optimum concentration of H{sub 2}SO{sub 4} and NaOH was determined with respect to ME Yield. The results indicated that both esterification and transesterification reaction are of first order rate reaction with reaction rate constant of 0.0031 min{sup -1} and 0.0078 min{sup -1} respectively showing that the former is a slower process than the later. The maximum yield of 21.50% of ME during esterification and 90.6% from transesterification of pretreated WCO has been obtained. This is the first study of its kind which deals with simplified kinetics of two step acid-base catalyzed transesterification process carried under the above optimum conditions and took about 6 h for complete conversion of TG to ME with least amount of activation energy. Also various parameters related to experiments are optimized with respect to ME yield. (author)

  14. Chloride-catalyzed corrosion of plutonium in glovebox atmospheres

    International Nuclear Information System (INIS)

    Characterization of glovebox atmospheres and the black reaction product formed on plutonium surfaces shows that the abnormally rapid corrosion of components in the fabrication line is consistent with a complex salt-catalyzed reaction involving gaseous hydrogen chloride (HCl) and water. Analytical data verify that chlorocarbon and HCl vapors are presented in stagnant glovebox atmospheres. Hydrogen chloride concentrations approach 7 ppm at some locations in the glovebox line. The black corrosion product is identified as plutonium monoxide monohydride (PuOH), a product formed by hydrolysis of plutonium in liquid water and salt solutions at room temperature. Plutonium trichloride (PuCl3) produced by reaction of HCl at the metal surface is deliquescent and apparently forms a highly concentrated salt solution by absorbing moisture from the glovebox atmosphere. Rapid corrosion is attributed to the ensuing salt-catalyzed reaction between plutonium and water. Experimental results are discussed, possible involvement of hydrogen fluoride (HF) is examined, and methods of corrective action are presented in this report

  15. Copper Catalyzed Oceanic Methyl Halide Production

    OpenAIRE

    Robin Kim, Jae Yun; Rhew, Robert

    2014-01-01

    Methyl halides are found in all of Earth’s biomes, produced naturally or through manmade means. Their presence in the atmosphere is problematic, as they catalyze depletion of stratospheric ozone. To understand the full environmental impact of these compounds, it is important to identify their chemical cycling processes. Iron increases methyl halide production in soils and oceans, yet copper’s influence remains unknown despite its similar chemical oxidation properties to iron. I experimentally...

  16. Antibody-Catalyzed Degradation of Cocaine

    Science.gov (United States)

    Landry, Donald W.; Zhao, Kang; Yang, Ginger X.-Q.; Glickman, Michael; Georgiadis, Taxiarchis M.

    1993-03-01

    Immunization with a phosphonate monoester transition-state analog of cocaine provided monoclonal antibodies capable of catalyzing the hydrolysis of the cocaine benzoyl ester group. An assay for the degradation of radiolabeled cocaine identified active enzymes. Benzoyl esterolysis yields ecgonine methyl ester and benzoic acid, fragments devoid of cocaine's stimulant activity. Passive immunization with such an artificial enzyme could provide a treatment for dependence by blunting reinforcement.

  17. Palladium(II)-Catalyzed Coupling Reactions

    OpenAIRE

    Lindh, Jonas

    2010-01-01

    Sustainable chemical processes are becoming increasingly important in all fields of synthetic chemistry. Catalysis can play an important role in developing environmentally benign chemical processes, and transition metals have an important role to play in the area of green chemistry. In particular, palladium(II) catalysis includes many key features for successful green chemistry methods, as demonstrated by a number of eco-friendly oxidation reactions catalyzed by palladium(II). The aim of the ...

  18. Palladium-catalyzed oxidative carbonylation reactions.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2013-02-01

    Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative carbonylation reactions. PMID:23307763

  19. Development and implementation of technical concepts for the final disposal in deep geological deposits in different host rocks (EUGENIA). Synthesis report

    International Nuclear Information System (INIS)

    The report on the development and implementation of technical concepts for the final disposal in deep geological deposits in different host rocks (EUGENIA) includes the following chapters: (1) Purpose of the studies. (2) Overview on the developed concepts for final high-level radioactive waste disposal in deep rock formations and differences of the underlying safety concepts. (3) Effects of the host rock properties on the site search and exploration. (4) Site selection and site exploration. (5) Technical concepts for high-level waste final repositories (Sweden, Finland, Belgium, France, Switzerland). (6) Construction, operation, control and closure of high-level waste repositories. (7) Licensing aspects (Sweden, Finland, Belgium, France, Switzerland, Germany). (8) Comparative presentation and evaluation of the internationally reached status concerning the realization of final high-level waste repositories.

  20. Deposited radionuclides

    International Nuclear Information System (INIS)

    The results presented are from the nationwide programme to survey the fall-out levels of radionuclides in Finland. This programme includes results from the vicinities of the nuclear power plants at Loviisa and Olkiluoto. Analysis of deposition samples for their 3H, 89Sr and 90Sr, as well as 137Cs and other gamma radionuclide contents was continued. The results are given as a follow-up to the previous results. The cumulative deposition of long-lived radionuclides retained in soil was measured near the Finnish nuclear power stations. The 90Sr and 137Cs levels in deposition in 1979 were lower than in the previous two years, and no 89Sr was detected. The trend to slightly increasing 3H concentrations of previous years was reversed in 1979. The mean annual deposition of tritium at different sampling stations varied from 85 nCi/m2 (3.1 kBq/m2) to 180 nCi/m2 (6.7 kBq/m2). The total annual deposits of various fission product radionuclides have decreased continuously since the maximum in 1977. No short-lived radionuclides originating from either nuclear explosions or nuclear power plants were observed in 1979. (author)

  1. Deposited radionuclides

    International Nuclear Information System (INIS)

    The measurements presented here were carried out for determination of the fallout levels of radionuclides throughout the country, including the areas surrounding the nuclear power plants at Loviisa and Olkiluoto. The 90Sr, 137Cs and 3H contents of deposition were determined and the results are given as a follow-up to the previous results. 89Sr and other gammaradionuclides in addition to 137Cs were measured from wet and dry deposition. Also 89-90Sr, 239-240Pu, 137Cs and other gammaradionuclides deposited in soil were measured. The radiochemical separation technique was used to determine 89Sr, 90Sr, 137Cs and 239-240Pu. Tritium contents were determined by liquid scintillation counting after electrolytic enrichment. Gammaradionuclides were measured by Ge(Li) spectrometry. In 1977 the contents of the long-lived radionuclides 90Sr and 137Cs in deposition increased to almost the same level as in the early '70s. This is due to the high-yield atmospheric nuclear weapon tests carried out by China. A slight increase in 3H deposition can also be noticed in 1977. The results of soil sample measurements indicate that practically all the activity is found in the top 20 cm layer. (author)

  2. Deposited radionuclides

    International Nuclear Information System (INIS)

    Measurements were carried out to determine the fall-out levels of radionuclides in Finland including those from the surroundings of the nuclear power plants at Loviisa and Olkiluoto. Deposition samples were analysed for their 3H, 89Sr and 90Sr as well as 137Cs and other gamma radionuclide contents. 90Sr, 239,240Pu, as well as 137Cs and other gamma radionuclides deposited in soil were also measured. The 90Sr and 137Cs levels in deposition in 1978 remained at almost the same level as in 1977. The slightly increasing trend in 3H concentrations continued in 1978. The mean annual deposition of tritium at different sampling stations varied from 120 nCi/m2 (4.4 kBq/m2) to 200 nCi/m2 (7.4 kBq/m2). The total annual deposits of various fission product radionuclides during 1978 were smaller than during 1977. No increase in radioactivity originating from nuclear power plants could be observed. (author)

  3. Biofuel-Promoted Polychlorinated Dibenzodioxin/furan Formation in an Iron-Catalyzed Diesel Particle Filter.

    Science.gov (United States)

    Heeb, Norbert V; Rey, Maria Dolores; Zennegg, Markus; Haag, Regula; Wichser, Adrian; Schmid, Peter; Seiler, Cornelia; Honegger, Peter; Zeyer, Kerstin; Mohn, Joachim; Bürki, Samuel; Zimmerli, Yan; Czerwinski, Jan; Mayer, Andreas

    2015-08-01

    Iron-catalyzed diesel particle filters (DPFs) are widely used for particle abatement. Active catalyst particles, so-called fuel-borne catalysts (FBCs), are formed in situ, in the engine, when combusting precursors, which were premixed with the fuel. The obtained iron oxide particles catalyze soot oxidation in filters. Iron-catalyzed DPFs are considered as safe with respect to their potential to form polychlorinated dibenzodioxins/furans (PCDD/Fs). We reported that a bimetallic potassium/iron FBC supported an intense PCDD/F formation in a DPF. Here, we discuss the impact of fatty acid methyl ester (FAME) biofuel on PCDD/F emissions. The iron-catalyzed DPF indeed supported a PCDD/F formation with biofuel but remained inactive with petroleum-derived diesel fuel. PCDD/F emissions (I-TEQ) increased 23-fold when comparing biofuel and diesel data. Emissions of 2,3,7,8-TCDD, the most toxic congener [toxicity equivalence factor (TEF) = 1.0], increased 90-fold, and those of 2,3,7,8-TCDF (TEF = 0.1) increased 170-fold. Congener patterns also changed, indicating a preferential formation of tetra- and penta-chlorodibenzofurans. Thus, an inactive iron-catalyzed DPF becomes active, supporting a PCDD/F formation, when operated with biofuel containing impurities of potassium. Alkali metals are inherent constituents of biofuels. According to the current European Union (EU) legislation, levels of 5 μg/g are accepted. We conclude that risks for a secondary PCDD/F formation in iron-catalyzed DPFs increase when combusting potassium-containing biofuels. PMID:26176879

  4. METALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111705 An Junbo(Team 603,Bureau of Nonferrous Metals Geological Exploration of Jilin Province,Hunchun 133300,China);Xu Renjie Geological Features and Ore Genesis of Baishilazi Scheelite Deposit in Yanbian Area(Jilin Geology,ISSN1001-2427,CN22-1099/P,29(3),2010,p.39-43,2 illus.,2 tables,7 refs.)Key words:tungsten ores,Jilin ProvinceThe Baishilazi scheelite deposit is located in contacting zone between the marble of the Late Palaeozoic Qinglongcun Group and the Hercynian biotite granite.The vein and lenticular major ore body is obviously controlled by NE-extending faults and con

  5. Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp2–H activation/C–O formation

    Directory of Open Access Journals (Sweden)

    Seohyun Shin

    2014-05-01

    Full Text Available We report an efficient Pd-catalyzed C(sp2–H activation/C–O bond formation for the synthesis of ethoxy dibenzooxaphosphorin oxides from 2-(arylarylphosphonic acid monoethyl esters under aerobic conditions.

  6. Hemoglobin-catalyzed fluorometric method for the determination of glutathione

    Science.gov (United States)

    Wang, Ruiqiang; Tang, Lin; Li, Hua; Wang, Yi; Gou, Rong; Guo, Yuanyuan; Fang, Yudong; Chen, Fengmei

    2016-01-01

    A new spectrofluorometric method for the determination of glutathione based on the reaction catalyzed by hemoglobin was reported. The reaction product gave a highly fluorescent intensity with the excitation and emission wavelengths of 320.0 nm and 413.0 nm, respectively. The optimum experimental conditions were investigated. Results showed that low concentration glutathione enhanced the fluorescence intensity significantly. The line ranges were 1.0 × 10-6-1.0 × 10-5 mol L-1 of glutathione and 6.0 × 10-10 mol L-1-1.0 × 10-8 mol L-1, respectively. The detection limit was calculated to be 1.1 × 10-11 mol L-1. The recovery test by the standard addition method gave values in the range of 90.78%-102.20%. This method was used for the determination of glutathione in synthetic and real samples with satisfactory results.

  7. Ti-catalyzed straightforward synthesis of exocyclic allenes.

    Science.gov (United States)

    Muñoz-Bascón, Juan; Hernández-Cervantes, Carmen; Padial, Natalia M; Alvarez-Corral, Míriam; Rosales, Antonio; Rodríguez-García, Ignacio; Oltra, J Enrique

    2014-01-13

    Exocyclic allenes constitute useful building blocks in organic synthesis and have recently been identified as key intermediates in the synthesis of natural products. Here the first general method for the most straightforward synthesis of exocyclic allenes reported to date is presented. This method is based on the Barbier-type cyclization of propargyl halides catalyzed by titanium; a safe, abundant, and ecofriendly metal. The reaction proceeds under mild conditions compatible with different functional groups and provides good yields of five-, six-, and seven-membered carbocycles and nitrogen-containing heterocycles bearing an exocyclic allene group. Experimental evidence supporting the proposed reaction mechanism is also provided. Moreover, this procedure can be carried out in an enantioselective manner by using chiral titanocene(III) catalysts. The utility of this method has been proved in the synthesis of the natural alkaloid stemoamide. PMID:24339337

  8. Nuclear performance of molten salt fusion--fission symbiotic systems for catalyzed DD and DT reactors

    International Nuclear Information System (INIS)

    The nuclear performance of a fusion-fission hybrid reactor having a molten salt composed of Na-Th-F-Be as the blanket fertile material and operating with a catalyzed DD plasma is compared to a similar system utilizing a Li-Th-F-Be salt and operating with a DT plasma. The production of fissile fuel via the 232Th-233U fuel cycle was considered on the basis of its potential nonproliferation aspects. The calculations were performed using one-dimensional discrete ordinates methods to compare neutron balances, fuel producion rates, energy deposition rates, and the radiation damage in the reactor structure

  9. METALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    20150904An Fang(State Key Laboratory of Continental Dynamics,Department of Geology,Northwest University,Xi’an 710069,China);Wang Juli Skarn Mineral Assemblage in Representative Ore Districts of Sayak Copper Orefield,Kazakhstan,and Its Genetic Implications(Mineral Deposits,ISSN0258-7106,CN11-1965/P,33(3),2014,p.521-540,

  10. NONMETALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131601 Gao Junbo(College of Resources and Environmental Engineering,Guizhou University,Guiyang 550003,China);Yang Ruidong Hydrothermal Venting-Flowing Sedimentation Characteristics of Devonian Barite Deposits from Leji,Zhenning County,Guizhou Province(Acta Sedimentologica Sinica,ISSN1000-0550,CN62-1038/P,30(3),

  11. Dissection of an antibody-catalyzed reaction.

    OpenAIRE

    Stewart, J D; Krebs, J F; Siuzdak, G; Berdis, A J; Smithrud, D B; Benkovic, S J

    1994-01-01

    Antibody 43C9 accelerates the hydrolysis of a p-nitroanilide by a factor of 2.5 x 10(5) over the background rate in addition to catalyzing the hydrolysis of a series of aromatic esters. Since this represents one of the largest rate accelerations achieved with an antibody, we have undertaken a series of studies aimed at uncovering the catalytic mechanism of 43C9. The immunogen, a phosphonamidate, was designed to mimic the geometric and electronic characteristics of the tetrahedral intermediate...

  12. Chiral Diamine-catalyzed Asymmetric Aldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LI Hui; XU Da-zhen; WU Lu-lu; WANG Yong-mei

    2012-01-01

    A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid(TFA) was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1.

  13. The Palmottu natural analogue project. The behaviour of natural radionuclides in and around uranium deposits. Summary report 1992-1994

    International Nuclear Information System (INIS)

    The Palmottu U-Th mineralization at Nummi-Pusula, southwestern Finland, has been studied as a natural analogue to deep disposal of radioactive wastes since 1988. The report gives a summary of the results of investigations carried out during the years 1992-1994. The Palmottu Analogue Project aims at a more profound understanding of radionuclide transport processes in fractured crystalline bedrock. The essential factors controlling transport are groundwater flow and interaction between water and rock. Accordingly, the study includes structural interpretations based in part on geophysical measurements, hydrological studies including hydraulic downhole measurements, flow modelling, hydrogeochemical characterization of groundwater, uranium chemistry and colloid chemistry, mineralogical studies, geochemical interpretation and modelling, including paleohydrogeological aspects, and studies of radionuclide mobilization and migration processes including numerical simulations. The project has produced a large amount of data related to natural analogue aspects. The data obtained have already been utilized in developing logical conceptual ideas of the time frames and processes operating in the bedrock of the site. (61 refs., 24 figs., 8 tabs.)

  14. A Case Report on the Progression of Myeloid Sarcoma to Form Multiple Metastatic Deposits without Developing Acute Myeloid Leukaemia

    Directory of Open Access Journals (Sweden)

    Sunita Kohli

    2015-01-01

    Full Text Available Introduction. Myeloid sarcomas (MS are rare tumours occurring at extramedullary sites. They are usually associated with other haematology disorders such as acute myeloid leukaemia, myelodysplastic syndrome, and chronic myeloproliferative neoplasms. They frequently occur with a diagnosis of acute myeloid leukaemia (AML or with relapse of preexisting disease. Patients with myeloid sarcomas without history or evidence of myeloid leukaemia typically progress to form AML. Case Presentation. A case report of a patient diagnosed with an isolated myeloid sarcoma that rarely did not transform to AML but instead spread to form multiple myeloid sarcomas throughout the body. Discussion. This case identifies the risk of metastatic spread of these tumours rather than the development of AML which is poorly documented in the literature, due to the rarity of cases, and may be significant in the investigation and management of isolated myeloid sarcomas. This case highlights the need for clinicians to consider repeat cross-sectional imaging to investigate unexplained clinical decline or symptoms, when there is no sign of AML progression and to consider radiotherapy treatment early.

  15. The Palmottu natural analogue project. The behaviour of natural radionuclides in and around uranium deposits. Summary report 1992-1994

    Energy Technology Data Exchange (ETDEWEB)

    Blomqvist, R.; Ruskeeniemi, T.; Ahonen, L. [Geological Survey of Finland, Espoo (Finland); Suksi, J. [Helsinki Univ. (Finland). Lab. of Radiochemistry; Niini, H. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Engineering Geology and Geophysics; Vuorinen, U. [VTT Chemical Technology, Espoo (Finland); Jakobsson, K. [Finnish Centre for Radiation and Nuclear Safety, Helsinki (Finland)

    1995-06-01

    The Palmottu U-Th mineralization at Nummi-Pusula, southwestern Finland, has been studied as a natural analogue to deep disposal of radioactive wastes since 1988. The report gives a summary of the results of investigations carried out during the years 1992-1994. The Palmottu Analogue Project aims at a more profound understanding of radionuclide transport processes in fractured crystalline bedrock. The essential factors controlling transport are groundwater flow and interaction between water and rock. Accordingly, the study includes structural interpretations based in part on geophysical measurements, hydrological studies including hydraulic downhole measurements, flow modelling, hydrogeochemical characterization of groundwater, uranium chemistry and colloid chemistry, mineralogical studies, geochemical interpretation and modelling, including paleohydrogeological aspects, and studies of radionuclide mobilization and migration processes including numerical simulations. The project has produced a large amount of data related to natural analogue aspects. The data obtained have already been utilized in developing logical conceptual ideas of the time frames and processes operating in the bedrock of the site. (61 refs., 24 figs., 8 tabs.).

  16. Manganese Catalyzed C-H Halogenation.

    Science.gov (United States)

    Liu, Wei; Groves, John T

    2015-06-16

    The remarkable aliphatic C-H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon-halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C-H bonds to C-Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L-Mn(V)═O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn-F fluorine source, effecting carbon-fluorine bond formation. Indeed, this idea

  17. Vein type uranium deposits

    International Nuclear Information System (INIS)

    Veins are tabular- or sheet-like masses of minerals occupying or following a fracture or a set of fractures in the enclosing rock. They have been formed later than the country rock and fractures, either by filling of the open spaces or by partial or complete replacement of the adjoining rock or most commonly by both of these processes combined. This volume begins with the occurrences and deposits known from old shield areas and the sedimentary belts surrounding them. They are followed by papers describing the European deposits mostly of Variscan age, and by similar deposits known from China being of Jurassic age. The volume is completed by two papers which do not fit exactly in the given scheme. A separate abstract was prepared for each of the 25 papers in this report

  18. Enzyme-Catalyzed Henry Reaction in Choline Chloride-Based Deep Eutectic Solvents.

    Science.gov (United States)

    Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

    2016-01-01

    The enzyme-catalyzed Henry reaction was realized using deep eutectic solvents (DESs) as a reaction medium. The lipase from Aspergillus niger (lipase AS) showed excellent catalytic activity toward the substrates aromatic aldehydes and nitromethane in choline chloride:glycerol at a molar ratio of 1:2. Addition of 30 vol% water to DES further improved the lipase activity and inhibited DES-catalyzed transformation. A final yield of 92.2% for the lipase AS-catalyzed Henry reaction was achieved under optimized reaction conditions in only 4 h. In addition, the lipase AS activity was improved by approximately 3-fold in a DES-water mixture compared with that in pure water, which produced a final yield of only 33.4%. Structural studies with fluorescence spectroscopy showed that the established strong hydrogen bonds between DES and water may be the main driving force that affects the spatial conformation of the enzyme, leading to a change in lipase activity. The methodology was also extended to the aza-Henry reaction, which easily occurred in contrast to that in pure water. The enantioselectivity of both Henry and aza-Henry reactions was not found. However, the results are still remarkable, as we report the first use of DES as a reaction medium in a lipase-catalyzed Henry reaction. PMID:26437947

  19. The deposition of highly uniform and adhesive nanocrystalline PbS film from solution

    International Nuclear Information System (INIS)

    Mirror-like PbS films have been deposited by chemical deposition on glass substrates from alkaline chemical bath containing lead nitrate, sodium thiosulfate and 1-thioglycerol, which was used to catalyze the hydrolysis of thiosulfate. Nanostructure characterization was carried out by x-ray diffraction and scanning electron microscopy in order to determine the average crystallite size (61 nm) and study the surface morphologies of the as-deposited films

  20. Synthetic applications of gold-catalyzed ring expansions

    Directory of Open Access Journals (Sweden)

    Cristina Nevado

    2011-06-01

    Full Text Available The development of new methodologies catalyzed by late transition metals involving cycloisomerizations of strained rings can open new venues for the synthesis of structurally complex molecules with interesting biological activities. Herein we summarize, from both a synthetic as well as a mechanistic point of view, the most recent developments in gold-catalyzed ring expansions.

  1. Hydrolysis of toxic natural glucosides catalyzed by cyclodextrin dicyanohydrins

    DEFF Research Database (Denmark)

    Bjerre, J.; Nielsen, Erik Holm Toustrup; Bols, M.

    2008-01-01

    The hydrolysis of toxic 7-hydroxycoumarin glucosides and other aryl and alkyl glucosides, catalyzed by modified a- and ß-cyclodextrin dicyanohydrins, was investigated using different UV, redox, or HPAEC detection assays. The catalyzed reactions all followed Michaelis-Menten kinetics, and an...

  2. The renaissance of palladium(II)-catalyzed oxidation chemistry

    OpenAIRE

    Sigman, Matthew S.; Schultz, Mitchell J.

    2004-01-01

    Palladium(II)-catalyzed oxidations constitute a paramount reaction class but have remained immature over the past few decades. Recently, this field has reappeared at the forefront of organometallic catalysis. This emerging area article outlines recent developments in palladium(II)-catalyzed oxidation chemistry with discussion of potential future growth.

  3. Annual report for 1979, Results of environmental radioactivity control on the 'B. Kidric' Institute site - precipitations, dust deposition, soil, plants, river sludge (Danube), Annex 2

    International Nuclear Information System (INIS)

    As previously, the control of the environmental radioactivity on the Institute site, was done by measuring the total beta activity of the following samples: precipitation, fallout deposits; water, soil, plants, and water and sediments from the Danube river at 1145 km. The regular control included 1706 samples. In addition to the regular control of the environment of the nuclear facility a number of water and heavy water samples were analyzed related to the repair and renewal actions at the RA reactor. Results of these analyses (total beta activity, electric conductivity and gamma spectrometry) were submitted in separate reports. Upon demand of the dosimetry service responsible for the control of the working environment of Radioisotope Laboratory 070, six samples (surface contamination, plants and soil) were taken from the area behind the HL building where radioactive waste is kept. Total beta activity of these samples has shown significant contamination of the soil and plants. Director and the decontamination service of the radiation protection laboratory were informed immediately about these results so that adequate measures could be undertaken

  4. Deposit insurance and international bank deposits

    OpenAIRE

    Harry Huizinga; Gaëtan Nicodème

    2003-01-01

    This paper examines how international depositors respond to national deposit insurance policies. Countries with explicit deposit insurance are found to be relatively attractive to international non-bank depositors. Deposit schemes characterized by co-insurance, a private administration, and a low deposit insurance premium appear to be particularly favored by these depositors. The sensitivity of non-bank deposits to deposit insurance policies opens up the possibility of international regulator...

  5. Catalyzed deuterium fueled tandem mirror reactor assessment

    International Nuclear Information System (INIS)

    This study was part of a Department of Energy supported alternate fusion fuels program at Science Applications International Corp. The purpose of this portion of the study is to perform an assessment of a conceptual tandem mirror reactor (TMR) that is fueled by the catalyzed-deuterium (Cat-d) fuel cycle with respect to the physics, technology, safety, and cost. Achievable stable betas and magnet configurations are found to be comparable for the Cat-d and d-t fueled TMR. A comparison with respect to cost, reactor performance, and technology requirements for a Cat-d fueled reactor and a comparable d-t fueled reactor such as MARS is also made

  6. Transition Metal Catalyzed Synthesis of Aryl Sulfides

    Directory of Open Access Journals (Sweden)

    Chad C. Eichman

    2011-01-01

    Full Text Available The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

  7. Thioglycoside hydrolysis catalyzed by β-glucosidase

    International Nuclear Information System (INIS)

    Sweet almond β-glucosidase (EC 3.2.1.21) has been shown to have significant thioglycohydrolase activity. While the Km values for the S- and O-glycosides are similar, the kcat values are about 1000-times lower for the S-glycosides. Remarkably, the pH-profile for kcat/Km for hydrolysis of p-nitrophenyl thioglucoside (pNPSG) shows the identical dependence on a deprotonated carboxylate (pKa 4.5) and a protonated group (pKa 6.7) as does the pH-profile for hydrolysis of the corresponding O-glycoside. Not surprisingly, in spite of the requirement for the presence of this protonated group in catalytically active β-glucosidase, thioglucoside hydrolysis does not involve general acid catalysis. There is no solvent kinetic isotope effect on the enzyme-catalyzed hydrolysis of pNPSG

  8. Gallium-Catalyzed Silicon Oxide Nanowire Growth

    Institute of Scientific and Technical Information of China (English)

    Zheng Wei Pan; Sheng Dai; Douglas H.Lowndes

    2005-01-01

    Silicon oxide nanowires tend to assemble into various complex morphologies through a metalcatalyzed vapor-liquid-solid (VLS) growth process. This article summarizes our recent efforts in the controlled growth of silicon oxide nanowire assemblies by using molten gallium as the catalyst and silicon wafer,SiO powder, or silane (SiH4) as the silicon sources. Silicon oxide nanowire assemblies with morphologies of carrotlike, cometlike, gourdlike, spindlelike, badmintonlike, sandwichlike, etc. were obtained. Although the morphologies of the nanowire assemblies are temperature- and silicon source-dependent, they share similar structural and compositional features: all the assemblies contain a microscale spherical liquid Ga ball and a highly aligned, closely packed amorphous silicon oxide nanowire bunch. The Ga-catalyzed silicon oxide nanowire growth reveals several interesting new nanowire growth phenomena that expand our knowledge of the conventional VLS nanowire growth mechanism.

  9. Direct conversion of muon catalyzed fusion energy

    International Nuclear Information System (INIS)

    In this paper a method of direct conversion of muon catalyzed fusion (MCF) energy is proposed in order to reduce the cost of muon production. This MCF concept is based on a pellet composed of many thin solid deuterium-tritium (DT) rods encircled by a metallic circuit immersed in a magnetic field. The direct energy conversion is the result of the heating of the pellet by beam injection and fusion alphas. The expanding DT rods causes the change of magnetic flux linked by the circuit. Our calculation shows that the direct conversion method reduces the cost of one muon by a factor of approximately 2.5 over the previous methods. The present method is compatible with a reactor using the pellet concept, where the muon sticking is reduced by the ion cyclotron resonance heating and the confinement of the exploding pellet is handled by magnetic fields and the coronal plasma. 17 refs., 6 figs

  10. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a...... properties to the widely discussed gold catalysts. Literature results were summarized for alcohol oxidation, epoxidation, amine oxidation, phenol hydroxylation, silane and sulfide oxidation, (side-chain) oxidation of alkyl aromatic compounds, hydroquinone oxidation and cyclohexane oxidation. It was found...

  11. Probing the antibody-catalyzed water-oxidation pathway at atomic resolution

    OpenAIRE

    Zhu, Xueyong; Wentworth, Paul; Wentworth, Anita D.; Eschenmoser, Albert; Lerner, Richard A.; Wilson, Ian A.

    2004-01-01

    Antibodies can catalyze the generation of hydrogen peroxide (H2O2) from singlet dioxygen (1O*2) and water via the postulated intermediacy of dihydrogen trioxide (H2O3) and other trioxygen species. Nine different crystal structures were determined to elucidate the chemical consequences to the antibody molecule itself of exposure to such reactive intermediates and to provide insights into the location on the antibody where these species could be generated. Herein, we report structural evidence ...

  12. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    OpenAIRE

    Zachary L. Palchak; Nguyen, Paula T; Larsen, Catharine H

    2015-01-01

    Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this unc...

  13. An Alternative Approach to Aldol Reactions: Gold-Catalyzed Formation of Boron Enolates from Alkynes

    OpenAIRE

    Korner, C; Starkov, P.; Sheppard, T. D.

    2010-01-01

    A new method for enolate generation via the gold-catalyzed addition of boronic acids to alkynes is reported. The formation of boron enolates from readily accessible ortho-alkynylbenzeneboronic acids proceeds rapidly with 2 mol % PPh3AuNTf2 at ambient temperature. The enolates undergo aldol reaction with an aldehyde present in the reaction mixture to give cyclic boronate esters, which can be subsequently transformed into phenols, biaryls, or dihydrobenzofurans via oxidation, Suzuki-Miyaura, or...

  14. Facile synthesis of aminooxy glycosides by gold(III)-catalyzed glycosidation.

    Science.gov (United States)

    Thadke, Shivaji A; Neralkar, Mahesh; Hotha, Srinivas

    2016-07-22

    The O-glycosidation of hydroxysuccinimides and hydroxyphthalimides with a variety of aldose derived propargyl 1,2-orthoesters under the gold(III)-catalyzed glycosidation conditions is reported. A wide range of hydroxysuccinimidyl and hydroxyphthalimidyl glycosides were synthesized from corresponding glycosyl orthoesters including glucosyl, mannosyl, galactosyl, ribofuranosyl, arabinofuranosyl, lyxofuranosyl and xylofuranosyl using gold catalysis repertoire. The protocol is identified to be compatible for the synthesis of aminooxy glycosides of higher oligosaccharides as well. PMID:27162194

  15. Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

    Science.gov (United States)

    Hemric, Brett N

    2016-01-01

    Summary This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates. PMID:26877805

  16. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  17. Catalyzing collective action to address natural resource conflict: Lessons from Cambodia's Tonle Sap Lake

    OpenAIRE

    Ratner, Blake D.; Halpern, Guy; Kosal; Mam

    2011-01-01

    This paper reports on outcomes and lessons learned from a 15-month initiative aimed at strengthening collective action to address natural resource conflict in Cambodia’s Tonle Sap Lake. Employing the Appreciation-Influence-Control (AIC) model of participatory stakeholder engagement, the initiative aimed in particular to build collective understanding of the sources of vulnerability in fisheries livelihoods and to catalyze efforts to support resilience in this valuable and productive sociale...

  18. Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands

    KAUST Repository

    Petersen, Kimberly S.

    2011-06-01

    Described in this report is a general method for the conversion of prochiral 3-substituted cyclobutanones to enantioenriched γ-lactones through a palladium-catalyzed Baeyer-Villiger oxidation using phosphinooxazoline ligands in up to 99% yield and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center. © 2011 Elsevier Ltd. All rights reserved.

  19. Heterogeneous Rhodium-Catalyzed Aerobic Oxidative Dehydrogenative Cross-Coupling: Nonsymmetrical Biaryl Amines.

    Science.gov (United States)

    Matsumoto, Kenji; Yoshida, Masahiro; Shindo, Mitsuru

    2016-04-18

    The first heterogeneously catalyzed oxidative dehydrogenative cross-coupling of aryl amines is reported herein. 2-Naphthylamine analogues were reacted with various electron-rich arenes using a heterogeneous Rh/C catalyst under mild aerobic conditions, thus affording nonsymmetrical biaryl amines in excellent yields with high selectivities. This reaction provides a mild, operationally simple, and efficient approach for the synthesis of biaryls which are important to pharmaceutical and materials chemistry. PMID:26996772

  20. Palladium-catalyzed insertion of N-tosylhydrazones and trapping with carbon nucleophiles.

    Science.gov (United States)

    Zhou, Ping-Xin; Ye, Yu-Ying; Liang, Yong-Min

    2013-10-01

    A Pd-catalyzed three-component cross-coupling reaction of vinyl iodide, N-tosylhydrazone, and carbon nucleophiles is reported, and a one-pot procedure is also developed. The cross-coupling is proposed to proceed through a palladium-carbene migratory insertion, carbopalladation other than classic palladium-carbene migratory insertion, and β-H elimination. Moreover, the reaction proceeds under mild conditions and with high stereoselectivity. PMID:24070001

  1. Enzyme-catalyzed degradation of carbon nanomaterials

    Science.gov (United States)

    Kotchey, Gregg P.

    Carbon nanotubes and graphene, the nanoscale sp 2 allotropes of carbon, have garnered widespread attention as a result of their remarkable electrical, mechanical, and optical properties and the promise of new technologies that harness these properties. Consequently, these carbon nanomaterials (CNMs) have been employed for diverse applications such as electronics, sensors, composite materials, energy conversion devices, and nanomedicine. The manufacture and eventual disposal of these products may result in the release of CNMs into the environment and subsequent exposure to humans, animals, and vegetation. Given the possible pro-inflammatory and toxic effects of CNMs, much attention has been focused on the distribution, toxicity, and persistence of CNMs both in living systems and the environment. This dissertation will guide the reader though recent studies aimed at elucidating fundamental insight into the persistence of CNMs such as carbon nanotubes (CNTs) and graphene derivatives (i.e., graphene oxide and reduced graphene oxide). In particular, in-testtube oxidation/degradation of CNMs catalyzed by peroxidase enzymes will be examined, and the current understanding of the mechanisms underlying these processes will be discussed. Finally, an outlook of the current field including in vitro and in vivo biodegradation experiments, which have benefits in terms of human health and environmental safety, and future directions that could have implications for nanomedical applications such as imaging and drug delivery will be presented. Armed with an understanding of how and why CNMs undergo enzyme-catalyzed oxidation/biodegradation, researchers can tailor the structure of CNMs to either promote or inhibit these processes. For example, in nanomedical applications such as drug delivery, the incorporation of carboxylate functional groups could facilitate biodegradation of the nanomaterial after delivery of the cargo. Also, the incorporation of CNMs with defect sites in consumer

  2. Mechanism of maltal hydration catalyzed by β-amylase: Role of protein structure in controlling the steric outcome of reactions catalyzed by a glycosylase

    International Nuclear Information System (INIS)

    Crystalline (monomeric) soybean and (tetrameric) sweet potato β-amylase were shown to catalyze the cis hydration of maltal (α-D-glucopyranosyl-2-deoxy-D-arabino-hex-1-enitol) to form β-2-deoxymaltose. As reported earlier with the sweet potato enzyme, maltal hydration in D2O by soybean β-amylase was found to exhibit an unusually large solvent deuterium kinetic isotope effect (VH/VD=6.5), a reaction rate linearly dependent on the mole fraction of deuterium, and 2-deoxy-[2(a)-2H]maltose as product. These results indicate (for each β-amylase) that protonation is the rate-limiting step in a reaction involving a nearly symmetric one-proton transition state and that maltal is specifically protonated from above the double bond. That maltal undergoes cis hydration provides evidence in support of a general-acid-catalyzed, carbonium ion mediated reaction. Of fundamental significance is that β-amylase protonates maltal from a direction opposite that assumed for protonating strach, yet creates products of the same anomeric configuration from both. Such stereochemical dichotomy argues for the overriding role of protein structures is dictating the steric outcome of reactions catalyzed by a glycosylase, by limiting the approach and orientation of water or other acceptors to the reaction center

  3. Synthesis of isoquinolines via Rh-catalyzed C-H activation/C-N cyclization with diazodiesters or diazoketoesters as a C2 source.

    Science.gov (United States)

    Wang, Jie; Zha, Shanke; Chen, Kehao; Zhang, Feifei; Zhu, Jin

    2016-06-01

    Synthesis of isoquinolines based on efficient C-C and C-N bond formation through Rh(iii)-catalyzed C-H activation and subsequent intramolecular cyclization is reported. Diazodiesters serving as a C2 source in the newly formed heterocycles are first demonstrated. Additionally, the Rh(iii)-catalyzed direct C-H activation/cyclization of benzimidates with diazoketoesters is also described. PMID:27146107

  4. Copper-catalyzed cross-coupling of boronic esters with aryl iodides and application to the carboboration of alkynes and allenes.

    Science.gov (United States)

    Zhou, Yiqing; You, Wei; Smith, Kevin B; Brown, M Kevin

    2014-03-24

    Copper-catalyzed Suzuki–Miyaura-type cross-coupling and carboboration processes are reported. The cross-couplings function well with a variety of substituted aryl iodides and aryl boronic esters and allows for orthogonal reactivity compared to palladium-catalyzed processes. The carboboration method includes both alkynes and allenes and provides access to highly substituted and stereodefined vinyl boronic esters. The alkyne carboboration method is highlighted in the simple one-pot synthesis of Tamoxifen. PMID:24677502

  5. On Transition Metal Catalyzed Reduction of N-nitrosodimethlamine

    CERN Document Server

    Zhou, Jun; Tian, Junhua; Zhao, Zhun

    2014-01-01

    This report provides a critical review on "Metal-Catalyzed Reduction of N-Nitrosodimethylamine with Hydrogen in Water", by Davie et al. N-nitrosodimethlamine (NDMA) is a contaminant in drinking and ground water which is difficult to remove by conventional physical methods, such as air stripping. Based on the reported robust capability of metal based powder shaped catalysts in hydrogen reduction, several monometallic and bimetallic catalyst are studied in this paper on the reduction of NDMA with hydrogen. Two kinds of kinetics, metal weight normalized and surface area normalized, are compared between each catalyst in terms of pseudo-first order reaction rate. Palladium, copper enhanced palladium and nickel are found to be very efficient in NDMA reduction, with half-lives on the order of hours per 10 mg/l catalyst metal. Preliminary LC-MS data and carbon balance showed no intermediates. Finally, a simple hydrogen and NMDA surface activated reaction mechanism is proposed by the author for palladium and nickel.

  6. NONMETALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111761 Chen Hua(115 Geological Party,Guizhou Bureau of Geology and Mineral Exploration & Development,Guiyang 551400,China);Deng Chao Analysis on the Metallogenic Environment of Maochang Bauxite in Guizhou Province(Guizhou Geology,ISSN1000-5943,CN52-1059/P,27(3),2010,p.198-201,2 illus.,1 table,8 refs.)Key words:bauxite deposit,Guizhou Province By long time physical and chemical process,the carbonate rock after Central Guizhou uplidft,becomes red clay,after further weathering,the red clay decomposed into the oxide,hydroxide of Al and Fe,in the dissolution hole and depression,it concentrates primary fragmentary tight and earthy karst bauxite ore.Because the variation of landform,it decomposes and cracks again,affords the material source

  7. Are international deposits tax-driven?

    OpenAIRE

    Huizinga, H.P.; Nicodeme, G.

    2004-01-01

    This paper investigates the impact of tax policy on international depositing. Non-bank international deposits are shown to be positively related to interest income and wealth taxes and to the presence of domestic bank interest reporting. This suggests that international deposits are in part intended to facilitate tax evasion. The tax sensitivity of international deposits is estimated to be higher in 1999 than before. At present, only part of international interest flow are covered by either n...

  8. Selective Synthesis of Unsaturated N-Acylethanolamines by Lipase-Catalyzed N-Acylation of Ethanolamine with Unsaturated Fatty Acids

    NARCIS (Netherlands)

    Plastina, P.; Vincken, J.P.; Gruppen, H.; Witkamp, R.F.; Gabriele, B.

    2009-01-01

    The selective synthesis of unsaturated N-acylethanolamines 1b-6b by lipase-catalyzed direct condensation between unsaturated fatty acids 1a-6a and ethanolamine is reported. Reactions were carried out in hexane at 40 °C, in the presence of Candida antarctica Lipase B as the catalyst, to give the corr

  9. Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

    Science.gov (United States)

    An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

  10. Rapid Access to Spirocyclized Indolenines via Palladium-Catalyzed Cascade Reactions of Tryptamine Derivatives and Propargyl Carbonate

    OpenAIRE

    Montgomery, Thomas D.; Nibbs, Antoinette E.; Zhu, Ye; Rawal, Viresh H.

    2014-01-01

    We report the intermolecular palladium-catalyzed reaction of tert-butyl propargyl carbonate with tryptamine derivatives or other indole-containing bis-nucleophiles. The reaction proceeds under mild conditions and with low catalyst loadings to afford novel spiroindolenine products in good to high yields.

  11. Poly(4-vinylpyridine efficiently catalyzed one-pot four-component synthesis of pyrano[2,3-c]pyrazoles

    Directory of Open Access Journals (Sweden)

    Jalal Albadi

    2014-10-01

    Full Text Available An efficient one-pot synthesis of pyrano[2,3-c]pyrazoles via four-component reaction of phenyl hydrazine, ethyl acetoacetate, malononitrile and aromatic aldehydes, catalyzed by poly(4-vinylpyridine is reported. This method provides many advantages such as, atom-economy, easy work up, clean procedure, short reaction times and high yields of products.

  12. Efficient Method for the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Sweeney, William; Lee, James; Abid, Nauman; DeMeo, Stephen

    2014-01-01

    An experiment is described that determines the activation energy (E[subscript a]) of the iodide-catalyzed decomposition reaction of hydrogen peroxide in a much more efficient manner than previously reported in the literature. Hydrogen peroxide, spontaneously or with a catalyst, decomposes to oxygen and water. Because the decomposition reaction is…

  13. Rh(iii)-catalyzed chemoselective C-H functionalizations of tertiary aniline N-oxides with alkynes.

    Science.gov (United States)

    Huang, Xiaolei; Liang, Wenbo; Shi, Yang; You, Jingsong

    2016-05-01

    In this work, we report novel Rh(iii)-catalyzed chemoselective functionalizations of tertiary aniline N-oxides with alkynes, including annulation via the sequential C(sp(2))-H and C(sp(3))-N activation for the formation of N-alkylindoles and an O-atom transfer (OAT) process for the synthesis of acetophenones. PMID:27121366

  14. Nickel-catalyzed Kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates.

    Science.gov (United States)

    Joshi-Pangu, Amruta; Wang, Chao-Yuan; Biscoe, Mark R

    2011-06-01

    We report a Ni-catalyzed process for the cross-coupling of tertiary alkyl nucleophiles and aryl bromides. This process is extremely general for a wide range of electrophiles and generally occurs with a ratio of retention to isomerization >30:1. The same procedure also accommodates the use of aryl triflates, vinyl chlorides, and vinyl bromides as the electrophilic component. PMID:21553878

  15. Metal-ion catalyzed polymerization in the eutectic phase in water-ice

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.

    2008-01-01

    The emergence of an RNA world requires among other processes the non-enzymatic, template-directed replication of genetic polymers such as RNA or related nucleic acids, possibly catalyzed by metal ions. The absence of uridilate derivative polymerization on adenine containing templates has been the...... main issue preventing an efficient template-directed RNA polymerization. We report here the investigation of template-directed RNA polymerization in the eutectic phase in water-ice. In particular, it was found that activated Uridilate monomers in the presence of metal-ion catalysts could efficiently......-pairing opportunities. These results suggest that a template-directed RNA polymerization catalyzed by metal-ions could be carried out under eutectic phase in water-ice conditions....

  16. A General Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl and Heteroaryl Chlorides.

    Science.gov (United States)

    Yuen, On Ying; So, Chau Ming; Man, Ho Wing; Kwong, Fuk Yee

    2016-05-01

    A general palladium-catalyzed Hiyama cross-coupling reaction of aryl and heteroaryl chlorides with aryl and heteroaryl trialkoxysilanes by a Pd(OAc)2 /L2 catalytic system is presented. A newly developed water addition protocol can dramatically improve the product yields. The conjugation of the Pd/L2 system and the water addition protocol can efficiently catalyze a broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl chlorides and heteroaryl chlorides with excellent yields within three hours and the catalyst loading can be down to 0.05 mol % Pd for the first time. Hiyama coupling of heteroaryl chlorides with heteroaryl silanes is also reported for the first time. The reaction can be easily scaled up 200 times (100 mmol) without any degasification and purification of reactants; this facilitates the practical application in routine synthesis. PMID:26998586

  17. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions.

    Science.gov (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter

    2015-02-17

    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  18. Chemistry and morphology of coal liquefaction. Quarterly report, January 1-March 30, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.

    1981-03-01

    In the course of observing by means of Auger spectroscopy graphite gasification reactions catalyzed by metals, it has been found that in the presence of hydrogen, nickel appears to diffuse from the surface into the bulk of the graphite. When potassium is deposited on graphite, it is volatilized above 400/sup 0/C. Surprisingly the production of methane and carbon dioxide from the reaction of graphite and steam was catalyzed by potassium at as low a temperature as 250/sup 0/C. It has been shown that literature on the alkylation of benzene with synthesis gas is erroneous and that the products reported are due to Lewis acid catalyzed cracking of benzene. A novel cobalt mediated, reversible cleavage of a vinyl-hydrogen bond has been discovered. All products from the thermal decomposition of tetralin have been identified. The stereochemistry of cis-1, 2 dihydrotetralin was determined. In the utilization of the water gas shift reaction as a reducing agent for model coal compounds it has been found that tributylphosphine ligands increase the life of transition metal hydride catalysts. Rates of demetallation of high metal content gas oils over cobalt-molybdena-alumina catalysts were measured for vanadium and iron. Kinetic analysis is under way. It is clearly shown that pore plugging of the catalyst occurs early and results in deposition of the metals on the external catalyst surface.

  19. NURE uranium deposit model studies

    International Nuclear Information System (INIS)

    The National Uranium Resource Evaluation (NURE) Program has sponsored uranium deposit model studies by Bendix Field Engineering Corporation (Bendix), the US Geological Survey (USGS), and numerous subcontractors. This paper deals only with models from the following six reports prepared by Samuel S. Adams and Associates: GJBX-1(81) - Geology and Recognition Criteria for Roll-Type Uranium Deposits in Continental Sandstones; GJBX-2(81) - Geology and Recognition Criteria for Uraniferous Humate Deposits, Grants Uranium Region, New Mexico; GJBX-3(81) - Geology and Recognition Criteria for Uranium Deposits of the Quartz-Pebble Conglomerate Type; GJBX-4(81) - Geology and Recognition Criteria for Sandstone Uranium Deposits in Mixed Fluvial-Shallow Marine Sedimentary Sequences, South Texas; GJBX-5(81) - Geology and Recognition Criteria for Veinlike Uranium Deposits of the Lower to Middle Proterozoic Unconformity and Strata-Related Types; GJBX-6(81) - Geology and Recognition Criteria for Sandstone Uranium Deposits of the Salt Wash Type, Colorado Plateau Province. A unique feature of these models is the development of recognition criteria in a systematic fashion, with a method for quantifying the various items. The recognition-criteria networks are used in this paper to illustrate the various types of deposits

  20. Mechanisms of bacterially catalyzed reductive dehalogenation

    Energy Technology Data Exchange (ETDEWEB)

    Picardal, F.W.

    1992-12-31

    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using {sup 14}C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  1. Horseradish peroxidase catalyzed hydroxylations: mechanistic studies.

    Science.gov (United States)

    Dordick, J S; Klibanov, A M; Marletta, M A

    1986-05-20

    The hydroxylation of phenol to hydroquinone and catechol in the presence of dihydroxyfumaric acid and oxygen catalyzed by horseradish peroxidase was studied under conditions where the product yield was high and the side reactions were minimal. The reaction is partially uncoupled with a molar ratio of dihydroxyfumaric acid consumed to hydroxylated products of 12:1. Hydrogen peroxide does not participate in the reaction as evidenced by the lack of effect of catalase and by the direct addition of hydrogen peroxide. Conversely, superoxide and hydroxyl radicals are involved as their scavengers are potent inhibitors. Experiments were all consistent with the involvement of compound III (oxygenated ferrous complex) of peroxidase in the reaction. Compound III is stable in the presence of phenol alone but decomposes rapidly in the presence of both phenol and dihydroxyfumaric acid with the concomitant formation of product. Therefore, phenol and dihydroxyfumaric acid must be present with compound III in order for the hydroxylation reaction to occur. A mechanism consistent with the experimental results is proposed. PMID:3718931

  2. Stereoselective Palladium Catalyzed Cyclizations of Enediyne Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Chang Ho; Rhim, Chul Yun; Jung, Hyung Hoon; Jung, Seung Hyun [Hanyang University, Seoul (Korea, Republic of)

    1999-06-15

    Hydropalladium carboxylates, formed from {pi}-allylpalladium chloride dimer plus carboxylic acids, have been shown to catalyze cyclization of structurally diverse enediynes to form the corresponding six- or five-membered rings depending upon the reaction conditions. Some enediynes having an oxygen linker in an appropriate position under the similar condition yielded the corresponding cyclopropanation products in highly stereoselective manner. A study using deuterated formic acid has proven that the alkylpalladium intermediates formed in our conditions were reduced by the pendant formate ligand. The dienediyne 10 yielded only the tricyclic product 12 in 67% yield, although it was expected to form the cyclic product 11. All these cyclizations seemed to occur via the corresponding alkylpalladium intermediates I, which could proceed to the corresponding cyclic products depending on the reaction conditions and the substrates. The study using deuterated formic acid could provide an important information to understand the present cyclization mechanism. Overall the present study could play an important role in developing new synthetic methodologies for constructing complex polycyclic compounds

  3. Lipase catalyzed synthesis of epoxy-fatty acids

    Institute of Scientific and Technical Information of China (English)

    CHEN, Qian; LI, Zu-Yi

    2000-01-01

    Lipase catalyzed synthesis of epoxy-fatty acidas from unsaturated carboxylic acids was investigated.Under mild conditions unsaturated arboxylic acids were convcveed to peroxide,then the unsaturated peroxycarboxylic acids epoxidised the C=C bond of themselves

  4. Functioned Calix[4]arenes as Artificial Enzymes Catalyze Aldol Condensation

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Aldolase models derived from calix[4]arene were designed and synthesized. The aldol condensation of p-nitrobenzaldehyde with acetone was catalyzed by the synthetic enzymes proceeded under mild conditions to offer chiefly aldol-type product in good yield.

  5. Pulsed laser deposition of pepsin thin films

    Energy Technology Data Exchange (ETDEWEB)

    Kecskemeti, G. [Department of Optics and Quantum Electronics, University of Szeged, H-6720 Szeged, Dom ter 9 (Hungary)]. E-mail: kega@physx.u-szeged.hu; Kresz, N. [Department of Optics and Quantum Electronics, University of Szeged, H-6720 Szeged, Dom ter 9 (Hungary); Smausz, T. [Hungarian Academy of Sciences and University of Szeged, Research Group on Laser Physics, H-6720 Szeged, Dom ter 9 (Hungary); Hopp, B. [Hungarian Academy of Sciences and University of Szeged, Research Group on Laser Physics, H-6720 Szeged, Dom ter 9 (Hungary); Nogradi, A. [Department of Ophthalmology, University of Szeged, H-6720, Szeged, Koranyi fasor 10-11 (Hungary)

    2005-07-15

    Pulsed laser deposition (PLD) of organic and biological thin films has been extensively studied due to its importance in medical applications among others. Our investigations and results on PLD of a digestion catalyzing enzyme, pepsin, are presented. Targets pressed from pepsin powder were ablated with pulses of an ArF excimer laser ({lambda} = 193 nm, FWHM = 30 ns), the applied fluence was varied between 0.24 and 5.1 J/cm{sup 2}. The pressure in the PLD chamber was 2.7 x 10{sup -3} Pa. The thin layers were deposited onto glass and KBr substrates. Our IR spectroscopic measurements proved that the chemical composition of deposited thin films is similar to that of the target material deposited at 0.5 and 1.3 J/cm{sup 2}. The protein digesting capacity of the transferred pepsin was tested by adapting a modified 'protein cube' method. Dissolution of the ovalbumin sections proved that the deposited layers consisted of catalytically active pepsin.

  6. Muon-catalyzed fusion-an energy production perspective

    International Nuclear Information System (INIS)

    The nuclear fission reaction can be catalyzed in a suitable fusion fuel by muons, which can temporarily form very tightly bound mu-molecules. Muons can be produced by the decay of negative pions, which, in turn, have been produced by an accelerated beam of light ions impinging on a target. Muon-catalyzed fusion is appropriately called cold fusion because the nuclear fusion also occurs at room temperature. For practical fusion energy generation, it appears to be necessary to have a fuel mixture of deuterium and tritium at about liquid density and at a temperature of the order of 1000 K. The current status of muon-catalyzed fusion is limited to demonstrations of scientific breakeven by showing that it is possible to sustain an energy balance between muon production and catalyzed fusion. Conceptually, a muon-catalyzed fusion reactor is seen to be an energy amplifier that increases by fusion reactions that energy invested in nuclear pion-muon beams. The physical quantity that determines this balance is Xμ, the number of fusion reactions each muon can catalyze before it is lost. Showing the feasibility of useful power production is equivalent to showing that Xμ can exceed a sufficiently large number, which is estimated to be ∼104 if standard technology is used or ∼103 if more advanced physics and technology can be developed. Since a muon can be produced with current technology for an expenditure of ∼5000 MeV and 17.6 MeV is produced per fusion event, it follows that Xμ ∼ 250 would be a significant demonstration of scientific breakeven. Therefore, the energy cost of producing muons must be reduced substantially before muon-catalyzed fusion reactors could seriously be considered. The physics of muon-catalyzed fusion is summarized and discussed. Muon catalysis is surveyed for the following systems: proton-deuteron, deuteron-deuteron, deuteron-triton, and non-hydrogen elements. 95 refs., 6 figs., 4 tabs

  7. Enzyme-catalyzed Sequential Reduction of Carbon Dioxide to Formaldehyde☆

    Institute of Scientific and Technical Information of China (English)

    Wenfang Liu; Yanhui Hou; Benxiang Hou; Zhiping Zhao

    2014-01-01

    It has been reported that enzymatic-catalyzed reduction of CO2 is feasible. Most of literature focuses on the con-version of CO2 to methanol. Herein we put emphasis on the sequential conversion of CO2 to formaldehyde and its single reactions. It appears that CO2 pressure plays a critical role and higher pressure is greatly helpful to form more HCOOH as well as HCHO. The reverse reaction became severe in the reduction of CO2 to formaldehyde after 10 h, decreasing HCHO production. Increasing the mass ratio of formate dehydrogenase to formaldehyde dehydrogenase could promote the sequential reaction. At concentrations of nicotinamide adenine dinucleotide lower than 100 mmol·L−1, the reduction of CO2 was accelerated by increasing cofactor concentration. The opti-mum pH value and concentration of phosphate buffer were determined as 6.0 and 0.05 mol·L−1, respectively, for the overall reaction. It seems that thermodynamic factor such as pH is restrictive to the sequential reaction due to distinct divergence in appropriate pH range between its single reactions.

  8. Lipase catalyzed ester synthesis for food processing industries

    Directory of Open Access Journals (Sweden)

    Aravindan Rajendran

    2009-02-01

    Full Text Available Lipases are one of the most important industrial biocatalyst which catalyzes the hydrolysis of lipids. It can also reverse the reaction at minimum water activity. Because of this pliable nature, it is widely exploited to catalyze the diverse bioconversion reactions, such as hydrolysis, esterification, interesterification, alcoholysis, acidolysis and aminolysis. The property to synthesize the esters from the fatty acids and glycerol promotes its use in various ester synthesis. The esters synthesized by lipase finds applications in numerous fields such as biodiesel production, resolution of the recemic drugs, fat and lipid modification, flavour synthesis, synthesis of enantiopure pharmaceuticals and nutraceuticals. It plays a crucial role in the food processing industries since the process is unaffected by the unwanted side products. Lipase modifications such as the surfactant coating, molecular imprinting to suit for the non-aqueous ester synthesis have also been reported. This review deals with lipase catalyzed ester synthesis, esterification strategies, optimum conditions and their applications in food processing industries.Lipases são catalizadores industriais dos mais importantes, os quais catalizam a hidrólise de lipídeos. Também podem reverter a reação a um mínimo de atividade de água. Devido sua natureza flexível, é amplamente explorada para catalizar uma diversidade de reações de bioconversão como hidrólise, esterificação, interesterificação, alcoólise, acidólise e aminólise. A propriedade de síntese de esteres a partir de ácidos graxos e glicerol promoveu seu uso em várias sínteses de esteres. Os esteres sintetizados por lipases encontram aplicação em numerosos campos como a produção de biodiesel, resolução de drogas racêmicas, modificação de gorduras e lipídios, sintese de aromas, síntese de produtos farmacêuticos enantiopuro e nutracêuticos. As lipases possuem um papel crucial nas indústrias de

  9. High power density yeast catalyzed microbial fuel cells

    Science.gov (United States)

    Ganguli, Rahul

    increase was shown to quickly saturate with cell mass attached on the electrode. Based on recent modelling data that suggested that the electrode currents might be limited by the poor electrical conductivity of the anode, the power density versus electrical conductivity of a yeast-immobilized anode was investigated. Introduction of high aspect ratio carbon fiber filaments to the immobilization matrix increased the electrical conductivity of the anode. Although a higher electrical conductivity clearly led to an increase in power densities, it was shown that the principal limitation to power density increase was coming from proton transfer limitations in the immobilized anode. Partial overcoming of the gradients lead a power density of ca. 250 microW cm-2, which is the highest reported for yeast powered MFCs. A yeast-catalyzed microbial fuel cell was investigated as a power source for low power sensors using raw tree sap. It was shown that yeast can efficiently utilize the sucrose present in the raw tree sap to produce electricity when excess salt is added to the medium. Therefore the salinity of a potential energy source is an important consideration when MFCs are being considered for energy harvesting from natural sources.

  10. Iron-catalyzed coupling of aryl sulfamates and aryl/vinyl tosylates with aryl Grignards.

    Science.gov (United States)

    Agrawal, Toolika; Cook, Silas P

    2014-10-01

    The iron-catalyzed coupling of aryl sulfamates and tosylates with aryl Grignard reagents is reported for the first time. The methodology employs air-stable, low-cost FeF3·3H2O and the N-heterocyclic carbene ligand IPr·HCl as the preligand to form a long-lived catalyst upon treatment with aryl Grignards. The reaction provides a range of cross-coupled products in good-to-excellent yields. In contrast to previous reports with aryl chlorides, these reactions proceed with low levels of Grignard homocoupling regardless of the iron source. PMID:25230097

  11. Conservation Kickstart- Catalyzing Conservation Initiatives Worldwide

    Science.gov (United States)

    Treinish, G.

    2014-12-01

    Adventurers and Scientists for Conservation (ASC) is a nonprofit organization that collects environmental data to catalyze conservation initiatives worldwide. Adventure athletes have the skills and motivation to reach the most remote corners of the world. ASC utilizes those skills to provide the scientific community with data while providing the outdoor community with purpose beyond the personal high of reaching a summit or rowing across an ocean. We carefully select projects, choosing partnerships that will maximize the impact of ASC volunteers. Each project must have a clear path to a tangible conservation outcome and demonstrate a clear need for our brand of volunteers. We partner with government agencies, universities, and independant reseachers to kickstart data collection efforts around the world. Last year, through a partnership with the Olympic National Forest, 20 volunteers from the Seattle area set up and monitored camera traps in an effort to survey for costal Pacific marten. Our work led to the species' listing as "critically imperiled" with NatureServe. A partnership with the inaugural Great Pacific Race, engaging trans-Pacific rowing teams, searched for microplastics in the Pacific Ocean as part of our ongoing microplastics campaign. In a multi-year partnership with the American Prairie Reserve (APR), ASC volunteer crews live and work on the Reserve collecting wildlife data year round. The data we obtain directly informs the Reserve's wildlife management decisions. On this project, our crews have safely and effectively navigated temperature extremes from -30 degrees to 100+ degrees while traveling in a remote location. We are currently scouting projects in the Okavango Delta of Botswana and the rainforest of Suriname where we will be able to cover large amounts of area in a short periord of time. ASC is at the crossroads of the adventure and coservation science communities. Our approach of answering specific questions by using highly skilled and

  12. Tyrosinase-catalyzed melanin as a contrast agent for photoacoustic tomography

    Science.gov (United States)

    Krumholz, Arie; Chavez, Sarah; Yao, Junjie; Fleming, Timothy; Gillanders, William E.; Wang, Lihong V.

    2011-03-01

    It is difficult to distinguish between tumor cells and surrounding cells without staining as is done in histology. We developed tyrosinase-catalyzed melanin as a reporter gene for photoacoustic tomography. Tyrosinase is the primary enzyme responsible for the production of melanin and alone is sufficient to produce melanin in non-melanogenic cells. Two cell lines were created: a stably transfected HeLa line and a transiently transfected 293 line. A phantom experiment was performed with the 293 transfected cells 48 hours post transfection and the results compared with oxygenated whole blood, B16 melanoma and 293 control cells. An in vivo experiment was performed using the transfected HeLa cells xenografted into a nude mouse ear, and then imaged. The results show strong contrast for tyrosinase-catalyzed melanin in both the 293 cells in the tube phantom as well as the in vivo result showing melanin in a nude mouse ear. Transfection increased expression in 293 cells 159 fold and image contrast compared to blood by as much as 50 fold. Due to the strong signal obtained at longer wavelengths and the decrease of blood signal at the same wavelengths, tyrosinase catalyzed melanin is a good candidate as a molecular imaging contrast agent for photoacoustic tomography.

  13. Magical Power of d-block transition metals. Pd-Catalyzed Cross-Coupling and Zr-Catalyzed Asymmetric Carboalumination (Zaca reaction)

    OpenAIRE

    Año Internacional de la Quimica 2011

    2011-01-01

    Magical Porwer of d-block Transition Metals. Pd-Catalyzed Cross-Coupling and Zr-Catalyzed Asymmetric Carboalumination (Zaca Reaction). Ei-ichi Negishi (Department of Chemistry - Purdue University). Premio Nobel de Química 2010

  14. A free-standing condensation enzyme catalyzing ester bond formation in C-1027 biosynthesis.

    Science.gov (United States)

    Lin, Shuangjun; Van Lanen, Steven G; Shen, Ben

    2009-03-17

    Nonribosomal peptide synthetases (NRPSs) catalyze the biosynthesis of many biologically active peptides and typically are modular, with each extension module minimally consisting of a condensation, an adenylation, and a peptidyl carrier protein domain responsible for incorporation of an amino acid into the growing peptide chain. C-1027 is a chromoprotein antitumor antibiotic whose enediyne chromophore consists of an enediyne core, a deoxy aminosugar, a benzoxazolinate, and a beta-amino acid moiety. Bioinformatics analysis suggested that the activation and incorporation of the beta-amino acid moiety into C-1027 follows an NRPS mechanism whereby biosynthetic intermediates are tethered to the peptidyl carrier protein SgcC2. Here, we report the biochemical characterization of SgcC5, an NRPS condensation enzyme that catalyzes ester bond formation between the SgcC2-tethered (S)-3-chloro-5-hydroxy-beta-tyrosine and (R)-1-phenyl-1,2-ethanediol, a mimic of the enediyne core. SgcC5 uses (S)-3-chloro-5-hydroxy-beta-tyrosyl-SgcC2 as the donor substrate and exhibits regiospecificity for the C-2 hydroxyl group of the enediyne core mimic as the acceptor substrate. Remarkably, SgcC5 is also capable of catalyzing amide bond formation, albeit with significantly reduced efficiency, between (S)-3-chloro-5-hydroxy-beta-tyrosyl-(S)-SgcC2 and (R)-2-amino-1-phenyl-1-ethanol, an alternative enediyne core mimic bearing an amine at its C-2 position. Thus, SgcC5 is capable of catalyzing both ester and amide bond formation, providing an evolutionary link between amide- and ester-forming condensation enzymes. PMID:19246381

  15. CTR plasma engineering studies. Annual progress report, 1 November 1983-30 October 1984

    International Nuclear Information System (INIS)

    This report covers research on the following topics: (1) transport in compact tori, (2) bremsstrahlung energy deposition in first wall materials, (3) Coulombic energy transfer collisions, (4) magnetic helicity injection study, (5) blankets for tritium catalyzed deuterium fusion reactors, (6) exploratory studies of applications of optimal control theory, (7) design of a burn dynamic experiment, (8) alpha driven low frequency fast magnetosonic wave microinstability in tandem mirror, (9) fusion product heating and confinement in a tandem mirror, and (10) velocity-space particle loss in field reversed configurations

  16. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    Science.gov (United States)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  17. Resting State and Elementary Steps of the Coupling of Aryl Halides with Thiols Catalyzed by Alkylbisphosphine Complexes of Palladium

    OpenAIRE

    Alvaro, Elsa; Hartwig, John F.

    2009-01-01

    Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-tBu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower t...

  18. Survey on effects of deposits mixing quantities on cement and other materials. Ningyo-Toge Environmental Engineering Center of Japan Nuclear Cycle Development Institute (An entrusted test report)

    International Nuclear Information System (INIS)

    In a refining conversion facility of the Ningyo-Toge Environmental Engineering Center, have been carried out some technical development from basic tests to practical scale tests on wet type UF6 conversion using natural uranium and dry type one using collected UF6. Wasted liquids containing uranium and fluorine formed together with the conversions are added by calcium hydroxide, to treat it at a shape of CaF2 of neutralized deposits. In future, the deposits will be necessary for rational countermeasure foreseeing their final disposal, but basic informations were short on presenting states and chemical forms of uranium and other impurity elements in the deposits at their formation, their physico-chemical properties, and so on, which are required for determination of their treating methods. To contribute to technical development of the rational treatment and disposal formed at the facility, together with carrying out understanding of their basic property, extraction of propositions and subjects on the deposit treatment was carried out on 1999 fiscal year. And, on 2000 fiscal year, successive survey on their forming shape and physico-chemical properties and physico-chemical survey on shapes of impurities in them were carried out. Furthermore, surveys on physical property of their added cements and on possibility of using them at cement production. As a result, on 2001 fiscal year, survey and investigation on application possibility of their mixing and kneading into cement materials to solidify solid radioactive wastes to solidifying materials. (G.K.)

  19. In-Situ Sensors for Process Control of CuIn(Ga)Se2 Module Deposition; Annual Technical Report, 15 February 1998-15 February 1999

    International Nuclear Information System (INIS)

    Materials Research Group (MRG), Inc., is developing in-situ sensors to improve yield, reproducibility, average efficiency, and prevention of ''lost processes.'' In-situ X-ray fluorescence (XRF) will be used to monitor composition and thickness of deposited layers, and in-situ optical emission spectroscopy (OES) will be used to provide real-time feedback describing the deposition plasma. Characterization techniques are to be examined ex-situ in the first two years of the contract, and applied to existing deposition systems in the final year. Progress toward achieving these goals during Phase I includes: Development and verification of an XRF simulation tool to troubleshoot measurements, to predict difficulties in XRF interpretation, and to calculate quantities needed in the translation from XRF signal to composition; Examination of the implication of sample conditions unique to CIGS photovoltaics - such as varying Ga gradients, intermediate film thicknesses where neither thick-film nor thin-film approximations are valid, variations in back-contact thickness, multiple layers, variations in substrate composition and thickness - on XRF interpretation; Fabrication of CIGS samples and test structures for XRF measurements; Execution and interpretation of XRF measurements examining system accuracy; Design of a prototype XRF sensor built entirely of cost-effective, commercially available components that are suitable for integration into closed-loop deposition control; Evaluation of pulsed DC sputtering of Se; and Interaction with CIS National Team industrial partners to specify and adapt sensor functions

  20. The control of graphene double-layer formation in copper-catalyzed chemical vapor deposition

    Czech Academy of Sciences Publication Activity Database

    Kalbáč, Martin; Frank, Otakar; Kavan, Ladislav

    2012-01-01

    Roč. 50, č. 10 (2012), s. 3682-3687. ISSN 0008-6223 R&D Projects: GA ČR(CZ) GAP208/12/1062 Institutional support: RVO:61388955 Keywords : graphene * electrochemistry * spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 5.868, year: 2012

  1. Tumoral calcium pyrophosphate deposition disease

    International Nuclear Information System (INIS)

    A report of two patients in which a soft tissue mass, initially regarded as a malignant tumor, was shown to be the result of calcium pyrophosphate deposition disease. The first case, a woman aged 71 years, presented with a mass involving the right fifth finger. In the second case, also a women aged 71 years, the lesion involved the tissues adjacent to the right hip. Each lesion consisted of a mass of highly cellular tissue containing deposits of calcium pyrophosphate dihydrate crystals. The clinical, radiological, and pathological features of the two cases are compared with those of seven similar cases reported in the literature. (orig.)

  2. Study of the mineral matter distribution in pulverized fuel coals with respect to slag deposit formation in boiler furnaces. Phase 1. Final report, 1 April 1976-30 June 1980

    Energy Technology Data Exchange (ETDEWEB)

    Austin, L.G..; Moza, A.K.; Abbott, M.F.; Singh, S.N.; Trimarchi, T.J.

    1980-07-01

    The work reported here is aimed at understanding the initiation of upper wall slag deposits in pulverized coal fired utility boilers, and characterizing pulverized coals for the mineral elements of significance. A scanning electron microscope with x-ray fluorescence capability, under computer control, has been used to analyze individual coal particles for the elements Si, Al, Ca, Fe and S. The required software for these analyses has been developed, as have suitable sample preparation techniques. The results show many different types of particles to exist in pulverized coal, some of which are likely to be bad-acting in terms of slagging. A test has been developed to study the sticking of melted pellets of ash or mineral matter dropped onto a metal substrate held at a controlled temperature. It was found that for a given drop composition and substrate material there is a substrate temperature below which the drop will not adhere. At higher substrate temperatures the strength of adhesion increases logarithmically. Sticking appears to be a function of the oxidation of the surface or of alkalies deposited on the surface. If the drop composition is such that material absorbed from the substrate fluxes the drop-substrate interface, then the apparent contact angle is reduced and sticking is enhanced, and vice-versa. A small-scale pulverized coal furnace designed to give a uniform temperature-time history for each particle was reconstructed and tested. Water-cooled probes were found to give the most accurate control of initial probe temperature. Deposits initiate on the probe in a few minutes, and the fall of probe temperature can be used to indicate the growth of deposit. Systematic investigation of the particles initiating the deposit have not yet been performed.

  3. RSC-Programme - Interim Report approach and basis for RSC development, layout determining features and preliminary criteria for tunnel and deposition hole scale

    International Nuclear Information System (INIS)

    Posiva Oy, jointly owned by Teollisuuden Voima Oyj, Fortum Power and Heat Oy, is responsible for implementing the programme for geological disposal of spent nuclear fuel in Finland. The Olkiluoto site has been studied for this purpose for over two decades. Since 2004, an underground research facility, ONKALO, is being constructed at the site, which will later become a part of the disposal facility. Posiva is preparing to submit an application to obtain a construction licence for the disposal facility by the end of 2012. To prepare for the licensing, host rock requirements are being developed to guide repository design and layout adaptation, as required by the regulators. The Rock Suitability Criteria (RSC) programme has been set up for this purpose. The aim of the RSC is to develop a classification scheme both to be applied to the repository layout design and to define suitable rock volumes for the deposition holes. The classification scheme considers both long-term safety and engineering aspects. Performance targets for the host rock consider rock properties relevant to safety, and therefore rock properties contributing to the function of the host rock as a natural barrier and affecting performance of the engineered barrier system. Consequently they are related to chemical composition of the groundwater, groundwater flow, groundwater transport properties and thermomechanical stability. The practical criteria, Rock Suitability Criteria (RSC) based on current site data and models, are defined on different scales, including repository, tunnel and deposition hole scales. The focus has been in the repository scale. Consequently, layout determining features (LDFs) and their respect distance volumes that are to be avoided when locating deposition tunnels and holes have been defined. Zones defined as LDFs are potentially mechanically instable in the current or future stress field or they are main groundwater flow routes important for transport of solutes and chemical

  4. Depositional sequence analysis and sedimentologic modeling for improved prediction of Pennsylvanian reservoirs (Annex 1). Annual report, February 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Watney, W.L.

    1992-08-01

    Interdisciplinary studies of the Upper Pennsylvanian Lansing and Kansas City groups have been undertaken in order to improve the geologic characterization of petroleum reservoirs and to develop a quantitative understanding of the processes responsible for formation of associated depositional sequences. To this end, concepts and methods of sequence stratigraphy are being used to define and interpret the three-dimensional depositional framework of the Kansas City Group. The investigation includes characterization of reservoir rocks in oil fields in western Kansas, description of analog equivalents in near-surface and surface sites in southeastern Kansas, and construction of regional structural and stratigraphic framework to link the site specific studies. Geologic inverse and simulation models are being developed to integrate quantitative estimates of controls on sedimentation to produce reconstructions of reservoir-bearing strata in an attempt to enhance our ability to predict reservoir characteristics.

  5. Ferroelectric thin films deposited by pulsed laser deposition

    Science.gov (United States)

    Dinu, Raluca; Vrejoiu, I.; Verardi, P.; Craciun, F.; Dinescu, Maria

    2001-06-01

    Influence of substrate and electrode on the properties of PbZr0.53Ti0.47O3 (PZT) thin films grown by pulsed laser deposition technique (1060 nm wavelength Nd:YAG laser light, 10 ns pulse duration, 10 Hz repetition rate, 0.35 J/pulse, 25 J/cm2 laser fluence, deposition rate about 1 angstrom/pulse) was studied. The substrate temperatures were in the range 380 degree(s)C-400 degree(s)C. Oriented crystalline PZT layers with 1-3 micrometers thickness were deposited on glass substrates plated with Au/Pt/NiCr electrodes, from a PZT commercial target in oxygen reactive atmosphere. The deposited PZT films with perovskite structure were preferentially oriented along the (111) direction as revealed from XRD spectra. Piezoelectric d33 coefficients up to 30 pC/N were obtained on as deposited films. Ferroelectric hysteresis loops at 100 Hz revealed a remanent polarization of 15 (mu) C/cm2 and a coercive field of 100 kV/cm. A comparison with properties of PZT films deposited using a KrF laser and with SrBi2Ta2O9 (SBT) films is reported.

  6. Chemical and mechanical properties of silica hybrid films from NaOH catalyzed sols for micromachining with diamond cutting tools

    International Nuclear Information System (INIS)

    Manufacturing of microstructured mold surfaces was realized by the micromachining of thick sol–gel silica hybrid coatings. The films were deposited onto pre-machined steel molds by spin coating using NaOH-catalyzed sols from organosilicate precursors. The effect of the sol synthesis and the heat treatment on the mechanical and chemical properties of these films was studied in order to develop thick and crack-free films with appropriate properties for micromachining with diamond cutting tools. The hardness was measured by nanoindentation as a function of the heat treatment temperature. The transition from soft organic gel films to hard glass-like films due to the thermal treatment was characterized by X-ray photoelectron spectroscopy, elastic recoil detection, and Raman and infrared spectroscopies. The films from NaOH catalyzed sols showed a complex transition from aliphatic carbon originating from hydrocarbon groups to carbonates, carboxylates and disordered carbon clusters. - Highlights: ► Thick silica hybrid films were micromachined with diamond cutting tools. ► The nanoindentation hardness increased with the heat treatment temperature. ► The role of sodium hydroxide in base catalyzed silica sols was studied. ► Formation of carbonates, carboxylates and disordered carbon was observed

  7. Chemical and mechanical properties of silica hybrid films from NaOH catalyzed sols for micromachining with diamond cutting tools

    Energy Technology Data Exchange (ETDEWEB)

    Prenzel, T., E-mail: tprenzel@uni-bremen.de [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Mehner, A. [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Lucca, D.A.; Qi, Y.; Harriman, T.A. [School of Mechanical and Aerospace Engineering, 218 Engineering North, Oklahoma State University, Stillwater, OK 74078 (United States); Mutlugünes, Y. [Labor für Mikrozerspanung — LFM, Badgasteiner Str. 2, 28359 Bremen (Germany); Shojaee, S.A. [School of Mechanical and Aerospace Engineering, 218 Engineering North, Oklahoma State University, Stillwater, OK 74078 (United States); Wang, Y.Q.; Williams, D. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Nastasi, M. [Nebraska Center for Energy Sciences Research, University of Nebraska, 230 Whittier Research Center, 2200 Vine Street Lincoln, NE 68583-0857 (United States); Zoch, H.-W. [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Swiderek, P. [Institute of Applied and Physical Chemistry, University of Bremen, Leobener Straße, 28359 Bremen (Germany)

    2013-03-01

    Manufacturing of microstructured mold surfaces was realized by the micromachining of thick sol–gel silica hybrid coatings. The films were deposited onto pre-machined steel molds by spin coating using NaOH-catalyzed sols from organosilicate precursors. The effect of the sol synthesis and the heat treatment on the mechanical and chemical properties of these films was studied in order to develop thick and crack-free films with appropriate properties for micromachining with diamond cutting tools. The hardness was measured by nanoindentation as a function of the heat treatment temperature. The transition from soft organic gel films to hard glass-like films due to the thermal treatment was characterized by X-ray photoelectron spectroscopy, elastic recoil detection, and Raman and infrared spectroscopies. The films from NaOH catalyzed sols showed a complex transition from aliphatic carbon originating from hydrocarbon groups to carbonates, carboxylates and disordered carbon clusters. - Highlights: ► Thick silica hybrid films were micromachined with diamond cutting tools. ► The nanoindentation hardness increased with the heat treatment temperature. ► The role of sodium hydroxide in base catalyzed silica sols was studied. ► Formation of carbonates, carboxylates and disordered carbon was observed.

  8. Atmospheric Pressure Chemical Vapor Deposition of CdTe for High-Efficiency Thin-Film PV Devices; Annual Report, 26 January 1998-25 January 1999

    International Nuclear Information System (INIS)

    ITN's 3-year project, titled ''Atmospheric Pressure Chemical Vapor Deposition (APCVD) of CdTe for High-Efficiency Thin-Film Photovoltaic (PV) Devices,'' has the overall objectives of improving thin-film CdTe PV manufacturing technology and increasing CdTe PV device power conversion efficiency. CdTe deposition by APCVD employs the same reaction chemistry as has been used to deposit 16%-efficient CdTe PV films, i.e., close-spaced sublimation, but employs forced convection rather than diffusion as a mechanism of mass transport. Tasks of the APCVD program center on demonstrating APCVD of CdTe films, discovering fundamental mass-transport parameters, applying established engineering principles to the deposition of CdTe films, and verifying reactor design principles that could be used to design high-throughput, high-yield manufacturing equipment. Additional tasks relate to improved device measurement and characterization procedures that can lead to a more fundamental understanding of CdTe PV device operation, and ultimately, to higher device conversion efficiency and greater stability. Specifically, under the APCVD program, device analysis goes beyond conventional one-dimensional device characterization and analysis toward two-dimension measurements and modeling. Accomplishments of the first year of the APCVD subcontract include: selection of the Stagnant Flow Reactor design concept for the APCVD reactor, development of a detailed reactor design, performance of detailed numerical calculations simulating reactor performance, fabrication and installation of an APCVD reactor, performance of dry runs to verify reactor performance, performance of one-dimensional modeling of CdTe PV device performance, and development of a detailed plan for quantification of grain-boundary effects in polycrystalline CdTe devices

  9. Remediation of spent block in Uvanas deposit

    International Nuclear Information System (INIS)

    In 2007 by 'Kazatomprom' and 'Mining company' board decision, the branch of 'Mining company', 'Steppe ore management body' is reorganized in structure subdivision, the basic activity of which is organization and carrying out remediation works on spent blocks of PSV uranium deposit. In 2002 works are completed on OVOS for operating deposits Uvanas, Kanjugan, Northern Karamurun and Eastern Minkuduk. The results of present work were reported in IAEA conference. The working project 'Remediation of spent blocks of PSV uranium deposit PV-17 polygon of Steppe ore management body' approved in 2005 was developed for carrying out the remediation works. Works funding were carried out from liquidation fund of the current deposit established in accordance with the Republic of Kazakhstan law 'About interior and interior use'. Deposits remediation is the part of deposit operation life cycle which obliges to operate deposits with minimum expenditures for remediation.

  10. Corrosion protection of solar-collctor heat exchangers with electrochemically deposited films. Final report, 15 May 1978-15 November 1979. [Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Koch, V.R.; Schnaper, G.H.; Brummer, S.B.

    1980-05-01

    The goal of this program was the demonstration of a novel corrosion protection technique for the common solar collector metals: Al, Cu, and Fe as mild steel. This involves the electrochemical deposition of thin, adherent polymer films on the interior of heat-exchanger tubes by application of a current in the presence of a suitable organic monomer. Polyphenylene oxide (PPO) films were anodically deposited onto Cu and Fe coupons from methanolic media. However, defects in these films afforded poor corrosion protection. In an attempt to circumvent this problem, suitably functionalized PPO films were cross-linked via Schiff base formation in a subsequent chemical step. While these chemically modified PPO films were demonstrably more resistant to ethylene glycol H/sub 2/O media at elevated temperatures, they were eventually undetermined by the thermal transfer fluid. Cinnamaldehyde, a styrene-type monomre, has been successfully electrodeposited onto Al coupons. This process involved a constant, albeit unreferenced potential technique in which the Al is made the negative electrode. Cathodic deposition onto Al avoids passivating Al/sub 2/O/sub 3/ barrier coating formation, and is amenable to the cross-linking technique. Filmed and cross-linked Al samples stored at elevated temperatures resisted corrosive processes compared to unfilmed control samples. Pitting, however, was the ultimate fate of all filmed samples.

  11. Background atmospheric sulfate deposition at a remote alpine site in the Southern Canadian Rocky Mountains

    Science.gov (United States)

    Wasiuta, Vivian; Norman, Ann-Lise; Lafrenière, Melissa J.; Hastings, Meredith G.

    2015-11-01

    We report observations of stable isotope ratios and ion concentrations from seasonal snowpack and summer bulk precipitation from remote alpine sites in the Southern Canadian Rocky Mountains. Spatial deposition patterns for sulfur (S) and δ34S-SO42- values indicate dominantly distant sources with little impact from local to regional pollution. Comparable S loads and total snowpack δ34S-SO42- values for glacier snowpack indicates S emissions were well mixed prior to dry deposition or incorporation into snowfall. A uniform S load and similar δ34S-SO42- values in a detailed study of summer bulk precipitation implies well-mixed distant emissions. We interpret the deposited 0.9 kg S ha-1yr-1 as atmospheric background deposition in midlatitude Western Canada. This study will improve calculations for sites impacted by point source emissions and provide a baseline for attributing changes associated with climate change, industrialization, and urban growth. Field evidence from this study supports theoretical and laboratory research on the relative importance of oxidation pathways on atmospheric δ34S-SO42- values for long-range transported sulfate. δ34S-SO42- of the dominant S source in summer bulk precipitation (~ +2‰) versus snowpack (≥ +9‰) cannot be explained by seasonal emission sources, temperature effects on fractionation, or Rayleigh distillation. The study supports a seasonal difference in the relative importance of the different SO2 to SO42- oxidation pathways with homogeneous oxidation by OH and heterogeneous oxidation by H2O2 most important in summer, and O2 catalyzed by transition metal ions in a radical chain reaction pathway more significant in winter.

  12. Atmospheric deposition 2000. NOVA 2003; Atmosfaerisk deposition 2000. NOVA 2003

    Energy Technology Data Exchange (ETDEWEB)

    Ellermann, T.; Hertel, O.; Hovmand, M.F.; Kemp, K.; Skjoeth, C.A.

    2001-11-01

    This report presents measurements and calculations from the atmospheric part of NOVA 2003 and covers results for 2000. It summarises the main results concerning concentrations and depositions of nitrogen, phosphorus and sulphur compounds related to eutrophication and acidification. Depositions of atmospheric compounds to Danish marine waters as well as land surface are presented. Measurements: In 2000 the monitoring program consisted of eight stations where wet deposition of ammonium, nitrate, phosphate (semi quantitatively) and sulphate were measured using bulk precipitation samplers. Six of the stations had in addition measurements of atmospheric content of A, nitrogen, phosphorus, and sulphur compounds in gas and particulate phase carried out by use of filter pack samplers. Filters were analysed at the National Environmental Research Institute. Furthermore nitrogen dioxide were measured using nitrogen dioxide filter samplers and monitors. Model calculations: The measurements in the monitoring program were supplemented with model calculations of concentrations and depositions of nitrogen and sulphur compounds to Danish land surface, marine waters, fjords and bays using the ACDEP model (Atmospheric Chemistry and Deposition). The model is a so-called trajectory model and simulates the physical and chemical processes in the atmosphere using meteorological and emission data as input. The advantage of combining measurements with model calculations is that the strengths of both methods is obtained. Conclusions concerning: 1) actual concentration levels at the monitoring stations, 2) deposition at the monitoring stations, 3) seasonal variations and 4) long term trends in concentrations and depositions are mainly based on the direct measurements. These are furthermore used to validate the results of the model calculations. Calculations and conclusions concerning: 1) depositions to land surface and to the individual marine water, 2) contributions from different emission

  13. Construction of a methodologically consistent time series of substance loads and their impacts in Germany. Pt. 2. Final report; Erstellung einer methodenkonsistenten Zeitreihe von Stoffeintraegen und ihren Wirkungen in Deutschland. T. 2. Abschlussbericht. Projektteile: (1) Kartierung von Deposition Loads fuer das Prognose-Jahr 2020: Modellierungs- und Kartierungsergebnisse, Kartenabbildungen, Grafiken und regionale Statistik. (2) Berechnung und Kartierung von Critical Loads und deren Ueberschreitungen fuer eine prognostizierte Deposition im Jahr 2020. Genfer Luftreinhaltekonvention der UNECE

    Energy Technology Data Exchange (ETDEWEB)

    Gauger, Thomas [Stuttgart Univ. (Germany). Inst. fuer Navigation; Nagel, Hans-Dieter; Schlutow, Angela; Scheuschner, Thomas [OEKO-DATA Gesellschaft fuer Oekosystemanalyse und Umweltdatenmanagement mbH, Strausberg (Germany)

    2013-01-15

    The contribution under consideration reports on the total deposition of anthropogenic emitted oxidized sulphur compounds, oxidized nitrogen compounds and reduced nitrogen compounds based on the emission prognosis of the BMU/UBA project 'Strategies for the reduction of the fine dust pollution for the year 2020. The emission prognoses are the fundament for the calculations with the LOTOS-EUROS model. The changes of the total deposition for sulphur compounds as well as nitrogen compounds between the years 2005 and 2020 are not large. For example, the total deposition of oxidized sulphur compounds from anthropogenic sources in the year 2020 is about 35% larger in comparison to the year 2005. In comparison to the year 2005, the total deposition of oxidized nitrogen compounds from anthropogenic sources in the year 2020 is about 21% larger.

  14. The Structural Basis of Ribozyme-Catalyzed RNA Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, M.P.; Scott, W.G.; /UC, Santa Cruz

    2007-07-12

    Life originated, according to the RNA World hypothesis, from self-replicating ribozymes that catalyzed ligation of RNA fragments. We have solved the 2.6 angstrom crystal structure of a ligase ribozyme that catalyzes regiospecific formation of a 5' to 3' phosphodiester bond between the 5'-triphosphate and the 3'-hydroxyl termini of two RNA fragments. Invariant residues form tertiary contacts that stabilize a flexible stem of the ribozyme at the ligation site, where an essential magnesium ion coordinates three phosphates. The structure of the active site permits us to suggest how transition-state stabilization and a general base may catalyze the ligation reaction required for prebiotic RNA assembly.

  15. Te-doping of self-catalyzed GaAs nanowires

    International Nuclear Information System (INIS)

    Tellurium (Te)-doping of self-catalyzed GaAs nanowires (NWs) grown by molecular beam epitaxy is reported. The effect of Te-doping on the morphological and crystal structure of the NWs is investigated by scanning electron microscopy and high-resolution transmission electron microscopy. The study reveals that the lateral growth rate increases and axial growth rate decreases with increasing Te doping level. The changes in the NW morphology can be reverted to some extent by changing the growth temperature. At high doping levels, formation of twinning superlattice is observed alongside with the (111)-facetted sidewalls. Finally, the incorporation of Te is confirmed by Raman spectroscopy

  16. Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation.

    Science.gov (United States)

    Yedage, Subhash L; Bhanage, Bhalchandra M

    2016-05-20

    This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level. PMID:27088815

  17. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak

    2015-08-01

    Full Text Available Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this uncommon class of hindered triazoles will accelerate exploration of their therapeutic potential. The superior activity of copper(II triflate in the formation of triazoles from sensitive alkyne substrates extends to simple terminal alkynes.

  18. Kinetics of the Esterification Reaction between Pentanoic Acid and Methanol Catalyzed by Noncorrosive Cation Exchange Resin

    OpenAIRE

    Sharma, M.; Toor, A. P.; R. K. Wanchoo

    2014-01-01

    Methyl pentanoate, commonly known as methyl valerate, is the methyl ester of pentanoic acid (valeric acid) with a fruity odour. Methyl pentanoate is commonly used in fragrances, beauty care, soap, laundry detergents at levels of 0.1 – 1 %. In its very pure form (purity 99.5 %) it is used as a plasticizer in the manufacture of plastics. In the present investigation, kinetics of esterification of pentanoic acid with methanol catalyzed by heterogeneous catalyst in a batch-type reactor is reporte...

  19. Synthesis of phytuberin. 4-endo-tet acid-catalyzed cyclization of alpha-hydroxy epoxides.

    Science.gov (United States)

    Prangé, Thierry; Rodríguez, María S; Suárez, Ernesto

    2003-05-30

    The total synthesis of phytuberin, a phytoalexin of the Solanum genus, from (-)-alpha-santonin is reported. The key steps include (a) reductive cleavage of the C-O bond of the gamma-lactone with concomitant protection of the C1 double bond, (b) Sharpless stereocontrolled hydroxy-assisted epoxidation of allylic alcohol 6 and simultaneous deprotection of the C1 double bond, (c) a rare 4-endo-tet acid-catalyzed cyclization of an alpha-hydroxy epoxide, and (d) an unprecedented 4-exo selenocyclization of a homoallylic alcohol. PMID:12762747

  20. Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

    Science.gov (United States)

    Schmid, Thibault E; Drissi-Amraoui, Sammy; Crévisy, Christophe; Baslé, Olivier

    2015-01-01

    Summary The copper-catalyzed asymmetric conjugate addition (ACA) of nucleophiles onto polyenic Michael acceptors represents an attractive and powerful methodology for the synthesis of relevant chiral molecules, as it enables in a straightforward manner the sequential generation of two or more stereogenic centers. In the last decade, various chiral copper-based catalysts were evaluated in combination with different nucleophiles and Michael acceptors, and have unambiguously demonstrated their usefulness in the control of the regio- and enantioselectivity of the addition. The aim of this review is to report recent breakthroughs achieved in this challenging field. PMID:26734090

  1. Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

    Directory of Open Access Journals (Sweden)

    Thibault E. Schmid

    2015-12-01

    Full Text Available The copper-catalyzed asymmetric conjugate addition (ACA of nucleophiles onto polyenic Michael acceptors represents an attractive and powerful methodology for the synthesis of relevant chiral molecules, as it enables in a straightforward manner the sequential generation of two or more stereogenic centers. In the last decade, various chiral copper-based catalysts were evaluated in combination with different nucleophiles and Michael acceptors, and have unambiguously demonstrated their usefulness in the control of the regio- and enantioselectivity of the addition. The aim of this review is to report recent breakthroughs achieved in this challenging field.

  2. Gold-catalyzed direct alkynylation of tryptophan in peptides using TIPS-EBX

    Science.gov (United States)

    Tolnai, Gergely L; Brand, Jonathan P

    2016-01-01

    Summary The selective functionalization of peptides containing only natural amino acids is important for the modification of biomolecules. In particular, the installation of an alkyne as a useful handle for bioconjugation is highly attractive, but the use of a carbon linker is usually required. Herein, we report the gold-catalyzed direct alkynylation of tryptophan in peptides using the hypervalent iodine reagent TIPS-EBX (1-[(triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one). The reaction proceeded in 50–78% yield under mild conditions and could be applied to peptides containing other nucleophilic and aromatic amino acids, such as serine, phenylalanine or tyrosine. PMID:27340466

  3. Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

    OpenAIRE

    Tenn, William J., III; Conley, Brian L.; Hovelmann, Claas H.; Ahlquist, Marten; Nielsen, Robert J.; Ess, Daniel H.; Oxgaard, Jonas; Bischof, Steven M.; Goddard, William A.; Periana, Roy A.

    2009-01-01

    We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. T...

  4. Temperature dependence of turnover in a Sc(OTf)3-catalyzed intramolecular Schmidt reaction

    Science.gov (United States)

    Fehl, Charlie; Hirt, Erin E.; Li, Sze-Wan; Aubé, Jeffrey

    2015-01-01

    The intramolecular Schmidt reaction of ketones and tethered azides is an efficient method for the generation of amides and lactams. This reaction is catalyzed by Lewis acids, which tightly bind the strongly basic amide product and result in product inhibition. We report herein conditions to achieve a catalytic Schmidt reaction using substoichiometric amounts of the heat-stable Lewis acid Sc(OTf)3. This species was shown to effectively release products of the Schmidt reaction in a temperature-dependent fashion. Thus, heat was able to promote catalyst turnover. A brief substrate scope was conducted using these conditions. PMID:26085693

  5. Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquids:Effect of Specific Ions and Reaction Parameters

    Institute of Scientific and Technical Information of China (English)

    王俊; 李晶; 张磊霞; 顾双双; 吴福安

    2013-01-01

    Caffeic acid phenethyl ester (CAPE) is a rare, naturally occurring phenolic food additive. This work systematically reported fundamental data on conversion of caffeic acid (CA), yield of CAPE, and reactive selectiv-ity during the lipase-catalyzed esterification process of CA and phenylethanol (PE) in ionic liquids (ILs). Sixteen ILs were selected as the reaction media, and the relative lipase-catalyzed synthesis properties of CAPE were meas-ured in an effort to enhance the yield of CAPE with high selectivity. The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE. [Emim][Tf2N] was selected as the optimal reaction media. The optimal parameters were as follows by response surface methodology (RSM):reaction temperature, 84.0 °C;mass ratio of Novozym 435 to CA, 14︰1;and molar ratio of PE to CA, 16︰1. The highest reactive selectivity of CAPE catalyzed by Novozym 435 in [Emim][Tf2N] reached 64.55%(CA conversion 98.76%and CAPE yield 63.75%, respectively). Thus, lipase-catalyzed esterifica-tion in ILs is a promising method suitable for CAPE production.

  6. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Qinhua Huang

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I{sub 2}, ICl, PhSeCl, PhSCl and p-O{sub 2}NC{sub 6}H{sub 4}SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that

  7. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou

    2015-12-01

    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  8. Nickel-Catalyzed Aromatic C-H Functionalization.

    Science.gov (United States)

    Yamaguchi, Junichiro; Muto, Kei; Itami, Kenichiro

    2016-08-01

    Catalytic C-H functionalization using transition metals has received significant interest from organic chemists because it provides a new strategy to construct carbon-carbon bonds and carbon-heteroatom bonds in highly functionalized, complex molecules without pre-functionalization. Recently, inexpensive catalysts based on transition metals such as copper, iron, cobalt, and nickel have seen more use in the laboratory. This review describes recent progress in nickel-catalyzed aromatic C-H functionalization reactions classified by reaction types and reaction partners. Furthermore, some reaction mechanisms are described and cutting-edge syntheses of natural products and pharmaceuticals using nickel-catalyzed aromatic C-H functionalization are presented. PMID:27573407

  9. Molecular Mechanism by which One Enzyme Catalyzes Two Reactions

    Science.gov (United States)

    Nishimasu, Hiroshi; Fushinobu, Shinya; Wakagi, Takayoshi

    Unlike ordinary enzymes, fructose-1,6-bisphosphate (FBP) aldolase/phosphatase (FBPA/P) catalyzes two distinct reactions : (1) the aldol condensation of dihydroxyacetone phosphate (DHAP) and glyceraldehyde-3-phosphate to FBP, and (2) the dephosphorylation of FBP to fructose-6-phosphate. We solved the crystal structures of FBPA/P in complex with DHAP (its aldolase form) and FBP (its phosphatase form). The crystal structures revealed that FBPA/P exhibits the dual activities through a dramatic conformational change in the active-site architecture. Our findings expand the conventional concept that one enzyme catalyzes one reaction.

  10. Muon-catalyzed fusion theory: Introduction and review

    International Nuclear Information System (INIS)

    Muon-catalyzed fusion (μCF) has proved to be a fruitful subject for basic physics research as well as a source of cold nuclear fusion. Experiments have demonstrated that over 100 fusions per muon can be catalyzed by formation of the dtμ molecule in mixtures of deuterium and tritium. After a brief review of the subject's history, the dtμ catalysis cycle and the principal relations used in its analysis are described. Some of the important processes in the μCF cycle are then discussed. Finally, the status of current research is appraised. 52 refs., 7 figs

  11. Recent advances in copper-catalyzed asymmetric coupling reactions

    Science.gov (United States)

    2015-01-01

    Summary Copper-catalyzed (or -mediated) asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds. PMID:26734106

  12. The mechanism of Fe (Ⅲ)-catalyzed ozonation of phenol

    Institute of Scientific and Technical Information of China (English)

    竹湘锋; 徐新华

    2004-01-01

    Fe (Ⅲ)-catalyzed ozonation yielded better degradation rate and extent of COD (Chemical Oxygen Demand) or oxalic acid as compared with oxidation by ozone alone. Two parameters with strong effects on the efficiency of ozonation are pH of the solution and the catalyst (Fe3+) dosage. The existence of a critical pH value determining the catalysis of Fe (Ⅲ) in acid conditions was observed in phenol and oxalic acid systems. The best efficiency of catalysis was obtained at a moderate concentration of the catalyst. A reasonable mechanism of Fe (Ⅲ)-catalyzed ozonation of phenol was obtained based on the results and literature.

  13. Distribution And Mineralogy Of The Clay Deposits In Saudi Arabia

    OpenAIRE

    Al Mohandis, Ahmed A. [احمد عبد القادر المهندس

    1993-01-01

    The main goal of this paper is to characterize the mineral clay deposits in Saudi Arabia; especially their mineral composition, deposit size, geological setting and possible uses. Different published reports and papers on clay deposits of Saudi Arabia have been reviewed. Three major clay deposits have been studied by XRD, DTA and chemical analyses. Saudi clay deposits consist generally of kaolinite as a major mineral, and small amounts other clay minerals, such as montmorillonite and illite. ...

  14. New simple deposition model based on reassessment of global fallout data 1954 – 1976. Final report from the NKS-B activity DepEstimates

    OpenAIRE

    Pálsson, Sigurður Emil; Bergan, Tone D.; Howard, Brenda J.; Ikäheimonen, Tarja K.; Isaksson, Mats; Nielsen, Sven P.; Paatero, Jussi

    2012-01-01

    Atmospheric testing of nuclear weapons began in 1945 and largely ceased in 1963. This testing is the major cause of distribution of man-made radionuclides over the globe and constitutes a background that needs to be considered when effects of other sources are estimated. The main radionuclides of long term (after the first months) concern are generally assumed to be 137Cs and 90Sr.It has been known for a long time that the deposition density of 137Cs and 90Sr is approximately proportional to ...

  15. Common Inorganic Salts Catalyze the Transformations of Organic Compounds in Atmospheric Aerosols

    Science.gov (United States)

    Noziere, B.; Dziedzic, P.; Cordova, A.

    2008-12-01

    This presentation reports the discovery that inorganic salts that are ubiquitous in atmospheric aerosols are efficient catalysts for the transformations of organic compounds in these aerosols, by reactions such as aldol condensation or acetal formation.1 For some of these salts, these catalytic properties were not even known in chemistry.2 Kinetic and product studies of these reactions will be presented for carbonyl compounds such as acetaldehyde, acetone, and glyoxal,1,3 and compared with previously known catalysts such as the recently discovered amino acids.4,5 These studies show that these salts make the reactions as fast in typical tropospheric aerosols as in concentrated sulfuric acid. These reactions produce secondary "fulvic" compounds that absorb light in the near UV and visible and would affect the optical properties of aerosols.1,5 They would also account for the depletion of glyoxal recently reported in Mexico city.3 Thus, while acid catalysis is several orders of magnitudes too slow to be significant in tropospheric aerosols, this work identifies new processes that should be ubiquitous in these aerosols and important for atmospheric chemistry. Refs. 1Noziere, B., Dziedzic, P., Cordova, A., Common inorganic ions catalyze chemical reactions of organic compounds in atmospheric aerosols, Submitted, 2008. 2 Noziere, B., Cordova, A., A novel catalyst for aldol condensation reaction, patent pending 02/10/2007. 3Noziere, B., Dziedzic, P., Cordova, A., Products and kinetics of the liquid-phase reaction of glyoxal catalyzed by inorganic ions, Submitted to J. Phys. Chem. A, 2008. 4Noziere, B., and Cordova, A., A Kinetic and Mechanistic Study of the Amino Acid-Catalyzed Aldol Condensation of Acetaldehyde in Aqueous and Salt Solutions, J. Phys. Chem. A, 112, 2827, 2008. 5Noziere, B., Dziedzic, P., and Cordova, A., The Formation of Secondary Light-Absorbing "fulvic-like" Oligomers: A Common Process in Aqueous and Ionic Atmospheric Particles?, Geophys. Res. Lett., 34

  16. Uranium deposits of Australia to 1975

    International Nuclear Information System (INIS)

    This bibliography provides a retrospective account of Australian uranium deposits, particularly the unpublished materials in the Australian Capital Territory. Some abstracts are included. Occurrences, mineralogy, ore genesis, structural controls and the eonomic geology of uranium deposits are covered but the mining of uranium, exploration reports, surveys, environmental aspects and controversial materials are not

  17. Plasma Deposition of Doped Amorphous Silicon

    Science.gov (United States)

    Calcote, H. F.

    1985-01-01

    Pair of reports present further experimental details of investigation of plasma deposition of films of phosphorous-doped amosphous silicon. Probe measurements of electrical resistance of deposited films indicated films not uniform. In general, it appeared that resistance decreased with film thickness.

  18. Energy deposition in NSRR test fuels

    International Nuclear Information System (INIS)

    Interpretation of fuel performance data collected during inpile testing in the NSRR requires a knowledge of the energy deposition or enthalpy increase in each sample tested. The report describes the results of absolute measurement of fission products and contents of uranium in irradiated test fuels which were performed to determine the energy deposition. (auth.)

  19. Conversion of aminodeoxychorismate synthase into anthranilate synthase with Janus mutations: mechanism of pyruvate elimination catalyzed by chorismate enzymes.

    Science.gov (United States)

    Culbertson, Justin E; Chung, Dong hee; Ziebart, Kristin T; Espiritu, Eduardo; Toney, Michael D

    2015-04-14

    The central importance of chorismate enzymes in bacteria, fungi, parasites, and plants combined with their absence in mammals makes them attractive targets for antimicrobials and herbicides. Two of these enzymes, anthranilate synthase (AS) and aminodeoxychorismate synthase (ADCS), are structurally and mechanistically similar. The first catalytic step, amination at C2, is common between them, but AS additionally catalyzes pyruvate elimination, aromatizing the aminated intermediate to anthranilate. Despite prior attempts, the conversion of a pyruvate elimination-deficient enzyme into an elimination-proficient one has not been reported. Janus, a bioinformatics method for predicting mutations required to functionally interconvert homologous enzymes, was employed to predict mutations to convert ADCS into AS. A genetic selection on a library of Janus-predicted mutations was performed. Complementation of an AS-deficient strain of Escherichia coli grown on minimal medium led to several ADCS mutants that allow growth in 6 days compared to 2 days for wild-type AS. The purified mutant enzymes catalyze the conversion of chorismate to anthranilate at rates that are ∼50% of the rate of wild-type ADCS-catalyzed conversion of chorismate to aminodeoxychorismate. The residues mutated do not contact the substrate. Molecular dynamics studies suggest that pyruvate elimination is controlled by the conformation of the C2-aminated intermediate. Enzymes that catalyze elimination favor the equatorial conformation, which presents the C2-H to a conserved active site lysine (Lys424) for deprotonation and maximizes stereoelectronic activation. Acid/base catalysis of pyruvate elimination was confirmed in AS and salicylate synthase by showing incorporation of a solvent-derived proton into the pyruvate methyl group and by solvent kinetic isotope effects on pyruvate elimination catalyzed by AS. PMID:25710100

  20. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Guohou [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); Chen, Xiaofeng, E-mail: chenxf@scut.edu.cn [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); Dong, Hua [National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); School of Biological Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China)

    2013-10-15

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. {sup 29}Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. - Graphical abstract: The morphologies and microstructures of acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were observed by scanning electron microscope and transmission electron microscope. MBGMs-A exhibits a dense structure and a porous can be observed in MBGMs-B. The microspheres have a quick inducing-apatite formation ability and show a sustained release of alendronate (AL). Highlights: • A rapid method was reported to prepare mesoporous bioactive glass microspheres. • The addition of ammonia significantly shortens the preparation time. • Acid and acid-alkali co-catalyzed microspheres were studied for the first time. • The materials exhibited excellent in vitro bioactivity and

  1. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery

    International Nuclear Information System (INIS)

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. 29Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. - Graphical abstract: The morphologies and microstructures of acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were observed by scanning electron microscope and transmission electron microscope. MBGMs-A exhibits a dense structure and a porous can be observed in MBGMs-B. The microspheres have a quick inducing-apatite formation ability and show a sustained release of alendronate (AL). Highlights: • A rapid method was reported to prepare mesoporous bioactive glass microspheres. • The addition of ammonia significantly shortens the preparation time. • Acid and acid-alkali co-catalyzed microspheres were studied for the first time. • The materials exhibited excellent in vitro bioactivity and drug

  2. In vivo activity in a catalytic antibody-prodrug system: Antibody catalyzed etoposide prodrug activation for selective chemotherapy

    OpenAIRE

    Shabat, Doron; Lode, Holger N.; Pertl, Ursula; Reisfeld, Ralph A.; Rader, Christoph; Lerner, Richard A.; Barbas, Carlos F.

    2001-01-01

    Effective chemotherapy remains a key issue for successful cancer treatment in general and neuroblastoma in particular. Here we report a chemotherapeutic strategy based on catalytic antibody-mediated prodrug activation. To study this approach in an animal model of neuroblastoma, we have synthesized prodrugs of etoposide, a drug widely used to treat this cancer in humans. The prodrug incorporates a trigger portion designed to be released by sequential retro-aldol/retro-Michael reactions catalyz...

  3. Copper-Catalyzed Coupling of 2-Siloxy-1-alkenes and Diazocarbonyl Compounds: Approach to Multisubstituted Furans, Pyrroles, and Thiophenes.

    Science.gov (United States)

    Tan, Wei Wen; Yoshikai, Naohiko

    2016-07-01

    We report herein copper(II)-catalyzed cyclization reactions of silyl enol ethers derived from methyl ketones with α-diazo-β-ketoesters or α-diazoketones to afford 2-siloxy-2,3-dihydrofuran derivatives or 2,3,5-trisubstituted furans, respectively, under mild conditions. The former cyclization products serve as versatile 1,4-diketone surrogates, allowing facile preparation of 2,3,5-trisubstituted furans, pyrroles, and thiophenes. PMID:27259097

  4. Anti-Markovnikov Hydroalkylation of Allylic Amine Derivatives via a Palladium–Catalyzed Reductive Cross-Coupling Reaction

    OpenAIRE

    DeLuca, Ryan J.; Sigman, Matthew S.

    2011-01-01

    A palladium-catalyzed hydroalkylation reaction of allylic amine derivatives by alkylzinc reagents is reported. This reductive cross-coupling yields anti-Markovnikov products using a variety of allylic amine protecting groups. Preliminary mechanistic studies suggest that a reversible β-hydride elimination/hydride insertion process furnishes the primary Pd-alkyl intermediate, which then undergoes transmetallation followed by reductive elimination to form a new sp3-sp3 carbon-carbon bond.

  5. Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides.

    Science.gov (United States)

    Zhang, Tao; Hu, Xuejiao; Wang, Zhen; Yang, Tiantian; Sun, Hao; Li, Guigen; Lu, Hongjian

    2016-02-24

    An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention. PMID:26712274

  6. Discovery of a P450-catalyzed step in vindoline biosynthesis: a link between the aspidosperma and eburnamine alkaloids.

    Science.gov (United States)

    Kellner, Franziska; Geu-Flores, Fernando; Sherden, Nathaniel H; Brown, Stephanie; Foureau, Emilien; Courdavault, Vincent; O'Connor, Sarah E

    2015-05-01

    Here we report the discovery of a cytochrome P450 that is required for the biosynthesis of vindoline, a plant-derived natural product used for semi-synthesis of several anti-cancer drugs. This enzyme catalyzes the formation of an epoxide that can undergo rearrangement to yield the vincamine-eburnamine backbone, thereby providing evidence for the long-standing hypothesis that the aspidosperma- and eburnamine-type alkaloids are biosynthetically related. PMID:25850027

  7. Palladium-Catalyzed Dearomative Allylic Alkylation of Indoles with Alkynes To Synthesize Indolenines with C3-Quarternary Centers.

    Science.gov (United States)

    Gao, Shang; Wu, Zijun; Fang, Xinxin; Lin, Aijun; Yao, Hequan

    2016-08-01

    A palladium-catalyzed dearomative allylic alkylation of indoles with alkynes to construct indolenines with C3-quarternary centers was reported. The in situ formed arylallene intermediate omitted the need to install leaving groups on the allylic compounds and employ extra oxidants to oxidize the allylic C-H bonds. The reaction exhibited good functional group tolerance and high atom economy. Moreover, the reaction was further expanded to synthesize pyrroloindolines and furanoindolines. PMID:27442021

  8. Tryptophanase-Catalyzed l-Tryptophan Synthesis from d-Serine in the Presence of Diammonium Hydrogen Phosphate

    OpenAIRE

    Fujii Noriko; Haruka Ozaki; Takeshi Saito; Akihiko Shimada

    2009-01-01

    Tryptophanase, an enzyme with extreme absolute stereospecificity for optically active stereoisomers, catalyzes the synthesis of L-tryptophan from L-serine and indole through a β-substitution mechanism of the ping-pong type, and has no activity on D-serine. We previously reported that tryptophanase changed its stereospecificity to degrade D-tryptophan in highly concentrated diammonium hydrogen phosphate, (NH4)2HPO4 solution. The present study provided the same stereospecific change seen in the...

  9. Convergent Synthesis of Diverse Nitrogen Heterocycles via Rh(III)-Catalyzed C-H Conjugate Addition/Cyclization Reactions.

    Science.gov (United States)

    Weinstein, Adam B; Ellman, Jonathan A

    2016-07-01

    The development of Rh(III)-catalyzed C-H conjugate addition/cyclization reactions that provide access to synthetically useful fused bi- and tricyclic nitrogen heterocycles is reported. A broad scope of C-H functionalization substrates and electrophilic olefin coupling partners is effective, and depending on the nature of the directing group, cyclic imide, amide, or heteroaromatic products are obtained. An efficient synthesis of a pyrrolophenanthridine alkaloid natural product, oxoassoanine, highlights the utility of this method. PMID:27337641

  10. Catalyzing Employee Change with Transformative Learning

    Science.gov (United States)

    Franz, Nancy

    2010-01-01

    Businesses, organizations, and government agencies have invested heavily in employee training. The American Society for Training and Development (ASTD) reports these costs as 2.15% of payroll (ASTD, 2008). A large amount of this investment is directed at improving employee knowledge and skills. Although most organizations are good at this, often a…

  11. Recent developments in gold-catalyzed cycloaddition reactions

    Directory of Open Access Journals (Sweden)

    Fernando López

    2011-08-01

    Full Text Available In the last years there have been extraordinary advances in the development of gold-catalyzed cycloaddition processes. In this review we will summarize some of the most remarkable examples, and present the mechanistic rational underlying the transformations.

  12. Ruthenium-catalyzed C–H activation of thioxanthones

    OpenAIRE

    Danny Wagner; Stefan Bräse

    2015-01-01

    Thioxanthones – being readily available in one step from thiosalicylic acid and arenes – were used in ruthenium-catalyzed C–H-activation reaction to produce 1-mono- or 1,8-disubstituted thioxanthones in good to excellent yields. Scope and limitation of this reaction are presented.

  13. Ruthenium-catalyzed C–H activation of thioxanthones

    Science.gov (United States)

    Wagner, Danny

    2015-01-01

    Summary Thioxanthones – being readily available in one step from thiosalicylic acid and arenes – were used in ruthenium-catalyzed C–H-activation reaction to produce 1-mono- or 1,8-disubstituted thioxanthones in good to excellent yields. Scope and limitation of this reaction are presented. PMID:25977717

  14. DNA strand exchange catalyzed by molecular crowding in PEG solutions

    KAUST Repository

    Feng, Bobo

    2010-01-01

    DNA strand exchange is catalyzed by molecular crowding and hydrophobic interactions in concentrated aqueous solutions of polyethylene glycol, a discovery of relevance for understanding the function of recombination enzymes and with potential applications to DNA nanotechnology. © 2010 The Royal Society of Chemistry.

  15. Oxo-rhenium catalyzed reductive coupling and deoxygenation of alcohols.

    Science.gov (United States)

    Kasner, Gabrielle R; Boucher-Jacobs, Camille; Michael McClain, J; Nicholas, Kenneth M

    2016-06-01

    Representative benzylic, allylic and α-keto alcohols are deoxygenated to alkanes and/or reductively coupled to alkane dimers by reaction with PPh3 catalyzed by (PPh3)2ReIO2 (1). The newly discovered catalytic reductive coupling reaction is a rare C-C bond-forming transformation of alcohols. PMID:27174412

  16. Transfer Methane to Fragrant Hydrocarbon by Direct Catalyzed Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ Sponsored by NSFC,a research project -"Transfer methane to fragrant hydrocarbon by direct catalyzed dehydrogenation",directed by Prof.Xin Bao from Dalian Institute of Chemical Physics of CAS,honored the 2nd class National Science & Technology Award in 2005.

  17. Polyphosphorous acid catalyzed cyclization in the synthesis of cryptolepine derivatives

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    11-Oxo-10,11-dihydroxy-5H-indolo[3,2,b]quinoline7-carboxylic acid was obtained specifically by polyphosphorous acid catalyzed cyclization with optimal reaction conditions. Biological assays showed that it potentially inhibits the proteasomal chymotrypsin-like activity in vitro and suppresses breast cancer cell growth.

  18. Kinetic Resolution of Aryl Alkenylcarbinols Catalyzed by Fc-PIP

    Institute of Scientific and Technical Information of China (English)

    胡斌; 孟萌; 姜山山; 邓卫平

    2012-01-01

    An effective kinetic resolution of a variety of aryl alkenylcarbinols catalyzed by nonenzymatic acyl transfer catalyst Fe-PIP was developed, affording corresponding unreacted alcohols in good to excellent ee value up to 99% and with selectivity factors up to 24.

  19. Lactam hydrolysis catalyzed by mononuclear metallo-ß-bactamases

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U;

    2003-01-01

    Two central steps in the hydrolysis of lactam antibiotics catalyzed by mononuclear metallo-beta-lactamases, formation of the tetrahedral intermediate and its breakdown by proton transfer, are studied for model systems using the density functional B3LYP method. Metallo-beta-lactamases have two met...

  20. Mechanistic approaches to palladium-catalyzed alkene difunctionalization reactions

    OpenAIRE

    Jensen, Katrina H.; Sigman, Matthew S.

    2008-01-01

    Alkene difunctionalization, the addition of two functional groups across a double bond, exemplifies a class of reactions with significant synthetic potential. This emerging area examines recent developments of palladium-catalyzed difunctionalization reactions, with a focus on mechanistic strategies that allow for functionalization of a common palladium alkyl intermediate.

  1. A Palladium-catalyzed Synthesis of 2-Substituted Indoles

    OpenAIRE

    Kasahara, Akira; YANAI, Hiroshi; Murakami, Satoshi

    1986-01-01

    Abstract In the presence of palladium (II) acetate, tri-o-tolylphosphine, and triethylamine, o-bromoaniline derivatives react readily with olefins such as ethylene, 1-hexene, styrene, ethyl acrylate, and acrylonitriIe, to produce o-alkenylaniline derivatives. A palladium (II) -catalyzed cyclization of o-alkenylaniline p-toluenesulfonamide led to a formation of a number of 1-tosylindole derivatives.

  2. Metal-Catalyzed Cleavage of tRNA[superscript Phe

    Science.gov (United States)

    Kirk, Sarah R.; Silverstein, Todd P.; McFarlane Holman, Karen L.

    2008-01-01

    This laboratory project is one component of a semester-long advanced biochemistry laboratory course that uses several complementary techniques to study tRNA[superscript Phe] conformational changes induced by ligand binding. In this article we describe a set of experiments in which students assay metal-catalyzed hydrolysis of tRNA[superscript Phe]…

  3. Gal3 Catalyzed Tetrahydropyranylation of Alcohols and Phenols

    Institute of Scientific and Technical Information of China (English)

    SUN, Pei-Pei(孙培培); HU, Zhi-Xin(胡志新)

    2004-01-01

    In dichloromethane, the nucleophilic addition of alcohols or phenols to 3,4-dihydro-2H-pyran (DHP) was catalyzed effectively by gallium triiodide which was generated in situ by the reaction of gallium metal and iodine to give the corresponding tetrahydropyranyl acetals in good to excellent yields.

  4. CU(II): catalyzed hydrazine reduction of ferric nitrate

    International Nuclear Information System (INIS)

    A method is described for producing ferrous nitrate solutions by the cupric ion-catalyzed reduction of ferric nitrate with hydrazine. The reaction is complete in about 1.5 hours at 400C. Hydrazoic acid is also produced in substantial quantities as a reaction byproduct

  5. Palladium(0)-catalyzed methylenecyclopropanation of norbornenes with vinyl bromides.

    Science.gov (United States)

    Mao, Jiangang; Bao, Weiliang

    2014-05-16

    Highly strained methylenecyclopropane derivatives have been achieved via a novel and efficient Pd(0)-catalyzed domino reaction. The formal [2 + 1] cycloaddition reaction of vinyl bromides to norbornenes involves a Heck-type coupling and a C(sp(2))-H bond activation. PMID:24784731

  6. Sediment-hosted stratabound copper deposit model: Chapter M in Mineral deposit model for resource assessment

    Science.gov (United States)

    Hayes, Timothy S.; Cox, Dennis P.; Bliss, James D.; Piatak, Nadine M.; Seal, Robert R., II

    2015-01-01

    This report contains a descriptive model of sediment-hosted stratabound copper (SSC) deposits that supersedes the model of Cox and others (2003). This model is for use in assessments of mineral resource potential. SSC deposits are the second most important sources of copper in the world behind porphyry copper deposits. Around 20 percent of the copper in the world is produced from this class of deposits. They are also the most important sources of cobalt in the world, and they are fourth among classes of ore deposits in production of silver. SSC deposits are the basis of the economies of three countries: Democratic Republic of Congo, Poland, and Zambia. This report provides a description of the key features of SSC deposits; it identifies their tectonic-sedimentary environments; it illustrates geochemical, geophysical, and geoenvironmental characteristics of SSC deposits; it reviews and evaluates hypotheses on how these deposits formed; it presents exploration and assessment guides; and it lists some gaps in our knowledge about the SSC deposits. A summary follows that provides overviews of many subjects concerning SSC deposits.

  7. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    Science.gov (United States)

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  8. Final report of the rock sealing project - Sealing of the near-field rock around deposition holes by use of bentonite grouts

    International Nuclear Information System (INIS)

    Test 1 of the rock sealing project comprised determ ination of the hydraulic properties of the rock around large-diameter holes like canister deposition holes or TBM tunnels and attempts were made to seal the fractures intersecting such holes with bentonite slurry. The heater holes from the buffer mass test which are 76 cm in diameter, were used and injection made from inside the holes with a specially designed device using dynamic injection technique. The hydraulic properties of the surrounding rock were tested by use of the same device before and after the injections, as well as after a 3 months heat pulse. The results were interpreted by applying a special derived grout flow model and by analyzing the rock response through different calculation techniques, as well as by localizing the injected grout by rock excavation. The experiments showed that grouting of fractured rock by using the applied technique can give very significant sealing. (au)

  9. Enhanced activity and interfacial durability study of ultra low Pt based electrocatalysts prepared by ion beam assisted deposition (IBAD) method

    International Nuclear Information System (INIS)

    Ultra low loading noble metal (0.04-0.12 mgPt/cm2) based electrodes were obtained by direct metallization of non-catalyzed gas diffusion layers via dual ion beam assisted deposition (IBAD) method. Fuel cell performance results reported earlier indicate significant improvements in terms of mass specific power density of 0.297 gPt/kW with 250 A thick IBAD deposit (0.04 mgPt/cm2 for a total MEA loading of 0.08 mgPt/cm2) at 0.65 V in contrast to the state of the art power density of 1.18 gPt/kW using 1 mgPt(MEA)/cm2 at 0.65 V. In this article we report the peroxide radical initiated attack of the membrane electrode assembly utilizing IBAD electrodes in comparison to commercially available E-TEK (now BASF Fuel Cell GmbH) electrodes and find the pathway of membrane degradation as well. A novel segmented fuel cell is used for this purpose to relate membrane degradation to peroxide generation at the electrode/electrolyte interface by means of systematic pre and post analyses of the membrane are presented. Also, we present the results of in situ X-ray absorption spectroscopy (XAS) experiments to elucidate the structure/property relationships of these electrodes that lead to superior performance in terms of gravimetric power density obtained during fuel cell operation.

  10. Electro-Deposition Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — The electro-deposition laboratory can electro-deposit various coatings onto small test samples and bench level prototypes. This facility provides the foundation for...

  11. Calcium Pyrophosphate Deposition (CPPD)

    Science.gov (United States)

    ... Patient / Caregiver Diseases & Conditions Calcium Pyrophosphate Deposition (CPPD) Calcium Pyrophosphate Deposition (CPPD) Fast Facts The risk of ... young people, too. Proper diagnosis depends on detecting calcium pyrophosphate crystals in the fluid of an affected ...

  12. 4-Dimenthylaminopyridine or Acid-Catalyzed Synthesis of Esters: A Comparison

    Science.gov (United States)

    van den Berg, Annemieke W. C.; Hanefeld, Ulf

    2006-01-01

    A set of highly atom-economic experiments was developed to highlight the differences between acid- and base-catalyzed ester syntheses and to introduce the principles of atom economy. The hydrochloric acid-catalyzed formation of an ester was compared with the 4-dimethylaminopyradine-catalyzed ester synthesis.

  13. Kinetics of Imidazole Catalyzed Ester Hydrolysis: Use of Buffer Dilutions to Determine Spontaneous Rate, Catalyzed Rate, and Reaction Order.

    Science.gov (United States)

    Lombardo, Anthony

    1982-01-01

    Described is an advanced undergraduate kinetics experiment using buffer dilutions to determine spontaneous rate, catalyzed rate, and reaction order. The reaction utilized is hydrolysis of p-nitro-phenyl acetate in presence of imidazole, which has been shown to enhance rate of the reaction. (Author/JN)

  14. PCDD/F formation in an iron/potassium-catalyzed diesel particle filter.

    Science.gov (United States)

    Heeb, Norbert V; Zennegg, Markus; Haag, Regula; Wichser, Adrian; Schmid, Peter; Seiler, Cornelia; Ulrich, Andrea; Honegger, Peter; Zeyer, Kerstin; Emmenegger, Lukas; Bonsack, Peter; Zimmerli, Yan; Czerwinski, Jan; Kasper, Markus; Mayer, Andreas

    2013-06-18

    Catalytic diesel particle filters (DPFs) have evolved to a powerful environmental technology. Several metal-based, fuel soluble catalysts, so-called fuel-borne catalysts (FBCs), were developed to catalyze soot combustion and support filter regeneration. Mainly iron- and cerium-based FBCs have been commercialized for passenger cars and heavy-duty vehicle applications. We investigated a new iron/potassium-based FBC used in combination with an uncoated silicon carbide filter and report effects on emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs). The PCDD/F formation potential was assessed under best and worst case conditions, as required for filter approval under the VERT protocol. TEQ-weighted PCDD/F emissions remained low when using the Fe/K catalyst (37/7.5 μg/g) with the filter and commercial, low-sulfur fuel. The addition of chlorine (10 μg/g) immediately led to an intense PCDD/F formation in the Fe/K-DPF. TEQ-based emissions increased 51-fold from engine-out levels of 95 to 4800 pg I-TEQ/L after the DPF. Emissions of 2,3,7,8-TCDD, the most toxic congener (TEF = 1.0), increased 320-fold, those of 2,3,7,8-TCDF (TEF = 0.1) even 540-fold. Remarkable pattern changes were noticed, indicating a preferential formation of tetrachlorinated dibenzofurans. It has been shown that potassium acts as a structural promoter inducing the formation of magnetite (Fe3O4) rather than hematite (Fe2O3). This may alter the catalytic properties of iron. But the chemical nature of this new catalyst is yet unknown, and we are far from an established mechanism for this new pathway to PCDD/Fs. In conclusion, the iron/potassium-catalyzed DPF has a high PCDD/F formation potential, similar to the ones of copper-catalyzed filters, the latter are prohibited by Swiss legislation. PMID:23713673

  15. DNA Polymerase-Catalyzed DNA Network Growth

    OpenAIRE

    Keller, Sascha; Wang, Jie; Chandra, Madhaviah; Berger, Rüdiger; Marx, Andreas

    2008-01-01

    The distinct base pairing property of DNA is an advantageous phenomenon that has been exploited in the usage of DNA as scaffold for directed self-organization to form nanometer-sized objects in a desirable fashion. Herein we report the construction of three-dimensional DNA-based networks that can be generated and amplified by the DNA polymerase chain reaction (PCR). The approach is flexible allowing tuning of the meshes of the network by variation of the size of the template. Additionally, fu...

  16. Investigation of Cu growth phenomena on Ru substrate during electroless deposition using hydrazine as a reducing agent

    International Nuclear Information System (INIS)

    Cu growth phenomena during electroless deposition (ELD) on Ru substrate were investigated in this study. Different to the formaldehyde based Cu ELD bath, the use of hydrazine based Cu ELD bath facilitated the observation of Cu growth phenomena during ELD. The whole surface-catalyzed ELD occurred on Ru, and electrochemical quartz crystal microbalance as well as linear sweep voltammetry studies revealed that Cu covered Ru surface within a few seconds of ELD. Measurement of sheet resistance change confirmed that Cu nucleation on Ru was continuous with forming a film. During the period, Cu film growth was monitored by an atomic force microscope imaging, indicating that Cu was deposited on Ru preferentially, rather than on the deposited Cu at the initial stage of the deposition. The whole surface-catalyzed ELD achieved 55 nm gap-filling, and this showed the possibility of the practical adoption of ELD as a method for metallization in ultralarge-scale integration

  17. B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes.

    Science.gov (United States)

    Dziedzic, Rafal M; Saleh, Liban M A; Axtell, Jonathan C; Martin, Joshua L; Stevens, Simone L; Royappa, A Timothy; Rheingold, Arnold L; Spokoyny, Alexander M

    2016-07-27

    Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters. PMID:27384544

  18. Synthesis of Oxacyclic Scaffolds via Dual Ruthenium Hydride/Brønsted Acid‐Catalyzed Isomerization/Cyclization of Allylic Ethers

    DEFF Research Database (Denmark)

    Ascic, Erhad; Ohm, Ragnhild Gaard; Petersen, Rico;

    2014-01-01

    A ruthenium hydride/Brønsted acid‐catalyzed tandem sequence is reported for the synthesis of 1,3,4,9‐tetrahydropyrano[3,4‐b]indoles (THPIs) and related oxacyclic scaffolds. The process was designed on the premise that readily available allylic ethers would undergo sequential isomerization, first to...

  19. Un-catalyzed tandem Knoevenagel-Michael reaction for the synthesis of 4,4'-(arylmethylene)bis(7H-pyrazol-5-ols) in aqueous medium

    Institute of Scientific and Technical Information of China (English)

    Nilesh P. Tale; Girdharilal B. Tiwari; Nandkishor N. Karade

    2011-01-01

    An environmentally benign un-catalyzed one-pot synthesis of 4,4'-(arylmethylene)bis(7H-pyrazol-5-ols) has been reported via tandem Knoevenagel-Michael reaction of aldehydes with two equivalents of 3-methyl-l-phenyl-lH-pyrazol-5(4H)-one in aqueous medium.

  20. New Palladium-Catalyzed Domino Reaction with Intramolecular Ring Closure of an N-(2-Chloro-3-heteroaryl) arylamide: First Synthesis of Oxazolo[4,5-b] pyrazines

    DEFF Research Database (Denmark)

    Demmer, Charles S.; Hansen, Jacob C.; Kehler, Jan;

    2014-01-01

    lipophilicity and target interaction points are often desired. In this respect, the oxazolo[4,5-b]pyrazine is an attractive heterocyclic scaffold as it possesses increased water solubility as well as two additional hydrogen bonding acceptors. We here report a new Pd(II)-catalyzed domino reaction comprising the...

  1. Rhodium-Catalyzed Highly Regioselective C-H Arylation of Imidazo[1,2-a]pyridines with Aryl Halides and Triflates

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yi; He, Lin [Guandong Pharmaceutical Univ., Zhongshan (China); Yin, Guoqiang; Wu, Guojie; Cui, Yingde [Zhongkai Univ. of Agriculture and Engineering, Guangzhou (China)

    2013-08-15

    A convenient Rh-catalyzed C-H arylation of imidazo[1,2-a]pyridines with a variety of aryl halides or triflates has been reported. This process afforded a range of biaryl compounds in excellent yields and showed high activity and broad scope.

  2. Palladium-catalyzed cross-coupling reaction of diazo compounds and vinyl boronic acids: an approach to 1,3-diene compounds.

    Science.gov (United States)

    Xia, Yamu; Xia, Ying; Liu, Zhen; Zhang, Yan; Wang, Jianbo

    2014-08-15

    A palladium-catalyzed oxidative cross-coupling of vinyl boronic acids and cyclic α-diazocarbonyl compounds has been reported. The reaction constitutes an efficient method for the synthesis of 1,3-diene compounds bearing a ring structure. Mechanistically, the reaction involves migratory insertion of palladium carbene as the key step. PMID:25019414

  3. Selection of bentonite deposits

    International Nuclear Information System (INIS)

    The selection of bentonite deposits is to offer a supply base of backfill/buffer materials for high-level radioactive waste repository in China. In this paper the comprehensive evaluation criteria were discussed first, then a comprehensive comment on bentonite deposits in China was given. The properties of geographic distribution, origin, reserves and ore quality of bentonite deposits were also discussed. The comprehensive comparison studies on 12 large-sized bentonite deposits was presented. Based on the results obtained Gaomiaozi bentonite deposit, Inner Mongolia, was recommended as the first choice of backfill/buffer materials for repository in China. (author)

  4. Effect of carbon on the Ni catalyzed methane cracking reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jingde; Croiset, Eric; Ricardez–Sandoval, Luis, E-mail: laricard@uwaterloo.ca

    2014-08-30

    Highlights: • Effect of carbon deposition on kinetic properties of methane dissociation is studied. • Existence of surface and subsurface C atoms destabilized CH{sub x} species adsorption. • CH{sub x} activation is hindered with the deposition of C on and in the Ni (1 1 1) surface. - Abstract: To understand the effects of carbon atoms on the Ni catalyzed methane cracking reactions, methane dissociation on clean, surface-carbon-covered, and subsurface-carbon-accumulated Ni(1 1 1) surfaces were investigated using density functional theory (DFT). The results show that the existence of surface and subsurface C atoms destabilized the adsorption of the surface hydrocarbon species when compared to the clean Ni(1 1 1) surface. The projected density state (PDOS) analysis shows that the deposition of C atoms on and into the Ni surface modified the electronic structure of the Ni surface, and thus reduced the catalytic activity of the bonded Ni atoms. Moreover, it was found that the presence carbon atoms increase the CH{sub x} (x = 4–1) species activation barriers especially on the surface carbon covered (1/4 ML) Ni(1 1 1) surface, where CH{sub x} (x = 4–1) species encounter highest energy barrier for dissociation due to the electronic deactivation induced by C-Ni bonding and the strong repulsive carbon -CH{sub x} interaction. The calculations also show that CH{sub x} dissociation barriers are not affected by its neighboring C atom at low surface carbon coverage (1/9 ML). This work can be used to estimate more realistic kinetic parameters for this system.

  5. Effect of carbon on the Ni catalyzed methane cracking reaction: A DFT study

    International Nuclear Information System (INIS)

    Highlights: • Effect of carbon deposition on kinetic properties of methane dissociation is studied. • Existence of surface and subsurface C atoms destabilized CHx species adsorption. • CHx activation is hindered with the deposition of C on and in the Ni (1 1 1) surface. - Abstract: To understand the effects of carbon atoms on the Ni catalyzed methane cracking reactions, methane dissociation on clean, surface-carbon-covered, and subsurface-carbon-accumulated Ni(1 1 1) surfaces were investigated using density functional theory (DFT). The results show that the existence of surface and subsurface C atoms destabilized the adsorption of the surface hydrocarbon species when compared to the clean Ni(1 1 1) surface. The projected density state (PDOS) analysis shows that the deposition of C atoms on and into the Ni surface modified the electronic structure of the Ni surface, and thus reduced the catalytic activity of the bonded Ni atoms. Moreover, it was found that the presence carbon atoms increase the CHx (x = 4–1) species activation barriers especially on the surface carbon covered (1/4 ML) Ni(1 1 1) surface, where CHx (x = 4–1) species encounter highest energy barrier for dissociation due to the electronic deactivation induced by C-Ni bonding and the strong repulsive carbon -CHx interaction. The calculations also show that CHx dissociation barriers are not affected by its neighboring C atom at low surface carbon coverage (1/9 ML). This work can be used to estimate more realistic kinetic parameters for this system

  6. New Insights into the Origins of Sb-Induced Effects on Self-Catalyzed GaAsSb Nanowire Arrays

    DEFF Research Database (Denmark)

    Ren, Dingding; Dheeraj, Dasa L.; Jin, Chengjun;

    2016-01-01

    development of high-performance nanowire devices based on such ternaries. Here, we report on the origins of Sb-induced effects affecting the morphology and crystal structure of self-catalyzed GaAsSb nanowire arrays. The, nanowire growth by molecular beam epitaxy is changed both kinetically and...... and the crystal phase evolution mechanism proposed in this Letter, the phase transition/stability in catalyst-assisted ternary III-V-V nanowire growth can be well explained. Wavelength tunability with good homogeneity of the optical emission from the self-catalyzed GaAsSb nanowire arrays with high......Tertiary semiconductor nanowire arrays enable scalable fabrication of nano-optoelectronic devices with tunable bandgap. However, the lack of insight into the effects of the incorporation of Vy element results in lack of control on the growth of ternary III-V1-yVy nanowires and hinders the...

  7. Short Synthesis of Sulfur Analogues of Polyaromatic Hydrocarbons through Three Palladium-Catalyzed C-H Bond Arylations.

    Science.gov (United States)

    Hagui, Wided; Besbes, Néji; Srasra, Ezzeddine; Roisnel, Thierry; Soulé, Jean-François; Doucet, Henri

    2016-09-01

    An expeditious synthesis of a wide range of phenanthro[9,10-b]thiophene derivatives, which are a class of polyaromatic hydrocarbon (PAH) containing a sulfur atom, is reported. The synthetic scheme involves only two operations from commercially available thiophenes, 2-bromobenzenesulfonyl chlorides and aryl bromides. In the first step, palladium-catalyzed desulfitative arylation using 2-bromobenzenesulfonyl chlorides allows the synthesis of thiophene derivatives, which are substituted at the C4 position by an aryl group containing an ortho-bromo substituent. Then, a palladium-catalyzed one-pot cascade intermolecular C5-arylation of thiophene using aryl bromides followed by intramolecular arylation led to the corresponding phenanthro[9,10-b]thiophenes in a single operation. In addition, PAHs containing two or three sulfur atoms, as well as both sulfur and nitrogen atoms, were also designed by this strategy. PMID:27550151

  8. Acid Deposition Phenomena

    International Nuclear Information System (INIS)

    Acid deposition, commonly known as acid rain, occurs when emissions from the combustion of fossil fuels and other industrial processes undergo complex chemical reactions in the atmosphere and fall to the earth as wet deposition (rain, snow, cloud, fog) or dry deposition (dry particles, gas). Rain and snow are already naturally acidic, but are only considered problematic when less than a ph of 5.0 The main chemical precursors leading to acidic conditions are atmospheric concentrations of sulfur dioxide (SO2) and nitrogen oxides (NOx). When these two compounds react with water, oxygen, and sunlight in the atmosphere, the result is sulfuric (H2SO4) and nitric acids (HNO3), the primary agents of acid deposition which mainly produced from the combustion of fossil fuel and from petroleum refinery. Airborne chemicals can travel long distances from their sources and can therefore affect ecosystems over broad regional scales and in locations far from the sources of emissions. According to the concern of petroleum ministry with the environment and occupational health, in this paper we will discussed the acid deposition phenomena through the following: Types of acidic deposition and its components in the atmosphere Natural and man-made sources of compounds causing the acidic deposition. Chemical reactions causing the acidic deposition phenomenon in the atmosphere. Factors affecting level of acidic deposition in the atmosphere. Impact of acid deposition. Procedures for acidic deposition control in petroleum industry

  9. HT deposition to snow

    International Nuclear Information System (INIS)

    A series of exposure chamber measurements of the deposition of HT to snow were conducted at a field site. These experiments indicate that deposition velocities for conversion of HT to HTO are likely 10-6 m s-1 or less, which is approximately two to three orders of magnitude slower than deposition to soils under growing season conditions. Previous measurements of deposition to soil under freezing or near-freezing conditions also indicated very low deposition velocities. Deposition under winder conditions is thus likely to be much slower than deposition to soil under growing season conditions. It is concluded that exposure to HTO formed by the conversion of HT to HTO during a winter release of HT over snow or frozen ground is likely to be small compared to the dose from the HT plume itself. (4 tabs., 5 figs., 14 refs.)

  10. Effects of deposition time in chemically deposited ZnS films in acidic solution

    Energy Technology Data Exchange (ETDEWEB)

    Haddad, H.; Chelouche, A., E-mail: azeddinechelouche@gmail.com; Talantikite, D.; Merzouk, H.; Boudjouan, F.; Djouadi, D.

    2015-08-31

    We report an experimental study on the synthesis and characterization of zinc sulfide (ZnS) single layer thin films deposited on glass substrates by chemical bath deposition technique in acidic solution. The effect of deposition time on the microstructure, surface morphology, optical absorption, transmittance, and photoluminescence (PL) was investigated by X-ray diffraction (XRD), scanning electronic microscopy (SEM), UV-Vis–NIR spectrophotometry and photoluminescence (PL) spectroscopy. The results showed that the samples exhibit wurtzite structure and their crystal quality is improved by increasing deposition time. The latter, was found to affect the morphology of the thin films as showed by SEM micrographs. The optical measurements revealed a high transparency in the visible range and a dependence of absorption edge and band gap on deposition time. The room temperature PL spectra indicated that all ZnS grown thin films emit a UV and blue light, while the band intensities are found to be dependent on deposition times. - Highlights: • Single layer ZnS thin films were deposited by CBD in acidic solution at 95 °C. • The effect of deposition time was investigated. • Coexistence of ZnS and ZnO hexagonal structures for time deposition below 2 h • Thicker ZnS films were achieved after monolayer deposition for 5 h. • The highest UV-blue emission observed in thin film deposited at 5 h.

  11. Effects of deposition time in chemically deposited ZnS films in acidic solution

    International Nuclear Information System (INIS)

    We report an experimental study on the synthesis and characterization of zinc sulfide (ZnS) single layer thin films deposited on glass substrates by chemical bath deposition technique in acidic solution. The effect of deposition time on the microstructure, surface morphology, optical absorption, transmittance, and photoluminescence (PL) was investigated by X-ray diffraction (XRD), scanning electronic microscopy (SEM), UV-Vis–NIR spectrophotometry and photoluminescence (PL) spectroscopy. The results showed that the samples exhibit wurtzite structure and their crystal quality is improved by increasing deposition time. The latter, was found to affect the morphology of the thin films as showed by SEM micrographs. The optical measurements revealed a high transparency in the visible range and a dependence of absorption edge and band gap on deposition time. The room temperature PL spectra indicated that all ZnS grown thin films emit a UV and blue light, while the band intensities are found to be dependent on deposition times. - Highlights: • Single layer ZnS thin films were deposited by CBD in acidic solution at 95 °C. • The effect of deposition time was investigated. • Coexistence of ZnS and ZnO hexagonal structures for time deposition below 2 h • Thicker ZnS films were achieved after monolayer deposition for 5 h. • The highest UV-blue emission observed in thin film deposited at 5 h

  12. Metal catalyzed atmospheric oxidation reactions. A challenge to coordination chemists

    Energy Technology Data Exchange (ETDEWEB)

    Coichev, N. (Sao Paulo Univ., SP (Brazil). Inst. de Quimica); Van Eldik, R. (Universitaet Witten/Herdecke (Germany))

    1994-01-01

    Oxidation reactions of SO[sub x] and NO[sub y] species in the aqueous phase can play an important role in atmospheric chemistry and are of major environmental concern. The auto-oxidation processes are known to be catalyzed by trace metal ions and complexes. An overview of the most important reactions in metal catalyzed autoxidation processes is presented. Attention is given to the oxidation of the SO[sub x] and NO[sub y] species separately, as well as to the combined chemistry that results from the interaction of SO[sub x] and NO[sub y] species in the absence and presence of metal ions. Our work has revealed a fascinating redox cycling of the metal ions and complexes during such autoxidation processes, which has turned out to present quite a challenge to coordination chemists. (authors). 118 refs., 4 figs., 1 tab.

  13. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.......Metal-catalyzed isomerization of N- and O-allylic systems is emerging as an effective method to form synthetically useful iminium and oxocarbenium intermediates. In the presence of tethered nucleophiles, several recent examples illuminate this approach as a powerful strategy for the synthesis...... of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...

  14. Microcalorimetric Study on Tyrosine Oxidation Catalyzed by Tyrosinase

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Through the method of initial heat release rate, the kinetic property of tyrosine oxidationcatalyzed by tyrosinase from Pseudomonas maltophilia was investigated using a LKB-2107 batchmicrocalorimeter. Tyrosine was catalyzed and oxidized into L-dopa, then into melanin catalyzed bytyrosinase. We found that the tyrosinase reaction obeyed the Michaelis-Menten kinetics, and at298.15K and pH 7.0, the initial exothermic rate (Ω0) are in the range of0.1567~0.5704 mJ@ s-1, themaximum exothermic rate (Ωmax) are in 0.4152 ~ 0.8143mol @ L-1, and mean value of the Michaelisconstant (Km) is 2.199±0.105×104 mol @ L-1.

  15. Transition-metal-catalyzed C-S bond coupling reaction.

    Science.gov (United States)

    Lee, Chin-Fa; Liu, Yi-Chen; Badsara, Satpal Singh

    2014-03-01

    Sulfur-containing molecules such as thioethers are commonly found in chemical biology, organic synthesis, and materials chemistry. While many reliable methods have been developed for preparing these compounds, harsh reaction conditions are usually required in the traditional methods. The transition metals have been applied in this field, and the palladium-catalyzed coupling of thiols with aryl halides and pseudo halides is one of the most important methods in the synthesis of thioethers. Other metals have also been used for the same purpose. Here, we summarize recent efforts in metal-catalyzed C-S bond cross-coupling reactions, focusing especially on the coupling of thiols with aryl- and vinyl halides based on different metals. PMID:24443103

  16. The Cigeo deposit project. Closure structures. Meeting of the Permanent Group of Experts for Wastes on the 1 July 2014. Synthesis of the IRSN report on closure structures envisaged for the industrial Centre of geological deposit (Cigeo project). Opinion of the Permanent Group of Experts and ASN standpoint

    International Nuclear Information System (INIS)

    A first document is a report by the IRSN on the relevance of performance objectives defined by the ANDRA agency for the sealing of galleries, surface-underground connections and high-activity chamber caps of the Cigeo project, the relevance of the proposed concepts to reach these objectives (notably with respect to reversibility), and the feasibility of the presented structures. A first chapter recalls the general context of the ASN request and presents the associated ANDRA file. The report then recalls the safety function associated with the different closure structures of the deposit, discusses the relevance of performance objectives and of design options of closure structures and chamber caps. A second document is a synthesis of this IRSN report. The same issues (performance objectives, concept relevance, and industrial feasibility) are addressed and discussed in a third document by a group of experts. The last documents give the opinion on the Cigeo project of the ASN and of groups of experts for installations aimed at the long term storage of radioactive wastes and for plants and wastes. They also address the coherence of the PWR fuel cycle in France, the safety of the Manche storage centre

  17. Silver ion catalyzed cerium(IV) mediated electrochemical oxidation of phenol in nitric acid medium

    International Nuclear Information System (INIS)

    Mediated electrochemical oxidation (MEO) is one of the sustainable processes for organic pollutant destruction and has been employed for organic mineralization reactions by many researchers. In the MEO a metal ion capable of exhibiting redox behavior is oxidized from lower oxidation state to higher oxidation state by an electrochemical cell and subsequently used as an oxidant for mineralizing the toxic organics into CO2 and water. The net result is the consumption of electrical energy for organic mineralization. Therefore, the current efficiency is an important factor and maximizing the current efficiency is one of the ways of reducing the running cost of the MEO process. It has been reported in the literature that the current efficiency could be increased using a metal ion catalyst having a good redox potential. In this study Ce(IV) mediated electrochemical oxidation of phenol was carried out with silver ion catalyst. The current efficiency for the electro-oxidation of cerium(III) in nitric acid was found to be increased by the addition of silver ions. This mixed mediator system was tested for the oxidation of phenol in order to optimize the parameters for organic pollutant destruction. The mineralization efficiency calculated based on the CO2 evolution was found to be higher for silver catalyzed Ce(IV) mediated oxidation compared to the non-silver catalyzed system

  18. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

    Science.gov (United States)

    Fu, Qi; Socki, R. A.; Niles, Paul B.

    2011-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

  19. Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

    Science.gov (United States)

    Casale, Mia T.; Richman, Aviva R.; Elrod, Matthew J.; Garland, Rebecca M.; Beaver, Melinda R.; Tolbert, Margaret A.

    Field observations of atmospheric aerosols have established that organic compounds compose a large fraction of the atmospheric aerosol mass. However, the physical/chemical pathway by which organic compounds are incorporated into atmospheric aerosols remains unclear. The potential role of acid-catalyzed reactions of organic compounds on acidic aerosols has been explored as a possible chemical pathway for the incorporation of organic material into aerosols. In the present study, ultraviolet-visible (UV-vis) spectroscopy was used to monitor the kinetics of formation of the products of the acid-catalyzed aldol condensation reaction of a range of aliphatic aldehydes (C 2-C 8). The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature. While the kinetic data are generally consistent with previous laboratory reports of aldehyde reactivity in various sulfuric acid media, the aldol condensation reactions involving aliphatic aldehydes do not appear fast enough to be responsible for significant transfer of organic material into atmospheric aerosols.

  20. Rice cytochrome P450 MAX1 homologs catalyze distinct steps in strigolactone biosynthesis

    KAUST Repository

    Zhang, Yanxia

    2014-10-26

    Strigolactones (SLs) are a class of phytohormones and rhizosphere signaling compounds with high structural diversity. Three enzymes, carotenoid isomerase DWARF27 and carotenoid cleavage dioxygenases CCD7 and CCD8, were previously shown to convert all-trans-β-carotene to carlactone (CL), the SL precursor. However, how CL is metabolized to SLs has remained elusive. Here, by reconstituting the SL biosynthetic pathway in Nicotiana benthamiana, we show that a rice homolog of Arabidopsis More Axillary Growth 1 (MAX1), encodes a cytochrome P450 CYP711 subfamily member that acts as a CL oxidase to stereoselectively convert CL into ent-2\\'-epi-5-deoxystrigol (B-C lactone ring formation), the presumed precursor of rice SLs. A protein encoded by a second rice MAX1 homolog then catalyzes the conversion of ent-2\\'-epi-5-deoxystrigol to orobanchol. We therefore report that two members of CYP711 enzymes can catalyze two distinct steps in SL biosynthesis, identifying the first enzymes involved in B-C ring closure and a subsequent structural diversification step of SLs.

  1. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun

    2012-08-01

    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  2. Elevation of neuron specific enolase and brain iron deposition on susceptibility-weighted imaging as diagnostic clues for beta-propeller protein-associated neurodegeneration in early childhood: Additional case report and review of the literature.

    Science.gov (United States)

    Takano, Kyoko; Shiba, Naoko; Wakui, Keiko; Yamaguchi, Tomomi; Aida, Noriko; Inaba, Yuji; Fukushima, Yoshimitsu; Kosho, Tomoki

    2016-02-01

    Beta-propeller protein-associated neurodegeneration (BPAN), also known as static encephalopathy of childhood with neurodegeneration in adulthood (SENDA), is a subtype of neurodegeneration with brain iron accumulation (NBIA). BPAN is caused by mutations in an X-linked gene WDR45 that is involved in autophagy. BPAN is characterized by developmental delay or intellectual disability until adolescence or early adulthood, followed by severe dystonia, parkinsonism, and progressive dementia. Brain magnetic resonance imaging (MRI) shows iron deposition in the bilateral globus pallidus (GP) and substantia nigra (SN). Clinical manifestations and laboratory findings in early childhood are limited. We report a 3-year-old girl with BPAN who presented with severe developmental delay and characteristic facial features. In addition to chronic elevation of serum aspartate transaminase, lactate dehydrogenase, creatine kinase, and soluble interleukin-2 receptor, she had persistent elevation of neuron specific enolase (NSE) in serum and cerebrospinal fluid. MRI using susceptibility-weighted imaging (SWI) demonstrated iron accumulation in the GP and SN bilaterally. Targeted next-generation sequencing identified a de novo splice-site mutation, c.831-1G>C in WDR45, which resulted in aberrant splicing evidenced by reverse transcriptase-PCR. Persistent elevation of NSE and iron deposition on SWI may provide clues for diagnosis of BPAN in early childhood. PMID:26481852

  3. Report on the access to the deposition areas of the repository. Shaft or Ramp?; Utredning roerande tilltraedesvaegar till djupfoervarets deponeringsomraaden. Schakt eller ramp?

    Energy Technology Data Exchange (ETDEWEB)

    Baeckblom, Goeran [Conrox (Sweden); Christiansson, Rolf; Hedin, Allan; Norman, Fredrik [Swedish Nuclear Fuel and Waste Management Co., Stockholm (Sweden); Lagerstedt, Leif [SwedPower AB, Stockholm (Sweden)

    2003-05-01

    During year 2002, SKB launched the site-specific engineering of the repository at the Oskarshamn and Oesthammar candidate sites. A part of the ongoing engineering work is to evaluate and possibly select type of access from surface to the underground deposition areas located at a depth of some 400 to 700 metres below the surface. The project objectives are to provide a basis for comparison and to compare generic options for access routes to the underground deposition areas, to formulate preliminary Design Justification Statements for the continued site-specific engineering of access routes to the underground repository and also to describe and exemplify methodology for optimisation of the repository engineering. In consideration of the requirements of SKB, several alternative access options are explored. The main alternatives are a ramp with one or two operational areas at the surface, a ramp with parallel excavation of a blind shaft and an alternative with shafts only. A suite of objective functions were employed in the evaluation of the main alternatives relating to long-term safety, occupational safety during construction and operation, environmental impact, sustainability of natural resources, total cost, schedules, flexibility and project risks. All alternatives studied are feasible and safe, but the alternative with a spiral ramp and a blind shaft is deemed to be the most favourable option. The alternative has the highest flexibility without any tangible disadvantages related neither to long-term safety, environmental impact nor to schedules. It is an advantage that ramp traffic is drastically reduced as rock and backfilling material is transported by the skip rather than by vehicles in the ramp, thereby reducing risks of accidents and fires in the ramp. The concurrent ramp and shaft excavation also shorten the construction period with 18 months for the underground excavations. The discounted total cost is however 100 million Swedish Kronor higher for this

  4. Iridium-catalyzed intramolecular [4 + 2] cycloadditions of alkynyl halides

    OpenAIRE

    Andrew Tigchelaar; William Tam

    2012-01-01

    Iridium-catalyzed intramolecular [4 + 2] cycloadditions of diene-tethered alkynyl halides were investigated by using [IrCl(cod)]2 as catalyst, and dppe was found to be the most suitable phosphine ligand for the reaction. No oxidative insertion of the iridium into the carbon–halide bond was observed, and the reactions proceeded to provide the halogenated cycloadducts in good yield (75–94%). These results are the first examples of cycloadditions of alkynyl halides using an iridium c...

  5. Polyoxometalate catalyzed ozonation of chemical pulps in organic solvent media

    OpenAIRE

    Shatalov, Anatoly A.; Pereira, Helena

    2009-01-01

    Polyoxometalate (POM) catalyzed ozonation of chemical pulps in organic solvent media was found to be particularly effective and selective environmentally benign bleaching approach providing a way for substantial increase in pulp brightness, viscosity and degree of delignification in comparison with other ozone-based bleaching techniques. A series of tested low-boiling polar aprotic and protic organic solvents showed awell-defined capacity for ozonation improvement in the presence ...

  6. A Simple Strategy for Glycosyltransferase-Catalyzed Aminosugar Nucleotide Synthesis

    OpenAIRE

    Zhang, Jianjun; Singh, Shanteri; Hughes, Ryan R.; Zhou, Maoquan; Sunkara, Manjula; Morris, Andrew J.; Thorson, Jon S.

    2014-01-01

    A set of 2-chloro-4-nitrophenyl glucosamino/xylosaminosides were synthesized and assessed as potential substrates in the context of glycosyltransferase-catalyzed formation of the corresponding UDP/TDP-α-D-glucosamino-/xylosaminosugars and single vessel transglycosylation reactions with a model acceptor. This study highlights a robust platform for aminosugar nucleotide synthesis and reveals OleD Loki as a proficient catalyst for U/TDP-aminosugar synthesis and utilization.

  7. Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

    OpenAIRE

    Xiaoman Zhao; Bansode, Sneha Ramrao; Ribeiro, Artur J.; Abreu, Ana S.; de Oliveira, César; Parpot, Pier; Gogate, P. R.; V. K. Rathod; Paulo, Artur Cavaco

    2016-01-01

    The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic ba...

  8. Blankets for tritium catalyzed deuterium (TCD) fusion reactors

    International Nuclear Information System (INIS)

    The TCD fusion fuel cycle - where the 3He from the D(D,n)3He reaction is transmuted, by neutron capture in the blanket, into tritium which is fed back to the plasma - was recently recognized as being potentially more promising than the Catalyzed Deuterium (Cat-D) fuel cycle for tokamak power reactors. It is the purpose of the present work to assess the feasibility of, and to identify promising directions for designing blankets for TCD fusion reactors

  9. Cobalt-Catalyzed Enantioselective Vinylation of Activated Ketones and Imines.

    Science.gov (United States)

    Huang, Yuan; Huang, Rui-Zhi; Zhao, Yu

    2016-05-25

    We present here an unprecedented cobalt-catalyzed enantioselective vinylation of α-ketoesters, isatins, and imines to deliver a range of synthetically useful allylic alcohols and amines in high enantiopurity. This method employs commercially available and easy to handle catalysts and reagents and exhibits a high degree of practicality. The efficiency, selectivity, and operational simplicity of this catalytic system coupled with the substrate generality render this method a valuable tool in organic synthesis. PMID:27139596

  10. Lipase-catalyzed polyester synthesis – A green polymer chemistry

    OpenAIRE

    Kobayashi, Shiro

    2010-01-01

    This article is a short comprehensive review describing in vitro polyester synthesis catalyzed by a hydrolysis enzyme of lipase, most of which has been developed for these two decades. Polyesters are prepared by repeated ester bond-formation reactions; they include two major modes, ring-opening polymerization (ROP) of cyclic monomers such as cyclic esters (lactones) and condensation polymerization via the reaction between a carboxylic acid or its ester group and an alcohol group. Polyester sy...

  11. Amylase catalyzed synthesis of glycosyl acrylates and their polymerization

    OpenAIRE

    Kloosterman, Wouter M. J.; Jovanovic, Danijela; Brouwer, Sander; Loos, Katja

    2014-01-01

    The enzymatic synthesis of novel (di)saccharide acrylates from starch and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate (2-HEA, 2-HEMA and 4-HBA) catalyzed by various commercially available amylase preparations is demonstrated. Both liquefaction and saccharification amylases were tested as biocatalysts. Transglycosidation products were only detected in reaction mixtures containing saccharification amylases. The glycoamylase from Aspergillus niger was found t...

  12. Synthesis of Optically Active Polystyrene Catalyzed by Monophosphine Pd Complexes.

    Science.gov (United States)

    Jouffroy, Matthieu; Armspach, Dominique; Matt, Dominique; Osakada, Kohtaro; Takeuchi, Daisuke

    2016-07-11

    Cationic Pd(II) monophosphine complexes derived from α- and β-cyclodextrins (CDs) promote the homopolymerization of styrene under carbon monoxide pressure. Although reversible CO coordination takes place under catalytic conditions according to (13) C NMR studies with (13) C-enriched CO, both complexes catalyze the formation of CO-free styrene polymers. These macromolecules display optical activity as a result of the presence of stereoregular sequences within the overall atactic polymer. PMID:27218801

  13. Palladium-Catalyzed Synthesis and Transformation of Organoboranes

    OpenAIRE

    Sebelius, Sara

    2006-01-01

    This thesis presents the development of new palladium-catalyzed transformations involving synthesis and application of allylborane reagents. In these reactions various palladium sources, including pincer complexes and commonly used catalysts were applied. A new transformation for allylation of aldehyde and imine substrates was devised using allyl acetates, diboronate reagents and catalytic amounts of Pd2(dba)3. By employment of commercially available chiral diboronates enantioenriched homoall...

  14. Novel Pincer Complex-Catalyzed Transformations : Including Asymmetric Catalysis

    OpenAIRE

    Aydin, Juhanes

    2009-01-01

    This thesis is focused on the development of new pincer complex-catalyzed transformations. Optimization of the catalytic properties (fine-tuning) was directed to increase the catalytic activity as well as the chemo-, stereo- and enantioselectivity of the complexes. This was achieved by varying the heteroatoms in the terdentate pincer ligand, by changing the electronic properties of the coordinated aryl moiety and by implementing chiral functionalities in the pincer complexes. In the cross-cou...

  15. Cost analysis of simulated base-catalyzed biodiesel production processes

    International Nuclear Information System (INIS)

    Highlights: • Two semi-continuous biodiesel production processes from sunflower oil are simulated. • Simulations were based on the kinetics of base-catalyzed methanolysis reactions. • The total energy consumption was influenced by the kinetic model. • Heterogeneous base-catalyzed process is a preferable industrial technology. - Abstract: The simulation and economic feasibility evaluation of semi-continuous biodiesel production from sunflower oil were based on the kinetics of homogeneously (Process I) and heterogeneously (Process II) base-catalyzed methanolysis reactions. The annual plant’s capacity was determined to be 8356 tonnes of biodiesel. The total energy consumption was influenced by the unit model describing the methanolysis reaction kinetics. The energy consumption of the Process II was more than 2.5 times lower than that of the Process I. Also, the simulation showed the Process I had more and larger process equipment units, compared with the Process II. Based on lower total capital investment costs and biodiesel selling price, the Process II was economically more feasible than the Process I. Sensitivity analysis was conducted using variable sunflower oil and biodiesel prices. Using a biodiesel selling price of 0.990 $/kg, Processes I and II were shown to be economically profitable if the sunflower oil price was 0.525 $/kg and 0.696 $/kg, respectively

  16. Airfoil deposition model

    Science.gov (United States)

    Kohl, F. J.

    1982-01-01

    The methodology to predict deposit evolution (deposition rate and subsequent flow of liquid deposits) as a function of fuel and air impurity content and relevant aerodynamic parameters for turbine airfoils is developed in this research. The spectrum of deposition conditions encountered in gas turbine operations includes the mechanisms of vapor deposition, small particle deposition with thermophoresis, and larger particle deposition with inertial effects. The focus is on using a simplified version of the comprehensive multicomponent vapor diffusion formalism to make deposition predictions for: (1) simple geometry collectors; and (2) gas turbine blade shapes, including both developing laminar and turbulent boundary layers. For the gas turbine blade the insights developed in previous programs are being combined with heat and mass transfer coefficient calculations using the STAN 5 boundary layer code to predict vapor deposition rates and corresponding liquid layer thicknesses on turbine blades. A computer program is being written which utilizes the local values of the calculated deposition rate and skin friction to calculate the increment in liquid condensate layer growth along a collector surface.

  17. Modelling the deposition of airborne radionuclides into the urban environment. First report of the VAMP Urban Working Group. Part of the IAEA/CEC co-ordinated research programme on the validation of environmental model predictions (VAMP)

    International Nuclear Information System (INIS)

    A co-ordinated research programme was begun at the IAEA in 1988 with the short title of Validation of Environmental Model Predictions (VAMP). The VAMP Urban Working Group aims to examine, by means of expert review combined with formal validation exercises, modelling for the assessment of the radiation exposure of urban populations through the external irradiation and inhalation pathways. An aim of the studies is to evaluate the lessons learned and to document the improvements in modelling capability as a result of experience gained following the Chernobyl accident. This Technical Document, the first report of the Group, addresses the subject of the deposition of airborne radionuclides into the urban environment. It summarizes not only the present status of modelling in this field, but also the results of a limited validation exercise that was performed under the auspices of VAMP. 42 refs, figs and tabs

  18. Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles

    2011-01-01

    This undergraduate organic laboratory exercise involves the sulfuric acid-catalyzed conversion of waste vegetable oil into biodiesel. The acid-catalyzed method, although inherently slower than the base-catalyzed methods, does not suffer from the loss of product or the creation of emulsion producing soap that plagues the base-catalyzed methods when…

  19. Shedding of ash deposits

    DEFF Research Database (Denmark)

    Zbogar, Ana; Frandsen, Flemming; Jensen, Peter Arendt;

    2009-01-01

    Ash deposits formed during fuel thermal conversion and located on furnace walls and on convective pass tubes, may seriously inhibit the transfer of heat to the working fluid and hence reduce the overall process efficiency. Combustion of biomass causes formation of large quantities of troublesome...... ash deposits which contain significant concentrations of alkali, and earth-alkali metals. The specific composition of biomass deposits give different characteristics as compared to coal ash deposits, i.e. different physical significance of the deposition mechanisms, lower melting temperatures, etc....... Low melting temperatures make straw ashes especially troublesome, since their stickiness is higher at lower temperatures, compared to coal ashes. Increased stickiness will eventually lead to a higher collection efficiency of incoming ash particles, meaning that the deposit may grow even faster...

  20. Experimental measurements of the thermal conductivity of ash deposits: Part 2. Effects of sintering and deposit microstructure

    Energy Technology Data Exchange (ETDEWEB)

    A. L. Robinson; S. G. Buckley; N. Yang; L. L. Baxter

    2000-04-01

    The authors report results from an experimental study that examines the influence of sintering and microstructure on ash deposit thermal conductivity. The measurements are made using a technique developed to make in situ, time-resolved measurements of the effective thermal conductivity of ash deposits formed under conditions that closely replicate those found in the convective pass of a commercial boiler. The technique is designed to minimize the disturbance of the natural deposit microstructure. The initial stages of sintering and densification are accompanied by an increase in deposit thermal conductivity. Subsequent sintering continues to densify the deposit, but has little effect on deposit thermal conductivity. SEM analyses indicates that sintering creates a layered deposit structure with a relatively unsintered innermost layer. They hypothesize that this unsintered layer largely determines the overall deposit thermal conductivity. A theoretical model that treats a deposit as a two-layered material predicts the observed trends in thermal conductivity.

  1. The Imouraren deposit, Niger

    International Nuclear Information System (INIS)

    Imouraren deposit has been discovered in the late sixties. It is located South of Arlit where two mines are mined, one open pit and one underground. The grades of reduced Imouraren Uranium ore are lesser than these of Arlit and Akouta. Imouraren deposit is owned by COGEMA (France): 70% and ONAREM (Niger): 30%. The concession area is about 45 square kilometers. The thickness of the deposit is between 50 and 60 meters and its depth reaches 110 to 170 meters. (author)

  2. Deposits and relationship lending

    OpenAIRE

    Mitchell Berlin; Mester, Loretta J.

    1998-01-01

    The authors empirically examine the hypothesis that access to deposits with inelastic rates (core deposits) permits a bank to make contractual agreements with borrowers that are infeasible if the bank must pay market rates for its funds. Access to core deposits insulates a bank's costs of funds from exogenous shocks, allowing the bank to insulate its borrowers against exogenous credit shocks. Using a large sample of loans from the Survey of the Terms of Bank Lending, the authors find that whe...

  3. Uraniferous surficial deposits

    International Nuclear Information System (INIS)

    As a result of the discovery of uranium in surficial deposits of Tertiary to Recent age, in Australia and Southern Africa, increasing attention is being paid to the location and understanding of the genesis of these deposits. The paper discusses the definitions and terminology currently in use and a classification of these deposits is presented. It is concluded that in order to obtain a measure of clarity, the terms calcrete, gypcrete and dolocrete should not be used to describe the uraniferous valley-fill deposits of Southern Africa and Australia

  4. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

  5. Development and industrial application of catalyzer for low-temperature hydrogenation hydrolysis of Claus tail gas

    Directory of Open Access Journals (Sweden)

    Honggang Chang

    2015-10-01

    Full Text Available With the implementation of more strict national environmental protection laws, energy conservation, emission reduction and clean production will present higher requirements for sulfur recovery tail gas processing techniques and catalyzers. As for Claus tail gas, conventional hydrogenation catalyzers are gradually being replaced by low-temperature hydrogenation catalyzers. This paper concentrates on the development of technologies for low-temperature hydrogenation hydrolysis catalyzers, preparation of such catalyzers and their industrial application. In view of the specific features of SO2 hydrogenation and organic sulfur hydrolysis during low-temperature hydrogenation, a new technical process involving joint application of hydrogenation catalyzers and hydrolysis catalyzers was proposed. In addition, low-temperature hydrogenation catalyzers and low-temperature hydrolysis catalyzers suitable for low-temperature conditions were developed. Joint application of these two kinds of catalyzers may reduce the inlet temperatures in the conventional hydrogenation reactors from 280 °C to 220 °C, at the same time, hydrogenation conversion rates of SO2 can be enhanced to over 99%. To further accelerate the hydrolysis rate of organic sulfur, the catalyzers for hydrolysis of low-temperature organic sulfur were developed. In lab tests, the volume ratio of the total sulfur content in tail gas can be as low as 131 × 10−6 when these two kinds of catalyzers were used in a proportion of 5:5 in volumes. Industrial application of these catalyzers was implemented in 17 sulfur recovery tail gas processing facilities of 15 companies. As a result, Sinopec Jinling Petrochemical Company had outstanding application performances with a tail gas discharging rate lower than 77.9 mg/m3 and a total sulfur recovery of 99.97%.

  6. Regional aerosol deposition in human upper airways

    International Nuclear Information System (INIS)

    During the report period significant progress on the quantitative understanding of regional upper airway deposition of airborne particle has been realized. Replicate models of the human upper airways obtained from post-mortem casting of the nasal, oral, pharyngeal, laryngeal and upper tracheal regions and in vivo magnetic resonance imaging (MRI) of the same regions of adults and children have been employed to determine the overall and local deposition characteristics of aerosols in the ultrafine (1--100 μm diameter) and fine (0.8--12 μm diameter) region. Studies have been carried out for both nasal and oral breathing during inspiratory and expiratory flow at constant flow rates representative of rest and states of exercise. The results of these investigations indicate that particles in the size range of ''unattached'' radon progeny (1--3 nm) are deposited in both the nasal and oral passages with high efficiency (60--80%) for both inspiration and expiration, with the nasal deposition being somewhat greater (5--10%) than oral deposition. The effect of flow rate on upper airway deposition for both pathways is not great; data analysis indicates that the deposition for all flow rates from 4--50 liters/minute can be grouped by plotting deposition vs Q-1/8, where Q is flow rate, a far weaker dependency than observed for inertial deposition. Diffusional transport is the primary mechanism of deposition, and size dependence can be accounted for by plotting, deposition percent vs Dn where D is particle diffusion coefficient and n ranges from 0.5--0.66. 2 refs

  7. Predicting particle deposition on HVAC heat exchangers

    Science.gov (United States)

    Siegel, Jeffrey A.; Nazaroff, William W.

    Particles in indoor environments may deposit on the surfaces of heat exchangers that are used in heating, ventilation and air conditioning (HVAC) systems. Such deposits can lead to performance degradation and indoor air quality problems. We present a model of fin-and-tube heat-exchanger fouling that deterministically simulates particle impaction, gravitational settling, and Brownian diffusion and uses a Monte Carlo simulation to account for impaction due to air turbulence. The model predicts that heat exchangers with air flows and fin spacings that are typical of HVAC systems. For supermicron particles, deposition increases with particle size. The dominant deposition mechanism for 1-10 μm particles is impaction on fin edges. Gravitational settling, impaction, and air turbulence contribute to deposition for particles larger than 10 μm. Gravitational settling is the dominant deposition mechanism for lower air velocities, and impaction on refrigerant tubes is dominant for higher velocities. We measured deposition fractions for 1-16 μm particles at three characteristic air velocities. On average, the measured results show more deposition than the model predicts for an air speed of 1.5 m s -1. The amount that the model underpredicts the measured data increases at higher velocities and especially for larger particles, although the model shows good qualitative agreement with the measured deposition fractions. Discontinuities in the heat-exchanger fins are hypothesized to be responsible for the increase in measured deposition. The model and experiments reported here are for isothermal conditions and do not address the potentially important effects of heat transfer and water phase change on deposition.

  8. The Palmottu natural analogue project. Summary report 1992-1994. The behaviour of natural radionuclides in and around uranium deposits, Nr. 8

    International Nuclear Information System (INIS)

    The Palmottu U-Th mineralization at Nummi-Pusula, southwestern Finland, has been studied as a natural analogue to deep disposal of radioactive wastes since 1988. The report gives a summary of the results of investigations carried out during the years 1992-1994. The Palmottu Analogue Project aims at a more profound understanding of radionuclide transport processes in fractured crystalline bedrock. The study includes the structural interpretations based in part on geophysical measurements, hydrological studies including hydraulic downhole measurements, flow modelling, hydrogeochemical characterization of groundwater, uranium chemistry and colloid chemistry, mineralogical studies, geochemical interpretation and modelling, including paleohydrogeological aspects, and studies of radionuclide mobilization and migration processes including numerical simulations. (121 refs., 24 figs., 8 tabs.)

  9. TEOS-based oxides: deposition dependent properties

    International Nuclear Information System (INIS)

    This paper reports the effects of three important parameters, deposition temperature, TEOS concentration and RF power in the plasma enhanced CVD of TEOS-based oxides on the resulting film characteristics such as impurity incorporation, film density, moisture absorption, intrinsic and thermal stresses. Ion-bombardment induced desorption of reactive precursor species is suggested to occur under certain conditions. Further, it is shown that the film properties continue to evolve until the film thickness exceeds 3000A. For 1 μm films deposited using typical settings of deposition parameters, the average TCE is estimated to be 0.9 ppm/ C using the stress-temperature characteristics. (orig.)

  10. Deposition patterns with Turbuhaler.

    Science.gov (United States)

    Borgström, L

    1994-01-01

    The degree of lung deposition is an important factor in the evaluation of different inhalation flow driven dry powder inhalers. A number of studies using radioactive and non-radioactive methods have been performed with Turbuhaler to assess lung deposition under different conditions. Mean total lung deposition of terbutaline sulfate or budesonide via Turbuhaler in healthy volunteers ranged from 21-32% of the dose when a normal inhalation flow (60L/min) was used. At a low flow (30L/min) a mean 15% of the dose was deposited in the lungs, a similar value as for a well-performed inhalation via a pressurized metered dose inhaler. Regional deposition of inhaled drug can be expressed as the ratio between the amount of drug deposited in the more peripheral parts of the lung relative to the more central parts. In a comparative study, budesonide and terbutaline sulfate were given by inhalation via Turbuhaler to healthy volunteers. The ratio of peripheral to central deposition was 2.03 for terbutaline and 1.72 for budesonide. Thus, both the water-soluble terbutaline sulfate and the non-water soluble budesonide seemed to behave in the same way when inhaled via Turbuhaler. In conclusion, Turbuhaler delivers over 20% of a metered dose to the lungs when inhaled at a normal inhalation flow rate. The regional deposition pattern in the lungs was the same for terbutaline sulfate and budesonide, in spite of differences in water solubility. PMID:10147081

  11. MAPLE deposition of nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Caricato, A.P., E-mail: annapaola.caricato@le.infn.it [Department of Mathematics and Physics “E. De Giorgi”, University of Salento, Via Arnesano, I-73100 Lecce (Italy); Arima, V.; Catalano, M. [National Nanotechnology Laboratory (NNL), CNR Istituto Nanoscienze, c/o Distretto Tecnologico, Via Arnesano n. 16, I-73100 Lecce (Italy); Cesaria, M. [Department of Mathematics and Physics “E. De Giorgi”, University of Salento, Via Arnesano, I-73100 Lecce (Italy); Cozzoli, P.D. [Department of Mathematics and Physics “E. De Giorgi”, University of Salento, Via Arnesano, I-73100 Lecce (Italy); National Nanotechnology Laboratory (NNL), CNR Istituto Nanoscienze, c/o Distretto Tecnologico, Via Arnesano n. 16, I-73100 Lecce (Italy); Martino, M. [Department of Mathematics and Physics “E. De Giorgi”, University of Salento, Via Arnesano, I-73100 Lecce (Italy); Taurino, A.; Rella, R. [Institute for Microelectronics and Microsystems, IMM-CNR, Via Monteroni, I-73100 Lecce (Italy); Scarfiello, R. [National Nanotechnology Laboratory (NNL), CNR Istituto Nanoscienze, c/o Distretto Tecnologico, Via Arnesano n. 16, I-73100 Lecce (Italy); Tunno, T. [Department of Mathematics and Physics “E. De Giorgi”, University of Salento, Via Arnesano, I-73100 Lecce (Italy); Zacheo, A. [Department of Mathematics and Physics “E. De Giorgi”, University of Salento, Via Arnesano, I-73100 Lecce (Italy); National Nanotechnology Laboratory (NNL), CNR Istituto Nanoscienze, c/o Distretto Tecnologico, Via Arnesano n. 16, I-73100 Lecce (Italy)

    2014-05-01

    The matrix-assisted pulsed laser evaporation (MAPLE) has been recently exploited for depositing films of nanomaterials by combining the advantages of colloidal inorganic nanoparticles and laser-based techniques. MAPLE-deposition of nanomaterials meeting applicative purposes demands their peculiar properties to be taken into account while planning depositions to guarantee a congruent transfer (in terms of crystal structure and geometric features) and explain the deposition outcome. In particular, since nanofluids can enhance thermal conductivity with respect to conventional fluids, laser-induced heating can induce different ablation thermal regimes as compared to the MAPLE-treatment of soft materials. Moreover, nanoparticles exhibit lower melting temperatures and can experience pre-melting phenomena as compared to their bulk counterparts, which could easily induce shape and or crystal phase modification of the material to be deposited even at very low fluences. In this complex scenario, this review paper focuses on examples of MAPLE-depositions of size and shape controlled nanoparticles for different applications highlights advantages and challenges of the MAPLE-technique. The influence of the deposition parameters on the physical mechanisms which govern the deposition process is discussed.

  12. An Efficient Procedure for Esterification of Aryloxyacetic Acid and Arylthioacetic Acid Catalyzed by Silica Sulfuric Acid

    Institute of Scientific and Technical Information of China (English)

    LI,Hong-Ya; LI,Ji-Tai; LI,Hui-Zhang

    2004-01-01

    @@ Aryloxyacetate and arylthioacetate are wildly used in herbicides, plant regulator and insecticides. Recently, Wille et al. have reported that methyl aryloxyacetate is an efficient agent to prevent and treat allergic contact dermatitis.[1] The most popular synthesis is by heating sodium phenoxide (mercaptide) with ethyl chloroacetate in DMF,[2] or by the esterification of acid with alcohol using concentrated H2SO4 as catalyst.[3] In this paper, synthesis of aryloxyacetate and aryl thioacetate from aryloxyacetic acid and arylthioacetic acid respectively in ether catalyzed by silica sulfuric acid in 83%~94% yields is described. The catalyst is reused for 3 times without significant loss of activity (Entry 4). Compared with common procedures, the present procedure possesses the advantages of the operational simplicity, short reaction time,less-corrosion, high yield and reusable catalyst.

  13. A Convenient Synthesis of Conjugated Acetylenic Ketones by Copper(l)-Catalyzed under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Alkynyl ketones are useful precursors and intermediates in synthetic organic chemistry1 and has evoked considerable interest. A number of methods for the synthesis of conjugated acetylenic ketones involve the reaction a metal acetylide with an acyl chlorides or another carboxylic acid derivative have been developed 2. Recently, the synthesis of α, β-conjugated acetylenic ketones catalyzed by Pd(Ⅱ) or by copper(Ⅰ)pd(Ⅱ) reaction of 1-alkynes and acyl chlorides have been described. The acylation of terminal alkynes by acyl chlorides in the presence of catalytic amounts copper(Ⅰ) salts leading to α, β-conjugated acetylenic ketones has also been reported. However, many of these reactions suffer from lack of high pressure (17 atm), long reaction time (30 h)and require low temperatures (-78℃). Our work involves the synthesis of conjugated acetylenic ketones via the reaction of terminal alkynes with aroyl chlorides in the presence of cuprous iodide under microwave irradiation conditions.

  14. Divergent Gold(I)-Catalyzed Skeletal Rearrangements of 1,7-Enynes.

    Science.gov (United States)

    Meiß, Rebecca; Kumar, Kamal; Waldmann, Herbert

    2015-09-21

    The gold(I) complex catalyzed cycloisomerization and skeletal rearrangement of 1,n-enynes (n=5-7) is a powerful methodology for the efficient synthesis of complex molecular architectures. In contrast to 1,6-enynes, readily accessible homologous 1,7-enynes are largely unexplored in such transformations. Here, the divergent skeletal rearrangement of all-carbon 1,7-enynes by catalysis with a cationic gold(I) complex is reported. Depending on electronic and steric factors, differently substituted 1,7-enynes react via different carbocations formed from a common gold carbene intermediate to yield on the one hand novel exocyclic allenes and on the other hand tricyclic hexahydro-anthracenes through a novel dehydrogenative Diels-Alder reaction. PMID:26356499

  15. Production of sunflower oil methyl esters by optimized alkali-catalyzed methanolysis

    Energy Technology Data Exchange (ETDEWEB)

    Rashid, Umer; Anwar, Farooq; Ashraf, Samia [Department of Chemistry, University of Agriculture, Faisalabad 38040 (Pakistan); Moser, Bryan R. [United States Department of Agriculture, National Center for Agricultural Utilization Research, Peoria, IL 61604 (United States); Agricultural Research Service, National Center for Agricultural Utilization Research, Peoria, IL 61604 (United States)

    2008-12-15

    We report the optimization of sunflower oil methyl esters (SOME/biodiesel) production via alkaline catalyzed transesterification of crude sunflower oil and subsequent physical and chemical characterization. The optimum conditions elucidated for the methanolysis of sunflower oil were found to be: methanol/sunflower oil molar ratio, 6:1; reaction temperature, 60 C; and NaOH catalyst concentration, 1.00% (w/w). An optimum SOME yield of 97.1% was achieved. SOME were analyzed by gas-liquid chromatography (GLC). A number of fuel properties of SOME as measured according to accepted methods were found to satisfy nearly all prescribed ASTM D 6751 specifications, where applicable. The results of the present study indicated that SOME could be a potential alternative to other common biodiesels and petrodiesel. (author)

  16. Enantioselective Oxidation of Alkenes with Potassium Permanganate Catalyzed by Chiral Dicationic Bisguanidinium.

    Science.gov (United States)

    Wang, Chao; Zong, Lili; Tan, Choon-Hong

    2015-08-26

    Chiral anion-controlled ion-pairing catalysis was demonstrated to be a wide-ranging strategy that can utilize a variety of cationic metal species. In a similar manner, we envision a complementary strategy using chiral cation in partnership with inorganic anionic metal salts. Herein, we report a chiral dicationic bisguanidinium-catalyzed asymmetric oxidation reaction of alkenes with potassium permanganate. Chiral induction is attributed to ion-pairing interaction between chiral cation and enolate anion. The success of the current permanganate oxidation reaction together with mechanistic insights should provide inspiration for expansion to other anionic metal salts and would open up new paradigms for asymmetric transition metal catalysis, phase-transfer catalysis, and ion-pairing catalysis. PMID:26237178

  17. Enantioselective Rhodium-Catalyzed Cycloisomerization of (E)-1,6-Enynes.

    Science.gov (United States)

    Deng, Xu; Ni, Shao-Fei; Han, Zheng-Yu; Guan, Yu-Qing; Lv, Hui; Dang, Li; Zhang, Xu-Mu

    2016-05-17

    An enantioselective rhodium(I)-catalyzed cycloisomerization reaction of challenging (E)-1,6-enynes is reported. This novel process enables (E)-1,6-enynes with a wide range of functionalities, including nitrogen-, oxygen-, and carbon-tethered (E)-1,6-enynes, to undergo cycloisomerization with excellent enantioselectivity, in a high-yielding and operationally simple manner. Moreover, this Rh(I) -diphosphane catalytic system also exhibited superior reactivity and enantioselectivity for (Z)-1,6-enynes. A rationale for the striking reactivity difference between (E)- and (Z)-1,6-enynes using Rh(I) -BINAP and Rh(I) -TangPhos is outlined using DFT studies to provide the necessary insight for the design of new catalyst systems and the application to synthesis. PMID:27061132

  18. Copper-catalyzed coupling of oxime acetates with sodium sulfinates: an efficient synthesis of sulfone derivatives.

    Science.gov (United States)

    Tang, Xiaodong; Huang, Liangbin; Xu, Yanli; Yang, Jidan; Wu, Wanqing; Jiang, Huanfeng

    2014-04-14

    Sulfone derivatives are important synthetic intermediates. However, the general method for their preparation is through traditional coupling reaction: the alkylation of sodium sulfinates with phenacyl halides. Based on our previous work on sodium sulfinates and oxime acetates, we herein report a novel method for sulfone derivatives by oxidative coupling with sodium sulfinates and oxime acetates using copper as catalyst. The sulfonylvinylamine products could be formed in excellent yields. Upon hydrolysis by silica gel in CH2 Cl2 , β-ketosulfones could also be efficiently constructed. Various sulfonylvinylamines and β-ketosulfones were obtained in good to excellent yields under the optimized reaction conditions. Mechanistic studies indicated that this transformation involved copper-catalyzed N-O bond cleavage, activation of a vinyl sp(2) C-H bond, and C-S bond formation. The oxime acetates act as both a substrate and an oxidant, thus the reaction needs no additional oxidants or additives. PMID:24677481

  19. Kinetics of allopregnanolone formation catalyzed by human 3 alpha-hydroxysteroid dehydrogenase type III (AKR1C2).

    Science.gov (United States)

    Trauger, John W; Jiang, Alice; Stearns, Brian A; LoGrasso, Philip V

    2002-11-12

    Allopregnanolone is a neurosteroid which exhibits anxiolytic and anticonvulsant activities through potentiation of the GABA(A) receptor. The reduction of 5alpha-dihydroprogesterone (5alpha-DHP), the last step in allopregnanolone biosynthesis, is catalyzed by 3alpha-hydroxysteroid dehydrogenases (3alpha-HSDs). While the mechanism of action of allopregnanolone and the physiological and pharmacological modulation of allopregnanolone concentrations in vivo have been extensively studied, there has been little characterization of the kinetics of human 3alpha-HSD catalyzed allopregnanolone formation. We report here determination of the kinetic mechanism for 5alpha-DHP reduction catalyzed by human 3alpha-HSD type III by using steady-state kinetics studies and assessment of the ability of fluoxetine and various other small molecules to activate 3alpha-HSD type III catalyzed allopregnanolone formation. Enzyme-catalyzed 5alpha-DHP reduction yielded two products, allopregnanolone and 5alpha,20alpha-tetrahydroprogesterone, as measured by using a radiometric thin-layer chromatography assay, while 5beta-DHP reduction yielded the neurosteroid pregnanolone as the only product. 5Beta-DHP reduction proceeded with a catalytic efficiency 10 times higher than that of 5alpha-DHP reduction. Two-substrate kinetic analysis and dead-end inhibition studies for 5alpha-DHP reduction and allopregnanolone oxidation indicated that 3alpha-HSD type III utilized a ternary complex (sequential) kinetic mechanism, with nicotinamide adenine dinucleotide cofactor binding before steroid substrate and leaving after steroid product. Since previous reports suggested that fluoxetine and certain other small molecules increased allopregnanolone concentrations in vivo by activating 3alpha-HSD type III, we investigated whether these small molecules were able to activate human 3alpha-HSD type III. Our results showed that, at concentrations up to 50 microM, fluoxetine, paroxetine, sertraline, norfluoxetine

  20. Biomimetic thin film deposition

    Energy Technology Data Exchange (ETDEWEB)

    Rieke, P.R.; Graff, G.E.; Campbell, A.A.; Bunker, B.C.; Baskaran, S.; Song, L.; Tarasevich, B.J.; Fryxell, G.E.

    1995-09-01

    Biological mineral deposition for the formation of bone, mollusk shell and other hard tissues provides materials scientists with illustrative materials processing strategies. This presentation will review the key features of biomineralization and how these features can be of technical importance. We have adapted existing knowledge of biomineralization to develop a unique method of depositing inorganic thin films and coating. Our approach to thin film deposition is to modify substrate surfaces to imitate the proteins found in nature that are responsible for controlling mineral deposition. These biomimetic surfaces control the nucleation and growth of the mineral from a supersaturated aqueous solution. This has many processing advantages including simple processing equipment, environmentally benign reagents, uniform coating of highly complex shapes, and enhanced adherence of coating. Many different types of metal oxide, hydroxide, sulfide and phosphate materials with useful mechanical, optical, electronic and biomedical properties can be deposited.

  1. Clear Cell Basal Cell Carcinoma with Sialomucin Deposition

    OpenAIRE

    Kim, Do Young; Cho, Sung Bin; Chung, Kee Yang; Kim, You Chan

    2006-01-01

    Clear cell basal cell carcinoma (BCC) is a variant of BCC with a characteristic clear cell component that may occupy all or part of the tumor islands. Periodic acid-Schiff (PAS) staining for glycogen is variably positive, and mild deposition of sulfated mucin has been noted. However, to our knowledge, clear cell BCC with sialomucin deposition has not been reported. Here we report a case of clear cell BCC showing sialomucin deposition. The clear tumor cells stained with PAS and showed incomple...

  2. Analytic studies on pollutant deposition through domestic coal combustion -influence of the current structural change on pollution in an urban region. Final report

    International Nuclear Information System (INIS)

    In the present paper the author reports on the continuation of an OEKOR part project in which he had undertaken a chemical characterisation of emissions from domestic brown coal combustion. On the basis of a partitioning by land use of the Greater Leipzig region he initiated long-term observations of local pollution levels for the various structural types of land. The aim of the work was to facilitate a comprehensive analysis of local air quality in terms of VOC levels. The current concern about VOCs results from the toxicological risk they have been proven to pose to the human organism and from their relevance to the chemistry of the atmosphere (e.g., as precursors of ground-level ozone and other oxidising agents). The task to be accomplished was broken down into the following main steps: Development and trial of a sampling and analysis method for determining an as wide a spectrum of environmental VOCs as possible; elaboration of a measuring strategy for obtaining results of high representativeness and power; installation and operation of pollution monitoring sites in selected structural types of area characteristic of Leipzig; execution of measuring campaigns of several weeks each at selected sites during both winter and summer periods. (orig./MSK)

  3. Self-catalyzed growth of pure zinc blende 〈110〉 InP nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Xin; Zhang, Xia, E-mail: xzhang@bupt.edu.cn; Li, Junshuai; Wu, Yao; Ren, Xiaomin [State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876 (China)

    2015-07-13

    We demonstrate the self-catalyzed vapor-liquid-solid growth of 〈110〉 InP nanowires (NWs) by metal organic chemical vapor deposition. The 〈110〉 InP nanowire is formed via a spontaneous kinking from the original 〈111〉 growth direction, which is attributed to instabilities at the liquid/solid interface caused by a fast In incorporation into the droplet. The NW length before kinking has a nearly linear relationship with the diameter, offering a way to control the NW morphology for different applications. The 〈110〉 nanowire exhibits pure zinc blende crystal structure and a narrower emission linewidth in comparison with a typical 〈111〉 nanowire, demonstrating its potential applications in high-performance electronic and photonic devices.

  4. Self-catalyzed growth of pure zinc blende 〈110〉 InP nanowires

    International Nuclear Information System (INIS)

    We demonstrate the self-catalyzed vapor-liquid-solid growth of 〈110〉 InP nanowires (NWs) by metal organic chemical vapor deposition. The 〈110〉 InP nanowire is formed via a spontaneous kinking from the original 〈111〉 growth direction, which is attributed to instabilities at the liquid/solid interface caused by a fast In incorporation into the droplet. The NW length before kinking has a nearly linear relationship with the diameter, offering a way to control the NW morphology for different applications. The 〈110〉 nanowire exhibits pure zinc blende crystal structure and a narrower emission linewidth in comparison with a typical 〈111〉 nanowire, demonstrating its potential applications in high-performance electronic and photonic devices

  5. An ab initio study of the nickel-catalyzed transformation of amorphous carbon into graphene in rapid thermal processing

    Science.gov (United States)

    Chen, Shuang; Xiong, Wei; Zhou, Yun Shen; Lu, Yong Feng; Zeng, Xiao Cheng

    2016-05-01

    Ab initio molecular dynamics (AIMD) simulations are employed to investigate the chemical mechanism underlying the Ni-catalyzed transformation of amorphous carbon (a-C) into graphene in the rapid thermal processing (RTP) experiment to directly grow graphene on various dielectric surfaces via the evaporation of surplus Ni and C at 1100 °C (below the melting point of bulk Ni). It is found that the a-C-to-graphene transformation entails the metal-induced crystallization and layer exchange mechanism, rather than the conventional dissolution/precipitation mechanism typically involved in Ni-catalyzed chemical vapor deposition (CVD) growth of graphene. The multi-layer graphene can be tuned by changing the relative thicknesses of deposited a-C and Ni thin films. Our AIMD simulations suggest that the easy evaporation of surplus Ni with excess C is likely attributed to the formation of a viscous-liquid-like Ni-C solution within the temperature range of 900-1800 K and to the faster diffusion of C atoms than that of Ni atoms above 600 K. Even at room temperature, sp3-C atoms in a-C are quickly converted to sp2-C atoms in the course of the simulation, and the graphitic C formation can occur at low temperature. When the temperature is as high as 1200 K, the grown graphitic structures reversely dissolve into Ni. Because the rate of temperature increase is considerably faster in the AIMD simulations than in realistic experiments, defects in the grown graphitic structures are kinetically trapped. In this kinetic growth stage, the carbon structures grown from sp3-carbon or from sp2-carbon exhibit marked differences.Ab initio molecular dynamics (AIMD) simulations are employed to investigate the chemical mechanism underlying the Ni-catalyzed transformation of amorphous carbon (a-C) into graphene in the rapid thermal processing (RTP) experiment to directly grow graphene on various dielectric surfaces via the evaporation of surplus Ni and C at 1100 °C (below the melting point of bulk

  6. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    Science.gov (United States)

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. PMID:25280108

  7. Ocular copper deposition associated with monoclonal gammopathy of undetermined significance: case report Depósito ocular de cobre associado a gamopatia monoclonal de significância indeterminada: relato de caso

    Directory of Open Access Journals (Sweden)

    Patrick F. Tzelikis

    2005-08-01

    Full Text Available To report a case of ocular copper deposition in both eyes at the level of Descemet's membrane associated with a monoclonal gammopathy of undetermined significance (MGUS. A 49-year-old white woman had golden-brown metallic dust-like deposits on Descemet's membrane of both eyes. A systemic examination revealed an elevated serum copper, normal serum ceruloplasmin and a normal level of total protein. Serum protein electrophoresis demonstrated a single peak (M-spike in the gamma region (M-protein in serum = 11 g/l. Flow cytometric analysis of the marrow aspirate identified a monoclonal plasma cell population that represents approximately 2% of the total marrow cells consistent with the diagnosis of monoclonal gammopathy of undetermined significance. Copper deposits at the level of Descemet's membrane may be a finding in a patient with monoclonal gammopathy of undetermined significance.Relatar um caso de depósito corneano de cobre em ambos os olhos a nível da membrana de Descemet associado a gamopatia monoclonal de significância indeterminada (GMSI. Paciente feminina, 49 anos, leucodérmica, apresentando depósito corneano de aspecto marrom-ouro a nível da membrana de Descemet em ambos os olhos. Exame sistêmico revelou cobre sérico elevado, ceruloplasmina sérica normal, e proteína total normal. Eletroforese de proteínas séricas demonstrou um pico único na região gama (proteína M = 11 g/l. Análise citométrica de aspirado medular evidenciou uma população de células plasmáticas monoclonais de aproximadamente 2% do total de células medulares consistente com o diagnóstico de gamopatia monoclonal de significância indeterminada. Depósitos de cobre a nível da membrana de Descemet podem ser encontrados em pacientes com gamopatia monoclonal de significância indeterminada.

  8. A SABATH Methyltransferase from the moss Physcomitrella patens catalyzes

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Nan [ORNL; Ferrer, Jean-Luc [Universite Joseph Fourier, France; Moon, Hong S [Department of Plant Sciences, University of Tennessee; Kapteyn, Jeremy [Institute of Biological Chemistry, Washington State University; Zhuang, Xiaofeng [Department of Plant Sciences, University of Tennessee; Hasebe, Mitsuyasu [Laboratory of Evolutionary Biology, National Institute for Biology, 38 Nishigounaka; Stewart, Neal C. [Department of Plant Sciences, University of Tennessee; Gang, David R. [Institute of Biological Chemistry, Washington State University; Chen, Feng [University of Tennessee, Knoxville (UTK)

    2012-01-01

    Known SABATH methyltransferases, all of which were identified from seed plants, catalyze methylation of either the carboxyl group of a variety of low molecular weight metabolites or the nitrogen moiety of precursors of caffeine. In this study, the SABATH family from the bryophyte Physcomitrella patens was identified and characterized. Four SABATH-like sequences (PpSABATH1, PpSABATH2, PpSABATH3, and PpSABATH4) were identified from the P. patens genome. Only PpSABATH1 and PpSABATH2 showed expression in the leafy gametophyte of P. patens. Full-length cDNAs of PpSABATH1 and PpSABATH2 were cloned and expressed in soluble form in Escherichia coli. Recombinant PpSABATH1 and PpSABATH2 were tested for methyltransferase activity with a total of 75 compounds. While showing no activity with carboxylic acids or nitrogen-containing compounds, PpSABATH1 displayed methyltransferase activity with a number of thiols. PpSABATH2 did not show activity with any of the compounds tested. Among the thiols analyzed, PpSABATH1 showed the highest level of activity with thiobenzoic acid with an apparent Km value of 95.5 lM, which is comparable to those of known SABATHs. Using thiobenzoic acid as substrate, GC MS analysis indicated that the methylation catalyzed by PpSABATH1 is on the sulfur atom. The mechanism for S-methylation of thiols catalyzed by PpSABATH1 was partially revealed by homology-based structural modeling. The expression of PpSABATH1 was induced by the treatment of thiobenzoic acid. Further transgenic studies showed that tobacco plants overexpressing PpSABATH1 exhibited enhanced tolerance to thiobenzoic acid, suggesting that PpSABATH1 have a role in the detoxification of xenobiotic thiols.

  9. Physio-pathological roles of transglutaminase-catalyzed reactions

    Institute of Scientific and Technical Information of China (English)

    Mariangela; Ricotta; Maura; Iannuzzi; Giulia; De; Vivo; Vittorio; Gentile

    2010-01-01

    Transglutaminases(TGs) are a large family of related and ubiquitous enzymes that catalyze post-translational modifications of proteins.The main activity of these enzymes is the cross-linking of a glutaminyl residue of a protein/peptide substrate to a lysyl residue of a protein/peptide co-substrate.In addition to lysyl residues,other second nucleophilic co-substrates may include monoamines or polyamines(to form mono-or bi-substituted/crosslinked adducts) or-OH groups(to form ester linkages) .In the absence of co-substrates,the nucleophile may be water,resulting in the net deamidation of the glutaminyl residue.The TG enzymes are also capable of catalyzing other reactions important for cell viability.The distribution and the physiological roles of TG enzymes have been widely studied in numerous cell types and tissues and their roles in several diseases have begun to be identified."Tissue" TG(TG2) ,a member of the TG family of enzymes,has definitely been shown to be involved in the molecular mechanisms responsible for a very widespread human pathology:i.e.celiac disease(CD) .TG activity has alsobeen hypothesized to be directly involved in the pathogenetic mechanisms responsible for several other human diseases,including neurodegenerative diseases,which are often associated with CD.Neurodegenerative diseases,such as Alzheimer’s disease,Parkinson’s disease,supranuclear palsy,Huntington’s disease and other recently identified polyglutamine diseases,are characterized,in part,by aberrant cerebral TG activity and by increased cross-linked proteins in affected brains.In this review,we discuss the physio-pathological role of TG-catalyzed reactions,with particular interest in the molecular mechanisms that could involve these enzymes in the physio-pathological processes responsible for human neurodegenerative diseases.

  10. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.;

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2...... effect on their reactivity: both electron-rich and electron-poor aryl chlorides and bromides or triflates led to good yields. Ortho-substituted aryl halides and heteroaryl halides, however, did not undergo the title reaction....

  11. Pt-Catalyzed Synthesis of Functionalized Symmetrical and Unsymmetrical Disilazanes.

    Science.gov (United States)

    Kuciński, Krzysztof; Szudkowska-Frątczak, Justyna; Hreczycho, Grzegorz

    2016-09-01

    In nearly every total synthesis, silylating agents are employed in synthetic steps to protect sensitive functional groups. A Pt-catalyzed hydrosilylation of various unsaturated substrates to prepare novel symmetrical and unsymmetrical disilazanes is described. The developed synthetic methodology is widely applicable and tolerates all manner of functional groups (e.g., amines, ethers, esters, halogens, silanes, etc.). To demonstrate the value of the described method, mono-substituted 1,1,3,3-tetramethyldisilazanes were further selectively converted to completely new unsymmetrical derivatives. PMID:27414042

  12. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-01-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

  13. Ruthenium-Catalyzed Cascade C—H Functionalization of Phenylacetophenones**

    OpenAIRE

    Mehta, Vaibhav P; García-López, José-Antonio; Greaney, Michael F.

    2014-01-01

    Three orthogonal cascade C—H functionalization processes are described, based on ruthenium-catalyzed C—H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc)2. Each transformation uses C—H functionalization methods to form C—C bonds sequentially, with the indeno furanone synthesis featuring a C—O bond formation as the terminat...

  14. Deoxyribonucleoside kinases: two enzyme families catalyze the same reaction

    DEFF Research Database (Denmark)

    Sandrini, Michael; Piskur, Jure

    2005-01-01

    Mammals have four deoxyribonucleoside kinases, the cytoplasmic (TK1) and mitochondrial (TK2) thymidine kinases, and the deoxycytidine (dCK) and deoxyguanosine (dGK) kinases, which salvage the precursors for nucleic acids synthesis. In addition to the native deoxyribonucleoside substrates, the kin...... kinases can phosphorylate and thereby activate a variety of anti-cancer and antiviral prodrugs. Recently, the crystal structure of human TK1 has been solved and has revealed that enzymes with fundamentally different origins and folds catalyze similar, crucial cellular reactions....

  15. Iron-Catalyzed C-H Functionalization Processes.

    Science.gov (United States)

    Cera, Gianpiero; Ackermann, Lutz

    2016-10-01

    Iron-catalyzed C-H activation has recently emerged as an increasingly powerful tool for the step-economical transformation of unreactive C-H bonds. Particularly, the recent development of low-valent iron catalysis has set the stage for novel C-H activation strategies via chelation assistance. The low-cost, natural abundance, and low toxicity of iron prompted its very recent application in organometallic C-H activation catalysis. An overview of the use of iron catalysis in C-H activation processes is summarized herein up to May 2016. PMID:27573499

  16. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    Energy Technology Data Exchange (ETDEWEB)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: luizfsjr@iq.usp.br [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental

    2013-09-15

    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  17. MOLYBDENUM CATALYZED ACID PEROXIDE BLEACHING OF EUCALYPTUS KRAFT PULP

    OpenAIRE

    Marcos S. Rabelo; Jorge L. Colodette; Vera M. Sacon; Marcelo R. Silva; Marco A. B. Azevedo

    2008-01-01

    Molybdenum catalyzed peroxide bleaching (PMo Stage) consists of pulp treatment with hydrogen peroxide under acidic conditions in the presence of a molybdenum catalyst. Molybdenum is applied in catalytic doses (50-200 mg/kg pulp) and may originate from various sources, including (NH4)6Mo7O24.4H2O, Na2MoO4.2H2O, siliconmolybdate, etc. This work is aimed at optimizing the PMo stage and evaluating its industrial application in the OAZDP sequence. Optimum PMo stage conditions for bleaching eucalyp...

  18. Triphenylphosphine-Catalyzed Michael Addition of Alcohols to Acrylic Compounds

    Institute of Scientific and Technical Information of China (English)

    LIU, Hai-Ling; JIANG, Huan-Feng; WANG, Yu-Gang

    2007-01-01

    A facile triphenylphosphine-catalyzed Michael addition of alcohols to acrylic compounds was described. The reaction was carried out in open air at refluxing temperature in the presence of 10 mol% PPh3. Michael addition of saturated and unsaturated alcohols to acrylonitrile or acrylates has been examined. The reaction gaveβ-alkoxy derivatives with isolated yields of 5%-79%. PPh3 is cheaper and more stable than those trialkylphosphines previously used for the similar reactions, and the products can be easily separated from the reaction mixture via distillation.

  19. Synthesis of Rosin Acid Starch Catalyzed by Lipase

    OpenAIRE

    Rihui Lin; He Li; Han Long; Jiating Su; Wenqin Huang

    2014-01-01

    Rosin, an abundant raw material from pine trees, was used as a starting material directly for the synthesis of rosin acid starch. The esterification reaction was catalyzed by lipase (Novozym 435) under mild conditions. Based on single factor experimentation, the optimal esterification conditions were obtained as follows: rosin acid/anhydrous glucose unit in the molar ratio 2 : 1, reaction time 4 h at 45°C, and 15% of lipase dosage. The degree of substitution (DS) reaches 0.098. Product from e...

  20. FBH1 Catalyzes Regression of Stalled Replication Forks

    DEFF Research Database (Denmark)

    Fugger, Kasper; Mistrik, Martin; Neelsen, Kai J;

    2015-01-01

    DNA replication fork perturbation is a major challenge to the maintenance of genome integrity. It has been suggested that processing of stalled forks might involve fork regression, in which the fork reverses and the two nascent DNA strands anneal. Here, we show that FBH1 catalyzes regression of a...... model whereby FBH1 promotes early checkpoint signaling by remodeling of stalled DNA replication forks....... model replication fork in vitro and promotes fork regression in vivo in response to replication perturbation. Cells respond to fork stalling by activating checkpoint responses requiring signaling through stress-activated protein kinases. Importantly, we show that FBH1, through its helicase activity, is...

  1. Update on muon-catalyzed fusion research at LAMPF

    International Nuclear Information System (INIS)

    An experimental investigation of muon-catalyzed fusion in mixtures of the hydrogen isotopes (and helium) began in 1982 at the Los Alamos Meson Physics Facility. The explorations cover a wide range of mixture densities (12 to 140% liquid hydrogen density) and temperatures (13 to 1800K). Many parameters of muon catalysis have been measured for the first time, including distinct dtμ-molecular formation rates as functions of temperature and density. The discovery that the effective α-μ sticking probability becomes quite small for elevated mixture densities is particularly intriguing and challenging to our understanding. Preliminary new results will be presented in the context of acquired results

  2. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Roman Vladimirovich Rozhkov

    2004-12-19

    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a {beta}-hydrogen in the vinylic halide results in {beta}-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the {alpha}-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  3. Biotinylated phosphoproteins from kinase-catalyzed biotinylation are stable to phosphatases: Implications for phosphoproteomics

    OpenAIRE

    Senevirathne, Chamara; Pflum, Mary Kay H.

    2013-01-01

    Kinase-catalyzed protein phosphorylation is involved in a wide variety of cellular events. Development of methods to monitor phosphorylation is critical to understand cell biology. Our lab recently discovered kinase-catalyzed biotinylation, where ATP-biotin is utilized by kinases to label phosphopeptides or phosphoproteins with a biotin tag. To exploit kinase-catalyzed biotinylation for phosphoprotein purification and identification in a cellular context, the susceptibility of the biotin tag ...

  4. Evaluating Transition-Metal Catalyzed Transformations for the Synthesis of Laulimalide

    OpenAIRE

    Trost, Barry M.; Amans, Dominique; Seganish, W. Michael; Chung, Cheol K.

    2009-01-01

    Laulimalide is a structurally unique 20-membered marine macrolide displaying microtubule stabilizing activity similar to that of paclitaxel and the epothilones. The use of atom economical transformations such as a rhodium-catalyzed cycloisomerization to form the endocyclic dihydropyran, a dinuclear zinc-catalyzed asymmetric glycolate aldol to prepare the syn 1,2-diol and an intramolecular ruthenium-catalyzed alkene-alkyne coupling to build the macrocycle enabled us to synthesize laulimalide v...

  5. Diversity synthesis using the complimentary reactivity of rhodium(II)- and palladium(II)-catalyzed reactions.

    Science.gov (United States)

    Ni, Aiwu; France, Jessica E; Davies, Huw M L

    2006-07-21

    Rhodium(II)-catalyzed reactions of aryldiazoacetates can be conducted in the presence of iodide, triflate, organoboron, and organostannane functionality, resulting in the formation of a variety of cyclopropanes or C-H insertion products with high stereoselectivity. The combination of the rhodium(II)-catalyzed reaction with a subsequent palladium(II)-catalyzed Suzuki coupling offers a novel strategy for diversity synthesis. PMID:16839138

  6. An ab initio study of the nickel-catalyzed transformation of amorphous carbon into graphene in rapid thermal processing.

    Science.gov (United States)

    Chen, Shuang; Xiong, Wei; Zhou, Yun Shen; Lu, Yong Feng; Zeng, Xiao Cheng

    2016-05-14

    Ab initio molecular dynamics (AIMD) simulations are employed to investigate the chemical mechanism underlying the Ni-catalyzed transformation of amorphous carbon (a-C) into graphene in the rapid thermal processing (RTP) experiment to directly grow graphene on various dielectric surfaces via the evaporation of surplus Ni and C at 1100 °C (below the melting point of bulk Ni). It is found that the a-C-to-graphene transformation entails the metal-induced crystallization and layer exchange mechanism, rather than the conventional dissolution/precipitation mechanism typically involved in Ni-catalyzed chemical vapor deposition (CVD) growth of graphene. The multi-layer graphene can be tuned by changing the relative thicknesses of deposited a-C and Ni thin films. Our AIMD simulations suggest that the easy evaporation of surplus Ni with excess C is likely attributed to the formation of a viscous-liquid-like Ni-C solution within the temperature range of 900-1800 K and to the faster diffusion of C atoms than that of Ni atoms above 600 K. Even at room temperature, sp(3)-C atoms in a-C are quickly converted to sp(2)-C atoms in the course of the simulation, and the graphitic C formation can occur at low temperature. When the temperature is as high as 1200 K, the grown graphitic structures reversely dissolve into Ni. Because the rate of temperature increase is considerably faster in the AIMD simulations than in realistic experiments, defects in the grown graphitic structures are kinetically trapped. In this kinetic growth stage, the carbon structures grown from sp(3)-carbon or from sp(2)-carbon exhibit marked differences. PMID:27117235

  7. Enzymatic deposition of Au nanoparticles on the designed electrode surface and its application in glucose detection.

    Science.gov (United States)

    Zhang, Hongfang; Liu, Ruixiao; Sheng, Qinglin; Zheng, Jianbin

    2011-02-01

    This paper reported the enzymatic deposition of Au nanoparticles (AuNPs) on the designed 3-mercapto-propionic acid/glucose oxidase/chitosan (MPA/GOD/Chit) modified glassy carbon electrode and its application in glucose detection. Chit served as GOD immobilization matrix and interacted with MPA through electrostatic attraction. AuNPs, without nano-seeds presented on the electrode surface, was produced through the glucose oxidase catalyzed oxidation of glucose. The mechanism of production of AuNPs was confirmed to be that enzymatic reaction products H(2)O(2) in the solution reduce gold complex to AuNPs. The characterizations of the electrode modified after each assembly step was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy showed the average particle size of the AuNPs is 40nm with a narrow particle size distribution. The content of AuNPs on the electrode surfaces was measured by differential pulse stripping voltammetry. The electrochemical signals on voltammogram showed a linear increase with the glucose concentration in the range of 0.010-0.12mM with a detection limit of 4μM. This provided a method to the determination of glucose. PMID:21115279

  8. Ruthenium(0)-catalyzed hydroarylation of alkynes via ketone-directed C-H functionalization using in situ-generated ruthenium complexes.

    Science.gov (United States)

    Hu, Feng; Szostak, Michal

    2016-08-11

    A versatile method for the Ru(0)-catalyzed hydroarylation of alkynes using weakly-coordinating ketones enabled by the in situ generation of a Ru(0) catalyst from an air-stable, inexpensive and user-friendly Ru(ii) precatalyst is reported for the first time. The method provides straightforward access to a wide range of functionalized ketone building blocks that would be difficult to access by conventional methods. Most crucially, this report demonstrates for the first time that the in situ generated Ru(0) catalysts advance the classic Ru(0)-catalyzed C-H functionalization platform to substrates that would otherwise be unreactive. Product manipulation and mechanistic studies are reported. PMID:27411592

  9. Mechanism of carbon monoxide reactions under high pressure catalyzed by acids and bases

    Energy Technology Data Exchange (ETDEWEB)

    Takezaki, Y.

    1978-05-01

    A review, based mainly on work done at Kyoto University, covers the mechanisms and kinetics of acid-catalyzed carbonylations, including the hydrogen fluoride-catalyzed addition of carbon monoxide to methallyl chloride, the sulfuric acid-catalyzed synthesis of succinic acid from acrylic acid, and the conversion of toluene to p-tolualdehyde in hydrogen fluoride/boron trifluoride by the Gattermann-Koch reaction; and of base-catalyzed reactions, including the production of methyl formate from methanol with 1,8-diazabicyclo (5,4,0)undec-7-ene catalyst and of malonic acid from potassium acetate and potassium carbonate. Graphs, tables, and 34 references.

  10. Metal-Catalyzed Oxidation and Photo-oxidation of Glucagon.

    Science.gov (United States)

    Zhang, Jian

    2016-08-01

    The oxidation of glucagon by the H2O2/Cu(2+) system and by simulated sunlight was studied using HPLC-MS methodologies. It was found that copper ion-catalyzed oxidation is much faster in the residue 1-12 region than in photo-oxidation, but it is slower than photo-oxidation in the residue 18-29 region. This difference is due to the unique feature of the primary sequence of glucagon. The residue 1-12 region contains His-1 and Asp-9 that can bind to Cu(2+) ions and catalyze the oxidation of His-1 and Tyr-10, while the residue 18-29 region lacks these charged residues near the liable Met-27 and Trp-25 and hence no catalysis by the neighboring groups occurs. Fragment (residue 13-17) was more stable than the other regions of the peptide toward photo-oxidation because it contains only one oxidizable residue, Tyr-13. These findings may help explain the mechanism of action of glucagon and provide some hints for the development of effective anti-diabetic drug molecules and stable glucagon formulations. PMID:27435200

  11. Muon catalyzed fusion: old and new aspects of energy production

    International Nuclear Information System (INIS)

    Muon catalyzed fusion of deuterium and tritium (μCF) yields the same energy gain per reaction as fusion with magnetic or inertial confinement (17.6 MeV). The crucial points of μCf are, however, very different, namely (a) the energy cost W(μ) for production of one μ- and (b) the number n of reactions a single muon can catalyze on the average. (b) is ultimately limited by the effective sticking probability ωf : n≤1/ωf. With ''standard'' methods one has W(μ)∼5 GeV, ωf = 0.5%. Hence a ''standard'' μCF reactor can never reach a net energy gain. To solve this problem, ways discussed since about a decade are to increase the efficiency by both (i) energy multiplication using a fissionable blanket and (ii) breeding. A new way to increase the safety of fission devices mostly due to Yu. Petrov is outlined. On the other hand there is a hope to lower W(μ) slightly and ωf drastically, the latter by artificial reactivation. New theoretical results for beam cooling in an omegatron type driven integrated μCF reactor, important for W(μ) and, in particular, ωf, is presented. (orig.)

  12. Porous silicon formation during Au-catalyzed etching

    International Nuclear Information System (INIS)

    The formation of “black” nano-textured Si during the Au-catalyzed wet-chemical etch process was investigated with respect to photovoltaic applications. Cross-sectional scanning electron microscopy (SEM) images recorded at different stages of the etch process exhibit an evolution of a two-layer structure, consisting of cone-like Si hillocks covered with a nano-porous Si (np-Si) layer. Optical measurements confirm the presence of a np-Si phase which appears after the first ∼10 s of the etch process and continuously increases with the etch time. Furthermore, the etch process was investigated on Si substrates with different doping levels (∼0.01–100 Ω cm). SEM images show a transition from the two-layer morphology to a structure consisting entirely of np-Si for higher doping levels (<0.1 Ω cm). The experimental results are discussed on the basis of the model of a local electrochemical etch process. A better understanding of the metal-catalyzed etch process facilitates the fabrication of “black” Si on various Si substrates, which is of significant interest for photovoltaic applications

  13. IRC analysis of methanol carbonylation reaction catalyzed by rhodium complex

    Institute of Scientific and Technical Information of China (English)

    HAO Maorong; FENG Wenlin; JI Yongqiang; LEI Ming

    2004-01-01

    In the reaction cycle for methanol carbonylation catalyzed by Rh complex, the structure geometries of the reactant, intermediates, transition states and product of each elemental reaction have been studied by using the energy gradient method at HF/LANL2DZ level, and the changes of their potential profiles have also been calculated. Through IRC analyses of the transition states for each elemental reaction, it is confirmed that the various structure geometries obtained are stationary points on the cycle reaction pathway of methanol carbonylation catalyzed by Rh complex, and the changes are given in energies and structure geometries of the reactant molecules along the reaction pathway of lowest energy. It has been proposed that the geometrical conversions of intermediates play an important role during the cycle reaction. Through analyses of structure geometries, it has been suggested that, in addition to cis- and trans- structure exchange linkage of catalysis reactive species, the two pathways, cis- and trans-cata- lyzed cycle reactions, can also be linked through geometrical conversion of intermediates, of which the activation energy is 49.79 kJ/mol. Moreover, the reductive elimination elemental reaction may be neither cis-cycle nor trans- one, showing that the cycle reaction can be achieved through various pathways. However different the pathway, the oxidative addition elemental reaction of CH3I is the rate-controlling step.

  14. Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

    Science.gov (United States)

    Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

    2013-05-01

    The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

  15. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Directory of Open Access Journals (Sweden)

    Marcio J. da Silva

    2008-09-01

    Full Text Available The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 is the catalyst on the first step of this process. It must be said, however, that major drawbacks such as substantial reactor corrosion and the great generation of wastes, including the salts formed due to neutralization of the mineral acid, are negative and virtually unsurmountable aspects of this protocol. In this paper, tin(II chloride dihydrate (SnCl2·2H2O, an inexpensive Lewis acid, was evaluated as catalyst on the ethanolysis of oleic acid, which is the major component of several fat and vegetable oils feedstocks. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl2 catalyst was shown to be as active as the mineral acid H2SO4. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. Herein, the effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl2·2H2O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl2 was very close those reported for H2SO4.

  16. Development of Copper-Catalyzed Electrophilic Trifluoromethylation and Exploiting Cu/Cu2O Nanowires with Novel Catalytic Reactivity

    KAUST Repository

    Li, Huaifeng

    2014-06-01

    area of the active component, thereby enhancing the contact between reactants and catalyst dramatically. Based on the above-mentioned concepts and with the aim of achieving one “green and sustainable” approach, C-S bond formation and click reactions catalyzed by Cu/Cu2O nanowires were investigated. It was found that the recyclable core-shell structured Cu/Cu2O nanowires could be applied as a highly reactive catalysts for the cross-coupling reaction between aryl iodides and the cycloaddition of terminal alkynes and azides under ligand-free conditions. Furthermore, these results were the first report for the crosscoupling reaction and click reaction catalyzed by one-dimensional (1D) copper nanowires.

  17. Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step.

    Science.gov (United States)

    Jayakumar, Jayachandran; Cheng, Chien-Hong

    2016-01-26

    A one-pot reaction of substituted benzaldehydes with alkyne-amines by a Rh-catalyzed C-H activation and annulation to afford various natural and unnatural protoberberine alkaloids is reported. This reaction provides a convenient route for the generation of a compound library of protoberberine salts, which recently have attracted great attention because of their diverse biological activities. In addition, pyridinium salt derivatives can also be formed in good yields from α,β-unsaturated aldehydes and amino-alkynes. This reaction proceeds with excellent regioselectivity and good functional group compatibility under mild reaction conditions by using O2 as the oxidant. PMID:26689172

  18. An Umpolung Strategy for the Synthesis of β-Aminoketones via Copper-Catalyzed Electrophilic Amination of Cyclopropanols.

    Science.gov (United States)

    Ye, Zhishi; Dai, Mingji

    2015-05-01

    A novel copper-catalyzed electrophilic amination of cyclopropanols with O-benzoyl-N,N-dialkylhydroxylamines to synthesize various β-aminoketones via a sequence that includes C-C bond cleavage and Csp(3)-N bond formation is reported. The reaction conditions are mild and tolerate a wide range of functional groups including benzoate, tosylate, expoxide, and α,β-unsaturated carbonyls, which are incompatible in the traditional amine nucleophilic conjugate addition and the Mannich reaction conditions. Preliminary mechanistic studies and a proposed catalytic cycle of this umpolung β-aminoketone synthesis process have been described as well. PMID:25885943

  19. Structural Determination of Copolymers from the Cross-catalyzed Reactions of Phenol-formaldehyde and Polymeric Methylenediphenyl Diisocyanate

    OpenAIRE

    Haupt, Robert A

    2013-01-01

    This work reports the elucidation of the structure of a copolymer generated by the cross- catalyzed reactions of PF and pMDI prepolymers.  The electronic behavior of phenolic monomers as perturbed by alkali metal hydroxides in an aqueous environment was studied with 1H and 13C NMR.  Changes in electronic structure and thus reactivity were related to solvated ionic radius, solvent dielectric constant, and their effect on ion generated electric field strength. NMR chemical shifts were used to p...

  20. Vapor-liquid-solid and vapor-solid growth of self-catalyzed GaAs nanowires

    OpenAIRE

    S. Ambrosini; M. Fanetti; V. Grillo; Franciosi, A.; Rubini, S.

    2011-01-01

    We report on the morphological and structural properties of GaAs nanowires nucleated by self-catalyzed vapor-liquid-solid processes by molecular beam epitaxy on Si-treated GaAs substrates. We found that GaAs nanowires display zincblende and/or wurtzite phase depending on the As/Ga abundance ratio at the growth front, that determines the size and supersaturation of the Ga nanoparticles at the nanowire tip. We also found that even when growth conditions lead to the disappearance of such Ga nano...

  1. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO2) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO2, an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  2. Uranium hydrothermal deposits

    Czech Academy of Sciences Publication Activity Database

    René, Miloš

    New York : Nova Science Publishers, 2012 - (Vasiliev, A.; Sidorov, M.), s. 211-244 ISBN 978-1-62081-207-5 Institutional research plan: CEZ:AV0Z30460519 Keywords : uranium * hydrothermal deposits * uraninite Subject RIV: DB - Geology ; Mineralogy

  3. Speleothem (Cave Deposit) Data

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Records of past temperature, precipitation, and other aspects of climate derived from mineral deposits found in caves. Parameter keywords describe what was measured...

  4. Modeled Wet Nitrate Deposition

    Data.gov (United States)

    U.S. Environmental Protection Agency — Modeled data on nitrate wet deposition was obtained from Dr. Jeff Grimm at Penn State Univ. Nitrate wet depostion causes acidification and eutrophication of surface...

  5. Uranium deposit research, 1983

    International Nuclear Information System (INIS)

    Research on uranium deposits in Canada, conducted as a prerequisite for assessment of the Estimated Additional Resources of uranium, revealed that (a) the uranium-gold association in rudites of the Huronian Supergroup preferably occurs in the carbon layers; (b) chloritized ore at the Panel mine, Elliot Lake, Ontario, occurs locally in tectonically disturbed areas in the vicinity of diabase dykes; (c) mineralization in the Black Sturgeon Lake area, Ontario, formed from solutions in structural and lithological traps; (d) the Cigar Lake deposit, Saskatchewan, has two phases of mineralization: monomineralic and polymetallic; (e) mineralization of the JEB (Canoxy Ltd.) deposit is similar to that at McClean Lake; (f) the uranium-carbon assemblage was identified in the Claude deposit, Carswell Structure; and (g) the Otish Mountains area, Quebec, should be considered as a significant uranium-polymetallic metallogenic province

  6. Podiform chromite deposits

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Location and characteristics of 1,124 individual mineral deposits of this type, with grade and tonnage models for chromium as well as several related elements.

  7. Alluvial Deposits in Iowa

    Data.gov (United States)

    Iowa State University GIS Support and Research Facility — This coverage maps alluvial deposits throughout Iowa. This generally would include areas of alluvial soils associated with modern streams that are identified on...

  8. Automatic Payroll Deposit System.

    Science.gov (United States)

    Davidson, D. B.

    1979-01-01

    The Automatic Payroll Deposit System in Yakima, Washington's Public School District No. 7, directly transmits each employee's salary amount for each pay period to a bank or other financial institution. (Author/MLF)

  9. Cluster Implantation and Deposition Apparatus

    DEFF Research Database (Denmark)

    Hanif, Muhammad; Popok, Vladimir

    In the current report, a design and capabilities of a cluster implantation and deposition apparatus (CIDA) involving two different cluster sources are described. The clusters produced from gas precursors (Ar, N etc.) by PuCluS-2 can be used to study cluster ion implantation in order to develop...... contributions to the theory of cluster stopping in matter as well as for practical applications requiring ultra-shallow implantation and modification of surfaces on the nanoscale. Metal clusters from the magnetron cluster source are of interest for the production of optical sensors to detect specific biological...

  10. Metallic mineral deposits

    OpenAIRE

    Crow, M J; van Leeuwen, T.M.

    2005-01-01

    This account concentrates on the the primary metallic mineral deposits and occurrences in Sumatra, in particular the recent discoveries of gold, tin and base metals. The residual and placer deposits are given less emphasis, as no significant discoveries have been made in recent years. The history of mineral exploration and discovery in Indonesia has been reviewed recently by van Leeuwen (1993, 1994), documenting the change in emphasis of mineral-based activities from western to eastern I...

  11. Oscillations in Electrochemical Deposition of Zinc

    Science.gov (United States)

    Wang, Sheng; Zhang, Ke-Qin; Xu, Qing-Yu; Wang, Mu; Peng, Ru-Wen; Zhang, Ze; Ming, Nai-ben

    2003-06-01

    In this article we report the systematic studies on the oscillation of contrast in front of a growing zinc dendrite in electrochemical deposition observed with interference contrast microscopy. The dependence of the oscillation frequency on the experimental conditions, such as the electric current, the resistance of ion transfer, pH of the electrolyte and the tilting of the electrodeposition cell, etc., has been investigated. The microstructures of the electrodeposits are analyzed with transmission electron microscopy. We conclude that the contrast oscillation in front of the zinc deposit is indeed associated with the concentration oscillation, and is synchronized with the electric voltage/current signals. Although the oscillation can be affected by mass transport in the system, we suggest that it roots from the alternating deposition of zinc and zinc hydroxide on the deposit-electrolyte interface.

  12. Stability of nanocrystalline electrochemically deposited layers

    DEFF Research Database (Denmark)

    Pantleon, Karen; Somers, Marcel A. J.

    2009-01-01

    The technological demand for manufacturing components with complex geometries of micrometer or sub-micrometer dimensions and ambitions for ongoing miniaturization have attracted particular attention to electrochemical deposition methods. Thin layers of electrochemically deposited metals and alloys...... have different microstructure and properties compared to bulk materials and the thermodynamic non-equilibrium state of as-deposited layers frequently results in changes of the microstructure as a function of time and/or temperature. The evolving microstructure affects the functionality and reliability...... of electrodeposited components, which can be beneficial, as for the electrical conductivity of copper interconnect lines, or detrimental, as for reduced strength of nickel in MEMS applications. The present work reports on in-situ studies of the microstructure stability of as-deposited nanocrystalline...

  13. Uranium deposits in Africa

    International Nuclear Information System (INIS)

    Africa is not only known for its spectacular diamond, gold, copper, chromium, platinum and phosphorus deposits but also for its uranium deposits. At least two uranium provinces can be distinguished - the southern, with the equatorial sub-province; and the south Saharan province. Uranium deposits are distributed either in cratons or in mobile belts, the first of sandstone and quartz-pebble conglomerate type, while those located in mobile belts are predominantly of vein and similar (disseminated) type. Uranium deposits occur within Precambrian rocks or in younger platform sediments, but close to the exposed Precambrian basement. The Proterozoic host rocks consist of sediments, metamorphics or granitoids. In contrast to Phanerozoic continental uranium-bearing sediments, those in the Precambrian are in marginal marine facies but they do contain organic material. The geology of Africa is briefly reviewed with the emphasis on those features which might control the distribution of uranium. The evolution of the African Platform is considered as a progressive reduction of its craton area which has been affected by three major Precambrian tectonic events. A short survey on the geology of known uranium deposits is made. However, some deposits and occurrences for which little published material is available are treated in more detail. (author)

  14. Optimization of NaOH-catalyzed steam pretreatment of empty fruit bunch

    Science.gov (United States)

    2013-01-01

    Background Empty fruit bunch (EFB) has many advantages, including its abundance, the fact that it does not require collection, and its year-round availability as a feedstock for bioethanol production. But before the significant costs incurred in ethanol production from lignocellulosic biomass can be reduced, an efficient sugar fractionation technology has to be developed. To that end, in the present study, an NaOH-catalyzed steam pretreatment process was applied in order to produce ethanol from EFB more efficiently. Results The EFB pretreatment conditions were optimized by application of certain pretreatment variables such as, the NaOH concentrations in the soaking step and, in the steam step, the temperature and time. The optimal conditions were determined by response surface methodology (RSM) to be 3% NaOH for soaking and 160°C, 11 min 20 sec for steam pretreatment. Under these conditions, the overall glucan recovery and enzymatic digestibility were both high: the glucan and xylan yields were 93% and 78%, respectively, and the enzymatic digestibility was 88.8% for 72 h using 40 FPU/g glucan. After simultaneous saccharification and fermentation (SSF), the maximum ethanol yield and concentration were 0.88 and 29.4 g/l respectively. Conclusions Delignification (>85%) of EFB was an important factor in enzymatic hydrolysis using CTec2. NaOH-catalyzed steam pretreatment, which can remove lignin efficiently and requires only a short reaction time, was proven to be an effective pretreatment technology for EFB. The ethanol yield obtained by SSF, the key parameter determining the economics of ethanol, was 18% (w/w), equivalent to 88% of the theoretical maximum yield, which is a better result than have been reported in the relevant previous studies. PMID:24286374

  15. Effect of deposition pressure and post deposition annealing on SmCo thin film properties

    International Nuclear Information System (INIS)

    In this article we report on the effect of the deposition pressure and the post deposition annealing conditions on the structural and magnetic properties of SmCo thin films deposited on Si(100) wafers employing Ta buffer and capping layers. The films were deposited by DC magnetron sputtering and annealed in vacuum at various temperatures. The films under investigation were isotropic with high remanence magnetization, maximum coercive field of 8 kOe and a squareness ratio of coercivity higher than 0.9. It was found that the Ar pressure during the deposition is a key factor in controlling the stoichiometry and the structural and magnetic properties of the SmCo films, while the effect of the annealing temperature is crucial in optimizing the magnetic properties of the films. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. Multispectral processing of ERTS-A (LANDSAT) data for uranium exploration in the Wind River Basin, Wyoming: a visible region ratio to enhance surface alteration associated with roll-type uraium deposits. Final report, June 1974--July 1975

    International Nuclear Information System (INIS)

    The purpose of this report is to document possible detection capabilities of the LANDSAT multispectral scanner data for use in exploration for uranium roll-type deposits. Spectral reflectivity, mineralogy, iron content, and color paramenters were measured for twenty natural surface samples collected from a semiarid region. The relationships of these properties to LANDSAT response-weighted reflectances and to reflectance ratios are discussed. It was found that the single ratio technique of multispectral processing is likely to be sensitive enough to separate hematitic stain, but not limonitic. A combination of the LANDSAT R/sub 5,4/ and R/sub 7,6/ ratios, and a processing technique sensitive to vegetative cover is recommended for detecting areas of limonitic stain. Digital level slicing of LANDSAT R/sub 5,4/ over the Wind River Basin, after geometric correction, resulted in adequate enhancement of Triassic redbeds and lighter red materials, but not for limonitic areas. No recommendations for prospects in the area were made. Information pertaining to techniques of evaluating laboratory reflectance spectra for remote sensing applications, ratio processing, and planimetric correction of LANDSAT data is presented qualitatively

  17. Oxidation of Cucurbitadienol Catalyzed by CYP87D18 in the Biosynthesis of Mogrosides from Siraitia grosvenorii.

    Science.gov (United States)

    Zhang, Jiangsheng; Dai, Longhai; Yang, Jiangang; Liu, Can; Men, Yan; Zeng, Yan; Cai, Yi; Zhu, Yueming; Sun, Yuanxia

    2016-05-01

    Mogrosides, the principally bioactive compounds extracted from the fruits of Siraitia grosvenorii, are a group of glycosylated cucurbitane-type tetracyclic triterpenoid saponins that exhibit a wide range of notable biological activities and are commercially available worldwide as natural sweeteners. The biosynthesis of mogrosides involves initial cyclization of 2,3-oxidosqualene to the triterpenoid skeleton of cucurbitadienol, followed by a series of oxidation reactions catalyzed by Cyt P450s (P450s) and then glycosylation reactions catalyzed by UDP glycosyltransferases (UGTs). We previously reported the identification of a cucurbitadienol synthase (SgCbQ) and a mogrol C-3 hydroxyl glycosyltransferase (UGT74AC1). However, molecular characterization of further transformation of cucurbitadienol to mogrol by P450s remains unavailable. In this study, we report the successful identification of a multifunctional P450 (CYP87D18) as being involved in C-11 oxidation of cucurbitadienol. In vitro enzymatic activity assays showed that CYP87D18 catalyzed the oxidation of cucurbitadienol at C-11 to produce 11-oxo cucurbitadienol and 11-hydroxy cucurbitadienol. Furthermore, 11-oxo-24,25-epoxy cucurbitadienol as well as 11-oxo cucurbitadienol and 11-hydroxy cucurbitadienol were produced when CYP87D18 was co-expressed with SgCbQ in genetic yeast, and their structures were confirmed by liquid chromatography-solid-phase extraction-nuclear magnetic resonance-mass spectrometry coupling (LC-SPE-NMR-MS). Taken together, these results suggest a role for CYP87D18 as a multifunctional cucurbitadienol oxidase in the mogrosides pathway. PMID:26903528

  18. Metal-catalyzed electroless etching and nanoimprinting silicon nanowire-based solar cells: Silicon nanowire defect reduction and efficiency enhancement by two-step H2 annealing

    Science.gov (United States)

    Jevasuwan, Wipakorn; Nakajima, Kiyomi; Sugimoto, Yoshimasa; Fukata, Naoki

    2016-06-01

    The effects of H2 annealing on material properties including defects of silicon nanowire (SiNW) surface and Si film layer for solar cell application were investigated. Single-junction solar cells consisting of n-SiNWs and chemical vapor deposition grown p-Si matrix were demonstrated using two-step H2 annealing. n-SiNWs formed by two different methods of metal-catalyzed electroless etching and nanoimprinting followed by the Bosch process were compared. Two-step H2 annealing at 900 °C for 10 min after both n-SiNW formations and subsequent p-Si matrix deposition effectively improved SiNW surface and p-Si crystallinity, resulting in higher solar cell efficiency.

  19. LIPASE-CATALYZED TRANSESTERIFICATION OF PALM KERNEL OIL WITH DIALKYLCARBONATES

    Directory of Open Access Journals (Sweden)

    Tjahjono Herawan

    2014-01-01

    Full Text Available Lipase-catalyzed transesterifications-especially in a solvent-free medium-are important for industrial applications because such systems would have an enormous advantage by avoiding the problem of separation, toxicity and flammability of organic solvents. However, the organic solvent-free alcoholysis, especially methanolysis, does not give high conversions. The same problem also occurs when ethyl or methyl acetate are used as acyl acceptors. The main problems of lipase-catalyzed organic solvent-free alcoholysis are first, the solubility of the plant oil in the substrate or solvent and second, the fact that transesterification is an equilibrium reaction. Dialkyl carbonates, versatile compounds due to their chemical reactivity and physical properties, may provide an alternative to solve both problems. Using dialkyl carbonates transesterification is not an equilibrium reaction, because the intermediate compound immediately decomposes to carbon dioxide and an alcohol. Moreover, dialkyl carbonates (especially dimethyl carbonate are cheap and widely available. For single step lipase-catalyzed transesterification of palm kernel oil, diakyl carbonates (in this case dimethyl and diethyl carbonate gave better yields compared to those of short chain alcohols. The rate of ester formation with dialkyl carbonates as substrate was about 6-7 times higher than that obtained with short chain alcohols. The formation of esters was gradually increased by a higher enzyme amount from 5-20% (w/w of oil for 8 h reaction time. However from the economic point of view, an enzyme amount of 10% on the weight base of oil was proposed for further reaction. Generally, the highest ester formation was observed when a temperature of 60°C was used. However, in the case of dimethyl carbonate little difference was observed at reaction temperatures of 60 and 70oC and the reactions proceeded nearly identically. The esters formation increased drastically up to more than 70% when water

  20. Gold-catalyzed tandem reactions of methylenecyclopropanes and vinylidenecyclopropanes.

    Science.gov (United States)

    Zhang, Di-Han; Tang, Xiang-Ying; Shi, Min

    2014-03-18

    Gold catalysis is often the key step in the synthesis of natural products, and is a powerful tool for tandem or domino reaction processes. Both gold salts and complexes are among the most powerful soft Lewis acids for electrophilic activation of carbon-carbon multiple bonds toward a variety of nucleophiles. The core of these reactions relies on the interaction between gold catalysts and π-bonds of alkenes, alkynes, and allenes. Activation of functional groups by gold complexes provides a useful and important method for facilitating many different organic transformations with high atom efficiency. Although they are highly strained, methylenecyclopropanes (MCPs) and vinylidenecyclopropanes (VDCPs) are readily accessible molecules that have served as useful building blocks in organic synthesis. Because of their unique structural and electronic properties, significant developments have been made in the presence of transition metal catalysts such as nickel, rhodium, palladium, and ruthenium during the past decades. However, less attention has been paid to the gold-catalyzed chemistry of MCPs and VDCPs. In this Account, we describe gold-catalyzed chemical transformations of MCPs and VDCPs developed both in our laboratory and by other researchers. Chemists have demonstrated that MCPs and VDCPs have amphiphilic properties. When MCPs or VDCPs are activated by a gold catalyst, subsequent nucleophilic attack by other reagents or ring-opening (ring-expansion) of the cyclopropane moiety will occur. However, the C-C double bonds of MCPs and VDCPs can also serve as nucleophilic reagents while more electrophilic reagents are present and activated by gold catalyst, and then further cascade reactions take place as triggered by the release of ring strain of cyclopropane. Based on this strategy, both our group and others have found some interesting gold-catalyzed transformations in recent years. These transformations of MCPs and VDCPs can produce a variety of polycyclic and

  1. Palladium- and Copper-Catalyzed Solution Phase Synthesis of a Diverse Library of Isoquinolines

    OpenAIRE

    Roy, Sudipta; Roy, Sujata; Neuenswander, Benjamin; Hill, David; Larock, Richard C.

    2009-01-01

    The solution phase synthesis of a 111 member isoquinoline library is described. The isoquinoline scaffold has been accessed through the palladium- and copper-catalyzed cyclization of iminoalkynes and the palladium-catalyzed iminoannulation of internal alkynes, followed by diversification of hydroxyl functionality where it is present.

  2. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2007-01-01

    A variety of interesting bulk chemicals is accessible by the acid-catalyzed hydrolysis of cellulose. An interesting example is levulinic acid, a versatile precursor for fuel additives, polymers, and resins. A detailed kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid is r

  3. ROLE OF COPPER,ZINC-SUPEROXIDE DISMUTASE IN CATALYZING NITROTYROSINE FORMATION IN MURINE LIVER

    Science.gov (United States)

    The solely known function of Cu,Zn-superoxide dismutase (SOD1) is to catalyze the dismutation of superoxide anion into hydrogen peroxide. Our objective was to determine if SOD1 catalyzed murine liver protein nitration induced by acetaminophen (APAP) and lipopolysaccharide (LPS). Liver and plasma ...

  4. Fe-Catalyzed reactions of 2-chloro-1,7-dienes and allylmalonates

    OpenAIRE

    Drabina, Pavel; Nečas, David; Sedlák, Miloš; Kotora, Martin

    2007-01-01

    Fe(III)(BIAP)Cl-3 complex catalyzes alkylative cyclization of 2-chloro-1,7-heptadiene in the presence of triethylaluminum. It also catalyzes deallylation of certain 2-allyl-2-substituted malonates under the same reaction conditions. (c) 2007 Elsevier Ltd. All rights reserved.

  5. Chemical vapor deposition growth. Annual report

    Energy Technology Data Exchange (ETDEWEB)

    Ruth, R.P.; Manasevit, H.M.; Johnson, R.E.; Kenty, J.L.; Moudy, L.A.; Simpson, W.I.; Yang, J.J.

    1976-10-01

    The formal objective of the contract is development of CVD techniques for producing large areas of Si sheet on inexpensive substrate materials, with sheet properties suitable for fabricating solar cells. The techniques developed are to be directed toward (1) minimum-cost processing, (2) production of sheet having properties adequate to result in cells with terrestrial array efficiency of 10 percent or more, and (3) eventual scale-up to large-quantity production. (WDM)

  6. Mild and Efficient Nickel-Catalyzed Heck Reactions with Electron-Rich Olefins

    DEFF Research Database (Denmark)

    Gøgsig, Thomas; Kleimark, Jonatan; Lill, Sten O. Nilsson;

    2012-01-01

    A new efficient protocol for the nickel-catalyzed Heck reaction of aryl triflates with vinyl ethers is presented. Mild reaction conditions that equal those of the corresponding palladium-catalyzed Heck reaction are applied, representing a practical and more sustainable alternative to the conventi......A new efficient protocol for the nickel-catalyzed Heck reaction of aryl triflates with vinyl ethers is presented. Mild reaction conditions that equal those of the corresponding palladium-catalyzed Heck reaction are applied, representing a practical and more sustainable alternative to the...... proved compatible, and the corresponding aryl methyl ketone could be secured after hydrolysis in yields approaching quantitative. Good functional group tolerance was observed matching the characteristics of the analogous Pd-catalyzed Heck reaction. The high levels of catalytic activity were explained by...

  7. Iron- and indium-catalyzed reactions toward nitrogen- and oxygen-containing saturated heterocycles.

    Science.gov (United States)

    Cornil, Johan; Gonnard, Laurine; Bensoussan, Charlélie; Serra-Muns, Anna; Gnamm, Christian; Commandeur, Claude; Commandeur, Malgorzata; Reymond, Sébastien; Guérinot, Amandine; Cossy, Janine

    2015-03-17

    diastereoselectivities observed in favor of the most stable cis-isomers. It is worth noting that spiroketals could be prepared by using this method, which was successfully applied to a synthetic approach toward natural products belonging to the bistramide family. We then turned our attention to heterocycles incorporating two heteroatoms such as isoxazolidines. These frameworks can be found in biologically active natural products, and in addition, they can be transformed into 1,3-amino alcohols, which are of importance in organic chemistry. The use of FeCl3·6H2O allowed the access to a large variety of 3,5-disubstituted isoxazolidines from δ-hydroxylamino allylic alcohol derivatives with good yields and diastereoselectivities in favor of the cis-isomer. Recently, a Lewis acid-catalyzed synthesis of six- and five-membered ring carbonates starting from linear tert-butyl carbonates was reported. In some cases, the mild and chemoselective InCl3 was preferred over FeCl3·6H2O to avoid side-product formation. The resulting cyclic carbonates were easily transformed into 1,3- or 1,2-diols, and a total synthesis of (3S,5S)-alpinikatin was achieved. PMID:25674664

  8. Cobalt catalyzed hydroesterification of a wide range of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Van Rensburg, H.; Hanton, M.; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St Andrews (United Kingdom)

    2011-07-01

    Petrochemical raw materials are an essential raw material for the production of detergents with a substantial portion of synthetic fatty alcohols being produced via hydroformylation of oil or coal derived olefins. Carbonylation processes other than hydroformylation have to date not been commercially employed for the production of fatty esters or alcohols. In this document we highlight the opportunities of converting olefins to esters using cobalt catalyzed alkoxycarbonylation. This process is highly versatile and applicable to a wide range of olefins, linear or branched, alpha or internal in combination with virtually any chain length primary or secondary alcohol allowing the synthesis of a diverse array of compounds such as ester ethoxylated surfactants, methyl branched detergents, lubricants and alkyl propanoates. Furthermore, alkoxycarbonylation of a broad olefin/paraffin hydrocarbon range could be used to produce the corresponding broad cut detergent alcohols. (orig.)

  9. Catalyzed deuterium fueled reversed-field pinch reactor assessment

    International Nuclear Information System (INIS)

    This study is part of a Department of Energy supported alternate fusion fuels program at Science Applications International Corporation. The purpose of this portion of the study is to perform an assessment of a conceptual compact reversed-field pinch reactor (CRFPR) that is fueled by the catalyzed-deuterium (Cat-d) fuel cycle with respect to physics, technology, safety, and cost. The Cat-d CRFPR is compared to a d-t fueled fusion reactor with respect to several issues in this study. The comparison includes cost, reactor performance, and technology requirements for a Cat-d fueled CRFPR and a comparable cost-optimized d-t fueled conceptual design developed by LANL

  10. Multi-enzyme catalyzed processes: Next generation biocatalysis

    DEFF Research Database (Denmark)

    Andrade Santacoloma, Paloma de Gracia; Sin, Gürkan; Gernaey, Krist;

    2011-01-01

    Biocatalysis has been attracting increasing interest in recent years. Nevertheless, most studies concerning biocatalysis have been carried out using single enzymes (soluble or immobilized). Currently, multiple enzyme mixtures are attractive for the production of many compounds at an industrial...... level. In this review, a classification of multienzyme-catalyzed processes is proposed. Special emphasis is placed on the description of multienzyme ex-vivo systems where several reactions are carried out by a combination of enzymes acting outside the cell. Furthermore, reaction and process...... considerations for mathematical modeling are discussed for the specific case where the synthetic reactions are carried out in a single reactor, the so-called multienzyme ‘in-pot’ process. In addition, options for multienzyme ‘in-pot’ process improvements via process engineering and enzyme immobilization...

  11. Towards a methanol economy: Zeolite catalyzed production of synthetic fuels

    DEFF Research Database (Denmark)

    Mentzel, Uffe Vie

    The main focus of this thesis is zeolite catalyzed conversion of oxygenates to hydrocarbon fuels and chemicals. Furthermore, conversion of ethane to higher hydrocarbons has also been studied. After a brief introduction to the concept of “the methanol economy” in the first chapter, the second...... chapter is a literature study of Mobil’s “methanol to hydrocarbons” (MTH) process, giving an overview of the history of the process, the nature of the employed catalysts, and the reaction mechanism. In the third chapter, a series of experiments concerning co conversion of ethane and methanol over a...... commercial H-ZSM-5 zeolite impregnated with gallium and/or molybdenum is described. The object was to investigate if the presence of methanol in the feed could enhance the conversion of ethane, but in all cases the opposite is observed; the presence of methanol actually suppresses the conversion of ethane...

  12. Solid acid catalyzed biodiesel production from waste cooking oil

    Energy Technology Data Exchange (ETDEWEB)

    Jacobson, Kathlene; Gopinath, Rajesh; Meher, Lekha Charan; Dalai, Ajay Kumar [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, SK, S7N 5A9 (Canada)

    2008-12-17

    Various solid acid catalysts were evaluated for the production of biodiesel from low quality oil such as waste cooking oil (WCO) containing 15 wt.% free fatty acids. The zinc stearate immobilized on silica gel (ZS/Si) was the most effective catalyst in simultaneously catalyzing the transesterification of triglycerides and esterification of free fatty acid (FFA) present in WCO to methyl esters. The optimization of reaction parameters with the most active ZS/Si catalyst showed that at 200 C, 1:18 oil to alcohol molar ratio and 3 wt.% catalysts loading, a maximum ester yield of 98 wt.% could be obtained. The catalysts were recycled and reused many times without any loss in activity. (author)

  13. Specific miRNA Stabilization by Gld2-Catalyzed Monoadenylation

    Directory of Open Access Journals (Sweden)

    Andrea D’Ambrogio

    2012-12-01

    Full Text Available MicroRNAs (miRNAs are small, noncoding RNAs that inhibit translation and promote mRNA decay. The levels of mature miRNAs are the result of different rates of transcription, processing, and turnover. The noncanonical polymerase Gld2 has been implicated in the stabilization of miR-122, possibly through catalyzing 3′ monoadenylation; however, there is little evidence that this relationship is one of cause and effect. Here, we biochemically characterize Gld2’s involvement in miRNA monoadenylation and its effect on miRNA stability. We find that Gld2 directly monoadenylates and stabilizes specific miRNA populations in human fibroblasts and that sensitivity to monoadenylation-induced stability depends on nucleotides in the miRNA 3′ end. These results establish a mechanism of miRNA stability and resulting posttranscriptional gene regulation.

  14. WILDCAT: a catalyzed D-D tokamak reactor

    International Nuclear Information System (INIS)

    WILDCAT is a conceptual design of a catalyzed D-D, tokamak, commercial, fusion reactor. WILDCAT utilizes the beneficial features of no tritium breeding, while not extrapolating unnecessarily from existing D-T designs. The reactor is larger and has higher magnetic fields and plasma pressures than typical D-T devices. It is more costly, but eliminates problems associated with tritium breeding and has tritium inventories and throughputs approximately two orders of magnitude less than typical D-T reactors. There are both a steady-state version with Alfven-wave current drive and a pulsed version. Extensive comparison with D-T devices has been made, and cost and safety analyses have been included. All of the major reactor systems have been worked out to a level of detail appropriate to a complete, conceptual design

  15. Synthesis of Rosin Acid Starch Catalyzed by Lipase

    Directory of Open Access Journals (Sweden)

    Rihui Lin

    2014-01-01

    Full Text Available Rosin, an abundant raw material from pine trees, was used as a starting material directly for the synthesis of rosin acid starch. The esterification reaction was catalyzed by lipase (Novozym 435 under mild conditions. Based on single factor experimentation, the optimal esterification conditions were obtained as follows: rosin acid/anhydrous glucose unit in the molar ratio 2 : 1, reaction time 4 h at 45°C, and 15% of lipase dosage. The degree of substitution (DS reaches 0.098. Product from esterification of cassava starch with rosin acid was confirmed by FTIR spectroscopy and iodine coloration analysis. Scanning electron microscopy and X-ray diffraction analysis showed that the morphology and crystallinity of the cassava starch were largely destroyed. Thermogravimetric analysis indicated that thermal stability of rosin acid starch decreased compared with native starch.

  16. Solvent effects in acid-catalyzed biomass conversion reactions.

    Science.gov (United States)

    Mellmer, Max A; Sener, Canan; Gallo, Jean Marcel R; Luterbacher, Jeremy S; Alonso, David Martin; Dumesic, James A

    2014-10-27

    Reaction kinetics were studied to quantify the effects of polar aprotic organic solvents on the acid-catalyzed conversion of xylose into furfural. A solvent of particular importance is γ-valerolactone (GVL), which leads to significant increases in reaction rates compared to water in addition to increased product selectivity. GVL has similar effects on the kinetics for the dehydration of 1,2-propanediol to propanal and for the hydrolysis of cellobiose to glucose. Based on results obtained for homogeneous Brønsted acid catalysts that span a range of pKa values, we suggest that an aprotic organic solvent affects the reaction kinetics by changing the stabilization of the acidic proton relative to the protonated transition state. This same behavior is displayed by strong solid Brønsted acid catalysts, such as H-mordenite and H-beta. PMID:25214063

  17. Radiochemical methods for studying lipase-catalyzed interesterification of lipids

    International Nuclear Information System (INIS)

    Reactions involving lipase-catalyzed interesterification of lipids, which are of commendable interest in biotechnology, have been monitored and assayed by radiochemical methods using 14C-labeled substrates. Medium chain (C12 plus C14) triacylglycerols were reacted in the presence of an immobilized lipase from Mucor miehei and hexane at 450C with methyl [1-14C]oleate, [1-14C]oleic acid, [carboxyl-14C]trioleoylglycerol, [1-14C]octadecenyl alcohol, and [U-14C]glycerol, each of known specific activity. The reactions were monitored and the rate of interesterification determined by radio thin layer chromatography from the incorporation of radioactivity into acyl moieties of triacylglycerols (from methyl oleate, oleic acid, and trioleoylglycerol), alkyl moieties of wax esters (from octadecenyl alcohol), and into glycerol backbone of monoacylglycerols and diacylglycerols (from glycerol). (orig.)

  18. De novo asymmetric synthesis of the mezzettiaside family of natural products via the iterative use of a dual B-/Pd-catalyzed glycosylation‡

    OpenAIRE

    Bajaj, Sumit O.; Sharif, Ehesan U.; Akhmedov, Novruz G.; O'Doherty, George A.

    2014-01-01

    The first synthesis of any and all members of the mezzettiaside family of natural products has been achieved. The reported synthesis features the iterative use of the Taylor catalyst in a dual nucleophilic boron/electrophilic palladium catalyzed regioselective glycosylation. In addition, the de novo approach utilizes atomless protecting groups and the minimal use of protecting groups (2 chloroacetates for the synthesis of 10 natural products). These divergent syntheses occurred in a range of ...

  19. Pd-Catalyzed Coupling of γ-C(sp(3))-H Bonds of Oxalyl Amide-Protected Amino Acids with Heteroaryl and Aryl Iodides.

    Science.gov (United States)

    Han, Jian; Zheng, Yongxiang; Wang, Chao; Zhu, Yan; Huang, Zhi-Bin; Shi, Da-Qing; Zeng, Runsheng; Zhao, Yingsheng

    2016-07-01

    Pd-catalyzed regioselective coupling of γ-C(sp(3))-H bonds of oxalyl amide-protected amino acids with heteroaryl and aryl iodides is reported. A wide variety of iodides are tolerated, giving the corresponding products in moderate to good yields. Various oxalyl amide-protected amino acids were compatible in this C-H transformation, thus representing a practical method for constructing non-natural amino acid derivatives. PMID:27286881

  20. Nickel-Catalyzed Intramolecular [3 + 2 + 2] Cycloadditions of Alkylidenecyclopropanes. A Straightforward Entry to Fused 6,7,5-Tricyclic Systems

    OpenAIRE

    Saya Codesal, Lucía; Fernández, Israel; López, Fernando; Mascareñas Cid, José Luis

    2014-01-01

    A highly diastereo- and chemoselective intramolecular nickel-catalyzed cycloaddition of alkene- and alkyne-tethered alkynylidenecyclopropanes is reported. The method constitutes the first fully intramolecular [3 + 2 + 2] alkylidenecyclopropropane cycloaddition occurring via a proximal cleavage of the cyclopropane and makes it possible to build relevant 6,7,5-tricyclic frameworks in a single-pot reaction. Importantly, the reaction outcome is highly dependent on the characteristics of the nicke...