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The transition-metal-catalyzed functionalization of C-H bonds is a powerful method for generating carbon-carbon...Full Text Available

Science.gov (United States)

A general palladium-catalyzed carbonylative Sonogashira coupling of benzyl chlorides with terminal acetylenes has been established. Depending on the alkyne 1,4-diaryl-3-butyn-2-ones or substituted furanones are obtained in moderate to good yields. Best catalytic performance is achieved applying a mixed Pd(PPh(3))Cl(2)/P(OPh)(3) catalyst system. PMID:21968528

British Library Electronic Table of Contents (United Kingdom)

Unsymmetric diaryl alkynes were synthesized from the palladium-catalyzed decarboxylative coupling of aryl halides and propiolic acid using a continuous flow reaction system. This flow chemistry system continuously gave the desired products in moderate to good yields, and produced less byproduct than was formed in the batch reaction.

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... where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si , ...

British Library Electronic Table of Contents (United Kingdom)

New palladium(II) complexes (2), bearing NHC/TPPTS ligands, (NHC=benzimidazol-2-ylidene; TPPTS=triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt) have been prepared and characterized by elemental analyses and spectroscopic methods. Their ability to catalyze the Suzuki-Miyaura reaction in neat water has been studied at 100^oC. Very high activities have been observed in the coupling of phenylboronic acid with aryl chlorides in the presence of 1% of the catalyst. We have compared the electronic properties of cis-[PdBr2(NHC)(TPPTS)] with the related complexes, [PdX2(NHC)]2 and [trans-PdBr2(NHC)(pdca)] (pdca=pyridine-2,6-dicarboxyic acid) (3) via three different techniques: cyclic voltammetry, thermogravimetric analysis and ^1^3C NMR spectroscopy.

Science.gov (United States)

indications of the formation of palladium silicides. 2, 4. It has been reported .... At room temperature, palladium silicides formed in a relatively narrow interface ...

International Nuclear Information System (INIS)

The cross-coupled interferometer is a new design for interferometric gravitational wave detectors. Similar to the baseline gravitational wave detectors proposed for Advanced LIGO, it uses long-arm cavities in which the signal is generated. The signal fields are then extracted from the arm cavities with an additional cavity behind the long-arm cavities. The tuning of this signal extraction cavity and the parallel tuning of the signal recycling mirror can be used to optimize the peak frequency and the bandwidth of the detector independently. If we replace the signal recycling mirror by a small cavity, it is possible to amplify signals in two different frequency bands.

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... 194 p. auger electron spectroscopy decomposition deposition interfaces oxygen

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Bio-inspired palladium nanoparticles were synthesized by using banana peel extract (BPE), a non-toxic eco-friendly material. Boiled, crushed, acetone precipitated, air-dried peel powder was used to reduce palladium chloride. The palladium nanoparticles were characterized by using UV-Visible spectroscopy, scanning electron microscope-energy dispersive spectra (SEM-EDS) and X-ray diffraction (XRD) analysis. Dynamic light scattering (DLS) studies revealed the average size of nanoparticles to be 50nm. Fourier transform infra red spectroscopy (FTIR) implicated the role of carboxyl, amine and hydroxyl groups in the synthetic process. This paper thus describes a novel green method for the synthesis of palladium nanoparticles.

UK PubMed Central (United Kingdom)

Reversible protein glutathionylation plays a key role in cellular regulation and cell signaling and protects protein thiols from hyperoxidation. Sulfiredoxin (Srx), an enzyme that catalyzes the reduction...Full Text Available

International Nuclear Information System (INIS)

The application of medium energy ion scattering in combination with channelling and blocking to the study of the initial stages of palladium silicide formation is discussed. After a brief description of the experimental arrangement and method, the effects on the Rutherford backscattering spectra of depositing small quantities of palladium on clean Si(111) are reported. The uniformity and thermal stability of thin palladium silicide films grown at room temperature were measured. Finally, channelling and blocking results were used to carry out a structural analysis of thin epitaxial Pd_2Si layers. (Auth.).

International Nuclear Information System (INIS)

... um. Water retention capacity is in the range from 40 to 46 %. Dowex

Science.gov (United States)

The formation of palladium silicides near the interface may decrease hydrogen solubility at the effective metal/semiconductor ...

Science.gov (United States)

A proposed metallization system for large area silicon solar cells with shallow junctions is outlined, and its desirable features are discussed. A baseline process sequence for the nickel palladium metallization system (NPMS) is delineated. This baseline process sequence is serving as the starting point from which process variations are being performed. The eventual goal is optimization of the NPMS process and determination of the control ranges for NPMS process variables. Initial studies of palladium displacement and electroless chemical plating solutions used in the baseline NPMS have begun and progress is reported. In support of this work, an annotated bibliography (45 citations) dealing primarily with palladium plating and palladium-silicon contact formation has been prepared (and will be subject to updating in the future reports).

International Nuclear Information System (INIS)

The theoretical hardness against total dose of the six-transistor SRAM cell is investigated in detail. An explicit analytical expression of the maximum tolerable threshold voltage shift is derived for two cross-coupled inverters. A numerical method is used to explore the hardness of the read and write operations. Both N- and P-channel access transistors designs are considered and their respective advantages are compared. The study points out that the radiation hardness mainly relies on the technology. Results obtained with the very robust Gate-All-Around process are finally presented.

Science.gov (United States)

Silicon carbide (SiC) based electronic devices are of great importance for applications under the condition of high temperature, high power and high radiation. Schottky diodes of Palladium/SiC are good candidates for hydrogen and hydrocarbon gas sensors at elevated temperature. The detection sensibility of the diodes has been found heavily temperature dependent. In this work, the electrical and chemical properties of Pd/SiC Schottky contacts were studied by XPS and AES at different annealing temperatures. Schottky diodes were made by depositing ultra-thin palladium films onto a silicon carbide substrate. No significant change in the Schottky barrier height of the Pd/SiC contact was found in the temperature range of 300-673K. Palladium diffusion into SiC and the formation of palladium silicides were observed at room temperature and became significant at 300^oC and higher temperature. The mechanism of ...

Energy Technology Data Exchange (ETDEWEB)

This paper reports the effectiveness of solvents on the liquefaction of 11 different Turkish lignites investigated by using tetralin, creosote, and anthracene oils. The highest total conversions were obtained with tetralin. The catalytic effects of CoMo and red mud were compared by using creosote oil as the solvent. It was found that red mud catalyzed mainly the asphaltene formation reaction for the given experimental conditions. The additional of CoMo significantly catalyzed the liquefaction reaction, thus increasing the lignite conversion and oil formation.

Energy Technology Data Exchange (ETDEWEB)

This paper describes the search for new potential chemotherapeutic agents based on transition metal complexes with planar ligands. In this study, palladium polypyridyl complexes were synthesized and characterized by elemental analysis, NMR, UV-VIS and IR spectroscopies. The interaction of the complexes with DNA was also investigated by spectroscopic methods. All metal-to-ligand charge transfer (MLCT) bands of the palladium polypyridyl complexes exhibited hypochromism and red shift in the presence of DNA. The binding constant and viscosity data suggested that the complexes [PdCl{sub 2}(phen)] and [PdCl{sub 2}(phendiamine)] interact with DNA by electrostatic forces. Additionally, these complexes induced an important leishmanistatic effect on L. (L.) mexicana promastigotes at the final concentration of 10 {mu}mol L{sup -1} in 48 h. (author)

International Nuclear Information System (INIS)

Marker experiments for studying the mass transport through a palladium silicide layer on a crystalline substrate during thermal oxidation at 700 to 850 deg C have been reported recently. In this work argon gas embedded in amorphous silicon during sputtering was implemented as the inert marker and the oxidation of PdSi was processed above 900 deg C. At this high-temperature oxidation silicon-rich silicide PdSisub(y), with y exceeding 5, may be obtained. This can be anticipated by considering the Pd-Si phase diagram which shows the liquid phase may appear at an annealing temperature above 892 deg C. As a result, a non-stoichiometric and non-uniform silicide layer may develop at the sample surface. Marker analysis showed that both palladium and silicon dissociated at the Pdsub(x)Si/ SiO_2 interface and moved to the substrate with the silicon being the dominant diffuser. The Rutherford backscattering spectra (RBS) showing the oxide film and ...

International Nuclear Information System (INIS)

Palladium/magnetite nanoparticulate catalysts were developed for efficient elimination of halogenated organic pollutants from contaminated wastewater. Particle recovery from treated water can be ensured via magnetic separation. However, in worst-case scenarios, this catalyst removal step might fail, leading to particle release into the environment. Therefore, a toxicological study was conducted to investigate the impact of both pure magnetite and palladium/magnetite nanoparticle exposure upon human skin (HaCaT) and human colon (CaCo-2) cell lines and a cell line from rainbow trout gills (RTgill-W1). To quantify cell viability after particle exposure, three endpoints were examined for all tested cell lines. Additionally, the formation of reactive oxygen species was studied for the human cells. The results showed only minor effects of the particles on the tested cell systems and support the assumption that palladium/magnetite ...

Science.gov (United States)

The vibrational states, absorption energies, and diffusions of H in Pd and Pd1-xAgx(0Pd-Ag alloys should avoid the Ag-rich areas.

British Library Electronic Table of Contents (United Kingdom)

Palladium silicide was formed on the sol-gel derived SiO2 supported Pd catalysts prepared by ion-exchange method (Pd/SiO2-SG-ion). However, the catalysts exhibited superior performances than commercial SiO2 supported ones in liquid-phase semihydrogenation of phenylacetylene. It was probably due to an inhibition of a product of styrene, which is adsorbed on the surface of Pd, more strongly on Pd/SiO2-SG in which Pd is electron-deficient as shown by larger binding energy from XPS results.

International Nuclear Information System (INIS)

Full text of publication follows: Slightly over-stoichiometric lithium orthosilicate pebbles have been selected as one optional breeder material for the European Helium Cooled Pebble Bed (HCPB) blanket. This material has been developed in collaboration of Research Center Karlsruhe and the Schott Glass, Mainz. The lithium orthosilicate pebbles are fabricated from lithium hydroxide and silica by a melting and spraying method in a semi-industrial scale facility. Lithium hydroxide was selected as the precursor since enriched lithium hydroxide is commercially available. The lithium orthosilicate pebbles produced by the process contains oxide phases besides orthosilicate, but it was also found that the oxide phases can be decomposed by annealing at high temperatures. The lithium orthosilicate pebbles produced in this way possesses satisfactory pebble characteristics. Therefore, the authors performed out-of-pile annealing tests using the lithium orthosilicate pebbles irradiated in a research ...

UK PubMed Central (United Kingdom)

We recently identified a cDNA encoding a putative isovaleryl-coenzyme A (CoA) dehydrogenase in Arabidopsis (AtIVD). In animals, this homotetrameric enzyme is located in mitochondria and catalyzes the...Full Text Available

UK PubMed Central (United Kingdom)

Phenylpropenes, a large group of plant volatile compounds that serve in multiple roles in defense and pollinator attraction, contain a propenyl side chain. Eugenol synthase (EGS) catalyzes the reductive...Full Text Available

UK PubMed Central (United Kingdom)

The speA gene in Bacillus subtilis encodes arginine decarboxylase, which catalyzes the conversion of arginine to agmatine. Arginine decarboxylase is an important enzyme...Full Text Available

UK PubMed Central (United Kingdom)

Phenylketonuria (PKU) is a common genetic disorder in humans that arises from deficient activity of phenylalanine hydroxylase (PAH), which catalyzes the conversion of phenylalanine to tyrosine....Full Text Available

UK PubMed Central (United Kingdom)

Combined QM(PM3)/MM molecular dynamics simulations together with QM(DFT)/MM optimizations for key configurations have been performed to elucidate the enzymatic catalysis mechanism on the detoxification...Full Text Available

UK PubMed Central (United Kingdom)

BackgroundThe immunoregulatory enzyme indoleamine 2,3-dioxygenase, which catalyzes the conversion of tryptophan into kynurenine, is expressed in a significant subset of patients...Full Text Available

UK PubMed Central (United Kingdom)

BackgroundCyclooxygenase (cox) is the rate-limiting enzyme, which catalyzes the conversion of arachidonic acid into prostaglandins and contributes to the inflammatory process. Cyclooxygenase-2...Full Text Available

UK PubMed Central (United Kingdom)

A cell-free system which catalyzes the biosynthesis of terpene hydrocarbons when supplemented with mevalonate, Mn²⁺, and ATP was prepared from the scutellum-embryonic axis region of maize...Full Text Available

UK PubMed Central (United Kingdom)

BackgroundWax esters are important ingredients in cosmetics, pharmaceuticals, lubricants and other chemical industries due to their excellent wetting property. Since the naturally...Full Text Available

UK PubMed Central (United Kingdom)

Social support is a critical, yet underutilized resource when undergoing cancer care. Underutilization occurs in two conditions: (a) when patients fail to seek out information, material assistance,...Full Text Available

Science.gov (United States)

The esterification reaction of a long-chain fatty acid and a fatty alcohol catalyzed by sugar ester-modified lipases in organic media was studied. The reaction activity was improved when the lipases were modified with sugar esters. Among four kinds of sugar esters and six kinds of lipases, lipase CES modified with sugar ester SE-7 showed the highest reaction activity. The pH, solvent and temperature on the reaction activity of SE-7 modified lipase CES were also studied. PMID:12142919

Science.gov (United States)

Most palladium thin film based hydrogen gas sensors have response and recovery times that are too long to make them useful in vehicular and stationary gas leak detection applications. In contrast, a palladium-silver thin film based microcantilever (MC) hydrogen gas microsensor is reported herein with near ideal response characteristics for use in these hydrogen economy related applications. Specifically, 3-10 second response and recovery times have been measured for these sensors in contrast to previous sensor response measurements of several to tens of minutes using Pd thin film and MC based sensing techniques. The much reduced response times observed in the present study are attributed to a wet chemical Pd-Ag thin film deposition technique and a gas conditioning protocol that produces a highly nanostructured, porous film that rapidly adsorbs and desorbs H2, allowing rapid equilibration with the H2 concentration in the surrounding air. The wet ...

Energy Technology Data Exchange (ETDEWEB)

Pd/sub 2/Si layers produced by evaporation or sputtering onto silicon substrates were examined by high resolution electron microscopy, microdiffraction, X-ray, energy loss and Auger spectroscopy. The Si-Pd/sub 2/Si interfaces produced by evaporation were in all cases rougher and more polycrystalline than those produced by sputtering. X-ray microanalysis showed the predictable variation in palladium distribution across the interface but quantification did not produce the expected palladium-to-silicon ratios, primarily because of probe broadening and X-ray-induced fluorescence. Energy loss spectra showed plasmon energy shifts and changes in Si L edge shape due to bond formation with palladium. Auger data provided evidence for a small amount of oxygen at the Si-Pd/sub 2/Si interface. Electrical measurements of the ideality factor for Schottky barriers made from the materials produced higher values for the rougher ...

Science.gov (United States)

Two major modes of CO adsorption on SiO{sub 2}-supported Pd reflect different extents of back-donation, which is, at least in part, controlled by the local electron density at the adsorption site. The fraction of CO in the bridging mode (B) increases and that of the linear mode (L) decreases, with increasing size of the Pd particles, indicating high electron density at Pd atoms in terraces of close-packed crystal faces, in agreement with Smoluchowski's classical model. For samples reduced at 300{degree}C our data points and those of other authors are located on a common curve of B/L vs metal dispersion. Extensive reduction at 600{degree}C results in significantly lower B/L values, attributed to the incipient formation of a palladium silicide. Oxidation followed by reduction at 300{degree}C destroys the silicide, and the B/L value returns to the original curve.

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Before electroless plating, polymer surfaces must be sensitized and/or activated by using either the conventional two-step or one-step process. The latter stage is a compulsory one to make such surfaces catalytic, e.g., for Ni-P deposition. These processes are performed here using O{sub 2}, NH{sub 3}, or N{sub 2} plasma pretreatments. Reaction mechanisms are proposed for each of the processes and for each type of surface considered (oxygenated or both oxygenated and nitrogenated by the plasma treatment). Direct palladium chemisorption onto nitrogenated groups is highlighted. This allows one to simplify the process making the surface catalytic via elimination of the use of SnCl{sub 2} and to extend the method to any polymer. An additional interest of the plasma treatments, besides their high efficiency in grafting chemical functions, is to perform this grafting at will on selected areas which results in selective metallization.

Science.gov (United States)

The use of Auger electron spectroscopy (AES) combined with in situ sputter etching for revealing the metallurgy of the metal-semiconductor interface is presented. The physical basis, measurement techniques, and data interpretation for Auger analysis of thin-film structures are briefly reviewed. Results of a detailed study of an alloyed multilayered contact (Ni/Au-Ge) on n-type epitaxial GaAs are summarized to illustrate how electrical and metallurgical contact properties can be correlated using AES. In addition, the results of a study of the growth kinetics and chemical phase identification of palladium silicide on single-crystal Si is given, as well as the initial results of a study of aluminum-palladium silicide interaction at elevated temperature. (auth)

Energy Technology Data Exchange (ETDEWEB)

Evaporated palladium films of 45 nm thickness on Si(111) were irradiated using 78 keV Ar/sup +/ ions with doses in the range of 1 x 10/sup 15/ to 1.5 x 10/sup 16/ cm/sup -2/ for the purpose of studying silicide formation. Rutherford backscattering analysis shows that intermixing has occurred across the Pd-Si interface at room temperature. The mixing behaviour increases with increasing dose of the bombarding ions, which agrees well with a theoretical model of isotropic cascade mixing for palladium, and radiation-enhanced diffusion associated with an interstitial mechanism for silicon.

Science.gov (United States)

In the course of observing by means of Auger spectroscopy graphite gasification reactions catalyzed by metals, it has been found that in the presence of hydrogen, nickel appears to diffuse from the surface into the bulk of the graphite. When potassium is deposited on graphite, it is volatilized above 400/sup 0/C. Surprisingly the production of methane and carbon dioxide from the reaction of graphite and steam was catalyzed by potassium at as low a temperature as 250/sup 0/C. It has been shown that literature on the alkylation of benzene with synthesis gas is erroneous and that the products reported are due to Lewis acid catalyzed cracking of benzene. A novel cobalt mediated, reversible cleavage of a vinyl-hydrogen bond has been discovered. All products from the thermal decomposition of tetralin have been identified. The stereochemistry of cis-1, 2 dihydrotetralin was determined. In the utilization of the water gas shift ...

Science.gov (United States)

Green crab (Scylla serrata) alkaline phosphatase (EC 3.1.3.1) is a metalloenzyme, which catalyzes the nonspecific hydrolysis of phosphate monoesters. The kinetics of inhibition of the enzyme by sodium (2, 2'-bipyridine) oxodiperoxovanadate, pV(bipy), has been studied. The time course of the hydrolysis of p-nitrophenyl-phosphate catalyzed by the enzyme in the presence of different pV(bipy) concentrations showed that at each pV(bipy) concentration, the rate decreased with increasing time until a straight line was approached, the straight line slopes are the same for all concentrations. The results suggest that the inhibition of the enzyme by pV(bipy) is a slow, reversible reaction with fractional remaining activity. The microscopic rate constants are determined for the reaction of inhibitor with the enzyme. PMID:10691182

International Nuclear Information System (INIS)

This paper describes a reactor design to facilitate a room-temperature nuclear fusion/fission reaction to generate heat without generating unwanted neutrons, gamma rays, tritium, or other radioactive products. The room-temperature fusion/fission reaction involves the sequential triggering of billions of single-molecule, "6LiD 'fusion energy pellets' distributed in lattices of a palladium ion accumulator that also acts as a catalyst to produce the molecules of "6LiD from a solution comprising D_2O, "6LiOD with D_2 gas bubbling through it. The D_2 gas is the source of the negative deuterium ions in the "6LiD molecules. The next step is to trigger a first nuclear fusion/fission reaction of some of the "6LiD molecules, according to the well-known nuclear reaction: "6Li + D #-># 2"4He + 22.4 MeV. The highly energetic alpha particles ("4He nuclei) generated by this nuclear reaction within the palladium will cause shock and vibrations in the ...

British Library Electronic Table of Contents (United Kingdom)

Only 15mol% of l-proline in ethanol proved to be a very efficient catalyst for the one-pot synthesis of a wide variety of highly substituted pyridines at room temperature. The methodology is mild, efficient, high yielding, and the products can be directly recrystallized from hot ethanol.

Energy Technology Data Exchange (ETDEWEB)

N,N-Dialkyl-P-phenylphosphonamidous iodides are formed in the reactions of phenylphosphonus diiodide with silylated secondary amines. N,N-Dialkyl-P-phenylphosphonamidous iodides react with electrophilic reagents (methyl iodide, benzenesulfonyl azide, and phenyl azide) by the usual schemes with the formation of alkylation and oxidative-imination products. Iodine catalyzes the disproportionation of morpholinophenylphosphinous iodide into dimorphomorpholinophenylphosphinous iodide with iodine are iododimorpholinophenylphosphonium triiodide and phenylphosphonous diiodide.

UK PubMed Central (United Kingdom)

Several cDNA clones encoding Δ¹-pyrroline-5-carboxylate reductase (P5CR, l-proline:NAD[P]⁺ 5-oxidoreductase, EC 1.5.1.2), which catalyzes the terminal step in...Full Text Available

International Nuclear Information System (INIS)

At the RIKEN-RAL Muon Facility, ?- to ? sticking K? X-rays were observed for the first time taking advantage of the pulsed beam structure. The precision of the present measurements was insufficient to distinguish between theoretical models, however the observed K?/K? X-ray intensity ratio tends to be smaller than most of these theoretical predictions.

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Details of a series of reactions for the production of ethylene glycol using a catalyst of Nafion solid perfluorosulfonic acid resin was detailed. The reactions included the carbonylation of formaldehyde and esterification and then hydrogenation of the product of the carbonylation, glycolic acid. Other preparations included in the work included methyl glycolate, acetylglycolic acid, methyl acetylglycolate, and methyl methoxyacetate.

UK PubMed Central (United Kingdom)

The first enzyme-catalyzed reaction leading from indole-3-acetic acid (IAA) to the myo-inositol esters of IAA is the synthesis of indole-3-acetyl-1-O-β-d-glucose...Full Text Available

Energy Technology Data Exchange (ETDEWEB)

A method for the hydroconversion of coal by solvent treatment at elevated temperatures and pressure wherein an alcohol having an alpha -hydrogen atom, particularly a secondary alcohol such as isopropanol, is utilized as a hydrogen donor solvent. In a particular embodiment, a base capable of providing a catalytically effective amount of the corresponding alcoholate anion under the solvent treatment conditions is added to catalyze the alcohol-coal reaction.

International Nuclear Information System (INIS)

Radiation defects produced by helium implantation were used to shape profiles of palladium (Pd) and platinum (Pt) atoms in-diffusing (for 20 min at temperatures 600-800 deg. C) either from surface silicide (Pd_2Si, PtSi) or implanted layers. Results show that this procedure allows a strong localization of substitutional Pd and Pt at the depth where the damage produced by helium peaks. This results in local reduction of carrier lifetime by an almost ideal recombination centers - the acceptor level of substitutional Pd (E _c - 0.22 eV) or Pt (E _c - 0.23 eV). While optimum conditions for Pt in-diffusion are about 700 deg. C, Pd gives the best results already at lower temperatures (600 deg. C) where it also exhibits higher peak solubility. Both methods were used for optimization of turn-off properties of high power PiN diodes. The devices, where the lifetime was killed locally by Pd and Pt, exhibited similar trade-off between the static and dynamic parameters as the ...

International Nuclear Information System (INIS)

Polycrystalline silicon films have been grown from Si_2H_6 by low-pressure chemical vapour deposition at 800 K and in situ laser annealing (LA) on amorphous silicon seed layers deposited on a metallic Ti/Pd/Ag multilayer. The crystalline volume fraction in the seed layer was controlled by thermal annealing. According to the metal-induced crystallization effect, the presence of the metal induces a lower-temperature crystallization of silicon in the seed layers. X-ray diffraction and scanning electron microscopy data show that the formation of palladium silicides in the seed layer drives the growth of wire-like columns which are found to change morphology depending on the seed layer microstructure and LA parameters. It is suggested that superficial palladium was found to affect also the growth rate by enhancing the Si_2H_6 dissociation.

International Nuclear Information System (INIS)

In the present work, a rapid deposition anodic stripping voltammetry (ASV) for determination of uranium is presented. For this purpose, the uranyl hexacyanoferrate (K2UO2[Fe(CN)6]) is deposited electrochemically on a thin palladium-aluminum electrode (Pd-Al) from a UO22+ solution in the presence of K3Fe(CN)6. Then, the well stable (K2UO2[Fe(CN)6]) on the electrode was stripped by anodic differential pulse voltammetry for measuring the UO22+ ion concentration. The effect of operational parameters, including: concentration of K3Fe(CN)6, solution pH, deposition potential, and deposition time were studied. In optimum conditions, the calibration graph was linear in the concentration range 105-7 x 10-4 mol L-1 with a detection limit of 6.2 x 10-6 mol L-1. The influence of some concomitant ions in K2UO2[Fe(CN)6] formation was investigated. The proposed method was used for the rapid determination of uranium in some uranium mineral ores. (orig.)

International Nuclear Information System (INIS)

The description is presented of binary phase diagrams of titanium alloyed with the following elements: silver, aluminium, arsenic, gold, boron, barium, beryllium, bismuth, carbon, calcium, cadmium, cobalt, chromium, copper, iron, gallium, germanium, hydrogen, hafnium, indium, iridium, potassium, lithium, magnesium, manganese, molybdenum, nitrogen, sodium, niobium, nickel, oxygen, osmium, phosphorus, lead, palladium, platinum, plutonium, rhenium, lanthanium, cerium, preseodymium, neodymium, gadolinium, erbium, terbium, thulium, lutetium, rhodium, ruthenium, scandium, silicon, tin, strontium, tantalum, technetium, thorium, uranium, vanadium, tungsten, yttrium, ytterbium, zinc and zirconium.

Science.gov (United States)

We have investigated the stability and catalytic activity of epitaxial overlayers of rhodium on Au(111) and Pd(111). Both surfaces show a strong affinity for hydrogen. We have calculated the energy of adsorption both for a strongly and a more weakly adsorbed species; the latter is the intermediate in the hydrogen evolution reaction. Both the energy of activation for hydrogen adsorption (Volmer reaction) and hydrogen recombination (Tafel reaction) are very low, suggesting that these overlayers are excellent catalysts. PMID:21847482

Science.gov (United States)

The title compounds were prepared by arc-melting of the elemental components. Whereas NdPdSi and SmPdSi are already present after the arc-melting, alpha-GdPdSi and alpha-TbPdSi are formed only during the annealing at 800 degC. The four compounds crystallize with the recently reported alpha-YbAuGe type structure, which was refined for alpha-GdPdSi: Pnma, a=2108.0(4) pm, b=433.9(1) pm, c=745.6(1) pm, Z=12, R=0.026 for 1447 structure factors and 62 variable parameters. The lanthanoid atoms are situated between two-dimensionally infinite nets of condensed, puckered hexagons formed by alternating palladium and silicon atoms, with Pd-Si distances varying between 251 and 262 pm. In the third dimension these nets are linked via weak Pd-Pd (300 pm), Pd-Si (283 pm), and Si-Si bonds (261 pm). The refinements of the occupancy parameters suggested that ca. 2% of the palladium sites are occupied by silicon atoms and vice versa. The structural relationships ...

Science.gov (United States)

The problem of homochirality is of crucial importance for the origins of Life. While most laboratory studies are focused on the search of physical and chemical sources of handedness in the Universe, they reflect only one aspect of the problem: the origin of homochiral biomolecules. At the same time, any space environments where biomolecules are expected to form and where they have to pass through before the first primitive forms of Life emerge, include strong irradiation or/and high temperatures. This automatically implies the possibility of losing the optical activity, i.e. racemization. The simulation experiments performed by our group deal with the following two aspects of amino acid abiotic chemistry: (1) amino acid pyrolysis associated with their extraterrestrial delivery; and (2) peptide formation from amino acids catalyzed by inorganic oxides. According to our observations, the racemization phenomena are very common in the systems considered, not only under ...

Energy Technology Data Exchange (ETDEWEB)

A detailed kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by Pt(II) complexes is reported. The two systems analyzed were (diphoe)Pt(CF/sub 3/)(OH)/1-octene/H/sub 2/O/sub 2//THF and ((diphoe)Pt(CF/sub 3/)(CH/sub 2/Cl/sub 2/))BF/sub 4//1-octene/H/sub 2/O/sub 2//H/sub 2/O/CH/sub 2/Cl/sub 2/. Rate data were determined with GLC from epoxide formed vs time plots. Evidence for many of the organometallic intermediates and the individual steps involved was gained from IR studies, /sup 19/F NMR studies, and especially designed experiments including studies of the acidity effect. In both cases the kinetic analysis suggests a mechanism in which the actual oxidant is a PtOOH species that interacts with a Pt-olefin complex in the oxygen-transfer step (second-order dependence on platinum). 29 references, 12 figures, 3 tables.

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The purpose of this project was to investigate the feasibility of an antiproton catalyzed fission fragment rocket (FFR). The FFR is characterized by the extraction of fission fragments from the fissile fuel, and the utilization of their kinetic energy for thrust generation. A significant drawback to previous FFR designs was the requirement to maintain a critical nuclear pile as the fission fragment source. The author examined the possibility of replacing the critical pile with a sub-critical pile driven by antiprotons. Recent experiments have revealed that antiprotons stimulate highly energetic fissions in {sup 238}U, with a neutron multiplicity of 13.7 neutrons per fission. This interaction was used as a throttled neutron source. The pile consisted of layers of fissile coated fibers which are designed to allow fission fragments to escape them, where the fragments collide with a fluid. The heated fluid is then ejected from the rocket to provide thrust. The ...

Energy Technology Data Exchange (ETDEWEB)

Ethylen and, recently, butadiene can be epoxidized directly with oxygen and for the epoxidation of propylene, the use of heterogeneous transition metals and organic peroxides (Halcon-Process) is the major player. But, beside from those notable exceptions, all other epoxidations, including large ones like the epoxidation of plant oils as PVC-stabilizers (about 200.000 t/year), are carried out with peroxy acids. Because mcpba is far to expensive for most applications, short chain peracids like peracetic acid are used. Being much less stable than mcpba and thus risky handled in large amounts and high concentrations, these peroxy acids were preferably prepared in-situ. However, conventional in-situ formation of peracids has the serious drawback, that a strong acid is necessary to catalyze peroxy acid formation from the carboxylic acid and hydrogen peroxide. The presence of a strong acid in the reaction mixture often results in decreased selectivity because of the ...

Science.gov (United States)

Two branches of research are conducted in this thesis. The first deals with nonlinear combustion response as a mechanism for triggering combustion instabilities in solid rocket motors. A nonlinear wave equation is developed to study a wide class of combustion response functions to second-order in fluctuation amplitude. Conditions for triggering are derived from analysis of limit cycles, and regions of triggering are found in parametric space. Introduction of linear cross-coupling and quadratic self-coupling among the acoustic modes appears to be how the nonlinear combustion response produces triggering to a stable limit cycle. Regions of initial conditions corresponding to stable pulses were found, suggesting that stability depends on initial phase angle and harmonic content, as well as the composite amplitude, of the pulse. Also, dependence of nonlinear stability upon system parameters is considered. The second part of this thesis presents research for a ...

British Library Electronic Table of Contents (United Kingdom)

Previous research has characterized insight as the product of internal processes, and has thus investigated the cognitive and motivational processes that immediately precede it. In this research, however, we investigate whether insight can be catalyzed by a cultural artifact, an external object imbued with learned meaning. Specifically, we exposed participants to an illuminating lightbulb - an iconic image of insight - prior to or during insight problem-solving. Across four studies, exposing participants to an illuminating lightbulb primed concepts associated with achieving an insight, and enhanced insight problem-solving in three different domains (spatial, verbal, and mathematical), but did not enhance general (non-insight) problem-solving.

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The vacuum polarization splitting of the M-shell states in muonic hydrogen can have a profound influence on the muonit de-excitation cascade in deuterium and tritium targets. The cascade also shows sensitive dependence on the precise rate of transfer processes between certain excited muonic deuterium and tritium atoms. Recent experimental data, where a much greater population of the (d..mu..) qs state (1/sub 1//sub //sub s/) was found than previously predicted, can be explained if the transfer rates from the (d..mu..) M-shell are assumed to be strongly suppressed.

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At the RIKEN-RAL Muon Facility, {mu}{sup -} to {alpha} sticking K{sub {beta}} X-rays were observed for the first time taking advantage of the pulsed beam structure. The precision of the present measurements was insufficient to distinguish between theoretical models, however the observed K{sub {beta}}/K{sub {alpha}} X-ray intensity ratio tends to be smaller than most of these theoretical predictions.

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Four high-sulphur low-rank coals have been treated at hydrogenation conditions with three iron-based catalyst precursors: Red Mud (Fe[sub 2]O[sub 3]), iron sulphide and iron pentacarbonyl. The obtained yields show a dependence with the sulphur content of the coals; the organic sulphur content correlates with the conversion and THF-solubles when Red Mud and iron sulphide are added. In spite of the high hydrogen sulphide partial pressure in the reaction, the addition of other sources of sulphur enhances the percentages in conversion products. 15 refs., 2 figs., 3 tabs.

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The review covers the development within the field of cleavable surfactants since 2003. Cleavable surfactants are amphiphiles in which a weak linkage has been deliberately inserted, normally, but not always, between the hydrophobic tail and the polar headgroup. Alkali labile linkages that have been used for the purpose include normal ester bonds, betaine esters, and carbonates. Ketals and ortho esters are example of bonds that are susceptible to acid hydrolysis. Several investigations deal with cationic ester-containing surfactants, both monomeric and dimeric species, the latter being gemini surfactants. Ester, amide and carbonate containing surfactants have been investigated with respect to enzyme catalyzed hydrolysis. The main incentive for the development of novel cleavable surfactants ...

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In this study, the thermodynamic stability of the grain boundaries and the grain growth of nanocrystalline Palladium (Pd) at various temperatures were investigated. For this purpose, the Gibbs free energy curves of grain boundaries were plotted in terms of the excess volume by the use of the equation of state (EOS) and Song's thermodynamic models. The results showed that, according to the prediction of these models, the nanocrystalline growth in metals was stopped at the grain sizes less than the critical grain size. Also, the results of the temperature variations and its effect on the Gibbs free energy curves showed that by the increase of the temperature, the possibility for the stoppage of grain growth is facilitated and the critical grain size is increased. To investigate the validity ...

International Nuclear Information System (INIS)

The transformation of Pd/Si to Pd_2Si/Si is studied using Auger electron spectroscopy over a wide temperature range of 370-1020 K. The Pd film gets totally converted to Pd_2Si upon annealing at 520 K, and beyond 570 K, Si starts segregating on the surface of silicide. It is found that the presence of surface oxygen influences the segregation of Si. The time evolution study of Si segregation reveals that segregation kinetics is very fast and the segregated Si concentration increases as the temperature is increased. Scanning electron microscopy measurements show that Pd_2Si is formed in the form of islands, which grow as the annealing temperature is increased.

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Membranes in Palladium and its alloys, in particular Pd/Ag alloys, are selectively permeable to hydrogen and can therefore be used to purify hydrogen. It is intended to use them as material for electrodes in fuel cells. As the manufacturing process of a substrate Pd/Ag-layer consists of several stages and is still not completely understood, it would be advantageous to be able to characterise separately the layers of noble metals obtained by electro-plating . Attempts are being made in this work to vary the cristallographical structure of the deposited alloy by the choice of test parameters and by sintering when depositing the Pd/Ag. The layers produced are to be examined using an interference microscope and X-ray diffraction. Moreover, the diffusion behaviour of the hydrogen is to be examined with an electro-chemical pulse method specifically developed for this purpose. figs., tabs., 27 refs.

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The magnetic susceptibility of the ternary compounds, RPd/sub 2/Si/sub 2/ (where R=Gd, Tb, Dy, Ho and Er) has been measured. GdPd/sub 2/Si/sub 2/ and TbPd/sub 2/Si/sub 2/ order antiferromagnetically at 13 and 20 K respectively; the rest of the compounds do not show clear ordering down to 4.2 K. Palladium carries no moment in these compounds. The De Gennes formula is not obeyed indicating that the exchange interaction between the 4f moments via conduction electrons is not isotropic.

International Nuclear Information System (INIS)

The initial growth process and surface structure of thin Pd(silicide) films on clean Si(111)-7x7 surfaces have been studied by low energy ion scattering (ISS) and LEED-Auger techniques. Considerable reaction between Pd and Si at room temperature is observed to extend up to 25 ML thickness of deposited Pd. Heat treatment of the room temperature film produced epitaxial silicide Pd_2Si(0001) films covered with the accumulated elementary Si layers of 1-2 ML thickness. Deposition of 1/3 ML Pd onto a heated substrate gives a Pd-embedded ordered surface of Si(111)-#sq root#3x#sq root#3R30"0, the feature being similar to the cases of Ag, Au/Si(111) systems. (orig.).

International Nuclear Information System (INIS)

By using megaelectronvolt "4He ion backscattering techniques and transmission electron microscopy, the authors have investigated the interactions of ion beams with thin film structures in a number of silicide-forming systems. The mixed layer was found to be an equilibrium compound for near-noble metals and an amorphous phase for refractory metals. Differences in behavior have also been observed in near-noble metal systems. For palladium, the Pd_2Si phase grew with ion dose and remained crystalline up to high dose. For nickel, the compound Ni_2Si was formed initially and became amorphous on prolonged irradiation. All the results indicate the significance of atomic mobility at target temperatures in determining the phase formation and in explaining the sensitivity of the silicides to ion bombardment. (Auth.).

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The evolution of strain in the Pd-Si system during the growth of Pd{sub 2}Si thin films on Si (100) substrate has been followed in situ using a double optical beam technique. As was observed for the Pt-Si system, the reaction to form Pd{sub 2}Si yields a compressive intrinsic surface film stress as well as for the silicon-rich suicides as proposed by Angilello et al. [Thin Film Interfaces and Interactions, edited by J. Baglin and J. Poate (The Electrochemical Society, Pennington, NJ, 1980)]. A transmission electron microscopy analysis has revealed grain growth during the formation of Pd{sub 2}Si which cannot account for the compressive film stresses. The formation of silicide at the interfaces rather than the overall change in volume agrees with the sign of the stresses formed. 29 refs., 4 figs., 3 tabs.

Science.gov (United States)

X-ray diffraction offers a unique combination of advantages for kinetic study which include the non-destructive nature of the measurement, the use of bulk crystals, and the convenience of the experimental arrangements. These attributes and the availability of position-sensitive detectors and high-flux synchrotron radiation sources make this technique most useful for in situ, dynamical investigations. When using diffraction techniques to determine a diffusion coefficient, the principle of analysis entails a scattering theory and a kinetic model. The former allows the kinetic parameter(s) to be extracted from measured intensity, while the latter relates the kinetic parameter(s) to the diffusion coefficient(s). Three examples are demonstrated: (1) Palladium Silicide (Pd{sub 2}Si) Layer Growth on Silicon, (2) Decomposition of an Ni-12.5at%Si Superalloy, and (3) Short-range Ordering in Cu-Au Solid Solutions.

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Microwave-hydrothermal processing was compared with conventional hydrothermal processing in the crystallization of hematite from 1M ferric nitrate and hydroxyapatite from calcium oxide and phosphoric acid. Microwave-hydrothermal processing led to the crystallization of hematite while convention-hydrothermal process led to the crystallization of a mixture of goethite and hematite under the same temperature conditions. Thus the crystallization of hematite which is the stable iron oxide phase at high temperatures has been catalyzed by microwaves. Microwave-hydrothermal processing also led to highly crystalline hydroxyapatite powders compared to the conventional hydrothermal processing which also points to the catalytic role of microwaves. The microwave induced effects may be attributed to the generation of localized high temperatures at the reaction sites which enhance reaction rates.

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The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)

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1,3-Dienes derived from steroidal D-ring C17-ketones undergo Ni(II)-catalyzed hydrovinylation to give 1,2- or 1,4-addition of ethylene. Using finely tuned phosphoramidite ligands it is possible to synthesize either the C20 (R)- or the C20 (S)-derivatives without mutual contamination. The proportion of the 1,4-adduct, which is also formed stereoselectively, can be minimized by optimizing the reaction conditions. Since the two alkenes in the resultant dienes have differing steric demands for many potential reactions, and are ideally juxtaposed for further D-ring functionalization, these intermediates could be useful for the preparation of biologically important compounds such as vitamin D analogs and various antitumor steroidal glycosides.

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Wheat leaves can be induced by excision to produce fructans. Fructose residues of newly made oligofructans in leaves labeled in vivo with {sup 14}CO{sub 2} are not equally labeled. We report here on a fructosyl transferase activity in wheat leaves catalyzing the reaction: G{sup *}-F{sup *} + G-F-F = G{sup *}-F{sup *}-F + G-F. This activity, described previously in J. artichoke was attributed to fructan:fructan fructosyl transferase (FFT). The rate of this reaction in vitro is much higher than that of net kestose synthesis by SST. Hence, appearance of labeled 1-kestose from sucrose may not be an accurate measure of SST, but a curious reshuffling of hexoses between pools of 1-kestose and sucrose.

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A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4prime-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-pha...

Science.gov (United States)

During this reporting period two direct coal liquefaction experiments have been completed and a third is underway. These experiments have produced conversion and selectivity data on samples of Alabama bituminous coal slurried in tetralin and catalyzed using iron-titanium hydride. The experiments address the liquefaction of an agglomerating coal. Conversions of 45 to 55% DAF in 30 min have been recorded at 500/sup 0/F and 520 psia. Equipment modifications were made in an attempt to eliminate the problem of alloy binding in the hydride formation vessel. 4 figs., 4 tabs.

Science.gov (United States)

During this report period, we have obtained a model of montmorillonite clay, and this model has been of great assistance in visualizing how the chemistry of substrate molecules might be altered as it occurs on the surface of the clay. A stereochemical representation of this montmorillonite model is shown. Of particular significance, this model indicates that hydroxyl groups are located in the center of each siloxane ring on the surface of the montmorillonite clay. These hydroxyl groups might serve to bond substrate molecules to the surface of the clay. The next step in our systematic examination of the radical cation-initiated dimerization of plant monomers from the C{sub 6}-C{sub 3} pool of shikimic acid metabolites was to study the dimerization of cinnamic acid and its derivatives. In the next block of research, we examined the reaction of montmorillonite clay (K-10) with methyleugenol. 2 refs.

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The objective of this work is to improve the process for CO{sub 2} capture by alkanolamine absorption/stripping by developing an alternative solvent, aqueous K{sub 2}CO{sub 3} promoted by piperazine. Thermodynamic modeling predicts that the heat of desorption of CO{sub 2} from 5m K+/2.5 PZ from 85 kJ/mole at 40 C to 30 kJ/mole at 120 C. Mass transfer modeling of this solvent suggests that carbonate and general salt concentration play a major role in catalyzing the rate of reaction of CO{sub 2} with piperazine. Stripper modeling suggests that with the multipressure stripper, the energy consumption with a generic solvent decreases by 15% as the heat of desorption is decreased from 23.8 to 18.5 kcal/gmol. A second pilot plant campaign with 5m K+/2.5 PZ was successfully completed.

International Nuclear Information System (INIS)

Stimulated bremsstrahlung in an undulating electric field in the lasing beam direction (electric wiggler) was shown to be possible from the quantum- mechanical viewpoint. Herein, this possibility is scrutinized from the viewpoint of classical electrodynamics. It is found that if stimulated bremsstrahlung in a transverse undulating magnetic field (magnetic wiggler) occurs, stimulated bremsstrahlung in the electric wiggler must also occur. We further show that a free electron laser (FEL) using a magnetic wiggler to provide a catalyzer field for stimulated bremsstrahlung cannot serve as a practical FEL operating in the soft x-ray region from both theoretical and experimental viewpoints. On the other hand, the authors demonstrate that the FEL using a traveling wake field in a two-beam elliptical pill-box cavity is well suited as a source of coherent radiation in the soft x-ray region.

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The palladium(II) and platinum(II)complexes(where, (M(L){sub 2}X{sub 2}), M=Pd(II), Pt(II); L=isoxazole (isox), 3, 5-dimethylisoxazole(3, 5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3, 5-di-methylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the {sigma}MO energy level (E{sub {sigma}}{sub (M-X)} between d{sub x}{sup 2}{sub -y}{sup 2} orbital of central metal and p{sub x} orbital of halogen atom is less than {sigma}MO energy level E{sub {sigma}}{sub (M-N)} between d{sub x}{sup 2}{sub -y}{sup 2} orbital of central metal and p{sub x} orbital of N atom, without exception. And judging, from the lower E{sub {sigma}}{sub (M-X)} value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of ...

International Nuclear Information System (INIS)

The nine title compounds were prepared from the elements by arc-melting and subsequent heat treatment in resistance and high-frequency furnaces. The crystal structure of these isotypic compounds was determined for YPdSi from single-crystal X-ray diffractometer data: Pmmn, a = 430.8(1) pm, b = 1391.2(1) pm, c = 743.1(1) pm, Z = 8, R = 0.024 for 417 structure factors and 40 variable parameters. The crystal structures of the isotypic compounds GdPdSi and ErPdSi were also refined from single-crystal data. The structure is of a new type. It consists of condensed, six-membered rings of alternating palladium and silicon atoms with Pd-Si bond distances varying between 249.6 and 258.8 pm. These two-dimensionally infinite nets are connected to each other via weak Pd-Si and Si-Si bonds with bond distances of 276.3 and 259.5 pm. The rare earth atoms are situated above and below the six-membered palladium-silicon rings in a manner as it is known for the ...

International Nuclear Information System (INIS)

The anodic reaction kinetics and interfacial mass transport of a direct polymer electrolyte membrane formic acid fuel cell have been investigated in an all solid-state electrochemical cell using a highly active nanostructured palladium-gold alloy microelectrode as an in situ probe. Well-defined 'S-shaped' steady-state cyclic voltammograms exhibiting current-rising region at lower overpotentials and limiting current region at higher overpotentials have been first obtained for the electrochemical oxidation of formic acid at varying temperature. The 'S-shaped' steady state polarization curves and chronoamperometric curves enable convenient measurements of the anodic reaction kinetics and interfacial mass transport of formic acid under real polymer electrolyte membrane conditions. It is encouragingly found that formic acid can be directly oxidized to CO2 with the first electron transfer being the likely rate-determining step and the formation of surface poison can be ...

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There is renewed interest in the development of natural gas vehicles in response to the challenge to reduce urban air pollution and consumption of petroleum. The natural gas/diesel dual fuel engine is one way to apply natural gas to the conventional diesel engine. Dual fuel engines operating on natural gas and diesel emit less nitrogen oxides, and less carbon soot to the air compared to conventional diesel engines. The problem is that at light loads, fuel efficiency is reduced and emissions of hydrocarbons and carbon monoxide are increased. This thesis focused on control methods for emissions of hydrocarbons and carbon monoxide in the dual fuel engine at light loads. This was done by developing a reverse flow catalytic converter to complement dual fuel engine exhaust characteristics. Experimental measurements and numerical simulations of reverse flow catalytic converters were conducted. Reverse flow creates a high reactor temperature even when the engine is run at low exhaust ...

Science.gov (United States)

The formation and properties of Pd{sub 2}Si formed by focused ion beam implantation of Pd ions into Si is presented in this thesis. An extensive microstructural study using transmission electron microscopy was undertaken and the as-implanted as well as annealed microstructure is shown. Results of other analysis techniques such as Rutherford back scattering and secondary ion mass spectrometry etc. are also presented. Kinetic information on the growth of Pd{sub 2}Si obtained by both microstructural and resistance measurements indicates that the activation energy for growth of the silicide is around 0.36 to 0.39 eV. This can be compared with the normally reported value of 1.5 eV for Pd{sub 2}Si formed by annealing thin film Pd on Si. The growth of the silicide was found to follow t{sup 1/2} kinetics. Microstructural observation of the as-implanted samples showed extensive in-situ formation of Pd{sub 2}Di and also surprisingly few defect structures. A heat transfer model for the ...

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This is the final report of a three year DOE funded project titled ''A real-time coal content/ore grade (C{sub 2}OG) sensor''. The sensor, which is based on hyperspectral imaging technology, was designed to give a machine vision assay of ore or coal. Sensors were designed and built at Resonon, Inc., and then deployed at the Stillwater Mining Company core room in southcentral Montana for analyzing platinum/palladium ore and at the Montana Tech Spectroscopy Lab for analyzing coal and other materials. The Stillwater sensor imaged 91' of core and analyzed this data for surface sulfides which are considered to be pathfinder minerals for platinum/palladium at this mine. Our results indicate that the sensor could deliver a relative ore grade provided tool markings and iron oxidation were kept to a minimum. Coal, talc, and titanium sponge samples were also imaged and analyzed for content and grade with ...

Science.gov (United States)

An important advantage of carrying out enzymatic catalysis in organic media is the increased solubility of hydrophobic substrates. This study compares a model lipase catalyzed esterification of cholesterol using vinyl acetate (VA) in two such nontraditional media: high-pressure hexane and supercritical (SCF) ethane. The effect of using one of the reactants (VA) as a cosolvent to increase the solubility of the other reactant (cholesterol) in SCF ethane has been investigated. The thermodynamic activity of water (a(w)) in the reaction media was controlled by the direct addition of the salt hydrate pair Na(4)P(2)O(7)/Na(4)P(2)O(7).10H(2)O. The a(w) of the salt hydrate system is shown to be a function of pressure and its variation over the pressure range 104-173 bar has been estimated. The initial reaction rate in pressurized hexane was found to vary linearly with the cholesterol concentration. The reaction rate was also a function of pressure-the effect being more ...

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A 2-stage cold (non-tritium) PMR system was tested with the ITER mix in61 days of continuous operation. No decrease in performance was observed over the duration of the test. Decontamination factor (DF) was found to increase with decreasing inlet rate. Decontamination factors in excess of 1.4 {times} 10{sup 5} were obtained, but the exact value of the highest DF could not be determined because of analysis limitations. Results of the 61-day test were used to design a 2-stage PMR system for use in tritium testing. The PMR system was scaled up by a factor of 6 and built into a glovebox in the Tritium Systems Test Assembly (TSTA) of the Los Alamos National Laboratory. This system is approximately 1/5th of the expected full ITER scale. The ITER mix was injected into the PMR system for 31 hours, during which 4.5 g of tritium were processed. The 1st stage had DF = 200 and the 2nd stage had DF = 2.9 {times} 10{sup 6}. The overall DF = 5.8 {times} 10{sup 8}, which is greater than ITER ...

Science.gov (United States)

Phase relations in the ternary system Ce-Pd-Si have been established for the isothermal section at 800 deg. C based on X-ray powder diffraction and EMPA techniques on about 130 alloys, which were prepared by arc-melting under argon or powder reaction sintering. Eighteen ternary compounds have been observed to participate in the phase equilibria at 800 deg. C. Atom order was determined by direct methods from X-ray single-crystal counter data for the crystal structures of tau{sub 8}-Ce{sub 3}Pd{sub 4}Si{sub 4} (U{sub 3}Ni{sub 4}Si{sub 4}-type, Immm; a=0.41618(1), b=0.42640(1), c=2.45744(7) nm), tau{sub 16}-Ce{sub 2}Pd{sub 14}Si (own structure type, P4/nmm; a=0.88832(2), c=0.69600(2) nm) and also for tau{sub 18}-CePd{sub 1-x}Si{sub x} (x=0.07; FeB-type, Pnma; a=0.74422(5), b=0.45548(3), c=0.58569(4) nm). Rietveld refinements established the atom arrangement in the structures of tau{sub 5}-Ce{sub 3}PdSi{sub 3} (Ba{sub 3}Al{sub 2}Ge{sub 2}-type, Immm; a=0.41207(1), b=0.43026(1), ...

International Nuclear Information System (INIS)

The crystal structure of the compound Sm_4Pd_4Si_3 was determined by the single-crystal method (KM-4 automatic diffractometer, Mo K#alpha# radiation). Sm_4Pd_4Si_3 has the monoclinic Nd_4Rh_4Ge_3 type structure: space group C2/c, mC44 (No. 15), a=20.693(6), b=5.584(1), c=7.699(2) A, #beta#=109.48(3) , V=838 A"3, Z=4, #mu#=36.23 mm"-"1, R_F=0.0537, R_W=0.0435 for 1652 unique reflections. The coordination numbers of samarium atoms are 17 and 18. For palladium and silicon atoms icosahedra and trigonal prisms with additional atoms are typical as coordination polyhedra. The structure of Sm_4Pd_4Si_3 is composed of fragments of the YPd_2Si and Y_3Rh_2Si_2 structure in a ratio 1:1. (orig.).

British Library Electronic Table of Contents (United Kingdom)

Platinum(II) complexes (1-4) with bidentate N,Nprime-ligands, O,Oprime-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), of (S,S)-ethylenediamine-N,Nprime-di-2-(4-methyl)pentanoic acid were synthesized and characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. DFT calculations were performed for the complexes and it was found that only one diastereoisomer could be formed. Cytotoxic activity of complexes 1-4 was determined against chronic lymphocytic leukemia cells (CLL) and compared to the activity of ligand precursors L12HCl-L42HCl and corresponding palladium(II) complexes, [PdCl2L] (L = L1-L4). The complexes were found to exhibit significantly higher antitumor activities than cisplatin on CLL cells. Cytotoxic effect of platinum(II) complexes on CLL cel...

International Nuclear Information System (INIS)

In a closed circuit formed by bypassing pipelines connected to carbon steel parts, low oxygen coolants pass there through during operation. A solution containing ions of metals more noble than iron are circulated to bring the solution into contact with the carbon steel surface of the inner wall of the parts to form a deposition membrane of the metal more noble than iron on the surface to prevent acceleration of corrosion of the carbon steel parts due to low oxygen coolants. The solution containing ions of metals more noble than iron is a solution of palladium nitrate containing ions of platinum elements. This operation is conducted under a temperature condition of from 50degC to 150degC. In addition, the metal ion concentration of the solution circulating in the closed circuit is measured, it is compared with metal ion concentration previously determined, and the results are feed back to a means for controlling water quality of the solution to control the metal ion ...

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One- and two-dimensional long-period superstructures (LPS), based on the L1{sub 2} substructure, are systematically investigated for the noble metal-palladium alloys Cu-Pd, Ag-Pd and Au-Pd with first-principles methods. Notwithstanding the fact that the experimental phase diagrams of these systems yield totally different features, quite similar behaviour with respect to formation of low temperature ordered LPS-phases (Cu{sub 3}Pd: LPS 3, Ag{sub 3}Pd: LPS 3, Au{sub 3}Pd: LPS 2; {l_brace}Cu, Au{r_brace}Pd{sub 3}: L1{sub 2}, AgPd{sub 3}: not a ground state) is predicted. As a lever between via LDA obtained formation enthalpies and a thorough ground state scan, the cluster expansion method in conjunction with a genetic algorithm provides adequate means for the extraction of effective interactions, which also allow for an enhanced ground state scan in the configurational space of LPS structures. As a result, the sequences and energetical hierarchies for stable LPSs in ...

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Alkaline fuel cells (AFCs) provide a less corrosive environment and can provide higher electrode reaction kinetics than proton exchange membrane fuel cells (PEMFCs). The alkaline media also allows for the replacement of platinum (Pt) based electrocatalysts with non-Pt electrocatalysts. Studies have shown that palladium (Pd) and silver (Ag) form a homogenous solid solution with a face-centred cubic structure within a large range of temperatures. This study described the results of an oxygen reduction reaction (ORR) on lead-silver (Pd-Ag) alloy electrodes in alkaline media. The reaction was compared with Pd and Ag electrodes. The alloys were synthesized as thin films using a sequential electroless deposition of Pd and Ag on stainless steel discs followed by an annealing procedure in an Ar stream. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to characterize catalyst structure, morphology, and ...

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In order to gain a wider knowledge of corrosion phenomena in OFHC (oxygen free high conductivity) copper pipes of the stator cooling circuit of a power plant turboalternator, a research program was laid out which is based on the use of an experimental loop simulating real operating conditions as closely as possible. The samples examined were either copper foils or hollow conductors of the type that is normally used in the stator cooling system, and the circulating fluid was high purity water with controlled O/sub 2/, H/sub 2/ and C0/sub 2/ contents. Investigations were focused on the kinetics of O/sub 2/ removal through catalytic resins covered with metallic palladium (at different temperatures and pressures) and on the kinetics of CO/sub 2/ removal through mixed bed resins. Subsequently, attention was directed to the corrosion of copper (in the form of foils or hollow conductors) under different experimental conditions simulating either optimal or anomalous ...

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Recent studies indicate that [Fe]-hydrogenases and H{sub 2} metabolism are widely distributed among green algae. The enzymes are simple structured and catalyze H{sub 2} evolution with similar rates than the more complex [Fe]-hydrogenases from bacteria. Different green algal species developed diverse strategies to survive under sulfur deprivation. Chlamydomonas reinhardtii evolves large quantities of hydrogen gas in the absence of sulfur. In a sealed culture of C. reinhardtii, the photosynthetic O{sub 2} evolution rate drops below the rate of respiratory O{sub 2} consumption due to a reversible inhibition of photosystem II, thus leading to an intracellular anaerobiosis. The algal cells survive under these anaerobic conditions by switching their metabolism to a kind of photo-fermentation. Although possessing a functional [Fe]-hydrogenase gene, the cells of Scenedesmus obliquus produce no significant amounts of H{sub 2} under S-depleted conditions. Biochemical ...

Science.gov (United States)

The exchange of Eu[sup 3+] for Na[sup +] cations into the sodalite cages of X zeolite (Eu[sub 25]Na[sub 11]X) leads selectively to the isomerization reaction of cyclopropane to propylene. The latter reaction is catalyzed by Broensted acid sites with an apparent activation energy of 10.6 kcal/mol. Sorption measurements of cyclopropane and propylene with Eu/NaX and NaX zeolites at 40 C support the view that Na[sup +] cations might be considered as sites for sorption of these molecules. Force fields created by Eu[sub 4]O[sup 10+] present in Eu/NaX zeolite may affect sorption. On the other hand, Broensted acid sites in Eu/NaX enhance sorption of cyclopropane and propylene at 40 C. Chemisorption of propylene on the Broensted acid sites of Eu/NaX is reversible and may occur via a propylene carbenium cation intermediate. Small amounts of hexene are formed during this sorption. The amount of Broensted acid sites in the present Eu/NaX is at least 0.6 mmol/g cat.

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Sucrose phosphate synthase (SPS) catalyzes the transfer of a glycosyl group from an activated donor sugar, such as uridine diphosphate glucose (UDP-Glc), to a saccharide acceptor D-fructose 6-phosphate (F6P), resulting in the formation of UDP and D-sucrose-6'-phosphate (S6P). This is a central regulatory process in the production of sucrose in plants, cyanobacteria, and proteobacteria. Here, we report the crystal structure of SPS from the nonphotosynthetic bacterium Halothermothrix orenii and its complexes with the substrate F6P and the product S6P. SPS has two distinct Rossmann-fold domains with a large substrate binding cleft at the interdomain interface. Structures of two complexes show that both the substrate F6P and the product S6P bind to the A-domain of SPS. Based on comparative analysis of the SPS structure with other related enzymes, the donor substrate, nucleotide diphosphate glucose, binds to the B-domain of SPS. Furthermore, we propose a ...

Energy Technology Data Exchange (ETDEWEB)

Microstructural analyses by advanced metallographic techniques were conducted on mockup welds and a cracked BWR core shroud weld fabricated from Type 304L stainless steel. heat-affected zones of the shroud weld and mockup shielded-metal-arc welds were free of grain-boundary carbide, martensite, delta ferrite, or Cr depletion near grain boundaries. However, as a result of exposure to welding fumes, the heat-affected zones of the welds were significantly contaminated by fluorine and oxygen which migrate to grain boundaries. Significant oxygen contamination promotes fluorine contamination and suppresses classical thermal sensitization, even in Type 304 steels. Results of slow-strain-rate tensile tests indicate that fluorine exacerbates the susceptibility of irradiated steels to intergranular stress corrosion cracking. These observations, combined with previous reports on the strong influence of weld flux, indicate that oxygen and fluorine contamination and ...

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The effect of neutralizing cations on the secondary reactions of the primary products from CO hydrogenation over ion-exchanged zeolite-supported Ru catalysts was investigated using zeolites with different alkali cations (Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/). The transformation of olefins (propylene and butene) on the zeolites without the metal, under conditions similar to those used for CO hydrogenation, was also studied in order to understand the effect of the various constituents of the support, i.e., the Broensted acid sites generated during catalyst preparation and the alkali cations, on possible secondary reactions of the primary olefinic products. It was established that secondary acid-catalyzed reactions of these primary products can play a major role in shaping product selectivity during CO hydrogenation over zeolite-supported catalysts. Depending on the concentration and the strength of the acid sites, various competitive reaction paths ...

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A multifunctional protein kinase, purified from rat liver as ATP-citrate lyase kinase, has been identified as a glycogen synthase kinase. This kinase catalyzed incorporation of up to 1.5 mol of and)2numberSPO4/mol of synthase subunit associated with a decrease in the glycogen synthase activity ratio from 0.85 to a value of 0.15. Approximately 65-70% of the TUPO4 was incorporated into site 3 and 30-35% into site 2 as determined by reverse phase high performance liquid chromatography. This multifunctional kinase was distinguished from glycogen synthase kinase-3 on the basis of nucleotide and protein substrate specificities. Since the phosphate contents in glycogen synthase of sites 3 and 2 are altered in diabetes and by insulin administration, the possible involvement of the multifunctional kinase was explored. Glycogen synthase purified from diabetic rabbits was phosphorylated in vitro by this multifunctional kinase at only 10% of the rate compared to synthase ...

Science.gov (United States)

Four proteins from NCBI cog1816, previously annotated as adenosine deaminases, have been subjected to structural and functional characterization. Pa0148 (Pseudomonas aeruginosa PAO1), AAur1117 (Arthrobacter aurescens TC1), Sgx9403e, and Sgx9403g have been purified and their substrate profiles determined. Adenosine is not a substrate for any of these enzymes. All of these proteins will deaminate adenine to produce hypoxanthine with k(cat)/K(m) values that exceed 10(5) M(-1) s(-1). These enzymes will also accept 6-chloropurine, 6-methoxypurine, N-6-methyladenine, and 2,6-diaminopurine as alternate substrates. X-ray structures of Pa0148 and AAur1117 have been determined and reveal nearly identical distorted (?/?)(8) barrels with a single zinc ion that is characteristic of members of the amidohydrolase superfamily. Structures of Pa0148 with adenine, 6-chloropurine, and hypoxanthine were also determined, thereby permitting identification of the residues responsible for coordinating the ...

DEFF Research Database (Denmark)

It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO2 acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO2 + H(+M) reversible arrow HOSO(+M), HOSO + H/OH reversible arrow SO2 + H-2/H2O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO2 interactions. We find that the interaction of SO, with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO2 recombination and with SO + H2O, rather than SO2 + H-2, as major products of the HOSO + H reaction is in agreement with a range of experimental results from ...

Energy Technology Data Exchange (ETDEWEB)

Ionic liquids can enhance the activity, selectivity, and stability of enzyme catalysts. Enzymes and ionic liquids as catalysts are seen as a more environmentally friendly technology than the use of traditional catalyst materials in biofuels production. This study investigated the lipase catalyzed esterification reaction for biodiesel production in the presence of the ionic liquid BMIM PF{sub 6}. Methyl acetate was used as the acyl acceptor. A titremetric assay was conducted to measure the activity of the lipase with various amounts of ionic liquid. Reaction parameters were investigated in order to determine their effects on biodiesel conversion. An 80 per cent overall methyl oleate biodiesel yield was successfully produced in the presence of the ionic liquid. The ionic liquid improved lipase activity as well as overall biodiesel yield. Results also showed that the addition of the ionic liquid facilitated the separation of methyl esters from triacetylglycerol ...

Science.gov (United States)

During this reporting period four direct coal liquefaction experiments have been completed and a fifth is underway. These experiments have produced conversion and selectivity data on samples of Utah coal slurried in tetralin and catalyzed using iron-titanium hydride. Hydrogen loading of the alloy, catalyst particle size, coal particle size, operating temperatures for alloy addition and liquefaction without the catalysts present, have all been studied during these four experiments. Conversions of 61% DAF in 30 min have been recorded at 485/sup 0/F and 520 psia. The fifth run using the same coal at a reduced particle size has begun, after which we will move to samples of Kentucky and Alabama coals. Equipment manufacture, delivery, and installation delays, totaling over 6 months, greatly reduced the time available for research, making a 6 month no cost extension necessary. The extended time will permit completion of the proposed research tasks. 4 figs., 4 tabs.

International Nuclear Information System (INIS)

An assay for the microsomal hydroxylation of lauric acid (LA), based on HPLC with flow-through radiochemical detection, has been developed. Conditions were optimized for resolution and quantitation of three microsomal metabolites of "1"4C-LA, one of which has not been reported previously as a metabolite of LA in mammalian microsomal incubations. These products, 12-(omega)-hydroxy-LA, 11-(omega-1)-hydroxy-LA, and a novel metabolite, 10-(omega-2)-hydroxy-LA, were isolated by HPLC and identified by gas chromatography/mass spectrometry. In the presence of NADPH, the formation of all three metabolites was linear with time and microsomal protein concentration. Hydrogen peroxide also supported the microsomal metabolism of LA, although the ratio of metabolites was substantially different than that produced by NADPH-supported microsomes. Several biochemical probes (metyrapone, #alpha#-naphthoflavone, 2-diethylaminoethyl-2,2-diphenylvalerate hydrochloride, and 10-undecynoic acid) were used to ...

Energy Technology Data Exchange (ETDEWEB)

The French strategy of high level radioactive aqueous waste management is an incorporation in glassy fission products containers. Therefore, nitric acid soluble organic reagents needed for minor actinides and lanthanides selective separation from fission product solutions have to be sufficiently removed to reach carbon concentrations compatible with calcinator working. Thus, the ability of reagents to be oxidized under concentration conditions with or without denitration becomes a criteria of selection and have been studied. Further, if not working, other operations like hot hydrogen peroxide oxidation, catalyzed or not, are investigated. Reagents involved in this work are mainly complexing products (N-(2-Hydroxyethyl) Ethylene-diamine-tri-acetic Acid), pH keeping reagents (carboxylic acids like citric, glycolic, tartaric and lactic acid) and alkaline species (Tetramethylammonium hydroxide). Behaviour of acetic acid, which is often the main degradation product, has ...

Energy Technology Data Exchange (ETDEWEB)

Three abiotic systems are described that catalyze the reductive dehalogenation of heavily halogenated environmental pollutants, including carbon tetrachloride, trichloroethene, and perchloroethene. These systems include (a) an electrolytic reactor in which the potential on the working electrode (cathode) is fixed by using a potentiostat, (b) a light-driven system consisting of a semiconductor and (covalently attached) macrocycle that can accept light transmitted via an optical fiber, and a light-driven, two-solvent (isopropanol/acetone) system that promotes dehalogenation reactions via an unknown mechanism. Each is capable of accelerating reductive dehalogenation reactions to very high rates under laboratory conditions. Typically, millimolar concentrations of aqueous-phase targets can be dehalogenated in minutes to hours. The description of each system includes the elements of reaction mechanism (to the extent known), typical kinetic data, and a discussion of the ...

Science.gov (United States)

The efficiency of two thin-film diffusion barriers to be used in silicide/aluminum metallization schemes for silicon integrated circuits were evaluated. Control samples of Si/CoSi{sub 2}/Al and Si/Pd{sub 2}Si/Al, and test samples of Si/CoSi{sub 2}/Ta{sub 2}N/Al, Si/CoSi{sub 2}/W/Al and Si/Pd{sub 2}Si/Ta{sub 2}N/Al were used for sheet resistance, X-ray diffraction, Rutherford backscattering, and Auger-electron spectroscopic measurements. TEM studies were carried out on representative samples to examine the nature of the interfaces. Results from the analytical tests indicated that all three types of test samples are resistant to gross diffusion and intermixing of Co, Pd, Al and Si. They also showed that in the control samples, annealing causes interdiffusion of these species, necessitating the presence of a diffusion barrier. For test contacts, results demonstrated that although diffusion barriers may be successful in preventing metallurgical interdiffusion, they may not be viable in ...

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New techniques were developed to construct Schottky barrier and homojunction solar cells on GaAs substrates. Schottky barrier metal-semiconductor solar cells were produced for the first time on p-type GaAs substrate using a sputter-deposition method to form the barrier. The sputter deposition of gold or gold/palladium is the key to the method since normal thermal evaporation of gold onto p-type GaAs produces ohmic contacts. The results of this investigation are consistent with the idea that sputter damage produces donor type surface states on GaAs. Barrier heights were measured for both p-type sputtered and n-type thermally evaporated diodes using current-voltage and capacitance-voltage methods. Deep-level transient spectroscopy was used to identify the trap center concentration and energy levels for both diodes in an effort to explain the relatively large dark current in the p-type sputtered diodes. Homojunction GaAs solar cells were fabricated using several ...

Energy Technology Data Exchange (ETDEWEB)

The authors developed a method, termed an H-blot, by which the poly(A) tract of any specific mRNA may be detected by RNA filter hybridization after its removal from the body of the mRNA by a RNase H-catalyzed endonucleolytic cleavage in the 3' untranslated region. Using this method, they studied the modulation of the length of the poly(A) tract of rat vasopressin mRNA in vivo during changes in the levels of this mRNA resulting from a physiologic stimulus, osmotic stress. The poly(A) tract of hypothalamic vasopressin mRNA in hydrated rats was, quite remarkably, --250 nucleotides in length, in contrast to that of somatostatin mRNA, which was --30 nucleotides long. Vasopressin mRNA poly(A) tail length increased progressively from --250 to --400 nucleotides with the application of the hyperosmotic stimulus and declined to base line after its removal; somatostatin mRNA poly(A) tail length did not change during osmotic stress. The poly(A) tract length of total ...

International Nuclear Information System (INIS)

Three cDNAs, designated IIA3, IIA3v, and IIA4, coding for P450s in the CYP2A gene subfamily were isolated from a #lambda#gt11 library prepared from human hepatic mRNA. Only three nucleotide differences and a single amino acid difference, Leu"1"6"0#->#His, were found between IIA3 and IIA3v, indicating that they are probably allelic variants. IIA4 displayed 94% amino acid similarity with IIA3 and IIA3v. The three cDNAs were inserted into vaccinia virus, and recombinant viruses were used to infect human hepatoma Hep G2 cells. Only IIA3 was able to produce an enzyme that had a reduced CO-bound spectrum with a #lambda#_m_a_x at 450 nm. This expressed enzyme was able to carry out coumarin 7-hydroxylation and ethoxycoumarin O-deethylation. cDNA-expressed IIA3v and IIA4 failed to incorporate heme and were enzymatically inactive. Analysis of IIA proteins in human liver microsomes, using antibody against rat IIA2, revealed two proteins of 49 and 50 kDa, the former of which appeared to ...

Science.gov (United States)

A WO(3)/TiO(2) composite, hollow-sphere photocatalyst with average diameter of 320 nm and shell thickness of 50 nm was successfully prepared using a template method. UV-vis diffuse reflectance spectra illustrated that the main absorption edges of the WO(3)/TiO(2) hollow spheres were red-shifted compared to the TiO(2) hollow spheres, indicating an extension of light absorption into the visible region of the composite photocatalyst. The WO(3) and TiO(2) phases were confirmed by X-ray diffraction analysis. BET isotherms revealed that the specific surface area and average pore diameter of the hollow spheres were 40.95 m(2)/g and 19 nm, respectively. Photocatalytic experiments indicate that 78% MB was degraded by WO(3)/TiO(2) hollow spheres under visible light within 80 min. Under the same conditions, only 24% MB can be photodegraded by TiO(2). The photocatalytic mineralization of MB, catalyzed by TiO(2) and WO(3)/TiO(2), proceeded at a significantly higher rate under ...

Energy Technology Data Exchange (ETDEWEB)

Trihydroxynaphthalene reductase catalyzes two intermediate steps in the fungal melanin biosynthetic pathway. The enzyme, a typical short-chain dehydrogenase, is the biochemical target of three commercial fungicides. The fungicides bind preferentially to the NADPH form of the enzyme. Three X-ray structures of the Magnaporthe grisea enzyme complexed with NADPH and two commercial and one experimental fungicide were determined at 1.7 {angstrom} (pyroquilon), 2.0 {angstrom} (2,3-dihydro-4-nitro-1H-inden-1-one, 1), and 2.1 {angstrom} (phthalide) resolutions. The chemically distinct inhibitors occupy similar space within the enzyme's active site. The three inhibitors share hydrogen bonds with the side chain hydroxyls of Ser-164 and Tyr-178 via a carbonyl oxygen (pyroquilon and 1) or via a carbonyl oxygen and a ring oxygen (phthalide). Active site residues occupy similar positions among the three structures. A buried water molecule that is hydrogen bonded to the ...

Science.gov (United States)

Lipase catalyzed esterification reactions between lactic acid and several fatty acids have been studied. Difficulties arise in esterifying lactic acid because of the potential for this substance to act both as an acyl donor and as a nucleophile. These difficulties were minimized via strategies which greatly increased the yield of the desired ester. Use of the companion fatty acid in excess with respect to lactic acid in an apolar solvent (n-hexane) in which the lactic is not completely dissolved has been employed to minimize the potential for lactic acid to act as an acyl donor in a self-polymerization reaction.Beneficial and sinergistic effects of both silica gel and molecular sieves on conversion to the desired product are described. However, careful control of the amount of molecular sieves used is required. This fact is a consequence of two opposing effects of this material: i.e. adsorption of both lactic acid and water from the reaction mixture. For reaction ...

Energy Technology Data Exchange (ETDEWEB)

By catalyzing the rate-limiting step in adipose tissue lipolysis, hormone-sensitive lipase (HSL) is an important regulator of energy homeostasis. The role and importance of HSL in tissues other than adipose are poorly understood. We report here the cloning and expression of a testicular isoform, designated HSL{sub tes}. Due to an addition of amino acids at the NH{sub 2}-termini, rat and human HSL{sub tes} consist of 1068 and 1076 amino acids, respectively, compared to the 768 and 775 amino acids, respectively, of the adipocyte isoform (HSL{sub adi}). A novel exon of 1.2 kb, encoding the human testis-specific amino acids, was isolated and mapped to the HSL gene, 16 kb upstream of the exons encoding HSL{sub adi}. The transcribed mRNA of 3.9 kb was specifically expressed in testis. No significant similarity with other known proteins was found for the testis-specific sequence. The amino acid composition differs from the HSL{sub adi} sequence, with a notable hydrophilic ...

International Nuclear Information System (INIS)

Thromboxane A2, the predominant product of arachidonic acid metabolism in the blood platelet, is a potent vasoconstrictor and platelet agonist. During its biosynthesis from cyclic endoperoxide, 12(S)-hydroxy-5Z,8E,10E-heptadecatrienoic acid (HHT) is formed in equal amounts. The further metabolism of HHT, catalyzed by 15-hydroxyprostaglandin dehydrogenase, leads to 12-oxo-5Z,8E,10E-heptadecatrienoic acid (Oxo-HT). Sample workup procedures are described which allow for the sensitive and reproducible determination of these two arachidonic acid metabolites in human plasma by gas chromatography-mass spectrometry in the presence of deuterated analogues as internal standards. HHT is derivatized to the pentafluorobenzyl ester tert-butyldimethylsilyl ether. In order to enable quantification of low concentrations of about 10 pg/ml in nonstimulated human plasma, the samples have to be purified by HPLC. Oxo-HT is derivatized to the pentafluorobenzyl ester, which is purified by ...

Energy Technology Data Exchange (ETDEWEB)

Improvement in efficiency and profitability of hydrogenation reaction of heavy hydrocarbon resources is the most important matter to be done. In this study, coprocessing of coal and heavy oil vacuum residue was conducted using syngas-water as a hydrogen source. For the investigation of effect of the reaction temperature during the coprocessing of Wandoan coal and Arabian heavy vacuum residue using Fe(CO)5 as a catalyst, the conversion, 66.0% was obtained at 425{degree}C. For the investigation of effect of reaction time, the yield of light fractions further increased during the two stage reaction at 400{degree}C for 60 minutes and at 425{degree}C for 60 minutes. Finally, almost 100% of THF-soluble matter was obtained through the reaction using 2 mmol of Fe(CO)5 catalyst at 400{degree}C for 60 minutes, and hydrogenation of heavy oil was proceeded simultaneously. When comparing coprocessing reactions using three kinds of hydrogen sources, i.e., hydrogen, CO-water, and syngas-water, the ...

Energy Technology Data Exchange (ETDEWEB)

Human senescence marker protein 30 (SMP30), which functions enzymatically as a lactonase, hydrolyzes various carbohydrate lactones. The penultimate step in vitamin-C biosynthesis is catalyzed by this enzyme in nonprimate mammals. It has also been implicated as an organophosphate hydrolase, with the ability to hydrolyze diisopropyl phosphofluoridate and other nerve agents. SMP30 was originally identified as an aging marker protein, whose expression decreased androgen independently in aging cells. SMP30 is also referred to as regucalcin and has been suggested to have functions in calcium homeostasis. The crystal structure of the human enzyme has been solved from X-ray diffraction data collected to a resolution of 1.4 {angstrom}. The protein has a 6-bladed {beta}-propeller fold, and it contains a single metal ion. Crystal structures have been solved with the metal site bound with either a Ca{sup 2+} or a Zn{sup 2+} atom. The catalytic role of the metal ion has been ...

Energy Technology Data Exchange (ETDEWEB)

Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in the chemical ...

International Nuclear Information System (INIS)

Interest to thin film of metals' silicides first of all is conditioned intrinsic al them unique physical properties. On their basis of it is possible to produce extremely sophisticated devices of solid-state electronics, production which needs the controlled change of physics, chemical and electrical properties with high-level of accuracy. On the present time most are in detail investigated composition, structure and properties of three-dimensional samples of metals' silicides. In the last years the intensive are led to researches in the direction of creation and study of physical-chemical properties thin (500-1000 Angstroms) and ultrafine (100-120 Angstroms) films silicides. It has information about composition, morphology of surface and emission of properties of thin film of silicides of barium, of cobalt and of palladium, was obtained in conditions of ultra-high vacuum. Low energy ion implantation and further annealing on composition, electronic and crystalline ...

Energy Technology Data Exchange (ETDEWEB)

Bis(diphenylphosphino)phenylamine can be selectivity oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoyl products Ph[sub 2]PN(PH)PPh[sub 2]=E, (E = S, Se). These compounds act as bidentate chelate ligands toward metal complexes forming (CO)[sub 4]M(LL) (M = Mo, W), CO(Cl)Rh(LL), and Cl[sub 2]M(LL), (M = Pt, Pd) where (LL) is the thioyl or selenoyl derivative of the aminobis(phosphine). IR and NMR data are given for all complexes. The carbonyl infrared stretching frequencies show that the chelates form with the phosphine cis to any CO which is present. The [sup 31]P NMR of all complexes of two doublets except for the Rh complexes wherein the Rh spin also couples to phosphorous to produce two doublets of doublets. The [sup 2]J[sub PP] values range from 56 to 112 Hz. [sup 1]J[sub PSe] coupling provide valuable assistance for the assignment of the phosphorus resonances which range widely from 55 to 126 ppm for P[sup III] and from 60 to 80 ppm for the ...

Energy Technology Data Exchange (ETDEWEB)

The objective of this work is to improve the process for CO{sub 2} capture by alkanolamine absorption/stripping by developing an alternative solvent, aqueous K{sub 2}CO3 promoted by piperazine (PZ). Pilot plant testing was performed in a 16.8-inch ID absorber and stripper with recirculation of air and CO{sub 2}. Three solvents (7 m MEA, 5 m K{sup +}/2.5 m PZ, and 6.4 m K{sup +}/1.6 m PZ) were tested in four campaigns with three different absorber packings. Pilot plant testing established that 5 m K{sup +}/2.5 m PZ requires two times less packing than 7 m MEA and three times less packing than 6.4 m K{sup +}/1.6 m PZ. A rigorous model of the thermodynamics and mass transfer was developed in the RateSep{trademark} block of AspenPlus{reg_sign}. The double matrix stripper reduces energy consumption by 5 to 15%. The best K{sup +}/PZ solvent, 4 m K{sup +}/4 m PZ, and the best process configuration, double matrix stripper with a double intercooled absorber, requires equivalent work of 40 ...