Sample records for catalyzed reporter deposition

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

    DEFF Research Database (Denmark)

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

    In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition   Michael V.W. Kofoed, Peter Stief, Morten Poulsen, and Andreas Schramm Department of Biological Sciences, Microbiology, University of Aarhus, Denmark Denitrification, the sequential...... reduction of nitrate to dinitrogen gas, is essential for the removal of fixed nitrogen from natural and engineered ecosystems. However, community structure and activity dynamics of denitrifying bacteria in most systems are poorly understood, partially due to difficulties in identifying and quantifying...... (active) denitrifiers. The goal of this study was therefore to develop a protocol for the in situ detection of denitrifying bacterial cells by targeting the mRNA of denitrification genes, hereby linking denitrification activity directly to the single-cell level. Target genes were narG (encoding nitrate...

  2. 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)


    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.

  3. A novel Ag catalyzation process using swelling impregnation method for electroless Ni deposition on Kevlar® fiber (United States)

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


    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.

  4. Palladium deposits spontaneously grown on nickel foam for electro-catalyzing methanol oxidation: Effect of precursors (United States)

    Niu, Xiangheng; Zhao, Hongli; Lan, Minbo


    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.

  5. Boron deposition from fused salts. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Smith, M.L.


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

  6. The fabrication of vertically aligned and periodically distributed carbon nanotube bundles and periodically porous carbon nanotube films through a combination of laser interference ablation and metal-catalyzed chemical vapor deposition. (United States)

    Yuan, Dajun; Lin, Wei; Guo, Rui; Wong, C P; Das, Suman


    Scalable fabrication of carbon nanotube (CNT) bundles is essential to future advances in several applications. Here, we report on the development of a simple, two-step method for fabricating vertically aligned and periodically distributed CNT bundles and periodically porous CNT films at the sub-micron scale. The method involves laser interference ablation (LIA) of an iron film followed by CNT growth via iron-catalyzed chemical vapor deposition. CNT bundles with square widths ranging from 0.5 to 1.5 µm in width, and 50-200 µm in length, are grown atop the patterned catalyst over areas spanning 8 cm(2). The CNT bundles exhibit a high degree of control over square width, orientation, uniformity, and periodicity. This simple scalable method of producing well-placed and oriented CNT bundles demonstrates a high application potential for wafer-scale integration of CNT structures into various device applications, including IC interconnects, field emitters, sensors, batteries, and optoelectronics, etc.

  7. Mineral deposits in western Saudi Arabia; a preliminary report (United States)

    Roberts, Ralph Jackson; Greenwood, William R.; Worl, Ronald G.; Dodge, F.C.W.; Kiilsgaard, Thor H.


    Mineral deposits in Saudi Arabia include a variety of deposits which were formed in many geologic environments. These include magmatic and late magmatic deposits in igneous masses, contact metamorphic deposits along the margins of igneous bodies, and stratiform sulfide deposits and veins. Notable deposits of sedimentary origin include deposits of iron oxides and phosphate.

  8. Submesothelial deposition of carbon nanoparticles after toner exposition: Case report

    Directory of Open Access Journals (Sweden)

    Philippou Stathis


    Full Text Available Abstract Inhalation of carbon nanoparticles (CNP from toner dust has been shown to have impact on the respiratory health of persons exposed. Office printers are known emitters of CNP. We report about a female open office worker who developed weight loss and diarrhoea. Laparoscopy done for suspected endometriosis surprisingly revealed black spots within the peritoneum. Submesothelial aggregates of CNP with a diameter of 31-67 nm were found by scanning and transmission electron microscopy in these tissue specimens. Colon biopsies showed inflammatory bowel disease with typically signs of Crohn disease, but no dust deposits. Transport of CNP via lymphatic and blood vessels after inhalation in the lungs has to be assumed. In this case respiratory symptoms were not reported, therefore no lung function tests were done. We have shown that workers with toner dust exposure from laser printers can develop submesothelial deposition of CNP in the peritoneum. Impact of toner dust exposure on the respiratory health of office workers, as suspected in other studies, has to be evaluated further.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yu, C.P.


    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.

  10. 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.


    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.

  11. 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


    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Swift, D.L.


    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.

  13. Atmospheric deposition, operational report for air pollution 2003. NOVA 2003; Atmosfaerisk deposition, driftsrapport for Luftforurening i 2003 NOVA 2003

    Energy Technology Data Exchange (ETDEWEB)

    Ellermann, T.; Hertel, O.; Ambelas Skjoeth, C.; Kemp, K.; Monies, C.


    This report presents measurements and calculations from the atmospheric part of NOVA 2003 and covers results for 2003. It summarises the main results concerning concentrations and depositions of nitrogen, phosphorous and sulphur compounds related to eutrofication and acidification and selected heavy metals. Depositions of atmospheric compounds to Danish marine waters as well as land surface are presented. The measurements in the monitoring programme are supplemented with model calculations of concentrations and depositions of nitrogen and sulphur compounds to Danish land surfaces as well as marine waters, fjords and bays using the ACDEP model (Atmospheric Chemistry and Deposition). The model is a so-called trajectory model and simulates the physical and chemical processes in the atmosphere using meteorological and emission data input. (BA)

  14. 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)


    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.

  15. Particle deposition in granular media. Annual progress report

    Energy Technology Data Exchange (ETDEWEB)

    Tien, C.


    Studies performed under Contract DE-AC02-79-ER10386.A000 Particle Deposition in Granular Media during the period June 1, 1979 to date are described. These studies include the design and construction of apparatus for filtration experiments and a complete trajectory analysis for the calculation of the initial collection efficiency of granular media. The results of the trajectory analysis have been used to develop a generalized correlation of the collection efficiency.

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

    Directory of Open Access Journals (Sweden)

    Farzaneh Moatamed


    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.

  17. Acid deposition in the United Kingdom 1992-1994. Fourth report of the Review Group on Acid Rain

    Energy Technology Data Exchange (ETDEWEB)



    The fourth report in the series examines the nature and extent of acid deposition throughout the United Kingdom. Topics are covered under the following headings: emissions of air pollutants leading to acidification, atmospheric transport and chemical conversion of acidifying air pollutants; wet deposition; concentrations of gases and particles; dry deposition processes, spatial patterns and recent trends; cloud droplet interception; total deposition; modelling of acid deposition in the United Kingdom; changes in concentrations and deposition of acidifying pollutants over the United Kingdom; and conclusions and recommendations. While emissions of SO{sub 2} are falling, emissions of nitrogen oxides have remained fairly constant since 1970. 240 refs., 128 figs., 34 tabs., 5 apps.

  18. Si nanowires grown by Al-catalyzed plasma-enhanced chemical vapor deposition: synthesis conditions, electrical properties and application to lithium battery anodes (United States)

    Toan, Le Duc; Moyen, Eric; Zamfir, Mihai Robert; Joe, Jemee; Kim, Young Woo; Pribat, Didier


    Silicon nanowires have been synhesized using Al as a catalyst. Silane (SiH4) diluted in H2 carrier gas was employed as Si precursor in a plasma enhanced chemical vapor deposition system operated at various temperatures (450 °C and 550 °C). Those growth temperatures, which are lower than the eutectic temperature in the Al-Si system (577 °C) suggests a vapor-solid-solid growth mechanism. Four point resistance measurements and back-gated current-voltage measurements indicated that silicon nanowires were heavily doped (p type), with a doping concentration of a few 1019 cm-3. We have measured hole mobility values of ˜16 cm2 V-1 s-1 at 450 °C and ˜30 cm2 V-1 s-1 at 550 °C. Transmission electron microscope analyses showed that the silicon nanowires were highly twinned even when they grow epitaxially on (111) Si substrates. We have also evaluated the use of those highly doped Si nanowires for lithium-ion battery anodes. We have observed a good cycling behavior during the first 65 charge-discharge cycles, followed by a slow capacity decay. After 150 cycles at a charge-discharge rate of 0.1 C, the electrode capacity was still 1400 mAh g-1. The ageing mechanism seems to be related to the delamination of the SiNWs from the stainless steel substrate on which they were grown.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mays, David C. [University of Colorado Denver


    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

  20. 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.


    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.

  1. 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)


    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.

  2. Demonstration test and evaluation of Ultraviolet/Ultraviolet Catalyzed Peroxide Oxidation for Groundwater Remediation at Oak Ridge K-25 Site. Final report [March 16, 1993--March 16, 1994

    Energy Technology Data Exchange (ETDEWEB)


    We demonstrated, tested and evaluated a new ultraviolet (UV) lamp integrated with an existing commercial technology employing UV catalyzed peroxide oxidation to destroy organics in groundwater at an Oak Ridge K-25 site. The existing commercial technology is the perox-pure{trademark} process of Peroxidation Systems Incorporated (PSI) that employs standard UV lamp technology to catalyze H{sub 2}O{sub 2} into OH radicals, which attack many organic molecules. In comparison to classical technologies for remediation of groundwater contaminated with organics, the perox-pure{trademark} process not only is cost effective but also reduces contaminants to harmless by-products instead of transferring the contaminants from one medium to another. Although the perox-pure{trademark} process is cost effective against many organics, it is not effective for some organic contaminants of interest to DOE such as TCA, which has the highest concentration of the organics at the K-25 test site. Contaminants such as TCA are treated more readily by direct photolysis using short wavelength UV light. WJSA has been developing a unique UV lamp which is very efficient in the short UV wavelength region. Consequently, combining this UV lamp with the perox-pure{trademark} process results in a means for treating essentially all organic contaminants. In the program reported here, the new UV lamp lifetime was improved and the lamp integrated into a PSI demonstration trailer. Even though this UV lamp operated at less than optimum power and UV efficiency, the destruction rate for the highest concentration organic (TCA) was more than double that of the commercial unit. An optimized UV lamp may double again the destruction rate; i.e., a factor of four greater than the commercial system. The demonstration at K-25 included tests with (1) the commercial PSI system, (2) the new UV lamp-based system and (3) the commercial PSI and new UV lamp systems in series.

  3. 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.


    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.

  4. Light-chain deposition disease of the kidney: a case report. (United States)

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


    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.

  5. A short report of the investigations made on the facies of German coal deposits

    Energy Technology Data Exchange (ETDEWEB)

    Dehmer, Janet [An den Rothen 96, D-97080 Wurzburg (Germany)


    In 1996, Commission II of the ICCP set up a coal facies working group. The first step was to collate literature on coal facies analysis for different countries. This report provides an overview on the investigations made on the facies interpretations of German coal deposits over the last 50 years with an emphasis on Tertiary coals. It outlines the major deposits present in Germany and gives the main facies interpretations of coals of lignite and bituminous rank. Furthermore, it points out that there lies a certain ambiguity in the interpretation of specific maceral associations, which could confuse facies analyses without the support of interdisciplinary studies and thus suggests that the working group should address this point for future work.

  6. 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)



    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.

  7. Thresholds for protecting Pacific Northwest ecosystems from atmospheric deposition of nitrogen: state of knowledge report (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Palo, Daniel R.


    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.

  9. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  10. Muon Catalyzed Fusion (United States)

    Armour, Edward A.G.


    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.

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

    Energy Technology Data Exchange (ETDEWEB)



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

  12. 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.


    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.

  13. 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


    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 differentsizes labelled with neutron activatable rare earth tracers. Experiments indicate that the deposition...

  14. 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


    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)

  15. Ossifying tendinitis of the rotator cuff after arthroscopic excision of calcium deposits: report of two cases and literature review. (United States)

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


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

  16. Enantioselective, iridium-catalyzed monoallylation of ammonia. (United States)

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F


    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.

  17. 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.


    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.

  18. A short report of the investigations made on the facies of Austrian coal deposits

    Energy Technology Data Exchange (ETDEWEB)

    Sachsenhofer, Reinhard F. [Department of Geological Sciences, University of Leoben, A-8700 Leoben (Austria)


    Petrological studies on Austrian coal deposits started in the 1940s. During the last decade, multi-disciplinary investigations involving petrology, geochemistry, and palynology were performed to study the relationship between geodynamics, coal-forming environments, and coal properties.

  19. 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.


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Ting-Horng


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

  1. 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.


    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.


    Energy Technology Data Exchange (ETDEWEB)



    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.

  3. Acid deposition: decision framework. Volume 1. Description of conceptual framework and decision-tree models. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Balson, W.E.; Boyd, D.W.; North, D.W.


    Acid precipitation and dry deposition of acid materials have emerged as an important environmental issue affecting the electric utility industry. This report presents a framework for the analysis of decisions on acid deposition. The decision framework is intended as a means of summarizing scientific information and uncertainties on the relation between emissions from electric utilities and other sources, acid deposition, and impacts on ecological systems. The methodology for implementing the framework is that of decision analysis, which provides a quantitative means of analyzing decisions under uncertainty. The decisions of interest include reductions in sulfur oxide and other emissions thought to be precursors of acid deposition, mitigation of acid deposition impacts through means such as liming of waterways and soils, and choice of strategies for research. The report first gives an overview of the decision framework and explains the decision analysis methods with a simplified caricature example. The state of scientific information and the modeling assumptions for the framework are then discussed for the three main modules of the framework: emissions and control technologies; long-range transport and chemical conversion in the atmosphere; and ecological impacts. The report then presents two versions of a decision tree model that implements the decision framework. The basic decision tree addresses decisions on emissions control and mitigation in the immediate future and a decade hence, and it includes uncertainties in the long-range transport and ecological impacts. The research emphasis decision tree addresses the effect of research funding on obtaining new information as the basis for future decisions. Illustrative data and calculations using the decision tree models are presented.

  4. 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.


    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)

  5. Membranoproliferative glomerulonephritis with isolated C3 deposits: case report and literature review. (United States)

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


    Membranoproliferative glomerulonephritis with isolated C3 deposits (MPGNC3) is an uncommon condition characterized by overt glomerular C3 deposits in the absence of immunoglobulins and intramembranous dense deposits. Here the authors describe the clinical and morphological features of primary MPGNC3 in a 13-year-old boy and critically review the previously published cases. The patient presented with nephrotic syndrome and microscopic hematuria. Blood tests revealed very low circulating C3 levels. The renal biopsy exhibited subendothelial, subepithelial, and mesangial deposits, with C3 but not immunoglobulins seen on immunofluorescence. This case and the review of the literature indicate that the serum complement profile with decreased levels of C3 and normal levels of classical pathway components together with glomerular deposits containing exclusively complement C3 is highly suggestive of alternative pathway activation. The diagnosis of acquired and/or genetic complement abnormalities in some cases supports that complement dysregulation is implicated in the pathogenesis of MPGNC3. Such data show great promise to provide new therapy strategies based on modulation of the complement system activity.

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


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


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

  7. LDRD Project 52523 final report :Atomic layer deposition of highly conformal tribological coatings.

    Energy Technology Data Exchange (ETDEWEB)

    Jungk, John Michael (University of Minnesota); Dugger, Michael Thomas; George, Steve M. (University of Colorado); Prasad, Somuri V.; Grubbs, Robert K.; Moody, Neville Reid; Mayer, Thomas Michael; Scharf, Thomas W.; Goeke, Ronald S.; Gerberich, William W. (University of Minnesota)


    Friction and wear are major concerns in the performance and reliability of micromechanical (MEMS) devices. While a variety of lubricant and wear resistant coatings are known which we might consider for application to MEMS devices, the severe geometric constraints of many micromechanical systems (high aspect ratios, shadowed surfaces) make most deposition methods for friction and wear-resistance coatings impossible. In this program we have produced and evaluate highly conformal, tribological coatings, deposited by atomic layer deposition (ALD), for use on surface micromachined (SMM) and LIGA structures. ALD is a chemical vapor deposition process using sequential exposure of reagents and self-limiting surface chemistry, saturating at a maximum of one monolayer per exposure cycle. The self-limiting chemistry results in conformal coating of high aspect ratio structures, with monolayer precision. ALD of a wide variety of materials is possible, but there have been no studies of structural, mechanical, and tribological properties of these films. We have developed processes for depositing thin (<100 nm) conformal coatings of selected hard and lubricious films (Al2O3, ZnO, WS2, W, and W/Al{sub 2}O{sub 3} nanolaminates), and measured their chemical, physical, mechanical and tribological properties. A significant challenge in this program was to develop instrumentation and quantitative test procedures, which did not exist, for friction, wear, film/substrate adhesion, elastic properties, stress, etc., of extremely thin films and nanolaminates. New scanning probe and nanoindentation techniques have been employed along with detailed mechanics-based models to evaluate these properties at small loads characteristic of microsystem operation. We emphasize deposition processes and fundamental properties of ALD materials, however we have also evaluated applications and film performance for model SMM and LIGA devices.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  9. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.


    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

  10. 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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sinha, R.; Small, M.J.


    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.

  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)


    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. A general strategy for antibody library screening via conversion of transient target binding into permanent reporter deposition. (United States)

    Maaß, Alexander; Heiseler, Tim; Maaß, Franziska; Fritz, Janine; Hofmeyer, Thomas; Glotzbach, Bernhard; Becker, Stefan; Kolmar, Harald


    We report here a generally applicable method for the selective covalent attachment of a reporter molecule to a replicating entity that allows one to obtain specific binders from a single round of library screening. We show that selective biotinylation of phage particles displaying a binder to any given target can be achieved by application of a coupled enzyme reaction on the surface of the target-binding phage particles that includes a peroxidase, an oxidase and a catalase. Due to the covalent linkage of biotin together with the tight and stable interaction of biotin with streptavidin, very stringent wash conditions for removal of nonspecific binders can be applied. The method termed (3)CARD (triple catalytic reporter deposition) was successfully applied to single-round screening of a phage display library of camelid single-domain antibodies against three different target proteins.

  14. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik


    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......, the networks of environmental professionals that work in the environmental organisation, in consulting and regulatory enforcement, and dominating business cultures. These have previously been identified in the literature as individually significant in relation to the evolving environmental agendas....... They are here used to describe the context in which environmental management is implemented. Based on findings from contributions to a research program studying the implementation and impact of EMS in different settings, we highlight the diverse roles that these systems play in the Thai context. EMS may over...

  15. Defect states in plasma-deposited a-Si:H. Technical progress report, May-July 1979

    Energy Technology Data Exchange (ETDEWEB)

    Knights, J C


    Three preprints are presented. The first, entitled ''Glow Discharge Optical Spectroscopy Measurement of Dopant Concentrations in a-Si:H,'' reports significant differences between the ratio of boron to silicon of the films and that of their deposition plasmas. The second, entitled ''Growth Morphology and Defects in Plasma-Deposited a-Si:H Films,'' presents structural studies that show that a major class of defect is an anisotropic density fluctuation. Studies of the hydrogen environment suggest that an inhomogeneous hydrogen distribution is associated with these fluctuations. From considerations of the deposition chemistry and nucleation theory, a model is proposed to describe the film growth process and its relationship to defects. The third, entitled ''Luminescence and ESR Studies of Defects in Hydrogenated Amorphous Silicon,'' demonstrates that the two experiments involve identical recombination transitions, and identify two separate processes. One process involves defect states, and from the doping dependence of light induced ESR, it is deduced that the electronically active defects are dangling bonds with positive electronic correlation energy. (LEW)

  16. Renal Light Chain Deposition Associated with the Formation of Intracellular Crystalline Inclusion Bodies in Podocytes: A Rare Case Report. (United States)

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


    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.

  17. Case Report of a Fatal Antifreeze Ingestion with a Record High Level and Impressive Renal Crystal Deposition (United States)


    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

  18. Copper-Catalyzed Aerobic C–H Trifluoromethylation of Phenanthrolines (United States)

    Zhu, Cheng-Liang; Zhang, Yong-Qiang; Yuan, Yong-An


    Direct C–H trifluoromethylation of heterocycles is a valuable transformation. In particular, nonprecious metal-catalyzed C–H trifluoromethylation processes, which do not proceed through CF3 radical species, have been less developed. In this cluster report, a new copper-catalyzed aerobic C–H trifluoromethylation of phenanthrolines is described. This transformation affords trifluoromethylated phenanthrolines that have not been synthesized and preliminary mechanistic studies suggest that the CF3 group transfer may occur through cooperative activation. PMID:26855477

  19. Liquid-Phase Deposition of CIS Thin Layers: Final Report, February 2003--July 2005

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, F.; Pirouz, P.


    The goal of this project was to fabricate single-phase CIS (a-Cu-In-Se, stoichiometric composition: CuInSe2) thin films for photovoltaic applications from a liquid phase - a Cu-In-Se melt of appropriate composition. This approach of liquid-phase deposition (LPD) is based on the new phase diagram we have established for Cu-In-Se, the first complete equilibrium phase diagram of this system. The liquidus projection exhibits four composition fields in which the primary solid phase, i.e., the first solid material that forms on cooling down from an entirely liquid state, is a-CuInSe2. Remarkably, none of the four composition fields is anywhere near the stoichiometric composition (CuInSe2) of a-CuInSe2. The results demonstrate that the proposed technique is indeed capable of producing films with a particularly large grain size and a correspondingly low density of grain boundaries. To obtain films sufficiently thin for solar cell applications and with a sufficiently smooth surface, it is advantageous to employ a sliding boat mechanism. Future work on liquid-phase deposition of CIS should focus on the interaction between the melt and the substrate surface, the resulting CIS interfaces, the surface morphology of the LPD-grown films, and, of course, the electronic properties of the material.

  20. Final Report: Vapor Transport Deposition for Thin Film III-V Photovoltaics

    Energy Technology Data Exchange (ETDEWEB)

    Boettcher, Shannon [Univ. of Oregon, Eugene, OR (United States); Greenaway, Ann [Univ. of Oregon, Eugene, OR (United States); Boucher, Jason [Univ. of Oregon, Eugene, OR (United States); Aloni, Shaul [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)


    Silicon, the dominant photovoltaic (PV) technology, is reaching its fundamental performance limits as a single absorber/junction technology. Higher efficiency devices are needed to reduce cost further because the balance of systems account for about two-thirds of the overall cost of the solar electricity. III-V semiconductors such as GaAs are used to make the highest-efficiency photovoltaic devices, but the costs of manufacture are much too high for non-concentrated terrestrial applications. The cost of III-V’s is driven by two factors: (1) metal-organic chemical vapor deposition (MOCVD), the dominant growth technology, employs expensive, toxic and pyrophoric gas-phase precursors, and (2) the growth substrates conventionally required for high-performance devices are monocrystalline III-V wafers. The primary goal of this project was to show that close-spaced vapor transport (CSVT), using water vapor as a transport agent, is a scalable deposition technology for growing low-cost epitaxial III-V photovoltaic devices. The secondary goal was to integrate those devices on Si substrates for high-efficiency tandem applications using interface nanopatterning to address the lattice mismatch. In the first task, we developed a CSVT process that used only safe solid-source powder precursors to grow epitaxial GaAs with controlled n and p doping and mobilities/lifetimes similar to that obtainable via MOCVD. Using photoelectrochemical characterization, we showed that the best material had near unity internal quantum efficiency for carrier collection and minority carrier diffusions lengths in of ~ 8 μm, suitable for PV devices with >25% efficiency. In the second task we developed the first pn junction photovoltaics using CSVT and showed unpassivated structures with open circuit photovoltages > 915 mV and internal quantum efficiencies >0.9. We also characterized morphological and electrical defects and identified routes to reduce those defects. In task three we grew epitaxial

  1. External quality assurance project report for the National Atmospheric Deposition Program’s National Trends Network and Mercury Deposition Network, 2013–14 (United States)

    Wetherbee, Gregory A.; Martin, RoseAnn


    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.

  2. Palladium-Catalyzed Environmentally Benign Acylation. (United States)

    Suchand, Basuli; Satyanarayana, Gedu


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Knights, J C


    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.

  4. 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.


    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.

  5. Probabilistic accident consequence uncertainty analysis -- Uncertainty assessment for deposited material and external doses. Volume 1: Main report

    Energy Technology Data Exchange (ETDEWEB)

    Goossens, L.H.J.; Kraan, B.C.P.; Cooke, R.M. [Delft Univ. of Technology (Netherlands); Boardman, J. [AEA Technology (United Kingdom); Jones, J.A. [National Radiological Protection Board (United Kingdom); Harper, F.T.; Young, M.L. [Sandia National Labs., Albuquerque, NM (United States); Hora, S.C. [Univ. of Hawaii, Hilo, HI (United States)


    The development of two new probabilistic accident consequence codes, MACCS and COSYMA, was completed in 1990. These codes estimate the consequence from the accidental releases of radiological material from hypothesized accidents at nuclear installations. In 1991, the US Nuclear Regulatory Commission and the Commission of the European Communities began cosponsoring a joint uncertainty analysis of the two codes. The ultimate objective of this joint effort was to systematically develop credible and traceable uncertainty distributions for the respective code input variables. A formal expert judgment elicitation and evaluation process was identified as the best technology available for developing a library of uncertainty distributions for these consequence parameters. This report focuses on the results of the study to develop distribution for variables related to the MACCS and COSYMA deposited material and external dose models.

  6. 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.


    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.

  7. Polymer multilayer films obtained by electrochemically catalyzed click chemistry. (United States)

    Rydzek, Gaulthier; Thomann, Jean-Sébastien; Ben Ameur, Nejla; Jierry, Loïc; Mésini, Philippe; Ponche, Arnaud; Contal, Christophe; El Haitami, Alae E; Voegel, Jean-Claude; Senger, Bernard; Schaaf, Pierre; Frisch, Benoît; Boulmedais, Fouzia


    We report the covalent layer-by-layer construction of polyelectrolyte multilayer (PEM) films by using an efficient electrochemically triggered Sharpless click reaction. The click reaction is catalyzed by Cu(I) which is generated in situ from Cu(II) (originating from the dissolution of CuSO(4)) at the electrode constituting the substrate of the film. The film buildup can be controlled by the application of a mild potential inducing the reduction of Cu(II) to Cu(I) in the absence of any reducing agent or any ligand. The experiments were carried out in an electrochemical quartz crystal microbalance cell which allows both to apply a controlled potential on a gold electrode and to follow the mass deposited on the electrode through the quartz crystal microbalance. Poly(acrylic acid) (PAA) modified with either alkyne (PAA(Alk)) or azide (PAA(Az)) functions grafted onto the PAA backbone through ethylene glycol arms were used to build the PEM films. Construction takes place on gold electrodes whose potentials are more negative than a critical value, which lies between -70 and -150 mV vs Ag/AgCl (KCl sat.) reference electrode. The film thickness increment per bilayer appears independent of the applied voltage as long as it is more negative than the critical potential, but it depends upon Cu(II) and polyelectrolyte concentrations in solution and upon the reduction time of Cu(II) during each deposition step. An increase of any of these latter parameters leads to an increase of the mass deposited per layer. For given buildup conditions, the construction levels off after a given number of deposition steps which increases with the Cu(II) concentration and/or the Cu(II) reduction time. A model based on the diffusion of Cu(II) and Cu(I) ions through the film and the dynamics of the polyelectrolyte anchoring on the film, during the reduction period of Cu(II), is proposed to explain the major buildup features.

  8. Alternative pathway dysfunction in kidney disease: a case report and review of dense deposit disease and C3 glomerulopathy. (United States)

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


    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.

  9. A First Report of Endoscopic Ultrasound for the Diagnosis of Pancreatic Amyloid Deposition in Immunoglobulin Light Chain (AL Amyloidosis (Primary Amyloidosis

    Directory of Open Access Journals (Sweden)

    Somashekar G Krishna


    Full Text Available Context Pancreatic involvement in systemic light chain (AL-amyloidosis is exceedingly rare. Prior reports of endoscopicultrasound (EUS for the diagnosis of amyloidosis are also limited. Case report We report the first description of EUS-guided fine needle aspiration (FNA for the diagnosis of primary AL-amyloidosis involving the pancreas. Conclusion EUS-FNA can be effectively utilized for the characterization and cytologic diagnosis of pancreatic amyloidosis and potentially other accessible extraluminal amyloid deposits.

  10. Secondary economic impact of acid deposition control legislation in six coal producing states: Final report

    Energy Technology Data Exchange (ETDEWEB)

    Scott, M.J.; Guthrie, S.J.


    Among the difficult policy questions on the US environmental agenda is what to do about emissions to the earth's atmosphere of pollutants that may result in ''acid rain''. The Congress has considered several pieces of legislation spelling out potential approaches to the problem and setting goals for emission reduction, mostly emphasizing the control of oxides of sulfur and nitrogen. Significant policy concern is the dollar costs to the nation's economy of achieving the intended effects of the legislation and the potential impacts on economic activity---in particular, losses of both coal mining and secondary service sector employment in states and regions dependent on the mining of high sulfur coal. There are several direct economic effects of regulations such as the acid rain control legislation. One of the more obvious effects was the switching from high sulfur coal to low sulfur coal. This would result in increases in employment and coal business procurements in low sulfur coal mining regions, but also would result in lower employment and lower coal business procurements in high sulfur coal mining areas. The potential negative effects are the immediate policy concern and are the focus of this report. 15 refs., 1 fig., 17 tabs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dudney, N.J.


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

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

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


    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

  13. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether. (United States)

    Andrews, Ian P; Kwon, Ohyun


    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethyl ethynyl ether using 0.1% palladium(0) catalyst and 1.0 equiv of tributyltin hydride. The product obtained is a mixture of regioisomers that can be carried forward with exclusive reaction of the beta-isomer. This method is highly reproducible; relative to previously reported procedures, it is more economical and involves a more facile purification procedure.

  14. 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.


    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.

  15. 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


    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

  16. 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.


    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.

  17. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin


    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.

  18. Rh-Catalyzed arylation of fluorinated ketones with arylboronic acids. (United States)

    Dobson, Luca S; Pattison, Graham


    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.

  19. Iron-Catalyzed Synthesis of Sulfur-Containing Heterocycles. (United States)

    Bosset, Cyril; Lefebvre, Gauthier; Angibaud, Patrick; Stansfield, Ian; Meerpoel, Lieven; Berthelot, Didier; Guérinot, Amandine; Cossy, Janine


    An iron-catalyzed synthesis of sulfur- and sulfone-containing heterocycles is reported. The method is based on the cyclization of readily available substrates and proceeded with high efficiency and diastereoselectivity. A variety of sulfur-containing heterocycles bearing moieties suitable for subsequent functionalization are prepared. Illustrative examples of such postcyclization modifications are also presented.

  20. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG XiaoMing


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

  1. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing


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

  2. Dry-deposition measurements of sulfur dioxide to a spruce-fir forest in the Black Forest: a data report. Technical memo

    Energy Technology Data Exchange (ETDEWEB)

    McMillen, R.T.; Matt, D.R.; Hicks, B.B.; Womack, J.D.


    Measurements of dry deposition of SO/sub 2/ are reported for a forested site in the Black Forest of West Germany. The measurements were made using the eddy-correlation method about 10 meters above the top of a spruce forest that was already affected by Waldsterben. These measurements were conducted as one component of TULLA, a large sulfur mass-balance experiment. The dry-deposition measurements were successful during times when SO/sub 2/ concentrations were greater than 5 micro grams/cu m.

  3. 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.


    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.

  4. Gold-Catalyzed Synthesis of Heterocycles (United States)

    Arcadi, Antonio


    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

  5. 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.)


    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.

  6. Biginelli reaction catalyzed by copper nanoparticles.

    Directory of Open Access Journals (Sweden)

    Manika Dewan

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

  7. 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)


    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).

  8. ReBr(CO)5-Catalyzed Knoevenagel Condensation

    Institute of Scientific and Technical Information of China (English)

    ZUO Wei-xiong; HUA Rui-mao; SUN Hong-bin


    Knoevenagel condensations are especially important reactions for the synthesis of alkene compounds having electron-withdrawing groups such as COR,CN,COOR,NO2 etc. Recently,transition metal hydride ruthenium1, hydride and polyhydride rhenium2, and polyhydride iridium complexes have been found to be the efficient catalysts for Knoevenagle condensation. However the mentioned-above transition metal hydride complexes are not easily prepared. In addition, all of them are oxygen and H2O-sensitive, unstable compands. Therefor the catalytic reactions are required to be carried out under an inert atmosphere, and using the prepurified reagent.In the paper, We wish to report the development of Knoevenagel condensation catalyzed by ReBr(CO)5 under an air atmosphere in the absence of solvent.All the experiments were carried out under 1atm, without solvent.The resuIts of the representative Knoevenagel condensations are summarized in Table 1.The Knoevenagel reaction with diethyl malonate can be catalyzed by ReBr(CO)5, while the present Knoevenagel reactions catalyzed by transition metal have at least one cyano group in active methylene compouds.A propose mechanism for present catalytic coupling dehydration reactions is also illustrated in the paper.Briefly, this paper reports the ReBr(CO)5-catalyzed Knoevenagel reaction. The reaction is a new method for the Konevenagel condensation.

  9. Regioselective Palladium-Catalyzed Cross-Coupling Reactions of 2,4,7-Trichloroquinazoline. (United States)

    Wipf, Peter; George, Kara M


    The regioselective palladium-catalyzed cross-coupling reactions of 2,4,7-trichloroquinazoline with various aryl- and heteroarylboronic acids are reported. An efficient, sequential strategy was developed that provides access to novel, functionalized heterocycles.

  10. 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.


    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.

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

    Directory of Open Access Journals (Sweden)

    Federico Pasardi


    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.

  12. Focal fat deposition developed in the segment IV of the liver following gastrectomy mimicking a hepatic metastasis: Two case reports

    Energy Technology Data Exchange (ETDEWEB)

    Sohn, Beom Seok; Lim, Joon Seok; Kim, Myeong Jin; Kim, Ki Whang; Hyung, Woo Jin [Yonsei Univ. College of Medicine, Seoul (Korea, Republic of)


    We present two cases of focal fat deposition developed at the posterior area of the segment IV in the liver, following gastrectomy in patients with gastric cancer. There was no focal lesion in this area of the liver at preoperative computed tomography (CT) in both cases, and the aberrant right gastric vein (ARGV) was found on the retrospective review of this CT. After gastrectomy, a focal, low attenuating lesion was developed in this area on a follow up CT in both cases, which was confirmed as a focal fat deposition, by other imaging studies. In addition to its typical imaging findings, confirmation of the presence of the ARGV also supported this lesion to be a focal fat deposition. Furthermore, understanding of our cases may be of help to prevent us from unnecessary invasive procedures, such as liver biopsy.

  13. 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


    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)

  14. 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. (United States)

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


    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.

  15. Thermodynamics of Enzyme-Catalyzed Reactions Database (United States)

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

  16. Iridium-Catalyzed Allylic Substitution (United States)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.


    Institute of Scientific and Technical Information of China (English)


    <正>20070291 Gong Ping (Northern Fujian Geological Party, Shaozou 354000) Discussion on Geological Characteristics and Control Factors of the Shimen Au-polymetallic Deposit in Zhenghe County, Fujian Province (Geology of Fujian, ISSN1001-3970, CN38-1080/P, 25(1), 2006, p.18-24, 2 illus., 2 tables, 1 ref.) Key words: gold deposits, polymetallic deposits, Fujian Province

  18. 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


    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.

  19. Glycerol Dehydration to Acrolein Catalyzed by ZSM‐5 Zeolite in Supercritical Carbon Dioxide Medium (United States)

    Zou, Bin; Ren, Shoujie


    Abstract Supercritical carbon dioxide (SC‐CO2) has been used for the first time as a reaction medium for the dehydration of glycerol to acrolein catalyzed by a solid acid. Unprecedented catalyst stability over 528 hours of time‐on‐stream was achieved and the rate of coke deposition on the zeolite catalyst was the lowest among extensive previous studies, showing potential for industrial application. Coking pathways in SC‐CO2 were also elucidated for future development. The results have potential implications for other dehydration reactions catalyzed by solid acids. PMID:27796088

  20. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

    Nikishkin, Nicolai I.; Huskens, Jurriaan; Verboom, Willem


    Transition metal-catalyzed reactions are generally used for carbon–carbon bond formation on pyrazines and include, but are not limited to, classical palladium-catalyzed reactions like Sonogashira, Heck, Suzuki, and Stille reactions. Also a few examples of carbon–heteroatom bond formation in pyrazine

  1. Assessment Of Surface-Catalyzed Reaction Products From High Temperature Materials In Plasmas (United States)

    Allen, Luke Daniel

    Current simulations of atmospheric entry into both Mars and Earth atmospheres for the design of thermal protections systems (TPS) typically invoke conservative assumptions regarding surface-catalyzed recombination and the amount of energy deposited on the surface. The need to invoke such assumptions derives in part from lack of adequate experimental data on gas-surface interactions at trajectory relevant conditions. Addressing this issue, the University of Vermont's Plasma Test and Diagnostics Laboratory has done extensive work to measure atomic specie consumption by measuring the concentration gradient over various material surfaces. This thesis extends this work by attempting to directly diagnose molecular species production in air plasmas. A series of spectral models for the A-X and B-X systems of nitric oxide (NO), and the B-X system of boron monoxide (BO) have been developed. These models aim to predict line positions and strengths for the respective molecules in a way that is best suited for the diagnostic needs of the UVM facility. From the NO models, laser induced fluorescence strategies have been adapted with the intent of characterizing the relative quantity and thermodynamic state of NO produced bysurface-catalyzed recombination, while the BO model adds a diagnostic tool for the testing of diboride-based TPS materials. Boundary layer surveys of atomic nitrogen and NO have been carried out over water-cooled copper and nickel surfaces in air/argon plasmas. Translation temperatures and relative number densities throughout the boundary layer are reported. Additional tests were also conducted over a water-cooled copper surface to detect evidence of highly non-equilibrium effects in the form of excess population in elevated vibrational levels of the A-X system of NO. The tests showed that near the sample surface there is a much greater population in the upsilon'' = 1ground state than is predicted by a Boltzmann distribution.

  2. Use of a palladium(II)-catalyzed oxidative kinetic resolution in synthetic efforts toward bielschowskysin. (United States)

    Meyer, Michael E; Phillips, John H; Ferreira, Eric M; Stoltz, Brian M


    Progress toward the cyclobutane core of bielshowskysin is reported. The core was thought to arise from a cyclopropane intermediate via a furan-mediated cyclopropane fragmentation, followed by a 1,4-Michael addition. The synthesis of the cyclopropane intermediate utilizes a Suzuki coupling reaction, an esterification with 2-diazoacetoacetic acid, and a copper catalyzed cyclopropanation. An alcohol intermediate within the synthetic route was obtained in high enantiopurity via a highly selective palladium(II)-catalyzed oxidative kinetic resolution (OKR).

  3. Cyclization strategies to polyenes using Pd(II)-catalyzed couplings of pinacol vinylboronates. (United States)

    Iafe, Robert G; Chan, Daniel G; Kuo, Jonathan L; Boon, Byron A; Faizi, Darius J; Saga, Tomomi; Turner, Jonathan W; Merlic, Craig A


    As a complement to Pd(0)-catalyzed cyclizations, seven Pd(II)-catalyzed cyclization strategies are reported. α,ω-Diynes are selectively hydroborated to bis(boronate esters), which cyclize under Pd(II)-catalysis producing a diverse array of small, medium, and macrocyclic polyenes with controlled E,E, Z,Z, or E,Z stereochemistry. Various functional groups are tolerated including aryl bromides, and applications are illustrated.

  4. Horseradish Peroxidase-Mediated, Iodide-Catalyzed Cascade Reaction for Plasmonic Immunoassays. (United States)

    Xianyu, Yunlei; Chen, Yiping; Jiang, Xingyu


    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.

  5. 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.


    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.

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

    CERN Document Server

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


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

  7. 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.


    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.

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

    Directory of Open Access Journals (Sweden)

    Wojciech I. Dzik


    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.

  9. Maternal Floor Infarction/Massive Perivillous Fibrin Deposition Associated with Hypercoiling of a Single-Artery Umbilical Cord: A Case Report. (United States)

    Taweevisit, Mana; Thorner, Paul Scott


    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.

  10. Nucleation and initial radius of self-catalyzed III-V nanowires (United States)

    Dubrovskii, V. G.; Borie, S.; Dagnet, T.; Reynes, L.; André, Y.; Gil, E.


    We treat theoretically the initial nucleation step of self-catalyzed III-V nanowires under simultaneously deposited group III and V vapor fluxes and with surface diffusion of a group III element. Our model is capable of describing the droplet size at which the very first nanowire monolayer nucleates depending on the element fluxes and surface temperature. This size determines the initial nanowire radius in growth techniques without pre-deposition of gallium. We show that useful self-catalyzed III-V nanowires can form only under the appropriately balanced V/III flux ratios and temperatures. Such balance is required to obtain nucleation from reasonably sized droplets that are neither too small under excessive arsenic flux nor too large in the arsenic-poor conditions.

  11. Advances in lipase-catalyzed esterification reactions. (United States)

    Stergiou, Panagiota-Yiolanda; Foukis, Athanasios; Filippou, Michalis; Koukouritaki, Maria; Parapouli, Maria; Theodorou, Leonidas G; Hatziloukas, Efstathios; Afendra, Amalia; Pandey, Ashok; Papamichael, Emmanuel M


    Lipase-catalyzed esterification reactions are among the most significant chemical and biochemical processes of industrial relevance. Lipases catalyze hydrolysis as well as esterification reactions. Enzyme-catalyzed esterification has acquired increasing attention in many applications, due to the significance of the derived products. More specifically, the lipase-catalyzed esterification reactions attracted research interest during the past decade, due to an increased use of organic esters in biotechnology and the chemical industry. Lipases, as hydrolyzing agents are active in environments, which contain a minimum of two distinct phases, where all reactants are partitioned between these phases, although their distribution is not fixed and changes as the reaction proceeds. The kinetics of the lipase-catalyzed reactions is governed by a number of factors. This article presents a thorough and descriptive evaluation of the applied trends and perspectives concerning the enzymatic esterification, mainly for biofuel production; an emphasis is given on essential factors, which affect the lipase-catalyzed esterification reaction. Moreover, the art of using bacterial and/or fungal strains for whole cell biocatalysis purposes, as well as carrying out catalysis by various forms of purified lipases from bacterial and fungal sources is also reviewed.


    Institute of Scientific and Technical Information of China (English)


    <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

  13. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes. (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


    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.

  14. 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


    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.


    Institute of Scientific and Technical Information of China (English)


    <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,


    Institute of Scientific and Technical Information of China (English)


    <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

  17. Fluorescence in situ hybridization and sequential catalysed reporter deposition (2C-FISH for the flow cytometric sorting of freshwater ultramicrobacteria

    Directory of Open Access Journals (Sweden)

    Stefan M Neuenschwander


    Full Text Available Flow cytometric sorting is a powerful tool to physically separate cells within mixed microbial communities. If combined with phylogenetic staining (fluorescence in situ hybridization, FISH it allows to specifically sort defined genotypic microbial populations from complex natural samples. However, the targeted enrichment of freshwater ultramicrobacteria, such as members of the LD12 clade of Alphaproteobacteria (SAR11-IIIb, is still challenging. Current FISH protocols, even in combination with signal amplification by catalysed reporter deposition (CARD, are not sufficiently sensitive for the distinction of these bacteria from background noise by flow cytometry, presumably due to their low ribosome content and small cell sizes. We, therefore, modified a CARD based flow sorting protocol with the aim of increasing its sensitivity to a level sufficient for ultramicrobacteria. This was achieved by a second signal amplification step mediated by horseradish peroxidase labelled antibodies targeted to the fluorophores that were previously deposited by CARD-FISH staining. The protocol was tested on samples from an oligo-mesotrophic lake. Ultramicrobacteria affiliated with LD12 Alphaproteobacteria could be successfully sorted to high purity by flow cytometry. The ratios of median fluorescence signal to background ranged around 20, and hybridization rates determined by flow cytometry were comparable to those obtained by fluorescence microscopy. Potential downstream applications of our modified cell staining approach range from the analysis of microdiversity within 16S rRNA-defined populations to that of functional properties, such as the taxon-specific incorporation rates of organic substrates.

  18. Heteroaromatic sulfonates and phosphates as electrophiles in iron-catalyzed cross-couplings. (United States)

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


    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.


    Institute of Scientific and Technical Information of China (English)


    <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.


    Institute of Scientific and Technical Information of China (English)


    <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

  1. Urea- and Thiourea-Catalyzed Aminolysis of Carbonates. (United States)

    Blain, Marine; Yau, Honman; Jean-Gérard, Ludivine; Auvergne, Rémi; Benazet, Dominique; Schreiner, Peter R; Caillol, Sylvain; Andrioletti, Bruno


    The aminolysis of (poly)carbonates by (poly)amines provides access to non-isocyanate polyurethanes (NIPUs) that are toxic-reagent-free analogues of polyurethanes (PUs). Owing to their low reactivity, the ring opening of cyclic carbonates requires the use of a catalyst. Herein, we report that the more available and cheaper ureas could advantageously be used for catalyzing the formation of NIPUs at the expense of the thiourea analogues. In addition, we demonstrate a medium-range pKa of the (thio)urea and an unqeual substitution pattern is critical for controlling the efficiency of the carbonate opening.


    Institute of Scientific and Technical Information of China (English)


    <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

  3. 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)


    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.).

  4. Attractor Explosions and Catalyzed Vacuum Decay

    Energy Technology Data Exchange (ETDEWEB)

    Green, Daniel; Silverstein, Eva; Starr, David


    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.


    Institute of Scientific and Technical Information of China (English)


    <正>20090243 Chen Zhibin (Hebei Institute of Geological Survey, Shijiazhuang 050081, China) Ore-Controlling Factors of the Beichagoumen Ag-Polymetallic Deposits in Northern Hebei Province (Geological Survey and Research, ISSN1672-4135, CN12-1353/P, 31(1), 2008, p.1-5, 3 illus., 10 refs.)


    Institute of Scientific and Technical Information of China (English)


    <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,


    Institute of Scientific and Technical Information of China (English)


    <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


    Institute of Scientific and Technical Information of China (English)


    <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),

  9. Potash—A vital agricultural nutrient sourced from geologic deposits (United States)

    Yager, Douglas B.


    This report summarizes the primary sources of potash in the United States. Potash is an essential nutrient that, along with phosphorus and nitrogen, is used as fertilizer for growing crops. Plants require sufficient potash to activate enzymes, which in turn catalyze chemical reactions important for water uptake and photosynthesis. When potassium is available in quantities necessary for healthy plant growth, disease resistance and physical quality are improved and crop yield and shelf life are increased. Potash is a water-soluble compound of potassium formed by geologic and hydrologic processes. The principal potash sources discussed are the large, stratiform deposits that formed during retreat and evaporation of intracontinental seas. The Paradox, Delaware, Holbrook, Michigan, and Williston sedimentary basins in the United States are examples where extensive potash beds were deposited. Ancient marine-type potash deposits that are close to the surface can be mined using conventional underground mining methods. In situ solution mining can be used where beds are too deep, making underground mining cost-prohibitive, or where underground mines are converted to in situ solution mines. Quaternary brine is another source of potash that is recovered by solar evaporation in manmade ponds. Groundwater from Pleistocene Lake Bonneville (Wendover, Utah) and the present-day Great Salt Lake in Utah are sources of potashbearing brine. Brine from these sources pumped to solar ponds is evaporated and potash concentrated for harvesting, processing, and refinement. Although there is sufficient potash to meet near-term demand, the large marine-type deposits are either geographically restricted to a few areas or are too deep to easily mine. Other regions lack sources of potash brine from groundwater or surface water. Thus, some areas of the world rely heavily on potash imports. Political, economic, and global population pressures may limit the ability of some countries from securing

  10. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun


    © 2016. Various Au-Pd/SiO2 catalysts with a fixed Au loading but different Au:Pd molar ratios were prepared via deposition-precipitation method followed by H2 reduction. The structures were characterized and the catalytic activities in CO oxidation were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface of Au-Pd alloy particles with large Au:Pd molar ratios while contiguous Pd atoms dominate the surface of Au-Pd alloy particles with small Au:Pd molar ratios. Few synergetic effect of Au-Pd alloy occurs on catalyzing CO oxidation under employed reaction conditions. Alloying Au with Pd reduces the intrinsic activity in catalyzing CO oxidation, and contiguous Pd atoms on the Au-Pd alloy particles are capable of catalyzing CO oxidation while isolated Pd atoms are not. These results advance the fundamental understandings of Au-Pd alloy surfaces in catalyzing CO oxidation.

  11. First Palladium-Catalyzed Addition of Organoboronic Acids to Allenes: A Magic Regioselectivity Switch by Using a Base or an Acid

    Institute of Scientific and Technical Information of China (English)

    MA Sheng-Ming; JIAO Ning


    @@ Organoboronic acids enjoy high prestige in the metal-catalyzed C-C bond formations. The most notable progress is the rhodium- and nickel-catalyzed conjugate addition with unsaturated carbon-carbon bond, aldehydes, N-sulfonyl imines reported by Miyaura, Hayashi and Shirakawa.[1

  12. Palladium-catalyzed picolinamide-directed iodination of remote ortho-C−H bonds of arenes: Synthesis of tetrahydroquinolines (United States)

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


    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

  13. Palladium catalyzed hydrogenation of bio-oils and organic compounds (United States)

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


    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.

  14. Zeolite 5A Catalyzed Etherification of Diphenylmethanol (United States)

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


    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…

  15. Catalyzing curriculum evolution in graduate science education. (United States)

    Gutlerner, Johanna L; Van Vactor, David


    Strategies in life science graduate education must evolve in order to train a modern workforce capable of integrative solutions to challenging problems. Our institution has catalyzed such evolution through building a postdoctoral Curriculum Fellows Program that provides a collaborative and scholarly education laboratory for innovation in graduate training.

  16. Mechanochemical ruthenium-catalyzed olefin metathesis. (United States)

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


    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.

  17. Pinacol Coupling Reactions Catalyzed by Active Zinc

    Institute of Scientific and Technical Information of China (English)

    Hui ZHAO; Wei DENG; Qing Xiang GUO


    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.

  18. Rhodium-catalyzed restructuring of carbon frameworks. (United States)

    Murakami, Masahiro


    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.

  19. Lysophosphatidylcholine synthesis by lipase-catalyzed ethanolysis. (United States)

    Yang, Guolong; Yang, Ruoxi; Hu, Jingbo


    Lysophosphatidylcholine (LPC) is amphiphilic substance, and possesses excellent physiological functions. In this study, LPC was prepared through ethanolysis of phosphatidylcholine (PC) in n-hexane or solvent free media catalyzed by Novozym 435 (from Candida antarctica), Lipozyme TLIM (from Thermomcyces lanuginosus) and Lipozyme RMIM (from Rhizomucor miehei). The results showed that three immobilized lipases from Candida Antarctica, Thermomcyces lanuginosus and Rhizomucor miehei could catalyze ethanolysis of PC efficiently. In n-hexane, the LPC conversions of ethanolysis of PC catalyzed by Novozyme 435, Lipozyme TLIM and Lipozyme RMIM could reach to 98.5 ± 1.6%, 94.6 ± 1.4% and 93.7 ± 1.8%, respectively. In solvent free media, the highest LPC conversions of ethanolysis of PC catalyzed by Novozyme 435, Lipozyme TL IM and Lipozyme RM IM were 97.7 ± 1.7%, 93.5 ± 1.2% and 93.8 ± 1.9%, respectively. The catalytic efficiencies of the three lipases were in the order of Novozyme 435 > Lipozyme TLIM > Lipozyme RMIM. Furthermore, their catalytic efficiencies in n-hexane were better than those in solvent free media.

  20. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.


    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.

  1. Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes%Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes

    Institute of Scientific and Technical Information of China (English)

    徐涛; 邱水发; 刘国生


    A novel palladium-catalyzed intramolecular oxidative aminofluorination of styrenes has been developed by using NFSI as fluorinating reagent. This reaction represented an efficient method for the synthesis of 2-aryl-3-fluoropyrrolidine derivatives.

  2. 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


    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.

  3. Rh(III)-Catalyzed meta-C-H Olefination Directed by a Nitrile Template. (United States)

    Xu, Hua-Jin; Lu, Yi; Farmer, Marcus E; Wang, Huai-Wei; Zhao, Dan; Kang, Yan-Shang; Sun, Wei-Yin; Yu, Jin-Quan


    A range of Rh(III)-catalyzed ortho-C-H functionalizations have been developed; however, extension of this reactivity to remote C-H functionalizations through large-ring rhodacyclic intermediates has yet to be demonstrated. Herein we report the first example of the use of a U-shaped nitrile template to direct Rh(III)-catalyzed remote meta-C-H activation via a postulated 12-membered macrocyclic intermediate. Because the ligands used for Rh(III) catalysts are significantly different from those of Pd(II) catalysts, this offers new opportunities for future development of ligand-promoted meta-C-H activation reactions.

  4. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis. (United States)

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


    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.

  5. ORGANIC CHEMISTRY. Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes. (United States)

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


    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.

  6. Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles. (United States)

    Kljajic, Marko; Puschnig, Johannes G; Weber, Hansjörg; Breinbauer, Rolf


    An additive-free Pd-catalyzed α-allylation of different imino-group-ontaining heterocycles is reported. The activation of α-CH pronucleophiles (pKa (DMSO) > 25) occurs without the addition of strong bases or Lewis acids using only the Pd/Xantphos catalyst system. The reaction scope has been studied for various 5- and 6-membered nitrogen-containing heterocycles (yields up to 96%). Mechanistic investigations suggest an initial allylation of the imine-N followed by a Pd-catalyzed formal aza-Claisen rearrangement.

  7. 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


    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.

  8. Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes. (United States)

    Zhang, Zhen-Qi; Zhang, Ben; Lu, Xi; Liu, Jing-Hui; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao


    A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.


    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...

  10. 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.


    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

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

    KAUST Repository

    Morandi, Bill


    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.

  12. Direct synthesis of diaryl sulfides by copper-catalyzed coupling of aryl halides with aminothiourea

    Institute of Scientific and Technical Information of China (English)

    Xiang Mei Wu; Wei Ya Hu


    An efficient and simple protocol of copper-catalyzed C-S bond formation between aryl halides and inexpensive and commercially available aminothiourea is reported.A variety of symmetrical diaryl sulfides can be synthesized in good to excellent yields up to 94% with the advantage of avoiding foul-smelling thiols.

  13. Mukaiyama Aldol Reaction of 1, 2-Bis(trimethylsiloxy) Cyclobutene Catalyzed by Magnesium(II) Iodide

    Institute of Scientific and Technical Information of China (English)


    Efficient Mukaiyama-type aldol reaction of 1, 2-bis(trimethylsiloxy)cyclobutene with aromatic aldehydes catalyzed by MgI2 is reported. The resulting succinoylation product of aldehyde was converted into the synthetic useful γ-lactone and butenolide derivatives.

  14. Palladium-catalyzed regioselective decarboxylative alkylation of arenes and heteroarenes with aliphatic carboxylic acids. (United States)

    Premi, Chanchal; Dixit, Ankit; Jain, Nidhi


    An unprecedented Pd(OAc)2-catalyzed decarboxylative alkylation of unactivated arenes, with aliphatic carboxylic acids as inexpensive alkyl sources, is reported. The alkylation, controlled by the directing group, is regioselective, shows high functional group tolerance, and provides mild access to alkylated indolines, 2-phenylpyridines, and azobenzenes under solvent-free conditions in moderate to high yields.

  15. Palladium-catalyzed cross-coupling reactions of allylic halides and acetates with indium organometallics. (United States)

    Rodríguez, David; Pérez Sestelo, José; Sarandeses, Luis A


    The palladium(0)-catalyzed cross-coupling reaction of allylic halides and acetates with indium organometallics is reported. In this synthetic transformation, triorganoindium compounds and tetraorganoindates (aryl, alkenyl, and methyl) react with cinnamyl and geranyl halides and acetates to afford the S(N)2 product regioselectively and in good yield. The reaction proceeds with net inversion of the stereochemical configuration.

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

    DEFF Research Database (Denmark)

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


    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...

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

    NARCIS (Netherlands)

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


    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

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

    Directory of Open Access Journals (Sweden)

    Bo Leng


    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.

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

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


    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

  20. Sn-free Ni-catalyzed reductive coupling of glycosyl bromides with activated alkenes. (United States)

    Gong, Hegui; Andrews, R Stephen; Zuccarello, Joseph L; Lee, Stephen J; Gagné, Michel R


    A mild, stereoselective method for the Ni-catalyzed synthesis of alpha-C-alkylglycosides is reported. This approach entails the reductive coupling of glycosyl bromides with activated alkenes at room temperature, with low alkene loading as an important feature. Diastereoselective coupling with 2-substituted acrylate derivatives was made possible through the use of 2,4-dimethyl-3-pentanol as a proton source.

  1. Microwave-Assisted Olefination Reaction of Alkylzinc with Aromatic Aldehyde Catalyzed by Nickel Complex

    Institute of Scientific and Technical Information of China (English)

    MEN Xiu-Qin; WANG Jin-Xian; SHI Xiao-Ning; WANG Ke-Hu


    @@ Carbon-carbon double bond-forming reactions have always been great importance in organic synthesis. Manymethods have been described for C =C bond formation. We[1] have reported the new method of C =C bond formation of nickel catalyzed organozinc with aromatic aldehydes in the presence of Me3SiC1.

  2. Copper-catalyzed oxidative alkynylation of diaryl imines with terminal alkynes: a facile synthesis of ynimines. (United States)

    Laouiti, Anouar; Rammah, Mohamed M; Rammah, Mohamed B; Marrot, Jérome; Couty, François; Evano, Gwilherm


    An efficient copper-mediated method for the oxidative alkynylation of diaryl imines with terminal alkynes is reported. This reaction provides the first catalytic and general synthesis of ynimines and allows for an easy preparation of these useful building blocks. An improved copper-catalyzed oxidative dimerization of imines to azines and the synthesis of dienes and azadienes from ynimines are also described.

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

    Directory of Open Access Journals (Sweden)

    Kayla M. Fisher


    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.

  4. 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:, E-mail: [Illuminex Corp., Lancaster, PA 17601 (United States)


    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.

  5. CF₃I synthesis catalyzed by activated carbon: a density functional theory study. (United States)

    Hu, Yingjie; Wu, Taiping; Liu, Weizhou; Zhang, Liyang; Pan, Renming


    A revised reaction mechanism of CF3I synthesis catalyzed by activated carbon is investigated with quantum chemistry methods using density functional theory (DFT). The adsorption configurations of possible intermediates are carefully examined. The reaction pathway and related transition states are also analyzed. According to our calculations, first, the dehydrofluorination of CHF3 is catalyzed by -COOH groups, which possesses the highest barrier and is accordingly identified as the rate-determining step. Second, the difluorocarbene disproportionation over graphite (001) surface proceeds instead of dimerization. The next reaction steps involving the association of fluoromethine and trifluoromethyl, the fluorine abstractions between intermediates and the iodine abstractions by the desorbed CF3 and CF2CF3 from molecular iodine are also feasible over graphite (001) surfaces. It is also found that the coke deposition in experiments is due to the fluorine abstraction from fluoromethine. This revised mechanism is in agreement with available experimental data and our theoretical computations.


    Institute of Scientific and Technical Information of China (English)


    <正>20110165 Chen Jiawei(The 3rd Geological Team,Henan Bureau of Geology and Mineral Resources,Xinyang 464000,China)Ore Control Conditions and Genetic Model for the Bodaoling Ag-Au Deposit in Guangshan,Henan Province(Acta Geologica Sichuan,ISSN1006-0995,CN51-1273/P,30(1),2010,p.28-30,5 illus.,1 ref.,with English abstract)Key words:gold ores,Henan Province20110166 Chen Mingquan(Geological Team 306,Yunnan Bureau of Nonferrous Geology,Kunming 650216,Ch


    Institute of Scientific and Technical Information of China (English)


    <正>20122389 Cai Lianyou ( No.332 Geological Team,Bureau of Geology and Mineral Resources Exploration of Anhui Province,Huangshan 245000,China );Weng Wangfei Geologic Characteristic and Ore-Control Factors of the Nanshan W-Mo Polymetallic Ore Deposit in South Anhui Province ( Geological Survey and Research,ISSN1672-4135,CN12-1353 / P,34 ( 4 ), 2011,p.290-298,3 illus.,1table,14refs. ) Key words:tungsten ores,molybdenum ores,ore guide of prospecting,Anhui Province

  8. 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)


    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)

  9. Solution-solid-solid mechanism: superionic conductors catalyze nanowire growth. (United States)

    Wang, Junli; Chen, Kangmin; Gong, Ming; Xu, Bin; Yang, Qing


    The catalytic mechanism offers an efficient tool to produce crystalline semiconductor nanowires, in which the choice, state, and structure of catalysts are active research issues of much interest. Here we report a novel solution-solid-solid (SSS) mechanism for nanowire growth catalyzed by solid-phase superionic conductor nanocrystals in low-temperature solution. The preparation of Ag2Se-catalyzed ZnSe nanowires at 100-210 °C is exampled to elucidate the SSS model, which can be extendable to grow other II-VI semiconductor (e.g., CdSe, ZnS, and CdS) nanowires by the catalysis of nanoscale superionic-phase silver or copper(I) chalcogenides (Ag2Se, Ag2S, and Cu2S). The exceptional catalytic ability of these superionic conductors originates from their structure characteristics, known for high-density vacancies and fast mobility of silver or copper(I) cations in the rigid sublattice of Se(2-) or S(2-) ions. Insights into the SSS mechanism are provided based on the formation of solid solution and the solid-state ion diffusion/transport at solid-solid interface between catalyst and nanowire.

  10. Arc-related porphyry molybdenum deposit model: Chapter D in Mineral deposit models for resource assessment (United States)

    Taylor, Ryan D.; Hammarstrom, Jane M.; Piatak, Nadine M.; Seal, Robert R., II


    This report provides a descriptive model for arc-related porphyry molybdenum deposits. Presented within are geological, geochemical, and mineralogical characteristics that differentiate this deposit type from porphyry copper and alkali-feldspar rhyolite-granite porphyry molybdenum deposits. The U.S. Geological Survey's effort to update existing mineral deposit models spurred this research, which is intended to supplement previously published models for this deposit type that help guide mineral-resource and mineral-environmental assessments.

  11. 预积炭对FER分子筛催化正丁烯骨架异构反应性能的影响%Effect of carbon pre-deposition on FER zeolite catalyzed reaction of n-butenes skeletal isomerization

    Institute of Scientific and Technical Information of China (English)

    范丹丹; 周峰; 于绍先; 马会霞; 乔凯


    A series of FER zeolites with different amount of pre-deposited carbon were prepared by pretreatment at high temperature using mixture of 1-butene and N2. The effect of pre-coking on the catalytic performances of FER zeolite in the skeletal isomerization ofn-butenes into isobutene were studied. TG-DTA results indicated that there were two kinds of carbon deposits,i.e. CarbonLT (mass loss at low temperature) and CarbonHT (mass loss at high temperature). The amount of CarbonLT increased linearly with the extension of pre-coking time,while the amount of CarbonHTremained constant after being treated for one hour. The amount of CarbonLT had closely related to the initial isobutene selectivity and the CarbonLT might deposit on the active sites where propylene and ethylene were produced.%采用1-丁烯和N2混合气对FER分子筛进行高温预积炭处理,得到一系列具有不同预积炭量的FER分子筛。对预积炭的FER分子筛进行表征,研究预积炭行为对其催化正丁烯骨架异构制异丁烯反应性能的影响。热重表征结果表明,预沉积在FER分子筛上的积炭有两种,即CarbonLT(低温失重峰)和CarbonHT(高温失重峰)。CarbonLT含量随预积炭处理时间增加而呈线性增加的趋势,而CarbonHT含量在预积炭处理1h后就基本保持不变。CarbonLT 量与初始异丁烯选择性具有较好的相关性,CarbonLT 可能沉积在诱发生成丙烯和乙烯的副反应活性中心上。


    Institute of Scientific and Technical Information of China (English)


    <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. Electron-microscopical Studies on the Sclerosed Dentin Second Report : Comparative observations on the intertubular deposits in the coronal dentin, dental calculus and salivary stone


    赤羽, 章司; 枝, 重夫; 川上, 敏行; 中村, 千仁; 河住, 信


    For the purpose of serchirg the origin of the intratubular deposits in the coronal sclerosed dentin, the deposits were compared with dental calculus and salivary stone by a scanning electron microscope and electron probe microanalysers with energy and wavelength dispersive x-ray spectroscopies including the contour map method. Results were as follows: 1. The layer of minute crystals covered on the attrition surface contained the elements of Na, Mg, Al, P, S, Cl, Ca, Mn, Fe, Zn, Br. 2. The rho...

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


    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.

  15. Organic Synthesis in Ionic Liquids: Condensation of 3-Methyl-1-phenyl-5-pyrazolone with Carbonyl Compounds Catalyzed by Ethylenediammonium Diacetate(EDDA)

    Institute of Scientific and Technical Information of China (English)


    An efficient and environmental benign method is reported for the condensation of 3-methyl-1-phenyl-5-pyrazolone with carbonyl compounds in ionic liquids [Bmim]BF4 and [Bmim]PF6 catalyzed by ethylenediammonium diacetate.

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

    Directory of Open Access Journals (Sweden)

    Seohyun Shin


    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.

  17. Silica nanospheres formation induced by peroxidase-catalyzed phenol polymerization

    Institute of Scientific and Technical Information of China (English)


    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.

  18. Thin Film Deposition Techniques (PVD) (United States)

    Steinbeiss, E.

    The most interesting materials for spin electronic devices are thin films of magnetic transition metals and magnetic perovskites, mainly the doped La-manganites [1] as well as several oxides and metals for passivating and contacting the magnetic films. The most suitable methods for the preparation of such films are the physical vapor deposition methods (PVD). Therefore this report will be restricted to these deposition methods.

  19. Rates of deposition, reserve alteration, and of the leaching of some trace substances in forest ecosystems. Final report. Raten der Deposition, der Vorratsaenderungen und des Austrages einiger Spurenstoffe in Waldoekosystemen. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, R.; Lamersdorf, N.; Heinrichs, H.; Mayer, R.; Ulrich, B.


    The investigation related to: the concentrations and flow rates of precipitation in the open field, of precipitation in stands, litter deposition, and seepage waters below the surface humus as well as in a depth of about 1 metre in the ground. Furthermore, trace substances were determined in leaves, wood, bark, fine roots, surface-humus layers and in different ranges of depth of the mineral soil, and inventories were made up from this for the ecosystems investigated. Sites comprise the medium-altitude mountain range as far as the tree species beech, spruce, oak and pine are concerned. Trace materials covered in the analysis are: manganese, cadmium, thallium, lead, bismuth, mercury, silver, beryllium, antimony, vanadium, molybdenum, and boron. To record molybdenum and boron, suitable methods to render these element soluble and for their determination were developed.

  20. Alternative diagenetic models for cretaceous talus deposits, Deep Sea Drilling Project Site 536, Gulf of Mexico: Chapter 8 in Initial reports of the Deep Sea Drilling Project (United States)

    Halley, Robert B.; Pierson, B. J.; Schlager, Wolfgang


    Talus deposits recovered from Site 536 show evidence of aragonite dissolution, secondary porosity development, and calcite cementation. Although freshwater diagenesis could account for the petrographic features of the altered talus deposits, it does not uniquely account for isotopic or trace-element characteristics. Also, the hydrologic setting required for freshwater alteration is not easily demonstrated for the Campeche Bank. A mixing-zone model does not account for the available trace-element data, but does require somewhat less drastic assumptions about the size of the freshwater lens. Although a seawater (bottom-water) alteration model requires no hydrologic difficulties, unusual circumstances are required to account for the geochemical characteristics of the talus deposits using this model.

  1. 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.


    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.

  2. 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


    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.

  3. 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.


    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.

  4. Deposit model for volcanogenic uranium deposits (United States)

    Breit, George N.; Hall, Susan M.


    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.

  5. 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.


    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.

  6. The Underpotential Deposition of Copper on Pt(311): Site Selective Deposition and Anion Effects (United States)


    AD-A278 022 OFFICE OF NAVAL RESEARCH CONTRACT N00014-84-k-0656/PP0002 R & T Code 4133034 Technical Report #36 The Underpotential Deposition of Copper...Include Security Clauffication) The Underpotential Deposition of Copper on Pt(311): Site Selective Deposition and Anion Effects 𔃼 OERSONAL AUTHOR(S...Alacant, Spain ABSTRACT The underpotential deposition of copper on Pt(31 1)=Pt[2(111 )x(100)] stepped surfaces has been studied and the results are compared

  7. Synthetic applications of gold-catalyzed ring expansions

    Directory of Open Access Journals (Sweden)

    Cristina Nevado


    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.

  8. Biocatalysts for cascade reaction: porcine pancreas lipase (PPL)-catalyzed synthesis of bis(indolyl)alkanes. (United States)

    Xiang, Ziwei; Liu, Zhiqiang; Chen, Xiang; Wu, Qi; Lin, XianFu


    A cascade reaction between aldehydes and indole catalyzed by lipase from porcine pancreas Type II (PPL) in solvent mixture at 50 °C was reported for the first time. Some control experiments had been designed to demonstrate that the PPL was responsible for the cascade reaction. After the optimization of the stepwise process, a series of bis(indolyl)alkanes were prepared in moderate to excellent yields under the catalysis of PPL.

  9. 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


    @@ 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.

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

    Directory of Open Access Journals (Sweden)

    Brett N. Hemric


    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.

  11. Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with secondary amine nucleophiles

    Directory of Open Access Journals (Sweden)

    Dingqiao Yang


    Full Text Available Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with various aliphatic and aromatic secondary amines are reported for the first time. The reaction gave the corresponding trans-1,2-dihydronaphthalenol derivatives in good yields with moderate enantioselectivities in the presence of 2.5 mol % [Ir(CODCl]2 and 5 mol % bisphosphine ligand (S-p-Tol-BINAP. The trans-configuration of 3f was confirmed by X-ray crystallography.

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

    Institute of Scientific and Technical Information of China (English)


    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.

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

    KAUST Repository

    Fava, Eleonora


    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.

  14. Palladium-catalyzed 1,4-difunctionalization of butadiene to form skipped polyenes. (United States)

    McCammant, Matthew S; Liao, Longyan; Sigman, Matthew S


    A palladium-catalyzed 1,4-addition across the commodity chemical 1,3-butadiene to afford skipped polyene products is reported. Through a palladium σ → π → σ allyl isomerization, two new carbon-carbon bonds are formed with high regioselectivity and trans stereoselectivity of the newly formed alkene. The utility of this method is highlighted by the successful synthesis of the ripostatin A skipped triene core.

  15. A novel copper-catalyzed reductive coupling of N-tosylhydrazones with H-phosphorus oxides. (United States)

    Wu, Lei; Zhang, Xio; Chen, Qing-Qing; Zhou, An-Kun


    We report here a novel C(sp(3))-P bonds formation via copper-catalyzed reductive coupling of N-tosylhydrazones with H-phosphorus oxides. A variety of aliphatic and aromatic substrates bearing electron-rich and electron-deficient substituents affords phosphine oxide derivatives with moderate to good yields. This work suggests a new transformation of aldehydes/ketones via N-tosylhydrazones to organophosphorus compounds.

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

    KAUST Repository

    Petersen, Kimberly S.


    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.

  17. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols (United States)


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

    KAUST Repository

    Zhu, Bo


    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.

  19. High Efficiency and High Rate Deposited Amorphous Silicon-Based Solar Cells: Final Technical Report, 1 September 2001--6 March 2005

    Energy Technology Data Exchange (ETDEWEB)

    Deng, X.


    The objectives for the University of Toledo are to: (1) establish a transferable knowledge and technology base for fabricating high-efficiency triple-junction a-Si-based solar cells, and (2) develop high-rate deposition techniques for the growing a-Si-based and related alloys, including poly-Si, c-Si, a-SiGe, and a-Si films and photovoltaic devices with these materials.

  20. 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.


    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.

  1. 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)


    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.

  2. 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


    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.

  3. Kinetics of acid base catalyzed transesterification of Jatropha curcas oil. (United States)

    Jain, Siddharth; Sharma, M P


    Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstock for biodiesel production in India. Limited work is reported on the kinetics of transesterification of high free fatty acids containing oil. The present study reports the results of kinetic study of two-step acid base catalyzed transesterification process carried out at an optimum temperature of 65 °C and 50 °C for esterification and transesterification respectively under the optimum methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH. The yield of methyl ester (ME) has been used to study the effect of different parameters. The results indicate that both esterification and transesterification reaction are of first order with reaction rate constant of 0.0031 min⁻¹ and 0.008 min⁻¹ respectively. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained.

  4. On Transition Metal Catalyzed Reduction of N-nitrosodimethlamine

    CERN Document Server

    Zhou, Jun; Tian, Junhua; Zhao, Zhun


    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.

  5. Rh-Catalyzed, Regioselective, C-H Bond Functionalization: Access to Quinoline-Branched Amines and Dimers. (United States)

    Reddy, M Damoder; Fronczek, Frank R; Watkins, E Blake


    Rh-catalyzed, chelation-induced, C-5 regioselective C-H functionalization of 8-amidoquinolines with a range of N-Boc aminals is reported for the first time. The addition of in situ generated imines to C(sp(2))-H bonds afforded branched amines in good to excellent yields. Moreover, this transformation features good functional group compatibility, broad substrate scope, and mild reaction conditions and is suitable for gram-scale synthesis. In addition, an unprecedented, chelation-induced, site-selective, remote dimerization of quinolines led to the formation of dimer frameworks in moderate yields under Rh-catalyzed conditions.

  6. Fluorobenzo[a]pyrenes as probes of the mechanism of cytochrome P450-catalyzed oxygen transfer in aromatic oxygenations

    NARCIS (Netherlands)

    Mulder, P.P.J.; Devanesan, P.; Alem, van K.; Lodder, G.; Rogan, E.G.; Cavalieri, E.L.


    Fluoro substitution of benzo[a]pyrene (BP) has been very useful in determining the mechanism of cytochrome P450-catalyzed oxygen transfer in the formation of 6-hydroxyBP (6-OHBP) and its resulting BP 1,6-, 3,6-, and 6,12-diones. We report here the metabolism of 1-FBP and 3-FBP, and PM3 calculations

  7. Efficient Method for the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of Hydrogen Peroxide (United States)

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


    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…

  8. Enantioselective Nickel-Catalyzed anti-Carbometallative Cyclizations of Alkynyl Electrophiles Enabled by Reversible Alkenylnickel E/Z Isomerization (United States)


    Nickel-catalyzed additions of arylboronic acids to alkynes, followed by enantioselective cyclizations of the alkenylnickel species onto tethered ketones or enones, are reported. These reactions are reliant upon the formal anti-carbonickelation of the alkyne, which is postulated to occur by the reversible E/Z isomerization of an alkenylnickel species. PMID:27333360

  9. An unexpected copper(II)-catalyzed three-component reaction of quinazoline 3-oxide, alkylidenecyclopropane, and water. (United States)

    An, Yuanyuan; Zheng, Danqing; Wu, Jie


    An unexpected copper(II)-catalyzed three-component reaction of quinazoline-3-oxide, alkylidenecyclopropane and water under mild conditions is reported. This transformation including [3+2] cycloaddition and intramolecular rearrangement leads to N-(2-(5-oxa-6-azaspiro[2.4]hept-6-en-7-yl)phenyl)formamides in good yields.

  10. Enzyme-Catalyzed Polymerization of Beta-alanine Esters, A Sustainable Route Towards the Formation of Poly-Beta-alanine

    NARCIS (Netherlands)

    Steunenberg, P.; Uiterweerd, M.; Sijm, M.; Scott, E.L.; Zuilhof, H.; Sanders, J.P.M.; Franssen, M.C.R.


    The synthesis of poly-ß-alanine by a lipase catalyzed polycondensation reaction between ß-alanine esters is reported. The effect of different solvents, reaction temperatures and substrate/enzyme concentrations on polymer yield and degree of polymerization (DP) was determined. Also the effect of meth

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

    Directory of Open Access Journals (Sweden)

    Jalal Albadi


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

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

  13. Phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates: synthesis of 2-pyrrolines. (United States)

    Tian, Junjun; Zhou, Rong; Sun, Haiyun; Song, Haibin; He, Zhengjie


    In this report, a phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates is described. This reaction represents the first realization of catalytic [4 + 1] cyclization of 1,3-azadienes with in situ formed phosphorus ylides, which provides highly efficient and diastereoselective synthesis of 2-pyrrolines.

  14. Assessment of Undiscovered Deposits of Gold, Silver, Copper, Lead, and Zinc in the United States: A Portable Document (PDF) Recompilation of USGS Open-File Report 96-96 and Circular 1178 (United States)

    U.S. Geological Survey National Mineral Resource Assessment Team Recompiled by Schruben, Paul G.


    This publication contains the results of a national mineral resource assessment study. The study (1) identifies regional tracts of ground believed to contain most of the nation's undiscovered resources of gold, silver, copper, lead, and zinc in conventional types of deposits; and (2) includes probabilistic estimates of the amounts of these undiscovered resources in most of the tracts. It also contains a table of the significant known deposits in the tracts, and includes descriptions of the mineral deposit models used for the assessment. The assessment was previously released in two major publications. The conterminous United States assessment was published in 1996 as USGS Open-File Report 96-96. Subsequently, the Alaska assessment was combined with the conterminous assessment in 1998 and released as USGS Circular 1178. This new recompilation was undertaken for several reasons. First, the graphical browser software used in Circular 1178 was ONLY compatible with the Microsoft Windows operating system. It was incompatible with the Macintosh operating system, Linux, and other types of Unix computers. Second, the browser on Circular 1178 is much less intuitive to operate, requiring most users to follow a tutorial to understand how to navigate the information on the CD. Third, this release corrects several errors and numbering inconsistencies in Circular 1178.

  15. 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.


    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.

  16. NOx Catalyzed Pathway of Stratospheric Ozone Depletion: A Coupled Cluster Investigation. (United States)

    Dutta, Achintya Kumar; Vaval, Nayana; Pal, Sourav


    We report a theoretical investigation on the NOx catalyzed pathways of stratospheric ozone depletion using highly accurate coupled cluster methods. These catalytic reactions represent a great challenge to state-of-the-art ab initio methods, while their mechanisms remain unclear to both experimentalists and theoreticians. In this work, we have used the so-called "gold standard of quantum chemistry," the CCSD(T) method, to identify the saddle points on NOx-based reaction pathways of ozone hole formation. Energies of the saddle points are calculated using the multireference variants of coupled cluster methods. The calculated activation energies and rate constants show good agreement with available experimental results. Tropospheric precursors to stratospheric NOx radicals have been identified, and their potential importance in stratospheric chemistry has been discussed. Our calculations resolve previous conflicts between ab initio and experimental results for a trans nitro peroxide intermediate, in the NOx catalyzed pathway of ozone depletion.

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

    Directory of Open Access Journals (Sweden)

    Ryan Pearson


    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.

  18. 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


    @@ 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.

  19. A General Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl and Heteroaryl Chlorides. (United States)

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


    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.

  20. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions. (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter


    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

  1. Mechanisms of bacterially catalyzed reductive dehalogenation

    Energy Technology Data Exchange (ETDEWEB)

    Picardal, F.W.


    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.

  2. High-pressure catalytic chemical vapor deposition of ferromagnetic ruthenium-containing carbon nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Khavrus, Vyacheslav O., E-mail:; Ibrahim, E. M. M.; Bachmatiuk, Alicja; Ruemmeli, Mark H.; Wolter, A. U. B.; Hampel, Silke; Leonhardt, Albrecht [IFW Dresden (Germany)


    We report on the high-pressure catalytic chemical vapor deposition (CCVD) of ruthenium nanoparticles (NPs) and single-walled carbon nanotubes (SWCNTs) by means of gas-phase decomposition of acetonitrile and ruthenocene in a tubular quartz flow reactor at 950 Degree-Sign C and at elevated pressures (between 2 and 8 bar). The deposited material consists of Ru metal cores with sizes ranging between 1 and 3 nm surrounded by a carbon matrix. The high-pressure CCVD seems to be an effective route to obtain composite materials containing metallic NPs, Ru in this work, inside a nanostructured carbon matrix protecting them from oxidation in ambient air. We find that in contradiction to the weak paramagnetic properties characterizing bulk ruthenium, the synthesized samples are ferromagnetic as predicted for nanosized particles of nonmagnetic materials. At low pressure, the very small ruthenium catalyst particles are able to catalyze growth of SWCNTs. Their yield decreases with increasing reaction pressure. Transmission electron microscopy, selected area energy-dispersive X-ray analysis, Raman spectroscopy, and magnetic measurements were used to analyze and confirm properties of the synthesized NPs and nanotubes. A discussion on the growth mechanism of the Ru-containing nanostructures is presented.

  3. 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


    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.

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

    Institute of Scientific and Technical Information of China (English)


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

  5. Diastereoselective Pt catalyzed cycloisomerization of polyenes to polycycles. (United States)

    Geier, Michael J; Gagné, Michel R


    Application of a tridentate NHC containing pincer ligand to Pt catalyzed cascade cyclization reactions has allowed for the catalytic, diastereoselective cycloisomerization of biogenic alkene terminated substrates to the their polycyclic counterparts.

  6. Lipase catalyzed synthesis of epoxy-fatty acids

    Institute of Scientific and Technical Information of China (English)

    CHEN, Qian; LI, Zu-Yi


    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

  7. Gold-Catalyzed Regioselective Dimerization of Aliphatic Terminal Alkynes. (United States)

    Sun, Sheng; Kroll, Julien; Luo, Yingdong; Zhang, Liming


    A gold-catalyzed regioselective homodimerization of aliphatic terminal alkynes is described. Bulky and less Lewis acidic tBuXPhosAuNTf(2) is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction.

  8. Homocoupling of Aryl Bromides Catalyzed by Nickel Chloride in Pyridine

    Institute of Scientific and Technical Information of China (English)

    TAO, Xiao-Chun; ZHOU, Wei; ZHANG, Yue-Ping; DAI, Chun-ya; SHEN, Dong; HUANG, Mei


    Pyridine was used as a solvent for homocoupling of aryl bromides catalyzed by nickel chloride/triarylphosphine in the presence of zinc and recycled easily. Triphenylphosphine was the best ligand for nickel in this coupling reaction.

  9. 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


    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.

  10. Development and industrial application of catalyzer for low-temperature hydrogenation hydrolysis of Claus tail gas


    Honggang Chang; Ronghai Zhu; Zongshe Liu; Jinlong He; Chongrong Wen; Sujuan Zhang; Yang Li


    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, prepar...



    Tjahjono Herawan; M. Rüsch Gen. Klaas


    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 solve...

  12. Water evaporation in silica colloidal deposits. (United States)

    Peixinho, Jorge; Lefèvre, Grégory; Coudert, François-Xavier; Hurisse, Olivier


    The results of an experimental study on the evaporation and boiling of water confined in the pores of deposits made of mono-dispersed silica colloidal micro-spheres are reported. The deposits are studied using scanning electron microscopy, adsorption of nitrogen, and adsorption of water through attenuated total reflection-infrared spectroscopy. The evaporation is characterized using differential scanning calorimetry and thermal gravimetric analysis. Optical microscopy is used to observe the patterns on the deposits after evaporation. When heating at a constant rate and above boiling temperature, the release of water out of the deposits is a two step process. The first step is due to the evaporation and boiling of the surrounding and bulk water and the second is due to the desorption of water from the pores. Additional experiments on the evaporation of water from membranes having cylindrical pores and of heptane from silica deposits suggest that the second step is due to the morphology of the deposits.

  13. High power density yeast catalyzed microbial fuel cells (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.

  14. Lipase catalyzed ester synthesis for food processing industries

    Directory of Open Access Journals (Sweden)

    Aravindan Rajendran


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

  15. Cascadia Tsunami Deposit Database (United States)

    Peters, Robert; Jaffe, Bruce; Gelfenbaum, Guy; Peterson, Curt


    The Cascadia Tsunami Deposit Database contains data on the location and sedimentological properties of tsunami deposits found along the Cascadia margin. Data have been compiled from 52 studies, documenting 59 sites from northern California to Vancouver Island, British Columbia that contain known or potential tsunami deposits. Bibliographical references are provided for all sites included in the database. Cascadia tsunami deposits are usually seen as anomalous sand layers in coastal marsh or lake sediments. The studies cited in the database use numerous criteria based on sedimentary characteristics to distinguish tsunami deposits from sand layers deposited by other processes, such as river flooding and storm surges. Several studies cited in the database contain evidence for more than one tsunami at a site. Data categories include age, thickness, layering, grainsize, and other sedimentological characteristics of Cascadia tsunami deposits. The database documents the variability observed in tsunami deposits found along the Cascadia margin.

  16. Colloid Deposit Morphology and Clogging in Porous Media: Fundamental Insights Through Investigation of Deposit Fractal Dimension. (United States)

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


    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.

  17. Celecoxib influences steroid sulfonation catalyzed by human recombinant sulfotransferase 2A1. (United States)

    Ambadapadi, Sriram; Wang, Peter L; Palii, Sergiu P; James, Margaret O


    Celecoxib has been reported to switch the human SULT2A1-catalyzed sulfonation of 17β-estradiol (17β-E2) from the 3- to the 17-position. The effects of celecoxib on the sulfonation of selected steroids catalyzed by human SULT2A1 were assessed through in vitro and in silico studies. Celecoxib inhibited SULT2A1-catalyzed sulfonation of dehydroepiandrosterone (DHEA), androst-5-ene-3β, 17β-diol (AD), testosterone (T) and epitestosterone (Epi-T) in a concentration-dependent manner. Low μM concentrations of celecoxib strikingly enhanced the formation of the 17-sulfates of 6-dehydroestradiol (6D-E2), 17β-dihydroequilenin (17β-Eqn), 17β-dihydroequilin (17β-Eq), and 9-dehydroestradiol (9D-E2) as well as the overall rate of sulfonation. For 6D-E2, 9D-E2 and 17β-Eqn, celecoxib inhibited 3-sulfonation, however 3-sulfonation of 17β-Eq was stimulated at celecoxib concentrations below 40 μM. Ligand docking studies in silico suggest that celecoxib binds in the substrate-binding site of SULT2A1 in a manner that prohibits the usual binding of substrates but facilitates, for appropriately shaped substrates, a binding mode that favors 17-sulfonation.

  18. Enantioselective epoxidation and carbon-carbon bond cleavage catalyzed by Coprinus cinereus peroxidase and myeloperoxidase. (United States)

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


    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.

  19. Conservation Kickstart- Catalyzing Conservation Initiatives Worldwide (United States)

    Treinish, G.


    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

  20. Electrical Transport Properties of Ni95Ti5 Catalyzed Multi wall Carbon Nanotubes Film

    Directory of Open Access Journals (Sweden)

    Zishan Husain Khan


    Full Text Available Carbon nanotubes (CNTs can be understood as one or more graphite sheets rolled up into a seamless cylinder. CNTs have gained much attention and scientific interest due to their unique properties and potential applications since their discovery in 1991. In the present work, we have deposited Ni95Ti5 film using thermal deposition method. Finally, the Ni95Ti5 catalyzed multi wall carbon nanotubes (MWNTs are grown on silicon substrate using low pressure chemical vapor deposition (LPCVD method and the electrical transport properties of this MWNTs film are studied over a temperature range (284–4K to explain the conduction mechanism. We have suggested two types of conduction mechanism for the entire temperature range. For the temperature region (284–220K, the conduction is due to thermally activated process, whereas the conduction takes place via variable range hopping (VRH for the temperature range of (220–4K. The VRH mechanism changes from three dimensions to two dimensions as we move down to the temperature below 50K. Therefore, the data for the temperature region (220–50K is plotted for three dimensional variable range hopping (3D VRH model and the two dimensional variable range hopping (2D VRH for lower temperature range of (50–4K. These VRH models give a good fit to the experimental data. Using these models, we have calculated various interesting electrical parameters such as activation energy, density of states, hopping distance and hopping energy.

  1. Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries. (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


    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.

  2. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry (United States)

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


    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).

  3. Improvement of silicon nanowire solar cells made by metal catalyzed electroless etching and nano imprint lithography (United States)

    Chen, Junyi; Subramani, Thiyagu; Jevasuwan, Wipakorn; Fukata, Naoki


    Silicon nanowires were fabricated by metal catalyzed electroless etching (MCEE) and nano imprint lithography (NIL), then a shell p-type layer was grown by thermal chemical vapor deposition (CVD) techniques. To reduce back surface recombination and also to activate the dopant, we used two techniques, back surface field (BSF) treatment and rapid thermal annealing (RTA), to improve device performance. In this study, we investigated BSF and RTA treatments in silicon nanowire solar cells, and improved the device performance and efficiency from 4.1 to 7.4% (MCEE device) and from 1.1 to 6.6% (NIL device) after introducing BSF and RTA treatments. Moreover, to achieve better metal contact without sacrificing the reflectance after the shell formation, the selective-area etching method was investigated. Finally, after combining all processes, silicon nanowire solar cells fabricated via the MCEE process exhibited 8.7% efficiency.

  4. Biomimetic thin film deposition (United States)

    Rieke, P. C.; Campbell, A. A.; Tarasevich, B. J.; Fryxell, G. E.; Bentjen, S. B.


    Surfaces derivatized with organic functional groups were used to promote the deposition of thin films of inorganic minerals. These derivatized surfaces were designed to mimic the nucleation proteins that control mineral deposition during formation of bone, shell, and other hard tissues in living organisms. By the use of derivatized substrates control was obtained over the phase of mineral deposited, the orientation of the crystal lattice and the location of deposition. These features are of considerable importance in many technically important thin films, coatings, and composite materials. Methods of derivatizing surfaces are considered and examples of controlled mineral deposition are presented.

  5. Bauxite Deposits in China

    Institute of Scientific and Technical Information of China (English)



    Bauxite deposits in China,rangin in age from Late Paleozoic to Cenozoic ,are distributed mainly in Shanxi,Shandong Henan,Guizhou,Guangxi and Yunnan.Based on stratigraphic relations they can be clas-sified as 6 types:inter-system marine,inter-system continental,intra-system marine,intra-system continent-tal,weathering lateritic and weathering accumulation types.But in terms of depositional environments,only four types are distinguished,I.e.the marine deposits,continental deposits,lateritic deposits and weath-ering-accumulation deposits.These deposits have been formed in two steps:firstly,the depression of paraplatform or front basin margins in paleocontinents and secondly,the development of littoral-lagoons on the eroded surface of karstified carbonate bedrocks.The aluminum may have been derived from the carbonate rocks with which the ores are associated,or from adjacent aluminosilicate rocks.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  8. Development and implementation of technical concepts for the final disposal in deep geological deposits in different host rocks (EUGENIA). Synthesis report; Entwicklung und Umsetzung von technischen Konzepten fuer Endlager in tiefen geologischen Formationen in unterschiedlichen Wirtsgesteinen (EUGENIA). Synthesebericht

    Energy Technology Data Exchange (ETDEWEB)

    Bollingerfehr, Wilhelm; Herklotz, Martin; Herzog, Christel (and others)


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

  9. Rhodium(III)-catalyzed indazole synthesis by C-H bond functionalization and cyclative capture. (United States)

    Lian, Yajing; Bergman, Robert G; Lavis, Luke D; Ellman, Jonathan A


    An efficient, one-step, and highly functional group-compatible synthesis of substituted N-aryl-2H-indazoles is reported via the rhodium(III)-catalyzed C-H bond addition of azobenzenes to aldehydes. The regioselective coupling of unsymmetrical azobenzenes was further demonstrated and led to the development of a new removable aryl group that allows for the preparation of indazoles without N-substitution. The 2-aryl-2H-indazole products also represent a new class of readily prepared fluorophores for which initial spectroscopic characterization has been performed.

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

    Directory of Open Access Journals (Sweden)

    Thibault E. Schmid


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

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

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak


    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.

  12. Ruthenium(II)-Catalyzed Regioselective Ortho Amidation of Imidazo Heterocycles with Isocyanates. (United States)

    Shakoor, S M Abdul; Kumari, Santosh; Khullar, Sadhika; Mandal, Sanjay K; Kumar, Anil; Sakhuja, Rajeev


    Direct ortho amidation at the phenyl ring of 2-phenylimidazo heterocycles with aryl isocyanates has been achieved via a chelation-assisted cationic ruthenium(II) complex catalyzed mechanism. The methodology provides a straightforward, high-yielding regioselective approach toward the synthesis of an array of ortho-amidated phenylimidazo heterocycles without prior activation of C(sp(2))-H. This also reports the first method for coupling of aryl isocyanates with the imidazo[1,2-a]pyridine system via a pentacyclometalated intermediate. The methodology is found to be easily scalable and could be applied toward the selective ortho amidation of 2-heteroarylimidazo[1,2-a]pyridine frameworks.

  13. Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids. (United States)

    Kan, Jian; Huang, Shijun; Lin, Jin; Zhang, Min; Su, Weiping


    A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.

  14. Alumina-entrapped Ag catalyzed nitro compounds coupled with alcohols using borrowing hydrogen methodology. (United States)

    Liu, Huihui; Chuah, Gaik Khuan; Jaenicke, Stephan


    Supported silver catalysts were reported for the first time to be able to catalyze the coupling reaction between nitroarenes and alcohols via the borrowing hydrogen scheme. The recyclable, non-leaching catalyst is synthesized by the entrapment method, which allows entrapping of silver nanoparticles in an alumina matrix. Alcohols, acting as the reducing agents for nitro-groups, alkylated the resultant amines smoothly over these silver catalysts giving a yield of >98% towards the N-substituted amines. In this process, multiple steps were realized in one-pot over a single catalyst with very high efficiency. It offers another clean and economic way to achieve amination of alcohols.

  15. An advantageous route to oxcarbazepine (trileptal) based on palladium-catalyzed arylations free of transmetallating agents. (United States)

    Carril, Mónica; SanMartin, Raul; Churruca, Fátima; Tellitu, Imanol; Domínguez, Esther


    [reaction: see text] A new route to oxcarbazepine (Trileptal), the most widely prescribed antiepileptic drug, starting from commercially available 2'-aminoacetophenone and 1,2-dibromobenzene, is reported. The sequentially accomplished key steps are palladium-catalyzed intermolecular alpha-arylation of ketone enolates and intramolecular N-arylation reactions. After several experiments to establish the best conditions for both arylation processes, the target oxcarbazepine is obtained in a satisfactory overall yield, minimizing the number of steps and employing scalable catalytic procedures developed in partially aqueous media.

  16. Te-doping of self-catalyzed GaAs nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Suomalainen, S., E-mail:; 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)


    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.

  17. Gold-catalyzed direct alkynylation of tryptophan in peptides using TIPS-EBX (United States)

    Tolnai, Gergely L; Brand, Jonathan P


    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

  18. Homogeneous Carbon Nanotube/Carbon Composites Prepared by Catalyzed Carbonization Approach at Low Temperature

    Directory of Open Access Journals (Sweden)

    Hongjiang Li


    Full Text Available We synthesize carbon nanotube (CNT/carbon composite using catalyzed carbonization of CNT/Epoxy Resin composite at a fairly low temperature of about 400∘C. The microstructure of the composite is characterized by scanning electron microscope (SEM, transmission electron microscope (TEM, and X-ray diffraction (XRD. The results indicate that CNTs and pyrolytic carbon blend well with each other. Pyrolytic carbon mainly stays in an amorphous state, with some of it forming crystalline structures. The catalyst has the effect of eliminating the interstices in the composites. Remarkable increases in thermal and electrical conductivity are also reported.

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

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


    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.

  20. Homologation of α-aryl amino acids through quinone-catalyzed decarboxylation/Mukaiyama-Mannich addition. (United States)

    Haugeberg, Benjamin J; Phan, Johnny H; Liu, Xinyun; O'Connor, Thomas J; Clift, Michael D


    A new method for amino acid homologation by way of formal C-C bond functionalization is reported. This method utilizes a 2-step/1-pot protocol to convert α-amino acids to their corresponding N-protected β-amino esters through quinone-catalyzed oxidative decarboxylation/in situ Mukaiyama-Mannich addition. The scope and limitations of this chemistry are presented. This methodology provides an alternative to the classical Arndt-Eistert homologation for accessing β-amino acid derivatives. The resulting N-protected amine products can be easily deprotected to afford the corresponding free amines.

  1. Shedding of ash deposits

    DEFF Research Database (Denmark)

    Zbogar, Ana; Frandsen, Flemming; Jensen, Peter Arendt;


    Ash deposits formed during fuel thermal conversion and located on furnace walls and on convective pass tubes, may seriously inhibit the transfer of heat to the working fluid and hence reduce the overall process efficiency. Combustion of biomass causes formation of large quantities of troublesome...... ash deposits which contain significant concentrations of alkali, and earth-alkali metals. The specific composition of biomass deposits give different characteristics as compared to coal ash deposits, i.e. different physical significance of the deposition mechanisms, lower melting temperatures, etc....... Low melting temperatures make straw ashes especially troublesome, since their stickiness is higher at lower temperatures, compared to coal ashes. Increased stickiness will eventually lead to a higher collection efficiency of incoming ash particles, meaning that the deposit may grow even faster...

  2. 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


    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.

  3. ElectroSpark Deposition (United States)


    ElectroSpark Deposition Hard Chrome Alternatives Team Joint Cadmium Alternatives Team Canadian Hard Chrome Alternatives Team Joint Group on Pollution...00-2007 to 00-00-2007 4. TITLE AND SUBTITLE ElectroSpark Deposition 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S...Processes, Inc. ElectroSpark Deposition (ESD) Results of Materials Testing and Technology Insertion January 25, 2007 Advanced Surfaces And Processes, Inc. 3

  4. The mechanism for iron-catalyzed alkene isomerization in solution

    Energy Technology Data Exchange (ETDEWEB)

    Sawyer, Karma R.; Glascoe, Elizabeth A.; Cahoon, James F.; Schlegel, Jacob P.; Harris, Charles B.


    Here we report nano- through microsecond time-resolved IR experiments of iron-catalyzed alkene isomerization in room-temperature solution. We have monitored the photochemistry of a model system, Fe(CO){sub 4}({eta}{sup 2}-1-hexene), in neat 1-hexene solution. UV-photolysis of the starting material leads to the dissociation of a single CO to form Fe(CO){sub 3}({eta}{sup 2}-1-hexene), in a singlet spin state. This CO loss complex shows a dramatic selectivity to form an allyl hydride, HFe(CO){sub 3}({eta}{sup 3}-C{sub 6}H{sub 11}), via an internal C-H bond-cleavage reaction in 5-25 ns. We find no evidence for the coordination of an alkene molecule from the bath to the CO loss complex, but do observe coordination to the allyl hydride, indicating that it is the key intermediate in the isomerization mechanism. Coordination of the alkene ligand to the allyl hydride leads to the formation of the bis-alkene isomers, Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) and Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2}. Because of the thermodynamic stability of Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) over Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2} (ca. 12 kcal/mol), nearly 100% of the alkene population will be 2-alkene. The results presented herein provide the first direct evidence for this mechanism in solution and suggest modifications to the currently accepted mechanism.

  5. A preliminary deposit model for lithium brines (United States)

    Bradley, Dwight; Munk, LeeAnn; Jochens, Hillary; Hynek, Scott; Labay, Keith A.


    This report is part of an effort by the U.S. Geological Survey to update existing mineral deposit models and to develop new ones. The global transition away from hydrocarbons toward energy alternatives increases demand for many scarce metals. Among these is lithium, a key component of lithium-ion batteries for electric and hybrid vehicles. Lithium brine deposits account for about three-fourths of the world’s lithium production. Updating an earlier deposit model, we emphasize geologic information that might directly or indirectly help in exploration for lithium brine deposits, or for assessing regions for mineral resource potential. Special attention is given to the best-known deposit in the world—Clayton Valley, Nevada, and to the giant Salar de Atacama, Chile.

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

    Directory of Open Access Journals (Sweden)

    Kevin H. Shaughnessy


    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.

  7. The Structural Basis of Ribozyme-Catalyzed RNA Assembly

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  8. 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


    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.

  9. A study of the source materials, depositional environments, mechanisms of generation and migration of oils in the Anadarko, Oklahoma. Progress report, September 15, 1990--September 14, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Philp, R.P.


    This report is for the final year of a three-year funded project. A new proposal has been submitted and it is hoped that funding will continue for another three years. It is felt that good progress is being made with our work on studying the oils and source rocks in the Anadarko Basin. Furthermore a number of associated projects have evolved during this period which have also produced many useful results and various analytical methods have been developed. In Appendix I lists of students totally or partially supported by this work plus various publications are given. It is hoped that these will testify to our productivity arising from the DOE support over the past few years.

  10. A new paradigm for XOR-catalyzed reactive species generation in the endothelium. (United States)

    Kelley, Eric E


    A plethora of vascular pathology is associated with inflammation, hypoxia and elevated rates of reactive species generation. A critical source of these reactive species is the purine catabolizing enzyme xanthine oxidoreductase (XOR) as numerous reports over the past 30 years have demonstrated XOR inhibition to be salutary. Despite this long standing association between increased vascular XOR activity and negative clinical outcomes, recent reports reveal a new paradigm whereby the enzymatic activity of XOR mediates beneficial outcomes by catalyzing the one electron reduction of nitrite (NO2(-)) to nitric oxide (NO) when NO2(-) and/or nitrate (NO3(-)) levels are enhanced either via dietary or pharmacologic means. These observations seemingly countervail numerous reports of improved outcomes in similar models upon XOR inhibition in the absence of NO2(-) treatment affirming the need for a more clear understanding of the mechanisms underpinning the product identity of XOR. To establish the micro-environmental conditions requisite for in vivo XOR-catalyzed oxidant and NO production, this review assesses the impact of pH, O2 tension, enzyme-endothelial interactions, substrate concentrations and catalytic differences between xanthine oxidase (XO) and xanthine dehydrogenase (XDH). As such, it reveals critical information necessary to distinguish if pursuit of NO2(-) supplementation will afford greater benefit than inhibition strategies and thus enhance the efficacy of current approaches to treat vascular pathology.

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

    Directory of Open Access Journals (Sweden)

    Syed Adnan Ali Shah


    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.

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

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland


    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......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...

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

    Institute of Scientific and Technical Information of China (English)

    竹湘锋; 徐新华


    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.

  14. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

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


    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

  15. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Qinhua Huang


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

  16. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou


    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.

  17. Esterification of phenolic acids catalyzed by lipases immobilized in organogels. (United States)

    Zoumpanioti, M; Merianou, E; Karandreas, T; Stamatis, H; Xenakis, A


    Lipases from Rhizomucor miehei and Candida antarctica B were immobilized in hydroxypropylmethyl cellulose organogels based on surfactant-free microemulsions consisting of n-hexane, 1-propanol and water. Both lipases kept their catalytic activity, catalyzing the esterification reactions of various phenolic acids including cinnamic acid derivatives. High reaction rates and yields (up to 94%) were obtained when lipase from C. antarctica was used. Kinetic studies have been performed and apparent kinetic constants were determined showing that ester synthesis catalyzed by immobilized lipases occurs via the Michaelis-Menten mechanism.

  18. Perivascular iron deposits are associated with protein nitration in cerebral experimental autoimmune encephalomyelitis. (United States)

    Sands, Scott A; Williams, Rachel; Marshall, Sylvester; LeVine, Steven M


    Nitration of proteins, which is thought to be mediated by peroxynitrite, is a mechanism of tissue damage in multiple sclerosis (MS). However, protein nitration can also be catalyzed by iron, heme or heme-associated molecules independent of peroxynitrite. Since microhemorrhages and perivascular iron deposits are present in the CNS of MS patients, we sought to determine if iron is associated with protein nitration. A cerebral model of experimental autoimmune encephalomyelitis (cEAE) was utilized since this model has been shown to have perivascular iron deposits similar to those present in MS. Histochemical staining for iron was used together with immunohistochemistry for nitrotyrosine, eNOS, or iNOS on cerebral sections. Leakage of the blood-brain barrier (BBB) was studied by albumin immunohistochemistry. Iron deposits were colocalized with nitrotyrosine staining around vessels in cEAE mice while control animals revealed minimal staining. This finding supports the likelihood that nitrotyrosine formation was catalyzed by iron or iron containing molecules. Examples of iron deposits were also observed in association with eNOS and iNOS, which could be one source of substrates for this reaction. Extravasation of albumin was present in cEAE mice, but not in control animals. Extravasated albumin may act to limit tissue injury by binding iron and/or heme as well as being a target of nitration, but the protection is incomplete. In summary, iron-catalyzed nitration of proteins is a likely mechanism of tissue damage in MS.

  19. Silver and gold-catalyzed multicomponent reactions

    Directory of Open Access Journals (Sweden)

    Giorgio Abbiati


    Full Text Available Silver and gold salts and complexes mainly act as soft and carbophilic Lewis acids even if their use as σ-activators has been rarely reported. Recently, transformations involving Au(I/Au(III-redox catalytic systems have been reported in the literature. In this review we highlight all these aspects of silver and gold-mediated processes and their application in multicomponent reactions.

  20. Regional aerosol deposition in human upper airways

    Energy Technology Data Exchange (ETDEWEB)

    Swift, D.L.


    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.

  1. 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


    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.

  2. MAPLE deposition of nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Caricato, A.P., E-mail: [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)


    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.

  3. Diastereoselective Synthesis of γ-Substituted 2-Butenolides via (CDC)-Rh-Catalyzed Intermolecular Hydroalkylation of Dienes with Silyloxyfurans. (United States)

    Goldfogel, Matthew J; Roberts, Courtney C; Manan, Rajith S; Meek, Simon J


    Catalytic intermolecular hydroalkylation of dienes with silyloxyfuran nucleophiles is reported. Reactions are catalyzed by 5 mol % of a (CDC)-Rh complex and proceed in up to 87% yield and 6:1 dr (syn/anti) to provide allylic butenolides bearing vicinal stereocenters. Reactions proceed with terminal aryl and alkyl dienes and with modified silyl enol ether nucleophiles including a thiophenone variant. Utility of the products is demonstrated in the synthesis of a polypropionate anti,syn-stereotriad.

  4. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli


    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

  5. Chiral magnesium BINOL phosphate-catalyzed phosphination of imines: access to enantioenriched α-amino phosphine oxides. (United States)

    Ingle, Gajendrasingh K; Liang, Yuxue; Mormino, Michael G; Li, Guilong; Fronczek, Frank R; Antilla, Jon C


    A new method to synthesize chiral α-amino phosphine oxides is reported. The reaction combines N-substituted imines and diphenylphosphine oxide and is catalyzed by a chiral magnesium phosphate salt. A wide variety of aliphatic and aromatic aldimines substituted by electron-neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The dibenzocycloheptene protected imines afforded improved enantioselectivity in the resulting products. Substituted diphenylphosphine oxide nucleophiles also showed good reactivity.

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


    Fujii Noriko; Haruka Ozaki; Takeshi Saito; Akihiko Shimada


    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...

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


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


    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...

  8. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

    Directory of Open Access Journals (Sweden)

    Jungho Jun


    Full Text Available Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion–dipole pair.

  9. Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines (United States)


    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

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

    Potter, Tyler J; Ellman, Jonathan A


    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.

  11. Copper-vapor-assisted chemical vapor deposition for high-quality and metal-free single-layer graphene on amorphous SiO2 substrate. (United States)

    Kim, Hyungki; Song, Intek; Park, Chibeom; Son, Minhyeok; Hong, Misun; Kim, Youngwook; Kim, Jun Sung; Shin, Hyun-Joon; Baik, Jaeyoon; Choi, Hee Cheul


    We report that high-quality single-layer graphene (SLG) has been successfully synthesized directly on various dielectric substrates including amorphous SiO2/Si by a Cu-vapor-assisted chemical vapor deposition (CVD) process. The Cu vapors produced by the sublimation of Cu foil that is suspended above target substrates without physical contact catalyze the pyrolysis of methane gas and assist nucleation of graphene on the substrates. Raman spectra and mapping images reveal that the graphene formed on a SiO2/Si substrate is almost defect-free and homogeneous single layer. The overall quality of graphene grown by Cu-vapor-assisted CVD is comparable to that of the graphene grown by regular metal-catalyzed CVD on a Cu foil. While Cu vapor induces the nucleation and growth of SLG on an amorphous substrate, the resulting SLG is confirmed to be Cu-free by synchrotron X-ray photoelectron spectroscopy. The SLG grown by Cu-vapor-assisted CVD is fabricated into field effect transistor devices without transfer steps that are generally required when SLG is grown by regular CVD process on metal catalyst substrates. This method has overcome two important hurdles previously present when the catalyst-free CVD process is used for the growth of SLG on fused quartz and hexagonal boron nitride substrates, that is, high degree of structural defects and limited size of resulting graphene, respectively.

  12. Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications. (United States)

    Tan, Yueming; Deng, Wenfang; Li, Yunyong; Huang, Zhao; Meng, Yue; Xie, Qingji; Ma, Ming; Yao, Shouzhuo


    We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.

  13. 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.


    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.

  14. Solid on liquid deposition

    Energy Technology Data Exchange (ETDEWEB)

    Charmet, J., E-mail: jerome.charmet@he-arc.c [Institut des Microtechnologies Appliquees ARC, HES-SO Arc, Eplatures-Grise 17, 2300 La Chaux-de-Fonds (Switzerland); Banakh, O.; Laux, E.; Graf, B.; Dias, F.; Dunand, A.; Keppner, H. [Institut des Microtechnologies Appliquees ARC, HES-SO Arc, Eplatures-Grise 17, 2300 La Chaux-de-Fonds (Switzerland); Gorodyska, G.; Textor, M. [BioInterface group, ETHZ, Wolfgang-Pauli-Strasse 10, ETH Hoenggerberg HCI H 525 8093 Zuerich (Switzerland); Noell, W.; Rooij, N.F. de [Ecole Polytechnique Federale de Lausanne, Institute of Microengineering, Sensors, Actuators and Microsystems laboratory, Rue Jaquet Droz 1, 2000 Neuchatel (Switzerland); Neels, A.; Dadras, M.; Dommann, A.; Knapp, H. [Centre Suisse d' Electronique et de Microtechnique SA, Rue Jacquet-Droz 1, 2002 Neuchatel (Switzerland); Borter, Ch.; Benkhaira, M. [COMELEC SA, Rue de la Paix 129, 2300 La Chaux-de-Fonds (Switzerland)


    A process for the deposition of a solid layer onto a liquid is presented. The polymer poly-di-chloro-para-xylylene, also known as Parylene C, was grown on low vapour pressure liquids using the conventional low pressure chemical vapour deposition process. A reactor was built and a process developed to enable the deposition of Parylene C at atmospheric pressure over high vapour pressure liquids. It was used to deposit Parylene C over water among others. In all cases Parylene C encapsulated the liquid without influencing its initial shape. The results presented here show also that the Parylene C properties are not affected by its growth on liquid templates and the roughness of the Parylene C surface in contact with the liquid during the deposition is extremely low.

  15. Catalyzing Employee Change with Transformative Learning (United States)

    Franz, Nancy


    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…

  16. Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes. (United States)

    Li, Meina; Kong, Duanyang; Zi, Guofu; Hou, Guohua


    A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.

  17. 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 o...

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

    KAUST Repository

    Feng, Bobo


    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.


    Institute of Scientific and Technical Information of China (English)

    LEIYanohui; LIHong; 等


    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.

  20. 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)


    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.

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

    NARCIS (Netherlands)

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


    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

  2. 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


    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.

  3. Recent developments in gold-catalyzed cycloaddition reactions

    Directory of Open Access Journals (Sweden)

    Fernando López


    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.

  4. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.;


    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 K2CO...

  5. Transfer Methane to Fragrant Hydrocarbon by Direct Catalyzed Dehydrogenation

    Institute of Scientific and Technical Information of China (English)


    @@ 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.

  6. Solvent-free lipase-catalyzed preparation of diacylglycerols. (United States)

    Weber, Nikolaus; Mukherjee, Kumar D


    Various methods have been applied for the enzymatic preparation of diacylglycerols that are used as dietary oils for weight reduction in obesity and related disorders. Interesterification of rapeseed oil triacylglycerols with commercial preparations of monoacylglycerols, such as Monomuls 90-O18, Mulgaprime 90, and Nutrisoft 55, catalyzed by immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) in vacuo at 60 degrees C led to extensive (from 60 to 75%) formation of diacylglycerols. Esterification of rapeseed oil fatty acids with Nutrisoft, catalyzed by Lipozyme RM in vacuo at 60 degrees C, also led to extensive (from 60 to 70%) formation of diacylglycerols. Esterification of rapeseed oil fatty acids with glycerol in vacuo at 60 degrees C, catalyzed by Lipozyme RM and lipases from Thermomyces lanuginosus (Lipozyme TL IM) and Candida antarctica (lipase B, Novozym 435), also provided diacylglycerols, however, to a lower extent (40-45%). Glycerolysis of rapeseed oil triacylglycerols with glycerol in vacuo at 60 degrees C, catalyzed by Lipozyme TL and Novozym 435, led to diacylglycerols to the extent of

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

    Institute of Scientific and Technical Information of China (English)


    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.

  8. Phosphine-catalyzed [3+2] annulation of cyanoallenes

    NARCIS (Netherlands)

    Kinderman, S.S.; van Maarseveen, J.H.; Hiemstra, H.


    Cyanoallenes were successfully used in organophosphine-catalyzed [3+2]-type annulation to give cyano-substituted dihydropyrroles in good yield. Chiral phosphines were also screened, leading to some initial results in the asymmetric version of cyano­allene-based annulations.

  9. Enantioselective N-heterocyclic carbene-catalyzed synthesis of trifluoromethyldihydropyridinones. (United States)

    Wang, Dong-Ling; Liang, Zhi-Qin; Chen, Kun-Quan; Sun, De-Qun; Ye, Song


    The enantioselective N-heterocyclic carbene-catalyzed [4 + 2] cyclocondensation of α-chloroaldehydes and trifluoromethyl N-Boc azadienes was developed, giving the corresponding 3,4-disubstituted-6-trifluoromethyldihydropyridin-2(1H)-ones in good yields with exclusive cis-selectivities and excellent enantioselectivities.

  10. Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions. (United States)

    Tanriver, Gamze; Dedeoglu, Burcu; Catak, Saron; Aviyente, Viktorya


    Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long

  11. Design and Synthesis of Bis-thioureas Ligands for Pd-Catalyzed Heck Reaction

    Institute of Scientific and Technical Information of China (English)

    CHEN Wei; CHEN Ying-Chun; WU Yong


    The palladium-catalyzed arylation of olefins (the Heck reaction) is one of the most versatile tools for C-C bond formation in organic synthesis. Phosphine ligands are generally used to stabilize the reactive palladium intermediates, the air-sensitivity of phosphine ligands, however,places significant limits on their synthetic applications. Recently, Yang1 and we2 have reported Heck and Suzuki reactions of highly active arenediazonium salts and halides catalyzed by air-stable monothiourea-Pd complexes.In this presentation, we disclose our results on the design and synthesis of novel bis-thiourea ligands. We report that the bis-thiourea-Pd(0) complexes are highly air-, moisture- and thermally stable catalysts for Heck reactions of aryl halides. We tested the catalytic activity of their complexes with Pd (0) in the Heck reaction between iodobenzene and n-butyl acrylate. Our work shows that in NMP at 180℃, quantitative yield was achieved within 0.5h when 0.001mol% Pd was used (TOF up to 200,000). Furthermore, solvent-free condition can be applied in our catalytic system and very high TON (up to 1,000,000) is obtained within 12h.Further investigations aimed at clarification of the reaction scope are currently in progress.

  12. Deposition of a-SiC:H, a-SiO{sub 2} and tetrahedral-C with programmable in-situ etching. Final performance report, March 1, 1988--November 30, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Collis, W.J.


    This research program was originally defined to investigate the deposition of semiconductor and dielectric thin films using a low pressure remote plasma chemical vapor deposition system incorporating a process for etching the films. This etching was to be performed in a periodic fashion during the deposition process to remove defect regions in the film being deposited. The goal was to remove voids and other defects which are characteristic of low temperature deposition processes. While the original research proposal suggested that the studies include the amorphous alloys (Si/C):H and (Si/Ge):H, subsequent funding reductions limited the work to the deposition of an amorphous silicon alloy material (a-Si:H). Intrinsic and doped forms of these materials have applications in the fabrication of single and multi-junction thin film solar cells.

  13. Palladium-Catalyzed, Enantioselective Heine Reaction. (United States)

    Punk, Molly; Merkley, Charlotte; Kennedy, Katlyn; Morgan, Jeremy B


    Aziridines are important synthetic intermediates for the generation of nitrogen-containing molecules. N-Acylaziridines undergo rearrangement by ring expansion to produce oxazolines, a process known as the Heine reaction. The first catalytic, enantioselective Heine reaction is reported for meso-N-acylaziridines where a palladium(II)-diphosphine complex is employed. The highly enantioenriched oxazoline products are valuable organic synthons and potential ligands for transition-metal catalysis.

  14. 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


    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.

  15. Copper-catalyzed aerobic C(sp2)-H functionalization for C-N bond formation: synthesis of pyrazoles and indazoles. (United States)

    Li, Xianwei; He, Li; Chen, Huoji; Wu, Wanqing; Jiang, Huanfeng


    A simple, practical, and highly efficient synthesis of pyrazoles and indazoles via copper-catalyzed direct aerobic oxidative C(sp(2))-H amination has been reported herein. This process tolerated a variety of functional groups under mild conditions. Further diversification of pyrazoles was also investigated, which provided its potential for drug discovery.

  16. Reusable ionic liquid-catalyzed oxidative coupling of azoles and benzylic compounds via sp(3) C-N bond formation under metal-free conditions. (United States)

    Liu, Wenbo; Liu, Chenjiang; Zhang, Yonghong; Sun, Yadong; Abdukadera, Ablimit; Wang, Bin; Li, He; Ma, Xuecheng; Zhang, Zengpeng


    The heterocyclic ionic liquid-catalyzed direct oxidative amination of benzylic sp(3) C-H bonds via intermolecular sp(3) C-N bond formation for the synthesis of N-alkylated azoles under metal-free conditions is reported for the first time. The catalyst 1-butylpyridinium iodide can be recycled and reused with similar efficacies for at least eight cycles.

  17. Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C-F Bond Cleavage. (United States)

    Zhou, Jing; Kuntze-Fechner, Maximilian W; Bertermann, Rüdiger; Paul, Ursula S D; Berthel, Johannes H J; Friedrich, Alexandra; Du, Zhenting; Marder, Todd B; Radius, Udo


    The [Ni(IMes)2]-catalyzed transformation of fluoroarenes into arylboronic acid pinacol esters via C-F bond activation and transmetalation with bis(pinacolato)diboron (B2pin2) is reported. Various partially fluorinated arenes with different degrees of fluorination were converted into their corresponding boronate esters.

  18. Microwave-assisted chemoselective copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aromatic amines under solvent free conditions

    Institute of Scientific and Technical Information of China (English)

    Yaghoub Sarrafi; Manijeh Mohadeszadeh; Kamal Alimohammadi


    Copper-catalyzed synthesis of N-aryl anthranilic acid derivatives using effective amination of 2-chloro and 2-bromobenzoic acid under microwave irradiation is reported. Some of the advantages of this method axe high chemoselectivity, short reaction times, ease of work up procedure and elimination of the need for acid protection.

  19. 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.


    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

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

    DEFF Research Database (Denmark)

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


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

  1. 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


    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.

  2. Speleothem (Cave Deposit) Data (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...

  3. Podiform chromite deposits (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.

  4. Modeled Wet Nitrate Deposition (United States)

    U.S. Environmental Protection Agency — Modeled data on nitrate wet deposition was obtained from Dr. Jeff Grimm at Penn State Univ. Nitrate wet depostion causes acidification and eutrophication of surface...

  5. Alluvial Deposits in Iowa (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...

  6. Chemically deposited tin sulphide

    Energy Technology Data Exchange (ETDEWEB)

    Akkari, A., E-mail: anis.akkari@ies.univ-montp2.f [Laboratoire de Physique de la Matiere Condensee, Faculte des Sciences de Tunis El Manar, Tunisie 2092 (Tunisia); Institut d' Electronique du Sud, Unite Mixte de Recherche 5214 UM2-CNRS (ST2i), Universite Montpellier 2, Place Eugene Bataillon, CC 082, 34095 Montpellier Cedex 5 (France); Guasch, C. [Institut d' Electronique du Sud, Unite Mixte de Recherche 5214 UM2-CNRS (ST2i), Universite Montpellier 2, Place Eugene Bataillon, CC 082, 34095 Montpellier Cedex 5 (France); Kamoun-Turki, N. [Laboratoire de Physique de la Matiere Condensee, Faculte des Sciences de Tunis El Manar, Tunisie 2092 (Tunisia)


    SnS thin films were deposited on glass substrates after multi-deposition runs by chemical bath deposition from aqueous solution containing 30 ml triethanolamine (TEA) (C{sub 6}H{sub 15}NO{sub 3}) (50%), 10 ml thioacetamide (CH{sub 3}CSNH{sub 2}), 8 ml ammonia (NH{sub 3}) solution and 10 ml of Sn{sup 2+}(0.1 M). These films were characterised with X-ray diffraction (XRD), with scanning electron microscopy, and with spectrophotometric measurements. The obtained thin films exhibit the zinc blend structure, the crystallinity seems to be improved as the film thickness increases and the band gap energy is found to be about 1.76 eV for film prepared after six depositions runs.

  7. Electrospark deposition coatings (United States)

    Sheely, W. F.


    Hard surfacing for wear resistant and low-friction coatings has been improved by means of advances in the computer controls in electronic circuitry of the electrospark deposition (ESD) process. coatings of nearly any electrically conductive metal alloy or cermet can be deposited on conductive materials. Thickness is usually two mils or less, but can be as high as 10 mils. ESD coatings can quadrupole cutting tool life.

  8. Cluster Implantation and Deposition Apparatus

    DEFF Research Database (Denmark)

    Hanif, Muhammad; Popok, Vladimir


    In the current report, a design and capabilities of a cluster implantation and deposition apparatus (CIDA) involving two different cluster sources are described. The clusters produced from gas precursors (Ar, N etc.) by PuCluS-2 can be used to study cluster ion implantation in order to develop...... contributions to the theory of cluster stopping in matter as well as for practical applications requiring ultra-shallow implantation and modification of surfaces on the nanoscale. Metal clusters from the magnetron cluster source are of interest for the production of optical sensors to detect specific biological...

  9. Gemstone deposits of Serbia (United States)

    Miladinović, Zoran; Simić, Vladimir; Jelenković, Rade; Ilić, Miloje


    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. Gemstone deposits of Serbia

    Directory of Open Access Journals (Sweden)

    Miladinović Zoran


    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.

  11. Mechanistic Insight into the Rh(III)-Catalyzed C-H Activation of 2-Acetyl-1-Arythydrazines in Water. (United States)

    Wu, Weirong; Liu, Tao; Huang, Caiyun; Zhang, Jing; Man, Xiaoping


    A mechanistic study of the Cp*Rh(III)-catalyzed C-H functionalization of 2-acetyl-1-arythydrazines with diazo compounds in water was carried out by using density functional theory calculations. The results reveal that the acetyl-bonded N-H deprotonation is prior to the phenyl C-H activation. The mechanisms from protonation by acetic acid disagree with the proposal by the Wang group. Different from the Rh(III)-catalyzed C-H activation reported by experimental literature, the rate-determining step of the whole catalytic cycle with an overall barrier of 31.7 kcal mol(-1) (IV → TS12-P') is the protonation process of hydroxy O rather than the C-H bond cleavage step. The present theoretical study rationalizes the experimental observation at the molecular level.

  12. Chemical vapor deposition growth. Annual report

    Energy Technology Data Exchange (ETDEWEB)

    Ruth, R.P.; Manasevit, H.M.; Johnson, R.E.; Kenty, J.L.; Moudy, L.A.; Simpson, W.I.; Yang, J.J.


    The formal objective of the contract is development of CVD techniques for producing large areas of Si sheet on inexpensive substrate materials, with sheet properties suitable for fabricating solar cells. The techniques developed are to be directed toward (1) minimum-cost processing, (2) production of sheet having properties adequate to result in cells with terrestrial array efficiency of 10 percent or more, and (3) eventual scale-up to large-quantity production. (WDM)

  13. Proline catalyzed α-aminoxylation reaction in the synthesis of biologically active compounds. (United States)

    Kumar, Pradeep; Dwivedi, Namrata


    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

  14. Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions. (United States)

    Hayashi, Masahiko


    In this Personal Account, various chiral Schiff base-metal-catalyzed enantioselective organic reactions are reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C1 symmetry. In particular, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes, enantioselective 1,4-addition of dialkylzinc to cyclic and acyclic enones, and asymmetric allylic oxidation are reported. Typically, ketimine-type Schiff base-metal complexes exhibited higher reactivity and enantioselectivity compared with the corresponding aldimine-type Schiff base-metal complexes. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products can be used as key intermediates for optically active natural products and pharmaceuticals.

  15. A Mercury-Catalyzed, High-Yield System for the Oxidation of Methane to Methanol (United States)

    Periana, Roy A.; Taube, Douglas J.; Evitt, Eric R.; Loffler, Daniel G.; Wentrcek, Paul R.; Voss, George; Masuda, Toshihiko


    A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate (~43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10-7 mole per cubic centimeter per second and Hg(II) turnover frequency of 10-3 per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH_3HgOSO_3H, 1. Under the reaction conditions, 1 readily decomposes to CH_3OSO_3H and the reduced mercurous species, Hg_22+. The catalytic cycle is completed by the reoxidation of Hg_22+ with H_2SO_4 to regenerate Hg(II) and byproducts SO_2 and H_2O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid.

  16. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures (United States)

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


    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.

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

    KAUST Repository

    Xu, Jun


    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.

  18. Direct Observation of an Oxepin from a Bacterial Cytochrome P450-Catalyzed Oxidation. (United States)

    Stok, Jeanette E; Chow, Sharon; Krenske, Elizabeth H; Farfan Soto, Clementina; Matyas, Csongor; Poirier, Raymond A; Williams, Craig M; De Voss, James J


    The cytochromes P450 are hemoproteins that catalyze a range of oxidative C-H functionalization reactions, including aliphatic and aromatic hydroxylation. These transformations are important in a range of biological contexts, including biosynthesis and xenobiotic biodegradation. Much work has been carried out on the mechanism of aliphatic hydroxylation, implicating hydrogen atom abstraction, but aromatic hydroxylation is postulated to proceed differently. One mechanism invokes as the key intermediate an arene oxide (and/or its oxepin tautomer). Conclusive isolation of this intermediate has remained elusive and, currently, direct formation of phenols from a Meisenheimer intermediate is believed to be favored. We report here the identification of a P450 [P450cam (CYP101A1) and P450cin (CYP176A1)]-generated arene oxide as a product of in vitro oxidation of tert-butylbenzene. Computations (CBS-QB3) predict that the arene oxide and oxepin have similar stabilities to other arene oxides/oxepins implicated (but not detected) in P450-mediated transformations, suggesting that arene oxides can be unstable terminal products of P450-catalyzed aromatic oxidation that can explain the origin of some observed metabolites.

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

    KAUST Repository

    Zhang, Yanxia


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  1. Microcalorimetric Study on Tyrosine Oxidation Catalyzed by Tyrosinase

    Institute of Scientific and Technical Information of China (English)


    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.

  2. Thermodynamics of Enzyme-Catalyzed Reactions. Part 3. Hydrolases (United States)

    Goldberg, Robert N.; Tewari, Yadu B.


    Equilibrium constants and enthalpy changes for reactions catalyzed by the hydrolase class of enzymes have been compiled. For each reaction the following information is given: The reference for the data; the reaction studied; the name of the enzyme used and its Enzyme Commission number; the method of measurement; the conditions of measurement [temperature, pH, ionic strength, and the buffer(s) and cofactor(s) used]; the data and an evaluation of it; and, sometimes, commentary on the data and on any corrections which have been applied to it or any calculations for which the data have been used. The data from 145 references have been examined and evaluated. Chemical Abstract Service registry numbers are given for the substances involved in these various reactions. There is a cross reference between the substances and the Enzyme Commission numbers of the enzymes used to catalyze the reactions in which the substances participate.

  3. Thermodynamics of Enzyme-Catalyzed Reactions: Part 4. Lyases (United States)

    Goldberg, Robert N.; Tewari, Yadu B.


    Equilibrium constants and enthalpy changes for reactions catalyzed by the lyase class of enzymes have been compiled. For each reaction the following information is given: the reference for the data; the reaction studied; the name of the enzyme used and its Enzyme Commission number; the method of measurement; the conditions of measurement (temperature, pH, ionic strength, and the buffer(s) and cofactor(s) used); the data and an evaluation of it; and, sometimes, commentary on the data and on any corrections which have been applied to it or any calculations for which the data have been used. The data from 106 references have been examined and evaluated. Chemical Abstract Service registry numbers are given for the substances involved in these various reactions. There is a cross reference between the substances and the Enzyme Commission numbers of the enzymes used to catalyze the reactions in which the substances participate.

  4. Thermodynamics of Enzyme-Catalyzed Reactions: Part 2. Transferases (United States)

    Goldberg, Robert N.; Tewari, Yadu B.


    Equilibrium constants and enthalpy changes for reactions catalyzed by the transferase class of enzymes have been compiled. For each reaction the following information is given: the reference for the data; the reaction studied; the name of the enzyme used and its Enzyme Commission number; the method of measurement; the conditions of measurement [temperature, pH, ionic strength, and the buffer(s) and cofactor(s) used]; the data and an evaluation of it; and, sometimes, commentary on the data and on any corrections which have been applied to it or any calculations for which the data have been used. The data from 285 references have been examined and evaluated. Chemical Abstract Service registry numbers are given for the substances involved in these various reactions. There is a cross reference between the substances and the Enzyme Commission numbers of the enzymes used to catalyze the reactions in which the substances participate.

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

    KAUST Repository

    Vummaleti, Sai V. C.


    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. Polymerization of phenols catalyzed by peroxidase in nonaqueous media

    Energy Technology Data Exchange (ETDEWEB)

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


    Polymers produced by horseradish-peroxidase-catalyzed coupling of phenols have been explored as potential substitutes for phenol-formaldehyde resins. To overcome low substrate solubilities and product molecular weights in water, enzymatic polymerizations in aqueous-organic mixtures have been examined. Peroxidase vigorously polymerizes a number of phenols in mixtures of water with water-miscible solvents such as dioxane, acetone, dimethylformamide, and methyl formate with the solvent content up to 95%. As a result, various phenolic polymers with average molecular weights from 400 to 2.6 x 10/sup 4/ D were obtained depending on the reaction medium composition and the nature of the phenol. Peroxidase-catalyzed copolymerization of different phenols in 85% dioxane was demonstrated. Poly(p-phenylphenol) and poly(p-cresol) were enzymatically prepared on a gram scale. They had much higher melting points, and in addition, poly(p-phenylphenol) was found to have a much higher electrical conductivity than phenol-formaldehyde resins.

  7. Effect of urate on the lactoperoxidase catalyzed oxidation of adrenaline. (United States)

    Løvstad, Rolf A


    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. Cascade reactions catalyzed by metal organic frameworks. (United States)

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo


    Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

  9. 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.


    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.

  10. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions. (United States)

    Ishoey, Mette; Nielsen, Thomas E


    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.

  11. Silver-Catalyzed C(sp(3))-H Chlorination. (United States)

    Ozawa, Jun; Kanai, Motomu


    A silver-catalyzed chlorination of benzylic, tertiary, and secondary C(sp(3))-H bonds was developed. The reaction proceeded with as low as 0.2 mol % catalyst loading at room temperature under air atmosphere with synthetically useful functional group compatibility. The regioselectivity and reactivity tendencies suggest that the chlorination proceeded through a radical pathway, but an intermediate alkylsilver species cannot be ruled out.

  12. Predictive Modeling of Metal-Catalyzed Polyolefin Processes


    Khare, Neeraj Prasad


    This dissertation describes the essential modeling components and techniques for building comprehensive polymer process models for metal-catalyzed polyolefin processes. The significance of this work is that it presents a comprehensive approach to polymer process modeling applied to large-scale commercial processes. Most researchers focus only on polymerization mechanisms and reaction kinetics, and neglect physical properties and phase equilibrium. Both physical properties and phase equilib...

  13. Comparing Ru and Fe-catalyzed olefin metathesis. (United States)

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


    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.

  14. Biodiesel by acid-catalyzed transesterification with butanol


    Bynes, Adrian


    Jatropha oil and Rapeseed oil was transesterified with n-butanol by the use of H2SO4. Before conducting the experiments a review of the effect of alcohol type was preformed. Alcohols from methanol to butanol, branched and straight, were reviewed for the effect on the acid catalyzed transesterification reaction. From the review it was found that propanol and butanol were the best for the acidic transesterification reaction. Variables such as time, temperature, alcohol amount and catalyst c...

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

    DEFF Research Database (Denmark)

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


    937 cell lysates, had the same amino termini as uPAR(2+3), generated by uPA in a purified system. In both cases cleavage had occurred at two positions in the hinge region connecting domain 1 and 2, between Arg83-Ala84 and Arg89-Ser90, respectively. The uPA-catalyzed cleavage of uPAR is a new negative...

  16. Synthesis of Optically Active Polystyrene Catalyzed by Monophosphine Pd Complexes. (United States)

    Jouffroy, Matthieu; Armspach, Dominique; Matt, Dominique; Osakada, Kohtaro; Takeuchi, Daisuke


    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.

  17. Gold-catalyzed oxidative cycloadditions to activate a quinoline framework. (United States)

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


    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.

  18. Lactoperoxidase-catalyzed activation of carcinogenic aromatic and heterocyclic amines. (United States)

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


    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.

  19. 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


    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

  20. Cobalt-catalyzed formation of symmetrical biaryls and its mechanism. (United States)

    Moncomble, Aurélien; Le Floch, Pascal; Gosmini, Corinne


    Effective devotion: An efficient cobalt-catalyzed method devoted to the formation of symmetrical biaryls is described avoiding the preparation of organometallic reagents. Various aromatic halides functionalized by a variety of reactive group reagents are employed. Preliminary DFT calculations have shown that the involvement of a Co(I)/Co(III) couple is realistic at least in the case of 1,3-diazadienes as ligands (FG = functional group).

  1. Aluminum-catalyzed silicon nanowires: Growth methods, properties, and applications (United States)

    Hainey, Mel F.; Redwing, Joan M.


    Metal-mediated vapor-liquid-solid (VLS) growth is a promising approach for the fabrication of silicon nanowires, although residual metal incorporation into the nanowires during growth can adversely impact electronic properties particularly when metals such as gold and copper are utilized. Aluminum, which acts as a shallow acceptor in silicon, is therefore of significant interest for the growth of p-type silicon nanowires but has presented challenges due to its propensity for oxidation. This paper summarizes the key aspects of aluminum-catalyzed nanowire growth along with wire properties and device results. In the first section, aluminum-catalyzed nanowire growth is discussed with a specific emphasis on methods to mitigate aluminum oxide formation. Next, the influence of growth parameters such as growth temperature, precursor partial pressure, and hydrogen partial pressure on nanowire morphology is discussed, followed by a brief review of the growth of templated and patterned arrays of nanowires. Aluminum incorporation into the nanowires is then discussed in detail, including measurements of the aluminum concentration within wires using atom probe tomography and assessment of electrical properties by four point resistance measurements. Finally, the use of aluminum-catalyzed VLS growth for device fabrication is reviewed including results on single-wire radial p-n junction solar cells and planar solar cells fabricated with nanowire/nanopyramid texturing.

  2. Protection of wood from microorganisms by laccase-catalyzed iodination. (United States)

    Schubert, M; Engel, J; Thöny-Meyer, L; Schwarze, F W M R; Ihssen, J


    In the present work, Norway spruce wood (Picea abies L.) was reacted with a commercial Trametes versicolor laccase in the presence of potassium iodide salt or the phenolic compounds thymol and isoeugenol to impart an antimicrobial property to the wood surface. In order to assess the efficacy of the wood treatment, a leaching of the iodinated and polymerized wood and two biotests including bacteria, a yeast, blue stain fungi, and wood decay fungi were performed. After laccase-catalyzed oxidation of the phenols, the antimicrobial effect was significantly reduced. In contrast, the enzymatic oxidation of iodide (I(-)) to iodine (I(2)) in the presence of wood led to an enhanced resistance of the wood surface against all microorganisms, even after exposure to leaching. The efficiency of the enzymatic wood iodination was comparable to that of a chemical wood preservative, VP 7/260a. The modification of the lignocellulose by the laccase-catalyzed iodination was assessed by the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique. The intensities of the selected lignin-associated bands and carbohydrate reference bands were analyzed, and the results indicated a structural change in the lignin matrix. The results suggest that the laccase-catalyzed iodination of the wood surface presents an efficient and ecofriendly method for wood protection.

  3. Enzyme-catalyzed biocathode in a photoelectrochemical biofuel cell (United States)

    Yang, Jing; Hu, Donghua; Zhang, Xiaohuan; Wang, Kunqi; Wang, Bin; Sun, Bo; Qiu, Zhidong


    A novel double-enzyme photoelectrochemical biofuel cell (PEBFC) has been developed by taking glucose dehydrogenase (GDH) and horseradish peroxidase (HRP) as the enzyme of the photoanode and biocathode to catalyze the oxidation of glucose and the reduction of oxygen. A H2-mesoporphyrin IX is used as a dye for a TiO2 film electrode to fabricate a photoanode. The horseradish peroxidase (HRP) is immobilized on a glassy carbon (GC) electrode to construct a biocathode which is used to catalyze the reduction of oxygen in the PEBFC for the first time. The biocathode exhibits excellent electrocatalytic activity in the presence of O2. The performances of the PEBFC are obtained by current-voltage and power-voltage curves. The short-circuit current density (Isc), the open-circuit voltage (Voc), maximum power density (Pmax), fill factor (FF) and energy conversion efficiency (η) are 439 μA cm-2, 678 mV, 79 μW cm-2, 0.39 and 0.016%, respectively, and the incident photon-to-collected electron conversion efficiency (IPCE) is 32% at 350 nm. The Isc is higher than that of the PEBFC with Pt cathode, and the Voc is higher than that of the dye-sensitized solar cell or the enzyme-catalyzed biofuel cell operating individually, which demonstrates that the HRP is an efficient catalyst for the biocathode in the PEBFC.

  4. Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization. (United States)

    Joshi, Prachi; Gorski, Christopher A


    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.

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

    Institute of Scientific and Technical Information of China (English)

    XU Wenying; LI Ping; FAN Jinhong


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Muenchausen, R.E.


    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.

  7. Properties of CdTe layers deposited by a novel method -Pulsed Plasma Deposition


    Ancora, C.; Nozar, P.; Mittica, G.; Prescimone, F.; A. Neri; Contaldi, S.; Milita, S.; Albonetti, C.; Corticelli, F.; Brillante, A.; Bilotti, I.; Tedeschi, G.; Taliani, C.


    CdTe and CdS are emerging as the most promising materials for thin film photovoltaics in the quest of the achievement of grid parity. The major challenge for the advancement of grid parity is the achievement of high quality at the same time as low fabrication cost. The present paper reports the results of the new deposition technique, Pulsed Plasma Deposition (PPD), for the growth of the CdTe layers on CdS/ZnO/quartz and quartz substrates. The PPD method allows to deposit at low temperature. ...

  8. Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory (United States)

    Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles


    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…

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

    Energy Technology Data Exchange (ETDEWEB)

    Galeazzi, M. E-mail:; Chen, C.; Cohn, J.L.; Gundersen, J.O


    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.

  10. Synthetic Study of Dragmacidin E: Construction of the Core Structure Using Pd-Catalyzed Cascade Cyclization and Rh-Catalyzed Aminoacetoxylation. (United States)

    Inoue, Naoya; Nakano, Shun-Ichi; Harada, Shingo; Hamada, Yasumasa; Nemoto, Tetsuhiro


    We developed a novel synthetic method of the core structure of dragmacidin E bearing a 7-membered ring-fused bis(indolyl)pyrazinone skeleton. Formation of the 7-membered ring-fused tricyclic indole skeleton was accomplished using a palladium-catalyzed Heck insertion-allylic amination cascade. Vicinal difunctionalization of the 7-membered ring was realized via a rhodium-catalyzed aminoacetoxylation.

  11. Enzyme-Catalyzed Synthesis of Water-Soluble Conjugated Poly[2-(3-thienyl-Ethoxy-4-Butylsulfonate

    Directory of Open Access Journals (Sweden)

    Yun Zhao


    Full Text Available An environmentally friendly water-soluble conjugated polythiophene poly[2-(3-thienyl-ethoxy-4-butylsulfonate] (PTEBS has been found to be effective for making hybrid solar cells. In this work, we first report the enzyme-catalyzed polymerization of (3-thienyl-ethoxy-4-butylsulfonate (TEBS using horseradish peroxidase (HRP enzyme as a catalyst and hydrogen peroxide (H2O2 as an oxidant in an aqueous buffer. This enzyme-catalyzed polymerization is a “green synthesis process” for the synthesis of water-soluble conjugated PTEBS, the benefits of which include a simple setting, high yields, and an environmentally friendly route. Fourier transform infrared spectra (FTIR and UV–Vis absorption spectra confirm the successful enzyme-catalyzed polymerization of TEBS. The thermo gravimetric (TG data show the obtained PTEBS is stable over a fairly high range of temperatures. The present PTEBS has a good solubility in water and ethanol, and photoluminescence quenching of PTEBS/titanium dioxide (TiO2 composite implies that the excitons dissociate and separate successfully at the interface of PTEBS and TiO2, which help to build solar cells using green processing methods.

  12. Cobalt(III)-catalyzed synthesis of indazoles and furans by C-H bond functionalization/addition/cyclization cascades. (United States)

    Hummel, Joshua R; Ellman, Jonathan A


    The development of operationally straightforward and cost-effective routes for the assembly of heterocycles from simple inputs is important for many scientific endeavors, including pharmaceutical, agrochemical, and materials research. In this article we describe the development of a new air-stable cationic Co(III) catalyst for convergent, one-step benchtop syntheses of N-aryl-2H-indazoles and furans by C-H bond additions to aldehydes followed by in situ cyclization and aromatization. Only a substoichiometric amount of AcOH is required as an additive that is both low-cost and convenient to handle. The syntheses of these heterocycles are the first examples of Co(III)-catalyzed additions to aldehydes, and reactions are demonstrated for a variety of aromatic, heteroaromatic, and aliphatic derivatives. The syntheses of both N-aryl-2H-indazoles and furans have been performed on 20 mmol scales and should be readily applicable to larger scales. The reported heterocycle syntheses also demonstrate the use of directing groups that have not previously been applied to Co(III)-catalyzed C-H bond functionalizations. Additionally, the synthesis of furans demonstrates the first example of Co(III)-catalyzed functionalization of alkenyl C-H bonds.

  13. Deposition of copper selenide thin films and nanoparticles (United States)

    Hu, Yunxiang; Afzaal, Mohammad; Malik, Mohammad A.; O'Brien, Paul


    A new method is reported for the growth of copper selenide thin films and nanoparticles using copper acetylacetonate and trioctylphosphine selenide. Aerosol-assisted chemical vapor deposition experiments lead to successful deposition of tetragonal Cu 2Se films. In contrast, hexadecylamine capped nanoparticles are composed of cubic Cu 2-xSe. The deposited materials are optically and structurally characterized. The results of this comprehensive study are described and discussed.

  14. Electro-Spark Deposited Coatings for Replacement of Chrome Electroplating (United States)


    Wear and Corrosion: the Electrospark Deposition Process", published in Proceedings, American Electroplaters and Surface Finishers Society, Jan. 2002. 6...Johnson, R.N., " ElectroSpark Deposition : Principals and Applications", Society of Vacuum Coaters 45th Annual Technical Conference Proceedings, Apr...AD AD-E403 050 Contractor Report ARAET-CR-05002 ELECTRO-SPARK DEPOSITED COATINGS FOR REPLACEMENT OF CHROME PLATING R. N. Johnson J. A. Bailey Pacific

  15. Bismuth-catalyzed and doped silicon nanowires for one-pump-down fabrication of radial junction solar cells. (United States)

    Yu, Linwei; Fortuna, Franck; O'Donnell, Benedict; Jeon, Taewoo; Foldyna, Martin; Picardi, Gennaro; Roca i Cabarrocas, Pere


    Silicon nanowires (SiNWs) are becoming a popular choice to develop a new generation of radial junction solar cells. We here explore a bismuth- (Bi-) catalyzed growth and doping of SiNWs, via vapor-liquid-solid (VLS) mode, to fabricate amorphous Si radial n-i-p junction solar cells in a one-pump-down and low-temperature process in a single chamber plasma deposition system. We provide the first evidence that catalyst doping in the SiNW cores, caused by incorporating Bi catalyst atoms as n-type dopant, can be utilized to fabricate radial junction solar cells, with a record open circuit voltage of V(oc) = 0.76 V and an enhanced light trapping effect that boosts the short circuit current to J(sc) = 11.23 mA/cm(2). More importantly, this bi-catalyzed SiNW growth and doping strategy exempts the use of extremely toxic phosphine gas, leading to significant procedure simplification and cost reduction for building radial junction thin film solar cells.


    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...

  17. Development and industrial application of catalyzer for low-temperature hydrogenation hydrolysis of Claus tail gas

    Directory of Open Access Journals (Sweden)

    Honggang Chang


    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%.

  18. 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)


    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.

  19. An ab initio study of the nickel-catalyzed transformation of amorphous carbon into graphene in rapid thermal processing (United States)

    Chen, Shuang; Xiong, Wei; Zhou, Yun Shen; Lu, Yong Feng; Zeng, Xiao Cheng


    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

  20. Ruthenium-Catalyzed Transformations of Alcohols: Mechanistic Investigations and Methodology Development

    DEFF Research Database (Denmark)

    Makarov, Ilya; Madsen, Robert; Fristrup, Peter

    in the transition state of the turnover-determining step. The value of the kinetic isotope effect of 2.290.15 indicated that the C–H bond breakage is not the rate-determining step, but that it is one of several slow steps in the catalytic cycle. Experiments with deuterium-labeled alcohols and amines revealed......The mechanism of the ruthenium-catalyzed dehydrogenative synthesis of amides from alcohols and amines was studied in detail by employing the combination of experimental and theoretical techniques. The Hammett study revealed that a small positive charge is formed at the benzylic position...... alcohols to give esters. Addition of 16.7 mol% of Mg3N2 to the reaction mixture gave esters from aliphatic alcohols in similar yields but at lower temperature as compared with previously a reported catalytic system. This additive also suppressed the decarbonylation of aromatic alcohols. A previously...

  1. Palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to a library of tetraphenylenes (United States)

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


    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.

  2. Ag-catalyzed InAs nanowires grown on transferable graphite flakes (United States)

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


    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.

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

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


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

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.


    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...

  5. 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


    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.

  6. Effect of temperature in cerium-ion-catalyzed bromate-driven oscillators (United States)

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


    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.

  7. A Convenient Synthesis of Conjugated Acetylenic Ketones by Copper(l)-Catalyzed under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)


    @@ 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.

  8. 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:, E-mail: [School of Materials Science and Engineering, Nanyang Technological University, 639798 (Singapore)


    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.

  9. 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


    @@ 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.

  10. An ab initio study of the nickel-catalyzed transformation of amorphous carbon into graphene in rapid thermal processing. (United States)

    Chen, Shuang; Xiong, Wei; Zhou, Yun Shen; Lu, Yong Feng; Zeng, Xiao Cheng


    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.

  11. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis. (United States)

    McCann, Scott D; Stahl, Shannon S


    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.

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


    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.

  13. Granitoid intrusions and related deposits

    Institute of Scientific and Technical Information of China (English)

    孟良义; 李绪俊


    Taking the Bainaimiao copper and gold deposits, Inner Mongolia and the Wushan copper deposits, Jiangxi Province as examples, a discussion is devoted to the relationship between the granitoid intrusions and related deposits from different lines of evidence: the spatial distribution, country rocks and alteration of the deposits, trace element contents and vertical zoning of elements in deposits, the metallogenic preference of granitoid intrusions, the metallogenic models and stable isotopic geology. It is concluded that the ore-bearing fluids mainly come from granitoid magmas and granitoid intrusions are closely associated with the related deposits in space.

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

    DEFF Research Database (Denmark)

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


    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......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 configuration enables a gentle treatment of sensitive materials like low-density polyethylene foils and biodegradable materials. SiOx coatings deposited in the novel setup were compared with other state of the art plasma coatings and were found to possess equally good or better barrier properties. The barrier...... effect of single-layer coatings deposited under different reaction conditions was studied. The coating thickness and the carbon content in the coatings were found to be the critical parameters for the barrier property. The novel barrier coating was applied on different polymeric materials...

  15. 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)


    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.

  16. 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


    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.

  17. On the Temperature Dependence of Enzyme-Catalyzed Rates. (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


    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.

  18. Theoretical Study of the Effects of Di-Muonic Molecules on Muon-Catalyzed Fusion (United States)


    MOLECULES ON MUON -CATALYZED FUSION DISSERTATION Eugene V. Sheely, Lieutenant Colonel, USA DEPARTMENT OF THE AIR FORCE AIR UNIVERSITY...THEORETICAL STUDY OF THE EFFECTS OF DI-MUONIC MOLECULES ON MUON -CATALYZED FUSION DISSERTATION Presented to the Faculty...potential of enhancing the muon -catalyzed fusion reaction rate. In order to study these di-muonic molecules a method of non-adiabatic quantum mechanics

  19. Lipase-catalyzed enantioselective esterification of flurbiprofen with n-butanol



    The influences of water activity and solvent hydrophobicity on the kinetics of the lipase-catalyzed enantioselective esterification of flurbiprofen with n-butanol were investigated. The solvent effect was not similar for lipases from Candida rugosa (Crl), Mucor javanicus (Mjl), and porcine pancreas (Ppl). The lipase-catalyzed reaction rates in different solvents across a wide range of water activities revealed that the Ppl-catalyzed reaction exhibited no enantioselectivity and no substantial ...

  20. High-energy high-rate pulsed-power processing of materials by powder consolidation and by railgun deposition. Technical report (Final), 10 April 1985-10 February 1987

    Energy Technology Data Exchange (ETDEWEB)

    Persad, C.; Marcus, H.L.; Weldon, W.F.


    This exploratory research program was initiated to investigate the potential of using pulse power sources for powder consolidation, deposition and other high-energy high-rate processing. The characteristics of the high-energy-high-rate (1MJ/s) powder consolidation using megampere current pulses from a homopolar generator, were defined. Molybdenum Alloy TZM, a nickel-based metallic glass, copper/graphite composites, and P/M aluminum alloy X7091 were investigated. The powder-consolidation process produced high densification rates. Density values of 80% to 99% could be obtained with subsecond high-temperature exposure. Specific energy input and applied pressure were controlling process parameters. Time temperature transformation (TTT) concepts underpin a fundamental understanding of pulsed power processing. Inherent control of energy input, and time-to-peak processing temperature developed to be held to short times. Deposition experiments were conducted using an exploding-foil device (EFD) providing an armature feed to railgun mounted in a vacuum chamber. The material to be deposited - in plasma, gas, liquid, or solid state - was accelerated electromagnetically in the railgun and deposited on a substrate. Deposits of a wide variety of single- and multi-specie materials were produced on several types of substrates. In a series of ancillary experiments, pulsed-skin-effect heating and self quenching of metallic conductors was discovered to be a new means of surface modification by high-energy high-rate-processing.

  1. Facile Rh(III)-Catalyzed Synthesis of Fluorinated Pyridines (United States)

    Chen, Shuming; Bergman, Robert G.; Ellman, Jonathan A.


    A Rh(III)-catalyzed C–H functionalization approach was developed for the preparation of multi-substituted 3-fluoropyridines from α-fluoro-α,β-unsaturated oximes and alkynes. Oximes substituted with aryl, heteroaryl and alkyl β-substituents were effective coupling partners, as were symmetrical and unsymmetrical alkynes with aryl and alkyl substituents. The first examples of coupling α,β-unsaturated oximes with terminal alkynes was also demonstrated and proceeded with uniformly high regioselectivity to provide single 3-fluoropyridine regioisomers. Reactions were also conveniently set up in air on the bench top. PMID:25992591

  2. Rhodium catalyzed asymmetric Pauson-Khand reaction using SDP ligands

    Institute of Scientific and Technical Information of China (English)


    The activity and enantiocontrol ability of the chiral catalysts prepared from spiro diphosphine ligands, SDP, and rhodium precursor were investigated in the asymmetric catalytic Pauson-Khand reaction. The results showed that SDP ligands were very effective in Rh-catalyzed Pauson-Khand reaction, and their complexes with rhodium could convert a variety of 1,6-enyne compounds into bicyclopentone derivatives under CO atmosphere in high yields with good enantioselectivities. The SbF6- was found to be a suitable counter anion of the catalyst, and 1,2-dichloroethane was the best choice of the solvent for Pauson-Khand reaction.

  3. Kinetics of acid-catalyzed cleavage of cumene hydroperoxide. (United States)

    Levin, M E; Gonzales, N O; Zimmerman, L W; Yang, J


    The cleavage of cumene hydroperoxide, in the presence of sulfuric acid, to form phenol and acetone has been examined by adiabatic calorimetry. As expected, acid can catalyze cumene hydroperoxide reaction at temperatures below that of thermally-induced decomposition. At elevated acid concentrations, reactivity is also observed at or below room temperature. The exhibited reactivity behavior is complex and is significantly affected by the presence of other species (including the products). Several reaction models have been explored to explain the behavior and these are discussed.

  4. FBH1 Catalyzes Regression of Stalled Replication Forks

    DEFF Research Database (Denmark)

    Fugger, Kasper; Mistrik, Martin; Neelsen, Kai J;


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

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


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


    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 conformity bias. We modified the Technology Acceptance Model (TAM) to include conformity bias. We then qualitatively applied the model to three examples from the literature, namely fuel stoves in Darfu...

  6. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert


    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.

  7. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  8. Lipase-catalyzed synthesis of monoacylglycerol in a homogeneous system. (United States)

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


    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.

  9. 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: [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental


    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)

  10. Production of Chemoenzymatic Catalyzed Monoepoxide Biolubricant: Optimization and Physicochemical Characteristics


    Jumat Salimon; Nadia Salih; Bashar Mudhaffar Abdullah


    Linoleic acid (LA) is converted to per-carboxylic acid catalyzed by an immobilized lipase from Candida antarctica (Novozym 435). This per-carboxylic acid is only intermediate and epoxidized itself in good yields and almost without consecutive reactions. Monoepoxide linoleic acid 9(12)-10(13)-monoepoxy 12(9)-octadecanoic acid (MEOA) was optimized using D-optimal design. At optimum conditions, higher yield% (82.14) and medium oxirane oxygen content (OOC) (4.91%) of MEOA were predicted at 15 μL ...

  11. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Roman Vladimirovich Rozhkov


    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a {beta}-hydrogen in the vinylic halide results in {beta}-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the {alpha}-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  12. 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


    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.

  13. Deoxyribonucleoside kinases: two enzyme families catalyze the same reaction

    DEFF Research Database (Denmark)

    Sandrini, Michael; Piskur, Jure


    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....

  14. Scaling in film growth by pulsed laser deposition and modulated beam deposition. (United States)

    Lee, Sang Bub


    The scalings in film growth by pulsed laser deposition (PLD) and modulated beam deposition (MBD) were investigated by Monte Carlo simulations. In PLD, an atomic pulse beam with a period t(0) were deposited instantaneously on a substrate, whereas in MBD, adatoms were deposited during a short time interval t(1) (0≤t(1)≤t(0)) within each period. If t(1)=0, MBD will be identical to PLD and, if t(1)=t(0), MBD will become usual molecular beam epitaxy (MBE). Specifically, logarithmic scaling was investigated for the nucleation density reported for PLD, and the scaling of island density was studied regarding the growth for 0MBE growth was observed as t(1) increased. The phase diagram was also presented.

  15. Microstructural and Electrical Characterization of Barium Strontium Titanate-Based Solid Solution Thin Films Deposited on Ceramic Substrates by Pulsed Laser Deposition (United States)


    Strontium Titanate-Based Solid Solution Thin Films Deposited on Ceramic Substrates by Pulsed Laser Deposition DISTRIBUTION: Approved for public...Society H2.4 Microstructural and Electrical Characterization of Barium Strontium Titanate- based Solid Solution Thin Films Deposited on Ceramic...investigated and report the microstructural and electrical characterization of selected barium strontium titanate-based solid solution thin films

  16. 78 FR 56583 - Deposit Insurance Regulations; Definition of Insured Deposit (United States)


    ... depositor has ever lost a penny of an insured deposit. The Federal Deposit Insurance Act (``FDI Act'') \\1... could affect deposits in a particular location. \\1\\ 12 U.S.C. 1811, et seq. \\2\\ See FDI Act section 11(f...(l) of the FDI Act.\\3\\ Since the establishment of the FDIC in 1933, Congress has made...

  17. Inkjet deposited circuit components (United States)

    Bidoki, S. M.; Nouri, J.; Heidari, A. A.


    All-printed electronics as a means of achieving ultra-low-cost electronic circuits has attracted great interest in recent years. Inkjet printing is one of the most promising techniques by which the circuit components can be ultimately drawn (i.e. printed) onto the substrate in one step. Here, the inkjet printing technique was used to chemically deposit silver nanoparticles (10-200 nm) simply by ejection of silver nitrate and reducing solutions onto different substrates such as paper, PET plastic film and textile fabrics. The silver patterns were tested for their functionality to work as circuit components like conductor, resistor, capacitor and inductor. Different levels of conductivity were achieved simply by changing the printing sequence, inks ratio and concentration. The highest level of conductivity achieved by an office thermal inkjet printer (300 dpi) was 5.54 × 105 S m-1 on paper. Inkjet deposited capacitors could exhibit a capacitance of more than 1.5 nF (parallel plate 45 × 45 mm2) and induction coils displayed an inductance of around 400 µH (planar coil 10 cm in diameter). Comparison of electronic performance of inkjet deposited components to the performance of conventionally etched items makes the technique highly promising for fabricating different printed electronic devices.

  18. Enantioselective Cyclopropanation of a Wide Variety of Olefins Catalyzed by Ru(II)-Pheox Complexes. (United States)

    Chanthamath, Soda; Iwasa, Seiji


    The transition-metal-catalyzed asymmetric cyclopropanation of olefins with diazoacetates has become one of the most important methods for the synthesis of optically active cyclopropane derivatives, which are key pharmaceutical building blocks and present in a large number of natural products. To date, significant progress has been made in this area of research, and efficient stereocontrolled synthetic approaches to cyclopropane derivatives have been developed using rhodium, ruthenium, copper, and cobalt catalysts. However, the vast majority of these strategies are limited to electron-rich olefins, such as styrene derivatives, due to the electrophilicity of the metal-carbene intermediates generated from the reaction of the metal with the diazo compound. Recently, the D2-symmetric Co(II)-phophyrin complexes developed by Zhang et al. were shown to be the most efficient catalysts for the asymmetric cyclopropanation of electron-deficient olefins. This catalytic system is mechanistically distinct from the previous rhodium and copper catalytic systems, proceeding via radical intermediates. However, the asymmetric cyclopropanation of vinyl carbamates, allenes, and α,β-unsaturated carbonyl compounds has rarely been reported. Therefore, the development of new powerful catalysts for the asymmetric cyclopropanation of a wide range of olefinic substrates is the next challenge in this field. In this Account, we summarize our recent studies on the Ru(II)-Pheox-catalyzed asymmetric cyclopropanation of various olefins, including vinyl carbamates, allenes, and α,β-unsaturated carbonyl compounds. We demonstrate that the developed catalytic system effectively promotes the asymmetric cyclopropanation of a wide variety of olefins to produce the desired cyclopropane products in high yields with excellent stereocontrol. The use of succinimidyl-, ketone-, and ester-functionalized diazoacetates as carbene sources was found to be crucial for the high stereoselectivity of the

  19. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Directory of Open Access Journals (Sweden)

    Marcio J. da Silva


    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.

  20. Human glutathione transferases catalyzing the conjugation of the hepatoxin microcystin-LR. (United States)

    Buratti, Franca M; Scardala, Simona; Funari, Enzo; Testai, Emanuela


    Many cyanobacterial species are able to produce cyanotoxins as secondary metabolites. Among them, microcystins (MC) are a group of around 80 congeners of toxic cyclic heptapeptides. MC-LR is the most studied MC congener, in view of its high acute hepatotoxicity and tumor promoting activity. Humans may be exposed to cyanotoxins through several routes, the oral one being the most important. The accepted pathway for MC-LR detoxication and excretion in the urine is GSH conjugation. The GSH adduct (GS-MCLR) formation has been shown to occur spontaneously and enzymatically, catalyzed by glutathione transferases (GSTs). The enzymatic reaction has been reported but not characterized both in vitro and in vivo in animal and plant species. No data are available on humans. In the present work, the MC-LR conjugation with GSH catalyzed by five recombinant human GSTs (A1-1, A3-3, M1-1, P1-1, and T1-1) has been characterized for the first time. All GSTs are able to catalyze the reaction; kinetic parameters K(m), k(cat), and their relative specific activities to form GS-MCLR were derived (T1-1 > A1-1 > M1-1 > A3-3 ≫ P1-1). In the range of MC tested concentrations used (0.25-50 μM) GSTT1-1 and A1-1 showed a typical saturation curve with similar affinity for MC-LR (≈80 μM; k(cat) values 0.18 and 0.10 min(-1), respectively), A3-3 and M1-1 were linear, whereas GSTP1-1 showed a temperature-dependent sigmoidal allosteric curve with a k(cat) = 0.11 min(-1). The enzymes mainly expressed in the liver and gastrointestinal tract, GSTA1-1, T1-1, and M1-1, seemed to be mainly involved in the MC-LR detoxification after oral exposure, whereas P1-1 kinetics and location in the skin suggest a role related to dermal exposure. Considering the high frequency of some GST polymorphism, especially M1 and T1 gene deletion, with complete loss in activity, this information could be the first step to identify groups of individual at higher risk associated with MC exposure.

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

    Directory of Open Access Journals (Sweden)

    Ronald Okoth


    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.

  2. Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step. (United States)

    Jayakumar, Jayachandran; Cheng, Chien-Hong


    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.

  3. Origin of stereoselectivity in a chiral N-heterocyclic carbene-catalyzed desymmetrization of substituted cyclohexyl 1,3-diketones. (United States)

    Reddi, Yernaidu; Sunoj, Raghavan B


    The mechanism and stereoselectivity in a chiral N-heterocyclic carbene-catalyzed desymmetrization of a 1,3-diketone is established by using density functional theory computations. The Breslow intermediate formation is identified to involve Hunig's base-assisted proton transfer. The relative energies of stereoselectivity-determining intramolecular aldol cyclization transition states reveal that in the most preferred mode the re-face of enolate adds to the si-face of carbonyl leading to a tricyclic lactone with a configuration (2aS,4aS,8'S) in excellent agreement with previous experimental reports.

  4. Chemical syntheses of inhibitory substrates of the RNA-RNA ligation reaction catalyzed by the hairpin ribozyme. (United States)

    Massey, Archna P; Sigurdsson, Snorri Th


    The chemical syntheses of RNA oligomers containing modifications on the 5'-carbon of the 5'-terminal nucleoside for crystallographic and mechanistic studies of the hairpin ribozyme are reported. Phosphoramidites 4 and 8 were prepared and used in solid phase syntheses of RNA oligomers containing the sequence 5'-N'UCCUCUCC, where N' indicates either 5'-chloro-5'-deoxyguanosine or 5'-amino-5'-deoxyguanosine, respectively. A ribozyme ligation assay with the 5'-chloro- and 5'-amino-modified RNA oligomers demonstrated their inhibition of the hairpin-catalyzed RNA-RNA ligation reaction.

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

  6. Intraosseous tophus deposits in the os trigonum. (United States)

    Ercin, Ersin; Gamsizkan, Mehmet; Avsar, Serdar


    High levels of uric acid cause accumulation of monosodium urate crystals. This formation of masses is called tophus. Intraosseous tophus deposits are rare, even for patients with gout. We report an unusual case of intraosseous tophus deposits in the os trigonum. The patient presented with ankle pain with no previous history of gout. On examination, tenderness on the posterior aspect of his ankle and limitation of plantarflexion was noted. Laboratory values were normal, except for an elevated serum uric acid value. Radiographs of the right ankle showed the presence of a large os trigonum with osteosclerotic changes, whereas magnetic resonance imaging showed intraosseous tophus deposits in the os trigonum. Conservative therapy failed, and the patient was admitted for an endoscopic resection of the os trigonum.Intraosseous chalky crystals were detected during endoscopic resection of the os trigonum. The histological diagnosis was tophaceous gout. The underlying pathological mechanism of intraosseous tophi is uncertain. Penetration of urate crystals from the joint due to hyperuricemia may be the mechanism of deposition in this patient.When a patient with hyperuricemia presents with posterior ankle impingement symptoms, intraosseous tophus deposits should be included in the differential diagnosis. Posterior endoscopic excision may be an option for treating intraosseous lesions of the os trigonum because of good visualization, satisfactory excision, and rapid recovery time.

  7. Development of Copper-Catalyzed Electrophilic Trifluoromethylation and Exploiting Cu/Cu2O Nanowires with Novel Catalytic Reactivity

    KAUST Repository

    Li, Huaifeng


    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.

  8. Metal-catalyzed electroless etching and nanoimprinting silicon nanowire-based solar cells: Silicon nanowire defect reduction and efficiency enhancement by two-step H2 annealing (United States)

    Jevasuwan, Wipakorn; Nakajima, Kiyomi; Sugimoto, Yoshimasa; Fukata, Naoki


    The effects of H2 annealing on material properties including defects of silicon nanowire (SiNW) surface and Si film layer for solar cell application were investigated. Single-junction solar cells consisting of n-SiNWs and chemical vapor deposition grown p-Si matrix were demonstrated using two-step H2 annealing. n-SiNWs formed by two different methods of metal-catalyzed electroless etching and nanoimprinting followed by the Bosch process were compared. Two-step H2 annealing at 900 °C for 10 min after both n-SiNW formations and subsequent p-Si matrix deposition effectively improved SiNW surface and p-Si crystallinity, resulting in higher solar cell efficiency.

  9. Study of microwave effects on the lipase-catalyzed hydrolysis. (United States)

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


    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.

  10. Metalloporphyrin solubility: a trigger for catalyzing reductive dechlorination of tetrachloroethylene. (United States)

    Dror, Ishai; Schlautman, Mark A


    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.

  11. Enzyme catalyzed electricity-driven water softening system. (United States)

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


    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.

  12. Ozonation of Indigo Carmine Catalyzed with Fe-Pillared Clay

    Directory of Open Access Journals (Sweden)

    Miriam Bernal


    Full Text Available The ozonation catalyzed by iron-pillared clays was studied. The degradation of dye indigo carmine (IC was elected as test reaction. Fe-pillared clays were synthesized by employing hydrolyzed FeCl3 solutions and bentonite. The pillared structure was verified by XRD and by XPS the oxidation state of iron in the synthesized material was established to be +2. By atomic absorption the weight percentage of iron was determined to be 16. The reaction was conducted in a laboratory scale up-flow bubble column reactor. From the studied variables the best results were obtained with a particle size of 60 microns, pH=3, ozone flow of 0.045 L/min, and catalyst concentration of 100 mg/L. IC was completely degraded and degradation rate was found to be double when using Fe-PILCS than with ozone alone. DQO reduction was also significantly higher with catalyzed than with noncatalyzed ozonation.

  13. Thermodynamics of Enzyme-Catalyzed Reactions: Part 1. Oxidoreductases (United States)

    Goldberg, Robert N.; Tewari, Yadu B.; Bell, Donna; Fazio, Kari; Anderson, Ellen


    Equilibrium constants and enthalpy changes for reactions catalyzed by oxidoreductases have been compiled. For each reaction the following information is given: the reference for the data; the reaction studied; the name of the enzyme used and its Enzyme Commission number; the method of measurement; the conditions of measurement (temperature, pH, ionic strength, and the buffer(s) and cofactor(s) used); the data and an evaluation of it; and, sometimes, commentary on the data and on any corrections which have been applied to it. The thermodynamic conventions pertinent to the tabulation of equilibrium data are discussed. A distinction is made between those thermodynamic quantities which pertain to the overall biochemical reaction and those which pertain to a reference reaction that involves specific species. The data from 205 references have been examined and evaluated. Chemical Abstract Service Registry Numbers have been assigned to the substances involved in these various reactions. There is a cross reference between the substances and the Enzyme Commission numbers of the enzymes used to catalyze the reactions in which the substances participated.

  14. 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


    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.

  15. Lipase-catalyzed polyester synthesis – A green polymer chemistry (United States)

    Kobayashi, Shiro


    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

  16. Lipase-catalyzed polyester synthesis--a green polymer chemistry. (United States)

    Kobayashi, Shiro


    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 chemoenzymatic 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'.

  17. Compilation of gallium resource data for bauxite deposits (United States)

    Schulte, Ruth F.; Foley, Nora K.


    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

  18. Deposition and tribological behaviour of sputtered carbon hard coatings

    Energy Technology Data Exchange (ETDEWEB)

    Yang, S.; Camino, D.; Jones, A.H.S.; Teer, D.G. [Teer Coatings Ltd., Hartlebury (United Kingdom)


    The exceptional tribological properties of low deposition temperature sputtered carbon coatings (Graphit-iC coatings) have been recently reported. This paper describes the latest development of these coatings and particularly how, by an optimisation of the deposition parameters, it has been possible to obtain relative soft to very hard coatings with extremely low specific wear rates. The coatings have been deposited in a closed field unbalanced magnetron sputter ion plating (CFUBMSIP) installation. By applying the appropriate conditions of deposition, carbon coatings with hardness from 1500 to 4000 HV can be routinely deposited. Preliminary analytical results are presented in order to characterise such hard coatings: high-resolution transmission electron microscopy, scanning electron microscopy and X-ray diffraction analysis are some of the different techniques used for this work. Finally, a number of the applications are reported with tribological test results. (orig.)

  19. Pseudovitelliform Subfoveal Deposit in Waldenström's Macroglobulinemia


    Aurélie Brolly; Claire Janon; Flavien Precausta; Jean-Marie Baudet; Salomon Yves Cohen


    Background: Waldenström’s macroglobulinemia may be complicated by retinal hemorrhages, retinal vein occlusion, serous macular detachment or macular edema. We report a patient with pseudovitelliform subfoveal deposit complicating Waldenström’s macroglobulinemia. Case Report: A 56-year-old man presented with hyperviscosity syndrome due to Waldenström’s macroglobulinemia. After systemic therapy, a large serous retinal detachment persisted in the left eye. A pseudovitelliform subfoveal deposit wa...

  20. 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)


    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.

  1. Mechanistic insights on platinum- and palladium-pincer catalyzed coupling and cyclopropanation reactions between olefins. (United States)

    Rajeev, Ramanan; Sunoj, Raghavan B


    The mechanism of M(II)-PNP-pincer catalyzed reaction between (i) ethene, (ii) trans-butene with 2-methylbut-2-ene, 2,3-dimethylbut-2-ene and tert-butylbutene is examined by using density functional theory methods (where M = Pt or Pd). All key intermediates and transition states involved in the reaction are precisely located on the respective potential energy surfaces using the popular DFT functionals such as mPW1K, M06-2X, and B3LYP in conjunction with the 6-31+G** basis set. The reaction between these olefins can lead to a linear coupling product or a substituted cyclopropane. The energetic comparison between coupling as well as cyclopropanation pathways involving four pairs of olefins for both platinum (1-4) and palladium (5-8) catalyzed reactions is performed. The key events in the lower energy pathway in the mechanistic course involves (i) a C-C bond formation between the metal bound olefin (ethene or trans-butene) and a free olefin, and (ii) two successive [1,2] hydrogen migrations in the ensuing carbocationic intermediates (1c-4c, and 1d-4d), toward the formation of the coupling product. The computed barriers for these steps in the reaction of metal bound ethene to free tert-butylbutene (or other butenes) are found to be much lower than the corresponding steps when trans-butene is bound to the metal pincer. The Gibbs free energy differences between the transition states leading to the coupling product (TS(d-e)) and that responsible for cyclopropanated product (TS(d-g)) are found to be diminishingly closer in the case of the platinum pincer as compared to that in the palladium system. The computed energetics indicate that the coupled product prefers to remain as a metal olefin complex, consistent with the earlier experimental reports.

  2. Pseudovitelliform Subfoveal Deposit in Waldenström’s Macroglobulinemia

    Directory of Open Access Journals (Sweden)

    Aurélie Brolly


    Full Text Available Background: Waldenström’s macroglobulinemia may be complicated by retinal hemorrhages, retinal vein occlusion, serous macular detachment or macular edema. We report a patient with pseudovitelliform subfoveal deposit complicating Waldenström’s macroglobulinemia. Case Report: A 56-year-old man presented with hyperviscosity syndrome due to Waldenström’s macroglobulinemia. After systemic therapy, a large serous retinal detachment persisted in the left eye. A pseudovitelliform subfoveal deposit was observed in the right eye. Conclusion: Pseudovitelliform subfoveal deposits may be part of the spectrum of ocular complications in Waldenström’s macroglobulinemia. They could be due to accumulation of macroglobulins.

  3. Pseudovitelliform Subfoveal Deposit in Waldenström's Macroglobulinemia (United States)

    Brolly, Aurélie; Janon, Claire; Precausta, Flavien; Baudet, Jean-Marie; Cohen, Salomon Yves


    Background Waldenström's macroglobulinemia may be complicated by retinal hemorrhages, retinal vein occlusion, serous macular detachment or macular edema. We report a patient with pseudovitelliform subfoveal deposit complicating Waldenström's macroglobulinemia. Case Report A 56-year-old man presented with hyperviscosity syndrome due to Waldenström's macroglobulinemia. After systemic therapy, a large serous retinal detachment persisted in the left eye. A pseudovitelliform subfoveal deposit was observed in the right eye. Conclusion Pseudovitelliform subfoveal deposits may be part of the spectrum of ocular complications in Waldenström's macroglobulinemia. They could be due to accumulation of macroglobulins. PMID:22949912

  4. Immobilization of Chiral Ferrocenyl Ligands on Silica Gel and their Testing in Pd-catalyzed Allylic Substitution and Rh-catalyzed Hydrogenation

    Directory of Open Access Journals (Sweden)

    Duncan J. Macquarrie


    Full Text Available Five different silica gels containing two chiral ferrocenyl ligands were prepared by various synthetic routes and tested in an enantioselective Pd(0-catalyzed allylic substitution and Rh-catalyzed hydrogenation. All the prepared anchored ligands were characterized by porosimetry data, DRIFTS spectra, thermal data and AAS. The aim of the work was to compare the influence of the carrier, surface properties and immobilization strategy on the performance of the catalyst.

  5. Ultrasensitive multiplexed immunoassay with electrochemical stripping analysis of silver nanoparticles catalytically deposited by gold nanoparticles and enzymatic reaction. (United States)

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


    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.

  6. Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids** (United States)

    Rydzik, Anna M; Leung, Ivanhoe K H; Kochan, Grazyna T; McDonough, Michael A; Claridge, Timothy D W; Schofield, Christopher J


    γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers. PMID:25164544


    The solely known function of Cu,Zn-superoxide dismutase (SOD1) is to catalyze the dismutation of superoxide anion into hydrogen peroxide. Our objective was to determine if SOD1 catalyzed murine liver protein nitration induced by acetaminophen (APAP) and lipopolysaccharide (LPS). Liver and plasma ...


    Directory of Open Access Journals (Sweden)

    Tjahjono Herawan


    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

  9. 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


    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.

  10. Application of a Palladium-Catalyzed C-H Functionalization/Indolization Method to Syntheses of cis-Trikentrin A and Herbindole B. (United States)

    Leal, Raul A; Bischof, Caroline; Lee, Youjin V; Sawano, Shota; McAtee, Christopher C; Latimer, Luke N; Russ, Zachary N; Dueber, John E; Yu, Jin-Quan; Sarpong, Richmond


    We describe herein formal syntheses of the indole alkaloids cis-trikentrin A and herbindole B from a common meso-hydroquinone intermediate prepared by a ruthenium-catalyzed [2+2+1+1] cycloaddition that has not been used previously in natural product synthesis. Key steps include a sterically demanding Buchwald-Hartwig amination as well as a unique C(sp(3) )-H amination/indole formation. Studies toward a selective desymmetrization of the meso-hydroquinone are also reported.

  11. Deposits of the Peruvian Pisco Formation compared to layered deposits on Mars (United States)

    Sowe, M.; Bishop, J. L.; Gross, C.; Walter, S.


    Deposits of the Peruvian Pisco Formation are morphologically similar to the mounds of Juventae Chasma at the equatorial region on Mars (Fig. 1). By analyzing these deposits, we hope to gain information about the environmental conditions that prevailed during sediment deposition and erosion, hence conditions that might be applicable to the Martian layered and hydrated deposits. Mariner 9 data of the Martian mid-latitudes have already shown evidence of the wind-sculptured landforms that display the powerful prevailing eolian regime [1]. In addition, [2] reported on similarities between Martian erosional landforms and those of the rainless coastal desert of central Peru from the Paracas peninsula to the Rio Ica. As indicated by similar erosional patterns, hyper-arid conditions and unidirectional winds must have dominated at least after deposition of the sediments, which are intermixed volcaniclastic materials and evaporate minerals at both locations. Likewise, variations in composition are displayed by alternating layers of different competence. The Pisco formation bears yardangs on siltstones, sandstones and clays with volcaniclastic admixtures [3] whereas the presence of sulphate minerals and the omnipresent mafic mineralogy has been reported for the layered mounds of Juventae Chasma equally [4]. Likewise, a volcanic airfall deposition and lacustrine formation have been proposed for the sulphate-rich deposits of Juventae Chasma [5,6]. In order to find out about potential spectral similarities, we performed a detailed spectral analysis of the surface by using LANDSAT and Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) VNIR/ SWIR data (visible to near-infrared and shortwave infrared region).

  12. Monitoring particle growth in deposition plasmas (United States)

    Schlebrowski, T.; Bahre, H.; Böke, M.; Winter, J.


    Plasma-enhanced chemical vapor deposition methods are frequently used to deposit barrier layers, e.g. on polymers for food packaging. These plasmas may suffer from particle (dust) formation. We report on a flexible monitoring system for dust. It is based on scanning a 3D plasma volume for particles by laser light scattering. The lower size limit of particles detected in the presented system is 20 nm. We report on existence diagrams for obtaining dust free or dust loaded capacitively or inductively coupled rf-plasmas in C2H2 depending on pressure, flow and rf-power. We further present growth rates for dust in these plasmas and show that monodisperse particles are only obtained during the first growth cycle.

  13. Iron- and indium-catalyzed reactions toward nitrogen- and oxygen-containing saturated heterocycles. (United States)

    Cornil, Johan; Gonnard, Laurine; Bensoussan, Charlélie; Serra-Muns, Anna; Gnamm, Christian; Commandeur, Claude; Commandeur, Malgorzata; Reymond, Sébastien; Guérinot, Amandine; Cossy, Janine


    diastereoselectivities observed in favor of the most stable cis-isomers. It is worth noting that spiroketals could be prepared by using this method, which was successfully applied to a synthetic approach toward natural products belonging to the bistramide family. We then turned our attention to heterocycles incorporating two heteroatoms such as isoxazolidines. These frameworks can be found in biologically active natural products, and in addition, they can be transformed into 1,3-amino alcohols, which are of importance in organic chemistry. The use of FeCl3·6H2O allowed the access to a large variety of 3,5-disubstituted isoxazolidines from δ-hydroxylamino allylic alcohol derivatives with good yields and diastereoselectivities in favor of the cis-isomer. Recently, a Lewis acid-catalyzed synthesis of six- and five-membered ring carbonates starting from linear tert-butyl carbonates was reported. In some cases, the mild and chemoselective InCl3 was preferred over FeCl3·6H2O to avoid side-product formation. The resulting cyclic carbonates were easily transformed into 1,3- or 1,2-diols, and a total synthesis of (3S,5S)-alpinikatin was achieved.

  14. Degradation and transformation of atrazine under catalyzed ozonation process with TiO2 as catalyst. (United States)

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


    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.

  15. 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


    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.

  16. Rh(II)-catalyzed Reactions of Diazoesters with Organozinc Reagents (United States)

    Panish, Robert; Selvaraj, Ramajeyam; Fox, Joseph M.


    Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethylacetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed. PMID:26241081

  17. 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.


    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.

  18. Chemical and genomic evolution of enzyme-catalyzed reaction networks. (United States)

    Kanehisa, Minoru


    There is a tendency that a unit of enzyme genes in an operon-like structure in the prokaryotic genome encodes enzymes that catalyze a series of consecutive reactions in a metabolic pathway. Our recent analysis shows that this and other genomic units correspond to chemical units reflecting chemical logic of organic reactions. From all known metabolic pathways in the KEGG database we identified chemical units, called reaction modules, as the conserved sequences of chemical structure transformation patterns of small molecules. The extracted patterns suggest co-evolution of genomic units and chemical units. While the core of the metabolic network may have evolved with mechanisms involving individual enzymes and reactions, its extension may have been driven by modular units of enzymes and reactions.

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

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U


    . For most studied systems, the tetrahedral structure is a stable intermediate. Moreover, the C-N bond in the lactam ring is intact in this intermediate, as well as in the following transition state-its cleavage is induced by proton transfer to the nitrogen atom in the lactam ring. However, for the model...... with Asp as a proton shuttle, attack of the zinc-bond hydroxide ion seems to be concerted with the proton transfer. We have also studied the effect of replacing one of the histidine ligands by an asparagine or glutamine residue, giving a zinc site representative of other subclasses of metallo......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...

  20. Mg-catalyzed autoclave synthesis of aligned silicon carbide nanostructures. (United States)

    Xi, Guangcheng; Liu, Yankuan; Liu, Xiaoyan; Wang, Xiaoqing; Qian, Yitai


    In this article, a novel magnesium-catalyzed co-reduction route was developed for the large-scale synthesis of aligned beta-SiC one-dimensional (1D) nanostructures at relative lower temperature (600 degrees C). By carefully controlling the reagent concentrations, we could synthesize beta-SiC rodlike and needlelike nanostructures. The possible growth mechanism of the as-synthesized beta-SiC 1D nanostructures has been investigated. The structure and morphology of the as-synthesized beta-SiC nanostructures are characterized using X-ray diffraction, Fourier transform infrared absorption, and scanning and transmission electron microscopes. Raman and photoluminescence properties are also investigated at room temperature. The as-synthesized beta-SiC nanostructures exhibit strong shape-dependent field emission properties. Corresponding to their shapes, the as-synthesized nanorods and nanoneedles display the turn-on fields of 12, 8.4, and 1.8 V/microm, respectively.

  1. Synthesis of Rosin Acid Starch Catalyzed by Lipase

    Directory of Open Access Journals (Sweden)

    Rihui Lin


    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.


    Institute of Scientific and Technical Information of China (English)

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


    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.

  3. FBH1 Catalyzes Regression of Stalled Replication Forks

    Directory of Open Access Journals (Sweden)

    Kasper Fugger


    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.

  4. Recent developments in lipase-catalyzed synthesis of polyesters. (United States)

    Kobayashi, Shiro


    Polyester synthesis by lipase catalyst involves two major polymerization modes: i) ring-opening polymerization of lactones, and, ii) polycondensation. Ring-opening polymerization includes the finding of lipase catalyst; scope of reactions; polymerization mechanism; ring-opening polymerization reactivity of lactones; enantio-, chemo- and regio-selective polymerizations; and, chemoenzymatic polymerizations. Polycondensation includes polymerizations involving condensation reactions between carboxylic acid and alcohol functional groups to form an ester bond. In most cases, a carboxylic acid group is activated as an ester form, such as a vinyl ester. Many recently developed polymerizations demonstrate lipase catalysis specific to enzymatic polymerization and appear very useful. Also, since lipase-catalyzed polyester synthesis provides a good opportunity for conducting "green polymer chemistry", the importance of this is described.

  5. 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)


    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.)

  6. WILDCAT: a catalyzed D-D tokamak reactor

    Energy Technology Data Exchange (ETDEWEB)

    Evans, K. Jr.; Baker, C.C.; Brooks, J.N.


    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.

  7. Laser deposition of bimetallic island films (United States)

    Kucherik, A. O.; Arakelyan, S. M.; Kutrovskaya, S. V.; Osipov, A. V.; Istratov, A. V.; Vartanyan, T. A.; Itina, T. E.


    In this work the results of a bimetallic Au-Ag structure deposition from the colloidal system by nanosecond laser radiation are presented. The formation of the extended arrays of gold and silver nanoparticles with controlled morphology is examined. We report the results of formation bimetallic islands films with various electrical and optical properties. The changes in the optical properties of the obtained thin films are found to depend on their morphology.

  8. FDIC Summary of Deposits (SOD) Download File (United States)

    Federal Deposit Insurance Corporation — The FDIC's Summary of Deposits (SOD) download file contains deposit data for branches and offices of all FDIC-insured institutions. The Federal Deposit Insurance...

  9. The general base in the thymidylate synthase catalyzed proton abstraction. (United States)

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


    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.

  10. 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)

    Energy Technology Data Exchange (ETDEWEB)



    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.

  11. In vitro Characterization of Phenylacetate Decarboxylase, a Novel Enzyme Catalyzing Toluene Biosynthesis in an Anaerobic Microbial Community. (United States)

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


    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.

  12. Acid deposition in Asia: Emissions, deposition, and ecosystem effects (United States)

    Duan, Lei; Yu, Qian; Zhang, Qiang; Wang, Zifa; Pan, Yuepeng; Larssen, Thorjørn; Tang, Jie; Mulder, Jan


    We review and synthesize the current state of knowledge regarding acid deposition and its environmental effects across Asia. The extent and magnitude of acid deposition in Asia became apparent only about one decade after this issue was well described in Europe and North America. In addition to the temperate zone, much of eastern and southern Asia is situated in the tropics and subtropics, climate zones hitherto little studied with respect to the effects of high loads of acid deposition. Surface waters across Asia are generally not sensitive to the effects of acid deposition, whereas soils in some regions are sensitive to acidification due to low mineral weathering. However, soil acidification was largely neutralized by such processes as base cation deposition, nitrate (NO3-) denitrification, and sulfate (SO42-) adsorption. Accompanying the decrease in S deposition in recent years, N deposition is of increasing concern in Asia. The acidifying effect of N deposition may be more important than S deposition in well drained tropical/subtropical soils due to high SO42- adsorption. The risk of regional soil acidification is a major threat in Eastern Asia, indicated by critical load exceedance in large areas.

  13. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry (United States)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.


    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  14. High Quality SiGe Layer Deposited by a New Ultrahigh Vacuum Chemical Vapor Deposition System

    Institute of Scientific and Technical Information of China (English)


    An ultrahigh vacuum chemical vapor deposition (UHV/CVD) system is developed and the details of its construction and operation are reported. Using high purity SiH4 and GeH4 reactant gases,the Si0.82Ge0.18 layer is deposited at 550℃. With the measurements by double crystal X-ray diffraction (DCXRD), transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS) techniques, it is shown that the crystalline quality of the SiGe layer is good,and the underlying SiGe/Si heterointerface is sharply defined.

  15. Preservation of Urban Archaeological Deposits: monitoring and characterisation of archaeological deposits at Marks & Spencer, 44-45 Parliament Street, York

    Directory of Open Access Journals (Sweden)

    M. Davis


    Full Text Available The City of York Council has been pursuing a strict policy of in situ preservation of archaeological deposits since April 1990. Planning consent is normally granted in the historic core of York for a new development so long as less than 5% of the archaeological deposits that are preserved on a site are destroyed. During archaeological evaluation work carried out as part of the redevelopment and expansion proposals for Marks & Spencer plc on Parliament Street, deposit monitoring devices were installed to investigate and monitor both the character of the archaeological deposits present and also the burial environment surrounding them (of particular importance because the burial environment, in terms both of its characteristics and stability, is thought to play a vital role in the preservation in situ of a site's archaeological deposits. The monitoring programme was undertaken between June 1995 and April 1998. As a result the data from a total of 30 site visits have been collected and are presented in this report. This article discusses results of the deposit monitoring project and presents evidence of changes that appear to be taking place in the archaeological deposits. Although the lower deposits at Parliament Street are stable, the upper deposits show considerable seasonal variations. The concept of preservation of archaeological deposits in situ is now deeply embedded both in Codes of Professional Conduct (IFA Code of Conduct and in national policy guidance (PPG 16. However, this emphasis on preservation in situ has been criticised. Does conservation archaeology in general and the City of York policy in particular achieve the preservation of the remaining 95% of the archaeology? Or are these deposits condemned to unseen, unrecorded destruction, sealed below new buildings; indeed if this is the case, shouldn't these deposits be excavated now while they are still viable?

  16. Some characteristics of electrospark deposition

    Energy Technology Data Exchange (ETDEWEB)

    Lesnjak, A. [Q-Techna, Krsko (Sierra Leone); Tusek, J. [Faculty of Mechanical Engineering, Ljubljana (Sierra Leone)


    The paper deals with some characteristics of electrospark deposition. A relevant device and the process are described, the material transfer is shown schematically, and the average droplet mass, the thickness of deposited layer, and the layer roughness are determined. Two types of substrate (tool steel, austenitic stainless steel), two types of shielding gas, (Ar, He), and three types of filler material, (WC, TiC, Stellite 6) were used. With some deposit, chemical analyses of deposit surfaces were performed and with some others through-thickness chemical analyses. Among the final conclusions the most important one is that the addition of a shielding gas results in a considerable increase in deposit quality. The device manufacturer, however, recommends deposition without the addition of a shielding gas. (orig.)


    Directory of Open Access Journals (Sweden)



    Full Text Available Robust immobilization techniques that preserve the activity of biomolecules havemany potential applications. In recent years, a number of new bioimobilisationmethods in sol-gel-derived materials were reported. The interactions between thebiomolecule and the inorganic material determine the degree to which thebiomolecule retains its native properties. The newer technological developments inthe field of immobilized biocatalysts can offer the possibility of a wider and moreeconomical exploitation of biocatalysts in biological applications, food and feedindustry, medicine, and in the development of bioprocess monitoring devices, like thebiosensors.The aim of this study was to obtain immobilized enzymatic preparations by methodswhich affect enzyme conformations and kinetic parameters as less as possible. Weimmobilized the enzymatic preparation with protease activity produced by a Bacilluslicheniformis B 40 local strain by physical bonding on ceramics and entrapment intosol-gel-derived glasses obtained from tetraethyl orthosilicate (TEOS, deposited inthin layer on a ceramic support (entrapment/deposition. Both physically adsorbedand entrapped/deposited enzymes follow Michaelis-Menten kinetics, similar with thesoluble enzyme. In the case of immobilized enzymes, the apparent Michaelisconstant, Km, was greater than that of the native one, as it was expected. The kineticparameters indicate that the enzymatic preparations adsorbed on ceramic supportand entrapped/deposited show less affinity for the substrate, Km being 1.3 and 2.1times higher than that of the native enzyme, respectively. The maximum velocityincreased also by 3.5 and 7.9 times respectively, compared with the free counterpart(according to Lineweaver-Burk linearization.

  18. Pulsed laser deposition of tantalum pentoxide film (United States)

    Zhang, J.-Y.; Boyd, I. W.

    We report thin tantalum pentoxide (Ta2O5) films grown on quartz and silicon substrates by the pulsed laser deposition (PLD) technique employing a Nd:YAG laser (wavelength λ=532 nm) in various O2 gas environments. The effect of oxygen pressure, substrate temperature, and annealing under UV irradiation using a 172-nm excimer lamp on the properties of the grown films has been studied. The optical properties determined by UV spectrophotometry were also found to be a sensitive function of oxygen pressure in the chamber. At an O2 pressure of 0.2 mbar and deposition temperatures between 400 and 500 °C, the refractive index of the films was around 2.18 which is very close to the bulk Ta2O5 value of 2.2, and an optical transmittance around 90% in the visible region of the spectrum was obtained. X-ray diffraction measurements showed that the as-deposited films were amorphous at temperatures below 500 °C and possessed an orthorhombic (β-Ta2O5) crystal structure at temperatures above 600 °C. The most significant result of the present study was that oxygen pressure could be used to control the composition and modulate optical band gap of the films. It was also found that UV annealing can significantly improve the optical and electrical properties of the films deposited at low oxygen pressures (<0.1 mbar).

  19. Cytochrome P4502D6 catalyzes the O-demethylation of the psychoactive alkaloid ibogaine to 12-hydroxyibogamine. (United States)

    Obach, R S; Pablo, J; Mash, D C


    Ibogaine is a psychoactive alkaloid that possesses potential as an agent to treat opiate and cocaine addiction. The primary metabolite arises via O-demethylation at the 12-position to yield 12-hydroxyibogamine. In this report, evidence is presented that the O-demethylation of ibogaine observed in human hepatic microsomes is catalyzed primarily by the polymorphically expressed cytochrome P-4502D6 (CYP2D6). An enzyme kinetic examination of ibogaine O-demethylase activity in pooled human liver microsomes suggested that two (or more) enzymes are involved in this reaction: one with a low KMapp (1.1 microM) and the other with a high KMapp (>200 microM). The low KMapp activity comprised >95% of total intrinsic clearance. Human liver microsomes from three individual donors demonstrated similar enzyme kinetic parameters (mean KMapp = 0.55 +/- 0.09 microM and 310 +/- 10 microM for low and high KM activities, respectively). However, a fourth human microsome sample that appeared to be a phenotypic CYP2D6 poor metabolizer possessed only the high KMapp activity. In hepatic microsomes from a panel of human donors, the low KMapp ibogaine O-demethylase activity correlated with CYP2D6-catalyzed bufuralol 1'-hydroxylase activity but not with other P450 isoform-specific activities. Quinidine, a CYP2D6-specific inhibitor, inhibited ibogaine O-demethylase (IC50 = 0.2 microM), whereas other P450 isoform-specific inhibitors did not inhibit this activity. Also, of a battery of recombinant heterologously expressed human P450 isoforms, only rCYP2D6 possessed significant ibogaine O-demethylase activity. Thus, it is concluded that ibogaine O-demethylase is catalyzed by CYP2D6 and that this isoform is the predominant enzyme of ibogaine O-demethylation in humans. The potential pharmacological implications of these findings are discussed.

  20. Demonstration test and evaluation of ultraviolet/ultraviolet catalyzed peroxide oxidation for groundwater remediation at Oak Ridge K-25 Site

    Energy Technology Data Exchange (ETDEWEB)



    In the UItraviolet/Ultraviolet Catalyzed Groundwater Remediation program, W.J. Schafer Associates, Inc. (WJSA) demonstrated, tested and evaluated a new ultraviolet (UV) lamp integrated with an existing commercial technology employing UV catalyzed peroxide oxidation to destroy organics in groundwater at an Oak Ridge K-25 site. The existing commercial technology is the perox-pure{trademark} process of Peroxidation Systems Incorporated (PSI) that employs standard UV lamp technology to catalyze H{sub 2}O{sub 2} into OH radicals, which attack many organic molecules. In comparison to classical technologies for remediation of groundwater contaminated with organics, the perox-pure{trademark} process not only is cost effective but also reduces contaminants to harmless by-products instead of transferring the contaminants from one medium to another (such as in activated carbon or air stripping). Although the perox-pure{trademark} process is cost effective against many organics, it is not effective for some organic contaminants of interest to DOE such as TCA, which has the highest concentration of the organics at the K-25 test site. Contaminants such as TCA are treated more readily by direct photolysis using short wavelength UV light. WJSA has been developing a unique UV lamp which is very efficient in the short UV wavelength region. Consequently, combining this UV lamp with the perox-pure{trademark} process results in a means for treating essentially all organic contaminants. In the program reported here, the new UV lamp lifetime was improved and the lamp integrated into a PSI demonstration trailer. Even though this UV lamp operated at less than optimum power and UV efficiency, the destruction rate for the TCA was more than double that of the commercial unit. An optimized UV lamp may double again the destruction rate; i.e., a factor of four greater than the commercial system.

  1. 2-haloacrylate hydratase, a new class of flavoenzyme that catalyzes the addition of water to the substrate for dehalogenation. (United States)

    Mowafy, Amr M; Kurihara, Tatsuo; Kurata, Atsushi; Uemura, Tadashi; Esaki, Nobuyoshi


    Enzymes catalyzing the conversion of organohalogen compounds are useful in the chemical industry and environmental technology. Here we report the occurrence of a new reduced flavin adenine dinucleotide (FAD) (FADH(2))-dependent enzyme that catalyzes the removal of a halogen atom from an unsaturated aliphatic organohalogen compound by the addition of a water molecule to the substrate. A soil bacterium, Pseudomonas sp. strain YL, inducibly produced a protein named Caa67(YL) when the cells were grown on 2-chloroacrylate (2-CAA). The caa67(YL) gene encoded a protein of 547 amino acid residues (M(r) of 59,301), which shared weak but significant sequence similarity with various flavoenzymes and contained a nucleotide-binding motif. We found that 2-CAA is converted into pyruvate when the reaction was carried out with purified Caa67(YL) in the presence of FAD and a reducing agent [NAD(P)H or sodium dithionite] under anaerobic conditions. The reducing agent was not stoichiometrically consumed during this reaction, suggesting that FADH(2) is conserved by regeneration in the catalytic cycle. When the reaction was carried out in the presence of H(2)(18)O, [(18)O]pyruvate was produced. These results indicate that Caa67(YL) catalyzes the hydration of 2-CAA to form 2-chloro-2-hydroxypropionate, which is chemically unstable and probably spontaneously dechlorinated to form pyruvate. 2-Bromoacrylate, but not other 2-CAA analogs such as acrylate and methacrylate, served as the substrate of Caa67(YL). Thus, we named this new enzyme 2-haloacrylate hydratase. The enzyme is very unusual in that it requires the reduced form of FAD for hydration, which involves no net change in the redox state of the coenzyme or substrate.

  2. The deposit size frequency method for estimating undiscovered uranium deposits (United States)

    McCammon, R.B.; Finch, W.I.


    The deposit size frequency (DSF) method has been developed as a generalization of the method that was used in the National Uranium Resource Evaluation (NURE) program to estimate the uranium endowment of the United States. The DSF method overcomes difficulties encountered during the NURE program when geologists were asked to provide subjective estimates of (1) the endowed fraction of an area judged favorable (factor F) for the occurrence of undiscovered uranium deposits and (2) the tons of endowed rock per unit area (factor T) within the endowed fraction of the favorable area. Because the magnitudes of factors F and T were unfamiliar to nearly all of the geologists, most geologists responded by estimating the number of undiscovered deposits likely to occur within the favorable area and the average size of these deposits. The DSF method combines factors F and T into a single factor (F??T) that represents the tons of endowed rock per unit area of the undiscovered deposits within the favorable area. Factor F??T, provided by the geologist, is the estimated number of undiscovered deposits per unit area in each of a number of specified deposit-size classes. The number of deposit-size classes and the size interval of each class are based on the data collected from the deposits in known (control) areas. The DSF method affords greater latitude in making subjective estimates than the NURE method and emphasizes more of the everyday experience of exploration geologists. Using the DSF method, new assessments have been made for the "young, organic-rich" surficial uranium deposits in Washington and idaho and for the solution-collapse breccia pipe uranium deposits in the Grand Canyon region in Arizona and adjacent Utah. ?? 1993 Oxford University Press.

  3. Synthesis and Microstructural Characterization of SnO2:F Thin Films Deposited by AACVD


    Chavarría-Castillo,Karen Alejandra; Amézaga-Madrid,Patricia; Esquivel-Pereyra,Oswaldo; Antúnez-Flores, Wilber; Pizá Ruiz, Pedro; Miki-Yoshida,Mario


    In this work, we report the synthesis and microstructural characterization of Tin oxide thin films doped with fluorine for applications such as transparent conductive oxides. Tin oxide doped with fluorine thin films were deposited by aerosol assisted chemical vapor deposition technique onto a borosilicate glass substrate, using a precursor solution of stannic chloride in ethanol and ammonium fluoride as the dopant. Deposition temperature was varied between 623-773 K. Also, other deposition pa...

  4. Momentum Deposition in Curvilinear Coordinates

    Energy Technology Data Exchange (ETDEWEB)

    Cleveland, Mathew Allen [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lowrie, Robert Byron [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rockefeller, Gabriel M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Thompson, Kelly Glen [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Wollaber, Allan Benton [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    The momentum imparted into a material by thermal radiation deposition is an important physical process in astrophysics and inertial confinement fusion (ICF) simulations. In recent work we presented a new method of evaluating momentum deposition that relies on the combination of a time-averaged approximation and a numerical integration scheme. This approach robustly and efficiently evaluates the momentum deposition in spherical geometry. Future work will look to extend this approach to 2D cylindrical geometries.

  5. Deposition features of Ni on self-assembled microtubule template from biolipid by electroless method

    Institute of Scientific and Technical Information of China (English)

    FU; Yubin; ZHANG; Lide; ZHENG; Jiyong; FU; Shangang; ZHU; M


    Diacetylenic glycero-phosphatidylcholine is a chiral molecule with amphiphilic property, and it can self-assembly into a lipid microtubular structure. The lipid microtubule is a stable structure formed by tightly wound helical ribbons, and the ribbon-wrapping patterns have a significant effect on their chemical deposition on the microtubules. The deposition of colloidal Pd catalyst occurs mainly on the helical edge of the wound helical ribbons to form helical deposition lines of colloidal Pd particles in the interior and exterior of the lipid microtubules, resulting in an uneven chemical deposition of Ni on the microtubules. Catalyzed by as-deposited colloidal Pd, metallized Ni microtubules are characterized by a helical form, which may be in relation to inner stress due to the thickness difference or the different deposition processes. The observation of microtom shows that metallized tubules have a hollow structure. Some metallized tubules have a kind of coaxial double layer structure observed in the direct experiment evidence, indicating that metallization can occur in the inner and outer surface of the lipid tubules. Both lipid microtubules and metallized microtubules can be used as vehicles for encapsulating biological active molecules to control their release and to develop micro-components in biological and mechanical systems.

  6. 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)


    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.

  7. L-Proline Catalyzed Michael Additions of Thiophenols to α,β-Unsaturated Compounds, Particularly α-Enones, in the Ionic Liquid [bmim]PF6

    Directory of Open Access Journals (Sweden)

    Stefan Toma


    Full Text Available L-Proline catalyzed additions of 13 different thiols to 11 different α-enoneMichael acceptors in [bmim] PF6 are reported. Reasonable to high yields of the reactionproducts were isolated in most cases.

  8. 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


    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.

  9. Synthesis of [2′-(N-Ethylamino-5′-Alkyl]phenyl-5,6,7,8-Tetrahydroacridine-9-Carboxy-2-Sulfone Derivatives by the Proton-Catalyzed Rearrangement of Corresponding Sulfonamides

    Directory of Open Access Journals (Sweden)

    Anamika Sharma


    Full Text Available Synthesis of a new series of heteroaryl sulfones 6(a–f in which the heteroaryl part is represented by acridine derivatives has been developed and reported here. The key step of this transformation involves the proton-catalyzed rearrangement of the sulphonamide derivatives 5(a–f to the corresponding sulfones 6(a–f.

  10. Gas Pressure Monitored Iodide-Catalyzed Decomposition Kinetics of H[subscript 2]O[subscript 2]: Initial-Rate and Integrated-Rate Methods in the General Chemistry Lab (United States)

    Nyasulu, Frazier; Barlag, Rebecca


    The reaction kinetics of the iodide-catalyzed decomposition of [subscript 2]O[subscript 2] using the integrated-rate method is described. The method is based on the measurement of the total gas pressure using a datalogger and pressure sensor. This is a modification of a previously reported experiment based on the initial-rate approach. (Contains 2…

  11. Multiphase flow wax deposition modelling

    Energy Technology Data Exchange (ETDEWEB)

    Matzain, A. [Petronas Research and Scientific Services, Kuala Lumpur (Malaysia); Zhang, H.-Q.; Volk, M.; Redus, C.L.; Brill, J.P. [University of Tulsa (United States); Apte, M.S. [Shell Technology EP (United States); Creek, J.L. [Chevron Petroleum Technology (United States)


    Results are presented from two-phase flow wax deposition tests using a state-of-the-art, high pressure, multiphase flow test facility. Wax deposition was found to be flow pattern dependent and occurs only along the pipe wall in contact with the waxy crude oil. The deposition buildup trend at low mixture velocities is similar to that observed in laminar single-phase flow tests. The buildup trend at high mixture velocities is similar to that observed in turbulent single-phase flow tests. Thinner and harder deposits at the bottom than at the top of the pipe were observed in horizontal intermittent flow tests. Thicker and harder deposits were observed at low liquid superficial velocity than at high liquid superficial velocity annular flow tests. No wax deposition was observed along the upper portion of the pipe in stratified flow tests. A semi-empirical kinetic model tailored for the wax deposition tests predicted wax thickness with an acceptable accuracy, especially at high oil superficial velocity. Deposition rate reduction due to shear stripping and rate enhancement due to entrapment of oil and other mechanisms not accounted for by the classical Fick's mass diffusion theory were incorporated through the use of dimensionless variables and empirical constants derived from the wax deposition data. The kinetic model, although semi-empirical, provides an insight for future model development. (author)

  12. 78 FR 11604 - Deposit Insurance Regulations; Definition of Insured Deposit (United States)


    ... (``FDI Act'') depositor preference regime, and would therefore be on an equal footing with domestic... insured deposit. The FDI Act, 12 U.S.C. 1811, et seq., mandates the payment of deposit insurance ``as soon... the financial markets of the United States. See FDI Act section 11(f), 12 U.S.C. 1821(f). The...

  13. A deposit model for Mississippi Valley-Type lead-zinc ores: Chapter A in Mineral deposit models for resource assessment (United States)

    Leach, David L.; Taylor, Ryan D.; Fey, David L.; Diehl, Sharon F.; Saltus, Richard W.


    This report is a descriptive model of Mississippi Valley-Type (MVT) lead-zinc deposits that presents their geological, mineralogical and geochemical attributes and is part of an effort by the U.S. Geological Survey Mineral Resources Program to update existing models and develop new models that will be used for an upcoming national mineral resource assessment. This deposit modeling effort by the USGS is intended to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Included in this report are geological, geophysical and geochemical assessment guides to assist in mineral resource estimation. The deposit attributes, including grade and tonnage of the deposits described in this report are based on a new mineral deposits data set of all known MVT deposits in the world.

  14. Deposition and characterization of CuInS2 thin films deposited over copper thin films (United States)

    Thomas, Titu; Kumar, K. Rajeev; Kartha, C. Sudha; Vijayakumar, K. P.


    Simple, cost effective and versatile spray pyrolysis method is effectively combined with vacuum evaporation for the deposition of CuIns2 thin films for photovoltaic applications. In the present study In2s3 was spray deposited over vacuum evaporated Cu thin films and Cu was allowed to diffuse in to the In2S3 layer to form CuInS2. To analyse the dependence of precursor volume on the formation of CuInS2 films structural, electrical and morphological analzes are carried out. Successful deposition of CuInS2thin films with good crystallinity and morphology with considerably low resistivity is reported in this paper.

  15. Gas permeation barriers deposited by atmospheric pressure plasma enhanced atomic layer deposition

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, Lukas, E-mail:; Theirich, Detlef; Hasselmann, Tim; Räupke, André; Schlamm, Daniel; Riedl, Thomas, E-mail: [Institute of Electronic Devices, University of Wuppertal, Rainer-Gruenter-Str. 21, 42119 Wuppertal (Germany)


    This paper reports on aluminum oxide (Al{sub 2}O{sub 3}) thin film gas permeation barriers fabricated by atmospheric pressure atomic layer deposition (APPALD) using trimethylaluminum and an Ar/O{sub 2} plasma at moderate temperatures of 80 °C in a flow reactor. The authors demonstrate the ALD growth characteristics of Al{sub 2}O{sub 3} films on silicon and indium tin oxide coated polyethylene terephthalate. The properties of the APPALD-grown layers (refractive index, density, etc.) are compared to that deposited by conventional thermal ALD at low pressures. The films films deposited at atmospheric pressure show water vapor transmission rates as low as 5 × 10{sup −5} gm{sup −2}d{sup −1}.

  16. Growth of straight carbon nanotubes by simple thermal chemical vapor deposition

    Institute of Scientific and Technical Information of China (English)

    ZOU Xiao-ping; H. ABE; T. SHIMIZU; A. ANDO; H. TOKUMOTO; ZHU Shen-ming; ZHOU Hao-shen


    Straight carbon nanotubes (CNTs) were achieved by simple thermal chemical vapor deposition(STCVD) catalyzed by Mo-Fe alloy catalyst on silica supporting substrate at 700 ℃. High-resolution transmission electron microscopy images show that the straight CNTs are well graphitized with no attached amorphous carbon. Mo-Fe alloy catalyst particles play a very crucial role in the growth of straight CNTs. The straight carbon nanotubes contain much less defects than the curved nanotubes and might have potential applications for nanoelectrical devices in the future. The simple synthesis of straight CNTs may have benefit for large-scale productions.

  17. Enhanced nitrogen deposition over China

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xuejun; Zhang, Ying; Han, Wenxuan; Tang, Aohan; Shen, Jianlin; Cui, Zhenling; Christie, Peter; Zhang, Fusuo [College of Resources and Environmental Sciences, China Agricultural University, Beijing 100193 (China); Vitousek, Peter [Department of Biology, Stanford University, Stanford, California 94305 (United States); Erisman, Jan Willem [VU University Amsterdam, 1081 HV Amsterdam (Netherlands); Goulding, Keith [The Sustainable Soils and Grassland Systems Department, Rothamsted Research, Harpenden AL5 2JQ (United Kingdom); Fangmeier, Andreas [Institute of Landscape and Plant Ecology, University of Hohenheim, 70593 Stuttgart (Germany)


    China is experiencing intense air pollution caused in large part by anthropogenic emissions of reactive nitrogen. These emissions result in the deposition of atmospheric nitrogen (N) in terrestrial and aquatic ecosystems, with implications for human and ecosystem health, greenhouse gas balances and biological diversity. However, information on the magnitude and environmental impact of N deposition in China is limited. Here we use nationwide data sets on bulk N deposition, plant foliar N and crop N uptake (from long-term unfertilized soils) to evaluate N deposition dynamics and their effect on ecosystems across China between 1980 and 2010. We find that the average annual bulk deposition of N increased by approximately 8 kilograms of nitrogen per hectare (P < 0.001) between the 1980s (13.2 kilograms of nitrogen per hectare) and the 2000s (21.1 kilograms of nitrogen per hectare). Nitrogen deposition rates in the industrialized and agriculturally intensified regions of China are as high as the peak levels of deposition in northwestern Europe in the 1980s, before the introduction of mitigation measures. Nitrogen from ammonium (NH4+) is the dominant form of N in bulk deposition, but the rate of increase is largest for deposition of N from nitrate (NO3-), in agreement with decreased ratios of NH3 to NOx emissions since 1980. We also find that the impact of N deposition on Chinese ecosystems includes significantly increased plant foliar N concentrations in natural and semi-natural (that is, non-agricultural) ecosystems and increased crop N uptake from long-term-unfertilized croplands. China and other economies are facing a continuing challenge to reduce emissions of reactive nitrogen, N deposition and their negative effects on human health and the environment.

  18. Computational studies on the regioselectivity of metal-catalyzed synthesis of 1,2,3 triazoles via click reaction: a review. (United States)

    Hosseinnejad, Tayebeh; Fattahi, Bahareh; Heravi, Majid M


    Recently, the experimental and computational chemists have been attracted widely to the click synthesis of 1,2,3 triazoles and their derivatives, mainly due to the fact that they are interesting from structural and mechanistic points of view. Moreover, catalyzed click have been well established as a successful strategy showing high regioselectivity and high yield for the synthesis of 1,2,3-triazoles. In this review, we try to highlight the recently reported computational assessments on the origins and predection of regioselectivity in the catalyzed click synthesis of triazoles from the mechanistic and thermodynamical points of view. In this light, density functional theory (DFT) calculations on the free energy profiles of azide-alkyne cycloaddition reactions have been underscored. The stereoelectronic features for the role of copper, ruthenium, and iridium as catalyst on regioselectivity of click reactions have also be discussed. Graphical Abstract Computational origins for the regioselective behavior of 1,2,3 triazoles click synthesis.

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

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


    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. Isotopic study of ceria-catalyzed soot oxidation in the presence of NOx


    Guillén Hurtado, Noelia; García García, Avelina; Bueno López, Agustín


    The ceria-catalyzed soot oxidation mechanism has been studied by a pulse technique with labeled O2 in the absence and presence of NO, using ceria–soot mixtures prepared in the loose contact mode. In the absence of soot, the ceria-catalyzed oxidation of NO to NO2 takes place with ceria oxygen and not with gas-phase O2. However, the oxygen exchange process between gas-phase O2 and ceria oxygen (to yield back O2, but with oxygen atoms coming from ceria) prevailed with regard to the ceria-catalyz...