WorldWideScience

Sample records for catalyzed reporter deposition

  1. 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 ...

  2. 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

  3. 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.

  4. 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

  5. Hot wire chemical vapor deposition: limits and opportunities of protecting the tungsten catalyzer from silicide with a cavity

    Energy Technology Data Exchange (ETDEWEB)

    Frigeri, P.A. [Dept. de Fisica Aplicada i Optica, Universitat de Barcelona, Barcelona-08028 (Spain); Nos, O., E-mail: oriol_nos@ub.ed [Dept. de Fisica Aplicada i Optica, Universitat de Barcelona, Barcelona-08028 (Spain); Ecotecnia (ALSTOM Group) (Spain); Bengoechea, S.; Frevert, C.; Asensi, J.M.; Bertomeu, J. [Dept. de Fisica Aplicada i Optica, Universitat de Barcelona, Barcelona-08028 (Spain)

    2009-04-30

    Hot Wire Chemical Vapor Deposition (HW-CVD) is one of the most promising techniques for depositing the intrinsic microcrystalline silicon layer for the production of micro-morph solar cells. However, the silicide formation at the colder ends of the tungsten wire drastically reduces the lifetime of the catalyzer, thus limiting its industrial exploitation. A simple but interesting strategy to decrease the silicide formation is to hide the electrical contacts of the catalyzer in a long narrow cavity which reduces the probability of the silane molecules to reach the colder ends of the wire. In this paper, the working mechanism of the cavity is elucidated. Measurements of the thickness profile of the silicon deposited in the internal walls of the cavity have been compared with those predicted using a simple diffusion model based on the assumption of Knudsen flow. A lifetime study of the protected and unprotected wires has been carried out. The different mechanisms which determine the deterioration of the catalyzer have been identified and discussed.

  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. 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

  9. 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.

  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. 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)

  12. 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

  13. 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

  14. 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

  15. 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

  16. Aerosol deposition in the human respiratory system. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Yu, C.P.

    1988-01-01

    Attempts were made to develop mathematical models for the deposition of aerosols in the human respiratory system. Expressions were obtained for the mean deposition efficiency for nasal inspiration, nasal expiration, and mouth inspiration. A determination was made of statistical properties associated with each deposition efficiency due to intersubject and intrasubject variabilities. Expressions were then derived for head deposition with combined nose and mouth breathing. In the lung, deposition is a result primarily of impaction, sedimentation, and diffusion. While there was no adequate model for impaction, several deposition formulae for sedimentation were derived as well as ones for diffusion. Studies were also made of the particle charge effect, as the electrostatic image force on a particle contributes to its deposition. There is, however, a threshold charge per particle below which the particle charge has no effect on deposition. Deposition data on ultrafine particles is scarce due to the difficulties in conducting proper experiments.

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

    NARCIS (Netherlands)

    Berger, Frank; Paulmurugan, Ramasamy; Bhaumik, Srabani; Gambhir, Sanjiv Sam

    2008-01-01

    Purpose 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 g

  18. Technology transfer report: Production base catalyzed decomposition process Guam, Mariana Islands. Final report, October 1992-June 1997

    Energy Technology Data Exchange (ETDEWEB)

    Benoit, S.D.; Gallagher, W.E.; Chan, D.B.; Fukumoto, J.L.; Crisostomo, F.Q.

    1997-10-01

    The first product base catalyzed decomposition process (BCDP) operated successfully on Guam April 1996 to June 1997. The unit treated 11,700 tons of soil at PCB levels over 2,000 ppm to below 0.05 ppm at rates up to 2 tons per hour. A novel air control system produces a stack gas cleaner than required by hazardous waste incinerators. The Naval Facilities Engineering Service Center managed the development of the unit for the Navy`s Pacific Division from the laboratory to a full production system over an 8-year period. Conventional remediation on Guam would have required that the contaminated material be placed in drums and shipped over 6,000 miles to a mainland disposal facility - a very expensive procedure. In finding a solution to this problem, the Navy created a remediation system that is cost-effective on the mainland as well as Guam, and environmentally safe to operate.

  19. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

    2005-12-15

    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  20. 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.

  1. 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.

  2. 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

  3. Hard-facing with electro-spark deposition. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Kees, K.P.

    1983-01-01

    A common method to improve wear resistance of metals in rubbing contact is to increase their surface hardness. Electro-Spark Deposition is a process which uses capacitive discharge pulses of high current passing through a hard carbide electrode in contact with and scanning the metal surface to be hardened. The result is a thin, hard, adherent coating of carbide deposited with a minimum of heat influence on the substrate and a significant increase in wear life of the coated metal. Electro-Spark Deposition is similar to a micro-welding process. It is a simple, portable and inexpensive coating method, which has great potential for commercial utilization. This thesis is an in depth study of the parameters associated with the ESD process and the wear resistance of the coatings.

  4. 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;

    reductase) and nosZ (encoding nitrous oxide reductase), to detect nitrate-reducing and completely denitrifying bacteria, respectively. Enzyme-labelled oligonucleotide probes and digoxygenin-labelled polynucleotide probes were evaluated for in situ hybridization in combination with immunochemical detection......Z in freshwater sediments and the guts of benthic invertebrates.    ...

  5. An analysis of the growth of silver catalyzed InxGa1-xAs nanowires on Si (100) by metal organic chemical vapor deposition

    Science.gov (United States)

    Sarkar, K.; Palit, M.; Chattopadhyay, S.; Banerji, P.

    2016-08-01

    A model is proposed here to understand the nucleation of III-V semiconductor nanowires (NW). Whereas the classical nucleation theory is not adequately sufficient in explaining the evolution of the shape of the NWs under different chemical environment such as flow rate or partial pressure of the precursors, the effect of adsorption and desorption mediated growth, and diffusion limited growth are taken into account to explain the morphology and the crystal structure of InxGa1-xAs nanowires (NW) on Silicon (100) substrates grown by a metalorganic chemical vapor deposition technique. It is found that the monolayer nucleus that originates at the triple phase line covers the entire nucleus-substrate (NS) region at a specific level of supersaturation and there are cases when the monolayer covers a certain fraction of the NS interface. When the monolayer covers the total NS interface, NWs grow with perfect cylindrical morphology and whenever a fraction of the interface is covered by the nucleus, the NWs become curved as observed from high resolution transmission electron microscopy images. The supersaturation, i.e., the chemical potential is found to be governed by the concentration of precursors into the molten silver which in the present case is taken as a catalyst. Our study provides new insights into the growth of ternary NWs which will be helpful in understanding the behavior of growth of different semiconducting NWs.

  6. 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.

  7. 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...

  8. 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

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. Fat deposition in the urinary bladder wall: Incidental finding on abdominal computed tomography: A case report

    Energy Technology Data Exchange (ETDEWEB)

    Park, Min Ho; Moon, Sung Kyoung; Ahn, Sung Eun; Park, Seong Jin; Lim, Joo Won; Lee, Dong Ho [Dept. of Radiology, Kyung Hee University Medical Center, Kyung Hee University School of Medicine, Seoul (Korea, Republic of)

    2015-02-15

    In a computed tomography (CT) scan, fat deposition in the urinary bladder wall is seen as a linear hypoattenuating band surrounded by soft tissue density. It is uncommon, but is often seen in normal cases. However, there is no report of fat deposition in the urinary bladder wall in Korea. The authors encountered a 62-year-old male patient who showed an incidental hypoattenuating band in the urinary bladder wall on abdominal CT. The patient showed no clinical signs related to fat deposition in the urinary bladder wall. When the patient's previous abdominal CT was retrospectively reviewed, the same CT finding was seen. This linear hypoattenuating band within the urinary bladder wall should be considered as a normal CT finding, although it is uncommon.

  15. 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.

  16. Evaluation of the full-scale Base Catalyzed Decomposition Process (BCDP) unit located in Guam. Research report, January 1996--July 1998

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-08-01

    In April 1996, IT Corporation began operating the first stage of a demonstration-scale system called the Base Catalyzed Decomposition Process (BCDP) on Guam for the US Navy. This report presents the results of a study funded by NRMRL. The purpose of the study was to obtain data which will facilitate a more thorough understanding of the BCD chemistry and the fate of soil-bound PCBs, polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) in the BCDP/APCS operating on Guam. The scope of this study entailed sampling and analyses of Guam soil (both before and after treatment) as well as sampling and analyses of the liquids, soil particles, and offgas streams from the APC during normal operation of the Guam BCDP system. The objectives of the study are as follows: (1) Determine the efficiency of the BCD first-stage rotary kiln reactor for removing PCBs, PCDDs, and PCDFs from Guam soil; (2) Concurrent with Objective 1, determine where in the Air Pollution Control System PCBs, PCDDs, and PCDFs are being removed.

  17. Light-chain deposition disease of the kidney: a case report.

    Science.gov (United States)

    Darouich, Sihem; Goucha, Rym; Jaafoura, Mohamed Habib; Zekri, Semy; Kheder, Adel; Maiz, Hedi Ben

    2012-04-01

    A 41-year-old man was admitted for evaluation of nephrotic syndrome associated with microhematuria, hypertension, and moderate renal failure. In serum and urine samples, monoclonal IgG-lambda was detected. Bone marrow examination showed normal representation of all cell lines with normal range of plasma cells. Renal biopsy demonstrated diabetes-like nodular glomerulosclerosis. Immunofluorescence failed to demonstrate the presence of kappa or lambda light chains in the kidney. Electron microcopy showed granular electron-dense deposits along the glomerular basement membranes and in the mesangial nodules. The patient was diagnosed as having light-chain deposition disease (LCDD) without evidence of plasma cell dyscrasia. This report was designed to stress the significant challenges that remain in the diagnosis of LCDD-related glomerulopathy. The salient morphological features that help in making an accurate diagnosis are discussed. PMID:22471437

  18. 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

  19. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  20. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    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 ...

  1. 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.

  2. 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.

  3. 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

  4. Thresholds for protecting Pacific Northwest ecosystems from atmospheric deposition of nitrogen: state of knowledge report

    Science.gov (United States)

    Cummings, Tonnie; Blett, Tamara; Porter, Ellen; Geiser, Linda; Graw, Rick; McMurray, Jill; Perakis, Steven S.; Rochefort, Regina

    2014-01-01

    The National Park Service and U.S. Forest Service manage areas in the states of Idaho, Oregon, and Washington – collectively referred to in this report as the Pacific Northwest - that contain significant natural resources and provide many recreational opportunities. The agencies are mandated to protect the air quality and air pollution-sensitive resources on these federal lands. Human activity has greatly increased the amount of nitrogen emitted to the atmosphere, resulting in elevated amounts of nitrogen being deposited in park and forest ecosystems. There is limited information in the Pacific Northwest about the levels of nitrogen that negatively affect natural systems, i.e., the critical loads. The National Park Service and U.S. Forest Service, with scientific input from the U.S. Geological Survey, have developed an approach for accumulating additional nitrogen critical loads information in the Pacific Northwest and using the data in planning and regulatory arenas. As a first step in that process, this report summarizes the current state of knowledge about nitrogen deposition, effects, and critical loads in the region. It also describes ongoing research efforts and identifies and prioritizes additional data needs.

  5. 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.

  6. Fundamental studies of the mechanisms of slag deposit formation: Final report

    Energy Technology Data Exchange (ETDEWEB)

    Austin, L.G.; Benson, S.; Rabinovich, A.; Tangsathitkulchai, M.; Schobert H.H.

    1987-07-01

    The kinetics of ash deposition on utility boilers have been studied. A heated tube furnace system was used in the study. Areas of consideration in the deposition mechanics were: close space knowledge of chemical composition and distribution of inorganic constituents in coal, transformations and reactions of the inorganic constituents in the flame, ash transport mechanisms, initial adhesion of ash particles to heat transfer surfaces and subsequently to each other to form a deposit, and further interactions of the deposited ash to grow a strong deposit. Interactions of deposited ash that cause changes in physical and chemical properties in an aged deposit are due to processes such as sintering, chemical reactions, and melting. The degree of these changes increases as the deposit grows from the heat transfer surfaces where it forms. All of these changes during the deposit formation process are coal-specific and are strongly dependent on the boiler configuration and operating conditions. 18 refs., 55 figs., 42 tabs.

  7. 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

  8. 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.

  9. 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...

  10. 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)

  11. 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.

  12. 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...

  13. 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)

  14. 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)

  15. 50 CFR 600.1014 - Fee collection deposits, disbursements, records, and reports.

    Science.gov (United States)

    2010-10-01

    ... each fish seller for the fee fish) are essential audit documentation. (h) Confidentiality of records... 50 Wildlife and Fisheries 8 2010-10-01 2010-10-01 false Fee collection deposits, disbursements... Fishing Capacity Reduction Framework § 600.1014 Fee collection deposits, disbursements, records,...

  16. 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.

  17. 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)

  18. 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)

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. Vacuum deposited polycrystalline silicon films for solar cell applications. Second quarterly technical progress report. January 1-March 31, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Feldman, C.; Arlington, III, C. H.; Blum, N. A.; Satkiewicz, F. G.

    1980-05-01

    A careful study of a specially formed thin silicon layer on TiB/sub 2/-coated sapphire reveals that the interaction layer of TiSi/sub 2/ is composed of larger grains. Processing steps were developed which lead closer to the goal of fabricating polycrystalline silicon photovoltaic devices completely by vacuum deposition. Both n-type and p-type silicon are now being deposited. New deposition masks were made for depositing the n-regions upon the p-layers. New electrode deposition masks were also made for a direct electroding process to replace the photolithographic process used previously. The TiB/sub 2/ bottom electrode fabrication has been achieved in a single vacuum chamber. Reaction constants and activation energy for TiB/sub 2/ layer formation were determined to be less than those reported by other authors for bulk material. Studies of crystallite growth and interfacial interactions have continued. Major sources of undesirable impurities have been identified and removed from the vacuum chambers. The changes made this quarter have not been incorporated into a completed photovoltaic device.

  4. 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

    , and 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 contaminated surface. The various parameters determined wereapplied 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 magnitudeas 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 ofcontamination, may have amounted to several...

  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. 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.

  7. 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

  8. 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

  9. 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.

  10. Altitude dependence of trace substance deposition from clouds to forests. Final report; Hoehenabhaengigkeit der Spurenstoffdeposition durch Wolken auf Waelder. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Pahl, S.; Winkler, P.

    1995-12-31

    Novel forest decline is particularly pronounced in the area of the ridges of medium-range mountains. Whereas acid precipitation was viewed as its sole cause early on in the discussions, it turned out later that the impact of trace gases, too, contributes to the damaging of forests. This report wants to point out the importance of fog interception, which equally plays a part in the pollutant receipts of forests. The deposition of fog water to a forest stand depends very much on altitude, so that trace substance deposition, too, is to be expected to be dependent on altitude. By attempting to quantify this effect, the report helps to pinpoint areas of relevance of this deposition pathway (orig./KW) [Deutsch] Die neuartigen Waldschaeden sind in den Kammlagen der Mittelgebirge besonders ausgepraegt. Waehrend in der anfaenglichen Diskussion die sauren Niederschlaege als alleinige Ursache angesehen wurden, zeigte sich spaeter, dass auch Einwirkungen von Spurengasen zur Schaedigung des Waldes beitragen. Dieser Bericht soll auf die Bedeutung der Nebelinterzeption aufmerksam machen, die ebenfalls zum Schadstoffeintrag in den Wald beitraegt. Die Deposition von Wolkenwasser auf einen Waldbestand ist stark abhaengig von der Hoehenlage, in der sich der Waldbestand befindet, so dass auch eine Hoehenabhaengigkeit des Spurenstoffeintrages zu erwarten ist. Durch den Versuch der Quantifizierung traegt dieser Bericht dazu bei, Gebiete zu erkennen, in denen dieser Eintragspfad eine Rolle spielt. (orig./KW)

  11. 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

  12. 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.

  13. 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)

  14. 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.

  15. 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.

  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. 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

  18. 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.

  19. Integrated assessment of acid deposition impacts using reduced-form modeling. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Sinha, R.; Small, M.J.

    1996-05-01

    Emissions of sulfates and other acidic pollutants from anthropogenic sources result in the deposition of these acidic pollutants on the earth`s surface, downwind of the source. These pollutants reach surface waters, including streams and lakes, and acidify them, resulting in a change in the chemical composition of the surface water. Sometimes the water chemistry is sufficiently altered so that the lake can no longer support aquatic life. This document traces the efforts by many researchers to understand and quantify the effect of acid deposition on the water chemistry of populations of lakes, in particular the improvements to the MAGIC (Model of Acidification of Groundwater in Catchments) modeling effort, and describes its reduced-form representation in a decision and uncertainty analysis tool. Previous reduced-form approximations to the MAGIC model are discussed in detail, and their drawbacks are highlighted. An improved reduced-form model for acid neutralizing capacity is presented, which incorporates long-term depletion of the watershed acid neutralization fraction. In addition, improved fish biota models are incorporated in the integrated assessment model, which includes reduced-form models for other physical and chemical processes of acid deposition, as well as the resulting socio-economic and health related effects. The new reduced-form lake chemistry and fish biota models are applied to the Adirondacks region of New York.

  20. Renal Light Chain Deposition Associated with the Formation of Intracellular Crystalline Inclusion Bodies in Podocytes: A Rare Case Report.

    Science.gov (United States)

    Wang, Yuan-da; Dong, Zhe-yi; Zhang, Xue-guang; Zhang, Wei; Yin, Zhong; Qiu, Qiang; Chen, Xiang-mei

    2016-01-01

    We herein report the case of an elderly woman with bone pain and proteinuria as the main clinical manifestations. The patient was diagnosed with the IgG κ type of multiple myeloma. Her renal pathology consisted of widespread κ light chain protein deposition associated with the formation of large quantities of rod-like crystals in podocytes. This phenomenon is very rare. We explored the significance of this crystal formation via a detailed and descriptive analysis and also performed a literature review, thus providing data to increase the available information about this type of disease.

  1. Case Report of a Fatal Antifreeze Ingestion with a Record High Level and Impressive Renal Crystal Deposition

    Science.gov (United States)

    2016-01-01

    Ethylene glycol, methanol, and diethylene glycol are readily available in many household and commercially available products. While these alcohols are relatively nontoxic themselves, their acidic metabolites are toxic and can result in significant morbidity and mortality. Herein we report a lethal case of massive ethylene glycol ingestion in a suicide with a record high level (1254 mg/dL) and images of the histologic examination of the kidneys revealing impressive calcium oxalate crystal deposition. Autopsy findings also showed evidence of mild cerebral edema. PMID:27747109

  2. 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

    2016-07-05

    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.

  3. 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.

  4. 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.

  5. 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).

  6. 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.

  7. 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.

  8. Deposition and properties of novel nitride superlattice coatings. Progress report, September 28, 1990--April 1993

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, S.A.; Sproul, W.D.; Wong, M.S.

    1993-04-01

    We have carried out detailed studies of the processing, structure, and properties of certain polycrystalline superlattice coatings, including TiN/NbN, TiN/VN, TiN/Ni, and TiN/NiCr, which were produced using an opposed, dual-cathode, high-rate, reactive, unbalanced-magnetron sputtering system. The coatings exhibited hardness values as high as 5200 kgf/mm{sup 2} for TiN/NbN, 5100 for TiN/VN, 3500 for TiN/Ni, and 3200 for TiN/NiCr. These hardness values are all twice higher than their corresponding rule-of-mixture hardness values. The structure and properties of the coatings are a strong function of superlattice period, partial pressure of N{sub 2}, and energy and flux of ion bombardment during deposition. Possible mechanisms for hardness enhancement in the polycrystalline superlattice appear to be a result of dislocation blocking due to coherency strains, difference in dislocation line energies between layers, and small grain sizes. In response to high interest shown by industry, BIRL formed a 2-year Industrial Group Program, currently with 12 members, to transfer the superlattice coating technology.

  9. 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

  10. Defect states in plasma-deposited a-Si:H. Final report, February 1979-January 1980

    Energy Technology Data Exchange (ETDEWEB)

    Knights, J C

    1980-02-15

    Studies of defects in plasma-deposited, hydrogenated amorphous silicon (a-Si:H), covering the period February 1979-January 1980 are described. Substantial progress has been made in understanding defect structures, their electronic properties and the influence of doping. The two most significant results are surprising, in one case for simplicity where complexity was expected, and in the other for complexity where simplicity had been presumed. In the first study we have clarified the nature of the defects by showing the connection between luminescence and light induced ESR experiments. The results indicate that dangling bonds having a positive electronic correlation energy are sufficient to explain most of the experimental information. The second study demonstrates the existence of microstructural inhomogeneities, arising from the nucleation and growth of the films. Thus the usual assumption of a uniform alloy with a random distribution of defects must be modified in considering processes such as electrical conduction, trapping, recombination, hydrogen effusion, etc. Of considerable technological and fundamental interest is the influence of doping on the defect behavior. Previous indications that doping introduces defect states have been confirmed. It remains to determine why this behavior occurs, and if there are any means of circumventing the problem.

  11. Bioorthogonal Catalysis: A General Method To Evaluate Metal-Catalyzed Reactions in Real Time in Living Systems Using a Cellular Luciferase Reporter System.

    Science.gov (United States)

    Hsu, Hsiao-Tieh; Trantow, Brian M; Waymouth, Robert M; Wender, Paul A

    2016-02-17

    The development of abiological catalysts that can function in biological systems is an emerging subject of importance with significant ramifications in synthetic chemistry and the life sciences. Herein we report a biocompatible ruthenium complex [Cp(MQA)Ru(C3H5)](+)PF6(-) 2 (Cp = cyclopentadienyl, MQA = 4-methoxyquinoline-2-carboxylate) and a general analytical method for evaluating its performance in real time based on a luciferase reporter system amenable to high throughput screening in cells and by extension to evaluation in luciferase transgenic animals. Precatalyst 2 activates alloc-protected aminoluciferin 4b, a bioluminescence pro-probe, and releases the active luminophore, aminoluciferin (4a), in the presence of luciferase-transfected cells. The formation and enzymatic turnover of 4a, an overall process selected because it emulates pro-drug activation and drug turnover by an intracellular target, is evaluated in real time by photon counting as 4a is converted by intracellular luciferase to oxyaminoluciferin and light. Interestingly, while the catalytic conversion (activation) of 4b to 4a in water produces multiple products, the presence of biological nucleophiles such as thiols prevents byproduct formation and provides almost exclusively luminophore 4a. Our studies show that precatalyst 2 activates 4b extracellularly, exhibits low toxicity at concentrations relevant to catalysis, and is comparably effective in two different cell lines. This proof of concept study shows that precatalyst 2 is a promising lead for bioorthogonal catalytic activation of pro-probes and, by analogy, similarly activatable pro-drugs. More generally, this study provides an analytical method to measure abiological catalytic activation of pro-probes and, by analogy with our earlier studies on pro-Taxol, similarly activatable pro-drugs in real time using a coupled biological catalyst that mediates a bioluminescent readout, providing tools for the study of imaging signal amplification

  12. 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

  13. 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...

  14. 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)

  15. 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.

  16. Fundamental studies of the chemical vapor deposition of diamond. Final technical report, April 1, 1988--December 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Nix, W.D.

    1995-05-01

    We submit here a final technical report for the research program entitled: Fundamental Studies of the Chemical Vapor Deposition of Diamond, DOE Grant No. DE-FG05-88ER45345-M006. This research program was initiated in 1988 under the direction of the late Professor David A. Stevenson and was renewed in 1992. Unfortunately, at the end of 1992, just as the last phase of this work was getting underway, Professor Stevenson learned that he had developed mesothelioma, a form of cancer based on asbestos. Professor Stevenson died from that disease in February of 1994. Professor William D. Nix, the Chairman of the Materials Science department at Stanford was named the Principal Investigator. Professor Nix has assembled this final technical report. Much of the work of this grant was conducted by Mr. Paul Dennig, a graduate student who will receive his Ph.D. degree from Stanford in a few months. His research findings are described in the chapters of this report and in the papers published over the past few years. The main discovery of this work was that surface topology plays a crucial role in the nucleation of diamond on silicon. Dennig and his collaborators demonstrated this by showing that diamond nucleates preferentially at the tips of asperities on a silicon surface rather than in the re-entrant comers at the base of such asperities. Some of the possible reasons for this effect are described in this report. The published papers listed on the next page of this report also describe this research. Interested persons can obtain copies of these papers from Professor Nix at Stanford. A full account of all of the research results obtained in this work is given in the regular chapters that follow this brief introduction. In addition, interested readers will want to consult Mr. Dennig`s Ph.D. dissertation when it is made available later this year.

  17. Alternative pathway dysfunction in kidney disease: a case report and review of dense deposit disease and C3 glomerulopathy.

    Science.gov (United States)

    Hawfield, Amret; Iskandar, Samy S; Smith, Richard J H

    2013-05-01

    Dysfunction of the alternative pathway of complement activation provides a pathophysiologic link between the C3 glomerulopathies dense deposit disease and glomerulonephritis with C3 deposition and the clinically and histologically distinct atypical hemolytic uremic syndrome. Previously, dense deposit disease was known as membranoproliferative glomerulonephritis type II, but paucity or complete lack of immunoglobulin deposition on immunofluorescence staining and advances in our understanding of alternative pathway dysregulation have separated it from immune complex-mediated membranoproliferative glomerulonephritis types I and III. We discuss a case of dense deposit disease and review the current pathologic classification, clinical course, treatment options, and related conditions.

  18. 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.

  19. 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.

  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. Rh-Catalyzed arylation of fluorinated ketones with arylboronic acids.

    Science.gov (United States)

    Dobson, Luca S; Pattison, Graham

    2016-09-25

    The Rh-catalyzed arylation of fluorinated ketones with boronic acids is reported. This efficient process allows access to fluorinated alcohols in high yields under mild conditions. Competition experiments suggest that difluoromethyl ketones are more reactive than trifluoromethyl ketones in this process, despite their decreased electronic activation, an effect we postulate to be steric in origin.

  2. 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.

  3. Gold-Catalyzed Synthesis of Heterocycles

    Science.gov (United States)

    Arcadi, Antonio

    2014-04-01

    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  4. 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

  5. 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.

  6. Predictive models for deposition of inhaled diesel exhaust particles in humans and laboratory species. Research report, July 1984-January 1987

    Energy Technology Data Exchange (ETDEWEB)

    Yu, C.P.; Xu, G.B.

    1987-07-01

    A deposition model for diesel-exhaust particles was formulated mathematically from available scientific data, and was used to predict the deposition of particles in the airways of laboratory animals and of humans of different ages. In addition, a lung-growth model was formulated for humans, from infancy to adulthood, to predict the effect of age on deposition. The investigators predicted from their models that: (1) deposition in the alveoli is markedly affected by changes in the size distribution of particles; (2) nose- versus mouth-breathing had little effect on deposition in the alveoli; (3) increased minute ventilation substantially increased the rate of particle deposition; and (4) age (in humans) influenced the levels of deposition observed in the unciliated regions of the airways (the highest levels of deposition occurred in infants under two years, decreased in children over two years, and decreased again in adults aged 25 years or older); and (5) the deposition rate in laboratory animals was higher than in humans of all ages.

  7. 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

  8. Instruction for evaluating deposit of bacillus thuringiensis formulas during aerial treatments. Information report No. LAU-X-54

    Energy Technology Data Exchange (ETDEWEB)

    Smirnoff, W.A.

    1982-01-01

    Studies carried out form many years revealed that the methods used for deposit assessment of chemical insecticides could not be used with Bacillus thuringiensis. A new method was developed giving the quantity of viable spores dispersed per surface unit. Details of this method are concisely described in this document. It specifically provides instructions for evaluating deposit of Bacillus thuringiensis formulas during aerial treatments.

  9. $MNO_2$ catalyzed carbon electrodes for dioxygen reduction in concentrated alkali

    OpenAIRE

    Manoharan, R; Shulka, AK

    1984-01-01

    A process to deposit $\\gamma-MnO_2$ catalytic oxide onto coconut-shell charcoal substrate is described. Current-potential curves for electroreduction of dioxygen with electrodes fabricated from this catalyzed substrate are obtained in 6M KOH under ambient conditions. The performance of these electrodes is competitive with platinized carbon electrodes.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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...

  15. 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...

  16. 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.

  17. 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).

  18. 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 [1]. That is, we present a more complete suite of validation results with respect to to the well-known Lockwood energy deposition experiment [2]. 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).

  19. 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...

  20. 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.

  1. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

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

    2015-01-01

    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin...

  2. Flexible CIGS solar cells on large area polymer foils with in-line deposition methods and application of alternative back contacts - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, A. N.

    2009-08-15

    This illustrated report for the Swiss Federal Office of Energy (SFOE) summarises the work performed within this project and also reports on synergies with other projects that helped to make a significant contribution to the development of CIGS thin film solar cells on flexible substrates such as polymer foils. The project's aims were to learn more about up-scaling issues and to demonstrate the abilities required for the processing of layers on large area polyimide foils for flexible CIGS solar cells. Custom-built evaporators that were designed and constructed in-house are described. A CIGS system for in-line deposition was also modified for roll-to-roll deposition and alternative electrical back contacts to conventional ones were evaluated on flexible polyimide foils. The objectives of the project and the results obtained are looked at and commented on in detail.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. Detailed investigation of Cl-corrosion initiated by deposits formed in biomass-fired boilers. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Frandsen, Flemming J.; Lith, S. van

    2009-10-15

    The aim was to investigate deposit-induced Cl-corrosion under well-controlled laboratory conditions, simulating the conditions in biomass-fired boilers. This has been done by exposing pieces of superheater tubes, covered by synthetic salts, at temperatures and gas mixtures simulating biomass-fired conditions. The corroded specimens have been studied in detail using a Scanning Electron Microscope (SEM), in order to determine the corrosion rate, and to investigate the chemistry and morphology of the corrosive attack. The project has been divided into four activities: A1: Relationship between the Cl-concentration in the deposit, and the corrosion rate. A2: Influence of cation type (K+ and Na+) on the mobility of Cl in the deposit. A3: Influence of metal temperature on the corrosion rate. A4: Critical evaluation of the existing experience for minimizing corrosion in full-scale boilers firing totally or partly with biomass. (LN)

  8. 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

  9. Foraminal deposition of calcium pyrophosphate dihydrate crystals in the thoracic spine: possible relationship with disc herniation and implications for surgical planning. Report of two cases.

    Science.gov (United States)

    Paolini, Sergio; Ciappetta, Pasquale; Guiducci, Antonio; Principi, Massimo; Missori, Paolo; Delfini, Roberto

    2005-01-01

    The authors report two cases of nodular calcium pyrophosphate dihydrate (CPPD) crystal deposition close to the thoracic neural foramen, which caused chronic radiculopathy. Preoperatively, the lesions were interpreted as calcified disc herniations. Both patients underwent surgery in which an extended transfacet pedicle-sparing approach was used. Incision of the posterior longitudinal ligament released soft degenerated material. In both cases, histological examination showed abundant degenerative debris along with CPPD crystals. Spinal CPPD deposition is a comparatively rare disease that almost invariably involves the posterior aspect of the spinal canal, typically the ligamentum flavum. The exceptional foraminal location of the lesions reported here, combined with the surgical findings, indicated that the CPPD crystals were deposited on a laterally herniated disc fragment. A distinctive feature in both cases was the soft consistency of the resected tissue. The consistency of the disc material and the location of the lesion in the axial plane (that is, median compared with lateral) are key factors in determining the optimal surgical approach to thoracic disc herniations. In describing consistency, terms such as "calcified" and "hard" have been used interchangeably in the literature. In the cases reported here, what appeared on computerized tomography and magnetic resonance imaging studies to be densely calcified lesions were shown intraoperatively to be soft herniations. The authors' experience underscores that not all densely calcified herniated discs are hard. Although detection of this discrepancy would have left surgical planning for the lateral disc herniations unchanged, it could have altered planning for centrally or centrolaterally located disc herniations.

  10. Horseradish Peroxidase-Mediated, Iodide-Catalyzed Cascade Reaction for Plasmonic Immunoassays.

    Science.gov (United States)

    Xianyu, Yunlei; Chen, Yiping; Jiang, Xingyu

    2015-11-01

    This report outlines an enzymatic cascade reaction for signal transduction and amplification for plasmonic immunoassays by using horseradish peroxidase (HRP)-mediated aggregation of gold nanoparticles (AuNPs). HRP-catalyzed oxidation of iodide and iodide-catalyzed oxidation of cysteine is employed to modulate the plasmonic signals of AuNPs. It agrees well with the current immunoassay platforms and allows naked-eye readout with enhanced sensitivity, which holds great promise for applications in resource-constrained settings.

  11. 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.)

  12. 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.)

  13. 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)

  14. Mild and efficient cyanuric chloride catalyzed Pictet–Spengler reaction

    Directory of Open Access Journals (Sweden)

    Ashish Sharma

    2013-06-01

    Full Text Available A practical, mild and efficient protocol for the Pictet–Spengler reaction catalyzed by cyanuric chloride (trichloro-1,3,5-triazine, TCT is described. The 6-endo cyclization of tryptophan/tryptamine and modified Pictet–Spengler substrates with both electron-withdrawing and electron-donating aldehydes was carried out by using a catalytic amount of TCT (10 mol % in DMSO under a nitrogen atmosphere. TCT catalyzed the Pictet–Spengler reaction involving electron-donating aldehydes in excellent yield. Thus, it has a distinct advantage over the existing methodologies where electron-donating aldehydes failed to undergo 6-endo cyclization. Our methodology provided broad substrate scope and diversity. This is indeed the first report of the use of TCT as a catalyst for the Pictet–Spengler reaction.

  15. Silylation of Dinitrogen Catalyzed by Hydridodinitrogentris(TriphenylphosphineCobalt(I

    Directory of Open Access Journals (Sweden)

    Wojciech I. Dzik

    2016-07-01

    Full Text Available Recently, homogeneous cobalt systems were reported to catalyze the reductive silylation of dinitrogen. In this study the investigations on the silylation of dinitrogen catalyzed by CoH(PPh33N2 are presented. We show that in the presence of the title compound, the reaction of N2 with trimethylsilylchloride and sodium yields, on average, 6.7 equivalents of tris(trimethylsilylamine per Co atom in THF (tetrahydrofuran. The aim was to elucidate whether the active catalyst is: (a the [Co(PPh33N2]− anion formed after two-electron reduction of the title compound; or (b a species formed via decomposition of CoH(PPh33N2 in the presence of the highly reactive substrates. Time profile, and IR and EPR spectroscopic investigations show instability of the pre-catalyst under the applied conditions which suggests that the catalytically active species is formed through in situ modification of the pre-catalyst.

  16. 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

  17. 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.

  18. 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.

  19. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    Science.gov (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

    2014-12-01

    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  20. 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...

  1. 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.

  2. The Synthesis of 2,4,6-Triisopropyl-1,3,5-trioxane Catalyzed by Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    Jian Guo YANG; Xin Yu YU; Hai Hong WU; Zhi Lin CHENG; Yue Ming LIU; Ming Yuan HE

    2005-01-01

    The synthesis of 2, 4, 6-triisopropyl- 1, 3, 5-trioxane with high yield and desirable selectivity from solvent-free cyclotrimerization of isobutyraldehyde catalyzed by ionic liquids was reported in this work.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. 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…

  8. Heteroaromatic sulfonates and phosphates as electrophiles in iron-catalyzed cross-couplings.

    Science.gov (United States)

    Gøgsig, Thomas M; Lindhardt, Anders T; Skrydstrup, Troels

    2009-11-01

    Employment of heteroaromatic tosylates and phosphates as suitable electrophiles in iron-catalyzed cross-coupling reactions with alkyl Grignard reagents is reported. These reactions are performed at low temperature allowing good functional group tolerance and full conversion is achieved within minutes. In addition, an aryl-aryl cross-coupling utilizing a heteroaryl sulfamate electrophile is reported.

  9. 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.

  10. Maternal Floor Infarction/Massive Perivillous Fibrin Deposition Associated with Hypercoiling of a Single-Artery Umbilical Cord: A Case Report.

    Science.gov (United States)

    Taweevisit, Mana; Thorner, Paul Scott

    2016-01-01

    Maternal floor infarction is a rare and idiopathic placental disorder associated with adverse obstetric outcomes and a high rate of recurrence in subsequent pregnancies. The pathogenesis of maternal floor infarction is unclear but has been linked to diverse underlying maternal conditions, including gestational hypertension/preeclampsia, immune-mediated diseases, and thrombophilia. Few reports link maternal floor infarction to fetoplacental conditions. We report a 34-week, macerated, growth-restricted male fetus for which the placenta showed maternal floor infarction. The umbilical cord showed excessive coiling and a single umbilical artery. These cord changes are postulated to have resulted in increased placental villous resistance and decreased fetal blood flow, creating a hydrostatic pressure gradient between the villous stroma and the intervillous space. The pressure changes could then lead to trophoblast damage and fibrinoid deposition, contributing to the maternal floor infarction in this case.

  11. NONMETALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20102406 Chen Gang(China University of Geosciences,Beijing 100083,China);Li Fengming Discussion on Geological Characteristics and Genesis of Yuquanshan Graphite Deposit of Xinjiang(Xinjiang Geology,ISSN1000-8845,CN65-1092/P,27(4),2009,p.325-329,4 illus.,4 tables,5 refs.)Key words:graphite deposit,XinjiangYuquanshan graphite deposit of Xinjiang occurs in mica-quartz schist of Xingeer Information which belongs to Xinditate Group of Lower Pt in Kuluketage Block of Tarim paleo-continent,and experiences two mineralizing periods of

  12. 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

  13. 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...

  14. 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

  15. Nitroreductase catalyzed biotransformation of CL-20.

    Science.gov (United States)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2004-09-10

    Previously, we reported that a salicylate 1-monooxygenase from Pseudomonas sp. ATCC 29352 biotransformed CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane) (C(6)H(6)N(12)O(12)) and produced a key metabolite with mol. wt. 346 Da corresponding to an empirical formula of C(6)H(6)N(10)O(8) which spontaneously decomposed in aqueous medium to produce N(2)O, NH(4)(+), and HCOOH [Appl. Environ. Microbiol. (2004)]. In the present study, we found that nitroreductase from Escherichia coli catalyzed a one-electron transfer to CL-20 to form a radical anion (CL-20(-)) which upon initial N-denitration also produced metabolite C(6)H(6)N(10)O(8). The latter was tentatively identified as 1,4,5,8-tetranitro-1,3a,4,4a,5,7a,8,8a-octahydro-diimidazo[4,5-b:4',5'-e]pyrazine [IUPAC] which decomposed spontaneously in water to produce glyoxal (OHCCHO) and formic acid (HCOOH). The rates of CL-20 biotransformation under anaerobic and aerobic conditions were 3.4+/-0.2 and 0.25+/-0.01 nmol min(-1)mg of protein(-1), respectively. The product stoichiometry showed that each reacted CL-20 molecule produced about 1.8 nitrite ions, 3.3 molecules of nitrous oxide, 1.6 molecules of formic acid, 1.0 molecule of glyoxal, and 1.3 ammonium ions. Carbon and nitrogen products gave mass-balances of 60% and 81%, respectively. A comparative study between native-, deflavo-, and reconstituted-nitroreductase showed that FMN-site was possibly involved in the biotransformation of CL-20. PMID:15313201

  16. NONMETALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20140876 Gao Junbo(College of Resources and Environmental Engineering,Guizhou University,Guiyang 550025,China);Yang Ruidong Study on the Strontium Isotopic Composition of Large Devonian Barite Deposits from Zhenning,Guizhou Province(Geochimica,

  17. NONMETALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    <正>20122457 Cai Jianshe ( Fujian Institute of Geological Survey and Drawing,Fuzhou 350011,China ) On the Geologic Characteristics and Genesis of the Longtangsi Fluorite Deposit in Pucheng County,Fujian Province ( Geology of Fujian,ISSN1001-3970,CN35-1080 / P,30 ( 4 ), 2011,p.301-306,3illus.,1table,6 refs.,with English abstract ) Key words:fluorspar deposit,Fujian Province

  18. 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.

  19. Palladium-catalyzed picolinamide-directed iodination of remote ortho-C−H bonds of arenes: Synthesis of tetrahydroquinolines

    Science.gov (United States)

    Nack, William A; Wang, Xinmou; Wang, Bo

    2016-01-01

    Summary A new palladium-catalyzed picolinamide (PA)-directed ortho-iodination reaction of ε-C(sp2)−H bonds of γ-arylpropylamine substrates is reported. This reaction proceeds selectively with a variety of γ-arylpropylamines bearing strongly electron-donating or withdrawing substituents, complementing our previously reported PA-directed electrophilic aromatic substitution approach to this transformation. As demonstrated herein, a three step sequence of Pd-catalyzed γ-C(sp3)−H arylation, Pd-catalyzed ε-C(sp2)−H iodination, and Cu-catalyzed C−N cyclization enables a streamlined synthesis of tetrahydroquinolines bearing diverse substitution patterns. PMID:27559375

  20. 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.

  1. 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...

  2. Mechanochemical ruthenium-catalyzed olefin metathesis.

    Science.gov (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav

    2015-02-25

    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid.

  3. Data, Leadership, and Catalyzing Culture Change

    Science.gov (United States)

    Benson, R. Todd; Trower, Cathy A.

    2012-01-01

    It is crucial to understand today's tenure-track workers so that colleges and universities can continue to attract and retain a large subset of them by understanding and supporting their satisfaction and success at work. In this article, the authors talk about data, leadership, and catalyzing culture change. They discuss data use in the academy…

  4. 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.

  5. Rhodium-catalyzed restructuring of carbon frameworks.

    Science.gov (United States)

    Murakami, Masahiro

    2010-10-01

    Metal-catalyzed reactions involving an elementary step which cleaves a carbon-carbon bond provide unique organic transformations. Restructuring reactions recently developed in our laboratory, through which the carbon framework of a starting substance is restructured into a totally different carbon framework, are discussed, with the possibility of applying such methods to the synthesis of natural products.

  6. Mechanochemical ruthenium-catalyzed olefin metathesis.

    Science.gov (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav

    2015-02-25

    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid. PMID:25668586

  7. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    Science.gov (United States)

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  8. 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.

  9. NONMETALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20110947 Chen Xinglong(Guizhou Bureau of Nonferrous Metal and Nuclear Geology,Guiyang 550005,China);Gong Heqiang Endowment Factors and Development & Utilization Strategy of Bauxite Resource in North Guizhou Province(Guizhou Geology,ISSN1000-5943,CN52-1059/P,27(2),2010,p.106-110,6 refs.,with English abstract)Key words:bauxite deposit,Guizhou Province20110948 Dang Yanxia(Mineral Resource & Reservoir Evaluation Center,Urumiq 830000,China);Fan Wenjun Geological Features and a Primary Study of Metallogenesis of the Wucaiwang Zeolite Deposit,Fuyun County(Xinjiang Geology,ISSN1000-8845,CN65-1092/P,28(2),2010,p.167-170,2 illus.,1 table,5 refs.)Key words:zeolite deposit,Xinjiang Nearly all zeolite deposits in the world result from low-temperature-alteration of glass-bearing volcanic rocks.The southern slope of the Kalamali Mountain is one of the regions where medium to acid volcanics are major lithological type,thus it is a preferred area to look for zeolite deposit.The Wucaiwang zeolite ore district consists of mainly acid volcanic-clastic rocks.

  10. METALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20091594 Bao Yafan(The Third Geologic Survey of Jilin Province,Siping 136000,China);Liu Yanjun Relations between Bashenerxi Granite,West Dongkunlun and Baiganhu Tungsten-Tin Deposit(Jilin Geology,ISSN1001-2427,CN22-1099/P,27(3),2008,p.56-59,67,5 illus.,2 tables,7 refs.,with English abstract)Key words:tungsten ores,tin ores,monzogranite,Kunlun Mountains20091595 Chen Fuwen(Yichang Institute of Geology and Mineral Resources,China Geological Survey,Yichang 443003,China);Dai Pingyun Metallogenetic and Isotopic Chronological Study on the Shenjiaya Gold Deposit in Xuefeng Mountains,Hunan Province(Acta Geologica Sinica,ISSN0001-5717,CN11-1951/P,82(7),2008,p.906-911,3 illus.,2 tables,30 refs.)Key words:gold ores,HunanThe Shenjiaya gold deposit is a representative one

  11. 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

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

    Institute of Scientific and Technical Information of China (English)

    Wang Hai-Feng; Lin Zhen-Quan; Gao Yan

    2008-01-01

    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 < 0 case, the irreversible aggregation dominates the process, and ak(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.

  13. 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

  14. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products. PMID:27431372

  15. 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...

  16. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products.

  17. ORGANIC CHEMISTRY. Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes.

    Science.gov (United States)

    Hoyt, Jordan M; Schmidt, Valerie A; Tondreau, Aaron M; Chirik, Paul J

    2015-08-28

    Cycloadditions, such as the [4+2] Diels-Alder reaction to form six-membered rings, are among the most powerful and widely used methods in synthetic chemistry. The analogous [2+2] alkene cycloaddition to synthesize cyclobutanes is kinetically accessible by photochemical methods, but the substrate scope and functional group tolerance are limited. Here, we report iron-catalyzed intermolecular [2+2] cycloaddition of unactivated alkenes and cross cycloaddition of alkenes and dienes as regio- and stereoselective routes to cyclobutanes. Through rational ligand design, development of this base metal-catalyzed method expands the chemical space accessible from abundant hydrocarbon feedstocks.

  18. 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...

  19. 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.

  20. Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water.

    Science.gov (United States)

    Liu, Mingxin; Li, Chao-Jun

    2016-08-26

    The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification. PMID:27505714

  1. 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...

  2. Enzyme-catalyzed ring-opening polymerization of unsubstituted beta-lactam

    NARCIS (Netherlands)

    Schwab, Leendert W.; Kroon, Renee; Schouten, Arend Jan; Loos, Katja

    2008-01-01

    The synthesis of poly(beta-alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring-opening of 2-azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(beta-alanine) is obtained. The formation of the polymer is confi

  3. 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.

  4. 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...

  5. 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

  6. EVALUATION OF THE FULL-SCALE BASE CATALYZED DECOMPOSITION PROCESS (BCDP) UNIT LOCATED IN GUAM

    Science.gov (United States)

    This report summarizes performance data collected in February 1997 on the removal of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) from soil fed to a first-stage rotary kiln reactor of the Base Catalyzed Dec...

  7. 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.

  8. A General and Efficient CuBr2-Catalyzed N-Arylation of Secondary Acyclic Amides

    Institute of Scientific and Technical Information of China (English)

    王满刚; 于华; 尤心稳; 吴军; 商志才

    2012-01-01

    A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene.

  9. 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.

  10. Gold(I)-Catalyzed Dearomative Rautenstrauch Rearrangement: Enantioselective Access to Cyclopenta[b]indoles

    Science.gov (United States)

    Zi, Weiwei; Wu, Hongmiao; Toste, F. Dean

    2016-01-01

    A highly enantioselective dearomative Rautenstrauch rearrangement catalyzed by cationic (S)-DTBM-Segphosgold(I) is reported. This reaction provides a straightforward method to prepare enantioenriched cyclopenta[b]indoles. These studies show vast difference in enantioselectivity in the reactions of propargyl acetates and propargyl acetals in the chiral ligand-controlled Rautenstrauch reaction. PMID:25710515

  11. 78 FR 56583 - Deposit Insurance Regulations; Definition of Insured Deposit

    Science.gov (United States)

    2013-09-13

    ... U.S. bank under deposit agreements governed by non-U.S. law to take advantage of a large bank's... 330 Bank deposit insurance, Banks, Banking, Reporting and recordkeeping requirements, Savings and Loan... of U.S. insured depository institutions (``IDI'' or ``U.S. bank''). The Final Rule clarifies...

  12. METALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131565 Cai Lianyou(No.332 Geological Team,Bureau of Geology and Mineral Resources Exploration of Anhui Province,Huangshan 245000,China);Weng Wangfei Geological Characteristics and Genesis Analysis of Guocun Navajoite Deposit in South Anhui Province(Mineral Resources and Geology,

  13. METALS DEPOSITS

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20102341 Bao Peisheng(Institute of Geology,Chinese Academy of Geological Science,Beijing 100037,China)Further Discussion on the Genesis of the Podiform Chromite Deposits in the Ophiolites-Questioning about the Rock:Melt Interaction Metallogeny(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,28(12),2009,p.1741-1761

  14. 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),

  15. 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,

  16. Brønsted Acid-Catalyzed Direct Substitution of 2-Ethoxytetrahydrofuran with Trifluoroborate Salts

    Directory of Open Access Journals (Sweden)

    Kayla M. Fisher

    2016-06-01

    Full Text Available Metal-free transformations of organotrifluoroborates are advantageous since they avoid the use of frequently expensive and sensitive transition metals. Lewis acid-catalyzed reactions involving potassium trifluoroborate salts have emerged as an alternative to metal-catalyzed protocols. However, the drawbacks to these methods are that they rely on the generation of unstable boron dihalide species, thereby resulting in low functional group tolerance. Recently, we discovered that in the presence of a Brønsted acid, trifluoroborate salts react rapidly with in situ generated oxocarbenium ions. Here, we report Brønsted acid-catalyzed direct substitution of 2-ethoxytetrahydrofuran using potassium trifluoroborate salts. The reaction occurs when tetrafluoroboric acid is used as a catalyst to afford functionalized furans in moderate to excellent yields. A variety of alkenyl- and alkynyltrifluoroborate salts readily participate in this transformation.

  17. 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.).

  18. 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.)

  19. Single wire radial junction photovoltaic devices fabricated using aluminum catalyzed silicon nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Y; Weng, X J; Kendrick, C E; Eichfeld, S M; Redwing, J M [Department of Materials Science and Engineering, Materials Research Institute, Pennsylvania State University, University Park, PA 16802 (United States); Wang, X; Yu, Y A; Yoon, H P; Mayer, T S [Department of Electrical Engineering, Materials Research Institute, Pennsylvania State University, University Park, PA 16802 (United States); Habib, Y M, E-mail: jmr31@psu.edu, E-mail: tsm2@psu.edu [Illuminex Corp., Lancaster, PA 17601 (United States)

    2011-11-04

    Single nanowire radial junction solar cell devices were fabricated using Si nanowires synthesized by Al-catalyzed vapor-liquid-solid growth of the p{sup +} core (Al auto-doping) and thin film deposition of the n{sup +}-shell at temperatures below 650 deg. C. Short circuit current densities of {approx} 11.7 mA cm{sup -2} were measured under 1-sun AM1.5G illumination, showing enhanced optical absorption. The power conversion efficiencies were limited to < 1% by the low open circuit voltage and fill factor of the devices, which was attributed to junction shunt leakage promoted by the high p{sup +}/n{sup +} doping. This demonstration of a radial junction device represents an important advance in the use of Al-catalyzed Si nanowire growth for low cost photovoltaics.

  20. 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)

  1. 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

  2. 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

  3. 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...

  4. 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.

  5. 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

  6. 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.

  7. 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.

  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. Silica nanospheres formation induced by peroxidase-catalyzed phenol polymerization

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    To examine whether lignin-like compound is correlated with silica precipitation in grass, a series of simulated chemical experiments were carried out at ambient temperature and pressure, close to cell wall pH, with phenol polymerization catalyzed by peroxidase in silicon solution. The experiments showed that phenol polymer (a kind of lignin-like substance) caused silica nanosphere precipitation similar to those caused by protein in diatom cell wall previously reported by other authors. The sphere diameter varied with different kinds of phenol and the concentrations of phenol and silicon. Silicon precipitation had phenol and silicon saturation effect, meaning that when the concentration ratio of soluble silicon to phenol exceeded a certain value, the amount of silicon precipitation would decrease.

  10. 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

  11. 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.

  12. 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

  13. Calcium-Catalyzed, Dehydrative, Ring-Opening Cyclizations of Cyclopropyl Carbinols Derived from Donor-Acceptor Cyclopropanes.

    Science.gov (United States)

    Sandridge, Matthew J; France, Stefan

    2016-09-01

    A calcium-catalyzed, dehydrative, ring-opening cyclization of (hetero)aryl cyclopropyl carbinols is reported. The cyclopropyl carbinols are prepared directly from the corresponding donor-acceptor (D-A) cyclopropanes. The calcium catalyst catalyzes the formation of putative (hetero)aryl cyclopropyl carbinyl cations that undergo ring-opening to allylcarbinyl cations. Subsequent intramolecular Friedel-Crafts reaction affords (hetero)aryl-fused cyclohexa-1,3-dienes in up to 97% yield. This approach represents the first example of catalysis for this intramolecular, dehydrative ring-opening cyclization and outperforms the previous reports using stoichiometric Lewis acids. PMID:27517711

  14. 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

  15. 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.

  16. 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.

  17. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    Science.gov (United States)

    2016-01-01

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. PMID:27442851

  18. 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

  19. 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.

  20. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora

    2016-07-21

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  1. Small Peptides Catalyzed Direct Aldol Reactions of Aldehydes with Hydroxyacetone with Regiocontrol in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    TANG,Zhuo; YANG,Zhi-Hua; CUN,Lin-Feng; GONG,Liu-Zhu; MI,Ai-Qiao; JIANG,Yao-Zhong

    2004-01-01

    @@ Very recently, we[1] found that L-proline amides and dipeptides acted as efficient catalysts for the asymmetric direct aldol reaction. We report here that L-proline-based peptides 1~5 can catalyze the aldol reactions of hydroxyacetone with aldehydes 6 in aqueous media, to give 1,4-diols (7), the disfavored products with either aldolase or L-proline. Both peptides 3 and 4 give good results.

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

    Directory of Open Access Journals (Sweden)

    Brett N. Hemric

    2016-01-01

    Full Text Available 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.

  3. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta;

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  4. 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...

  5. 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...

  6. Cu2+-Catalyzed Oscillatory Oxidation of Ascorbic Acid by O2 Flow

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel heterogeneous oscillator, the Cu2+-catalyzed oscillatory oxidation of ascorbic acid (Vitamin C) in aqueous solution by O2 flow was reported. Both the potential oscillations on Pt-electrode corresponding to [Cu2+] and the absorbance oscillations at l=260 nm corresponding to [ascorbic acid] were observed. Oscillations in the completely homogeneous system were also observed. Effects of several factors on the oscillations were investigated.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    . Compared to alcohol oxidation the epoxidation of olefins with molecular oxygen is more difficult. Using N,N-dimethylformamide (DMF) as a solvent the Co-based metal-organic framework (MOF) STA-12(Co) catalyzed the epoxidation of styrene, (E)- and (Z)-stilbene. While the stilbene isomers were converted....... XAS revealed that silver was in the metallic state. Silver particle sizes estimated from XAS were significantly smaller (2- 3 nm) than from transmission electron microscopy (TEM) and X-ray diffraction (XRD; ca. 30 nm). It was proposed that silver-oxygen species might cause local disorder which would...... of silver was observed with the impregnated silver catalyst. By using silver supported on CeO2-SiO2 prepared by flame spray pyrolysis, leaching could be limited significantly. XAS investigation revealed that the active catalyst is most likely metallic silver. Compared to silver on silica calcined at 500 °C...

  13. 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

  14. 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

  15. 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.

  16. Atmospheric pressure chemical vapor deposition of CdTe for high efficiency thin film PV devices: Annual subcontract report, 26 January 1999--25 January 2000

    Energy Technology Data Exchange (ETDEWEB)

    Meyers, P. V.; Kee, R.; Wolden, C.; Kestner, J.; Raja, L.; Kaydanov, V.; Ohno, T.; Collins, R.; Fahrenbruch, A.

    2000-05-30

    ITN's three year project Atmospheric Pressure Chemical Vapor Deposition (APCVD) of CdTe for High Efficiency Thin Film 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 demonstration of APCVD of CdTe films, discovery of fundamental mass transport parameters, application of established engineering principles to the deposition of CdTe films, and verification of reactor design principles which 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. Under the APCVD program, device analysis goes beyond conventional one-dimensional device characterization and analysis toward two dimension measurements and modeling. Accomplishments of the second year of the APCVD subcontract include: deposition of the first APCVD CdTe; identification of deficiencies in the first generation APCVD reactor; design, fabrication and testing of a ``simplified'' APCVD reactor; deposition of the first dense, adherent APCVD CdTe films; fabrication of the first APCVD CdTe PV device; modeling effects of CdSTe and SnOx layers; and electrical modeling of grain boundaries.

  17. 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.

  18. Deposit model for volcanogenic uranium deposits

    Science.gov (United States)

    Breit, George N.; Hall, Susan M.

    2011-01-01

    Volcanism is a major contributor to the formation of important uranium deposits both close to centers of eruption and more distal as a result of deposition of ash with leachable uranium. Hydrothermal fluids that are driven by magmatic heat proximal to some volcanic centers directly form some deposits. These fluids leach uranium from U-bearing silicic volcanic rocks and concentrate it at sites of deposition within veins, stockworks, breccias, volcaniclastic rocks, and lacustrine caldera sediments. The volcanogenic uranium deposit model presented here summarizes attributes of those deposits and follows the focus of the International Atomic Energy Agency caldera-hosted uranium deposit model. Although inferred by some to have a volcanic component to their origin, iron oxide-copper-gold deposits with economically recoverable uranium contents are not considered in this model.

  19. 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

  20. N-Heterocyclic Carbene-Catalyzed [2+2+2] Annulation of Allenoates with Trifluoromethylketones%N-Heterocyclic Carbene-Catalyzed [2+2+2] Annulation of Allenoates with Trifluoromethylketones

    Institute of Scientific and Technical Information of China (English)

    孙利辉; 王统; 叶松

    2012-01-01

    In contrast with the reported phosphine- and DABCO-catalyzed [3 + 2] and [2 +2] annulation of allenoates with trifluoromethylketone, the [2+2+2] annulation of allenoates and two molecules of trifluoromethylketone was found under the condition of N-heterocyclic carbene catalysis.

  1. Processing of CuInSe{sub 2}-based solar cells: Characterization of deposition processes in terms of chemical reaction analyses. Phase 2 Annual Report, 6 May 1996--5 May 1997

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, T.

    1999-10-20

    This report describes research performed by the University of Florida during Phase 2 of this subcontract. First, to study CIGS, researchers adapted a contactless, nondestructive technique previously developed for measuring photogenerated excess carrier lifetimes in SOI wafers. This dual-beam optical modulation (DBOM) technique was used to investigate the differences between three alternative methods of depositing CdS (conventional chemical-bath deposition [CBD], metal-organic chemical vapor deposition [MOCVD], and sputtering). Second, a critical assessment of the Cu-In-Se thermochemical and phase diagram data using standard CALPHAD procedures is being performed. The outcome of this research will produce useful information on equilibrium vapor compositions (required annealing ambients, Sex fluxes from effusion cells), phase diagrams (conditions for melt-assisted growth), chemical potentials (driving forces for diffusion and chemical reactions), and consistent solution models (extents of solid solutions and extending phase diagrams). Third, an integrated facility to fabricate CIS PV devices was established that includes migration-enhanced epitaxy (MEE) for deposition of CIS, a rapid thermal processing furnace for absorber film formation, sputtering of ZnO, CBD or MOCVD of CdS, metallization, and pattern definition.

  2. 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.

  3. 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.

  4. 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

  5. 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…

  6. 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.

  7. 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.

  8. Gold-Catalyzed Enantio- and Diastereoselective Syntheses of Left Fragments of Azadirachtin/Meliacarpin-Type Limonoids.

    Science.gov (United States)

    Shi, Hang; Tan, Ceheng; Zhang, Weibin; Zhang, Zichun; Long, Rong; Gong, Jianxian; Luo, Tuoping; Yang, Zhen

    2016-02-01

    Meliacarpin-type limonoids are an important class of organic insecticides. Their syntheses are challenging due to their chemical complexity. Here, we report the highly enantio- and diastereoselective synthesis of the left fragments of azadirachtin I and 1-cinnamoylmelianolone, being two important family members of meliacarpin-type limonoids, via pairwise palladium- and gold-catalyzed cascade reactions. Gold-catalyzed reactions of 1,7-diynes were performed as model studies, and the efficient construction of tetracyclic late-stage intermediates was achieved on the basis of this key transformation. Our unique route gave both of the left fragments in 23 steps from the commercially available chiral starting material (-)-carvone. This study significantly advances research on the synthesis of the meliacarpin-type limonoids. PMID:26765324

  9. Efficient Hydration of Olefins Catalyzed by Wool-Supported Palladium Complex

    Institute of Scientific and Technical Information of China (English)

    Dan-Ni SUI; Si-Qian WANG; Xin WANG; Mei-Yu HUANG; Ying-Yan JIANG

    2005-01-01

    @@ 1Introduction The hydration of olefins is one of the most important prxesses for the production of alcohols[1]. Both transition metal complexes[2] and enzymes[3] have been reported to catalyze the hydration of alkenes, but their catalysts are usually tither unstable or difficult to prepare, expensive and sometimes can not be easily recovered.In our previous papers, some natural biopolymer-metal complexes[4-6] have been used as effective catalysts in hydration to overcome above disadvantages. Recently, wool-Palladium complex(Wool-Pd) has been prepared and found to be able to effficiently catalyze the hydration of olefins to alcohols, such as cinnamyl alcohol(1a) to 1-phenyl-1,3-propanediol(1b), acrylic acid(2a) to lactic acid(2b), 4-vinyl pyridine(3a) to α-methyl-4-pyridinemethanol (3b) and acrylamide(4a) to 1-hydroxyethylamide(4b) respectively in high yields under mild conditions. See scheme 1.

  10. Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

    Directory of Open Access Journals (Sweden)

    Ryan Pearson

    2013-05-01

    Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

  11. 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.

  12. 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.

  13. Cadmium sulfide/copper sulfide heterojunction cell research by sputter deposition. Quarterly technical progress report, March 1, 1981-June 30, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Thornton, J.A.; Anderson, W.W.; Meakin, J.D.

    1981-08-01

    A second series of hybrid cells with sputter-deposited Cu/sub 2/S layers has been fabricated. An efficiency of about 4 3/4%, without antireflection coating, was achieved for one of the cells. This result approaches the 5 3/4% which was achieved in the first set (different Cu/sub 2/S deposition conditions) and confirms the viability of the sputtering process for this application. Significant progress has been made in fabricating all-sputtered cells with CdS layers deposited by planar magnetron reactive sputtering. Efficiencies of approximately 3%, without antireflection coatings, have been achieved in the as-deposited state for seven cells. Individual cells have yielded a J/sub sc/ of 12 mA/cm/sup 2/, a V/sub oc/ of 0.53V, and a fill factor of 0.72. Taken together these parameters would yield an efficiency of 4 1/2%. A strong coupling is found between the properties of the Cu/sub 2/S and CdS layers. However, the conditions which maximize J/sub sc/, V/sub oc/ and the fill factor do not appear to be mutually exclusive. Reflectance measurements indicate that 30% or more of the incident radiation is being reflected from the front surface of the cells over the wavelength range of the solar spectrum. Thus optimization of the cell parameters with a suitable antireflection coating should yield cell efficiencies of about 6%. Characterization of the junctions formed in the all-sputtered cells under near-optimum deposition conditions indicates that they have remarkable properties in their as-deposited state, being very similar to high performance conventional cells after heat treatment. Junction ideality factors are about unity in the light, with J/sub 0/ values of about 2 x 10/sup -8/ mA/cm/sup 2/. Interface recombination velocities are as low as a few times 10/sup 5/ cm/sec. CdS depletion layer widths are about 2000 nm in the dark and collapse to about 200 nm under illumination.

  14. 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

  15. 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

  16. 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.

  17. 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

  18. 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

  19. 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.

  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. 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

  2. Cyclopalladated Ferrocenylimine Catalyzed Chlorination of 2-Arylbenzoxazoles%Cyclopalladated Ferrocenylimine Catalyzed Chlorination of 2-Arylbenzoxazoles

    Institute of Scientific and Technical Information of China (English)

    冷瑜婷; 杨帆; 吴养洁; 李克

    2011-01-01

    An efficient and facile protocol for palladacycle-catalyzed chlorination of 2-arylbenzoxazoles was developed. The results represent the first examples involving the palladacycle as the catalyst for such chlorination. This chlori- nation was not a ligand-directed ortho-C--H activation, but an electrophilic substitution process at the para-position of the nitrogen atom in the benzo ring of benzoxazole moiety, the regiochemistry of which had been confirmed by HMBC spectral analysis. The catalytic system could tolerate various halogen atoms, such as F, Cl and Br, affording the corresponding products in moderate to excellent yields.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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. ...

  10. Enantioselective epoxidation and carbon-carbon bond cleavage catalyzed by Coprinus cinereus peroxidase and myeloperoxidase.

    Science.gov (United States)

    Tuynman, A; Spelberg, J L; Kooter, I M; Schoemaker, H E; Wever, R

    2000-02-01

    We demonstrate that myeloperoxidase (MPO) and Coprinus cinereus peroxidase (CiP) catalyze the enantioselective epoxidation of styrene and a number of substituted derivatives with a reasonable enantiomeric excess (up to 80%) and in a moderate yield. Three major differences with respect to the chloroperoxidase from Caldariomyces fumago (CPO) are observed in the reactivity of MPO and CiP toward styrene derivatives. First, in contrast to CPO, MPO and CiP produced the (S)-isomers of the epoxides in enantiomeric excess. Second, for MPO and CiP the H(2)O(2) had to be added very slowly (10 eq in 16 h) to prevent accumulation of catalytically inactive enzyme intermediates. Under these conditions, CPO hardly showed any epoxidizing activity; only with a high influx of H(2)O(2) (300 eq in 1.6 h) was epoxidation observed. Third, both MPO and CiP formed significant amounts of (substituted) benzaldehydes as side products as a consequence of C-alpha-C-beta bond cleavage of the styrene derivatives, whereas for CPO and cytochrome c peroxidase this activity is not observed. C-alpha-C-beta cleavage was the most prominent reaction catalyzed by CiP, whereas with MPO the relative amount of epoxide formed was higher. This is the first report of peroxidases catalyzing both epoxidation reactions and carbon-carbon bond cleavage. The results are discussed in terms of mechanisms involving ferryl oxygen transfer and electron transfer, respectively.

  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. 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 ...

  13. 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

  14. Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries.

    Science.gov (United States)

    Ma, Shunchao; Wu, Yang; Wang, Jiawei; Zhang, Yelong; Zhang, Yantao; Yan, Xinxiu; Wei, Yang; Liu, Peng; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Xu, Ye; Peng, Zhangquan

    2015-12-01

    The aprotic Li-O2 battery has attracted a great deal of interest because, theoretically, it can store far more energy than today's batteries. Toward unlocking the energy capabilities of this neotype energy storage system, noble metal-catalyzed high surface area carbon materials have been widely used as the O2 cathodes, and some of them exhibit excellent electrochemical performances in terms of round-trip efficiency and cycle life. However, whether these outstanding electrochemical performances are backed by the reversible formation/decomposition of Li2O2, i.e., the desired Li-O2 electrochemistry, remains unclear due to a lack of quantitative assays for the Li-O2 cells. Here, noble metal (Ru and Pd)-catalyzed carbon nanotube (CNT) fabrics, prepared by magnetron sputtering, have been used as the O2 cathode in aprotic Li-O2 batteries. The catalyzed Li-O2 cells exhibited considerably high round-trip efficiency and prolonged cycle life, which could match or even surpass some of the best literature results. However, a combined analysis using differential electrochemical mass spectrometry and Fourier transform infrared spectroscopy, revealed that these catalyzed Li-O2 cells (particularly those based on Pd-CNT cathodes) did not work according to the desired Li-O2 electrochemistry. Instead the presence of noble metal catalysts impaired the cells' reversibility, as evidenced by the decreased O2 recovery efficiency (the ratio of the amount of O2 evolved during recharge/that consumed in the preceding discharge) coupled with increased CO2 evolution during charging. The results reported here provide new insights into the O2 electrochemistry in the aprotic Li-O2 batteries containing noble metal catalysts and exemplified the importance of the quantitative assays for the Li-O2 reactions in the course of pursuing truly rechargeable Li-O2 batteries.

  15. 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

  16. 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...

  17. 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).

  18. Depositional sequence analysis and sedimentologic modeling for improved prediction of Pennsylvanian reservoirs (annex I). Eleventh quarterly technical progress report, July 1, 1992--September 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Watney, W.L.

    1994-09-01

    The objectives of this research are to: (1) assist producers in locating and producing petroleum not currently being produced because of technological problems or the inability to identify details of reservoir compartmentalization, (2) to decrease risk in field development, and (3) accelerate the retrieval and analysis of baseline geoscience information for initial reservoir description. The interdisciplinary data sought in this research will be used to resolve specific problems in correlation of strata and to establish the mechanisms responsible for the Upper Pennsylvanian stratigraphic architecture in the Midcontinent. The data will better constrain ancillary problems related to the validation of depositional sequence and subsequence correlation, subsidence patterns, sedimentation rates, sea-level changes, and the relationship of sedimentary sequences to basement terrains. The geoscientific information, including data from field studies, surface and near-surface reservoir analogues, and regional data base development, will also be used for development of geologic computer process-based simulation models tailored to specific depositional sequences for use in improving prediction of reservoir characteristics.

  19. 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.

  20. 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)

  1. 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.

  2. Growth of high-quality self-catalyzed core-shell GaAsP nanowires on Si substrates

    Science.gov (United States)

    Zhang, Yunyan; Aagesen, Martin; Sanchez, Ana M.; Wu, Jiang; Beanland, Richard; Ward, Thomas; Kim, Dongyoung; Jurczak, Pamela; Huo, Suguo; Liu, Huiyun

    2016-03-01

    Self-catalyzed GaAsP nanowires (NWs) have a band gap that is capable of covering the working wavelengths from green to infrared. However, the difficulties in controlling P and the complexities of the growth of ternary NWs make it challenging to fabricate them. In this work, self-catalyzed GaAsP NWs were successfully grown on Si substrates by solid-source molecular beam epitaxy and demonstrated almost stacking fault free zinc blend crystal structure, Growth of high-quality shell has been realized on the core NWs. In the shell, a quasi-3-fold composition symmetry has been observed for the first time. Moreover, these growth techniques have been successfully applied for growth on patterned Si substrates after some creative modifications such as high-temperature substrate cleaning and Ga pre-deposition. These results open up new perspectives for integrating III-V nanowire photovoltaics and visible light emitters on the silicon platform using self-catalyzed GaAsP core-shell nanowires.

  3. Length distributions of Au-catalyzed and In-catalyzed InAs nanowires

    Science.gov (United States)

    Dubrovskii, V. G.; Sibirev, N. V.; Berdnikov, Y.; Gomes, U. P.; Ercolani, D.; Zannier, V.; Sorba, L.

    2016-09-01

    We present experimental data on the length distributions of InAs nanowires grown by chemical beam epitaxy with Au catalyst nanoparticles obtained by thermal dewetting of Au film, Au colloidal nanoparticles and In droplets. Poissonian length distributions are observed in the first case. Au colloidal nanoparticles produce broader and asymmetric length distributions of InAs nanowires. However, the distributions can be strongly narrowed by removing the high temperature annealing step. The length distributions for the In-catalyzed growth are instead very broad. We develop a generic model that is capable of describing the observed behaviors by accounting for both the incubation time for nanowire growth and secondary nucleation of In droplets. These results allow us to formulate some general recipes for obtaining more uniform length distributions of III-V nanowires.

  4. Atmospheric Deposition Modeling Results

    Data.gov (United States)

    U.S. Environmental Protection Agency — This asset provides data on model results for dry and total deposition of sulfur, nitrogen and base cation species. Components include deposition velocities, dry...

  5. 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...

  6. 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 ...

  7. Colloid Deposit Morphology and Clogging in Porous Media: Fundamental Insights Through Investigation of Deposit Fractal Dimension.

    Science.gov (United States)

    Roth, Eric J; Gilbert, Benjamin; Mays, David C

    2015-10-20

    Experiments reveal a wide discrepancy between the permeability of porous media containing colloid deposits and the available predictive equations. Evidence suggests that this discrepancy results, in part, from the predictive equations failing to account for colloid deposit morphology. This article reports a series of experiments using static light scattering (SLS) to characterize colloid deposit morphology within refractive index matched (RIM) porous media during flow through a column. Real time measurements of permeability, specific deposit, deposit fractal dimension, and deposit radius of gyration, at different vertical positions, were conducted with initially clean porous media at various ionic strengths and fluid velocities. Decreased permeability (i.e., increased clogging) corresponded with higher specific deposit, lower fractal dimension, and smaller radius of gyration. During deposition, fractal dimension, radius of gyration, and permeability decreased with increasing specific deposit. During flushing with colloid-free fluid, these trends reversed, with increased fractal dimension, radius of gyration, and permeability. These observations suggest a deposition scenario in which large and uniform aggregates become deposits, which reduce porosity, lead to higher fluid shear forces, which then decompose the deposits, filling the pore space with small and dendritic fragments of aggregate.

  8. 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...

  9. Enzyme-catalyzed ring-opening polymerization of unsubstituted beta-lactam

    OpenAIRE

    Schwab, Leendert W.; Kroon, Renee; Schouten, Arend Jan; Loos, Katja

    2008-01-01

    The synthesis of poly(beta-alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring-opening of 2-azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(beta-alanine) is obtained. The formation of the polymer is confirmed with (1)H NMR spectroscopy and MALDI-TOF mass spectrometry. The average degree of polymerization of the obtained polymer is limited to DP=8 by its solubility in the reaction medium. Control ex...

  10. 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

  11. Lewis Acid Catalyzed Selective Reactions of Donor-Acceptor Cyclopropanes with 2-Naphthols.

    Science.gov (United States)

    Kaicharla, Trinadh; Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G; Biju, Akkattu T

    2016-08-16

    Lewis acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with 2-naphthols is reported. The reaction exhibits tunable selectivity depending on the nature of Lewis acid employed and proceed as a dearomatization/rearomatization sequence. With Bi(OTf)3 as the Lewis acid, a highly selective dehydrative [3+2] cyclopentannulation takes place leading to the formation of naphthalene-fused cyclopentanes. Interestingly, engaging Sc(OTf)3 as the Lewis acid, a Friedel-Crafts-type addition of 2-naphthols to cyclopropanes takes place, thus affording functionalized 2-naphthols. Both reactions furnished the target products in high regioselectivity and moderate to high yields. PMID:27391792

  12. 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...

  13. Te-doping of self-catalyzed GaAs nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Suomalainen, S., E-mail: soile.suomalainen@tut.fi; Hakkarainen, T. V.; Salminen, T.; Koskinen, R.; Guina, Mircea [Optoelectronics Research Centre, Tampere University of Technology, FI-33101 Tampere (Finland); Honkanen, M. [Department of Material Science, Tampere University of Technology, FI-33101 Tampere (Finland); Luna, E. [Paul-Drude-Institut für Festkörperelektronik, Hausvogteiplatz 5-7, 10117 Berlin (Germany)

    2015-07-06

    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.

  14. 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

  15. Development of a Rhodium(II)-Catalyzed Chemoselective C(sp(3) )-H Oxygenation.

    Science.gov (United States)

    Lin, Yun; Zhu, Lei; Lan, Yu; Rao, Yu

    2015-10-12

    We report the first example of Rh(II) -catalyzed chemoselective double C(sp(3) )-H oxygenation, which can directly transform various toluene derivatives into highly valuable aromatic aldehydes with great chemoselectivity and practicality. The critical combination of catalyst Rh(OAc)2 , oxidant Selectfluor, and solvents of TFA/TFAA promises the successful delivery of the oxidation with satisfactory yields. A possible mechanism involving a unique carbene-Rh complex is proposed, and has been supported by both experiments and theoretical calculations.

  16. 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.

  17. 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.

  18. Palladium-Catalyzed Modification of Unprotected Nucleosides, Nucleotides, and Oligonucleotides

    Directory of Open Access Journals (Sweden)

    Kevin H. Shaughnessy

    2015-05-01

    Full Text Available Synthetic modification of nucleoside structures provides access to molecules of interest as pharmaceuticals, biochemical probes, and models to study diseases. Covalent modification of the purine and pyrimidine bases is an important strategy for the synthesis of these adducts. Palladium-catalyzed cross-coupling is a powerful method to attach groups to the base heterocycles through the formation of new carbon-carbon and carbon-heteroatom bonds. In this review, approaches to palladium-catalyzed modification of unprotected nucleosides, nucleotides, and oligonucleotides are reviewed. Polar reaction media, such as water or polar aprotic solvents, allow reactions to be performed directly on the hydrophilic nucleosides and nucleotides without the need to use protecting groups. Homogeneous aqueous-phase coupling reactions catalyzed by palladium complexes of water-soluble ligands provide a general approach to the synthesis of modified nucleosides, nucleotides, and oligonucleotides.

  19. 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.

  20. 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.

  1. 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

  2. Microbial-Catalyzed Biotransformation of Multifunctional Triterpenoids Derived from Phytonutrients

    Directory of Open Access Journals (Sweden)

    Syed Adnan Ali Shah

    2014-07-01

    Full Text Available Microbial-catalyzed biotransformations have considerable potential for the generation of an enormous variety of structurally diversified organic compounds, especially natural products with complex structures like triterpenoids. They offer efficient and economical ways to produce semi-synthetic analogues and novel lead molecules. Microorganisms such as bacteria and fungi could catalyze chemo-, regio- and stereospecific hydroxylations of diverse triterpenoid substrates that are extremely difficult to produce by chemical routes. During recent years, considerable research has been performed on the microbial transformation of bioactive triterpenoids, in order to obtain biologically active molecules with diverse structures features. This article reviews the microbial modifications of tetranortriterpenoids, tetracyclic triterpenoids and pentacyclic triterpenoids.

  3. 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

  4. 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.

  5. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

    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 I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl 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

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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...

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

    OpenAIRE

    Shimada, Akihiko; Ozaki, Haruka; Saito, Takeshi; Fujii, Noriko

    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...

  16. Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors.

    Science.gov (United States)

    Potter, Tyler J; Ellman, Jonathan A

    2016-08-01

    A Rh(III)-catalyzed C-H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C-H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C-H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.

  17. 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

  18. Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines

    Science.gov (United States)

    2016-01-01

    Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides with high enantiomeric excess. The new process is demonstrated on a wide range of substrates and leads to products that are well-established P-chiral catalysts and ligands. PMID:27689432

  19. 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

  20. 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…

  1. 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

  2. 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.

  3. 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

  4. Catalyzing new product adoption at the base of the pyramid

    NARCIS (Netherlands)

    Marinakis, Y.D.; Walsh, S.T.; Harms, R.

    2016-01-01

    One of the more perplexing of the entrepreneurial issues at the Base of the Pyramid (BoP) is how to catalyze new product adoption by BoP consumers. Because S-shaped adoption dynamics are the result of cultural transmission bias, the question can be rephrased as, how can an entrepreneur overcome conf

  5. 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...

  6. 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.

  7. 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.

  8. 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]…

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. ASYMMETRIC HYDROSILYLATION CATALYZED BY POLYMER—SUPPORTED THIAZOLIDINE RHODIUM CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等

    1999-01-01

    Asymmetric hydrisilylation catalyzed by polymeric thiazolidine rhodium catalysts was conducted.Almost the same optical yields have been obtained when comb-shaped polymeric ligands and their corresponding monomer complexed rhodium cataltysts were used to asymmetric hydrosilylation of acetophenone.Optical yield of chiral 1-methylbenzyl alcohol reaches as high as 71.5%.Temperature dependence of enantioselective hydrosilylation of acetophenone was discussed.

  14. 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.

  15. 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.

  16. 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.

  17. Amylase catalyzed synthesis of glycosyl acrylates and their polymerization

    NARCIS (Netherlands)

    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 saccharificatio

  18. 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

  19. 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.

  20. 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

  1. Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp2–H bond arylations

    Directory of Open Access Journals (Sweden)

    Fatiha Abdelmalek

    2015-10-01

    Full Text Available We report herein a two or three step synthesis of fluorinated π-conjugated oligomers through iterative C–H bond arylations. Palladium-catalyzed desulfitative arylation of heteroarenes allowed in a first step the synthesis of fluoroaryl-heteroarene units in high yields. Then, the next steps involve direct arylation with aryl bromides catalyzed by PdCl(C3H5(dppb to afford triad or tetrad heteroaromatic compounds via regioselective activation of C(sp2–H bonds.

  2. 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.)

  3. 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.

  4. Synthesis of solution-phase phosphoramidite and phosphite ligand libraries and their in situ screening in the rhodium-catalyzed asymmetric addition of arylboronic acids

    NARCIS (Netherlands)

    Jagt, Richard B. C.; Toullec, Patrick Y.; Schudde, Ebe P.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.

    2007-01-01

    Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is show

  5. Regional aerosol deposition in human upper airways

    Energy Technology Data Exchange (ETDEWEB)

    Swift, D.L.

    1991-11-01

    During the current report experimental studies of upper respiratory deposition of radon progeny aerosols and stimulant aerosols were carried out in replicate casts of nasal and oral passages of adults and children. Additionally, preliminary studies of nasal passage deposition of unattached Po{sup 218} particles was carried out in four human subjects. Data on nasal inspiratory deposition in replicate models of adults and infants from three collaborating laboratories were compared and a best-fit curve of deposition efficiency for both attached and unattached particles was obtained, showing excellent inter-laboratory agreement. This curve demonstrates that nasal inspiratory deposition of radon progeny is weakly dependent upon flow rate over physiologically realistic ranges of flow, does not show a significant age effect, and is relatively independent of nasal passage dimensions for a given age range. Improved replicate models of the human adult oral passage extending to the mid-trachea were constructed for medium and higher flow mouth breathing states; these models were used to assess the deposition of unattached Po{sup 218} particles during oronasal breathing in the oral passage and demonstrated lower deposition efficiency than the nasal passage. Measurements of both Po{sup 218} particle and attached fraction particle size deposition were performed in replicate nasal passage of a four week old infant. 5 refs., 1 fig.

  6. 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.

  7. 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.)

  8. 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

  9. 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.

  10. Sediment-Hosted Copper Deposits of the World: Deposit Models and Database

    Science.gov (United States)

    Cox, Dennis P.; Lindsey, David A.; Singer, Donald A.; Diggles, Michael F.

    2003-01-01

    Introduction This publication contains four descriptive models and four grade-tonnage models for sediment hosted copper deposits. Descriptive models are useful in exploration planning and resource assessment because they enable the user to identify deposits in the field and to identify areas on geologic and geophysical maps where deposits could occur. Grade and tonnage models are used in resource assessment to predict the likelihood of different combinations of grades and tonnages that could occur in undiscovered deposits in a specific area. They are also useful in exploration in deciding what deposit types meet the economic objectives of the exploration company. The models in this report supersede the sediment-hosted copper models in USGS Bulletin 1693 (Cox, 1986, and Mosier and others, 1986) and are subdivided into a general type and three subtypes. The general model is useful in classifying deposits whose features are obscured by metamorphism or are otherwise poorly described, and for assessing regions in which the geologic environments are poorly understood. The three subtypes are based on differences in deposit form and environments of deposition. These differences are described under subtypes in the general model. Deposit models are based on the descriptions of geologic environments and physical characteristics, and on metal grades and tonnages of many individual deposits. Data used in this study are presented in a database representing 785 deposits in nine continents. This database was derived partly from data published by Kirkham and others (1994) and from new information in recent publications. To facilitate the construction of grade and tonnage models, the information, presented by Kirkham in disaggregated form, was brought together to provide a single grade and a single tonnage for each deposit. Throughout the report individual deposits are defined as being more than 2,000 meters from the nearest adjacent deposit. The deposit models are presented here as

  11. 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.

  12. 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

  13. 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...

  14. Proline catalyzed α-aminoxylation reaction in the synthesis of biologically active compounds.

    Science.gov (United States)

    Kumar, Pradeep; Dwivedi, Namrata

    2013-02-19

    The search for new and efficient ways to synthesize optically pure compounds is an active area of research in organic synthesis. Asymmetric catalysis provides a practical, cost-effective, and efficient method to create a variety of complex natural products containing multiple stereocenters. In recent years, chemists have become more interested in using small organic molecules to catalyze organic reactions. As a result, organocatalysis has emerged both as a promising strategy and as an alternative to catalysis with expensive proteins or toxic metals. One of the most successful and widely studied secondary amine-based organocatalysts is proline. This small molecule can catalyze numerous reactions such as the aldol, Mannich, Michael addition, Robinson annulation, Diels-Alder, α-functionalization, α-amination, and α-aminoxylation reactions. Catalytic and enantioselective α-oxygenation of carbonyl compounds is an important reaction to access a variety of useful building blocks for bioactive molecules. Proline catalyzed α-aminoxylation using nitrosobenzene as oxygen source, followed by in situ reduction, gives enantiomerically pure 1,2-diol. This molecule can then undergo a variety of organic reactions. In addition, proline organocatalysis provides access to an assortment of biologically active natural products including mevinoline (a cholesterol lowering drug), tetrahydrolipstatin (an antiobesity drug), R(+)-α-lipoic acid, and bovidic acid. In this Account, we present an iterative organocatalytic approach to synthesize both syn- and anti-1,3-polyols, both enantio- and stereoselectively. This method is primarily based on proline-catalyzed sequential α-aminoxylation and Horner-Wadsworth-Emmons (HWE) olefination of aldehyde to give a γ-hydroxy ester. In addition, we briefly illustrate the broad application of our recently developed strategy for 1,3-polyols, which serve as valuable, enantiopure building blocks for polyketides and other structurally diverse and

  15. 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.

  16. Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling

    KAUST Repository

    Xu, Jun

    2016-01-12

    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  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. 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.

  1. Absence of polychlorinated dibenzodioxins and dibenzofurans after lactoperoxidase-catalyzed transformation of chlorophenols

    Energy Technology Data Exchange (ETDEWEB)

    Oeberg, L.G.; Swanson, S.E.

    1987-06-01

    Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) have been detected in many species and environments their bioresistance and toxicity being of great concern. PCDDs and PCDFs, or the predioxins and -furans, are formed from chlorophenols (CPs) by burning and pyrolysis by arcing and by photolysis. PCDDs and PCDFs have also been found in emissions from automobiles, municipal waste incinerators, and nickel and copper smelting. Peroxidases (POs), a group of heme-proteins, are found in many organs and organisms. They are exceptional enzymes because of low substrate specificity and multiple reaction mechanisms. This enzyme-catalyzed free radical reaction resembles reactions in pyrolysis, arcing, and photolysis. Halogenated phenols are among the peroxidase substrates, and phenolic substrates have been found to yield dibenzodioxin- and dibenzofuran like products. The question then arose whether CP's in peroxidase-mediated reactions could yield chlorinated dibenzodioxins and dibenzofurans. Since no-one has yet reported a biological formation of PCDDs and PCDFs the authors have analyzed the rpdoct mixture from the lactoperoxidase-catalyzed oxidation of some chlorophenols.

  2. Stereoselectivity in (Acyloxy)borane-Catalyzed Mukaiyama Aldol Reactions.

    Science.gov (United States)

    Lee, Joshua M; Zhang, Xin; Norrby, Per-Ola; Helquist, Paul; Wiest, Olaf

    2016-07-01

    The origin of diastereo- and enantioselectivity in a Lewis acid-catalyzed Mukaiyama aldol reaction is investigated using a combination of dispersion corrected DFT calculations and transition state force fields (TSFF) developed using the quantum guided molecular mechanics (Q2MM) method. The reaction proceeds via a closed transition structure involving a nontraditional hydrogen bond that is 3.3 kJ/mol lower in energy than the corresponding open transition structure. The correct prediction of the diastereoselectivity of a Mukaiyama aldol reaction catalyzed by the conformationally flexible Yamamoto chiral (acyloxy) borane (CAB) requires extensive conformational sampling at the transition structure, which is achieved using a Q2MM-derived TSFF, followed by DFT calculations of the low energy conformational clusters. Finally, a conceptual model for the rationalization of the observed diastereo- and enantioselectivity of the reaction using a closed transition state model is proposed. PMID:27247023

  3. 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.

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

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    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...... 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....

  5. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.

    2015-11-13

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  6. 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.

  7. Effect of urate on the lactoperoxidase catalyzed oxidation of adrenaline.

    Science.gov (United States)

    Løvstad, Rolf A

    2004-12-01

    Lactoperoxidase is an iron containing enzyme, which is an essential component of the defense system of mammalian secretary fluids. The enzyme readily oxidizes adrenaline and other catecholamines to coloured aminochrome products. A Km-value of 1.21 mM and a catalytic constant (k = Vmax/[Enz]) of 15.5 x 10(3) min(-1) characterized the reaction between lactoperoxidase and adrenaline at pH 7.4. Urate was found to activate the enzyme catalyzed oxidation of adrenaline in a competitive manner, the effect decreasing with increasing adrenaline concentration. Lactoperoxidase was able to catalyze the oxidation of urate. However, urate was a much poorer substrate than adrenaline, and it seems unlikely that urate activates by functioning as a free, redox cycling intermediate between enzyme and adrenaline. The activation mechanism probably involves an urate-lactoperoxidase complex.

  8. Investigations on catalyzed steam gasification of biomass

    Energy Technology Data Exchange (ETDEWEB)

    Mudge, L.K.; Weber, S.L.; Mitchell, D.H.; Sealock, L.J. Jr.; Robertus, R.J.

    1981-01-01

    The purpose of the study is to evaluate the technical and economic feasibility of producing specific gas products via the catalytic gasification of biomass. This report presents the results of research conducted from December 1977 to October 1980. The study was comprised of laboratory studies, process development, and economic analyses. The laboratory studies were conducted to develop operating conditions and catalyst systems for generating methane-rich gas, synthesis gases, hydrogen, and carbon monoxide; these studies also developed techniques for catalyst recovery, regeneration, and recycling. A process development unit (PDU) was designed and constructed to evaluate laboratory systems at conditions approximating commercial operations. The economic analyses, performed by Davy McKee, Inc. for PNL, evaluated the feasibility of adapting the wood-to-methane and wood-to-methanol processes to full-scale commercial operations. Plants were designed in the economic analyses to produce fuel-grade methanol from wood and substitute natural gas (SNG) from wood via catalytic gasification with steam.

  9. 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...

  10. 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.

  11. Gold-catalyzed oxidative cycloadditions to activate a quinoline framework.

    Science.gov (United States)

    Huple, Deepak B; Ghorpade, Satish; Liu, Rai-Shung

    2013-09-23

    Going for gold! Gold-catalyzed reactions of 3,5- and 3,6-dienynes with 8-alkylquinoline oxides results in an oxidative cycloaddition with high stereospecificity (see scheme; EWG = electron-withdrawing group); this process involves a catalytic activation of a quinoline framework. The reaction mechanism involves the intermediacy of α-carbonyl pyridinium ylides (I) in a concerted [3+2]-cycloaddition with a tethered alkene.

  12. Comparing Ru and Fe-catalyzed olefin metathesis.

    Science.gov (United States)

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-08-01

    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.

  13. 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

  14. 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

  15. Lactoperoxidase-catalyzed activation of carcinogenic aromatic and heterocyclic amines.

    Science.gov (United States)

    Gorlewska-Roberts, Katarzyna M; Teitel, Candee H; Lay, Jackson O; Roberts, Dean W; Kadlubar, Fred F

    2004-12-01

    Lactoperoxidase, an enzyme secreted from the human mammary gland, plays a host defensive role through antimicrobial activity. It has been implicated in mutagenic and carcinogenic activation in the human mammary gland. The potential role of heterocyclic and aromatic amines in the etiology of breast cancer led us to examination of the lactoperoxidase-catalyzed activation of the most commonly studied arylamine carcinogens: 2-amino-1-methyl-6-phenylimidazo[4,5-b]-pyridine (PhIP), benzidine, 4-aminobiphenyl (ABP), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx). In vitro activation was performed with lactoperoxidase (partially purified from bovine milk or human milk) in the presence of hydrogen peroxide and calf thymus DNA. Products formed during enzymatic activation were monitored by HPLC with ultraviolet and radiometric detection. Two of these products were characterized as hydrazo and azo derivatives by means of mass spectrometry. The DNA binding level of 3H- and 14C-radiolabeled amines after peroxidase-catalyzed activation was dependent on the hydrogen peroxide concentration, and the highest levels of carcinogen binding to DNA were observed at 100 microM H2O2. Carcinogen activation and the level of binding to DNA were in the order of benzidine > ABP > IQ > MeIQx > PhIP. One of the ABP adducts was identified, and the level at which it is formed was estimated to be six adducts/10(5) nucleotides. The susceptibility of aromatic and heterocyclic amines for lactoperoxidase-catalyzed activation and the binding levels of activated products to DNA suggest a potential role of lactoperoxidase-catalyzed activation of carcinogens in the etiology of breast cancer.

  16. Asymmetric Aldol Reaction Catalyzed by Modularly Designed Organocatalysts

    Institute of Scientific and Technical Information of China (English)

    Sinha, Debarshi; Mandal, Tanmay; Gogoi, Sanjib; Goldman, Joshua J.; 赵从贵

    2012-01-01

    The self-assembly of the precatalyst modules, which are amino acids and cinchona alkaloid derivatives, leads to the direct formation of the desired organocatalysts without any synthesis. These modularly designed organocatalysts (MDOs) may be used for catalyzed asymmetric aldol reaction the corresponding aldol products may be obtained in mediocre diastereoselectivities (up to 79 : 21 dr). Depending on structure of the aldehyde substrates, to excellent ee values (up to 92% ee) with moderate

  17. Modeling Lewis catalyzed reactions in Metal Organic Frameworks

    OpenAIRE

    Vandichel, Matthias; Cottenie, Stijn; Vermoortele, Frederik; De Vos, Dirk; Waroquier, Michel; Van Speybroeck, Veronique

    2011-01-01

    Recently, the spectrum of nanoporous materials like zeolites and zeotype structures has been further expanded through the discovery of a new class of hybrid porous solids [1]. Those materials, nowadays also known as metal organic frameworks or MOFs, consist of both inorganic and organic moieties. Certain MOFs exhibit a very interesting adsorption and even catalytic behavior [2]. Within this study, we will focus on the modeling of different Lewis acid catalyzed reactions in various MOFs: Cu co...

  18. Acid-catalyzed oxygen-18 labeling of peptides.

    Science.gov (United States)

    Niles, Richard; Witkowska, H Ewa; Allen, Simon; Hall, Steven C; Fisher, Susan J; Hardt, Markus

    2009-04-01

    In enzymatic (18)O-labeling strategies for quantitative proteomics, the exchange of carboxyl oxygens at low pH is a common, undesired side reaction. We asked if acid-catalyzed back exchange could interfere with quantitation and whether the reaction itself could be used as method for introducing (18)O label into peptides. Several synthetic peptides were dissolved in dilute acid containing 50% (v/v) H(2)(18)O and incubated at room temperature. Aliquots were removed over a period of 3 weeks and analyzed by tandem mass spectrometry (MS/MS). (18)O-incorporation ratios were determined by linear regression analysis that allowed for multiple stable-isotope incorporations. At low pH, peptides exchanged their carboxyl oxygen atoms with the aqueous solvent. The isotope patterns gradually shifted to higher masses until they reached the expected binomial distribution at equilibrium after approximately 11 days. Reaction rates were residue- and sequence-specific. Due to its slow nature, the acid-catalyzed back exchange is expected to minimally interfere with enzymatic (18)O-labeling studies provided that storage and analysis conditions minimize low-pH exposure times. On its own, acid-catalyzed (18)O labeling is a general tagging strategy that is an alternative to the chemical, metabolic, and enzymatic isotope-labeling schemes currently used in quantitative proteomics. PMID:19243188

  19. Reduction of nitrobenzene by the catalyzed Fe/Cu process

    Institute of Scientific and Technical Information of China (English)

    XU Wenying; LI Ping; FAN Jinhong

    2008-01-01

    The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams. The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions and cathodically controlled under the alkaline conditions. Batch experiments were performed to study the effect of solution pH, reaction duration, concentration, type of electrolyte and dissolved oxygen (DO) on the reduction of nitrobenzene by the catalyzed Fe/Cu process. This process proved effective in the pH range of 3 to 11. The conversion efficiency of nitrobenzene at pH ≈ 10.1 was almost the same as that under highly acid conditions (pH ≈ 3). The degradation of nitrobenzene fell into two phases: adsorption and surface reduction, and the influence of adsorption and mass transfer became more extensive with solution concentration. The reduction rate decreased in the presence of DO in the solution, indicating that a need for aeration was eliminated in the catalyzed Fe/Cu process. Accordingly, spending on energy consumption would be reduced. Economic analysis indicated that merely 0.05 kg was required for the treatment of a ton of nitrobenzene-containing water with pH from 3 to 11. The catalyzed Fe/Cu process is cost-effective and of practical value.

  20. Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

    Science.gov (United States)

    Joshi, Prachi; Gorski, Christopher A

    2016-07-19

    When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

  1. 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…

  2. 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)

  3. 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...

  4. 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.

  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. 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...

  7. 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...

  8. 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

  9. Gemstone deposits of Serbia

    Directory of Open Access Journals (Sweden)

    Miladinović Zoran

    2016-06-01

    Full Text Available Gemstone minerals in Serbia have never been regarded as an interesting and significant resource. Nevertheless, more than 150 deposits and occurrences have been recorded and some of them preliminarily explored in the last 50 years. The majority of deposits and occurrences are located within the Serbo-Macedonian metallogenic province and the most significant metallogenic units at the existing level of knowledge are the Fruska Gora ore district, Cer ore district, Sumadija metallogenic zone, Kopaonik metallogenic zone and Lece-Halkidiki metallogenic zone. The most important genetic type of deposits is hydrothermal, particularly in case of serpentinite/peridotite as host/parent rock. Placer deposits are also economically important. The dominant gemstones are silica minerals: chalcedony (Chrysoprase, carnelian, bluish chalcedony etc., jasper (picture, landscape, red etc., common opal (dendritic, green, milky white etc., silica masses (undivided, and quartz (rock crystal, amethyst etc.. Beside silica minerals significant gemstones in Serbia include also beryl (aquamarine, garnet (almandine and pyrope, tourmaline, fluorite, rhodochrosite, carbonate-silica breccia, carbonate-silica onyx, silicified wood, howlite, serpentinite, marble onyx, and kyanite. This paper aims to present an overview of Serbian gemstone deposits and occurrences and their position based on a simplified gemstone metallogenic map of Serbia, as well as genetic-industrial classification of gemstone deposits and gemstone varieties.

  10. 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)

  11. 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.

  12. 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%.

  13. 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.)

  14. 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

  15. 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

  16. 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

  17. 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.

  18. Effect of temperature in cerium-ion-catalyzed bromate-driven oscillators

    Science.gov (United States)

    Nagy, Gabriella; Körös, Endre; Oftedal, Norunn; Tjelflaat, Kjetil; Ruoff, Peter

    1996-03-01

    The influence of substrate composition and initial reagent concentrations on activation energies in closed Ce-ion catalyzed Belousov-Zhabotinsky (BZ) reactions is reported. While changes in the initial concentration of organic substrate, bromate ion or sulfuric acid showed different changes in activation energies for the various organic substrate BZ systems, for all systems it was found that lowering the Ce-ion concentration leads to a significant decrease in the overall activation energy of the oscillator. When comparing the performance of a malonic acid oscillator run in a batch or in a continuous stirred flow reactor (CSTR), it was found that under CSTR conditions Q10 values may become as low as 1.3, while for the batch system the corresponding Q10 values are about 2.3.

  19. Palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to a library of tetraphenylenes

    Science.gov (United States)

    Zhu, Chendan; Zhao, Yue; Wang, Di; Sun, Wei-Yin; Shi, Zhuangzhi

    2016-09-01

    Aryl–aryl bond formation constitutes one of the most important subjects in organic synthesis. The recent developments in direct arylation reactions forming aryl–aryl bond have emerged as very attractive alternatives to traditional cross-coupling reactions. Here, we describe a general palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to build a library of tetraphenylenes. This transformation represents one of the very few examples of C-H activation process that involves simultaneous formation of two aryl–aryl bonds. Oxygen plays a vital role by ensuring high reactivity, with air as the promoter furnished the best results. We anticipate this ligand-free and aerobic catalytic system will simplify the synthesis of tetraphenylenes as many of the reported methods involve use of preformed organometallic reagents and will lead to the discovery of highly efficient new direct arylation process.

  20. 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...... elongate RNA hairpins whose 5’-overhangs served as the templating sequence. The same applies for every other pyrimidine and purine nucleobase. Moreover, the initial elongation rates were always higher in the presence of a template complementary to the nucleotide than in systems without proper base...

  1. Ag-catalyzed InAs nanowires grown on transferable graphite flakes

    Science.gov (United States)

    Meyer-Holdt, Jakob; Kanne, Thomas; Sestoft, Joachim E.; Gejl, Aske; Zeng, Lunjie; Johnson, Erik; Olsson, Eva; Nygård, Jesper; Krogstrup, Peter

    2016-09-01

    Semiconducting nanowires grown by quasi-van-der-Waals epitaxy on graphite flakes are a new class of hybrid materials that hold promise for scalable nanostructured devices within opto-electronics. Here we report on high aspect ratio and stacking fault free Ag-seeded InAs nanowires grown on exfoliated graphite flakes by molecular beam epitaxy. Ag catalyzes the InAs nanowire growth selectively on the graphite flakes and not on the underlying InAs substrates. This allows for easy transfer of the flexible graphite flakes with as-grown nanowire ensembles to arbitrary substrates by a micro-needle manipulator. Besides the possibilities for fabricating novel nanostructure device designs, we show how this method is used to study the parasitic growth and bicrystal match between the graphite flake and the nanowires by transmission electron microscopy.

  2. 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.

  3. Enzyme-catalyzed synthesis of heptyl-β-glycosides: effect of water coalescence at high temperature.

    Science.gov (United States)

    Montiel, Carmina; Bustos-Jaimes, Ismael; Bárzana, Eduardo

    2013-09-01

    Alkyl glycosides can be synthesized by glycosidases in organic media with limited amounts of water. These systems, however, limit the solubility of the sugar substrates and decrease reaction yields. Herein we report the enzymatic synthesis of heptyl-β-glycosides in heptanol catalyzed by a hyperthermophilic β-glycosidase at 90°C. Our results indicate that dispersion of water in heptanol changes with time producing coalescence of water at the bottom of the reactor, playing a key role in the reaction yield. Water-soluble substrate, enzyme and products are concentrated in the aqueous phase, according to their partition coefficients, promoting side reactions that inactivate the enzyme. Reaction yield of heptyl-β-glycosides was 35% relative to lactose, at 7% water. The increase in the water phase to 12% diminished the enzyme inactivation and increased the heptyl-β-glycosides yield to 52%. Surface-active compounds, SDS and octyl glucoside, increased water dispersion but were unable to prevent coalescence.

  4. 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)

  5. 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

  6. Ultrathin single-crystal ZnO nanobelts: Ag-catalyzed growth and field emission property

    Energy Technology Data Exchange (ETDEWEB)

    Xing, G Z; Zhang, Z; Wang, D D; Liao, L; Zheng, Z; Xu, H R; Yu, T; Shen, Z X; Huan, C H A; Sum, T C; Wu, T [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, 637371 (Singapore); Fang, X S [Department of Materials Science, Fudan University, Shanghai 200433 (China); Huang, X; Guo, J; Zhang, H, E-mail: xing0012@ntu.edu.sg, E-mail: tomwu@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 639798 (Singapore)

    2010-06-25

    We report the growth of ultrathin single-crystal ZnO nanobelts by using a Ag-catalyzed vapor transport method. Extensive transmission electron microscopy and atomic force microscopy measurements reveal that the thickness of the ultrathin ZnO nanobelts is {approx} 2 nm. Scanning electron microscopy and post-growth annealing studies suggest a '1D branching and 2D filling' growth process. Our results demonstrate the critical role of catalyst in the deterministic synthesis of nanomaterials with the desired morphology. In addition, these ultrafine nanobelts exhibit stable field emission with unprecedented high emission current density of 40.17 mA cm{sup -2}. These bottom-up building blocks of ultrathin ZnO nanobelts may facilitate the construction of advanced electronic and photonic nanodevices.

  7. Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

    Institute of Scientific and Technical Information of China (English)

    WANG Ying; FU Ai-ping; LI Hong-liang; TIAN Feng-hui; YUAN Shu-ping; SI Hong-zong; DUAN Yun-bo; WANG Zong-hua

    2011-01-01

    The effects of two different amino acid catalysts on the stereoselectivities in the direct Mannich reactions of cyclohexanone,p-anisidine and p-nitrobenzaldehyde were studied with the aid of density functional theory.Transition states of the stereo-determining C-C bond-forming step with the addition of enamine intermediate to the imine for the L-proline(α-amino acid) and (R)-3-pyrrolidinecarboxylic acid(β-amino acid)-catalyzed processes were reported.B3LYP/6-31G** calculations provide a good explanation for the opposite syn vs.anti diastereoselectivities of these two different kinds of catalysts(syn-selectivity for the α-amino acid catalysts,anti-selectivity for the β-amino acid catalysts).Calculated and observed diastereomeric ratio and enantiomeric excess values are in reasonable agreement.

  8. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    Science.gov (United States)

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions. PMID:26694091

  9. Tyrosyl-DNA phosphodiesterase I catalytic mutants reveal an alternative nucleophile that can catalyze substrate cleavage.

    Science.gov (United States)

    Comeaux, Evan Q; Cuya, Selma M; Kojima, Kyoko; Jafari, Nauzanene; Wanzeck, Keith C; Mobley, James A; Bjornsti, Mary-Ann; van Waardenburg, Robert C A M

    2015-03-01

    Tyrosyl-DNA phosphodiesterase I (Tdp1) catalyzes the repair of 3'-DNA adducts, such as the 3'-phosphotyrosyl linkage of DNA topoisomerase I to DNA. Tdp1 contains two conserved catalytic histidines: a nucleophilic His (His(nuc)) that attacks DNA adducts to form a covalent 3'-phosphohistidyl intermediate and a general acid/base His (His(gab)), which resolves the Tdp1-DNA linkage. A His(nuc) to Ala mutant protein is reportedly inactive, whereas the autosomal recessive neurodegenerative disease SCAN1 has been attributed to the enhanced stability of the Tdp1-DNA intermediate induced by mutation of His(gab) to Arg. However, here we report that expression of the yeast His(nuc)Ala (H182A) mutant actually induced topoisomerase I-dependent cytotoxicity and further enhanced the cytotoxicity of Tdp1 His(gab) mutants, including H432N and the SCAN1-related H432R. Moreover, the His(nuc)Ala mutant was catalytically active in vitro, albeit at levels 85-fold less than that observed with wild type Tdp1. In contrast, the His(nuc)Phe mutant was catalytically inactive and suppressed His(gab) mutant-induced toxicity. These data suggest that the activity of another nucleophile when His(nuc) is replaced with residues containing a small side chain (Ala, Asn, and Gln), but not with a bulky side chain. Indeed, genetic, biochemical, and mass spectrometry analyses show that a highly conserved His, immediately N-terminal to His(nuc), can act as a nucleophile to catalyze the formation of a covalent Tdp1-DNA intermediate. These findings suggest that the flexibility of Tdp1 active site residues may impair the resolution of mutant Tdp1 covalent phosphohistidyl intermediates and provide the rationale for developing chemotherapeutics that stabilize the covalent Tdp1-DNA intermediate.

  10. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    Science.gov (United States)

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions.

  11. 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.

  12. Pulsed laser deposition: Prospects for commercial deposition of epitaxial films

    Energy Technology Data Exchange (ETDEWEB)

    Muenchausen, R.E.

    1999-03-01

    Pulsed laser deposition (PLD) is a physical vapor deposition (PVD) technique for the deposition of thin films. The vapor source is induced by the flash evaporation that occurs when a laser pulse of sufficient intensity (about 100 MW/cm{sup 2}) is absorbed by a target. In this paper the author briefly defines pulsed laser deposition, current applications, research directed at gaining a better understanding of the pulsed laser deposition process, and suggests some future directions to enable commercial applications.

  13. 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.

  14. On the Temperature Dependence of Enzyme-Catalyzed Rates.

    Science.gov (United States)

    Arcus, Vickery L; Prentice, Erica J; Hobbs, Joanne K; Mulholland, Adrian J; Van der Kamp, Marc W; Pudney, Christopher R; Parker, Emily J; Schipper, Louis A

    2016-03-29

    One of the critical variables that determine the rate of any reaction is temperature. For biological systems, the effects of temperature are convoluted with myriad (and often opposing) contributions from enzyme catalysis, protein stability, and temperature-dependent regulation, for example. We have coined the phrase "macromolecular rate theory (MMRT)" to describe the temperature dependence of enzyme-catalyzed rates independent of stability or regulatory processes. Central to MMRT is the observation that enzyme-catalyzed reactions occur with significant values of ΔCp(‡) that are in general negative. That is, the heat capacity (Cp) for the enzyme-substrate complex is generally larger than the Cp for the enzyme-transition state complex. Consistent with a classical description of enzyme catalysis, a negative value for ΔCp(‡) is the result of the enzyme binding relatively weakly to the substrate and very tightly to the transition state. This observation of negative ΔCp(‡) has important implications for the temperature dependence of enzyme-catalyzed rates. Here, we lay out the fundamentals of MMRT. We present a number of hypotheses that arise directly from MMRT including a theoretical justification for the large size of enzymes and the basis for their optimum temperatures. We rationalize the behavior of psychrophilic enzymes and describe a "psychrophilic trap" which places limits on the evolution of enzymes in low temperature environments. One of the defining characteristics of biology is catalysis of chemical reactions by enzymes, and enzymes drive much of metabolism. Therefore, we also expect to see characteristics of MMRT at the level of cells, whole organisms, and even ecosystems.

  15. 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.

  16. Heavy metal deposition mapping: concentrations and deposition of heavy metals in rural areas of the UK

    OpenAIRE

    Malcolm, Heath; Fowler, David; Crossley, Alan; Kentisbeer, John; Hallsworth, Steve; Lawlor, Alan; Rowland, Phil; Guyatt, Hayley; Beith, Sarah; Thacker, Sarah; Halford, Alan; ROGERS Stuart; Cape, J. Neil; Leeson, Sarah; Harmens, Harry

    2012-01-01

    CEH has been monitoring the concentrations of a range of heavy metals in rural locations across the UK since 2004. This report presents the annual average concentrations and deposition of heavy metals in air and rainfall samples collected from rural locations during 2011 and it reviews the temporal and spatial trends in heavy metal concentrations and deposition between 2004 and 2011. The monitoring network was established to measure the background concentration of a range of heavy meta...

  17. Iridium thin films deposited via pulsed laser deposition for future applications as transition-edge sensors

    Energy Technology Data Exchange (ETDEWEB)

    Galeazzi, M. E-mail: galeazzi@physics.miami.edu; Chen, C.; Cohn, J.L.; Gundersen, J.O

    2004-03-11

    The University of Miami has recently started developing and studying high-resolution microcalorimeters operating near 100 mK for X-ray and particle physics and astrophysics. These detectors will be based on Transition Edge Sensors technology fabricated using iridium thin films deposited via the Pulsed Laser Deposition technique. We report here the preliminary result of the room temperature characterization of the Ir thin films, and an overview of future plans to use the films as transition edge sensors.

  18. Oxygen Barrier Coating Deposited by Novel Plasma-enhanced Chemical Vapor Deposition

    DEFF Research Database (Denmark)

    Jiang, Juan; Benter, M.; Taboryski, Rafael Jozef;

    2010-01-01

    We report the use of a novel plasma-enhanced chemical vapor deposition chamber with coaxial electrode geometry for the SiOx deposition. This novel plasma setup exploits the diffusion of electrons through the inner most electrode to the interior samples space as the major energy source. This confi...... increased the barrier property of the modified low-density polyethylene, polyethylene terephthalate, and polylactide by 96.48%, 99.69%, and 99.25%, respectively....

  19. 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

  20. 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...

  1. Lipase-catalyzed synthesis of monoacylglycerol in a homogeneous system.

    Science.gov (United States)

    Monteiro, Julieta B; Nascimento, Maria G; Ninow, Jorge L

    2003-04-01

    The 1,3-regiospecifique lipase, Lipozyme IM, catalyzed the esterification of lauric acid and glycerol in a homogeneous system. To overcome the drawback of the insolubility of glycerol in hexane, which is extensively used in enzymatic synthesis, a mixture of n-hexane/tert-butanol (1:1, v/v) was used leading to a monophasic system. The conversion of lauric acid into monolaurin was 65% in 8 h, when a molar ratio of glycerol to fatty acid (5:1) was used with the fatty acid at 0.1 M, and the phenomenon of acyl migration was minimized.

  2. 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.

  3. 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

  4. Low-temperature, self-catalyzed growth of Si nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Cuscuna, Massimo; Convertino, Annalisa; Mariucci, Luigi; Fortunato, Guglielmo; Pecora, Alessandro; Martelli, Faustino [Istituto per la Microelettronica e i Microsistemi del Consiglio Nazionale delle Ricerche, via del Fosso del Cavaliere 100, I-00133 Rome (Italy); Felisari, Laura [Istituto Officina dei Materiali del Consiglio Nazionale delle Ricerche, Basovizza, I-34149 Trieste (Italy); Nicotra, Giuseppe; Spinella, Corrado, E-mail: faustino.martelli@cnr.it [Istituto per la Microelettronica e i Microsistemi del Consiglio Nazionale delle Ricerche, Stradale Primosole 50, I-95121 Catania (Italy)

    2010-06-25

    High densities of self-catalyzed Si nanowires have been grown at temperatures down to 320 deg. C on different Si substrates, whose surfaces have been roughened by simple physical or chemical treatments. The particular substrates are Si(110) cleavage planes, chemically etched Si(111) surfaces and microcrystalline Si obtained by laser annealing thin amorphous Si layers. The NW morphology depends on the growth surface. Transmission electron microscopy indicates that the NWs are made of pure Si with a crystalline core structure. Reflectivity measurements confirm this latter finding.

  5. 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...

  6. 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...

  7. 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.

  8. 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 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...... a model whereby FBH1 promotes early checkpoint signaling by remodeling of stalled DNA replication forks....

  9. 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

  10. 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

  11. Aldol Reactions Catalyzed by Proline Functionalized Polyacrylonitrile Fiber

    Institute of Scientific and Technical Information of China (English)

    XIAO Jia; LI Guo-wei; ZHANG Wen-qin

    2013-01-01

    A proline functionalized fiber catalyst was employed for aldol reactions in water.In the presence of the fiber catalyst,the aldol reactions proceeded smoothly at 40 C and the products were obtained in excellent yields which were higher than those obtained for the reactions catalyzed by L-proline or trans-4-hydroxy-L-proline.This newly developed fiber catalyst is applicable to the reactions of a wide range of aromatic aldehydes and exhibits excellent reusability(up to 6 times) without any additional treatment.

  12. Comparing Ru and Fe-catalyzed olefin metathesis.

    Science.gov (United States)

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-08-01

    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. PMID:24821502

  13. 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)

  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......, the 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. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, Roman Vladimirovich [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    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 β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-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.

  16. Lipase-Catalyzed Modification of Canola Oil with Caprylic Acid

    DEFF Research Database (Denmark)

    Wang, Yingyao; Luan, Xia; Xu, Xuebing;

    Lipase-catalyzed acidolysis of canola oil with caprylic acid was performed to produce structured lipids. Six commercial lipases from different sources were screened for their ability to incorporate the caprylic acid into the canola oil. The positional distribution of FA on the glycerol backbone...... parameters studied included substrate mole ratio, enzyme load, reaction time and temperature. Incorporation of caprylic acid was higher when reactions were carried with 10% lipase of the total weight of substrates at a mole ratio of oil to caprylic acid of 1:4. The optimal time course and temperature...

  17. 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

  18. 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....... 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...

  19. DRY DEPOSITION OF POLLUTANTS TO FORESTS

    Science.gov (United States)

    We report on the results of an extensive field campaign to measure dry deposition of ozone and sulfur dioxide to a sample of forest types in the United States. Measurements were made for full growing seasons over a deciduous forest in Pennsylvania and a mixed deciduous-conifer...

  20. Iron and manganese deposits in Uruguay

    International Nuclear Information System (INIS)

    This report is the results of the study carried out for the United Nations expert which the main object was: the study of the information available about iron and manganese formation in Uruguay, as well as the main researching deposit to determinate economical possibilities in the exportation.

  1. Uranium deposits in magmatic and metamorphic rocks

    International Nuclear Information System (INIS)

    The association of uranium with certain types of magmatic and metamorphic rocks is well known. They have consequently been explored and studied quite extensively. In recent years interest in them has been eclipsed by the discovery of larger, lower cost deposits in other geological environments. Nonetheless, magmatic and metamorphic rocks continue to be important sources of uranium and large areas of the Earth's crust with such rocks are prospective locations for additional discoveries. As future exploration and development could be more difficult the full importance of individual deposits may not be recognized until after many years of investigation and experience. In addition to being important host rocks, magmatic and metamorphic rocks have been of considerable interest to uranium geologists as they are considered to be important source rocks for uranium and thus can lead to deposits nearby in other environments. Furthermore, these rocks provide important information on the geochemical cycle of uranium in the Earth's crust and mantle. Such information can lead to identification of uranium provinces and districts and to a basic understanding of processes of formation of uranium deposits. The International Atomic Energy Agency convened a Technical Committee Meeting on Uranium Deposits in Magmatic and Metamorphic Rocks. The meeting was held in Salamanca, Spain, from 29 September to 3 October 1986. It was followed by a two day field trip to uranium deposits in the Ciudad Rodrigo and Don Benito areas. The meeting was attended by 48 participants from 22 countries. Two panels were organized for discussion of the following topics: (1) ore deposit genesis and characterization and (2) exploration and resource assessment. The technical papers together with the panel reports form this publication. The scope and variety of the papers included and the panel reports provide a good coverage of current knowledge and thinking on uranium in magmatic and metamorphic rocks

  2. 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.

  3. Metalloporphyrin solubility: a trigger for catalyzing reductive dechlorination of tetrachloroethylene.

    Science.gov (United States)

    Dror, Ishai; Schlautman, Mark A

    2004-02-01

    Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants.

  4. 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

  5. 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.

  6. Lipase-catalyzed polyester synthesis – A green polymer chemistry

    Science.gov (United States)

    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 synthesis is, therefore, a reaction in reverse way of in vivo lipase catalysis of ester bond-cleavage with hydrolysis. The lipase-catalyzed polymerizations show very high chemo-, regio-, and enantio-selectivities and involve various advantageous characteristics. Lipase is robust and compatible with other chemical catalysts, which allows novel chemo-enzymatic processes. New syntheses of a variety of functional polyesters and a plausible reaction mechanism of lipase catalysis are mentioned. The polymerization characteristics are of green nature currently demanded for sustainable society, and hence, desirable for conducting ‘green polymer chemistry’. PMID:20431260

  7. Enzyme catalyzed electricity-driven water softening system.

    Science.gov (United States)

    Arugula, Mary A; Brastad, Kristen S; Minteer, Shelley D; He, Zhen

    2012-12-10

    Hardness in water, which is caused by divalent cations such as calcium and magnesium ions, presents a major water quality problem. Because hard water must be softened before use in residential applications, there is great interest in the saltless water softening process because, unlike ion exchange softeners, it does not introduce additional ions into water. In this study, a saltless hardness removal driven by bioelectrochemical energy produced through enzymatic oxidation of glucose was proposed and investigated. Glucose dehydrogenase was coated on a carbon electrode to catalyze glucose oxidation in the presence of NAD⁺ as a cofactor/mediator and methylene green as an electrocatalyst. The results showed that electricity generation stimulated hardness removal compared with non-electricity conditions. The enzymatic water softener worked upon a 6h batch operation per day for eight days, and achieved an average hardness removal of 46% at a high initial concentration of 800 mg/L as CaCO₃. More hardness was removed at a lower initial concentration. For instance, at 200mg/L as CaCO₃ the enzymatic water softener removed 76.4±4.6% of total hardness. The presence of magnesium ions decreased hardness removal because of its larger hydrated radius than calcium ions. The enzymatic water softener removed 70-80% of total hardness from three actual hard water samples. These results demonstrated a proof-of-concept that enzyme catalyzed electricity generation can be used to soften hard water.

  8. Study of microwave effects on the lipase-catalyzed hydrolysis.

    Science.gov (United States)

    Chen, Chia-Chen; Reddy, P Muralidhar; Devi, C Shobha; Chang, Po-Chi; Ho, Yen-Peng

    2016-01-01

    The effect of microwave heating on lipase-catalyzed reaction remains controversial. It is not clear whether the reaction rate enhancements are purely due to thermal/heating effects or to non-thermal effects. Therefore, quantitative mass spectrometry was used to conduct accurate kinetic analysis of lipase-catalyzed hydrolysis of triolein by microwave and conventional heating. Commercial lipases from Candida rugosa (CRL), Porcine Pancreas (PPL), and Burkholderia cepacia (BCL) were used. Hydrolysis reactions were performed at various temperatures and pH levels, along with various amounts of buffer and enzymes. Hydrolysis product yields at each time point using an internal-standard method showed no significant difference between microwave and conventional heating conditions when the reaction was carried out at the same temperature. CRL showed optimum catalytic activity at 37 °C, while PPL and BCL had better activities at 50 °C. The phosphate buffer was found to give a better hydrolysis yield than the Tris-HCl buffer. Overall results prove that a non-thermal effect does not exist in microwave-assisted lipase hydrolysis of triolein. Therefore, conventional heating at high temperatures (e.g., 50 °C) can be also used to accelerate hydrolysis reactions.

  9. 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.

  10. Influence of organic acids on oscillations and waves in the ferroin-catalyzed Belousov-Zhabotinsky reaction

    Science.gov (United States)

    Krüger, Frank; Nagy-Ungvárai, Zsuzsanna; Müller, Stefan C.

    Experiments of the influence of mesoxalic and tartronic acid on the oscillatory behavior and on the spiral tip motion in a ferroin-catalyzed Belousov-Zhabotinsky (BZ) solution are reported. The oscillations were observed in batch and CSTR systems, and for the investigations of the spiral tip motion an open gel reactor was used. A characteristic shoulder in the oscillations is associated with an additional Br - production phase. The chemical parameters for a transition from a hypocycloidal to a circular tip trajectory are found. The findings are compared with the temporal and spatial dynamic behavior, occurring during the ageing process of the solution.

  11. End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Ronald Okoth

    2013-03-01

    Full Text Available Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I-catalyzed azide–alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.

  12. 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...

  13. 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

  14. 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

  15. 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.

  16. "Total Deposition (TDEP) Maps"

    Science.gov (United States)

    The presentation provides an update on the use of a hybrid methodology that relies on measured values from national monitoring networks and modeled values from CMAQ to produce of maps of total deposition for use in critical loads and other ecological assessments. Additionally, c...

  17. ErbB3/HER3 intracellular domain is competent to bind ATP and catalyze autophosphorylation

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Fumin; Telesco, Shannon E.; Liu, Yingting; Radhakrishnan, Ravi; Lemmon, Mark A. (UPENN); (UPENN-MED)

    2010-06-21

    ErbB3/HER3 is one of four members of the human epidermal growth factor receptor (EGFR/HER) or ErbB receptor tyrosine kinase family. ErbB3 binds neuregulins via its extracellular region and signals primarily by heterodimerizing with ErbB2/HER2/Neu. A recently appreciated role for ErbB3 in resistance of tumor cells to EGFR/ErbB2-targeted therapeutics has made it a focus of attention. However, efforts to inactivate ErbB3 therapeutically in parallel with other ErbB receptors are challenging because its intracellular kinase domain is thought to be an inactive pseudokinase that lacks several key conserved (and catalytically important) residues - including the catalytic base aspartate. We report here that, despite these sequence alterations, ErbB3 retains sufficient kinase activity to robustly trans-autophosphorylate its intracellular region - although it is substantially less active than EGFR and does not phosphorylate exogenous peptides. The ErbB3 kinase domain binds ATP with a K{sub d} of approximately 1.1 {micro}M. We describe a crystal structure of ErbB3 kinase bound to an ATP analogue, which resembles the inactive EGFR and ErbB4 kinase domains (but with a shortened {alpha}C-helix). Whereas mutations that destabilize this configuration activate EGFR and ErbB4 (and promote EGFR-dependent lung cancers), a similar mutation conversely inactivates ErbB3. Using quantum mechanics/molecular mechanics simulations, we delineate a reaction pathway for ErbB3-catalyzed phosphoryl transfer that does not require the conserved catalytic base and can be catalyzed by the 'inactive-like'configuration observed crystallographically. These findings suggest that ErbB3 kinase activity within receptor dimers may be crucial for signaling and could represent an important therapeutic target.

  18. Skin deposits in hereditary cystatin C amyloidosis

    DEFF Research Database (Denmark)

    Benedikz, Eirikur; Blöndal, H; Gudmundsson, G

    1990-01-01

    Clinically normal skin from 47 individuals aged 9-70 years was investigated. Cystatin C amyloid deposits were found in various locations of the skin by light and/or electron microscopy, in all 12 patients with a clinical history of hereditary cystatin C amyloidosis (HCCA). Six asymptomatic...... individuals, who had the Alu 1 restriction fragment length polymorphism (RFLP) marker reported to cosegregate with the disease, also had cystatin C amyloid deposits in the skin. Three asymptomatic individuals (age 17-46) belonging to the HCCA families were without amyloid in the skin but had Alu 1 RFLP marker...

  19. 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

  20. Texture control during laser deposition of nickel-based superalloy

    International Nuclear Information System (INIS)

    A nickel-based superalloy was deposited on a nickel-based superalloy substrate by a laser-aided direct metal deposition process. The age-hardening behavior of the as-deposited clad was studied. The effect of laser beam scanning pattern on dendrite growth morphology was investigated using electron backscatter diffraction. Unidirectional laser beam scanning pattern developed a fiber texture; conversely, a backward and forward scanning pattern developed a rotated cube texture in the deposit. This paper reports a route to produce texture-controlled laser clad on a polycrystalline substrate.

  1. 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

  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. 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.

  4. Thorium ore deposits

    International Nuclear Information System (INIS)

    The main occurences of the thorium minerals of the Argentine Republic which have not been exploited, due to their reduced volume, are described. The thoriferous deposits have three genetic types: pegmatitic, hydrothermal and detritic, being the most common minerals: monazite, thorite and thorogummite. The most important thorium accumulations are located in Salta, being of less importance those of Cordoba, Jujuy and San Juan. (M.E.L.)

  5. Metal-Free Oxidation of α-Hydroxy Ketones to 1,2-Diketones Catalyzed by Mesoporous Carbon Nitride with Visible Light

    Institute of Scientific and Technical Information of China (English)

    郑志硕; 周小松

    2012-01-01

    As a photocatalyst, mesoporous carbon nitride (mpg-C3N4) shows higher photocatalytic activities in organic synthesis. Herein we report an mpg-C3N4-catalyzed oxidation of α-hydroxy ketones to synthesize 1,2-diketones using visible light. This transformation represents a green and highly efficient synthetic route to synthesize 1,2-diketones for which catalytic approaches are scarce.

  6. 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 ...

  7. 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

  8. Degradation and transformation of atrazine under catalyzed ozonation process with TiO2 as catalyst.

    Science.gov (United States)

    Yang, Yixin; Cao, Hongbin; Peng, Pai; Bo, Hongmiao

    2014-08-30

    Degradation of atrazine by heterogeneously catalyzed ozonation was carried out with TiO2 in the form of rutile as the catalyst. Some experimental factors such as catalyst dose, ozone dose and initial concentration of atrazine were investigated for their influence on catalyzed ozonation process. Although atrazine was effectively removed from aqueous solution by catalyzed ozonation process, the mineralization degree only reached 56% at the experimental conditions. Five transformation products were identified by GC/MS analysis. The degradation of atrazine involved de-alkylation, de-chlorination and de-amination. Diaminotriazine and 5-azauracil were the de-chlorinated and de-aminated products, respectively. The evolution of concentration of transformation products during catalyzed ozonation process was compared with uncatalyzed ozonation to show the degradation pathway. Toxicity tests based on the inhibition of the luminescence emitted by Vibrio fisheri indicated the detoxification of atrazine by catalyzed ozonation.

  9. FBH1 Catalyzes Regression of Stalled Replication Forks

    Directory of Open Access Journals (Sweden)

    Kasper Fugger

    2015-03-01

    Full Text Available 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 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 required for early phosphorylation of ATM substrates such as CHK2 and CtIP as well as hyperphosphorylation of RPA. These phosphorylations occur prior to apparent DNA double-strand break formation. Furthermore, FBH1-dependent signaling promotes checkpoint control and preserves genome integrity. We propose a model whereby FBH1 promotes early checkpoint signaling by remodeling of stalled DNA replication forks.

  10. Trypsin-catalyzed oxygen-18 labeling for quantitative proteomics

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Weijun; Petritis, Brianne O.; Nicora, Carrie D.; Smith, Richard D.

    2011-07-01

    Stable isotope labeling based on relative peptide/protein abundance measurements is commonly applied for quantitative proteomics. Recently, trypsin-catalyzed oxygen-18 labeling has grown in popularity due to its simplicity, cost-effectiveness, and its ability to universally label peptides with high sample recovery. In (18)O labeling, both C-terminal carboxyl group atoms of tryptic peptides can be enzymatically exchanged with (18)O, thus providing the labeled peptide with a 4 Da mass shift from the (16)O-labeled sample. Peptide (18)O labeling is ideally suited for generating a labeled "universal" reference sample used for obtaining accurate and reproducible quantitative measurements across large number of samples in quantitative discovery proteomics.

  11. Trypsin-catalyzed oxygen-18 labeling for quantitative proteomics.

    Science.gov (United States)

    Qian, Wei-Jun; Petritis, Brianne O; Nicora, Carrie D; Smith, Richard D

    2011-01-01

    Stable isotope labeling based on relative peptide/protein abundance measurements is commonly applied for quantitative proteomics. Recently, trypsin-catalyzed oxygen-18 labeling has grown in popularity due to its simplicity, cost-effectiveness, and its ability to universally label peptides with high sample recovery. In (18)O labeling, both C-terminal carboxyl group atoms of tryptic peptides can be enzymatically exchanged with (18)O, thus providing the labeled peptide with a 4 Da mass shift from the (16)O-labeled sample. Peptide (18)O labeling is ideally suited for generating a labeled "universal" reference sample used for obtaining accurate and reproducible quantitative measurements across large number of samples in quantitative discovery proteomics. PMID:21604114

  12. 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.

  13. 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 metal...... ion binding sites, one of which is occupied in the mononuclear species. In this work it is assumed that catalysis takes place at zinc site 1, which is modeled by the metal ion, three imidazole rings, and a hydroxide ion. The lactam ring, a minimal model of beta-lactam antibiotics, is initially...... coordinating to the zinc ion. Potential proton shuttles from the second (unoccupied) metal-binding site (water, Asp, or Cys) are included in some calculations. The calculated reaction barrier for formation of the tetrahedral intermediate is 13 kcal/mol, close to what is observed experimentally for the rate...

  14. Muon Catalyzed Fusion in 3 K Solid Deuterium

    CERN Document Server

    Knowles, P E; Bailey, J M; Beer, G A; Beveridge, J L; Fujiwara, M C; Huber, T M; Jacot-Guillarmod, R; Kammel, P; Kim, S K; Kunselman, A R; Marshall, G M; Martoff, C J; Mason, G R; Mulhauser, F; Olin, A; Petitjean, C; Porcelli, T A; Zmeskal, J; Zmeskal, and J.

    1997-01-01

    Muon catalyzed fusion in deuterium has traditionally been studied in gaseous and liquid targets. The TRIUMF solid-hydrogen-layer target system has been used to study the fusion reaction rates in the solid phase of D_2 at a target temperature of 3 K. Products of two distinct branches of the reaction were observed; neutrons by a liquid organic scintillator, and protons by a silicon detector located inside the target system. The effective molecular formation rate from the upper hyperfine state of $\\mu d$ and the hyperfine transition rate have been measured: $\\tilde{\\lambda}_(3/2)=2.71(7)_{stat.}(32)_{syst.} The molecular formation rate is consistent with other recent measurements, but not with the theory for isolated molecules. The discrepancy may be due to incomplete thermalization, an effect which was investigated by Monte Carlo calculations. Information on branching ratio parameters for the s and p wave d+d nuclear interaction has been extracted.

  15. CRYSTAL DEFECTS IN PLASMA NITRIDED LAYER CATALYZED BY RARE EARTH

    Institute of Scientific and Technical Information of China (English)

    F.S. Chen; Y.X. Liu; D.K. Liang; L.M. Xiao

    2002-01-01

    The microstructure of plasma nitrided layer catalyzed by rare-earth elements has beenstudied with TEM. The results show that the grains of γ'-Fe4N phase are refinedby rare-earth elements and the plane defects in boundary are increased by rare-earthelements. The addition of rare-earth element increases the bombardment effect andthe number of crystal defects such as vacancies, dislocation loops, twins and stackingfaults in γ'-Fe4N phase and can produce the high-density dislocations in the ferrite ofdiffusion layer at a distance 0. 08mm from the surface. The production of a numberof crystal defects is one of important reasons why rare-earth element accelerates thediffusion of nitrogen atoms during plasma-nitridiug.

  16. 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)

  17. 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

  18. 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

  19. 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.)

  20. 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.

  1. 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.)

  2. The general base in the thymidylate synthase catalyzed proton abstraction.

    Science.gov (United States)

    Ghosh, Ananda K; Islam, Zahidul; Krueger, Jonathan; Abeysinghe, Thelma; Kohen, Amnon

    2015-12-14

    The enzyme thymidylate synthase (TSase), an important chemotherapeutic drug target, catalyzes the formation of 2'-deoxythymidine-5'-monophosphate (dTMP), a precursor of one of the DNA building blocks. TSase catalyzes a multi-step mechanism that includes the abstraction of a proton from the C5 of the substrate 2'-deoxyuridine-5'-monophosphate (dUMP). Previous studies on ecTSase proposed that an active-site residue, Y94 serves the role of the general base abstracting this proton. However, since Y94 is neither very basic, nor connected to basic residues, nor located close enough to the pyrimidine proton to be abstracted, the actual identity of this base remains enigmatic. Based on crystal structures, an alternative hypothesis is that the nearest potential proton-acceptor of C5 of dUMP is a water molecule that is part of a hydrogen bond (H-bond) network comprised of several water molecules and several protein residues including H147, E58, N177, and Y94. Here, we examine the role of the residue Y94 in the proton abstraction step by removing its hydroxyl group (Y94F mutant). We investigated the effect of the mutation on the temperature dependence of intrinsic kinetic isotope effects (KIEs) and found that these KIEs are more temperature dependent than those of the wild-type enzyme (WT). These results suggest that the phenolic -OH of Y94 is a component of the transition state for the proton abstraction step. The findings further support the hypothesis that no single functional group is the general base, but a network of bases and hydroxyls (from water molecules and tyrosine) sharing H-bonds across the active site can serve the role of the general base to remove the pyrimidine proton.

  3. Dry deposition to vegetated surfaces: parametric dependencies

    International Nuclear Information System (INIS)

    The dry deposition velocity of airborne pollutants to vegetated surfaces depends on the physico-chemical form of the pollutant, on meteorological conditions (windspeed, atmospheric stability) and on characteristics of the surface cover. This report examines these dependencies, drawing on experimental data and on information from theoretical analyses. A canopy model is outlined which uses first-order closure of the equations for turbulent transport of momentum (or matter), with losses of momentum (or matter) to individual canopy elements parameterised in terms of the mean windspeed: the model has previously been tested against experimental data on an artificial 'grass' canopy. The model is used to elucidate the features of the dependence of deposition velocity on windspeed and on whether the pollutant is in gaseous or particulate form: in the former case, the dependence on the molecular diffusivity of the gas is shown; in the latter case, dependencies on particle diameter and density are deduced. The predictions are related to available measurements. Additional hypotheses are introduced to treat the influence of atmospheric stability on deposition, and the analysis is used to shed light on the somewhat confusing picture that has emerged from past experimental studies. In considering the dependence of deposition velocity on the structural properties of the vegetation, it is established that more parameters than the single one conventionally used -aerodynamic roughness length - are needed to characterise the surface cover. Some indications of the extent of variation in deposition velocity from one type of vegetation to another are elicited from the model. (author)

  4. Compilation of gallium resource data for bauxite deposits

    Science.gov (United States)

    Schulte, Ruth F.; Foley, Nora K.

    2014-01-01

    Gallium (Ga) concentrations for bauxite deposits worldwide have been compiled from the literature to provide a basis for research regarding the occurrence and distribution of Ga worldwide, as well as between types of bauxite deposits. In addition, this report is an attempt to bring together reported Ga concentration data into one database to supplement ongoing U.S. Geological Survey studies of critical mineral resources. The compilation of Ga data consists of location, deposit size, bauxite type and host rock, development status, major oxide data, trace element (Ga) data and analytical method(s) used to derive the data, and tonnage values for deposits within bauxite provinces and districts worldwide. The range in Ga concentrations for bauxite deposits worldwide is

  5. The classification of minerals deposits

    International Nuclear Information System (INIS)

    In this part of book author present the classification of minerals deposits. Deposit formation take place as a result of complicated and long geology processes in the wide temperature intervals (from 1500 digC to usual) and pressures (from usual and to tens kilobars). Deposits of minerals as other investigation objects require in definite systematization on the base of definite characteristics

  6. In vitro Characterization of Phenylacetate Decarboxylase, a Novel Enzyme Catalyzing Toluene Biosynthesis in an Anaerobic Microbial Community.

    Science.gov (United States)

    Zargar, K; Saville, R; Phelan, R M; Tringe, S G; Petzold, C J; Keasling, J D; Beller, H R

    2016-08-10

    Anaerobic bacterial biosynthesis of toluene from phenylacetate was reported more than two decades ago, but the biochemistry underlying this novel metabolism has never been elucidated. Here we report results of in vitro characterization studies of a novel phenylacetate decarboxylase from an anaerobic, sewage-derived enrichment culture that quantitatively produces toluene from phenylacetate; complementary metagenomic and metaproteomic analyses are also presented. Among the noteworthy findings is that this enzyme is not the well-characterized clostridial p-hydroxyphenylacetate decarboxylase (CsdBC). However, the toluene synthase under study appears to be able to catalyze both phenylacetate and p-hydroxyphenylacetate decarboxylation. Observations suggesting that phenylacetate and p-hydroxyphenylacetate decarboxylation in complex cell-free extracts were catalyzed by the same enzyme include the following: (i) the specific activity for both substrates was comparable in cell-free extracts, (ii) the two activities displayed identical behavior during chromatographic separation of cell-free extracts, (iii) both activities were irreversibly inactivated upon exposure to O2, and (iv) both activities were similarly inhibited by an amide analog of p-hydroxyphenylacetate. Based upon these and other data, we hypothesize that the toluene synthase reaction involves a glycyl radical decarboxylase. This first-time study of the phenylacetate decarboxylase reaction constitutes an important step in understanding and ultimately harnessing it for making bio-based toluene.

  7. Electrolysis of ammonia for hydrogen production catalyzed by Pt and Pt-Ir deposited on nickel foam

    Institute of Scientific and Technical Information of China (English)

    Min; Jiang; Dandan; Zhu; Xuebo; Zhao

    2014-01-01

    Electrolysis of ammonia in alkaline electrolyte solution was applied for the production of hydrogen. Both Pt-loaded Ni foam and Pt-Ir loaded Ni foam electrodes were prepared by electrodeposition and served as anode and cathode in ammonia electrolytic cell, respectively. The electrochemical behaviors of ammonia in KOH solution were individually investigated via cyclic voltammetry on three electrodes, i.e. bare Ni foam electrode, Pt-loaded Ni foam electrode and Pt-Ir loaded Ni foam electrode. The morphology and composition of the prepared Ni foam electrode were analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Effects of the concentration of electrolyte solution and temperature of electrolytic cell on the electrolysis reaction were examined in order to enhance the efficiency of ammonia electrolysis. The competition of ammonia electrolysis and water electrolysis in the same alkaline solution was firstly proposed to explain the changes of cell voltage with the electrolysis proceeding. At varying current densities, different cell voltages could be obtained from galvanostatic curves.The low cell voltage of 0.58 V, which is less than the practical electrolysis voltage of water(1.6 V), can be obtained at a current density of2.5 mA/cm2. Based on some experimental parameters, such as the applied current, the resulting cell voltage and output of hydrogen gas, the power consumption per gram of H2produced can be estimated.

  8. Effect of substrate on the nucleation and growth of aluminum films deposited from methylpyrrolidine alane

    International Nuclear Information System (INIS)

    Methylpyrrolidine alane complex was used to deposit aluminum films on various types of substrates in a low pressure chemical vapor deposition reactor. The films grow easily on metallic and transition metal oxide surfaces, but not on any other tested semiconductor and dielectric substrates below 200 deg. C, showing strong substrate dependency. The free energies of precursor adsorption, surface dissociation reaction and product desorption, as well as the film wettability to substrate are among the key factors which affect the energy barrier for nucleation or deposition selectivity. In general, a metal substrate can enhance nucleation because it catalyzes the surface reactions and bonds strongly with aluminum. The oxidation-reduction reaction may occur between the precursor and substrate on a metal oxide surface. The reduced metal sites can be the seed nuclei and are possibly responsible for Al growth on the surfaces of transition metal oxides

  9. Ultrasensitive multiplexed immunoassay with electrochemical stripping analysis of silver nanoparticles catalytically deposited by gold nanoparticles and enzymatic reaction.

    Science.gov (United States)

    Lai, Guosong; Yan, Feng; Wu, Jie; Leng, Chuan; Ju, Huangxian

    2011-04-01

    A novel ultrasensitive multiplexed immunoassay method was developed by combining alkaline phosphatase (ALP)-labeled antibody functionalized gold nanoparticles (ALP-Ab/Au NPs) and enzyme-Au NP catalyzed deposition of silver nanoparticles at a disposable immunosensor array. The immunosensor array was prepared by covalently immobilizing capture antibodies on chitosan modified screen-printed carbon electrodes. After sandwich-type immunoreactions, the ALP-Ab/Au NPs were captured on an immunosensor surface to catalyze the hydrolysis of 3-indoxyl phosphate, which produced an indoxyl intermediate to reduce Ag(+). The silver deposition process was catalyzed by both ALP and Au NPs, which amplified the detection signal. The deposited silver was then measured by anodic stripping analysis in KCl solution. Using human and mouse IgG as model analytes, this multiplexed immunoassay method showed wide linear ranges over 4 orders of magnitude with the detection limits down to 4.8 and 6.1 pg/mL, respectively. Acceptable assay results for practical samples could be obtained. The newly designed strategy avoided cross talk and the need of deoxygenation for the electrochemical immunoassay and, thus, provided a promising potential in clinical applications.

  10. Limited Deposit Insurance Coverage and Bank Competition

    OpenAIRE

    Shy, Oz; Stenbacka, Rune; Yankov, Vladimir

    2014-01-01

    Deposit insurance designs in many countries place a limit on the coverage of deposits in each bank. However, no limits are placed on the number of accounts held with different banks. Therefore, under limited deposit insurance, some consumers open accounts with different banks to achieve higher or full deposit insurance coverage. We compare three regimes of deposit insurance: No deposit insurance, unlimited deposit insurance, and limited deposit insurance. We show that limited deposit insuranc...

  11. Ag-catalyzed InAs nanowires grown on transferable graphite flakes

    DEFF Research Database (Denmark)

    Meyer-Holdt, Jakob; Kanne, Thomas; Sestoft, Joachim E.;

    2016-01-01

    Semiconducting nanowires grown by quasi-van-der-Waals epitaxy on graphite flakes are a new class of hybrid materials that hold promise for scalable nanostructured devices within opto-electronics. Here we report on high aspect ratio and stacking fault free Ag-seeded InAs nanowires grown on exfolia......Semiconducting nanowires grown by quasi-van-der-Waals epitaxy on graphite flakes are a new class of hybrid materials that hold promise for scalable nanostructured devices within opto-electronics. Here we report on high aspect ratio and stacking fault free Ag-seeded InAs nanowires grown...... on exfoliated graphite flakes by molecular beam epitaxy. Ag catalyzes the InAs nanowire growth selectively on the graphite flakes and not on the underlying InAs substrates. This allows for easy transfer of the flexible graphite flakes with as-grown nanowire ensembles to arbitrary substrates by a micro......-needle manipulator. Besides the possibilities for fabricating novel nanostructure device designs, we show how this method is used to study the parasitic growth and bicrystal match between the graphite flake and the nanowires by transmission electron microscopy....

  12. Demonstration of base catalyzed decomposition process, Navy Public Works Center, Guam, Mariana Islands

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, A.J.; Freeman, H.D.; Brown, M.D.; Zacher, A.H.; Neuenschwander, G.N.; Wilcox, W.A.; Gano, S.R. [Pacific Northwest National Lab., Richland, WA (United States); Kim, B.C.; Gavaskar, A.R. [Battelle Columbus Div., OH (United States)

    1996-02-01

    Base Catalyzed Decomposition (BCD) is a chemical dehalogenation process designed for treating soils and other substrate contaminated with polychlorinated biphenyls (PCB), pesticides, dioxins, furans, and other hazardous organic substances. PCBs are heavy organic liquids once widely used in industry as lubricants, heat transfer oils, and transformer dielectric fluids. In 1976, production was banned when PCBs were recognized as carcinogenic substances. It was estimated that significant quantities (one billion tons) of U.S. soils, including areas on U.S. military bases outside the country, were contaminated by PCB leaks and spills, and cleanup activities began. The BCD technology was developed in response to these activities. This report details the evolution of the process, from inception to deployment in Guam, and describes the process and system components provided to the Navy to meet the remediation requirements. The report is divided into several sections to cover the range of development and demonstration activities. Section 2.0 gives an overview of the project history. Section 3.0 describes the process chemistry and remediation steps involved. Section 4.0 provides a detailed description of each component and specific development activities. Section 5.0 details the testing and deployment operations and provides the results of the individual demonstration campaigns. Section 6.0 gives an economic assessment of the process. Section 7.0 presents the conclusions and recommendations form this project. The appendices contain equipment and instrument lists, equipment drawings, and detailed run and analytical data.

  13. LDRD Final Report - Investigations of the impact of the process integration of deposited magnetic films for magnetic memory technologies on radiation hardened CMOS devices and circuits - LDRD Project (FY99)

    International Nuclear Information System (INIS)

    This project represented a coordinated LLNL-SNL collaboration to investigate the feasibility of developing radiation-hardened magnetic non-volatile memories using giant magnetoresistance (GMR) materials. The intent of this limited-duration study was to investigate whether giant magnetoresistance (GMR) materials similar to those used for magnetic tunnel junctions (MTJs) were process compatible with functioning CMOS circuits. Sandia's work on this project demonstrated that deposition of GMR materials did not affect the operation nor the radiation hardness of Sandia's rad-hard CMOS technology, nor did the integration of GMR materials and exposure to ionizing radiation affect the magnetic properties of the GMR films. Thus, following deposition of GMR films on rad-hard integrated circuits, both the circuits and the films survived ionizing radiation levels consistent with DOE mission requirements. Furthermore, Sandia developed techniques to pattern deposited GMR films without degrading the completed integrated circuits upon which they were deposited. The present feasibility study demonstrated all the necessary processing elements to allow fabrication of the non-volatile memory elements onto an existing CMOS chip, and even allow the use of embedded (on-chip) non-volatile memories for system-on-a-chip applications, even in demanding radiation environments. However, funding agencies DTRA, AIM, and DARPA did not have any funds available to support the required follow-on technology development projects that would have been required to develop functioning prototype circuits, nor were such funds available from LDRD nor from other DOE program funds

  14. Solar thermochemical reactions Ⅲ: A convenient one-pot synthesis of 1,2,4,5-tetrasubstituted imidazoles catalyzed by high surface area SiO2 and induced by solar thermal energy

    Institute of Scientific and Technical Information of China (English)

    Ramadan A. Mekheimer; Afaf M. Abdel Hameed; Seham A.A. Mansour; Kamal Usef Sadek

    2009-01-01

    A simple, convenient and efficient method for the synthesis of 1,2,4,5-tetrasubstituted imidazole derivatives using benzoin, an aromatic aldehyde, an aromatic amine in the presence of ammonium acetate catalyzed by high surface area SiO2 and induced by free solar thermal energy was reported.

  15. Fundamentals of heterogeneously catalyzed reactions of environmental importance

    Science.gov (United States)

    Deshmukh, Subodh Shrinivas

    Reaction kinetics and spectroscopic characterization are valuable tools for understanding heterogeneously catalyzed chemical reactions. The objective of this work was to apply the tools of catalysis and reaction kinetics to understand the fundamentals of chemical surface phenomena for environmentally important reactions. This thesis presents our work in two areas of catalytic reactions for pollution abatement---"chlorofluorocarbon (CFC) treatment chemistry" and "sulfur-tolerant auto exhaust catalysts." The ozone depletion potential of CFCs has resulted in a great interest in the academic and industrial communities to find replacements for these chemicals. Hydrofluorocarbons (HFCs) are amongst the best "environmentally benign" candidates for CFC replacement. One selective pathway for the synthesis of HFCs is via the hydrodechlorination of CFCs. This route has the added benefit of destroying harmful CFC stockpiles and converting them into more useful chemicals. The work in Chapter 3 shows that parallel hydrogenation pathways starting from a common CF2 species can explain the formation of the products CH2F2 and CH4 for the hydrodechlorination of CF2Cl2 over Pd/AlF3. Transient kinetics experiments using C2H4 as a trapping agent for surface carbenes have provided evidence for the presence of CH2 species on the catalyst surface during this reaction. The absence of either coupling products or trapped products containing F suggests that the rate of hydrogenation of surface CF2 species is faster than that of surface CH2 species. Another important class of CFC reactions is oxide-catalyzed disproportionations to control the number and position of halogen atoms in the CFC/HFC molecule. Chapter 4 combines the use of reaction kinetics tools and spectroscopic characterization techniques to understand the adsorption and reaction of CF3CFCl 2 over gamma-Al2O3. The CF3CFCl 2 reaction over gamma-Al2O3 lead to a modification of the gamma-Al2O3 surface due to fluorination and the

  16. UFOMOD - atmospheric dispersion and deposition

    International Nuclear Information System (INIS)

    The report gives an introduction into the modelling of atmospheric dispersion and deposition which has been implemented in the new program system UFOMOD for assessing the consequences after nuclear accidents. According to the new structure of UFOMOD, different trajectory models with ranges of validity near to the site and at far distances are applied. Emphasis is laid on the description of the segmented plume model MUSEMET and its affilated submodels, being the removal of activity from the cloud by dry and wet deposition, and special effects like plume rise and the behaviour of plumes released into building wakes. In addition, the evaluation of γ-dose correction factors to take account of the finite extent of the radioactive plume in the near range (up to about 20 km) are described. Only brief introductions are given into the principles of the other models available: the puff model RIMPUFF, the long-range puff model MESOS, and the special straight-line Gaussian model ISOLA which are used if low-level long-duration releases are considered. To define starting times of weather sequences and the probabilities of occurrence of these sequences, it is convenient to perform stratified sampling. Therefore, the preprocessing program package METSAM has been developed to perform for generic ACAs a random sampling of weather sequences out off a population of classified weather conditions. The sampling procedure and a detailed input/output (I/O) description is presented and an additional appendix, respectively. A general overview on the I/O structure of MUSEMET as well as a brief user guide to run the KfK version of the MESOS code are also given in the appendix. (orig.)

  17. Update on calcium pyrophosphate deposition.

    Science.gov (United States)

    Abhishek, Abhishek; Doherty, Michael

    2016-01-01

    Calcium pyrophosphate crystal deposition (CPPD) associates with ageing, osteoarthritis (OA), uncommon metabolic diseases, mutations and polymorphisms in the ankylosis human gene (ANKH). CPPD is frequently polyarticular, occurs due to a generalised articular predisposition, and the association between CPPD and OA is joint specific, for example CPPD associates with knee OA, but not with hip OA. Other recently identified associations include knee malalignment (knee CC), low cortical BMD and soft-tissue calcification. CPPD is generally asymptomatic. A recent study reported that knees with OA plus CC at the index joint, or at distant joints (in absence of index joint CC), were more likely to have attrition. CPPD can cause acute CPP crystal arthritis, chronic CPP crystal inflammatory arthritis, and is frequently present in joints with OA. Joint aspiration remains the gold standard for diagnosing CPPD, although other promising techniques are emerging. Patients with polyarticular or young onset CPPD should be screened for underlying metabolic abnormalities, however, such testing can be unrewarding. The treatment of CPPD is symptomatic. Acute CPP crystal arthritis is treated with rest, local application of ice-packs, joint aspiration, colchicine and/or intra-articular corticosteroid injection (once infection is excluded). Colchicine, low-dose corticosteroids, hydroxychloroquine and radiosynovectomy are recommended for the treatment of chronic or recurrent acute CPP crystal arthritis. Recent RCTs did not confirm any benefit from methotrexate, and although there is increasing interest in the use of anti-IL1 agents for acute or chronic CPP crystal arthritis, their efficacy has not been formally examined. Unlike gout, currently there are no treatments to eliminate CPP crystal deposits. PMID:27586801

  18. Orientational anisotropy in simulated vapor-deposited molecular glasses

    International Nuclear Information System (INIS)

    Enhanced kinetic stability of vapor-deposited glasses has been established for a variety of glass organic formers. Several recent reports indicate that vapor-deposited glasses can be orientationally anisotropic. In this work, we present results of extensive molecular simulations that mimic a number of features of the experimental vapor deposition process. The simulations are performed on a generic coarse-grained model and an all-atom representation of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), a small organic molecule whose vapor-deposited glasses exhibit considerable orientational anisotropy. The coarse-grained model adopted here is found to reproduce several key aspects reported in experiments. In particular, the molecular orientation of vapor-deposited glasses is observed to depend on substrate temperature during deposition. For a fixed deposition rate, the molecular orientation in the glasses changes from isotropic, at the glass transition temperature, Tg, to slightly normal to the substrate at temperatures just below Tg. Well below Tg, molecular orientation becomes predominantly parallel to the substrate. The all-atom model is used to confirm some of the equilibrium structural features of TPD interfaces that arise above the glass transition temperature. We discuss a mechanism based on distinct orientations observed at equilibrium near the surface of the film, which get trapped within the film during the non-equilibrium process of vapor deposition

  19. Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation.

    Science.gov (United States)

    Jia, Teng; Zhao, Chongyang; He, Ruoyu; Chen, Hui; Wang, Congyang

    2016-04-18

    Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step.

  20. A deposit model for carbonatite and peralkaline intrusion-related rare earth element deposits: Chapter J in Mineral deposit models for resource assessment

    Science.gov (United States)

    Verplanck, Philip L.; Van Gosen, Bradley S.; Seal, Robert R., II; McCafferty, Anne E.

    2014-01-01

    Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. A wide variety of other commodities have been exploited from carbonatites and alkaline igneous rocks including niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other elements enriched in these deposits include manganese, strontium, tantalum, thorium, vanadium, and uranium. Carbonatite and peralkaline intrusion-related rare earth element deposits are presented together in this report because of the spatial, and potentially genetic, association between carbonatite and alkaline rocks. Although these rock types occur together at many locations, carbonatite and peralkaline intrusion-related rare earth element deposits are not generally found together.