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Sample records for water-gas shift reaction

  1. Water-gas-shift reaction on metal nanoparticles and surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Ping; Rodriguez, José A.

    2007-04-01

    Density functional theory was employed to investigate the water-gas-shift reaction (WGS, CO +H2O→H2+CO2) on Au29 and Cu29 nanoparticles seen with scanning tunneling microscopy in model Au /CeO2(111) and Cu /CeO2(111) catalysts. Au(100) and Cu(100) surfaces were also included for comparison. According to the calculations of the authors, the WGS on these systems operate via either redox or associative carboxyl mechanism, while the rate-limiting step is the same, water dissociation. The WGS activity decreases in a sequence: Cu29>Cu(100)>Au29>Au(100), which agrees well with the experimental observations. Both nanoparticles are more active than their parent bulk surfaces. The nanoscale promotion on the WGS activity is associated with the low-coordinated corner and the edge sites as well as the fluxionality of the particles, which makes the nanoparticles more active than the flat surfaces for breaking the O-H bond. In addition, the role of the oxide support during the WGS was addressed by comparing the activity seen in the calculations of the authors for the Au29 and Cu29 nanoparticles and activity reported for X /CeO2(111) and X /ZnO(000ı¯)(X =Cu or Au) surfaces.

  2. Zeolite Membrane Reactor for Water Gas Shift Reaction for Hydrogen Production

    SciTech Connect

    Lin, Jerry Y.S.

    2013-01-29

    Gasification of biomass or heavy feedstock to produce hydrogen fuel gas using current technology is costly and energy-intensive. The technology includes water gas shift reaction in two or more reactor stages with inter-cooling to maximize conversion for a given catalyst volume. This project is focused on developing a membrane reactor for efficient conversion of water gas shift reaction to produce a hydrogen stream as a fuel and a carbon dioxide stream suitable for sequestration. The project was focused on synthesizing stable, hydrogen perm-selective MFI zeolite membranes for high temperature hydrogen separation; fabricating tubular MFI zeolite membrane reactor and stable water gas shift catalyst for membrane reactor applications, and identifying experimental conditions for water gas shift reaction in the zeolite membrane reactor that will produce a high purity hydrogen stream. The project has improved understanding of zeolite membrane synthesis, high temperature gas diffusion and separation mechanisms for zeolite membranes, synthesis and properties of sulfur resistant catalysts, fabrication and structure optimization of membrane supports, and fundamentals of coupling reaction with separation in zeolite membrane reactor for water gas shift reaction. Through the fundamental study, the research teams have developed MFI zeolite membranes with good perm-selectivity for hydrogen over carbon dioxide, carbon monoxide and water vapor, and high stability for operation in syngas mixture containing 500 part per million hydrogen sulfide at high temperatures around 500°C. The research teams also developed a sulfur resistant catalyst for water gas shift reaction. Modeling and experimental studies on the zeolite membrane reactor for water gas shift reaction have demonstrated the effective use of the zeolite membrane reactor for production of high purity hydrogen stream.

  3. Enhancement of water-gas shift reaction efficiency: catalysts and the catalyst bed arrangement

    NASA Astrophysics Data System (ADS)

    Baronskaya, Natal'ya A.; Minyukova, Tat'yana P.; Khassin, Aleksandr A.; Yurieva, Tamara M.; Parmon, Valentin N.

    2010-12-01

    The results of studies devoted to the search for catalysts of water-gas shift (WGS) reaction that are highly active in a wide temperature interval are generalized. New compositions based on traditional and alternative, as regards the chemical composition, catalysts of high- and low-temperature WGS reaction are considered in detail. The single-stage arrangement of WGS reaction ensuring small temperature gradients in the radial direction of the catalyst bed are discussed.

  4. Minimization of steam requirements and enhancement of water-gas shift reaction with warm gas temperature CO2 removal

    DOEpatents

    Siriwardane, Ranjani V; Fisher, II, James C

    2013-12-31

    The disclosure utilizes a hydroxide sorbent for humidification and CO.sub.2 removal from a gaseous stream comprised of CO and CO.sub.2 prior to entry into a water-gas-shift reactor, in order to decrease CO.sub.2 concentration and increase H.sub.2O concentration and shift the water-gas shift reaction toward the forward reaction products CO.sub.2 and H.sub.2. The hydroxide sorbent may be utilized for absorbtion of CO.sub.2 exiting the water-gas shift reactor, producing an enriched H.sub.2 stream. The disclosure further provides for regeneration of the hydroxide sorbent at temperature approximating water-gas shift conditions, and for utilizing H.sub.2O product liberated as a result of the CO.sub.2 absorption.

  5. Harnessing the Power of the Water-Gas Shift Reaction for Organic Synthesis.

    PubMed

    Ambrosi, Andrea; Denmark, Scott E

    2016-09-26

    Since its original discovery over a century ago, the water-gas shift reaction (WGSR) has played a crucial role in industrial chemistry, providing a source of H2 to feed fundamental industrial transformations such as the Haber-Bosch synthesis of ammonia. Although the production of hydrogen remains nowadays the major application of the WGSR, the advent of homogeneous catalysis in the 1970s marked the beginning of a synergy between WGSR and organic chemistry. Thus, the reducing power provided by the CO/H2 O couple has been exploited in the synthesis of fine chemicals; not only hydrogenation-type reactions, but also catalytic processes that require a reductive step for the turnover of the catalytic cycle. Despite the potential and unique features of the WGSR, its applications in organic synthesis remain largely underdeveloped. The topic will be critically reviewed herein, with the expectation that an increased awareness may stimulate new, creative work in the area.

  6. Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions

    SciTech Connect

    Zhai, Y.; Pierre, D; Si, R; Deng, W; Ferrin, P; Nilekar, A; Peng, G; Herron, J; Bell, D; et. al.

    2010-01-01

    We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H{sub 2}O + CO {yields} H{sub 2} + CO{sub 2}) used for producing H{sub 2}. The alkali ion-associated surface OH groups are activated by CO at low temperatures ({approx}100 C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O{sub x}(OH){sub y} species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.

  7. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    SciTech Connect

    Pizarro, C.; Escudey, M.; Moya, S.A.; Fabris, J.D.

    2005-04-26

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124 deg. C to 500 deg. C. The room temperature Moessbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 deg. C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  8. On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper

    SciTech Connect

    Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos

    2008-01-30

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Periodic, self-consistent density functional theory (DFT-GGA) calculations are used to investigate the water gas shift reaction (WGSR) mechanism on Cu(111). The thermochemistry and activation energy barriers for all the elementary steps of the commonly accepted redox mechanism, involving complete water activation to atomic oxygen, are presented. Through our calculations, we identify carboxyl, a new reactive intermediate, which plays a central role in WGSR on Cu(111). The thermochemistry and activation energy barriers of the elementary steps of a new reaction path, involving carboxyl, are studied. A detailed DFTbased microkinetic model of experimental reaction rates, accounting for both the previous and the new WGSR mechanism show that, under relevant experimental conditions, (1) the carboxyl-mediated route is the dominant path, and (2) the initial hydrogen abstraction from water is the rate-limiting step. Formate is a stable “spectator” species, formed predominantly through CO₂ hydrogenation. In addition, the microkinetic model allows for predictions of (i) surface coverage of intermediates, (ii) WGSR apparent activation energy, and (iii) reaction orders with respect to CO, H₂O, CO₂, and H₂.

  9. Gold catalysts for pure hydrogen production in the water-gas shift reaction: activity, structure and reaction mechanism.

    PubMed

    Burch, Robbie

    2006-12-21

    The production of hydrogen containing very low levels of carbon monoxide for use in polymer electrolyte fuel cells requires the development of catalysts that show very high activity at low temperatures where the equilibrium for the removal of carbon monoxide using the water-gas shift reaction is favourable. It has been claimed that oxide-supported gold catalysts have the required high activity but there is considerable uncertainty in the literature about the feasibility of using these catalysts under real conditions. By comparing the activity of gold catalysts with that of platinum catalysts it is shown that well-prepared gold catalysts are significantly more active than the corresponding platinum catalysts. However, the method of preparation and pre-treatment of the gold catalysts is critical and activity variations of several orders of magnitude can be observed depending on the methods chosen. It is shown that an intimate contact between gold and the oxide support is important and any preparative procedure that does not generate such an interaction, or any subsequent treatment that can destroy such an interaction, may result in catalysts with low activity. The oxidation state and structure of active gold catalysts for the water-gas shift reaction is shown to comprise gold primarily in a zerovalent metallic state but in intimate contact with the support. This close contact between small metallic gold particles and the support may result in the "atoms" at the point of contact having a net charge (most probably cationic) but the high activity is associated with the presence of metallic gold. Both in situ XPS and XANES appear unequivocal on this point and this conclusion is consistent with similar measurements on gold catalysts even when used for CO oxidation. In situ EXAFS measurements under water gas shift conditions show that the active form of gold is a small gold cluster in intimate contact with the oxide support. The importance of the gold/oxide interface is

  10. Hydrodesulphurization of Light Gas Oil using hydrogen from the Water Gas Shift Reaction

    NASA Astrophysics Data System (ADS)

    Alghamdi, Abdulaziz

    2009-12-01

    The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391°C for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas

  11. One-Dimensional Ceria as Catalyst for the Low-Temperature Water-Gas Shift Reaction

    SciTech Connect

    Han, W.; Wen, W; Hanson, J; Teng, X; Marinkovic, N; Rodriguez, J

    2009-01-01

    Synchrotron-based in situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to study pure ceria and Pd-loaded ceria nanotubes and nanorods (1D-ceria) as catalysts for the water-gas shift (WGS) reaction. While bulk ceria is very poor as WGS catalysts, pure 1D-ceria displayed catalytic activity at a temperature as low as 300 C. The reduction of the pure 1D-ceria in pure hydrogen started at 150 C, which is a much lower temperature than those previously reported for the reduction of 3D ceria nanoparticles. This low reduction temperature reflects the novel morphology of the oxide systems and may be responsible for the low-temperature WGS catalytic activity seen for the 1D-ceria. Pd-loaded 1D ceria displayed significant WGS activity starting at 200 C. During pretreatment in H{sub 2}, the ceria lattice parameter increased significantly around 60 C, which indicates that Pd-oxygen interactions may facilitate the reduction of Pd-loaded 1D-ceria. Pd and ceria both participate in the formation of the active sites for the catalytic reactions. The low-temperature hydrogen pretreatment results in higher WGS activity for Pd-loaded 1D-ceria.

  12. SiC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Paul K.T. Liu

    2001-10-16

    This technical report summarizes our activities conducted in Yr II. In Yr I we successfully demonstrated the feasibility of preparing the hydrogen selective SiC membrane with a chemical vapor deposition (CVD) technique. In addition, a SiC macroporous membrane was fabricated as a substrate candidate for the proposed SiC membrane. In Yr II we have focused on the development of a microporous SiC membrane as an intermediate layer between the substrate and the final membrane layer prepared from CVD. Powders and supported thin silicon carbide films (membranes) were prepared by a sol-gel technique using silica sol precursors as the source of silicon, and phenolic resin as the source of carbon. The powders and films were prepared by the carbothermal reduction reaction between the silica and the carbon source. The XRD analysis indicates that the powders and films consist of SiC, while the surface area measurement indicates that they contain micropores. SEM and AFM studies of the same films also validate this observation. The powders and membranes were also stable under different corrosive and harsh environments. The effects of these different treatments on the internal surface area, pore size distribution, and transport properties, were studied for both the powders and the membranes using the aforementioned techniques and XPS. Finally the SiC membrane materials are shown to have satisfactory hydrothermal stability for the proposed application. In Yr III, we will focus on the demonstration of the potential benefit using the SiC membrane developed from Yr I and II for the water-gas-shift (WGS) reaction.

  13. Water-gas shift reaction on alumina-supported Pt-CeOx catalysts prepared by supercritical fluid deposition

    DOE PAGES

    Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

    2016-08-25

    Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeOx catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

  14. Photoassisted Water-Gas Shift Reaction over Platinized TiO2 Catalysts.

    DTIC Science & Technology

    1980-07-15

    level diagram, (2) that holes will be found at both the Pt/ TiO2 and the TiO2 /gas Interfaces and (3) that electrons will be captured at the Pt...T10 2 which enhances photoconductivity . We expect this sa~e change in conductivity to be important in our powdered catalysts. Changes in electronic band...02 during the photoassisted water-gas shiit reaction over Pt/ TIO2 at 25 0 C. p W24 tort. I20 figure a Pictorial Model of the photoinduced redox

  15. In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

    NASA Astrophysics Data System (ADS)

    Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

    2016-05-01

    Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

  16. Influence of the monoclinic and tetragonal zirconia phases on the water gas shift reaction. A theoretical study.

    PubMed

    Cerón, María Luisa; Herrera, Barbara; Araya, Paulo; Gracia, Francisco; Toro-Labbé, Alejandro

    2013-07-01

    We present a theoretical study of the water gas shift reaction taking place on zirconia surfaces modeled by monoclinic and tetragonal clusters. In order to understand the charge transfer between the active species, in this work we analyze the influence of the geometry of monoclinic and tetragonal zirconia using reactivity descriptors such as electronic chemical potential (μ), charge transfer (ΔN) and molecular hardness (η). We have found that the most preferred surface is tetragonal zirconia (tZrO2) indicating also that low charge transfer systems will generate less stable intermediates, that will allow to facilitate desorption process.

  17. Heat Integration of the Water-Gas Shift Reaction System for Carbon Sequestration Ready IGCC Process with Chemical Looping

    SciTech Connect

    Juan M. Salazara; Stephen E. Zitney; Urmila M. Diwekara

    2010-01-01

    Integrated gasification combined cycle (IGCC) technology has been considered as an important alternative for efficient power systems that can reduce fuel consumption and CO2 emissions. One of the technological schemes combines water-gas shift reaction and chemical-looping combustion as post gasification techniques in order to produce sequestration-ready CO2 and potentially reduce the size of the gas turbine. However, these schemes have not been energetically integrated and process synthesis techniques can be applied to obtain an optimal flowsheet. This work studies the heat exchange network synthesis (HENS) for the water-gas shift reaction train employing a set of alternative designs provided by Aspen energy analyzer (AEA) and combined in a process superstructure that was simulated in Aspen Plus (AP). This approach allows a rigorous evaluation of the alternative designs and their combinations avoiding all the AEA simplifications (linearized models of heat exchangers). A CAPE-OPEN compliant capability which makes use of a MINLP algorithm for sequential modular simulators was employed to obtain a heat exchange network that provided a cost of energy that was 27% lower than the base case. Highly influential parameters for the pos gasification technologies (i.e. CO/steam ratio, gasifier temperature and pressure) were calculated to obtain the minimum cost of energy while chemical looping parameters (oxidation and reduction temperature) were ensured to be satisfied.

  18. Structure Sensitivity of the Low-temperature Water-gas Shift Reaction on Cu–CeO2 catalysts

    SciTech Connect

    Si, R.; Zhang, L.; Raitano, J.; Yi, N.; Chan, S.-W.; Flytzani-Stephanopoulos, M.

    2012-01-17

    We have investigated the structure sensitivity of the water-gas shift (WGS) reaction on Cu-CeO{sub 2} catalysts prepared at the nanoscale by different techniques. On the surface of ceria, different CuO{sub x} structures exist. We show here that only the strongly bound Cu-[O{sub x}]-Ce species, probably associated with the surface oxygen vacancies of ceria, are active for catalyzing the low-temperature WGS reaction. Weakly bound CuO{sub x} clusters and CuO nanoparticles are spectator species in the reaction. Isolated Cu{sup 2+} ions doping the ceria surface are not active themselves, but they are important in that they create oxygen vacancies and can be used as a reservoir of copper to replenish surface Cu removed by leaching or sintering. Accordingly, synthesis techniques such as coprecipitation that allow for extensive solubility of Cu in ceria should be preferred over impregnation, deposition-precipitation, ion exchange or another two-step method whereby the copper precursor is added to already made ceria nanocrystals. For the synthesis of different structures, we have used two methods: a homogeneous coprecipitation (CP), involving hexamethylenetetramine as the precipitating agent and the pH buffer; and a deposition-precipitation (DP) technique. In the latter case, the ceria supports were first synthesized at the nanoscale with different shapes (rods, cubes) to investigate any potential shape effect on the reaction. Cu-CeO{sub 2} catalysts with different copper contents up to ca. 20 at.% were prepared. An indirect shape effect of CeO{sub 2}, manifested by the propensity to form oxygen vacancies and strongly bind copper in the active form, was established; i.e. the water-gas shift reaction is not structure-sensitive. The apparent activation energy of the reaction on all samples was similar, 50 {+-} 10 kJ/mol, in a product-free (2% CO-10% H{sub 2}O) gas mixture.

  19. Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory

    SciTech Connect

    Liu, P.

    2010-11-28

    Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO{sub 2}/Cu(111), ZrO{sub 2}/Cu(111) < MoO{sub 3}/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.

  20. SIC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Paul K.T. Liu

    2003-12-01

    A hydrogen selective membrane as a membrane reactor (MR) can significantly improve the power generation efficiency with a reduced capital and operating cost for the waster-gas-shift reaction. Existing hydrogen selective ceramic membranes are not suitable for the proposed MR due to their poor hydrothermal stability. In this project we have focused on the development of innovative silicon carbide (SiC) based hydrogen selective membranes, which can potentially overcome this technical barrier. SiC macro-porous membranes have been successfully fabricated via extrusion of commercially available SiC powder. Also, an SiC hydrogen selective thin film was prepared via our CVD/I technique. This composite membrane demonstrated excellent hydrogen selectivity at high temperature ({approx}600 C). More importantly, this membrane also exhibited a much improved hydrothermal stability at 600 C with 50% steam (atmospheric pressure) for nearly 100 hours. In parallel, we have explored an alternative approach to develop a H{sub 2} selective SiC membrane via pyrolysis of selected pre-ceramic polymers and sol-gel techniques. Building upon the positive progress made in the membrane development study, we conducted an optimization study to develop an H{sub 2} selective SiC membrane with sufficient hydrothermal stability suitable for the WGS environment. In addition, mathematical simulation has been performed to compare the performance of the membrane reactor (MR) vs conventional packed bed reactor for WGS reaction. Our result demonstrates that >99.999% conversion can be accomplished via WGS-MR using the hydrogen selective membrane developed by us. Further, water/CO ratio can be reduced, and >97% hydrogen recovery and <200 ppm CO can be accomplished according to the mathematical simulation. Thus, we believe that the operating economics of WGS can be improved significantly based upon the proposed MR concept. In parallel, gas separations and hydrothermal and long-term-storage stability of the

  1. Application of dual descriptor to understand the activity of C u/Z r O 2 catalysts in the water gas shift reaction.

    PubMed

    Cerón, María Luisa; Calatayud, Mònica

    2017-02-01

    A comparative theoretical study applying Dual Descriptor has been performed using Water Gas Shift reaction, catalyzed by copper supported on monoclinic and tetragonal zirconia. The Dual Descriptor and thermodynamic considerations were used to understand the structural effects that occur in the reaction when it is catalyzed by C u on both zirconia phases. It was found that the formation of carbonates in the C u supported on tetragonal zirconia dehydrogenates consistently with experimental results.

  2. Water-Gas Shift and CO Methanation Reactions over Ni-CeO2(111) Catalysts

    SciTech Connect

    Senanayake, Sanjaya D; Evans, Jaime; Agnoli, Stefano; Barrio, Laura; Chen, Tsung-Liang; Hrbek, Jan; Radriguez, Jose

    2011-01-01

    X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO2(111) surfaces. Upon adsorption on CeO2(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500 800 K) leads to partial reduction of the ceria substrate with the formation of Ni2? species that exists as NiO and/or Ce1-xNixO2-y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO2(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce?3 cations, CO dissociates on the surface at 300 K forming NiCx compounds that may be involved in the formation of CH4 at higher temperatures. At medium and large Ni coverages ([0.3 ML), the Ni/CeO2(111) surfaces are able to catalyze the production of methane from CO and H2, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (\\0.3 ML), the Ni/CeO2(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water gas shift reaction.

  3. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS-SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2005-07-15

    A high temperature membrane reactor (MR) has been developed to enhance the water-gas-shift (WGS) reaction efficiency with concomitant CO{sub 2} removal for sequestration. This improved WGS-MR with CO{sub 2} recovery capability is ideally suitable for integration into the Integrated Gasification Combined-Cycle (IGCC) power generation system. Two different CO{sub 2}-affinity materials were selected in this study. The Mg-Al-CO{sub 3}-layered double hydroxide (LDH) was investigated as an adsorbent or a membrane for CO{sub 2} separation. The adsorption isotherm and intraparticle diffusivity for the LDH-based adsorbent were experimentally determined, and suitable for low temperature shift (LTS) of WGS. The LDH-based membranes were synthesized using our commercial ceramic membranes as substrate. These experimental membranes were characterized comprehensively in terms of their morphology, and CO{sub 2} permeance and selectivity to demonstrate the technical feasibility. In parallel, an alternative material-base membrane, carbonaceous membrane developed by us, was characterized, which also demonstrated enhanced CO{sub 2} selectivity at the LTS-WGS condition. With optimization on membrane defect reduction, these two types of membrane could be used commercially as CO{sub 2}-affinity membranes for the proposed application. Based upon the unique CO{sub 2} affinity of the LDHs at the LTS/WGS environment, we developed an innovative membrane reactor, Hybrid Adsorption and Membrane Reactor (HAMR), to achieve {approx}100% CO conversion, produce a high purity hydrogen product and deliver a concentrated CO{sub 2} stream for disposal. A mathematical model was developed to simulate this unique one -step process. Finally a benchtop reactor was employed to generate experimental data, which were consistent with the prediction from the HAMR mathematical model. In summary, the project objective, enhancing WGS efficiency for hydrogen production with concomitant CO{sub 2} removal for

  4. Water-gas shift reaction on alumina-supported Pt-CeOx catalysts prepared by supercritical fluid deposition

    SciTech Connect

    Deal, Jacob W.; Le, Phong; Corey, C. Blake; More, Karren; West, Christy Wheeler

    2016-08-25

    Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreated exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeOx catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.

  5. Supported Copper, Nickel and Copper-Nickel Nanoparticle Catalysts for Low Temperature Water-Gas-Shift Reaction

    NASA Astrophysics Data System (ADS)

    Lin, Jiann-Horng

    Hydrogen is being considered worldwide as a future replacement for gasoline, diesel fuel, natural gas in both the transportation and non-transportation sectors. Hydrogen is a versatile energy carrier that can be produced from a variety of widely available primary energy sources, including coal, natural gas, biomass, solar, wind, and nuclear power. Coal, the most abundant fossil fuel on the planet, is being looked at as the possible future major source of H2, due to the development of the integrated gasification combined cycle (IGCC) and integrated gasification fuel cell technologies (IGFC). The gasification of coal produces syngas consisting of predominately carbon monoxide and hydrogen with some remaining hydrocarbons, carbon dioxide and water. Then, the water-gas shift reaction is used to convert CO to CO2 and additional hydrogen. The present work describes the synthesis of model Cu, Ni and Cu-Ni catalysts prepared from metal colloids, and compares their behavior in the WGS reaction to that of traditional impregnation catalysts. Initially, we systematically explored the performance of traditional Cu, Ni and Cu-Ni WGS catalysts made by impregnation methods. Various bimetallic Cu-Ni catalysts were prepared by supported impregnation and compared to monometallic Cu and Ni catalysts. The presence of Cu in bimetallic catalysts suppressed undesirable methanation side reaction, while the Ni component was important for high WGS activity. Colloidal Cu, Ni and Cu-Ni alloy nanoparticles obtained by chemical reduction were deposited onto alumina to prepare supported catalysts. The resulting Cu and Ni nanoparticle catalysts were found to be 2.5 times more active in the WGS reaction per unit mass of active metal as compared to catalysts prepared by the conventional impregnation technique. The powder XRD and HAADF-STEM provided evidence supporting the formation of Cu-Ni particles containing the Cu core and Cu-Ni alloy shell. The XPS data indicated surface segregation of Cu in

  6. The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)

    NASA Astrophysics Data System (ADS)

    Nakamura, I.; Fujitani, T.; Uchijima, T.; Nakamura, J.

    1998-03-01

    The catalytic activity of Zn vapor-deposited Cu(100) and Cu(110) surfaces for methanol synthesis by the hydrogenation of CO 2 and the reverse water-gas shift reaction were studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). At a reaction temperature of 523 K, no promotional effect of Zn was observed for the methanol synthesis on both Zn/Cu(100) and Zn/Cu(110). The results were quite different from those for Zn/Cu(111), on which a significant promotion of methanol synthesis activity appeared to be due to the deposition of Zn, indicating that the promotional effect of Zn was sensitive to the surface structure of Cu. However, hysteresis was observed in the catalytic activity for methanol synthesis over the Zn/Cu(110) surface upon heating above 543 K in the reaction mixture. The activity became twice that measured before heating, which was close to the methanol synthesis activity of Zn/Cu(111) at the same Zn coverage. On the other hand, no such hysteresis was observed for the reverse water-gas shift reaction on Zn/Cu(110), indicating that the active site for methanol synthesis was not identical to that for the reverse water-gas shift reaction. In the post-reaction surface analysis, formate species was detected on both Zn/Cu(100) and Zn/Cu(110), whose coverage increased with increasing Zn coverage at 0< ΘZn<0.2. No correlation between the formate coverage and the methanol synthesis activity was obtained, which was in contrast to the results for Zn/Cu(111). Thus, the structure sensitivity observed in the catalytic activity of methanol synthesis over Zn-deposited Cu surfaces is ascribed to the significant difference in the reactivity of the formate intermediate.

  7. Advanced Water-Gas Shift Membrane Reactor

    SciTech Connect

    Sean Emerson; Thomas Vanderspurt; Susanne Opalka; Rakesh Radhakrishnan; Rhonda Willigan

    2009-01-07

    The overall objectives for this project were: (1) to identify a suitable PdCu tri-metallic alloy membrane with high stability and commercially relevant hydrogen permeation in the presence of trace amounts of carbon monoxide and sulfur; and (2) to identify and synthesize a water gas shift catalyst with a high operating life that is sulfur and chlorine tolerant at low concentrations of these impurities. This work successfully achieved the first project objective to identify a suitable PdCu tri-metallic alloy membrane composition, Pd{sub 0.47}Cu{sub 0.52}G5{sub 0.01}, that was selected based on atomistic and thermodynamic modeling alone. The second objective was partially successful in that catalysts were identified and evaluated that can withstand sulfur in high concentrations and at high pressures, but a long operating life was not achieved at the end of the project. From the limited durability testing it appears that the best catalyst, Pt-Re/Ce{sub 0.333}Zr{sub 0.333}E4{sub 0.333}O{sub 2}, is unable to maintain a long operating life at space velocities of 200,000 h{sup -1}. The reasons for the low durability do not appear to be related to the high concentrations of H{sub 2}S, but rather due to the high operating pressure and the influence the pressure has on the WGS reaction at this space velocity.

  8. Analysis and modeling of PEM fuel cell stack performance: Effect of in situ reverse water gas shift reaction and oxygen bleeding

    NASA Astrophysics Data System (ADS)

    Karimi, G.; Li, Xianguo

    In this study the performance of a polymer electrolyte membrane (PEM) fuel cell stack is analyzed with a mathematical model when the stack operates on hydrocarbon reformate gas as the anode feed stream. It is shown that the effect of carbon dioxide dilution of the hydrogen dominated reformate gas has a minimal impact on the stack performance. However, the CO-poisoning effect due to the in situ reverse water gas shift reaction in the anode feed stream could have a very serious adverse impact on the stack performance, especially at high current densities. Thermodynamic calculations indicate that the equilibrium concentrations of CO could be as high as 100 ppm, generated by the in situ reverse water gas shift reaction, under the typical conditions of PEM fuel cell operation; and are influenced by the stack operating temperature and water content of the reformate anode feed. This CO-poisoning of the stack performance is shown mitigated effectively by introducing about 0.5-1% oxygen to the anode feed.

  9. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    SciTech Connect

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), such as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).

  10. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    DOE PAGES

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; ...

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), suchmore » as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).« less

  11. Atomically Dispersed Au-(OH)x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction

    SciTech Connect

    Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

    2013-03-27

    We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au–O–TiOx sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this “excess” gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

  12. On the Importance of the Associative Carboxyl Mechanism for the Water-Gas Shift Reaction at Pt/CeO2 Interface Sites

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-03-06

    Periodic density functional theory calculations and microkinetic modeling are used to investigate the associative carboxyl pathways of the water-gas shift (WGS) reaction at the Pt/CeO2 (111) interface. Analysis of a microkinetic model based on parameters obtained from first principles suggests that the turnover frequencies for the CO-assisted associative carboxyl mechanism are comparable to experimental results. However, this microkinetic model containing various associative carboxyl pathways at interface sites cannot explain the experimentally observed activation barriers and reaction orders of Pt/CeO2 catalysts. Considering furthermore that a model of an associative carboxyl mechanism with redox regeneration, also derived from first principles and recently published by us, accurately predicts all kinetic parameters while displaying a 2 orders of magnitude higher turnover frequency, we conclude that at Pt/CeO2 interface sites, the WGS reaction follows a bifunctional Mars-van Krevelen mechanism in which support oxygen vacancies facilitate water dissociation.

  13. Magnetic Ni-Co alloys induced by water gas shift reaction, Ni-Co oxides by CO oxidation and their supercapacitor applications

    NASA Astrophysics Data System (ADS)

    Lee, Seungwon; Kang, Jung-Soo; Leung, Kam Tong; Kim, Seog K.; Sohn, Youngku

    2016-11-01

    Ni-Co alloys and oxides have attracted considerable attention in diverse fields, such as magnetic materials, energy storage and environmental/energy producing catalysts. Herein, the formation of magnetic Ni-Co alloys was induced by the water-gas shift reaction (WGSR) and the oxides were prepared by post-annealing and a CO oxidation reaction. The materials were characterized using a range of techniques. The annealed and post-CO oxidation Ni and Co-rich samples showed the crystal structures of NiCo2O4(Co3O4)/NiO and NiCo2O4/Co3O4, respectively. The Ni-Co oxides showed better supercapacitor performance than the corresponding Ni-Co alloys. The Co-rich samples exhibited better supercapacitor performance and CO oxidation activity than the Ni-rich sample. In addition, the Co-rich alloy showed a magnetization of 114 emu/g, which was approximately 2× larger than that of the Ni-rich alloy. The WGS reaction and the wide application tests are useful for designing new materials applicable to a wide range of areas.

  14. A common single-site Pt(II)-O(OH)x- species stabilized by sodium on "active" and "inert" supports catalyzes the water-gas shift reaction.

    PubMed

    Yang, Ming; Liu, Jilei; Lee, Sungsik; Zugic, Branko; Huang, Jun; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

    2015-03-18

    While it has long been known that different types of support oxides have different capabilities to anchor metals and thus tailor the catalytic behavior, it is not always clear whether the support is a mere carrier of the active metal site, itself not participating directly in the reaction pathway. We report that catalytically similar single-atom-centric Pt sites are formed by binding to sodium ions through -O ligands, the ensemble being equally effective on supports as diverse as TiO2, L-zeolites, and mesoporous silica MCM-41. Loading of 0.5 wt % Pt on all of these supports preserves the Pt in atomic dispersion as Pt(II), and the Pt-O(OH)x- species catalyzes the water-gas shift reaction from ∼120 to 400 °C. Since the effect of the support is "indirect," these findings pave the way for the use of a variety of earth-abundant supports as carriers of atomically dispersed platinum for applications in catalytic fuel-gas processing.

  15. Gold(III)-CO and gold(III)-CO2 complexes and their role in the water-gas shift reaction

    PubMed Central

    Roşca, Dragoş-Adrian; Fernandez-Cestau, Julio; Morris, James; Wright, Joseph A.; Bochmann, Manfred

    2015-01-01

    The water-gas shift (WGS) reaction is an important process for the generation of hydrogen. Heterogeneous gold catalysts exhibit good WGS activity, but the nature of the active site, the oxidation state, and competing reaction mechanisms are very much matters of debate. Homogeneous gold WGS systems that could shed light on the mechanism are conspicuous by their absence: gold(I)–CO is inactive and gold(III)–CO complexes were unknown. We report the synthesis of the first example of an isolable CO complex of Au(III). Its reactivity demonstrates fundamental differences between the CO adducts of the neighboring d8 ions Pt(II) and Au(III): whereas Pt(II)-CO is stable to moisture, Au(III)–CO compounds are extremely susceptible to nucleophilic attack and show WGS reactivity at low temperature. The key to understanding these dramatic differences is the donation/back-donation ratio of the M–CO bond: gold-CO shows substantially less back-bonding than Pt-CO, irrespective of closely similar ν(CO) frequencies. Key WGS intermediates include the gold-CO2 complex [(C^N^C)Au]2(μ-CO2), which reductively eliminates CO2. The species identified here are in accord with Au(III) as active species and a carboxylate WGS mechanism. PMID:26601313

  16. Development of Ni-Mo/Al2O3 catalyst for reverse water gas shift (RWGS) reaction.

    PubMed

    Kharaji, Abolfazl Gharibi; Shariati, Ahmad; Ostadi, Mohammad

    2014-09-01

    In the present study, Mo/Al2O3 catalyst was prepared using impregnation method. Then it was promoted with Ni ions to produce Ni-Mo/Al2O3 catalyst. The structures of the catalysts were studied using X-ray diffraction (XRD), Energy dispersive X-ray (EDAX), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), CO chemisorption, temperature programmed reduction of hydrogen (H2-TPR) and scanning electron microscope (SEM) techniques. Catalytic performances of the two catalysts were investigated in a fixed-bed reactor for RWGS reaction. The results indicated that addition of nickel promoter to Mo/Al2O3 catalyst enhances its activity. It is reasonable for the electron deficient state of the Ni species and existence of NiMoO4 phase to possess high activity in RWGS reaction. Stability test of Ni-Mo/Al2O3 catalyst was carried out in a fixed bed reactor and a high CO2 conversion for 60 h time on stream was demonstrated. This study introduces a new catalyst, Ni-Mo/Al2O3, with high activity and stability for RWGS reaction.

  17. Theoretical studies on the catalysis of the reverse water-gas shift reaction using first-row transition metal beta-diketiminato complexes.

    PubMed

    Liu, Cong; Munjanja, Lloyd; Cundari, Thomas R; Wilson, Angela K

    2010-06-03

    The reverse water-gas shift reaction CO(2) + H(2) --> H(2)O + CO has been investigated using a set of homogeneous catalyst models L'M(I) (L' = beta-diketiminate, C(3)N(2)H(5)(-); M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). The thermodynamics of prototypical reaction pathways were simulated at two levels of theory: B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ. The modeled catalytic reaction has been considered in the following steps: coordination of CO(2) by the catalyst to generate a carbon dioxide complex, L'M(CO(2)); scission of L'M(CO(2)) to yield L'M(CO) and L'M(O); L'M(O) hydrogenation to form L'M(H(2)O). The final products, H(2)O and CO, were obtained from the dissociation of L'M(H(2)O) and L'M(CO). All of the reactants, intermediates, and products were modeled, where different possible conformers and multiplicities were identified and considered as potential minima. The reaction enthalpy DeltaH, of all steps for each catalyst as a function of transition metal have been determined. The Mn and Fe catalysts show more thermodynamically accessible pathways than the other catalyst models studied. The overall reaction enthalpy has been determined not only by B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ but also via a more rigorous ab initio electron-correlation-based approach, the correlation consistent Composite Approach (ccCA).

  18. Interaction of CO with OH on Au(111): HCOO, CO3, and HOCO as Key Intermediates in the Water-Gas Shift Reaction

    SciTech Connect

    Senanayake, S.; Stacchiola, D; Liu, P; Mullins, C; Hrbek, J; Rodriguez, J

    2009-01-01

    We have investigated the role of formate (HCOO), carbonate (CO{sub 3}), and carboxyl (HOCO) species as possible intermediates in the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction on Au(111) using synchrotron-based core level photoemission, near-edge X-ray absorption fine structure (NEXAFS), and infrared absorption spectroscopy (IR). Adsorbed HCOO, CO{sub 3}, and OH species were prepared by adsorbing formic acid, carbon dioxide, and water on a Au(111) surface precovered with 0.2 ML of atomic oxygen, respectively. HCOOH interacts weakly with Au(111), but on O/Au(111) it dissociates its acidic H to yield adsorbed formate. The results of NEXAFS, IR, and density-functional calculations indicate that the formate adopts a bidentate configuration on Au(111). Since the HCOO groups are stable on Au(111) up to temperatures near 350 K, it is not likely that formate is a key intermediate for the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction at low temperatures. In fact, the formation of this species could lead eventually to surface poisoning. When compared to a formate species, a carbonate species formed by the reaction of CO{sub 2} with O/Au(111) has low stability, decomposing at temperatures between 100 and 125 K, and should not poison the gold surface. Neither HCOO nor CO{sub 3} was detected during the reaction of CO with OH on Au(111) at 90-120 K. The results of photoemission and IR spectroscopy point to HO {leftrightarrow} CO interactions, consistent with the formation of an unstable HOCO intermediate which has a very short lifetime on the gold surface. The possible mechanism for the low-temperature water-gas shift on gold catalysts is discussed in light of these results.

  19. CO{sub 2} SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS-SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO{sub 2}

    SciTech Connect

    Paul K. T. Liu

    2005-01-31

    Our CO{sub 2}-affinity material synthesis activities thus far have offered two base materials suitable for hydrogen production via low temperature water gas shift reaction (LTS-WGS) with concomitant removal of CO{sub 2} for sequestration. They include (i) a nanoporous CO{sub 2}-affinity membrane and (ii) a hydrotalcite based CO-affinity adsorbent. These two materials offer a commercially viable opportunity for implementing an innovative process concept termed the hybrid adsorbent-membrane reactor (HAMR) for LTS-WGS, proposed by us in a previous quarterly report. A complete mathematical model has been developed in this quarter to describe the HAMR system, which offers process flexibility to incorporate both catalysts and adsorbents in the reactor as well as permeate sides. In comparison with the preliminary mathematical model we reported previously, this improved model incorporates ''time'' as an independent variable to realistically simulate the unsteady state nature of the adsorptive portion of the process. In the next quarterly report, we will complete the simulation to demonstrate the potential benefit of the proposed process based upon the performance parameters experimentally obtained from the CO{sub 2}-affinity adsorbent and membrane developed from this project.

  20. The mechanism of the water-gas shift reaction on Cu/TiO2(110) elucidated from application of density-functional theory.

    PubMed

    Peng, Shih-Feng; Ho, Jia-Jen

    2011-12-07

    The Cu/TiO(2)(110) surface displays a great catalytic activity toward the water-gas shift reaction (WGSR), for which Cu is considered to be the most active metal on a TiO(2)(110)-supported surface. Experiments revealed that Cu nanoparticles bind preferentially to the terrace and steps of the TiO(2)(110) surface, which would not only affect the growth mode of the surface cluster but also enhance the catalytic activity, unlike Au nanoparticles for which occupancy of surface vacancies is favored, resulting in poorer catalytic performance than Cu. With density-functional theory we calculated some possible potential-energy surfaces for the carboxyl and redox mechanisms of the WGSR at the interface between the Cu cluster and the TiO(2) support. Our results show that the redox mechanism would be the dominant path; the resident Cu clusters greatly diminish the barrier for CO oxidation (22.49 and 108.68 kJ mol(-1), with and without Cu clusters, respectively). When adsorbed CO is catalytically oxidized by the bridging oxygen of the Cu/TiO(2)(110) surface to form CO(2), the release of CO(2) from the surface would result in the formation of an oxygen vacancy on the surface to facilitate the ensuing water splitting (barrier 34.90 vs. 50.49 kJ mol(-1), with and without the aid of a surface vacancy).

  1. Water-gas shift reaction over gold nanoparticles dispersed on nanostructured CeOx-TiO2(110) surfaces: Effects of high ceria coverage

    NASA Astrophysics Data System (ADS)

    Grinter, D. C.; Park, J. B.; Agnoli, S.; Evans, J.; Hrbek, J.; Stacchiola, D. J.; Senanayake, S. D.; Rodriguez, J. A.

    2016-08-01

    Scanning tunnelling microscopy has been used to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO2(110)-(1 × 1). The other half of the surface comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the water-gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. For Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3 + formed during WGS reaction conditions.

  2. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    PubMed Central

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P.; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G.; Kazantzis, Nikolaos K.; Ma, Yi Hua

    2016-01-01

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields. PMID:27657143

  3. Morphological effects of the nanostructured ceria support on the activity and stability of CuO/CeO2 catalysts for the water-gas shift reaction.

    PubMed

    Yao, S Y; Xu, W Q; Johnston-Peck, A C; Zhao, F Z; Liu, Z Y; Luo, S; Senanayake, S D; Martínez-Arias, A; Liu, W J; Rodriguez, J A

    2014-08-28

    Three CuO/CeO2 catalyst with different morphologies of ceria, namely nanospheres, nanorods and nanocubes, were synthesized and used to catalyze the water-gas shift (WGS) reaction. The reactivity tests showed that the Cu supported on the ceria nanospheres exhibited both the highest activity and superior stability when compared with the nanocube and nanorod ceria catalysts. Operando X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) methods were used to characterize these catalysts in their working state. High resolution electron microscopy (HRTEM, STEM) was used to look at the local atomic structure and nano-scale morphology. Our results show that the morphology of the ceria support, which can involve different crystal faces and concentrations of defects and imperfections, has a critical impact on the catalytic properties and influences: (1) the dispersion of CuO in the as-synthesized catalyst; (2) the particle size of metallic Cu upon reduction during the WGS reaction, (3) the stability of the metallic Cu upon variations of temperature, and (4) the dissociation of water on the ceria support. The nanosphere ceria catalyst showed an excellent water dissociation capability, the best dispersion of Cu and a strong Cu-Ce interaction, therefore delivering the best performance among the three WGS catalysts. The metallic Cu, which is the active species during the WGS reaction, was more stabilized on the nanospheres than on the nanorods and nanocubes and thus led to a better stability of the nanosphere catalyst than the other two architectures. Each catalyst exhibited a distinctive line-shape in the 800-1600 cm(-1) region of the DRIFTS spectra, pointing to the existence of different types of carbonate or carboxylate species as surface intermediates for the WGS.

  4. Flame Synthesis of Nanosized Cu-Ce-O, Ni-Ce-O, and Fe-Ce-O Catalysts for the Water-Gas Shift (WGS) Reaction

    DTIC Science & Technology

    2009-11-04

    transition-metal-doped ceria materials, which include coprecipitation (19-21), hydro- thermal (22), microemulsion (23-25), sol - gel (26, 27), and solution...examined toward water-gas shift (WGS) activity for fuel processing applications. The WGS activity of metal ceria catalysts decreases in the order Cu-Ce...Nonsto- ichiometric CeO2-x-based nanocrystalline catalysts have been shown to provide excellent activity for SO2 reduction by CO, CO oxidation

  5. Ceria-based Catalysts for the Production of H2 Through the Water-gas-shift Reaction: Time-Resolved XRD and XAFS Studies

    SciTech Connect

    Wang,X.; Rodriguez, J.; Hanson, J.; Gamarra, D.; Marinez-Arias, A.; Fernandez-Garcia, M.

    2008-01-01

    Hydrogen is a potential alternate energy source for satisfying many of our energy needs. In this work, we studied H2 production from the water-gas-shift (WGS) reaction over Ce1-x Cu x O2 catalysts, prepared with a novel microemulsion method, using two synchrotron-based techniques: time-resolved X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). The results are compared with those reported for conventional CuO x /CeO2 and AuO x /CeO2 catalysts obtained through impregnation of ceria. For the fresh Ce1-x Cu x O2 catalysts, the results of XAFS measurements at the Cu K-edge indicate that Cu is in an oxidation state higher than in CuO. Nevertheless, under WGS reaction conditions the Ce1-x Cu x O2 catalysts undergo reduction and the active phase contains very small particles of metallic Cu and CeO2-x . Time-resolved XRD and XAFS results also indicate that Cud+ and Aud+ species present in fresh CuO x /CeO2 and AuO x /CeO2 catalysts do not survive above 200 C under the WGS conditions. In all these systems, the ceria lattice displayed a significant increase after exposure to CO and a decrease in H2O, indicating that CO reduced ceria while H2O oxidized it. Our data suggest that H2O dissociation occurred on the Ovacancy sites or the Cu-Ovacancy and Au-Ovacancy interfaces. The rate of H2 generation by a Ce0.95Cu0.05O2 catalyst was comparable to that of a 5 wt% CuO x /CeO2 catalyst and much bigger than those of pure ceria or CuO.

  6. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    SciTech Connect

    Rodriguez, J.A.; Barrio, L.; Kubacka, A.; Zhou, G.; Estrella, M.; Martınez-Arias, A.; Hanson, J.C.; Fernandez-Garcıa, M.

    2010-07-29

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni?O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate?carbonate route is operative for the production of hydrogen.

  7. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    SciTech Connect

    Barrio, L.; Kubacka, A; Zhou, G; Estrella, M; Martinez-Arias, A; Hanson, J; Fernandez-Garcia, M; Rodriguez, J

    2010-01-01

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni-O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate-carbonate route is operative for the production of hydrogen.

  8. Process Intensification with Integrated Water-Gas-Shift Membrane Reactor

    SciTech Connect

    2009-11-01

    This factsheet describes a research project whose objective is to develop hydrogen-selective membranes for an innovative gas-separation process based on a water-gas-shift membrane reactor (WGS-MR) for the production of hydrogen.

  9. WATER-GAS SHIFT WITH INTEGRATED HYDROGEN SEPARATION PROCESS

    SciTech Connect

    Maria Flytzani-Stephanopoulos; Xiaomei Qi; Scott Kronewitter

    2004-02-01

    This project involved fundamental research and development of novel cerium oxide-based catalysts for the water-gas-shift reaction and the integration of these catalysts with Pd-alloy H{sub 2} -separation membranes supplying high purity hydrogen for fuel cell use. Conditions matching the requirements of coal gasifier-exit gas streams were examined in the project. Cu-cerium oxide was identified as the most promising high-temperature water-gas shift catalyst for integration with H{sub 2}-selective membranes. Formulations containing iron oxide were found to deactivate in the presence of CO{sub 2}. Cu-containing ceria catalysts, on the other hand, showed high stability in CO{sub 2}-rich gases. This type gas will be present over much of the catalyst, as the membrane removes the hydrogen produced from the shift reaction. The high-temperature shift catalyst composition was optimized by proper selection of dopant type and amount in ceria. The formulation 10at%Cu-Ce(30at%La)O{sub x} showed the best performance, and was selected for further kinetic studies. WGS reaction rates were measured in a simulated coal-gas mixture. The apparent activation energy, measured over aged catalysts, was equal to 70.2 kJ/mol. Reaction orders in CO, H{sub 2}O, CO{sub 2} and H{sub 2} were found to be 0.8, 0.2, -0.3, and -0.3, respectively. This shows that H{sub 2}O has very little effect on the reaction rate, and that both CO{sub 2} and H{sub 2} weakly inhibit the reaction. Good stability of catalyst performance was found in 40-hr long tests. A flat (38 cm{sup 2}) Pd-Cu alloy membrane reactor was used with the catalyst washcoated on oxidized aluminum screens close coupled with the membrane. To achieve higher loadings, catalyst granules were layered on the membrane itself to test the combined HTS activity/ H{sub 2} -separation efficiency of the composite. Simulated coal gas mixtures were used and the effect of membrane on the conversion of CO over the catalyst was evidenced at high space

  10. Cr-free Fe-based metal oxide catalysts for high temperature water gas shift reaction of fuel processor using LPG

    SciTech Connect

    lee, Joon Y.; Lee, Dae-Won; Lee, Kwan Young; Wang, Yong

    2009-08-15

    The goal of this study was to identify the most suitable chromium-free iron-based catalysts for the HTS (high temperature shift) reaction of a fuel processor using LPG. Hexavalent chromium (Cr6+) in the commercial HTS catalyst has been regarded as hazardous material. We selected Ni and Co as the substitution for chromium in the Fe-based HTS catalyst and investigated the HTS activities of these Crfree catalysts at LPG reformate condition. Cr-free Fe-based catalysts which contain Ni, Zn, or Co instead of Cr were prepared by coprecipitation method and the performance of the catalysts in HTS was evaluated under gas mixture conditions (42% H2, 10% CO, 37% H2O, 8% CO2, and 3% CH4; R (reduction factor): about 1.2) similar to the gases from steam reforming of LPG (100% conversion at steam/carbon ratio = 3), which is higher than R (under 1) of typically studied LNG reformate condition. Among the prepared Cr-free Febased catalysts, the 5 wt%-Co/Fe/20 wt%-Ni and 5 wt%-Zn/Fe/20 wt%-Ni catalysts showed good catalytic activity under this reaction condition simulating LPG reformate gas.

  11. Catalytic, nucleophilic allylation of aldehydes with 2-substituted allylic acetates: carbon-carbon bond formation driven by the water-gas shift reaction.

    PubMed

    Denmark, Scott E; Matesich, Zachery D

    2014-07-03

    The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO2-t-Bu, COMe, Ph, CH(OEt)2, and Me) undergo high-yielding additions with aromatic, α,β-unsaturated, and aliphatic aldehydes. The conditions of the reaction were found to be mild (75 °C, 24-48 h) and only required the use of 2-3 mol % of the triruthenium dodecacarbonyl catalyst under 40-80 psi of CO. The stoichiometries of water and allylic acetate employed were found to be critical to reaction efficiency.

  12. Development of Novel Water-Gas Shift Membrane Reactor

    SciTech Connect

    Ho, W. S. Winston

    2004-12-29

    This report summarizes the objectives, technical barrier, approach, and accomplishments for the development of a novel water-gas-shift (WGS) membrane reactor for hydrogen enhancement and CO reduction. We have synthesized novel CO{sub 2}-selective membranes with high CO{sub 2} permeabilities and high CO{sub 2}/H{sub 2} and CO{sub 2}/CO selectivities by incorporating amino groups in polymer networks. We have also developed a one-dimensional non-isothermal model for the countercurrent WGS membrane reactor. The modeling results have shown that H{sub 2} enhancement (>99.6% H{sub 2} for the steam reforming of methane and >54% H{sub 2} for the autothermal reforming of gasoline with air on a dry basis) via CO{sub 2} removal and CO reduction to 10 ppm or lower are achievable for synthesis gases. With this model, we have elucidated the effects of system parameters, including CO{sub 2}/H{sub 2} selectivity, CO{sub 2} permeability, sweep/feed flow rate ratio, feed temperature, sweep temperature, feed pressure, catalyst activity, and feed CO concentration, on the membrane reactor performance. Based on the modeling study using the membrane data obtained, we showed the feasibility of achieving H{sub 2} enhancement via CO{sub 2} removal, CO reduction to {le} 10 ppm, and high H{sub 2} recovery. Using the membrane synthesized, we have obtained <10 ppm CO in the H{sub 2} product in WGS membrane reactor experiments. From the experiments, we verified the model developed. In addition, we removed CO{sub 2} from a syngas containing 17% CO{sub 2} to about 30 ppm. The CO{sub 2} removal data agreed well with the model developed. The syngas with about 0.1% CO{sub 2} and 1% CO was processed to convert the carbon oxides to methane via methanation to obtain <5 ppm CO in the H{sub 2} product.

  13. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS

    SciTech Connect

    Carl R.F. Lund

    2002-08-02

    The kinetics of water-gas shift were studied over ferrochrome catalysts under conditions with high carbon dioxide partial pressures, such as would be expected in a membrane reactor. The catalyst activity is inhibited by increasing carbon dioxide partial pressure. A microkinetic model of the reaction kinetics was developed. The model indicated that catalyst performance could be improved by decreasing the strength of surface oxygen bonds. Literature data indicated that adding either ceria or copper to the catalyst as a promoter might impart this desired effect. Ceria-promoted ferrochrome catalysts did not perform any better than unpromoted catalyst at the conditions tested, but copper-promoted ferrochrome catalysts did offer an improvement over the base ferrochrome material. A different class of water-gas shift catalyst, sulfided CoMo/Al{sub 2}O{sub 3} is not affected by carbon dioxide and may be a good alternative to the ferrochrome system, provided other constraints, notably the requisite sulfur level and maximum temperature, are not too limiting. A model was developed for an adiabatic, high-temperature water-gas shift membrane reactor. Simulation results indicate that an excess of steam in the feed (three moles of water per mole of CO) is beneficial even in a membrane reactor as it reduces the rate of adiabatic temperature rise. The simulations also indicate that much greater improvement can be attained by improving the catalyst as opposed to improving the membrane. Further, eliminating the inhibition by carbon dioxide will have a greater impact than will increasing the catalyst activity (assuming inhibition is still operative). Follow-up research into the use of sulfide catalysts with continued kinetic and reactor modeling is suggested.

  14. Water-gas shift on gold catalysts: catalyst systems and fundamental studies.

    PubMed

    Tao, Franklin Feng; Ma, Zhen

    2013-10-07

    Since the pioneering finding by Haruta et al. that small gold nanoparticles on reducible supports can be highly active for low-temperature CO oxidation, the synthesis, characterization, and application of supported gold catalysts have attracted much attention. The water-gas shift reaction (WGSR: CO + H2O = CO2 + H2) is important for removing CO and upgrading the purity of H2 for fuel cell applications, ammonia synthesis, and selective hydrogenation processes. In recent years, much attention has been paid to exploration the possibility of using supported gold nanocatalysts for WGSR and understanding the fundamental aspects related to catalyst deactivation mechanisms, nature of active sites, and reaction mechanisms. Here we summarize recent advances in the development of supported gold catalysts for this reaction and fundamental insights that can be gained, and furnish our assessment on the status of research progress.

  15. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides.

    PubMed

    Thalinger, Ramona; Opitz, Alexander K; Kogler, Sandra; Heggen, Marc; Stroppa, Daniel; Schmidmair, Daniela; Tappert, Ralf; Fleig, Jürgen; Klötzer, Bernhard; Penner, Simon

    2015-05-28

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic-electronic conducting perovskite-type materials La0.6Sr0.4FeO3-δ (LSF) and SrTi0.7Fe0.3O3-δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities.

  16. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

    PubMed Central

    2015-01-01

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

  17. The Integration of a Structural Water Gas Shift Catalyst with a Vanadium Alloy Hydrogen Transport Device

    SciTech Connect

    Barton, Thomas; Argyle, Morris; Popa, Tiberiu

    2009-06-30

    component of conventional high temperature water gas shift iron oxide based catalysts. The catalysts contained Fe-Al-Cr-Cu-O and were synthesized by co-precipitation. A series of catalysts were prepared with 5 to 50 wt% Al2O3, with 8 wt% Cr2O3, 4 wt% CuO, and the balance Fe2O3. All of the catalysts were compared to a reference WGS catalyst (88 wt% FeOx, 8 wt% Cr2O3, and 4 wt% CuO) with no alumina. Alumina addition to conventional high temperature water gas shift catalysts at concentrations of approximately 15 wt% increased CO conversion rates and increase thermal stability. A series of high temperature water gas shift catalysts containing iron, chromia, and copper oxides were prepared with small amounts of added ceria in the system Fe-Cr-Cu-Ce-O. The catalysts were also tested kinetically under WGS conditions. 2-4 wt% ceria addition (at the expense of the iron oxide content) resulted in increased reaction rates (from 22-32% higher) compared to the reference catalyst. The project goal of a 10,000 liter per day WGS-membrane reactor was achieved by a device operating on coal derived syngas containing significant amounts of carbon monoxide and hydrogen sulfide. The membrane flux was equivalent to 52 scfh/ft2 based on a 600 psi syngas inlet pressure and corresponded to membranes costing $191 per square foot. Over 40 hours of iv exposure time to syngas has been achieved for a double membrane reactor. Two modules of the Chart reactor were tested under coal syngas for over 75 hours with a single module tested for 50 hours. The permeance values for the Chart membranes were similar to the REB reactor though total flux was reduced due to significantly thicker membranes. Overall testing of membrane reactors on coal derived syngas was over 115 hours for all reactors tested. Testing of the REB double membrane device exceeded 40 hours. Performance of the double membrane reactor has been similar to the results for the single reactor with good maintenance of flux even after these long

  18. Operation, Modeling and Analysis of the Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2001-01-01

    The Reverse Water Gas Shift process is a candidate technology for water and oxygen production on Mars under the In-Situ Propellant Production project. This report focuses on the operation and analysis of the Reverse Water Gas Shift (RWGS) process, which has been constructed at Kennedy Space Center. A summary of results from the initial operation of the RWGS, process along with an analysis of these results is included in this report. In addition an evaluation of a material balance model developed from the work performed previously under the summer program is included along with recommendations for further experimental work.

  19. A Cu/Pt Near-Surface Alloy for Water-Gas Shift Catalysis.

    SciTech Connect

    Knudsen, Jan; Nilekar, Anand U.; Vang, Ronnie T.; Schnadt, Joachim; Kunkes, Edward L.; Dumesic, James A.; Mavrikakis, Manos; Besenbacher, Fleming

    2007-05-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The primary route to hydrogen production from fossil fuels involves the water-gas shift (WGS) reaction, and an improvement in the efficiency of WGS catalysts could therefore lead to a major leap forward in the realization of hydrogen economy. On the basis of a combination of high-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, we suggest the existence of a new thermodynamically stable Cu/Pt near-surface alloy (NSA). Temperature-programmed desorption and DFT reveal that this Cu/Pt NSA binds CO significantly more weakly than does Pt alone, thereby implying a considerable reduction in the potential for CO poisoning of the Cu/Pt NSA surface as compared to that of pure Pt. In addition, DFT calculations show that this Cu/Pt NSA is able to activate H2O easily, which is the rate-determining step for the WGS on several metal surfaces, and, at the same time, to bind the products of that reaction and formate intermediates rather weakly, thus avoiding possible poisoning of the catalyst surface. The Cu/Pt NSA is thus a promising candidate for an improved WGS catalyst.

  20. Simulation and control of water-gas shift packed bed reactor with inter-stage cooling

    NASA Astrophysics Data System (ADS)

    Saw, S. Z.; Nandong, J.

    2016-03-01

    Water-Gas Shift Reaction (WGSR) has become one of the well-known pathways for H2 production in industries. The issue with WGSR is that it is kinetically favored at high temperatures but thermodynamically favored at low temperatures, thus requiring careful consideration in the control design in order to ensure that the temperature used does not deactivate the catalyst. This paper studies the effect of a reactor arrangement with an inter-stage cooling implemented in the packed bed reactor to look at its effect on outlet temperature. A mathematical model is developed based on one-dimensional heat and mass transfers which incorporate the intra-particle effects. It is shown that the placement of the inter-stage cooling and the outlet temperature exiting the inter-stage cooling have strong influence on the reaction conversion. Several control strategies are explored for the process. It is shown that a feedback- feedforward control strategy using Multi-scale Control (MSC) is effective to regulate the reactor temperature profile which is critical to maintaining the catalysts activity.

  1. Integrated Water Gas Shift Membrane Reactors Utilizing Novel, Non Precious Metal Mixed Matrix Membrane

    SciTech Connect

    Ferraris, John

    2013-09-30

    Nanoparticles of zeolitic imidazolate frameworks and other related hybrid materials were prepared by modifying published synthesis procedures by introducing bases, changing stoichiometric ratios, or adjusting reaction conditions. These materials were stable at temperatures >300 °C and were compatible with the polymer matrices used to prepare mixed- matrix membranes (MMMs). MMMs tested at 300 °C exhibited a >30 fold increase in permeability, compared to those measured at 35 °C, while maintaining H{sub 2}/CO{sub 2} selectivity. Measurements at high pressure (up to 30 atm) and high temperature (up to 300 °C) resulted in an increase in gas flux across the membrane with retention of selectivity. No variations in permeability were observed at high pressures at either 35 or 300 °C. CO{sub 2}-induced plasticization was not observed for Matrimid®, VTEC, and PBI polymers or their MMMs at 30 atm and 300 °C. Membrane surface modification by cross-linking with ethanol diamine resulted in an increase in H{sub 2}/CO{sub 2} selectivity at 35 °C. Spectrometric analysis showed that the cross-linking was effective to temperatures <150 °C. At higher temperatures, the cross-linked membranes exhibit a H{sub 2}/CO{sub 2} selectivity similar to the uncross-linked polymer. Performance of the polybenzimidazole (PBI) hollow fibers prepared at Santa Fe Science and Technology (SFST, Inc.) showed increased flux o to a flat PBI membrane. A water-gas shift reactor has been built and currently being optimized for testing under DOE conditions.

  2. Catalytic and surface properties of nanocrystalline gold water gas shift catalysts

    NASA Astrophysics Data System (ADS)

    Kim, Chang Hwan

    A series of CeO2 supported gold catalysts were prepared and found to possess a high activities for the water gas shift reaction (WGS), a critical step in the production of H2 for use in petroleum refining, chemicals synthesis, and proton exchange membrane fuel cells. The deposition-precipitation method was employed in synthesizing these highly active, nanocrystalline gold catalysts. X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and dynamic sorption analyses were performed to characterize the gold catalysts. While some of these catalysts were initially four times more active than a commercial Cu-based catalyst, they were susceptible to deactivation. Characterization using techniques including temperature programmed oxidation, XPS, and FT-IR indicated that the deactivation was caused primarily by blockage of the active sites by carbonates and/or formates. Formation of these carbonaceous species appeared to be facilitated by oxygen deficient sites on the ceria surface and may have been associated with hydroxyl groups formed on the nanocrystalline gold particles under the H2 rich conditions. The deactivation could be managed by conditioning the CeO2 surface or adding constituents to minimize oxygen deficiency. The catalytic activity was fully recovered by calcining the deactivated materials in flowing air at elevated temperatures. The gold catalyst was washcoated onto microporous Fe-Al alloy foams for use in a micro-channel WGS reactor. The performance of these coated foams was inferior to that of the powder catalyst; however, a two stage micro-channel WGS reactor employing the gold catalyst was sufficient for a 100 W fuel processor system.

  3. Model-Based Design of Energy Efficient Palladium Membrane Water Gas Shift Fuel Processors for PEM Fuel Cell Power Plants

    NASA Astrophysics Data System (ADS)

    Gummalla, Mallika; Vanderspurt, Thomas Henry; Emerson, Sean; She, Ying; Dardas, Zissis; Olsommer, Benoît

    An integrated, palladium alloy membrane Water-Gas Shift (WGS) reactor can significantly reduce the size, cost and complexity of a fuel processor for a Polymer Electrolyte Membrane fuel cell power system.

  4. An Investigation of the Reverse Water Gas Shift Process and Operating Alternatives

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2002-01-01

    The Reverse Water Gas Shift (RWGS) process can produce water and ultimately oxygen through electrolysis. This technology is being investigated for possible use in the exploration of Mars as well as a potential process to aid in the regeneration of oxygen from carbon dioxide. The initial part of this report summarizes the results obtained from operation of the RWGS process at Kennedy Space Center during May and June of this year. It has been demonstrated that close to complete conversion can be achieved with the RWGS process under certain operating conditions. The report also presents results obtained through simulation for an alternative staged configuration for RWGS which eliminates the recycle compressor. This configuration looks promising and hence seems worthy of experimental investigation.

  5. X-ray structure and reactivity of (Ru(bpy)/sub 2/(CO)H)PF/sub 6/ x 1/2 C/sub 3/H/sub 6/O (bpy = 2,2'-bipyridyl), a possible intermediate in the water-gas shift reaction catalyzed by ruthenium polypyridyl complexes

    SciTech Connect

    Haasnoot, J.G.; Hinrichs, W.; Weir, O.; Vos, J.G.

    1986-11-05

    The structure of (Ru(C/sub 10/H/sub 8/N/sub 2/)/sub 2/(CO)H)PF/sub 6/ x 1/2 C/sub 3/H/sub 6/O is reported. The compound crystallizes in the monoclinic C2/c space group with unit cell parameters a = 26.680 (4) A, b = 7.005 (3) A, c = 25.936 (2) A, and ..beta.. = 93.96 (2)/sup 0/ (V = 4836.04 A/sup 3/, Z = 8). The cationic species has a cis geometry for CO and H. The ruthenium-hydride and ruthenium-carbon distances are 1.68 (4) and 1.804 (6) A, respectively. The average ruthenium-nitrogen distance is 2.109 A. In acidic solution the title compound acts as a hydride donor to produce dihydrogen gas in a pseudo-first-order reaction; the second-order rate constant for this reaction is 0.105 -/+ 0.01 dm/sup 3/ mol/sup -1/ s/sup -1/ at 303 K with an activation energy 56 -/+ 2 kJ mol/sup -1/. A value of -100 -/+ 8 J mol/sup -1/ deg/sup -1/ has been obtained for the entropy of activation. The consequences of these results for the possible reaction mechanism of the homogeneous water-gas shift reaction catalyzed by (Ru(bpy)/sub 2/(CO)Cl)/sup +/ are discussed. 15 references, 4 figures, 6 tables.

  6. In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

    PubMed

    Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

    2013-08-07

    In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually

  7. In-situ Characterization of Water-Gas Shift Catalysts using Time-Resolved X-ray Diffraction

    SciTech Connect

    Rodriguez, J.; Hanson, J; Wen, W; Wang, X; Brito, J; Martnez-Arias, A; Fernandez-Garca, M

    2009-01-01

    Time-resolved X-ray diffraction (XRD) has emerged as a powerful technique for studying the behavior of heterogeneous catalysts (metal oxides, sulfides, carbides, phosphides, zeolites, etc.) in-situ during reaction conditions. The technique can identify the active phase of a heterogeneous catalyst and how its structure changes after interacting with the reactants and products (80 K < T < 1200 K; P < 50 atm). In this article, we review a series of recent works that use in-situ time-resolved XRD for studying the water-gas shift reaction (WGS, CO + H2O ? H2 + CO2) over several mixed-metal oxides: CuMoO4, NiMoO4, Ce1-xCuxO2-d and CuFe2O4. Under reaction conditions the oxides undergo partial reduction. Neutral Cu0 (i.e. no Cu1+ or Cu2+ cations) and Ni0 are the active species in the catalysts, but interactions with the oxide support are necessary in order to obtain high catalytic activity. These studies illustrate the important role played by O vacancies in the mechanism for the WGS. In the case of Ce1-xCuxO2-d, Rietveld refinement shows expansions/contractions in the oxide lattice which track steps within the WGS process: CO(gas) + O(oxi) ? CO2(gas) + O(vac); H2O(gas) + O(vac) ? O(oxi) + H2(gas).

  8. Modeling and Analysis of the Reverse Water Gas Shift Process for In-Situ Propellant Production

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2000-01-01

    This report focuses on the development of mathematical models and simulation tools developed for the Reverse Water Gas Shift (RWGS) process. This process is a candidate technology for oxygen production on Mars under the In-Situ Propellant Production (ISPP) project. An analysis of the RWGS process was performed using a material balance for the system. The material balance is very complex due to the downstream separations and subsequent recycle inherent with the process. A numerical simulation was developed for the RWGS process to provide a tool for analysis and optimization of experimental hardware, which will be constructed later this year at Kennedy Space Center (KSC). Attempts to solve the material balance for the system, which can be defined by 27 nonlinear equations, initially failed. A convergence scheme was developed which led to successful solution of the material balance, however the simplified equations used for the gas separation membrane were found insufficient. Additional more rigorous models were successfully developed and solved for the membrane separation. Sample results from these models are included in this report, with recommendations for experimental work needed for model validation.

  9. Design of water gas shift catalysts for hydrogen production in fuel processors.

    PubMed

    Opalka, S M; Vanderspurt, T H; Radhakrishnan, R; She, Y; Willigan, R R

    2008-02-13

    Low sulfur hydrocarbon fuels can be converted to fuel cell grade H(2) using a compact fuel processor architecture. The necessary high volumetric activity water gas shift (WGS) Pt on ceria-zirconia catalysts reacts CO-rich reformate with steam to yield H(2) and CO(2). Such highly selective, non-pyrophoric noble metal/Ce([1-(x+y)])Zr(x)Dp(y)O(2) catalysts were developed through coordinated atomic modeling, syntheses, structural characterization, kinetic performance tests, and micro-kinetic analyses. Density functional simulations made with the VASP code suggested that the undoped catalyst WGS activity would be limited by the strong binding of CO intermediates, blocking the reoxidation of the reduced oxide by water. These predictions were confirmed by in situ cylindrical internal reflection-Fourier transform infrared spectroscopy and by micro-kinetic analyses of the micro-reactor results. Atomic simulations were used to evaluate the impact transition metal dopants had on the surface chemistry of cubic ceria-zirconia. VASP predicted that acidic transition metal dopants such as Nb, Mo, Ta, and W would increase the oxide surface affinity for water and thus increase the turnover rate of the catalyst. The efficacy of Mo-doped ceria-zirconia compositions was confirmed at lower temperatures in replicated catalyst synthesis-reactor studies.

  10. Design of water gas shift catalysts for hydrogen production in fuel processors

    NASA Astrophysics Data System (ADS)

    Opalka, S. M.; Vanderspurt, T. H.; Radhakrishnan, R.; She, Y.; Willigan, R. R.

    2008-02-01

    Low sulfur hydrocarbon fuels can be converted to fuel cell grade H2 using a compact fuel processor architecture. The necessary high volumetric activity water gas shift (WGS) Pt on ceria-zirconia catalysts reacts CO-rich reformate with steam to yield H2 and CO2. Such highly selective, non-pyrophoric noble metal/Ce[1-(x+y)]ZrxDpyO2 catalysts were developed through coordinated atomic modeling, syntheses, structural characterization, kinetic performance tests, and micro-kinetic analyses. Density functional simulations made with the VASP code suggested that the undoped catalyst WGS activity would be limited by the strong binding of CO intermediates, blocking the reoxidation of the reduced oxide by water. These predictions were confirmed by in situ cylindrical internal reflection-Fourier transform infrared spectroscopy and by micro-kinetic analyses of the micro-reactor results. Atomic simulations were used to evaluate the impact transition metal dopants had on the surface chemistry of cubic ceria-zirconia. VASP predicted that acidic transition metal dopants such as Nb, Mo, Ta, and W would increase the oxide surface affinity for water and thus increase the turnover rate of the catalyst. The efficacy of Mo-doped ceria-zirconia compositions was confirmed at lower temperatures in replicated catalyst synthesis-reactor studies.

  11. Kinetic and spectroscopic study of catalysts for water-gas shift and nitrogen oxide removal

    NASA Astrophysics Data System (ADS)

    Kispersky, Vincent Frederick

    Hy variants modeled on Cu. The redox nature of the Cu active site was further investigated in a follow up study isolating the reducing portion of the SCR by removing O 2 from the reaction feed. Cutting off O2 drove the catalyst into a highly reduced state dominated by Cu(I) while removing a reductant drove the Cu into the fully oxidized state. Our research shows that not only is redox a vital part of the SCR reaction on Cu/zeolites, but that the oxidation state of the active site is highly sensitive to the gas environment. The water-gas shift (WGS) reaction is an industrially important step in H2 generation from steam reforming. I have had the opportunity to contribute to a number of studies in WGS by studying the catalysts in FTIR. We studied numerous catalytic formulations including Fe promoted Pd/Al 2O3 and Au/TiO2. We found that the Fe promoted the WGS rate of the catalyst by a factor of 160 compared to the Fe free Pd/Al 2O3. The reduced Fe promoter efficiently split H2O, typically the role performed by reducible supports, and the nearby noble metal particles provided spillover H2 to maintain the reduced Fe phase necessary to split H2O. Our study of Au/TiO2 involved the development of a modified operando transmission IR cell with ultra-low dead volume allowing for fast switching isotope experiments over the catalyst. The isotope switching experiments showed that only CO adsorbed on Au0 sites was an active surface intermediate at 120°C. Counting the amount of active surface Au atoms for the reaction ruled out the Au particle surface and perimeter atoms as the dominant active sites and confirmed our previous finding that the active site was composed mostly of low coordinated corner Au atoms.

  12. Pilot Scale Water Gas Shift - Membrane Device for Hydrogen from Coal

    SciTech Connect

    Barton, Tom

    2013-06-30

    The objectives of the project were to build pilot scale hydrogen separation systems for use in a gasification product stream. This device would demonstrate fabrication and manufacturing techniques for producing commercially ready facilities. The design was a 2 lb/day hydrogen device which included composite hydrogen separation membranes, a water gas shift monolith catalyst, and stainless steel structural components. Synkera Technologies was to prepare hydrogen separation membranes with metallic rims, and to adjust the alloy composition in their membranes to a palladium-gold composition which is sulfur resistant. Chart was to confirm their brazing technology for bonding the metallic rims of the composite membranes to their structural components and design and build the 2 lbs/day device incorporating membranes and catalysts. WRI prepared the catalysts and completed the testing of the membranes and devices on coal derived syngas. The reactor incorporated eighteen 2'' by 7'' composite palladium alloy membranes. These membranes were assembled with three stacks of three paired membranes. Initial vacuum testing and visual inspection indicated that some membranes were cracked, either in transportation or in testing. During replacement of the failed membranes, while pulling a vacuum on the back side of the membranes, folds were formed in the flexible composite membranes. In some instances these folds led to cracks, primarily at the interface between the alumina and the aluminum rim. The design of the 2 lb/day device was compromised by the lack of any membrane isolation. A leak in any membrane failed the entire device. A large number of tests were undertaken to bring the full 2 lb per day hydrogen capacity on line, but no single test lasted more than 48 hours. Subsequent tests to replace the mechanical seals with brazing have been promising, but the technology remains promising but not proven.

  13. Kinetics of oxygen-enhanced water gas shift on bimetallic catalysts and the roles of metals and support

    NASA Astrophysics Data System (ADS)

    Kugai, Junichiro

    The post-processing of reformate is an important step in producing hydrogen (H2) with low carbon monoxide (CO) for low temperature fuel cells from syn-gas. However, the conventional process consists of three steps, i.e. two steps of water gas shift (WGS) and preferential oxidation (PROX) of CO, and it is not suitable for mobile applications due to the large volume of water gas shift (WGS) catalysts and conditioning and/or regeneration necessary for these catalysts. Aiming at replacing those three steps by a simple one-step process, small amount of oxygen was added to WGS (the reaction called oxygen-enhanced water gas shift or OWGS) to promote the reaction kinetics and low pyrophoric ceria-supported bimetallic catalysts were employed for stable performance in this reaction. Not only CO conversion, but also H2 yield was found to increase by the O2 addition on CeO2-supported catalysts. The characteristics of OWGS, high H2 production rate at 200 to 300°C at short contact time where unreacted O2 exists, evidenced the impact of O2 addition on surface species on the catalyst. Around 1.5 of reaction order in CO for various CeO2-supported metal catalysts for OWGS compared to reaction orders in CO ranging from -0.1 to 0.6 depending on metal species for WGS shows O2 addition decreases CO coverage to free up the active sites for co-reactant (H2O) adsorption and activation. Among the monometallic and bimetallic catalysts, Pt-Cu and Pd-Cu bimetallic catalysts were superior to monometallic catalysts in OWGS. These bimetallic components were found to form alloys where noble metal is surrounded mainly by Cu to have strong interaction between noble metal and copper resulting in high OWGS activity and low pyrophoric property. The metal loadings were optimized for CeO2-supported Pd-Cu bimetallic system and 2 wt% Pd with 5 -- 10 wt% Cu were found to be the optimum for the present OWGS condition. In the kinetic study, Pd in Pd-Cu was shown to increase the active sites for H2O

  14. Parametric Gasification of Oak and Pine Feedstocks Using the TCPDU and Slipstream Water-Gas Shift Catalysis

    SciTech Connect

    Hrdlicka, J.; Feik, C.; Carpenter, D.; Pomeroy, M.

    2008-12-01

    With oak and pine feedstocks, the Gasification of Biomass to Hydrogen project maximizes hydrogen production using the Full Stream Reformer during water-gas shift fixed-bed reactor testing. Results indicate that higher steam-to-biomass ratio and higher thermal cracker temperature yield higher hydrogen concentration. NREL's techno-economic models and analyses indicate hydrogen production from biomass may be viable at an estimated cost of $1.77/kg (current) and $1.47/kg (advanced in 2015). To verify these estimates, NREL used the Thermochemical Process Development Unit (TCPDU), an integrated system of unit operations that investigates biomass thermochemical conversion to gaseous and liquid fuels and chemicals.

  15. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Final technical progress report, September 12, 1991--December 11, 1994

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.; Richards-Babb, M.; Carr, T.

    1995-07-01

    The objective of this research was to investigate sulfur-resistant catalysts for the conversion of synthesis gas having H{sub 2}/CO {le} 1 into C{sub 1}--C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway, while also promoting the water gas shift reaction (WGSR). The catalysts chosen are bifunctional, base-hydrogenation, sulfur-tolerant transition metal sulfides with heavy alkali, e.g. Cs{sup +}, promoter dispersed on their surfaces. The modes of activation of H{sub 2} and CO on MoS{sub 2} and alkali-doped MoS{sub 2} were considered, and computational analyses of the thermodynamic stability of transition metal sulfides and of the electronic structure of these sulfide catalysts were carried out. In the preparation of the cesium-promoted MoS{sub 2} catalysts, a variety of preparation methods using CsOOCH were examined. In all cases, doping with CsOOCH led to a lost of surface area. The undoped molybdenum disulfide catalyst only produced hydrocarbons. Cs-doped MoS{sub 2} catalysts all produced linear alcohols, along with smaller amounts of hydrocarbons. With a 20 wt% CsOOCH/MoS{sub 2} catalyst, temperature, pressure, and flow rate dependences of the synthesis reactions were investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 synthesis gas during short term testing experiments. It was shown that with a carefully prepared 10 wt% CsOOCH/MoS{sub 2} catalyst, reproducible and high alcohol synthesis activity could be obtained. For example, at 295 C with H{sub 2}/CO = 1 synthesis gas at 8.3 MPa and with GHSV = 7,760 l/kg cat/hr, the total alcohol space time yield was ca 300 g/kg cat/hr (accompanied with a hydrocarbon space time yield of ca 60 g/kg cat/hr). Over a testing period of ca 130 hr, no net deactivation of the catalyst was observed. 90 refs., 82 figs., 14 tabs.

  16. Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

    DOEpatents

    Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

    2003-09-23

    Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

  17. Robust Low-Cost Water-Gas Shift Membrane Reactor for High-Purity Hydrogen Production form Coal-Derived Syngas

    SciTech Connect

    James Torkelson; Neng Ye; Zhijiang Li; Decio Coutinho; Mark Fokema

    2008-05-31

    This report details work performed in an effort to develop a low-cost, robust water gas shift membrane reactor to convert coal-derived syngas into high purity hydrogen. A sulfur- and halide-tolerant water gas shift catalyst and a sulfur-tolerant dense metallic hydrogen-permeable membrane were developed. The materials were integrated into a water gas shift membrane reactor in order to demonstrate the production of >99.97% pure hydrogen from a simulated coal-derived syngas stream containing 2000 ppm hydrogen sulfide. The objectives of the program were to (1) develop a contaminant-tolerant water gas shift catalyst that is able to achieve equilibrium carbon monoxide conversion at high space velocity and low steam to carbon monoxide ratio, (2) develop a contaminant-tolerant hydrogen-permeable membrane with a higher permeability than palladium, (3) demonstrate 1 L/h purified hydrogen production from coal-derived syngas in an integrated catalytic membrane reactor, and (4) conduct a cost analysis of the developed technology.

  18. Water-Gas-Shift Membrane Reactor for High-Pressure Hydrogen Production. A comprehensive project report (FY2010 - FY2012)

    SciTech Connect

    Klaehn, John; Peterson, Eric; Orme, Christopher; Bhandari, Dhaval; Miller, Scott; Ku, Anthony; Polishchuk, Kimberly; Narang, Kristi; Singh, Surinder; Wei, Wei; Shisler, Roger; Wickersham, Paul; McEvoy, Kevin; Alberts, William; Howson, Paul; Barton, Thomas; Sethi, Vijay

    2013-01-01

    Idaho National Laboratory (INL), GE Global Research (GEGR), and Western Research Institute (WRI) have successfully produced hydrogen-selective membranes for water-gas-shift (WGS) modules that enable high-pressure hydrogen product streams. Several high performance (HP) polymer membranes were investigated for their gas separation performance under simulated (mixed gas) and actual syngas conditions. To enable optimal module performance, membranes with high hydrogen (H2) selectivity, permeance, and stability under WGS conditions are required. The team determined that the VTEC PI 80-051 and VTEC PI 1388 (polyimide from Richard Blaine International, Inc.) are prime candidates for the H2 gas separations at operating temperatures (~200°C). VTEC PI 80-051 was thoroughly analyzed for its H2 separations under syngas processing conditions using more-complex membrane configurations, such as tube modules and hollow fibers. These membrane formats have demonstrated that the selected VTEC membrane is capable of providing highly selective H2/CO2 separation (α = 7-9) and H2/CO separation (α = 40-80) in humidified syngas streams. In addition, the VTEC polymer membranes are resilient within the syngas environment (WRI coal gasification) at 200°C for over 1000 hours. The information within this report conveys current developments of VTEC PI 80-051 as an effective H2 gas separations membrane for high-temperature syngas streams.

  19. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

    SciTech Connect

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; Wasserscheid, Peter

    2015-01-29

    Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid film of alkali hydroxide forms on the alumina surface, which increases the availability of H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.

  20. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

    DOE PAGES

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; ...

    2015-01-29

    Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid filmmore » of alkali hydroxide forms on the alumina surface, which increases the availability of H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.« less

  1. Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

    PubMed

    Kadyk, Thomas; Eikerling, Michael

    2015-08-14

    The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.

  2. Water Gas Shift Reaction with A Single Stage Low Temperature Membrane Reactor

    SciTech Connect

    Ciora, Richard J; Liu, Paul KT

    2013-12-31

    Palladium membrane and Palladium membrane reactor were developed under this project for hydrogen separation and purification for fuel cell applications. A full-scale membrane reactor was designed, constructed and evaluated for the reformate produced from a commercial scale methanol reformer. In addition, the Pd membrane and module developed from this project was successfully evaluated in the field for hydrogen purification for commercial fuel cell applications.

  3. Ceria-based model catalysts: fundamental studies on the importance of the metal-ceria interface in CO oxidation, the water-gas shift, CO2 hydrogenation, and methane and alcohol reforming.

    PubMed

    Rodriguez, José A; Grinter, David C; Liu, Zongyuan; Palomino, Robert M; Senanayake, Sanjaya D

    2017-04-03

    Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO2, and the production of hydrogen through the water-gas shift reaction and the reforming of methane or alcohols. Using model catalysts it has been possible to examine in detail correlations between the structural, electronic and catalytic properties of ceria-metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C-O, C-H and C-C bonds. Several studies with model ceria catalysts have shown the importance of strong metal-support interactions. In general, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.

  4. Determination of the Effect of Coal/Biomass-Derived Syngas Contaminants on the Performance of Fischer-Tropsch and Water-Gas-Shift Catalysts

    SciTech Connect

    Trembly, Jason; Cooper, Matthew; Farmer, Justin; Turk, Brian; Gupta, Raghubir

    2010-12-31

    Today, nearly all liquid fuels and commodity chemicals are produced from non-renewable resources such as crude oil and natural gas. Because of increasing scrutiny of carbon dioxide (CO{sub 2}) emissions produced using traditional fossil-fuel resources, the utilization of alternative feedstocks for the production of power, hydrogen, value-added chemicals, and high-quality hydrocarbon fuels such as diesel and substitute natural gas (SNG) is critical to meeting the rapidly growing energy needs of modern society. Coal and biomass are particularly attractive as alternative feedstocks because of the abundant reserves of these resources worldwide. The strategy of co-gasification of coal/biomass (CB) mixtures to produce syngas for synthesis of Fischer-Tropsch (FT) fuels offers distinct advantages over gasification of either coal or biomass alone. Co-feeding coal with biomass offers the opportunity to exploit economies of scale that are difficult to achieve in biomass gasification, while the addition of biomass to the coal gasifier feed leverages proven coal gasification technology and allows CO{sub 2} credit benefits. Syngas generated from CB mixtures will have a unique contaminant composition because coal and biomass possess different concentrations and types of contaminants, and the final syngas composition is also strongly influenced by the gasification technology used. Syngas cleanup for gasification of CB mixtures will need to address this unique contaminant composition to support downstream processing and equipment. To investigate the impact of CB gasification on the production of transportation fuels by FT synthesis, RTI International conducted thermodynamic studies to identify trace contaminants that will react with water-gas-shift and FT catalysts and built several automated microreactor systems to investigate the effect of single components and the synergistic effects of multiple contaminants on water-gas-shift and FT catalyst performance. The contaminants

  5. Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

    SciTech Connect

    Alptekin, Gokhan

    2013-02-15

    Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H2S, NH3, HCN, AsH3, PH3, HCl, NaCl, KCl, AS3, NH4NO3, NH4OH, KNO3, HBr, HF, and HNO3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

  6. Hydrogen production from a combination of the water-gas shift and redox cycle process of methane partial oxidation via lattice oxygen over LaFeO3 perovskite catalyst.

    PubMed

    Dai, Xiao Ping; Wu, Qiong; Li, Ran Jia; Yu, Chang Chun; Hao, Zheng Ping

    2006-12-28

    A redox cycle process, in which CH4 and air are periodically brought into contact with a solid oxide packed in a fixed-bed reactor, combined with the water-gas shift (WGS) reaction, is proposed for hydrogen production. The sole oxidant for partial oxidation of methane (POM) is found to be lattice oxygen instead of gaseous oxygen. A perovskite-type LaFeO3 oxide was prepared by a sol-gel method and employed as an oxygen storage material in this process. The results indicate that, under appropriate reaction conditions, methane can be oxidized to CO and H2 by the lattice oxygen of LaFeO3 perovskite oxide with a selectivity higher than 95% and the consumed lattice oxygen can be replenished in a reoxidation procedure by a redox operation. It is suggested that the POM to H2/CO by using the lattice oxygen of the oxygen storage materials instead of gaseous oxygen should be possibly applicable. The LaFeO3 perovskite oxide maintained relatively high catalytic activity and structural stability, while the carbonaceous deposits, which come from the dissociation of CH4 in the pulse reaction, occurred due to the low migration rate of lattice oxygen from the bulk toward the surface. A new dissociation-oxidation mechanism for this POM without gaseous oxygen is proposed based on the transient responses of the products checked at different surface states via both pulse reaction and switch reaction over the LaFeO3 catalyst. In the absence of gaseous-phase oxygen, the rate-determining step of methane conversion is the migration rate of lattice oxygen, but the process can be carried out in optimized cycles. The product distribution for POM over LaFeO3 catalyst in the absence of gaseous oxygen was determined by the concentration of surface oxygen, which is relevant with the migration rate of lattice oxygen from the bulk toward the surface. This process of hydrogen production via selective oxidation of methane by lattice oxygen is better in avoiding the deep oxidation (to CO2) and

  7. Water gas furnace

    SciTech Connect

    Gallaro, C.

    1985-12-03

    A water gas furnace comprising an outer container to provide a housing in which coke is placed into its lower part. A water container is placed within the housing. The coke is ignited and heats the water in the container converting it into steam. The steam is ejected into the coke, which together with air, produces water gas. Preferably, pumice stones are placed above the coke. The water gas is accepted into the pores of the pumice stones, where the heated pumice stones ignite the water gas, producing heat. The heat is extracted by a heat exchanger provided about the housing.

  8. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2002-08-01

    As part of our optimization effort, we have conducted a comprehensive study to investigate the morphology and crystal growth kinetics of hydrotalcite powder formation. Based upon the information obtained from this study, we resumed the membrane optimization activities. Although the selectivity of the membrane remains in the Knudsen regime, the permeance decreases along with the number of impregnation. Thus, the permeance could be reduced to a minimum through repeated impregnation. Then, the membrane can be sealed with chemical vapor deposition technique. More characterization results on the membranes prepared will be available in the next quarterly report.

  9. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Dennis Sparks; Khalid Azzam; Janet Chakkamadathil Mohandas; Wilson Shafer; Venkat Ramana Rao Pendyala

    2011-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H

  10. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Janet ChakkamadathilMohandas; Wilson Shafer

    2009-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.

  11. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burtron Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Dennis Sparks; Wilson Shafer

    2010-09-30

    The successful adaptation of conventional cobalt and iron-based Fischer-Tropsch synthesis catalysts for use in converting biomass-derived syngas hinges in part on understanding their susceptibility to byproducts produced during the biomass gasification process. With the possibility that oil production will peak in the near future, and due to concerns in maintaining energy security, the conversion of biomass-derived syngas and syngas derived from coal/biomass blends to Fischer-Tropsch synthesis products to liquid fuels may provide a sustainable path forward, especially considering if carbon sequestration can be successfully demonstrated. However, one current drawback is that it is unknown whether conventional catalysts based on iron and cobalt will be suitable without proper development because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using an entrained-flow oxygen-blown gasifier) than solely from coal, other byproducts may be present in higher concentrations. The current project examines the impact of a number of potential byproducts of concern from the gasification of biomass process, including compounds containing alkali chemicals like the chlorides of sodium and potassium. In the second year, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities.

  12. Evaluation of C-14 as a natural tracer for injected fluids at theAidlin sector of The Geysers geothermal system through modeling ofmineral-water-gas Reactions

    SciTech Connect

    Dobson, Patrick; Sonnenthal, Eric; Lewicki, Jennifer; Kennedy, Mack

    2006-06-01

    A reactive-transport model for 14C was developed to test its applicability to the Aidlin geothermal system. Using TOUGHREACT, we developed a 1-D grid to evaluate the effects of water injection and subsequent water-rock-gas interaction on the compositions of the produced fluids. A dual-permeability model of the fracture-matrix system was used to describe reaction-transport processes in which the permeability of the fractures is many orders of magnitude higher than that of the rock matrix. The geochemical system included the principal minerals (K-feldspar, plagioclase, calcite, silica polymorphs) of the metagraywackes that comprise the geothermal reservoir rocks. Initial simulation results predict that the gas-phase CO2 in the reservoir will become more enriched in 14C as air-equilibrated injectate water (with a modern carbon signature) is incorporated into the system, and that these changes will precede accompanying decreases in reservoir temperature. The effects of injection on 14C in the rock matrix will be lessened somewhat because of the dissolution of matrix calcite with ''dead'' carbon.

  13. Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

    NASA Technical Reports Server (NTRS)

    Grodzka, P.; Facemire, B.

    1977-01-01

    Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

  14. Density Functional Theory and Reaction Kinetics Studies of the Water–Gas Shift Reaction on Pt–Re Catalysts

    SciTech Connect

    Carrasquillo-Flores, Ronald; Gallo, Jean Marcel R.; Hahn, Konstanze; Dumesic, James A.; Mavrikakis, Manos

    2013-11-05

    Periodic, self-consistent density functional theory calculations (DFT-GGA-PW91) on Pt(111) and Pt3Re(111) surfaces, reaction kinetics measurements, and microkinetic modeling are employed to study the mechanism of the water–gas shift (WGS) reaction over Pt and Pt–Re catalysts. The values of the reaction rates and reaction orders predicted by the model are in agreement with the ones experimentally determined; the calculated apparent activation energies are matched to within 6% of the experimental values. The primary reaction pathway is predicted to take place through adsorbed carboxyl (COOH) species, whereas formate (HCOO) is predicted to be a spectator species. We conclude that the clean Pt(111) is a good representation of the active site for the WGS reaction on Pt catalysts, whereas the active sites on the Pt–Re alloy catalyst likely contain partially oxidized metal ensembles.

  15. Theoretical Investigation of Intramolecular Hydrogen Shift Reactions in 3-Methyltetrahydrofuran (3-MTHF) Oxidation.

    PubMed

    Parab, Prajakta R; Sakade, Naoki; Sakai, Yasuyuki; Fernandes, Ravi; Heufer, K Alexander

    2015-11-05

    3-Methyltetrahydrofuran (3-MTHF) is proposed to be a promising fuel component among the cyclic oxygenated species. To have detailed insight of its combustion kinetics, intramolecular hydrogen shift reactions for the ROO to QOOH reaction class are studied for eight ROO isomers of 3-MTHF. Rate constants of all possible reaction paths that involve formation of cyclic transition states are computed by employing the CBS-QB3 composite method. A Pitzer-Gwinn-like approximation has been applied for the internal rotations in reactants, products, and transition states for the accurate treatment of hindered rotors. Calculated relative barrier heights highlight that the most favorable reaction channel proceeds via a six membered transition state, which is consistent with the computed rate constants. Comparing total rate constants in ROO isomers of 3-MTHF with the corresponding isomers of methylcyclopentane depicts faster kinetics in 3-MTHF than methylcyclopentane reflecting the effect of ring oxygen on the intramolecular hydrogen shift reactions.

  16. Electronic shift register memory based on molecular electron-transfer reactions

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

    1989-01-01

    The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

  17. The posterior shift anticipatory postural adjustment in choice reaction step initiation.

    PubMed

    Sun, Ruopeng; Guerra, Richard; Shea, John B

    2015-05-01

    The ability to step quickly in response to a perturbation has been shown to be critical for prevention of falls. The cognitive processing, weight shifting, and locomotion must be well timed to execute a successful step. The purpose of this study was to compare the response preparation and response execution processes between a simple (SRST) and a choice reaction stepping task (CRST). Nine healthy young subjects were recruited to participate in this study. Subjects were required to stand on a forceplate and maintain their balance, and step forward on a second forceplate with either the left or right foot after hearing an auditory tone. The center of pressure (COP) was analyzed to determine the types of anticipatory postural adjustment (APA) prior to a step. The APA phase and stepping phase timing was calculated based on the COP trajectory. Findings showed that reaction time (RT), APA phase and overall stepping latency were slower for CRST than for SRST. We also identified an intermediate type of APA response (posterior shift APA) in addition to the correct and error APA response, and found the posterior shift APA response had the fastest execution time for CRST, and may be beneficial for falls prevention.

  18. High-Throughput Electrophoretic Mobility Shift Assays for Quantitative Analysis of Molecular Binding Reactions

    PubMed Central

    2015-01-01

    We describe a platform for high-throughput electrophoretic mobility shift assays (EMSAs) for identification and characterization of molecular binding reactions. A photopatterned free-standing polyacrylamide gel array comprised of 8 mm-scale polyacrylamide gel strips acts as a chassis for 96 concurrent EMSAs. The high-throughput EMSAs was employed to assess binding of the Vc2 cyclic-di-GMP riboswitch to its ligand. In optimizing the riboswitch EMSAs on the free-standing polyacrylamide gel array, three design considerations were made: minimizing sample injection dispersion, mitigating evaporation from the open free-standing polyacrylamide gel structures during electrophoresis, and controlling unit-to-unit variation across the large-format free-standing polyacrylamide gel array. Optimized electrophoretic mobility shift conditions allowed for 10% difference in mobility shift baseline resolution within 3 min. The powerful 96-plex EMSAs increased the throughput to ∼10 data/min, notably more efficient than either conventional slab EMSAs (∼0.01 data/min) or even microchannel based microfluidic EMSAs (∼0.3 data/min). The free-standing polyacrylamide gel EMSAs yielded reliable quantification of molecular binding and associated mobility shifts for a riboswitch–ligand interaction, thus demonstrating a screening assay platform suitable for riboswitches and potentially a wide range of RNA and other macromolecular targets. PMID:25233437

  19. Hydrogen shift reactions in four methyl-buten-ol (MBO) peroxy radicals and their impact on the atmosphere

    NASA Astrophysics Data System (ADS)

    Knap, Hasse C.; Schmidt, Johan A.; Jørgensen, Solvejg

    2016-12-01

    We investigate the hydrogen shift (H-shift) reactions in the peroxy radicals derived from four different methyl-buten-ol (MBO) molecules; 2-methyl-3-buten-2-ol (MBO232), 2-methyl-3-buten-1-ol (MBO231), 3-Methyl-3-buten-2-ol (MBO332) and 3-methyl-3-buten-1-ol (MBO331), with quantum mechanical calculations. The rate constants of the 1,5 H-shift reactions in all four MBO peroxy radicals are greater than the rate constants of the 1,4 or 1,6 H-shift reactions. The rate constants for the 1,5 H-shift reaction from either a CH group or an OH group are approximately 1 s-1 and 10-3 s-1, respectively. The atmospheric impact of the MBO232 oxidation is investigated with the global chemical transport model (GEOS-Chem). The 1,4-CH and 1,5-OH H-shift reactions in the MBO232 peroxy radical play a minor role with a total yield of about 2%. The major atmospheric reactions of the MBO232 peroxy radical are the reactions with NO and HO2, with reaction yield of 85% and 13%, respectively.

  20. UV light-mediated difunctionalization of alkenes through aroyl radical addition/1,4-/1,2-aryl shift cascade reactions.

    PubMed

    Zheng, Lewei; Huang, Hongli; Yang, Chao; Xia, Wujiong

    2015-02-20

    UV light-mediated difunctionalization of alkenes through an aroyl radical addition/1,4-/1,2-aryl shift has been described. The resulted aroyl radical from a photocleavage reaction added to acrylamide compounds followed by cyclization led to the formation of oxindoles, whereas the addition to cinnamic amides aroused a unique 1,4-aryl shift reaction. Furthermore, the difunctionalization of alkenes of prop-2-en-1-ols was also achieved through aroyl radical addition and a sequential 1,2-aryl shift cascade reaction.

  1. Catalysis by Single Atoms: Water Gas Shift and Ethylene Hydrogenation

    DTIC Science & Technology

    2009-04-20

    sizes and shapes to hold the powder materials. The graphite sample holders are 3/8" thick, with a width and length greater than y2" x Vi" but less...ZrB2 grains . Note both Ta and Ti have particle size of-325 mesh (< 44 urn). 20 urn k*- (a) (b) Figure 9. Top view of sintered objects using SEM: (a...probability of arcing. Our experiments used powder with -15 urn and ~2 urn particle sizes , with both shaped very irregularly and with jagged edges

  2. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.

    1992-06-01

    During this quarter, the high pressure (up to 100 atm), high temperature (up to 350{degrees}C) catalyst testing system was rebuilt with clean tubing, etc. A new preparation of MoS{sub 2} catalyst was carried out, and this catalyst will be doped with alkali and tested during the next quarter of research.

  3. Nonclassical aryl radicals: Intermediates or transition states for the hydrogen shift reactions?

    SciTech Connect

    Cioslowski, J.; Liu, G.; Moncrieff, D.

    1996-06-14

    Electronic properties of aryl radicals obtained by removing single hydrogen atoms from the sterically congested regions of benzo[c]phenanthrene, biphenyl, triphenylene, phenanthrene, and perylene are studied at the UBLYP/6-311G** level of theory. Two structures are considered by each radical, the classical one involving a C-H{hor_ellipsis}C arrangement of atoms and the nonclassical one possessing a three-center C-H-C linkage. The five nonclassical radicals under study are found to be transition states for degenerate 1,4- and 1,5-hydrogen shift reactions that interconvert the classical species. However, the results of the present calculations indicate that the nonclassical structures with the C-H distances in the C-H-C linkages shorter than 1.34 {angstrom} should be energy minima representing potentially observable chemical systems. The predicted energy barrier to the 1,5-hydrogen shift in the 1-benzo[c]phenanthrenyl radical is only 9.3 kcal/mol with the zero-point energies included, making the hydrogen migration in this system facile at relatively low temperatures. Rigorous analysis of the computed electronic wave functions provides a clear-cut picture of bonding in both the classical and nonclassical aryl radicals. 2 figs., 4 tabs.

  4. Utilizing the dynamic stark shift as a probe for dielectric relaxation in photosynthetic reaction centers during charge separation.

    PubMed

    Guo, Zhi; Lin, Su; Woodbury, Neal W

    2013-09-26

    In photosynthetic reaction centers, the electric field generated by light-induced charge separation produces electrochromic shifts in the transitions of reaction center pigments. The extent of this Stark shift indirectly reflects the effective field strength at a particular cofactor in the complex. The dynamics of the effective field strength near the two monomeric bacteriochlorophylls (BA and BB) in purple photosynthetic bacterial reaction centers has been explored near physiological temperature by monitoring the time-dependent Stark shift during charge separation (dynamic Stark shift). This dynamic Stark shift was determined through analysis of femtosecond time-resolved absorbance change spectra recorded in wild type reaction centers and in four mutants at position M210. In both wild type and the mutants, the kinetics of the dynamic Stark shift differ from those of electron transfer, though not in the same way. In wild type, the initial electron transfer and the increase in the effective field strength near the active-side monomer bacteriochlorophyll (BA) occur in synchrony, but the two signals diverge on the time scale of electron transfer to the quinone. In contrast, when tyrosine is replaced by aspartic acid at M210, the kinetics of the BA Stark shift and the initial electron transfer differ, but transfer to the quinone coincides with the decay of the Stark shift. This is interpreted in terms of differences in the dynamics of the local dielectric environment between the mutants and the wild type. In wild type, comparison of the Stark shifts associated with BA and BB on the two quasi-symmetric halves of the reaction center structure confirm that the effective dielectric constants near these cofactors are quite different when the reaction center is in the state P(+)QA(-), as previously determined by Steffen et al. at 1.5 K (Steffen, M. A.; et al. Science 1994, 264, 810-816). However, it is not possible to determine from static, low-temperature measurments if the

  5. Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8 + 2] Isomers via Tandem [4 + 2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms.

    PubMed

    Chen, Kai; Wu, Feng; Ye, Lijuan; Tian, Zi-You; Yu, Zhi-Xiang; Zhu, Shifa

    2016-09-16

    An experimental test of designed [8 + 2] reaction of vinylphenylfuran and dimethyl acetylenedicarboxylate (DMAD) has been carried out, showing that the reaction gave unexpected addition products under different conditions. When the reaction was conducted under thermal conditions in toluene, expoxyphenanthrene, which was named as a [8 + 2] isomer, was generated. The scope of this reaction has been investigated in the present study. In addition, experiments and DFT calculations have been conducted to investigate how the reaction between vinylphenylfuran and DMAD took place. Surprisingly, the reaction did not involve the expected [8 + 2] intermediate, o-quinodimethane. Instead, the reaction starts from intermolecular Diels-Alder reactions between DMAD and the furan moiety of vinylphenylfuran, followed by unexpected intramolecular alkene-alkene coupling. This step generates a diradical species, which then undergoes [1,3]-H shift to give the experimentally observed expoxyphenanthrene. DFT calculations revealed that, the [8 + 2] cycloadduct cannot be obtained because the [1,5]-H shift process from the [1,5]-vinyl shift intermediate is disfavored kinetically compared to the [1,3]-H shift to the [8 + 2] isomer.

  6. Graphical imaging system for shifted spectrum in daughter nuclei of charged-current v-nucleus reactions

    NASA Astrophysics Data System (ADS)

    Sinatkas, J.; Kosmas, T. S.; Tsakstara, V.

    2015-09-01

    In this work, we improve the automated algorithm derived previously for drawing the quantum energy levels, in order to be efficient for plotting the theoretical spectra of the daughter nuclei in charged-current neutrino-nucleus reactions. Such calculated spectra need to be shifted so as the charged-current transition energies to be measured from the ground state of the daughter nucleus. The improvement involves the development of a computational code and graphical imaging system able to treat appropriately and as accurate as possible the energy-shifting which is different for the various multipole sets of nuclear states. The method is applied in the case of antineutrino-nucleus reaction which is of current experimental interest.

  7. Palladium-catalyzed cross-coupling reactions of silanolates: a paradigm shift in silicon-based cross-coupling reactions.

    PubMed

    Denmark, Scott E; Baird, John D

    2006-06-23

    This paper chronicles the conceptual development, proof of principle experiments, and recent advances in the palladium-catalyzed cross-coupling reactions of the conjugate bases of organosilanols. The discovery that led to the design and refinement of this process represents a classical illustration of how mechanistic studies can provide a fertile ground for the invention of new reactions. On the basis of a working hypothesis (which ultimately proved to be incorrect) and the desire to effect silicon-based cross-coupling without the agency of fluoride activation, a mild and practical palladium-catalyzed cross-coupling of alkenyl-, aryl-, and heteroaryl silanolates has been developed. The mechanistic underpinnings, methodological extensions, and the successful applications of this technology to the synthesis of complex molecules are described.

  8. Lifetime measurements by the Doppler-shift attenuation method in the Sn115(α,nγ)Te118 reaction

    NASA Astrophysics Data System (ADS)

    Mihai, C.; Pasternak, A. A.; Pascu, S.; Filipescu, D.; Ivaşcu, M.; Bucurescu, D.; Căta-Danil, G.; Căta-Danil, I.; Deleanu, D.; Ghiţă, D. G.; Glodariu, T.; Mărginean, N.; Mărginean, R.; Negret, A.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.

    2011-05-01

    γ rays were measured at several angles in both singles and coincidence modes in the Sn115(α,nγ)118Te reaction at 15 MeV on a thick target. Multipolarities and mixing ratios were determined from the γ-ray angular distribution analysis. Lifetimes of 11 low- and medium-spin excited states in Te118 were determined from a Monte Carlo Doppler-shift attenuation method analysis of the Doppler broadened line shapes of γ rays deexciting the levels. The results are discussed in comparison with the predictions of the interacting boson model.

  9. Nitrate attenuation in agricultural catchments: Shifting balances between transport and reaction

    NASA Astrophysics Data System (ADS)

    Ocampo, Carlos J.; Oldham, Carolyn E.; Sivapalan, Murugesu

    2006-01-01

    Simultaneous observations, across multiple spatial and temporal scales, are needed to understand the complex interactions between hydrological and biogeochemical processes in catchments and the primary controls on NO3- availability and mobility. This paper addresses these issues by using data collected from a detailed field experiment, carried out on two topographically different hillslopes (one steep and the other flat) located within an agricultural catchment in Western Australia. Continuous hydrometric data and measurements of chemical tracers, geochemical parameters, and NO3- concentrations taken from the shallow perched aquifer across riparian, midslope, and upland locations were analyzed and interpreted through a simple process-based numerical model of transport and reaction. The NO3- concentration data indicated that the temporal and spatial patterns of NO3- concentrations within the hillslopes are linked to the state of hydrological connectivity of the three landscape units as the shallow perched aquifer developed during the winter. Significant NO3- attenuation occurs within the riparian zones after the transport of NO3- from midslope sources begins. Application of a mixing model, which partitions the riparian zones into three water source components, and the numerical model of NO3- transport and reaction indicates that different mechanisms, dilution in the steep hillslope and denitrification in the flat hillslope, are responsible for much of the observed NO3- attenuation in the riparian zones. In this way, this work highlights the importance of hillslope topography in determining the relative roles of transport and reaction in NO3- attenuation and export from riparian zones. The experimental results also supported the use of the Damköhler number, a simple dimensionless number that is a measure of the competition between transport and reaction processes, which allowed a favorable comparison of our findings with previous results published in the literature

  10. Side feeding patterns and nuclear lifetime determinations by the Doppler shift attenuation method in (α,nγ) reactions

    NASA Astrophysics Data System (ADS)

    Mihai, C.; Pasternak, A. A.; Filipescu, D.; Ivaşcu, M.; Bucurescu, D.; Căta-Danil, G.; Căta-Danil, I.; Deleanu, D.; Ghiţă, D.; Glodariu, T.; Lobach, Yu. N.; Mărginean, N.; Mărginean, R.; Negret, A.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.

    2010-03-01

    γ rays were measured at several angles in both singles and coincidence mode in the Sn119(α,nγ)Te122 reaction at 15 MeV on a thick target. Lifetimes of excited states in Te122 were determined from a Monte Carlo Doppler shift attenuation method (DSAM) analysis of the Doppler broadened lines shapes of γ rays de-exciting the levels. A comparison of several deduced lifetimes with recent results obtained with the (n,n') reaction allowed us to validate the choice of a parameter used to calculate the contribution of the side feeding times. The ingredients of the DSAM line-shape analysis (stopping power, description of instrumental line shapes, and side feeding evaluation) are presented in some detail. It is concluded that with proper treatment of side feeding, a DSAM line-shape analysis of peaks in singles or coincidence spectra obtained following the (α,nγ) reaction is able to provide rather accurate values for the lifetimes of levels with low and medium spins.

  11. Side feeding patterns and nuclear lifetime determinations by the Doppler shift attenuation method in ({alpha},n{gamma}) reactions

    SciTech Connect

    Mihai, C.; Filipescu, D.; Ivascu, M.; Bucurescu, D.; Cata-Danil, G.; Cata-Danil, I.; Deleanu, D.; Ghita, D.; Glodariu, T.; Marginean, N.; Marginean, R.; Negret, A.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.; Pasternak, A. A.; Lobach, Yu. N.

    2010-03-15

    {gamma} rays were measured at several angles in both singles and coincidence mode in the {sup 119}Sn({alpha},n{gamma}){sup 122}Te reaction at 15 MeV on a thick target. Lifetimes of excited states in {sup 122}Te were determined from a Monte Carlo Doppler shift attenuation method (DSAM) analysis of the Doppler broadened lines shapes of {gamma} rays de-exciting the levels. A comparison of several deduced lifetimes with recent results obtained with the (n,n{sup '}) reaction allowed us to validate the choice of a parameter used to calculate the contribution of the side feeding times. The ingredients of the DSAM line-shape analysis (stopping power, description of instrumental line shapes, and side feeding evaluation) are presented in some detail. It is concluded that with proper treatment of side feeding, a DSAM line-shape analysis of peaks in singles or coincidence spectra obtained following the ({alpha},n{gamma}) reaction is able to provide rather accurate values for the lifetimes of levels with low and medium spins.

  12. CO2 mitigation in coal gasification cogeneration systems with integration of the shift reaction, CO2 absorption and methanol production

    NASA Astrophysics Data System (ADS)

    Duan, Yuanyuan; Zhang, Jin

    2004-08-01

    Cogeneration of electricity and liquid fuel can achieve higher efficiencies than electricity generation alone in Integrated Gasification Combined Cycle (IGCC), and cogeneration systems are also expected to mitigate CO2 emissions. A proposed methanol-electricity cogeneration system was analyzed in this paper using exergy method to evaluate the specified system. A simple cogeneration scheme and a complicated scheme including the shift reaction and CO2 removal were compared. The results show that the complicated scheme consumes more energy, but has a higher methanol synthesis ratio with partial capture of CO2. In those methanol and electricity cogeneration systems, the CO2 mitigation is not merely an additional process that consumes energy and reduces the overall efficiency, but is integrated into the methanol production.

  13. [The development of a static water/gas separator].

    PubMed

    Zhou, K H; Ai, S K; Lu, X Y; Liu, C L

    2000-10-01

    Objective. To develop a device for separating water from gas in small flow rate under zero "G". Method. Beginning with the study of surface characteristic of materials, a capillary material was developed according to the requirement and the water/gas separator using this single separating material was designed. Result. The water/gas separator worked well in the range of gas flow below 10.0 L/min and water flow below 10.0 ml/min. No gas was found in the separated water and no water was found in the separated gas. Conclusion. The structure of the separator was reasonable and the water/gas separating method using a single separating material was feasible.

  14. Thermodynamic parameters monitoring the equilibrium shift of enzyme-catalyzed hydrolysis/synthesis reactions in favor of synthesis in mixtures of water and organic solvent.

    PubMed

    Deschrevel, Brigitte; Vincent, Jean-Claude; Ripoll, Camille; Thellier, Michel

    2003-01-20

    The main strategy developed to shift the equilibrium state of a hydrolase-catalyzed hydrolysis/synthesis reaction consists in reducing water activity by addition of organic solvents in the reaction medium. We have used several mixtures of water and 1,4-butanediol, ranging from pure water to pure 1,4-butanediol, to study the hydrolysis/synthesis reaction of the N-Cbz-L-tryptophanyl-glycineamide dipeptide, catalyzed by alpha-chymotrypsin. In the presence of 1,4-butanediol, alpha-chymotrypsin also catalyzed the esterification reaction between this diol and N-Cbz-L-tryptophan; this ester hydrolysis/synthesis reaction has thus also been examined. The dipeptide and ester equilibrium concentrations increase when the water content of the reaction medium is decreased. Using our experimental data, we have determined the equilibrium constants of the hydrolysis/synthesis equilibria involving the nonionized forms of the protected amino acids, the estimated values of which are Ksp = 8 10(5) for the dipeptide and Kse = 78 for the ester respectively. They are true thermodynamic equilibrium constants, each related to a single, well-defined reaction equilibrium and with water activity being taken into account. If an organic solvent is added to the reaction medium these equilibria can be shifted towards synthesis by decreasing the water activity but also by modifying the ionization/neutralization equilibrium constant of the ionizable groups. These two effects depend both on the water content and on the nature of the organic solvent used, and, in particular, on its dielectric constant. Because of the importance of this parameter in our study, we discuss using it as an indicator to select an appropriate organic solvent to perform an enzyme-catalyzed synthesis.

  15. Computational Chemistry-Based Identification of Ultra-Low Temperature Water-Gas-Shift Catalysts

    SciTech Connect

    Manos Mavrikakis

    2008-08-31

    The current work seeks to identify novel, catalytically-active, stable, poison-resistant LWGS catalysts that retain the superior activity typical of conventional Cu catalysts but can be operated at similar or lower temperatures. A database for the Binding Energies (BEs) of the LWGS relevant species, namely CO, O and OH on the most-stable, close-packed facets of a set of 17 catalytically relevant transition metals was established. This BE data and a database of previously established segregation energies was utilized to predict the stability of bimetallic NSAs that could be synthesized by combinations of the 17 parent transition metals. NSAs that were potentially stable both in vacuo and under the influence of strong-binding WGS intermediates were then selected for adsorption studies. A set of 40 NSAs were identified that satisfied all three screener criteria and the binding energies of CO, O and OH were calculated on a set of 66, 43 and 79 NSA candidates respectively. Several NSAs were found that bound intermediates weaker than the monometallic catalysts and were thus potentially poison-resistant. Finally, kinetic studies were performed and resulted in the discovery of a specific NSA-based bimetallic catalyst Cu/Pt that is potentially a promising LWGS catalyst. This stable Cu/Pt subsurface alloy is expected to provide facile H{sub 2}O activation and remain relatively resistant from the poisoning by CO, S and formate intermediates.

  16. Lifetime measurements by the Doppler-shift attenuation method in the {sup 115}Sn({alpha},n{gamma}){sup 118}Te reaction

    SciTech Connect

    Mihai, C.; Pasternak, A. A.; Pascu, S.; Filipescu, D.; Ivascu, M.; Bucurescu, D.; Cata-Danil, I.; Deleanu, D.; Ghita, D. G.; Glodariu, T.; Marginean, N.; Marginean, R.; Negret, A.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.; Cata-Danil, G.

    2011-05-15

    {gamma} rays were measured at several angles in both singles and coincidence modes in the {sup 115}Sn({alpha},n{gamma}){sup 118}Te reaction at 15 MeV on a thick target. Multipolarities and mixing ratios were determined from the {gamma}-ray angular distribution analysis. Lifetimes of 11 low- and medium-spin excited states in {sup 118}Te were determined from a Monte Carlo Doppler-shift attenuation method analysis of the Doppler broadened line shapes of {gamma} rays deexciting the levels. The results are discussed in comparison with the predictions of the interacting boson model.

  17. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    PubMed

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order.

  18. Importance of low dimensional CeOx nanostructures in Pt/CeOx –TiO2 catalysts for the water–gas shift reaction

    DOE PAGES

    Luo, Si; Barrio, Laura; Nguyen-Phan, Thuy -Duong; ...

    2017-02-28

    CO2 and H2 production from the water–gas shift (WGS) reaction was studied over Pt/CeOx–TiO2 catalysts with incremental loadings of CeOx, which adopts variations in the local morphology. The lowest loading of CeOx (1 wt % to 0.5 at. %) that is configured in its smallest dimensions exhibited the best WGS activity over larger dimensional structures. We attribute this to several factors including the ultrafine dispersed one-dimensional nanocluster geometry, a large concentration of Ce3+ and enhanced reducibility of the low loadings. We utilized several in situ experiments to monitor the active state of the catalyst during the WGS reaction. X-ray diffractionmore » (XRD) results showed lattice expansion that indicated reduced ceria was prevalent during the WGS reaction. On the surface, Ce3+ related hydroxyl groups were identified by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The enhanced reducibility of the catalyst with the introduction of ceria was further revealed by H2-temperature programed reduction (H2-TPR) and good thermal stability was confirmed by in situ environmental transmission electron microscopy (ETEM). Finally, we also investigated the formation of the low dimensional structures during catalyst preparation, through a two-stage crystal growth of ceria crystallite on TiO2 nanoparticle: fine crystallites ~1D formed at ~250 °C, followed by crystal growth into 2D chain and 3D particle from 250–400 °C.« less

  19. Importance of Low Dimensional CeO x Nanostructures in Pt/CeO x –TiO 2 Catalysts for the Water–Gas Shift Reaction

    DOE PAGES

    Luo, Si; Barrio, Laura; Nguyen-Phan, Thuy-Duong; ...

    2017-03-15

    CO2 and H2 production from the water–gas shift (WGS) reaction was studied over Pt/CeOx–TiO2 catalysts with incremental loadings of CeOx, which adopts variations in the local morphology. The lowest loading of CeOx (1 wt % to 0.5 at. %) that is configured in its smallest dimensions exhibited the best WGS activity over larger dimensional structures. We attribute this to several factors including the ultrafine dispersed one-dimensional nanocluster geometry, a large concentration of Ce3+ and enhanced reducibility of the low loadings. We utilized several in situ experiments to monitor the active state of the catalyst during the WGS reaction. X-ray diffractionmore » (XRD) results showed lattice expansion that indicated reduced ceria was prevalent during the WGS reaction. On the surface, Ce3+ related hydroxyl groups were identified by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The enhanced reducibility of the catalyst with the introduction of ceria was further revealed by H2-temperature programed reduction (H2-TPR) and good thermal stability was confirmed by in situ environmental transmission electron microscopy (ETEM). Finally, we also investigated the formation of the low dimensional structures during catalyst preparation, through a two-stage crystal growth of ceria crystallite on TiO2 nanoparticle: fine crystallites ~1D formed at ~250 °C, followed by crystal growth into 2D chain and 3D particle from 250–400 °C.« less

  20. SurfKin: an ab initio kinetic code for modeling surface reactions.

    PubMed

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts.

  1. The Effect of Rain on Air-Water Gas Exchange

    NASA Technical Reports Server (NTRS)

    Ho, David T.; Bliven, Larry F.; Wanninkhof, Rik; Schlosser, Peter

    1997-01-01

    The relationship between gas transfer velocity and rain rate was investigated at NASA's Rain-Sea Interaction Facility (RSIF) using several SF, evasion experiments. During each experiment, a water tank below the rain simulator was supersaturated with SF6, a synthetic gas, and the gas transfer velocities were calculated from the measured decrease in SF6 concentration with time. The results from experiments with IS different rain rates (7 to 10 mm/h) and 1 of 2 drop sizes (2.8 or 4.2 mm diameter) confirm a significant and systematic enhancement of air-water gas exchange by rainfall. The gas transfer velocities derived from our experiment were related to the kinetic energy flux calculated from the rain rate and drop size. The relationship obtained for mono-dropsize rain at the RSIF was extrapolated to natural rain using the kinetic energy flux of natural rain calculated from the Marshall-Palmer raindrop size distribution. Results of laboratory experiments at RSIF were compared to field observations made during a tropical rainstorm in Miami, Florida and show good agreement between laboratory and field data.

  2. On the Importance of Metal–Oxide Interface Sites for the Water–Gas Shift Reaction Over Pt/CeO2 Catalysts

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-01-01

    The mechanism of water–gas shift reaction at the three-phase boundary of Pt/CeO2 catalysts has been investigated using density functional theory and microkinetic modeling to better understand the importance of metal–oxide interface sites in heterogeneous catalysis. Analysis of a microkinetic model based on parameters obtained from first principles suggests that both the “Redox pathway” and the “Associative carboxyl pathway with redox regeneration” could operate on Pt/CeO2 catalysts. Although (1) only few interfacial Pt atoms are found to be catalytically active at low temperatures due to strong adsorption of CO and (2) interfacial O–H bond breakage is difficult due to the high reducibility of ceria, interface sites are 2–3 orders of magnitude more active than Pt (1 1 1) and stepped Pt surface sites and therefore effectively determine the overall activity of Pt/CeO2. The high activity of Pt/CeO2 interface sites originates from a significantly enhanced water activation and dissociation at interfacial oxygen vacancies.

  3. Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeOx–TiO2(110) surfaces: Effects of high ceria coverage

    DOE PAGES

    Grinter, D. C.; Park, J. B.; Agnoli, S.; ...

    2015-10-22

    In this study, scanning tunnelling microscopy has been used to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO2(110)-(1 × 1). The other half of the surface comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 ×more » 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. For Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3+ formed during WGS reaction conditions.« less

  4. Separation of intron 22 inversion type 1 and 2 of hemophilia A by modified inverse-shifting polymerase chain reaction and capillary gel electrophoresis.

    PubMed

    Pan, Tzu-Yu; Chiou, Shyh-Shin; Wang, Chun-Chi; Wu, Shou-Mei

    2014-12-01

    An inverse-shifting polymerase chain reaction (IS-PCR) combined with short-end capillary gel electrophoresis (CGE) was developed for genotyping of intron 22 inversion Type 1 (Inv22-1) and Type 2 (Inv22-2) of hemophilia A (HA). Severe HA cases are affected by intron 22 inversion around 45-50%. Inv22-1 has higher frequency than Inv22-2. The aim of this study is to distinguish them by genotyping. In order to improve Inv22 genotyping efficiency, five primers were designed and applied to differentiate the wild type, Inv22-1, Inv22-2 and carrier. Three amplicons of 405, 457 and 512 bp were recognized for wild type; 333, 457 and 584 bp for Inv22-1; 385, 405 and 584 bp for Inv22-2. The Inv22-1 carrier has 5 amplicons including 333, 405, 457, 512, 584 bp and Inv22-2 carrier is differentiated by 385, 405, 457, 512 and 584 bp. The amplicons between Inv22-1 and Inv22-2 carriers are only different in 333 bp for Inv22-1 carrier and 385 bp for Inv22-2 carrier. Capillary gel electrophoresis (CGE) was used for separation within 5 min. The separation voltage was set at 8 kV (cathode at detector), and the temperature was kept at 25°C. The sieving matrix was 89 mM Tris, 89 mM boric acid, 2mM EDTA containing 0.4% (w/v) HPMC and 1 μM of YO-PRO(®)-1 Iodide. Total of 50 HA patients (including 35 non-Inv22, 14 Inv22-1, and one Inv22-2 patients) and 7 HA carriers were diagnosed in the application. Seven random samples (5 patients and 2 carriers) were subjected to comparison and gave identical results of DNA sequencing and this modified IS-PCR.

  5. A second-order Godunov method for wave problems in coupled solid-water-gas systems

    SciTech Connect

    Tang, H.S.; Sotiropoulos, F.

    1999-05-20

    Wave problems in solid-water-gas systems with distinct phase interfaces are commonly encountered in practice, such as in water entry of a recovered body, reservoir-dam interaction during earthquakes, and spallation of steel plates caused by blast waves. Here, the authors present a second-order Godunov method for computing unsteady, one-dimensional wave problems with a fracture and cavitation in coupled solid-water-gas systems. The method employs a hydro-elasto-plastic body, the Tait equation, and the ideal gas law for solid, water, and gaseous phases, respectively, and models both fractures and cavities as vacuum zones with distinct borders. The numerical approach utilizes a Lagrangian formulation in conjunction with local solid-water-gas-vacuum Riemann problems, which have unique solutions and can be solved efficiently. The various phases are treated in a unified manner and no supplementary interface conditions are necessary for tracking material boundaries. Calculations are carried out for Riemann problems, wave propagation and reflection in a water-rock-air system, and spallation and cavitation in an explosion-steel-water-gas system. It is shown that the Godunov method has high resolution for shocks and phase interfaces, clearly resolves elastic and plastic waves, and successfully describes onset and propagation of fracture and cavitation zones.

  6. KINETIC UNDERSTANDING OF THE SYNGAS-TO-DME REACTION SYSTEM AND ITS IMPLICATIONS TO PROCESS AND ECONOMICS

    SciTech Connect

    Xiang-Dong Peng

    2002-12-01

    In a single-step synthesis gas-to-dimethyl ether process, synthesis gas (or syngas, a mixture of H{sub 2} and CO) is converted into dimethyl ether (DME) in a single reactor. The three reactions involved in this process, methanol synthesis, methanol dehydration and water gas shift, form an interesting reaction network. The interplay among these three reactions results in excellent syngas conversion or reactor productivity. A fundamental understanding of this interplay helps to explain many experimental and simulation observations, to identify optimal reaction conditions, and to provide guidelines for process development. The higher syngas conversion or reactor productivity in the syngas-to-DME reaction system, compared to that in the syngas-to-methanol reaction system, is referred to as chemical synergy. This synergy exhibits a strong dependence on the composition of the reactor feed. To demonstrate the extent of this dependence, simulations with adjusted activity for each reaction were performed to reveal the relative rate of each reaction. The results show that the water gas shift reaction is the most rapid, being practically controlled by the equilibrium. Both methanol synthesis and methanol dehydration reactions are kinetically controlled. The kinetics of the dehydration reactions is greater than that of the methanol synthesis reaction in the CO-rich regime. However, the rates of these two reactions come closer as the H{sub 2} concentration in the reactor feed increases. The role of the dehydration reaction is to remove the equilibrium barrier for the methanol synthesis reaction. The role of the water gas shift reaction is more complex; it helps the kinetics of methanol dehydration by keeping the water concentration low, which in turn enhances methanol synthesis. It also readjusts the H{sub 2}:CO ratio in the reactor as the reactions proceed. In the CO-rich regime, the water gas shift reaction supplements the limiting reactant, H{sub 2}, by reacting water with

  7. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, March--May 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.

    1992-06-01

    During this quarter, the high pressure (up to 100 atm), high temperature (up to 350{degrees}C) catalyst testing system was rebuilt with clean tubing, etc. A new preparation of MoS{sub 2} catalyst was carried out, and this catalyst will be doped with alkali and tested during the next quarter of research.

  8. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, June 1993--August 1993

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.; Carr, T.

    1993-09-01

    Various preparation methods of synthesizing molybdenum disulfide and various alkali doping procedures were studied to determine if various preparation paramenters affected catalyst activity. Testing was performed on an undoped molybdenum disulfide sample with H{sub 2}/CO = 1 synthesis gas at 8.1 MPa and at temperatures of 245, 255, 265, 275, 280, 300, 320, and 295C, and only hydrocarbons were formed. A methanol injection experiment with undoped catalyst showed that homologation of methanol did not occur over the undoped MOS{sub 2}. Catalytic testing on a cesium formate doped molybdenum disulfide catalyst corresponding to 9 wt% Cs/MoS{sub 2} at 8.1 MPa and temperatures of 245, 255, 265, 275, 285, and 295C, mostly linear alcohols. The CS/MOS{sub 2} sample was protected from air exposure during preparation and testiag. As with the other recently tested alkali-promoted MOS{sub 2} catalysts, this cataylst was not as active as previous CS/MOS{sub 2} catalysts [1], and some deactivation during these systematic studies was observed. X-Ray powder diffraction and BET surface area measurements are being used to characterize the catalysts, and electron microscopy analyses are being carried out.

  9. Shifting Attention

    ERIC Educational Resources Information Center

    Ingram, Jenni

    2014-01-01

    This article examines the shifts in attention and focus as one teacher introduces and explains an image that represents the processes involved in a numeric problem that his students have been working on. This paper takes a micro-analytic approach to examine how the focus of attention shifts through what the teacher and students do and say in the…

  10. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, C.E.; Robinson, P.R.

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  11. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, Carlos E.; Robinson, Paul R.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  12. Ultrasonic sensing for noninvasive characterization of oil-water-gas flow in a pipe

    NASA Astrophysics Data System (ADS)

    Chillara, Vamshi Krishna; Sturtevant, Blake T.; Pantea, Cristian; Sinha, Dipen N.

    2017-02-01

    A technique for noninvasive ultrasonic characterization of multiphase crude oil-water-gas flow is discussed. The proposed method relies on determining the sound speed in the mixture. First, important issues associated with making real-time noninvasive measurements are discussed. Then, signal processing approach adopted to determine the sound speed in the multiphase mixture is presented. Finally, results from controlled experiments on crude oil-water mixture in both the presence and absence of gas are presented.

  13. Bridging silyl groups in sigma-bond metathesis and [1, 2] shifts. An experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3

    SciTech Connect

    Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Andersen, Richard

    2010-04-21

    The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference in energy required to form a pentacoordinate silicon or carbon atom in the transition state. This difference clearly distinguishes a silyl from an alkyl group as shown in the study of"Pyrolysis of Tetramethylsilane Yielding Free d-orbitals by Seyferth and Pudvin in ChemTech 1981, 11, 230-233".

  14. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M. B.; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Laurie, S.; Garcia, K.; Sargsyan, A.; Martin, D.; Lui, J.; Macias, B.; Arbeille, P.; Danielson, R.; Chang, D.; Gunga, H.; Johnston, S.; Westby, C.; Ribeiro, L.; Ploutz-Snyder, R.; Smith, S.

    2015-01-01

    INTRODUCTION: Mechanisms responsible for the ocular structural and functional changes that characterize the visual impairment and intracranial pressure (ICP) syndrome (VIIP) are unclear, but hypothesized to be secondary to the cephalad fluid shift experienced in spaceflight. This study will relate the fluid distribution and compartmentalization associated with long-duration spaceflight with VIIP symptoms. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as the VIIP-related effects of those shifts, can be predicted preflight with acute hemodynamic manipulations, and also if lower body negative pressure (LBNP) can reverse the VIIP effects. METHODS: Physiologic variables will be examined pre-, in- and post-flight in 10 International Space Station crewmembers including: fluid compartmentalization (D2O and NaBr dilution); interstitial tissue thickness (ultrasound); vascular dimensions and dynamics (ultrasound and MRI (including cerebrospinal fluid pulsatility)); ocular measures (optical coherence tomography, intraocular pressure, ultrasound); and ICP measures (tympanic membrane displacement, otoacoustic emissions). Pre- and post-flight measures will be assessed while upright, supine and during 15 deg head-down tilt (HDT). In-flight measures will occur early and late during 6 or 12 month missions. LBNP will be evaluated as a countermeasure during HDT and during spaceflight. RESULTS: The first two crewmembers are in the preflight testing phase. Preliminary results characterize the acute fluid shifts experienced from upright, to supine and HDT postures (increased stroke volume, jugular dimensions and measures of ICP) which are reversed with 25 millimeters Hg LBNP. DISCUSSION: Initial results indicate that acute cephalad fluid shifts may be related to VIIP symptoms, but also may be reversible by LBNP. The effect of a chronic fluid shift has yet to be evaluated. Learning Objectives: Current spaceflight VIIP research is described

  15. Air-water gas exchange of mercury in the Bay Saint François wetlands: Observation and model parameterization

    NASA Astrophysics Data System (ADS)

    Zhang, Hong H.; Poissant, Laurier; Xu, Xiaohong; Pilote, Martin; Beauvais, Conrad; Amyot, Marc; Garcia, Edenise; Laroulandie, Jerome

    2006-09-01

    Total gaseous mercury (TGM) air-water flux measurements were taken using a dynamic flux chamber (DFC) coupled with a gaseous mercury (Hg) analyzer at the Bay St. François (BSF) wetlands (Quebec, Canada) in summer 2003. The measured TGM fluxes over water exhibited a consistent diurnal pattern, with maximum emissions during daytime and minimum fluxes occurring at night. Pearson correlation analysis showed that solar radiation was the most influential environmental parameter in TGM air-water exchange. Significant correlations were also found between TGM fluxes and 1 hour time-lagged water temperature, indicating the enhancement of fluxes by bacterial activities or chemical reactions. The concentrations of dissolved gaseous mercury (DGM) in water were measured during the 2003 sampling period and indicated that DGM was always supersaturated, which implied that the water body acted primarily as a source of mercury to the atmosphere. Several empirical models of mercury air-water gas exchange were developed and evaluated. Compared to the published models, these proposed models were capable of producing good results, leading to a better agreement between the measured and modeled fluxes (improvements by 48-98%). Among these empirical models, the ones linking TGM fluxes with net radiation were superior because of their strong predictive capability. Two preferred models were selected for air-water TGM flux estimation from Lake St. Pierre's surrounding wetlands. These two models yield a mean emission of 0.19-0.24 kg mercury during May-September each year from 1999 to 2003.

  16. A novel reaction-based colorimetric and ratiometric fluorescent sensor for cyanide anion with a large emission shift and high selectivity.

    PubMed

    Wang, Shaodan; Fei, Xiaoliang; Guo, Jing; Yang, Qingbiao; Li, Yaoxian; Song, Yan

    2016-01-01

    A hybrid carbazole-hemicyanine dye (Cac) has been developed as a novel colorimetric and ratiometric fluorescent sensor for cyanide detection. Upon treatment with cyanide, Cac displayed a remarkable fluorescence ratiometric response, with the emission wavelength displaying a very large emission shift (214 nm). The detection of cyanide was performed via the nucleophilic addition of cyanide anion to the indolium group of the sensor, which resulted in the blocking of the intramolecular charge transfer (ICT) process in the sensor, inducing a ratiometric fluorescence change and simultaneously an obvious color change. Furthermore, competitive anions did not showed any significant changes both in color and emission intensity ratio (I381/I595), indicating the high selectivity of the sensor to CN(-).

  17. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M.; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Lauriie, S.; Garcia, K.; Sargsyan, A.; Martin, D.; Ribeiro, L.; Lui, J.; Macias, B.; Arbeille, P.; Danielson, R.; Chang, D.; Johnston, S.; Ploutz-Snyder, R.; Smith, S.

    2016-01-01

    NASA is focusing on long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low-Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but more than 50% of ISS astronauts experienced more profound, chronic changes with objective structural and functional findings such as papilledema and choroidal folds. Globe flattening, optic nerve sheath dilation, and optic nerve tortuosity also are apparent. This pattern is referred to as the visual impairment and intracranial pressure (VIIP) syndrome. VIIP signs and symptoms, as well as postflight lumbar puncture data, suggest that elevated intracranial pressure (ICP) may be associated with the spaceflight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration spaceflight, and to correlate these findings with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as the VIIP-related effects of those shifts, is predicted by the crewmember's preflight conditions and responses to acute hemodynamic manipulations (such as head-down tilt). Lastly, we will evaluate the patterns of fluid distribution in ISS astronauts during acute reversal of fluid shifts through application of lower body negative pressure (LBNP) interventions to characterize and explain general and individual responses. METHODS: We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the Figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, calcaneus tissue thickness (by

  18. A fully coupled model for water-gas-heat reactive transport with methane oxidation in landfill covers.

    PubMed

    Ng, C W W; Feng, S; Liu, H W

    2015-03-01

    Methane oxidation in landfill covers is a complex process involving water, gas and heat transfer as well as microbial oxidation. The coupled phenomena of microbial oxidation, water, gas, and heat transfer are not fully understood. In this study, a new model is developed that incorporates water-gas-heat coupled reactive transport in unsaturated soil with methane oxidation. Effects of microbial oxidation-generated water and heat are included. The model is calibrated using published data from a laboratory soil column test. Moreover, a series of parametric studies are carried out to investigate the influence of microbial oxidation-generated water and heat, initial water content on methane oxidation efficiency. Computed and measured results of gas concentration and methane oxidation rate are consistent. It is found that the coupling effects between water-gas-heat transfer and methane oxidation are significant. Ignoring microbial oxidation-generated water and heat can result in a significant difference in methane oxidation efficiency by 100%.

  19. On the Model Dependence of Kinetic Shifts in Unimolecular Reactions: The Dissociation of the Cations of Benzene and n-Butylbenzene

    DTIC Science & Technology

    2005-07-08

    important access to bond dissociation energies, E0, of the fragmenting species and, hence, to their CAH6 C6H5+ + H (1) thermochemical data . There is...initio results for V(r) from ref formed in ref 13 and related to k(E) data . Reaction 2 is an 10, modeled short-range and long-range potentials VSR(r) and...the accuracy of thermochemical data . the corresponding V(r). We represent the 2B 1 potential inside the curve-crossing by a short-range potential J/SR

  20. Acetic Acid Reforming over Rh Supported on La2O3/CeO2-ZrO2: Catalytic Performance and Reaction Pathway Analysis

    SciTech Connect

    Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

    2013-07-11

    Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C, steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.

  1. Effect of intramolecular Paternò-Büchi reaction on the thermodynamics and kinetics of nearly degenerate [3,3]-sigmatropic shift in fluxional polycycles.

    PubMed

    Valiulin, Roman A; Dressen, Donald G; Riggs, Jennifer R; Habte, Faven M; Kutateladze, Andrei G

    2009-05-01

    In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier.

  2. 2DCOR-GC: an application of the generalized two-dimensional correlation analysis as a route to optimization of continuous flow supercritical fluid reactions.

    PubMed

    Hyde, Jason R; Bourne, Richard A; Noda, Isao; Stephenson, Phil; Poliakoff, Martyn

    2004-11-01

    A new approach for optimization and monitoring of continuous reactions has been developed using 2D correlation methods for the analysis of GC data (2DCOR-GC). 2DCOR-GC maps are obtained following perturbation of the system that allow the effect of changing reaction parameters such as time, temperature, pressure, or concentration to be both monitored and sequenced with regard to changes in the raw GC data. In this paper, we describe the application of the 2DCOR-GC technique to monitoring the reverse water-gas shift reaction in scCO(2). 2DCOR-GC is combined with FT-IR data to validate the methodology. We also report the application of 2DCOR-GC to probe the mechanism of the alkylation of m-cresol with isopropyl alcohol in scCO(2) using Nafion SAC-13 as the catalyst. These results identify coeluting peaks that could easily be missed without exhaustive method development.

  3. The adsorption behavior of octafluoropropane at the water/gas interface

    SciTech Connect

    Giebel, Friederike; Paulus, Michael; Nase, Julia Bieder, Steffen; Kiesel, Irena; Tolan, Metin

    2014-12-14

    We studied the adsorption behavior of the gas octafluoropropane at the water/gas interface as a function of different pressures. In a custom-made measurement cell, the gas pressure was varied in a range between 1 bar and close to the condensation pressure of octafluoropropane. The electron density profiles of the adsorption layers show that the layer thickness increases with pressure. The evolution of the layer electron density indicates that the bulk electron density is reached if a layer consisting of more than one monolayer of octafluoropropane is adsorbed on the water surface.

  4. Turbulence and wave breaking effects on air-water gas exchange

    PubMed

    Boettcher; Fineberg; Lathrop

    2000-08-28

    We present an experimental characterization of the effects of turbulence and breaking gravity waves on air-water gas exchange in standing waves. We identify two regimes that govern aeration rates: turbulent transport when no wave breaking occurs and bubble dominated transport when wave breaking occurs. In both regimes, we correlate the qualitative changes in the aeration rate with corresponding changes in the wave dynamics. In the latter regime, the strongly enhanced aeration rate is correlated with measured acoustic emissions, indicating that bubble creation and dynamics dominate air-water exchange.

  5. The reaction of European lobster larvae (Homarus gammarus) to different quality food: effects of ontogenetic shifts and pre-feeding history.

    PubMed

    Schoo, Katherina L; Aberle, Nicole; Malzahn, Arne M; Schmalenbach, Isabel; Boersma, Maarten

    2014-02-01

    Young larval stages of many organisms represent bottlenecks in the life-history of many species. The high mortality commonly observed in, for example, decapod larvae has often been linked to poor nutrition, with most studies focussing on food quantity. Here, we focus instead on the effects of quality and have investigated its effects on the nutritional condition of lobster larvae. We established a tri-trophic food chain consisting of the cryptophyte Rhodomonas salina, the calanoid copepod Acartia tonsa and larvae of the European lobster Homarus gammarus. In a set of experiments, we manipulated the C:N:P stoichiometry of the primary producers, and accordingly those of the primary consumer. In a first experiment, R. salina was grown under N- and P-limitation and the nutrient content of the algae was manipulated by addition of the limiting nutrient to create a food quality gradient. In a second experiment, the effect on lobster larvae of long- and short-term exposure to food of varying quality during ontogenetic development was investigated. The condition of the lobster larvae was negatively affected even by subtle N- and P-nutrient limitations of the algae. Furthermore, younger lobster larvae were more vulnerable to nutrient limitation than older ones, suggesting an ontogenetic shift in the capacity of lobster larvae to cope with low quality food. The results presented here might have substantial consequences for the survival of lobster larvae in the field, as, in the light of future climate change and re-oligotrophication of the North Sea, lobster larvae might face marked changes in temperature and nutrient conditions, thus significantly altering their condition and growth.

  6. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, Michael; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Sargsyan, A.; Martin, D.; Lui, J.; Macias, B.; Arbeille, P.; Platts, S.

    2014-01-01

    NASA is focusing on long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but more than 30% of ISS astronauts experience more profound, chronic changes with objective structural and functional findings such as papilledema and choroidal folds. Globe flattening, optic nerve sheath dilation, and optic nerve tortuosity also are apparent. This pattern is referred to as the visual impairment and intracranial pressure (VIIP) syndrome. VIIP signs and symptoms, as well as postflight lumbar puncture data, suggest that elevated intracranial pressure (ICP) may be associated with the space flight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration space flight, and to correlate these findings with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during space flight, as well as the VIIP-related effects of those shifts, is predicted by the crewmember's pre-flight condition and responses to acute hemodynamic manipulations (such as head-down tilt). Lastly, we will evaluate the patterns of fluid distribution in ISS astronauts during acute reversal of fluid shifts through application of lower body negative pressure (LBNP) interventions to characterize and explain general and individual responses. We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the Figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, calcaneus tissue thickness (by ultrasound

  7. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M. B.; Hargens, A. R.; Dulchavsky, S. A.; Arbeille, P.; Danielson, R. W.; Ebert, D. J.; Garcia, K. M.; Johnston, S. L.; Laurie, S. S.; Lee, S. M. C.; Liu, J.; Macias, B.; Martin, D. S.; Minkoff, L.; Ploutz-Snyder, R.; Ribeiro, L. C.; Sargsyan, A.; Smith, S. M.

    2017-01-01

    Introduction. NASA's Human Research Program is focused on addressing health risks associated with long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but now more than 50 percent of ISS astronauts have experienced more profound, chronic changes with objective structural findings such as optic disc edema, globe flattening and choroidal folds. These structural and functional changes are referred to as the visual impairment and intracranial pressure (VIIP) syndrome. Development of VIIP symptoms may be related to elevated intracranial pressure (ICP) secondary to spaceflight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration spaceflight and to determine if a relation exists with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as any VIIP-related effects of those shifts, are predicted by the crewmember's pre-flight status and responses to acute hemodynamic manipulations, specifically posture changes and lower body negative pressure. Methods. We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, and calcaneus tissue thickness (by ultrasound); (3) vascular dimensions by ultrasound (jugular veins, cerebral and carotid arteries, vertebral arteries and veins, portal vein); (4) vascular dynamics by MRI (head/neck blood flow, cerebrospinal fluid

  8. First principles (DFT) characterization of Rh(I) /dppp-catalyzed C-H activation by tandem 1,2-addition/1,4-Rh shift reactions of norbornene to phenylboronic acid.

    PubMed

    Kantchev, Eric Assen B; Pangestu, Surya R; Zhou, Feng; Sullivan, Michael B; Su, Hai-Bin

    2014-11-17

    The C-H activation in the tandem, "merry-go-round", [(dppp)Rh]-catalyzed (dppp=1,3-bis(diphenylphosphino)propane), four-fold addition of norborene to PhB(OH)2 has been postulated to occur by a C(alkyl)H oxidative addition to square-pyramidal Rh(III) -H species, which in turn undergoes a C(aryl)-H reductive elimination. Our DFT calculations confirm the Rh(I) /Rh(III) mechanism. At the IEFPCM(toluene, 373.15 K)/PBE0/DGDZVP level of theory, the oxidative addition barrier was calculated to be 12.9 kcal mol(-1) , and that of reductive elimination was 5.0 kcal mol(-1) . The observed selectivity of the reaction correlates well with the relative energy barriers of the cycle steps. The higher barrier (20.9 kcal mol(-1) ) for norbornyl-Rh protonation ensures that the reaction is steered towards the 1,4-shift (total barrier of 16.3 kcal mol(-1) ), acting as an equilibration shuttle. The carborhodation (13.2 kcal mol(-1) ) proceeds through a lower barrier than the protonation (16.7 kcal mol(-1) ) of the rearranged aryl-Rh species in the absence of o- or m-substituents, ensuring multiple carborhodations take place. However, for 2,5-dimethylphenyl, which was used as a model substrate, the barrier for carborhodation is increased to 19.4 kcal mol(-1) , explaining the observed termination of the reaction at 1,2,3,4-tetra(exo-norborn-2-yl)benzene. Finally, calculations with (Z)-2-butene gave a carborhodation barrier of 20.2 kcal mol(-1) , suggesting that carborhodation of non-strained, open-chain substrates would be disfavored relative to protonation.

  9. Shifting sugars and shifting paradigms.

    PubMed

    Siegal, Mark L

    2015-02-01

    No organism lives in a constant environment. Based on classical studies in molecular biology, many have viewed microbes as following strict rules for shifting their metabolic activities when prevailing conditions change. For example, students learn that the bacterium Escherichia coli makes proteins for digesting lactose only when lactose is available and glucose, a better sugar, is not. However, recent studies, including three PLOS Biology papers examining sugar utilization in the budding yeast Saccharomyces cerevisiae, show that considerable heterogeneity in response to complex environments exists within and between populations. These results join similar recent results in other organisms that suggest that microbial populations anticipate predictable environmental changes and hedge their bets against unpredictable ones. The classical view therefore represents but one special case in a range of evolutionary adaptations to environmental changes that all organisms face.

  10. Near-surface physics during convection affecting air-water gas transfer

    NASA Astrophysics Data System (ADS)

    Fredriksson, S. T.; Arneborg, L.; Nilsson, H.; Handler, R. A.

    2016-05-01

    The gas flux at the water surface is affected by physical processes including turbulence from wind shear, microscale wave breaking, large-scale breaking, and convection due to heat loss at the surface. The main route in the parameterizations of the gas flux has been to use the wind speed as a proxy for the gas flux velocity, indirectly taking into account the dependency of the wind shear and the wave processes. The interest in the contributions from convection processes has increased as the gas flux from inland waters (with typically lower wind and sheltered conditions) now is believed to play a substantial role in the air-water gas flux budget. The gas flux is enhanced by convection through the mixing of the mixed layer as well as by decreasing the diffusive boundary layer thickness. The direct numerical simulations performed in this study are shown to be a valuable tool to enhance the understanding of this flow configuration often present in nature.

  11. Air-water gas exchange of organochlorine compounds in Lake Baikal, Russia

    SciTech Connect

    McConnell, L.L.; Kucklick, J.R.; Bidleman, T.F.; Ivanov, G.P.; Chernyak, S.M.

    1996-10-01

    Air and surface water samples were collected at Lake Baikal, Russia, during June 1991 to determine concentrations of organochlorine pesticides and polychlorinated biphenyl (PCB) congeners. These data were combined with Henry`s law constants to estimate the gas flux rate across the air-water interface of each compound class. Air samples were collected at Lake Baikal and from nearby Irkutsk. Water samples were collected from three mid-lake stations and at the mouth of two major tributaries. Average air concentrations of chlorinated bornanes (14 pg m{sup -3}), chlordanes (4.9 pg m{sup -3}), and hexachlorobenzene (HCB) (194 pg m{sup -3}) were similar to global backgound of Arctic levels. However, air concentrations of hexachlorocyclohexanes (HCHs), DDTs, and PCBs were closer to those observed in the Great Lakes region. Significantly higher levels of these three compound classes in air over Irkutsk suggests that regional atmospheric transport and deposition may be an important source of these persistent compounds to Lake Baikal. Air-water gas exchange calculations resulted in net depositional flux values for {alpha}-HCH, {gamma}-HCH, DDTs, and chlorinated bornanes at 112, 23, 3.6, and 2.4 ng m{sup -2} d{sup -1}, respectively. The total net flux of 22 PCB congeners, chlordanes, and HCB was from water to air (volatilization) at 47, 1.8, and 32 ng m{sup -2} d{sup -1}, respectively. 50 refs., 7 figs., 5 tabs.

  12. Sorption enhanced reaction process (SERP) for production of hydrogen

    SciTech Connect

    Sircar, S.; Anand, M.; Carvill, B.

    1995-09-01

    Sorption Enhanced Reaction (SER) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process, the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The consequences of SER are: (1) reformation reaction at a significantly lower temperature (300-500{degrees}C) than conventional SMR (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (2) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 99+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (3) downstream hydrogen purification step is either eliminated or significantly reduced in size. The early focus of the program will be on the identification of an adsorbent/chemisorbent for CO{sub 2} and on the demonstration of the SER concept for SMR in our state-of-the-art bench scale process. In the latter stages, a pilot plant will be built to scale-up the technology and to develop engineering data. The program has just been initiated and no significant results for SMR will be reported. However, results demonstrating the basic principles and process schemes of SER technology will be presented for reverse water gas shift reaction as the model reaction. If successful, this technology will be commercialized by Air Products and Chemicals, Inc. (APCI) and used in its existing hydrogen business. APCI is the world leader in merchant hydrogen production for a wide range of industrial applications.

  13. Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeOx–TiO2(110) surfaces: Effects of high ceria coverage

    SciTech Connect

    Grinter, D. C.; Park, J. B.; Agnoli, S.; Evans, J.; Hrbek, J.; Stacchiola, D. J.; Senanayake, S. D.; Rodriguez, J. A.

    2015-10-22

    In this study, scanning tunnelling microscopy has been used to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO2(110)-(1 × 1). The other half of the surface comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. For Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3+ formed during WGS reaction conditions.

  14. Integrated reformer and shift reactor

    DOEpatents

    Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

    2006-06-27

    A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

  15. Psychopathology of Shift Work.

    ERIC Educational Resources Information Center

    Akinnawo, Ebenezer Olutope

    1989-01-01

    Examined incidence and nature of general psychopathology among Nigerian shift workers (N=320). Found shift workers more significantly psychopathological than non-shift workers (p<0.001). Prominent disorders among shift workers were intellectual, sleep, mood, and general somatic disorders. No significant difference could be attributed to gender…

  16. Gear shift control mechanism

    SciTech Connect

    Janson, D.A.

    1987-03-10

    A gear shift control mechanism is described comprising: multiple shift rods directed substantially parallel to one another, each rod carrying a shift fork for axial movement; a shift lever supported for pivotal movement about a first axis directed parallel to the axes of the shift rods and for pivotal movement about a second axis directed substantially perpendicular to the axes of the shift rods. The lever is moveable about the first axis and the second axis into engagement with a selected shift fork; interlock means located on each lateral side of the shift lever and mounted for pivotal movement about the first axis for blocking engagement with the shift forks; detent means for holding the shift lever in multiple predetermined angular positions about the second axis; and spring means located on a lateral side of the shift lever and mounted for pivotal movement about the first axis into interference contact with the shift forks for producing a force tending to resiliently bias the shift lever out of engagement with the selected shift fork.

  17. Molecular implementation of molecular shift register memories

    NASA Technical Reports Server (NTRS)

    Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

    1991-01-01

    An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

  18. Ammonia reactions with the stored oxygen in a commercial lean NOx trap catalyst

    DOE PAGES

    Bartova, Sarka; Mracek, David; Koci, Petr; ...

    2014-10-12

    Ammonia is an important intermediate of the NOx reduction in a NOx storage and reduction catalyst (aka lean NOx trap). NH3 formed under rich conditions in the reduced front part of the catalyst is transported by convection downstream to the unregenerated (still oxidized) zone of the catalyst, where it further reacts with the stored oxygen and NOx. In this paper, the kinetics and selectivity of NH3 reactions with the stored oxygen are studied in detail with a commercial Ba-based NOx storage catalyst containing platinum group metals (PGM), Ba and Ce oxides. Furthermore, steady-state NH3 decomposition, NH3 oxidation by O2 andmore » NO, and N2O decomposition are examined in light-off experiments. Periodic lean/rich cycling is measured first with O2 and NH3, and then with NOx + O2 and NH3 to discriminate between the NH3 reactions with the stored oxygen and the stored NOx. The reaction of NH3 with the stored O2 is highly selective towards N2, however a certain amount of NOx and N2O is also formed. The formed NOx by-product is efficiently adsorbed on the NOx storage sites such that the NOx is not detected at the reactor outlet except at high temperatures. The stored NOx reacts with NH3 feed in the next rich phase, contributing to the N2O formation. Water inhibits the reactions of NH3 with the stored oxygen. On the contrary, the presence of CO2 increases the NH3 consumption. Furthermore, CO2 is able to provide additional oxygen for NH3 oxidation, forming –CO in analogy to the reverse water gas shift reaction.« less

  19. Influence of current velocity and wind speed on air-water gas exchange in a mangrove estuary

    NASA Astrophysics Data System (ADS)

    Ho, David T.; Coffineau, Nathalie; Hickman, Benjamin; Chow, Nicholas; Koffman, Tobias; Schlosser, Peter

    2016-04-01

    Knowledge of air-water gas transfer velocities and water residence times is necessary to study the fate of mangrove derived carbon exported into surrounding estuaries and ultimately to determine carbon balances in mangrove ecosystems. For the first time, the 3He/SF6 dual tracer technique, which has been proven to be a powerful tool to determine gas transfer velocities in the ocean, is applied to Shark River, an estuary situated in the largest contiguous mangrove forest in North America. The mean gas transfer velocity was 3.3 ± 0.2 cm h-1 during the experiment, with a water residence time of 16.5 ± 2.0 days. We propose a gas exchange parameterization that takes into account the major sources of turbulence in the estuary (i.e., bottom generated shear and wind stress).

  20. Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

    2017-01-01

    High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.

  1. Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations

    PubMed Central

    Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

    2017-01-01

    High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results. PMID:28120896

  2. Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations.

    PubMed

    Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

    2017-01-25

    High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.

  3. 20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean.

    PubMed

    Jantunen, Liisa M; Wong, Fiona; Gawor, Anya; Kylin, Henrik; Helm, Paul A; Stern, Gary A; Strachan, William M J; Burniston, Deborah A; Bidleman, Terry F

    2015-12-01

    The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals.

  4. Making Shifts toward Proficiency

    ERIC Educational Resources Information Center

    McGatha, Maggie B.; Bay-Williams, Jennifer M.

    2013-01-01

    The Leading for Mathematical Proficiency (LMP) Framework (Bay-Williams et al.) has three components: (1) The Standards for Mathematical Practice; (2) Shifts in classroom practice; and (3) Teaching skills. This article briefly describes each component of the LMP framework and then focuses more in depth on the second component, the shifts in…

  5. Shifting scintillator neutron detector

    DOEpatents

    Clonts, Lloyd G; Cooper, Ronald G; Crow, Jr., Morris Lowell; Hannah, Bruce W; Hodges, Jason P; Richards, John D; Riedel, Richard A

    2014-03-04

    Provided are sensors and methods for detecting thermal neutrons. Provided is an apparatus having a scintillator for absorbing a neutron, the scintillator having a back side for discharging a scintillation light of a first wavelength in response to the absorbed neutron, an array of wavelength-shifting fibers proximate to the back side of the scintillator for shifting the scintillation light of the first wavelength to light of a second wavelength, the wavelength-shifting fibers being disposed in a two-dimensional pattern and defining a plurality of scattering plane pixels where the wavelength-shifting fibers overlap, a plurality of photomultiplier tubes, in coded optical communication with the wavelength-shifting fibers, for converting the light of the second wavelength to an electronic signal, and a processor for processing the electronic signal to identify one of the plurality of scattering plane pixels as indicative of a position within the scintillator where the neutron was absorbed.

  6. Instantaneous phase shifting deflectometry.

    PubMed

    Trumper, Isaac; Choi, Heejoo; Kim, Dae Wook

    2016-11-28

    An instantaneous phase shifting deflectometry measurement method is presented and implemented by measuring a time varying deformable mirror with an iPhone ® 6. The instantaneous method is based on multiplexing phase shifted fringe patterns with color, and decomposing them in x and y using Fourier techniques. Along with experimental data showing the capabilities of the instantaneous deflectometry system, a quantitative comparison with the Fourier transform profilometry method, which is a distinct phase measuring method from the phase shifting approach, is presented. Sources of error, nonlinear color-multiplexing induced error correction, and hardware limitations are discussed.

  7. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  8. Data for phase angle shift with frequency

    PubMed Central

    Paul, T.; Banerjee, D.; Kargupta, K.

    2016-01-01

    Phase angle shift between the current and voltage with frequency has been reported for a single phosphoric acid fuel cell in the cell temperature from 100 °C to 160 °C and the humidifier temperature from 40 °C to 90 °C. An electrochemical workbench is employed to find the shift. The figure of phase angle shift shows a peak in high humidifier temperatures. The peak in phase angle shift directs to lower frequency side with decreasing humidifier temperature. The estimation of electrochemical reaction time is also evaluated in the humidifier temperature zone from 50 °C to 90 °C. PMID:27158655

  9. Thermochemical properties, DeltafH degrees (298), S degrees (298), and Cp degrees (T), for n-butyl and n-pentyl hydroperoxides and the alkyl and peroxy radicals, transition states, and kinetics for intramolecular hydrogen shift reactions of the peroxy radicals.

    PubMed

    Zhu, Li; Bozzelli, Joseph W; Kardos, Lisa M

    2007-07-19

    Alkyl radicals in atmospheric and combustion environments undergo a rapid association with molecular oxygen (3O2) to form an alkyl peroxy radical (ROO*). One important reaction of these peroxy radicals is the intramolecular H-shift (intramolecular abstraction) to form a hydroperoxide alkyl radical (R'*COOH), where the hydroperoxide alkyl radical may undergo chemical activation reaction with O2 and result in chain branching at moderate to low temperatures. The thermochemistry and trends in kinetic parameters for the hydrogen shift reactions from each carbon (4-8-member-ring TST's) in n-butyl and n-pentyl peroxy radicals (CCCCOO* and CCCCCOO*) are analyzed using density functional and ab initio calculation methods. Thermochemical properties, DeltafH degrees (298 K), C-H bond energies, S degrees (298 K), and Cp degrees (T) of saturated linear C4 and C5 aliphatic peroxides (ROOH), as well as the corresponding hydroperoxide alkyl radicals (R'*COOH), are determined. DeltafH degrees (298 K) are obtained from isodesmic reactions and the total energies of the CBS-QB3 and B3LYP computational methods. Contributions to the entropy and the heat capacity from translation, vibration, and external rotation are calculated using the rigid-rotor-harmonic-oscillator approximation based on the CBS-QB3 frequencies and structures. The results indicate that pre-exponential factors, A(T), decrease with the increase of the ring size (4-8-member-ring TS, H-atom included). The DeltaH for 4-, 5-, 6-, and 7-member rings in n-butyl (and n-pentyl) peroxy are 40.8 (40.8), 31.4 (31.5), 20.5 (20.0), 22.6-p (19.4) kcal mol(-1), respectively. The DeltaH for the 8-member ring in n-pentylperoxy is 23.8-p kcal mol(-1), All abstractions are from secondary (-CH2-) groups except those marked (-p), which are from primary sites. Enthalpy and barrier values from the B3LYP/6-311++G(2d,p) and BHandHLYP/6-311G(d,p) methods are compared with CBS-QB3 results. The B3LYP results show good agreement with the higher

  10. Improved feedback shift register

    NASA Technical Reports Server (NTRS)

    Perlman, M.

    1972-01-01

    Design of feedback shift register with three tap feedback decoding scheme is described. Application for obtaining sequence synchronization patterns is examined. Operation of the circuitry is described and drawings of the systems are included.

  11. Shape-Shifting Plastic

    SciTech Connect

    2015-05-20

    A new plastic developed by ORNL and Washington State University transforms from its original shape through a series of temporary shapes and returns to its initial form. The shape-shifting process is controlled through changes in temperature

  12. Our World: Fluid Shift

    NASA Video Gallery

    Learn about the circulatory system and how gravity aids blood flow in our bodies here on Earth. Find out how NASA flight surgeons help the astronauts deal with the fluid shift that happens during s...

  13. Shift Verification and Validation

    SciTech Connect

    Pandya, Tara M.; Evans, Thomas M.; Davidson, Gregory G; Johnson, Seth R.; Godfrey, Andrew T.

    2016-09-07

    This documentation outlines the verification and validation of Shift for the Consortium for Advanced Simulation of Light Water Reactors (CASL). Five main types of problems were used for validation: small criticality benchmark problems; full-core reactor benchmarks for light water reactors; fixed-source coupled neutron-photon dosimetry benchmarks; depletion/burnup benchmarks; and full-core reactor performance benchmarks. We compared Shift results to measured data and other simulated Monte Carlo radiation transport code results, and found very good agreement in a variety of comparison measures. These include prediction of critical eigenvalue, radial and axial pin power distributions, rod worth, leakage spectra, and nuclide inventories over a burn cycle. Based on this validation of Shift, we are confident in Shift to provide reference results for CASL benchmarking.

  14. Straddling a paradigm shift

    SciTech Connect

    Landgren, D.

    1995-05-01

    Paul Meagher made a big mistake when he asked me about my speech. I asked him what I should talk about. He reiterated the title of the conference {open_quotes}Forecasting and DSM: Organizing for Success,{close_quotes} and said that whatever issues I wanted to cover were fine with him. As a result I will cover those areas I`ve been thinking about recently. It is hard for me to extract either Forecasting or Demand-Side Management out from the broader issues unwinding in the industry today. I`ve been around long enough to be involved in two major shifts in the industry. I call these paradigm shifts because as a planner I tend to build models in my mind to represent business or regulatory structure. Since a paradigm is defined as a clear model of something, I tend to talk about structural shifts in the industry as paradigm shifts. The first paradigm shift was brought about by the rapid escalation of energy prices in the 1970s. The second paradigm shift, brought about in part because of the first and because of growing concerns about the environment, ushered in the era of utility conservation and load management programs (components of a broader DSM concept - unfortunately today many people limit DSM to only these two pieces). The third paradigm shift is just starting, driven by partial deregulation and the subsequent increase in competition. My talk today will focus on issues related to the second paradigm, particularly in terms of utility planners getting more organized to deal with the synergies in the fields of forecasting, demand-side planning, and evaluation. I will also reflect on two new issues within the existing paradigm that influence these functional areas, namely beneficial electrification and integration of DSM into T&D planning. Finally I will talk about what I see coming as we go through another paradigm shift, particularly as it impacts forecasting and DSM.

  15. Molecular Electronic Shift Registers

    NASA Technical Reports Server (NTRS)

    Beratan, David N.; Onuchic, Jose N.

    1990-01-01

    Molecular-scale shift registers eventually constructed as parts of high-density integrated memory circuits. In principle, variety of organic molecules makes possible large number of different configurations and modes of operation for such shift-register devices. Several classes of devices and implementations in some specific types of molecules proposed. All based on transfer of electrons or holes along chains of repeating molecular units.

  16. AUDITORY-VISUAL PERCEPTUAL SHIFTING IN SPEECH HANDICAPPED CHILDREN.

    ERIC Educational Resources Information Center

    FLOWERS, ARTHUR

    INTERACTION BETWEEN VISION AND HEARING WERE STUDIED IN 35 SPEECH HANDICAPPED FIRST-GRADE CHILDREN. THE ABILITY TO SHIFT ATTENTION FROM ONE SENSORY MODALITY TO ANOTHER WAS LABELED AS "PERCEPTUAL SHIFTING." A DEVICE DEVELOPED BY EXPERIMENTAL PSYCHOLOGISTS PRESENTED VARIOUS STIMULI TO EACH SUBJECT AND RECORDED THE SUBJECT'S REACTION TIME.…

  17. Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

    NASA Technical Reports Server (NTRS)

    Beratan, D.

    1993-01-01

    A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

  18. Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions.

    PubMed

    Li, Shuirong; Gong, Jinlong

    2014-11-07

    Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal-support interaction were discussed. A second approach-the promotion in the mobility of the surface oxygen-is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design

  19. Trophic shift, not collapse

    USGS Publications Warehouse

    Madenjian, Charles P.; Rutherford, Edward S.; Stow, Craig A.; Roseman, Edward F.; He, Ji X.

    2013-01-01

    scientists who are closely monitoring Lake Huron’s food web, we believe that the ongoing changes are more accurately characterized as a trophic shift in which benthic pathways have become more prominent. While decreases in abundance have occurred for some species, others are experiencing improved reproduction resulting in the restoration of several important native species.

  20. Eluding catastrophic shifts.

    PubMed

    Villa Martín, Paula; Bonachela, Juan A; Levin, Simon A; Muñoz, Miguel A

    2015-04-14

    Transitions between regimes with radically different properties are ubiquitous in nature. Such transitions can occur either smoothly or in an abrupt and catastrophic fashion. Important examples of the latter can be found in ecology, climate sciences, and economics, to name a few, where regime shifts have catastrophic consequences that are mostly irreversible (e.g., desertification, coral reef collapses, and market crashes). Predicting and preventing these abrupt transitions remains a challenging and important task. Usually, simple deterministic equations are used to model and rationalize these complex situations. However, stochastic effects might have a profound effect. Here we use 1D and 2D spatially explicit models to show that intrinsic (demographic) stochasticity can alter deterministic predictions dramatically, especially in the presence of other realistic features such as limited mobility or spatial heterogeneity. In particular, these ingredients can alter the possibility of catastrophic shifts by giving rise to much smoother and easily reversible continuous ones. The ideas presented here can help further understand catastrophic shifts and contribute to the discussion about the possibility of preventing such shifts to minimize their disruptive ecological, economic, and societal consequences.

  1. Eluding catastrophic shifts

    PubMed Central

    Villa Martín, Paula; Bonachela, Juan A.; Levin, Simon A.; Muñoz, Miguel A.

    2015-01-01

    Transitions between regimes with radically different properties are ubiquitous in nature. Such transitions can occur either smoothly or in an abrupt and catastrophic fashion. Important examples of the latter can be found in ecology, climate sciences, and economics, to name a few, where regime shifts have catastrophic consequences that are mostly irreversible (e.g., desertification, coral reef collapses, and market crashes). Predicting and preventing these abrupt transitions remains a challenging and important task. Usually, simple deterministic equations are used to model and rationalize these complex situations. However, stochastic effects might have a profound effect. Here we use 1D and 2D spatially explicit models to show that intrinsic (demographic) stochasticity can alter deterministic predictions dramatically, especially in the presence of other realistic features such as limited mobility or spatial heterogeneity. In particular, these ingredients can alter the possibility of catastrophic shifts by giving rise to much smoother and easily reversible continuous ones. The ideas presented here can help further understand catastrophic shifts and contribute to the discussion about the possibility of preventing such shifts to minimize their disruptive ecological, economic, and societal consequences. PMID:25825772

  2. Understanding NMR Chemical Shifts

    NASA Astrophysics Data System (ADS)

    Jameson, Cynthia J.

    1996-10-01

    The NMR chemical shift serves as a paradigm for molecular electronic properties. We consider the factors that determine the general magnitudes of the shifts, the state of the art in theoretical calculations, the nature of the shielding tensor, and the multidimensional shielding surface that describes the variation of the shielding with nuclear positions. We also examine the nature of the intermolecular shielding surface as a general example of a supermolecule property surface. The observed chemical shift in the zero-pressure limit is determined not only by the value of the shielding at the equilibrium geometry, but the dynamic average over the multidimensional shielding surface during rotation and vibration of the molecule. In the gas, solution, or adsorbed phase it is an average of the intermolecular shielding surface over all the configurations of the molecule with its neighbors. The temperature dependence of the chemical shift in the isolated molecule, the changes upon isotopic substitution, the changes with environment, are well characterized experimentally so that quantum mechanical descriptions of electronic structure and theories related to dynamics averaging of any electronic property can be subjected to stringent test.

  3. On the coefficients of small eddy and surface divergence models for the air-water gas transfer velocity

    NASA Astrophysics Data System (ADS)

    Wang, Binbin; Liao, Qian; Fillingham, Joseph H.; Bootsma, Harvey A.

    2015-03-01

    Recent studies suggested that under low to moderate wind conditions without bubble entraining wave breaking, the air-water gas transfer velocity k+ can be mechanistically parameterized by the near-surface turbulence, following the small eddy model (SEM). Field measurements have supported this model in a variety of environmental forcing systems. Alternatively, surface divergence model (SDM) has also been shown to predict the gas transfer velocity across the air-water interface in laboratory settings. However, the empirically determined model coefficients (α in SEM and c1 in SDM) scattered over a wide range. Here we present the first field measurement of the near-surface turbulence with a novel floating PIV system on Lake Michigan, which allows us to evaluate the SEM and SDM in situ in the natural environment. k+ was derived from the CO2 flux that was measured simultaneously with a floating gas chamber. Measured results indicate that α and c1 are not universal constants. Regression analysis showed that α˜log>(ɛ>) while the near-surface turbulence dissipation rate ɛ is approximately greater than 10-6 m2 s-3 according to data measured for this study as well as from other published results measured in similar environments or in laboratory settings. It also showed that α scales linearly with the turbulent Reynolds number. Similarly, coefficient c1 in the SDM was found to linearly scale with the Reynolds number. These findings suggest that larger eddies are also important parameters, and the dissipation rate in the SEM or the surface divergence β' in the SDM alone may not be adequate to determine k+ completely.

  4. New shifted hybrid inflation

    NASA Astrophysics Data System (ADS)

    Jeannerot, Rachel; Khalil, Shaaban; Lazarides, George

    2002-07-01

    A new shifted hybrid inflationary scenario is introduced which, in contrast to the older one, relies only on renormalizable superpotential terms. This scenario is automatically realized in a concrete extension of the `minimal' supersymmetric Pati-Salam model which naturally leads to a moderate violation of Yukawa unification so that, for μ>0, the predicted b-quark mass is acceptable even with universal boundary conditions. It is shown that this extended model possesses a classically flat `shifted' trajectory which acquires a slope via one-loop radiative corrections and can be used as inflationary path. The constraints from the cosmic background explorer can be met with natural values of the relevant parameters. Also, there is no disastrous production of magnetic monopoles after inflation since the Pati-Salam gauge group is already broken on the `shifted' path. The relevant part of inflation takes place at values of the inflaton field which are not much smaller than the `reduced' Planck scale and, thus, supergravity corrections could easily invalidate inflation. It is, however, shown that inflation can be kept intact provided that an extra gauge singlet with a superheavy vacuum expectation value, which originates from D-terms, is introduced and a specific form of the Kähler potential is used. Moreover, it is found that, although the supergravity corrections are sizable, the constraints from the cosmic background explorer can again be met by readjusting the values of the parameters which were obtained with global supersymmetry.

  5. Simplified power shift transmission

    SciTech Connect

    Michael, R.A.

    1987-04-21

    A multi-speed transmission is described for transferring power between a first shaft and a second shaft, the transmission comprising: a compound planetary assembly including a sun gear, a ring gear concentric with the sun gear, a reaction gear concentric with the ring gear, a planetary gear carrier rotatably supporting first and second sets of planet gears, the first planet gear set intermeshing with the ring gear. The sun gear and the second planet gear set intermesh with the first planet gear set and the reaction gear, means for selectively coupling the first shaft with the sun gear and the reaction gear, and means for selectively preventing rotation of the ring gear, and reaction gear and the planetary carrier; a simple planetary assembly comprising a sun gear component concentric with the sun gear of the compound planetary assembly, a ring gear component concentric with both of the sun gears, and a planetary gear carrier component rotatably supporting a set of planet gears, the planet gear set meshing with the sun gear and the ring gear of the simple planetary.

  6. In-Cylinder Reaction Chemistry and Kinetics During Negative Valve Overlap Fuel Injection Under Low-Oxygen Conditions

    SciTech Connect

    Kalaskar, Vickey B; Szybist, James P; Splitter, Derek A; Pihl, Josh A; Gao, Zhiming; Daw, C Stuart

    2013-01-01

    Fuel injection into the negative valve overlap (NVO) period is a common method for controlling combustion phasing in homogeneous charge compression ignition (HCCI) as well as other forms of advanced combustion. During this event, at least a portion of the fuel hydrocarbons can be converted to products containing significant levels of H2 and CO, as well as other short chain hydrocarbons by means of thermal cracking, water-gas shift, and partial oxidation reactions, depending on the availability of oxygen and the time-temperature-pressure history. The resulting products alter the autoignition properties of the combined fuel mixture for HCCI. Fuel-rich chemistry in a partial oxidation environment is also relevant to other high efficiency engine concepts (e.g., the dedicated EGR (D-EGR) concept from SWRI). In this study, we used a unique 6-stroke engine cycle to experimentally investigate the chemistry of a range of fuels injected during NVO under low oxygen conditions. Fuels investigated included iso-octane, iso-butanol, ethanol, and methanol. Products from NVO chemistry were highly dependent on fuel type and injection timing, with iso-octane producing less than 1.5% hydrogen and methanol producing more than 8%. We compare the experimental trends with CHEMKIN (single zone, 0-D model) predictions using multiple kinetic mechanisms available in the current literature. Our primary conclusion is that the kinetic mechanisms investigated are unable to accurately predict the magnitude and trends of major species we observed.

  7. Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

    PubMed

    Sad, María E; Neurock, Matthew; Iglesia, Enrique

    2011-12-21

    This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions.

  8. Biological conversion of synthesis gas culture development

    SciTech Connect

    Klasson, K.T.; Basu, R.; Johnson, E.R.; Clausen, E.C.; Gaddy, J.L.

    1992-03-01

    Research continues on the conversion of synthesis by shift reactions involving bacteria. Topics discussed here include: biological water gas shift, sulfur gas utilization, experimental screening procedures, water gas shift studies, H{sub 2}S removal studies, COS degradation by selected CO-utilizing bacteria, and indirect COS utilization by Chlorobia. (VC)

  9. Transmission shift control assembly

    SciTech Connect

    Dzioba, D.L.

    1989-04-18

    This patent describes a transmission shift control assembly mounted on a steering column having a longitudinal axis comprising: bracket means secured to the steering column; transmission shift cable means having a portion secured to the bracket means and a portion linearly movable relative to the secured portion; mounting means on the bracket cable drive arm means having an axis and being rotatably mounted on the rotary axis on the mounting means oblique to the longitudinal axis and including a cable connecting portion secured to the movable portion of the cable means and lever mounting means adjacent the mounting means; operator control means including lever means, pin means for pivotally mounting the lever means on the lever mounting means on an axis substantially perpendicular to the rotary axis and positioning arm means formed on the lever means and extending from the pin means; and detent gate means disposed on the bracket means in position to abut the positioning arm means for limiting the extent of pivotal movement of the lever means.

  10. Shift Work: Improving Daytime Sleep

    MedlinePlus

    Healthy Lifestyle Adult health I just started working the night shift, and I'm having trouble sleeping during ... as long as you work the shift. Make healthy lifestyle choices. Eat a healthy diet and include physical ...

  11. Phase shifting diffraction interferometer

    DOEpatents

    Sommargren, G.E.

    1996-08-29

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of {lambda}/1000 where {lambda} is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about {lambda}/50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms. 8 figs.

  12. Phase shifting interferometer

    DOEpatents

    Sommargren, Gary E.

    1999-01-01

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of .lambda./1000 where .lambda. is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about .lambda./50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. Whereas current interferometers illuminate the optic to be tested with an aberrated wavefront which also limits the accuracy of the measurement, this interferometer uses an essentially perfect spherical measurement wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms.

  13. Phase shifting diffraction interferometer

    DOEpatents

    Sommargren, Gary E.

    1996-01-01

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of .lambda./1000 where .lambda. is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about .lambda./50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms.

  14. Phase shifting interferometer

    DOEpatents

    Sommargren, G.E.

    1999-08-03

    An interferometer is disclosed which has the capability of measuring optical elements and systems with an accuracy of {lambda}/1000 where {lambda} is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about {lambda}/50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. Whereas current interferometers illuminate the optic to be tested with an aberrated wavefront which also limits the accuracy of the measurement, this interferometer uses an essentially perfect spherical measurement wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms. 11 figs.

  15. [Shifting path of industrial pollution gravity centers and its driving mechanism in Pan-Yangtze River Delta].

    PubMed

    Zhao, Hai-Xia; Jiang, Xiao-Wei; Cui, Jian-Xin

    2014-11-01

    Shifting path of industrial pollution gravity centers is the response of environmental special formation during the industry transfer process, in order to prove the responding of industrial pollution gravity centers to industry transfer in economically developed areas, this paper calculates the gravity centers of industrial wastewater, gas and solid patterns and reveals the shifting path and its driving mechanism, using the data of industrial pollution in the Pan-Yangtze River Delta from 2000 to 2010. The results show that the gravity center of the industrial waste in Pan-Yangtze River Delta shifts for sure in the last 10 years, and gravity center of solid waste shifts the maximum distance within the three wastes, which was 180.18 km, and shifting distances for waste gas and waste water were 109.51 km and 85.92 km respectively. Moreover, the gravity center of the industrial waste in Pan-Yangtze River Delta shifts westwards, and gravity centers of waste water, gas and solid shift for 0.40 degrees, 0.17 degrees and 0.03 degrees respectively. The shifting of industrial pollution gravity centers is driven by many factors. The rapid development of the heavy industry in Anhui and Jiangxi provinces results in the westward shifting of the pollutions. The optimization and adjustment of industrial structures in Yangtze River Delta region benefit to alleviating industrial pollution, and high-polluting industries shifted to Anhui and Jiangxi provinces promotes pollution gravity center shifting to west. While the development of massive clean enterprise, strong environmental management efforts and better environmental monitoring system slow the shifting trend of industrial pollution to the east in Yangtze River Delta. The study of industrial pollution gravity shift and its driving mechanism provides a new angle of view to analyze the relationship between economic development and environmental pollution, and also provides academic basis for synthetical management and control of

  16. Hydraulically actuated well shifting tool

    SciTech Connect

    Roth, B.A.

    1992-10-20

    This patent describes a hydraulically actuated shifting tool for actuating a sliding member in a well tool. It comprises: a housing having a hydraulic fluid bore therein; shifting dog means positioned on the housing for movement away and toward the housing; locking dog means positioned on the housing for movement away and toward the body; shifting dog hydraulic actuating means in fluid communication with the bore for causing engagement of the shifting dogs with the sliding member; locking dog hydraulic actuating means in communication with the bore for causing engagement of the locking dogs with the locking means; and hydraulic shifting means in communication with the bore for causing relative movement between the shifting dog means and the locking dog means for shifting the sliding sleeve.

  17. Transmission shift mechanism

    SciTech Connect

    Smith, R.R.

    1989-06-20

    This patent describes a mechanism for selecting the gear of an automatic transmission in a vehicle. The mechanism consists of: a pressure source; a gear selection valve having an inlet means for receiving fluid from the pressure source, first outlet ports, and second outlet ports; a manual override means for opening and blocking communication between the pressure source and the first ports and for simultaneously opening and blocking communication between the pressure source and the second outlet ports; a port selector means within the valve for controlling flow through the second ports, the port selector means being movable to a plurality of positions, each position permitting a selected second outlet port to open; a selector control mans for moving the port selector means from one position to another, the selector control means including a planetary gear set connected by an input shaft to the transmission and connected to a vehicle load by an output shaft, the planetary gear set having a ring gear whose angular position is a function of reaction torque imposed by the load on the output shaft, the selector control means further including an arm assembly connected between the ring gear and the port selector means so that the position of the port selector means is a function of the reaction torque on the output shaft.

  18. Antiretroviral therapy: Shifting sands

    PubMed Central

    Sashindran, V.K.; Chauhan, Rajeev

    2016-01-01

    HIV/AIDS has been an extremely difficult pandemic to control. However, with the advent of antiretroviral therapy (ART), HIV has now been transformed into a chronic illness in patients who have continued treatment access and excellent long-term adherence. Existing indications for ART initiation in asymptomatic patients were based on CD4 levels; however, recent evidence has broken the shackles of CD4 levels. Early initiation of ART in HIV patients irrespective of CD4 counts can have profound positive impact on morbidity and mortality. Early initiation of ART has been found not only beneficial for patients but also to community as it reduces the risk of transmission. There have been few financial concerns about providing ART to all HIV-positive people but various studies have proven that early initiation of ART not only proves to be cost-effective but also contributes to economic and social growth of community. A novel multidisciplinary approach with early initiation and availability of ART at its heart can turn the tide in our favor in future. Effective preexposure prophylaxis and postexposure prophylaxis can also lower transmission risk of HIV in community. New understanding of HIV pathogenesis is opening new vistas to cure and prevention. Various promising candidate vaccines and drugs are undergoing aggressive clinical trials, raising optimism for an ever-elusive cure for HIV. This review describes various facets of tectonic shift in management of HIV. PMID:26900224

  19. Lamb shift for static atoms outside a Schwarzschild black hole

    SciTech Connect

    Zhou Wenting; Yu Hongwei

    2010-11-15

    We study, by separately calculating the contributions of vacuum fluctuations and radiation reaction to the atomic energy level shift, the Lamb shift of a static two-level atom interacting with real massless scalar fields in the Boulware, Unruh, and Hartle-Hawking vacuums outside a Schwarzschild black hole. We find that in the Boulware vacuum, the Lamb shift gets a correction arising as a result of the backscattering of vacuum field modes off the space-time curvature, which is reminiscent of the correction to the Lamb shift induced by the presence of cavities. However, when the Unruh and Hartle-Hawking vacua are concerned, our results show that the Lamb shift behaves as if the atom were irradiated by a thermal radiation or immersed in a thermal bath at the Hawking temperature, depending on whether the scalar field is in the Unruh or the Hartle-Hawking vacuum. Remarkably, the thermal radiation is always backscattered by the space-time geometry.

  20. Considerations Based on Reaction Rate on Char Gasification Behavior in Two-stage Gasifier for Biomass

    NASA Astrophysics Data System (ADS)

    Taniguchi, Miki; Nishiyama, Akio; Sasauchi, Kenichi; Ito, Yusuke; Akamatsu, Fumiteru

    In order to develop a small-scale gasifier in which biomass can be converted to energy with high efficiency, we planned a gasification process that consists of two parts: pyrolysis part (rotary kiln) and gasification part (downdraft gasifier). We performed fundamental experiments on gasification part and discussed the appropriate conditions such as air supply location, air ratio, air temperature and hearth load. We considered the results by calculating reaction rates of representative reactions on char gasification part and found that water gas reaction is dominant in the reduction area and its behavior gives important information to decide the adequate length of the char layer.

  1. Phase-shift coherence holography.

    PubMed

    Naik, Dinesh N; Ezawa, Takahiro; Miyamoto, Yoko; Takeda, Mitsuo

    2010-05-15

    We propose and experimentally demonstrate a new reconstruction scheme for coherence holography using computer-generated phase-shift coherence holograms. A 3D object encoded into the spatial coherence function is reconstructed directly from a set of incoherently illuminated computer-generated holograms with numerically introduced phase shifts. Although a rotating ground glass is used to introduce spatially incoherent illumination, the phase-shifting portion of the system is simple and free from mechanically moving components.

  2. Zero-shifted accelerometer outputs

    NASA Astrophysics Data System (ADS)

    Galef, Arnold

    1986-08-01

    It is claimed that the commonly appearing zero-shift in pyroshock data is usually a symptom of a malfunctioning measurement system, so that the data can not be repaired (by high-pass filtering or equivalent) unless tests can be devised that permit the demonstration that the system is operating in a linear mode in all respects other than the shift. The likely cause of the zero-shift and its prevention are discussed.

  3. Quantized beam shifts in graphene

    SciTech Connect

    de Melo Kort-Kamp, Wilton Junior; Sinitsyn, Nikolai; Dalvit, Diego Alejandro Roberto

    2015-10-08

    We predict the existence of quantized Imbert-Fedorov, Goos-Hanchen, and photonic spin Hall shifts for light beams impinging on a graphene-on-substrate system in an external magnetic field. In the quantum Hall regime the Imbert-Fedorov and photonic spin Hall shifts are quantized in integer multiples of the fine structure constant α, while the Goos-Hanchen ones in multiples of α2. We investigate the influence on these shifts of magnetic field, temperature, and material dispersion and dissipation. An experimental demonstration of quantized beam shifts could be achieved at terahertz frequencies for moderate values of the magnetic field.

  4. Thermochromic shifts in supercritical fluids

    SciTech Connect

    Yonker, C.R.; Smith, R.D. )

    1989-02-23

    Thermochromic shifts of organic solute molecules in supercritical CO{sub 2} under conditions of both constant pressure and density are compared to previous studies of solvatochromic shifts at isothermal conditions. Similar solvatochromic and thermochromic shifts are seen as a function of density for supercritical CO{sub 2}. At constant density a small thermochromic shift ({approx}400 cm{sup {minus}1}) for supercritical CO{sub 2} was seen for both 2-nitroanisole and 4-ethylnitrobenzene. The excited-state dipole moments for 2-nitroanisole, as calculated from the thermochromic and solvatochromic data, were in agreement.

  5. Shifts in fisheries management: adapting to regime shifts

    PubMed Central

    King, Jacquelynne R.; McFarlane, Gordon A.; Punt, André E.

    2015-01-01

    For many years, fisheries management was based on optimizing yield and maintaining a target biomass, with little regard given to low-frequency environmental forcing. However, this policy was often unsuccessful. In the last two to three decades, fisheries science and management have undergone a shift towards balancing sustainable yield with conservation, with the goal of including ecosystem considerations in decision-making frameworks. Scientific understanding of low-frequency climate–ocean variability, which is manifested as ecosystem regime shifts and states, has led to attempts to incorporate these shifts and states into fisheries assessment and management. To date, operationalizing these attempts to provide tactical advice has met with limited success. We review efforts to incorporate regime shifts and states into the assessment and management of fisheries resources, propose directions for future investigation and outline a potential framework to include regime shifts and changes in ecosystem states into fisheries management.

  6. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    SciTech Connect

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

  7. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    DOE PAGES

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; ...

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

  8. In situ Characterization of Pt Catalysts Supported on Ceria Modified TiO(2) for the WGS reaction: Influence of Ceria Loading

    SciTech Connect

    Rodriguez J. A.; Barrio, L.; Zhou, G.; Gonzalez, I.D.; Estrella, M.; Hanson, J.; Navarro, R.M.; Fierro, J.L.G.

    2012-01-01

    This work analyzes the influence of cerium content (6-15 wt%) on a TiO{sub 2} support over the structure and water gas shift (WGS) activity of Pt catalysts. The structural properties of these Pt/Ce-TiO{sub 2} catalysts were characterized by XRD, TEM and XANES. Physicochemical characterization of the catalysts showed differences in the structure and dispersion of Ce entities on the support with Ce loading. For the samples with low ceria content (6 wt%), cerium is deposited on the support in the form of CeO{sub x} clusters in a highly dispersed state in close interaction with the Ti atoms. The formation of CeO{sub x} clusters at low Ce-loading on the support facilitates the dispersion of small particles of Pt and improves the reducibility of ceria component at low temperatures. The changes in platinum dispersion and support reducibility with Ce-loading on the TiO{sub 2} support lead to significant differences in the WGS activity. Pt supported on the sample with lower Ce content (6 wt%) shows better activity than those corresponding to catalysts with higher Ce content (15 wt%). Activity measurements coupled with catalysts characterization suggest that the improvement in the reducibility of the support with lower Ce content was associated with the presence of CeO{sub x} clusters of high reducibility that improve the chemical activity of the oxide-metal interfaces at which the WGS reaction takes place.

  9. Metabolic impact of shift work.

    PubMed

    Zimberg, Ioná Zalcman; Fernandes Junior, Silvio A; Crispim, Cibele Aparecida; Tufik, Sergio; de Mello, Marco Tulio

    2012-01-01

    In developing countries, shift work represents a considerable contingent workforce. Recently, studies have shown that overweight and obesity are more prevalent in shift workers than day workers. In addition, shift work has been associated with a higher propensity for the development of many metabolic disorders, such as insulin resistance, diabetes, dislipidemias and metabolic syndrome. Recent data have pointed that decrease of the sleep time, desynchronization of circadian rhythm and alteration of environmental aspects are the main factors related to such problems. Shortened or disturbed sleep is among the most common health-related effects of shift work. The plausible physiological and biological mechanisms are related to the activation of the autonomic nervous system, inflammation, changes in lipid and glucose metabolism, and related changes in the risk for atherosclerosis, metabolic syndrome, and type II diabetes. The present review will discuss the impact of shift work on obesity and metabolic disorders and how disruption of sleep and circadian misalignment may contribute to these metabolic dysfunctions.

  10. Health Effects of Shift Work

    PubMed Central

    LaDou, Joseph

    1982-01-01

    More than 13.5 million American workers, close to 20 percent of the work force, are assigned to evening or night shifts. In some industries such as automobile, petrochemical and textile manufacturing the proportion of shift workers is greater than 50 percent. As the popularity of shift work and other “alternative work schedules” grows, concern is increasing over the disturbance created in the lives of workers and their families by these economically and socially useful innovations. Twenty percent of workers are unable to tolerate shift work. Daily physiologic variations termed circadian rhythms are interactive and require a high degree of phase relationship to produce subjective feelings of wellbeing. Disturbance of these activities, circadian desynchronization, whether from passage over time zones or from shift rotation, results in health effects such as disturbance of the quantity and quality of sleep, disturbance of gastrointestinal and other organ system activities, and aggravation of diseases such as diabetes mellitus, epilepsy and thyrotoxicosis. Worker selection can reduce the number of health problems resulting from shift work. The periodic examination of shift workers is recommended. PMID:6962577

  11. Can small shifts in circadian phase affect performance?

    PubMed Central

    Burgess, Helen J.; Legasto, Carlo S.; Fogg, Louis F.; Smith, Mark R.

    2012-01-01

    Small shifts in circadian timing occur frequently as a result of daylight saving time or later weekend sleep. These subtle shifts in circadian phase have been shown to influence subjective sleepiness, but it remains unclear if they can significantly affect performance. In a retrospective analysis we examined performance on the Psychomotor Vigilance Test before bedtime and after wake time in 11 healthy adults on fixed sleep schedules based on their habitual sleep times. The dim light melatonin onset, a marker of circadian timing, was measured on two occasions. An average 1.1 hour shift away from a proposed optimal circadian phase angle (6 hours between melatonin onset and midpoint of sleep) significantly slowed mean, median and fastest 10% reaction times before bedtime and after wake time (p<0.05). These results add to previous reports that suggest that humans may be sensitive to commonly occurring small shifts in circadian timing. PMID:22695081

  12. Can small shifts in circadian phase affect performance?

    PubMed

    Burgess, Helen J; Legasto, Carlo S; Fogg, Louis F; Smith, Mark R

    2013-01-01

    Small shifts in circadian timing occur frequently as a result of daylight saving time or later weekend sleep. These subtle shifts in circadian phase have been shown to influence subjective sleepiness, but it remains unclear if they can significantly affect performance. In a retrospective analysis we examined performance on the Psychomotor Vigilance Test before bedtime and after wake time in 11 healthy adults on fixed sleep schedules based on their habitual sleep times. The dim light melatonin onset, a marker of circadian timing, was measured on two occasions. An average 1.1 h shift away from a proposed optimal circadian phase angle (6 h between melatonin onset and midpoint of sleep) significantly slowed mean, median and fastest 10% reaction times before bedtime and after wake time (p < 0.05). These results add to previous reports that suggest that humans may be sensitive to commonly occurring small shifts in circadian timing.

  13. Drug Reactions

    MedlinePlus

    Most of the time, medicines make our lives better. They reduce aches and pains, fight infections, and control problems such as high blood pressure or diabetes. But medicines can also cause unwanted reactions. One problem is ...

  14. Refining the shifted topological vertex

    SciTech Connect

    Drissi, L. B.; Jehjouh, H.; Saidi, E. H.

    2009-01-15

    We study aspects of the refining and shifting properties of the 3d MacMahon function C{sub 3}(q) used in topological string theory and BKP hierarchy. We derive the explicit expressions of the shifted topological vertex S{sub {lambda}}{sub {mu}}{sub {nu}}(q) and its refined version T{sub {lambda}}{sub {mu}}{sub {nu}}(q,t). These vertices complete results in literature.

  15. Goos-Hänchen shift.

    PubMed

    Snyder, A W; Love, J D

    1976-01-01

    An extremely simple derivation of the Goos-Hänchen shift is presented for total internal reflection at a plane interface between two semiinfinite dielectric media, as well as for optical waveguides of plane arid circular cross section. The derivation is based on energy considerations, requires knowledge of Fresnel's equation only, and shows explicitly that the shift is due to the flow of energy across the dielectric boundary.

  16. Ammonia reactions with the stored oxygen in a commercial lean NOx trap catalyst

    SciTech Connect

    Bartova, Sarka; Mracek, David; Koci, Petr; Marek, Milos; Choi, Jae -Soon

    2014-10-12

    Ammonia is an important intermediate of the NOx reduction in a NOx storage and reduction catalyst (aka lean NOx trap). NH3 formed under rich conditions in the reduced front part of the catalyst is transported by convection downstream to the unregenerated (still oxidized) zone of the catalyst, where it further reacts with the stored oxygen and NOx. In this paper, the kinetics and selectivity of NH3 reactions with the stored oxygen are studied in detail with a commercial Ba-based NOx storage catalyst containing platinum group metals (PGM), Ba and Ce oxides. Furthermore, steady-state NH3 decomposition, NH3 oxidation by O2 and NO, and N2O decomposition are examined in light-off experiments. Periodic lean/rich cycling is measured first with O2 and NH3, and then with NOx + O2 and NH3 to discriminate between the NH3 reactions with the stored oxygen and the stored NOx. The reaction of NH3 with the stored O2 is highly selective towards N2, however a certain amount of NOx and N2O is also formed. The formed NOx by-product is efficiently adsorbed on the NOx storage sites such that the NOx is not detected at the reactor outlet except at high temperatures. The stored NOx reacts with NH3 feed in the next rich phase, contributing to the N2O formation. Water inhibits the reactions of NH3 with the stored oxygen. On the contrary, the presence of CO2 increases the NH3 consumption. Furthermore, CO2 is able to provide additional oxygen for NH3 oxidation, forming –CO in analogy to the reverse water gas shift reaction.

  17. Blue shifts vs red shifts in sigma-hole bonding.

    PubMed

    Murray, Jane S; Concha, Monica C; Lane, Pat; Hobza, Pavel; Politzer, Peter

    2008-08-01

    Sigma-hole bonding is a noncovalent interaction between a region of positive electrostatic potential on the outer surface of a Group V, VI, or VII covalently-bonded atom (a sigma-hole) and a region of negative potential on another molecule, e.g., a lone pair of a Lewis base. We have investigated computationally the occurrence of increased vibration frequencies (blue shifts) and bond shortening vs decreased frequencies (red shifts) and bond lengthening for the covalent bonds to the atoms having the sigma-holes (the sigma-hole donors). Both are possible, depending upon the properties of the donor and the acceptor. Our results are consistent with models that were developed earlier by Hermansson and by Qian and Krimm in relation to blue vs red shifting in hydrogen bond formation. These models invoke the derivatives of the permanent and the induced dipole moments of the donor molecule.

  18. Information storage at the molecular level - The design of a molecular shift register memory

    NASA Technical Reports Server (NTRS)

    Beratan, David N.; Onuchic, Jose Nelson; Hopfield, J. J.

    1989-01-01

    The control of electron transfer rates is discussed and a molecular shift register memory at the molecular level is described. The memory elements are made up of molecules which can exist in either an oxidized or reduced state and the bits can be shifted between the cells with photoinduced electron transfer reactions. The device integrates designed molecules onto a VLSI substrate. A control structure to modify the flow of information along a shift register is indicated schematically.

  19. Inositol phosphates induce DAPI fluorescence shift.

    PubMed

    Kolozsvari, Bernadett; Parisi, Federica; Saiardi, Adolfo

    2014-06-15

    The polymer inorganic polyP (polyphosphate) and inositol phosphates, such as IP6 (inositol hexakisphosphate; also known as phytic acid), share many biophysical features. These similarities must be attributed to the phosphate groups present in these molecules. Given the ability of polyP to modify the excitation-emission spectra of DAPI we decided to investigate whether inositol phosphates possess the same property. We discovered that DAPI-IP6 complexes emit at approximately 550 nm when excited with light of wavelength 410-420 nm. IP5 (inositol pentakisphosphate) is also able to induce a similar shift in DAPI fluorescence. Conversely, IP3 (inositol trisphosphate) and IP4 (inositol tetrakisphosphate) are unable to shift DAPI fluorescence. We have employed this newly discovered feature of DAPI to study the enzymatic activity of the inositol polyphosphate multikinase and to monitor phytase phosphatase reactions. Finally, we used DAPI-IP6 fluorescence to determine the amount of IP6 in plant seeds. Using an IP6 standard curve this straight-forward analysis revealed that among the samples tested, borlotti beans possess the highest level of IP6 (9.4 mg/g of dry mass), whereas the Indian urad bean the lowest (3.2 mg/g of dry mass). The newly identified fluorescence properties of the DAPI-IP5 and DAPI-IP6 complexes allow the levels and enzymatic conversion of these two important messengers to be rapidly and reliably monitored.

  20. A molecular shift register based on electron transfer

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Josenelson; Beratan, David N.

    1988-01-01

    An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a 'molecular electronic device' that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density.

  1. The Modality Shift Experiment in Adults and Children with High Functioning Autism

    ERIC Educational Resources Information Center

    Williams, Diane L.; Goldstein, Gerald; Minshew, Nancy J.

    2013-01-01

    This study used the modality shift experiment, a relatively simple reaction time measure to visual and auditory stimuli, to examine attentional shifting within and across modalities in 33 children and 42 adults with high-functioning autism as compared to matched numbers of age- and ability-matched typical controls. An exaggerated "modality shift…

  2. Paradigm Shifts in Ophthalmic Diagnostics*

    PubMed Central

    Sebag, J.; Sadun, Alfredo A.; Pierce, Eric A.

    2016-01-01

    Purpose Future advances in ophthalmology will see a paradigm shift in diagnostics from a focus on dysfunction and disease to better measures of psychophysical function and health. Practical methods to define genotypes will be increasingly important and non-invasive nanotechnologies are needed to detect molecular changes that predate histopathology. Methods This is not a review nor meant to be comprehensive. Specific topics have been selected to illustrate the principles of important paradigm shifts that will influence the future of ophthalmic diagnostics. It is our impression that future evaluation of vision will go beyond visual acuity to assess ocular health in terms of psychophysical function. The definition of disease will incorporate genotype into what has historically been a phenotype-centric discipline. Non-invasive nanotechnologies will enable a paradigm shift from disease detection on a cellular level to a sub-cellular molecular level. Results Vision can be evaluated beyond visual acuity by measuring contrast sensitivity, color vision, and macular function, as these provide better insights into the impact of aging and disease. Distortions can be quantified and the psychophysical basis of vision can be better evaluated than in the past by designing tests that assess particular macular cell function(s). Advances in our understanding of the genetic basis of eye diseases will enable better characterization of ocular health and disease. Non-invasive nanotechnologies can assess molecular changes in the lens, vitreous, and macula that predate visible pathology. Oxygen metabolism and circulatory physiology are measurable indices of ocular health that can detect variations of physiology and early disease. Conclusions This overview of paradigm shifts in ophthalmology suggests that the future will see significant improvements in ophthalmic diagnostics. The selected topics illustrate the principles of these paradigm shifts and should serve as a guide to further

  3. Allergic Reactions

    MedlinePlus

    ... that is right for you. In many instances, allergy immunotherapy in the form of shots or tablets is an effective, cost-efficient long term treatment approach. While there is not yet ... Healthy Tips • Allergy symptoms are the result of a chain reaction ...

  4. U.S. Geological Survey Georgia Water Science Center and Albany Water, Gas, and Light Commission Cooperative Water Program-Summary of Activities, July 2005 through June 2006

    USGS Publications Warehouse

    Gordon, Debbie W.

    2006-01-01

    The U.S. Geological Survey (USGS) has been working with the Albany Water, Gas, and Light Commission to monitor ground-water quality and availability since 1977. This report presents the findings for July 2005 through June 2006 and summarizes the ground-water and surface-water conditions for 2005. Water levels in 14 wells were continuously monitored in Dougherty County, Georgia. Water levels in 12 of those wells were above normal, one was normal, and one was below normal. Ground-water samples collected from the Upper Floridan aquifer indicate that nitrate levels have increased in 13 wells and decreased in two wells from a year earlier. A sample also was collected from the Flint River. A trilinear diagram showing the percent composition of selected major cations and anions indicates that the ground-water quality of the Upper Floridan aquifer at the Albany wellfield is distinctly different from the water quality of the Flint River. To improve the understanding of the ground-water flow system and nitrate movement in the Upper Floridan aquifer, the USGS is developing a ground-water flow model in the southwest Albany area, Georgia.

  5. Wavelength-shifted Cherenkov radiators

    NASA Technical Reports Server (NTRS)

    Krider, E. P.; Jacobson, V. L.; Pifer, A. E.; Polakos, P. A.; Kurz, R. J.

    1976-01-01

    The scintillation and Cherenkov responses of plastic Cherenkov radiators containing different wavelength-shifting fluors in varying concentrations have been studied in beams of low energy protons and pions. For cosmic ray applications, where large Cherenkov to scintillation ratios are desired, the optimum fluor concentrations are 0.000025 by weight or less.

  6. Leadership Shifts in Changing Field

    ERIC Educational Resources Information Center

    Zubrzycki, Jaclyn

    2013-01-01

    As groups representing local and state education players struggle to remain relevant in a policy conversation often dominated by foundations, think tanks, new advocacy groups, and political and business figures, a shift in leadership has been under way at major associations. Most of the changes have come as part of the natural churn; former…

  7. Anthropometric changes and fluid shifts

    NASA Technical Reports Server (NTRS)

    Thornton, W. E.; Hoffler, G. W.; Rummel, J. A.

    1974-01-01

    Several observations of body size, shape, posture, and configuration were made to document changes resulting from direct effects of weightlessness during the Skylab 4 mission. After the crewmen were placed in orbit, a number of anatomical and anthropometric changes occurred including a straightening of the thoracolumbar spine, a general decrease in truncal girth, and an increase in height. By the time of the earliest in-flight measurement on mission day 3, all crewmen had lost more than two liters of extravascular fluid from the calf and thigh. The puffy facies, the bird legs effect, the engorgement of upper body veins, and the reduced volume of lower body veins were all documented with photographs. Center-of-mass measurements confirmed a fluid shift cephalad. This shift remained throughout the mission until recovery, when a sharp reversal occurred; a major portion of the reversal was completed in a few hours. The anatomical changes are of considerable scientific interest and of import to the human factors design engineer, but the shifts of blood and extravascular fluid are of more consequence. It is hypothesized that the driving force for the fluid shift is the intrinsic and unopposed lower limb elasticity that forces venous blood and then other fluid cephalad.

  8. Illinois Shifting Gears Policy Evaluation

    ERIC Educational Resources Information Center

    Weitzel, Peter C.

    2009-01-01

    Illinois Shifting Gears is a multilevel initiative that has simultaneously created bridge programs in the field and altered state policy to facilitate the creation of more programs in the future. These efforts have informed each other, giving policymakers the opportunity to interact with practitioners, troubleshoot bridge programs, and make…

  9. Technology Counts 2012: Virtual Shift

    ERIC Educational Resources Information Center

    Education Week, 2012

    2012-01-01

    Virtual education is moving into that intersection where rising popularity meets calls for greater accountability. How the virtual education movement responds to those calls will have a significant impact on how it evolves in K-12 over the next five to 10 years. This report tackles this shift in the virtual education landscape. It examines the…

  10. The Shift Needed for Sustainability

    ERIC Educational Resources Information Center

    Smith, Peter A. C.; Sharicz, Carol

    2011-01-01

    Purpose: The purpose of this action research is to begin to assess to what extent organizations have in practice begun to make the shift towards triple bottom line (TBL) sustainability. Design/methodology/approach: A definition of TBL sustainability is provided, and key elements of TBL sustainability considered necessary to success are identified…

  11. Lamb shift in muonic hydrogen

    SciTech Connect

    Borie, E.

    2005-03-01

    The Lamb shift in muonic hydrogen continues to be a subject of experimental and theoretical investigation. Here my older work on the subject is updated to provide a complementary calculation of the energies of the 2p-2s transitions in muonic hydrogen.

  12. Size-Dependent Raman Shifts for nanocrystals

    PubMed Central

    Gao, Yukun; Zhao, Xinmei; Yin, Penggang; Gao, Faming

    2016-01-01

    Raman spectroscopy is a very sensitive tool for probing semiconductor nanocrystals. The underlying mechanism behind the size-dependent Raman shifts is still quite controversial. Here we offer a new theoretical method for the quantum confinement effects on the Raman spectra of semiconductor nanocrystals. We propose that the shift of Raman spectra in nanocrystals can result from two overlapping effects: the quantum effect shift and surface effect shift. The quantum effect shift is extracted from an extended Kubo formula, the surface effect shift is determined via the first principles calculations. Fairly good prediction of Raman shifts can be obtained without the use of any adjustable parameter. Closer analysis shows that the size-dependent Raman shifts in Si nanocrystals mainly result from the quantum effect shifts. For nanodiamond, the proportion of surface effect shift in Raman shift is up to about 40%. Such model can also provide a good baseline for using Raman spectroscopy as a tool to measure size. PMID:27102066

  13. Doppler phase shifting using dual, switched phase shifting devices

    NASA Technical Reports Server (NTRS)

    Gutierrez, Roman C. (Inventor)

    2002-01-01

    A system of inducing a phase shift using moving reflector elements. The moving reflectors can be moving mirrors or an acousto-optical filter. The moving reflectors oscillate i.e. the move first in a first direction and then in a second direction. Two different reflectors are used so that the light can be switched between the reflectors. During a first portion of the cycle the light is coupled to the first modulator which moves the reflector in the first direction. The second modulator is out of phase with the first modulator, and the light is switched to that second modulator during a second portion of the cycle. The second modulator is also moving in the first direction when the light is applied thereto. In this way, the light obtains a constant direction Doppler shift.

  14. Transition to 12-hour shifts - The process and the product

    SciTech Connect

    Suter, P. )

    1992-01-01

    This paper examines Yankee Atomic Electric Company's (YAEC's) transition to a 12-h shift schedule for the operations department staff. It presents the approach to implementation, reactions of both shift workers and management to the new schedule (including perceived benefits and shortcomings), and provides recommendations to others considering this change. Experience demonstrates the ease of any transition when the desire for change originates with the individuals directly affected. Close cooperation with any union representation is also vital to its success. When all parties are in apparent agreement (e.g., that a 12-h rotation should commence), this allows for a trial period (in this case of at least two shift cycles) in order to evaluate and refine the program, thus leaving the option open to revert back to the previous condition if things prove unsatisfactory. At all costs, mutual respect must be maintained for all parties.

  15. Anthropometric changes and fluid shifts

    NASA Technical Reports Server (NTRS)

    Thornton, W. E.; Hoffler, G. W.; Rummel, J. A.

    1977-01-01

    In an effort to obtain the most comprehensive and coherent picture of changes under weightlessness, a set of measurements on Skylab 2 was initiated and at every opportunity, additional studies were added. All pertinent information from ancillary sources were gleaned and collated. On Skylab 2, the initial anthropometric studies were scheduled in conjunction with muscle study. A single set of facial photographs was made in-flight. Additional measurements were made on Skylab 3, with photographs and truncal and limb girth measurements in-flight. Prior to Skylab 4, it was felt there was considerable evidence for large and rapid fluid shifts, so a series of in-flight volume and center of mass measurements and infrared photographs were scheduled to be conducted in the Skylab 4 mission. A number of changes were properly documented for the first time, most important of which were the fluid shifts. The following description of Skylab anthropometrics address work done on Skylab 4 primarily.

  16. Lamb shift in muonic deuterium

    SciTech Connect

    Gorchtein, Mikhail; Vanderhaeghen, Marc; Carlson, Carl E.

    2013-11-07

    We consider the two-photon exchange contribution to the 2P-2S Lamb shift in muonic deuterium in the framework of forward dispersion relations. The dispersion integrals are evaluated with minimal model dependence using experimental data on elastic deuteron form factors and inelastic electron-deuteron scattering, both in the quasielastic and hadronic range. The subtraction constant that is required to ensure convergence of the dispersion relation for the forward Compton amplitude T{sub 1} (ν,Q{sup 2}) is related to the deuteron magnetic polarizability β(Q{sup 2}) and represents the main source of uncertainty in our analysis. We obtain for the Lamb shift ΔE{sub 2P-2S} = 1.620±0.190 meV and discuss ways to further reduce this uncertainty.

  17. Looping through the Lamb Shift

    SciTech Connect

    Hazi, A U

    2007-02-06

    Sometimes in science, a small measurement can have big ramifications. For a team of Livermore scientists, such was the case when they measured a small shift in the spectrum of extremely ionized atoms of uranium. The measurement involves the Lamb shift, a subtle change in the energy of an electron orbiting an atom's nucleus. The precision of the Livermore result was 10 times greater than that of existing measurements, making it the best measurement to date of a complicated correction to the simplest quantum description of how atoms behave. The measurement introduces a new realm in the search for deviations between the theory of quantum electrodynamics (QED), which is an extension of quantum mechanics, and the real world. Such deviations, if discovered, would have far-reaching consequences, indicating that QED is not a fundamental theory of nature.

  18. KVI Lamb-shift polarimeter

    SciTech Connect

    Beijers, J.P.M.; Kremers, H.R.; Kalantar-Nayestanaki, N.

    2006-03-15

    The design and operation of a Lamb-shift polarimeter is discussed. This polarimeter is used to measure the polarization of proton and deuteron beams extracted from the KVI polarized-ion source. The major components of the Lamb-shift polarimeter (LSP) are described in some detail. These include the deceleration lens system, cesium neutralization oven, spin filter, metastable-atom detection system, and the solenoid. Typical operating parameters of the LSP will be given together with some representative spin-polarization measurements. The design criterion of measuring the polarization of a H{sup +} or D{sup +} beam within 60 s and with a statistical uncertainty smaller than 2% has been met.

  19. Multicolor Holography With Phase Shifting

    NASA Technical Reports Server (NTRS)

    Vikram, Chandra S.

    1996-01-01

    Prototype apparatus constructed to test feasibility of two-color holographic interferometric scheme in which data for reconstructing holographic wavefront obtained with help of phase-shifting technique. Provides two sets of data needed to solve equations for effects of temperature and concentration. Concept extended to holography at three or more wavelengths to measure three or more phenomena associated with significant variations in index of refraction

  20. Shift and Scale Invariant Preprocessor.

    DTIC Science & Technology

    1981-12-01

    1982 THESIS D V SHIFT AND SCALE INVARIANT ?PREPROCESSOR by Norman E. Huston, Jr. December 1981 0 Thesis Advisor: L. A. Wilson Approved for public...SCHOOL December 1981 Author: - . 4 ,/ A pp ro0ved by: rYY. ( Thesis Advisor Co-Ad isor Chairman, De artment of 4n n eing Dean of Science and...large range of problems/disciplines. Fields where it is particularly common include optical imagery, acoustic signal processing , radiology, radio

  1. Generalized phase-shifting color digital holography

    NASA Astrophysics Data System (ADS)

    Nomura, Takanori; Kawakami, Takaaki; Shinomura, Kazuma

    2016-06-01

    Two methods to apply the generalized phase-shifting digital holography to color digital holography are proposed. One is wave-splitting generalized phase-shifting color digital holography. This is realized by using a color Bayer camera. Another is multiple exposure generalized phase-shifting color digital holography. This is realized by the wavelength-dependent phase-shifting devices. Experimental results for both generalized phase-shifting color digital holography are presented to confirm the proposed methods.

  2. Frequency shifts in gravitational resonance spectroscopy

    DOE PAGES

    Baeßler, S.; Nesvizhevsky, V. V.; Pignol, G.; ...

    2015-02-25

    Quantum states of ultracold neutrons in a gravitational field are characterized through gravitational resonance spectroscopy. This paper discusses systematic effects that appear in the spectroscopic measurements. The discussed frequency shifts-which we call the Stern-Gerlach shift, interference shift, and spectator-state shift-appear in conceivable measurement schemes and have general importance. Lastly, these shifts have to be taken into account in precision experiments.

  3. Strategies for brain shift evaluation.

    PubMed

    Hastreiter, Peter; Rezk-Salama, Christof; Soza, Grzegorz; Bauer, Michael; Greiner, Günther; Fahlbusch, Rudolf; Ganslandt, Oliver; Nimsky, Christopher

    2004-12-01

    For the analysis of the brain shift phenomenon different strategies were applied. In 32 glioma cases pre- and intraoperative MR datasets were acquired in order to evaluate the maximum displacement of the brain surface and the deep tumor margin. After rigid registration using the software of the neuronavigation system, a direct comparison was made with 2D- and 3D visualizations. As a result, a great variability of the brain shift was observed ranging up to 24 mm for cortical displacement and exceeding 3 mm for the deep tumor margin in 66% of all cases. Following intraoperative imaging the neuronavigation system was updated in eight cases providing reliable guidance. For a more comprehensive analysis a voxel-based nonlinear registration was applied. Aiming at improved speed of alignment we performed all interpolation operations with 3D texture mapping based on OpenGL functions supported in graphics hardware. Further acceleration was achieved with an adaptive refinement of the underlying control point grid focusing on the main deformation areas. For a quick overview the registered datasets were evaluated with different 3D visualization approaches. Finally, the results were compared to the initial measurements contributing to a better understanding of the brain shift phenomenon. Overall, the experiments clearly demonstrate that deformations of the brain surface and deeper brain structures are uncorrelated.

  4. Shift work and endocrine disorders.

    PubMed

    Ulhôa, M A; Marqueze, E C; Burgos, L G A; Moreno, C R C

    2015-01-01

    The objective of this review was to investigate the impact of shift and night work on metabolic processes and the role of alterations in the sleep-wake cycle and feeding times and environmental changes in the occurrence of metabolic disorders. The literature review was performed by searching three electronic databases for relevant studies published in the last 10 years. The methodological quality of each study was assessed, and best-evidence synthesis was applied to draw conclusions. The literature has shown changes in concentrations of melatonin, cortisol, ghrelin, and leptin among shift workers. Melatonin has been implicated for its role in the synthesis and action of insulin. The action of this hormone also regulates the expression of transporter glucose type 4 or triggers phosphorylation of the insulin receptor. Therefore, a reduction in melatonin can be associated with an increase in insulin resistance and a propensity for the development of diabetes. Moreover, shift work can negatively affect sleep and contribute to sedentarism, unhealthy eating habits, and stress. Recent studies on metabolic processes have increasingly revealed their complexity. Physiological changes induced in workers who invert their activity-rest cycle to fulfill work hours include disruptions in metabolic processes.

  5. A Theoretical Study of the Hydration of Methane, from the Aqueous Solution to the sI Hydrate-Liquid Water-Gas Coexistence

    PubMed Central

    Luis, Daniel Porfirio; García-González, Alcione; Saint-Martin, Humberto

    2016-01-01

    Monte Carlo and molecular dynamics simulations were done with three recent water models TIP4P/2005 (Transferable Intermolecular Potential with 4 Points/2005), TIP4P/Ice (Transferable Intermolecular Potential with 4 Points/ Ice) and TIP4Q (Transferable Intermolecular Potential with 4 charges) combined with two models for methane: an all-atom one OPLS-AA (Optimal Parametrization for the Liquid State) and a united-atom one (UA); a correction for the C–O interaction was applied to the latter and used in a third set of simulations. The models were validated by comparison to experimental values of the free energy of hydration at 280, 300, 330 and 370 K, all under a pressure of 1 bar, and to the experimental radial distribution functions at 277, 283 and 291 K, under a pressure of 145 bar. Regardless of the combination rules used for σC,O, good agreement was found, except when the correction to the UA model was applied. Thus, further simulations of the sI hydrate were performed with the united-atom model to compare the thermal expansivity to the experiment. A final set of simulations was done with the UA methane model and the three water models, to study the sI hydrate-liquid water-gas coexistence at 80, 230 and 400 bar. The melting temperatures were compared to the experimental values. The results show the need to perform simulations with various different models to attain a reliable and robust molecular image of the systems of interest. PMID:27240339

  6. The AirWaterGas Teacher Professional Development Program: Lessons Learned by Pairing Scientists and Teachers to Develop Curriculum on Global Climate Change and Regional Unconventional Oil and Gas Development

    NASA Astrophysics Data System (ADS)

    Gardiner, L. S.; Hatheway, B.; Rogers, J. D.; Casey, J. G.; Lackey, G.; Birdsell, D.; Brown, K.; Polmear, M.; Capps, S.; Rosenblum, J.; Sitterley, K.; Hafich, K. A.; Hannigan, M.; Knight, D.

    2015-12-01

    The AirWaterGas Teacher Professional Development Program, run by the UCAR Center for Science Education, brought together scientists and secondary science teachers in a yearlong program culminating in the development of curriculum related to the impacts of unconventional oil and gas development. Graduate students and research scientists taught about their research area and its relationship to oil and gas throughout three online courses during the 2015-16 school year, during which teachers and scientists engaged in active online discussions. Topics covered included climate change, oil and gas infrastructure, air quality, water quality, public health, and practices and policies relating to oil and gas development. Building upon their initial online interactions and a face-to-face meeting in March, teachers were paired with appropriate AirWaterGas team members as science advisors during a month-long residency in Boulder, Colorado. During the residency, graduate student scientists provided resources and feedback as teachers developed curriculum projects in collaboration with each other and UCAR science educators. Additionally, teachers and AirWaterGas researchers shared experiences on an oil and gas well site tour, and a short course on drilling methods with a drilling rig simulator. Here, we share lessons learned from both sides of the aisle, including initial results from program assessment conducted with the participating teachers.

  7. Chemical Shift Anisotropy Selective Inversion*

    PubMed Central

    Caporini, Marc. A.; Turner, Christopher. J.; Bielecki, Anthony; Griffin, Robert G.

    2009-01-01

    Magic Angle Spinning (MAS) is used in solid-state NMR to remove the broadening effects of the chemical shift anisotropy (CSA). In this work we investigate a technique that can reintroduce the CSA in order to selectively invert transverse magnetization. The technique involves an amplitude sweep of the radio frequency field through a multiple of the spinning frequency. The selectivity of this inversion mechanism is determined by the size of the CSA. We develop a theoretical framework to describe this process and demonstrate the CSA selective inversion with numerical simulations and experimental data. We combine this approach with cross polarization (CP) for potential applications in multi-dimensional MAS NMR. PMID:19648036

  8. Phase-shifting Gabor holography.

    PubMed

    Micó, Vicente; García, Javier; Zalevsky, Zeev; Javidi, Bahram

    2009-05-15

    We present a modified Gabor-like setup able to recover the complex amplitude distribution of the object wavefront from a set of inline recorded holograms. The proposed configuration is characterized by the insertion of a condenser lens and a spatial light modulator (SLM) into the classical Gabor configuration. The phase shift is introduced by the SLM that modulates the central spot (dc term) in an intermediate plane, without an additional reference beam. Experimental results validate the proposed method and produce superior results to the Gabor method.

  9. Geometric phase shifting digital holography.

    PubMed

    Jackin, Boaz Jessie; Narayanamurthy, C S; Yatagai, Toyohiko

    2016-06-01

    A new phase shifting digital holographic technique using a purely geometric phase in Michelson interferometric geometry is proposed. The geometric phase in the system does not depend upon either optical path length or wavelength, unlike dynamic phase. The amount of geometric phase generated is controllable through a rotating wave plate. The new approach has unique features and major advantages in holographic measurement of transparent and reflecting three-dimensional (3D) objects. Experimental results on surface shape measurement and imaging of 3D objects are presented using the proposed method.

  10. Sectoral shifts and aggregate unemployment

    SciTech Connect

    Loungani, P.

    1986-01-01

    Some recent research has taken the view that sectoral or industry-specific shocks significantly affect aggregate unemployment by increasing the amount of inter-industry labor reallocation required. The empirical evidence for this view rests on the finding that during the 1950s - and again during the 1970s - there was a positive correlation between aggregate unemployment and the dispersion of employment growth rates. This thesis demonstrates that this correlation arises largely because oil price shocks affect both unemployment and the dispersion of employment growth. Once the dispersion due to oil shocks is accounted for, the residual dispersion in employment has very low explanatory power for unemployment. Since the dispersion index does not measure pure sectoral shifts, an alternate measure of dispersion is developed that serves as a better proxy for the amount of inter-industry labor reallocation required each period. Estimates using this measure suggest that, during the 1950s, temporary increases in the relative price of oil were responsible for generating the observed correlation. On the other hand, sectoral shifts were important during the 1970s; in particular, the 1973 oil price increase has had significant reallocative effects on the economy. This contention is subjected to further tests by looking at the time-series behavior of employment in durable-goods industries and also by following the inter-industry movements of workers over time through the use of panel data.

  11. Shift register generators and applications to coding

    NASA Technical Reports Server (NTRS)

    Morakis, J. C.

    1968-01-01

    The most important properties of shift register generated sequences are exposed. The application of shift registers as multiplication and division circuits leads to the generation of some error correcting and detecting codes.

  12. Newtonian normal shift in multidimensional Riemannian geometry

    SciTech Connect

    Sharipov, Ruslan A

    2001-06-30

    An explicit description of all Newtonian dynamical systems admitting normal shift in Riemannian manifolds of dimension n{>=}3 is obtained. On this basis the kinematics of the normal shift of hypersurfaces along trajectories of such dynamical systems is studied.

  13. Water in low-mass star-forming regions with Herschel. The link between water gas and ice in protostellar envelopes

    NASA Astrophysics Data System (ADS)

    Schmalzl, M.; Visser, R.; Walsh, C.; Albertsson, T.; van Dishoeck, E. F.; Kristensen, L. E.; Mottram, J. C.

    2014-12-01

    Aims: Our aim is to determine the critical parameters in water chemistry and the contribution of water to the oxygen budget by observing and modelling water gas and ice for a sample of eleven low-mass protostars, for which both forms of water have been observed. Methods: A simplified chemistry network, which is benchmarked against more sophisticated chemical networks, is developed that includes the necessary ingredients to determine the water vapour and ice abundance profiles in the cold, outer envelope in which the temperature increases towards the protostar. Comparing the results from this chemical network to observations of water emission lines and previously published water ice column densities, allows us to probe the influence of various agents (e.g., far-ultraviolet (FUV) field, initial abundances, timescales, and kinematics). Results: The observed water ice abundances with respect to hydrogen nuclei in our sample are 30-80 ppm, and therefore contain only 10-30% of the volatile oxygen budget of 320 ppm. The keys to reproduce this result are a low initial water ice abundance after the pre-collapse phase together with the fact that atomic oxygen cannot freeze-out and form water ice in regions with Tdust ≳ 15 K. This requires short prestellar core lifetimes ≲0.1 Myr. The water vapour profile is shaped through the interplay of FUV photodesorption, photodissociation, and freeze-out. The water vapour line profiles are an invaluable tracer for the FUV photon flux and envelope kinematics. Conclusions: The finding that only a fraction of the oxygen budget is locked in water ice can be explained either by a short pre-collapse time of ≲0.1 Myr at densities of nH ~ 104 cm-3, or by some other process that resets the initial water ice abundance for the post-collapse phase. A key for the understanding of the water ice abundance is the binding energy of atomic oxygen on ice. Herschel is an ESA space observatory with science instruments provided by European

  14. Understanding covariate shift in model performance

    PubMed Central

    McGaughey, Georgia; Walters, W. Patrick; Goldman, Brian

    2016-01-01

    Three (3) different methods (logistic regression, covariate shift and k-NN) were applied to five (5) internal datasets and one (1) external, publically available dataset where covariate shift existed. In all cases, k-NN’s performance was inferior to either logistic regression or covariate shift. Surprisingly, there was no obvious advantage for using covariate shift to reweight the training data in the examined datasets. PMID:27803797

  15. Continuous-data FIFO bubble shift register

    NASA Technical Reports Server (NTRS)

    Chen, T. T.

    1977-01-01

    Simple loop first-in-first-out (FIFO) bubble memory shift register has continuous storage capability. Bubble shift register simplifies chip-control electronics by enabling all control functions to be alined at same bit. FIFO shift register is constructed from passive replicator and annihilator combinations.

  16. Mean shift is a bound optimization.

    PubMed

    Fashing, Mark; Tomasi, Carlo

    2005-03-01

    We build on the current understanding of mean shift as an optimization procedure. We demonstrate that, in the case of piecewise constant kernels, mean shift is equivalent to Newton's method. Further, we prove that, for all kernels, the mean shift procedure is a quadratic bound maximization.

  17. Shift of voltage reversal in stacked microbial fuel cells

    NASA Astrophysics Data System (ADS)

    An, Junyeong; Kim, Bongkyu; Chang, In Seop; Lee, Hyung-Sool

    2015-03-01

    We proved that sluggish kinetics on the cathode and the imbalance of cathode kinetics cause voltage reversal in a stacked microbial fuel cell (MFC) equipped with a non-Pt cathode. Catholyte aeration to a unit MFC against passive air diffusion to the cathode in the other unit MFC shifted voltage reversal between the two units, due to improved mass transport and O2 concentration effects in the aerated MFC. The shifted voltage reversal returned to an original status when catholyte aeration was stopped. A Pt-coated cathode increased the rate of oxygen reduction reaction (ORR) by a factor of ∼20, as compared to the non-Pt cathode. As a result, the anodic reaction rate that became slower than the rate on the Pt-cathode limited current density to overpotential in the stacked MFC equipped with the Pt-cathode. This work shows that dominant kinetic bottlenecks, which are the primary cause of voltage reversal, can be shifted between individual MFCs of stacked MFCs or electrodes depending on relative kinetics.

  18. Speeding Up Sigmatropic Shifts-To Halve or to Hold.

    PubMed

    Tantillo, Dean J

    2016-04-19

    Catalysis is common. Rational catalyst design, however, is at the frontier of chemical science. Although the histories of physical organic and synthetic organic chemistry boast key chapters involving [3s,3s] sigmatropic shifts, catalysis of these reactions is much less common than catalysis of ostensibly more complex processes. The comparative dearth of catalysts for sigmatropic shifts is perhaps a result of the perception that transition state structures for these reactions, like their reactants, are nonpolar and therefore not amenable to selective stabilization and its associated barrier lowering. However, as demonstrated in this Account, transition state structures for [3s,3s] sigmatropic shifts can in fact have charge distributions that differ significantly from those of reactants, even for hydrocarbon substrates, allowing for barriers to be decreased and rates increased. In some cases, differences in charge distribution result from the inclusion of heteroatoms at specific positions in reactants, but in other cases differences are actually induced by catalysts. Perhaps surprisingly, strategies for complexation of transition state structures that remain nonpolar are also possible. In general, the strategies for catalysis employed can be characterized as involving either mechanistic intervention, where a catalyst induces a change from the concerted mechanism expected for a [3s,3s] sigmatropic shift to a multistep process (cutting the transformation into halves or smaller pieces) whose overall barrier is decreased relative to the concerted process, or transition state complexation, where a catalyst simply binds (holds) more tightly to the transition state structure for a [3s,3s] sigmatropic shift than to the reactant, leading to a lower barrier in the presence of the catalyst. Both of these strategies can be considered to be biomimetic in that enzymes frequently induce multistep processes and utilize selective transition state stabilization for the steps involved

  19. Time evolution of the Lamb shift.

    PubMed

    Wang, Da-Wei; Li, Zheng-Hong; Wang, Li-Gang; Zhu, Shi-Yao; Zubairy, M Suhail

    2010-09-01

    The time evolution of the Lamb shift that accompanies the real photon emission is studied for the first time (to our knowledge). The investigation of the explicit time dependence of the Lamb shift becomes possible because the self-energy of the free electron, which is divergent, is subtracted from the Hamiltonian after a unitary transformation. The Lamb shift can then be separated into two parts: one is the time-independent shift due to the virtual photon exchange, and the other is the time-dependent shift due to the real photon emission. The time evolution depends on the nature of the coupling spectrum of the reservoir.

  20. Gear-shift mechanism for manual transmission

    SciTech Connect

    Fukuchi, H.

    1986-07-22

    This patent describes a gear-shift mechanism for a manual transmission comprising a housing for the transmission; a movable shaft mounted in place within the housing for both axial and rotary movements and being operatively connected to a manual shift lever to be axially shifted from its neutral position to a forward or reverse position in selecting operation of the manual shift lever and to be rotated at its shifted position in shifting operation of the manual shift lever; a shift-and-select lever fixed to an intermediate portion of the movable shaft; an interlock member rotatably mounted in place on the movable shaft and having a pair of interlock arms located at the opposite sides of the shift-and-select lever; means for restricting rotary movement of the interlock member and permitting axial movement of the same; a pair of resilient means for centering the movable shaft to retain the shift-and-select lever and the interlock member in their neutral positions; and first, second and third shift heads arranged in sequence within the housing.

  1. Reverse shift mechanism for automotive manual transmission

    SciTech Connect

    Inui, M.; Ogawa, S.

    1987-03-03

    A reverse shift mechanism is described for an automotive manual transmission of a type having a reverse idler gear which is movable to selectively complete a reverse gear train, the reverse shift mechanism comprising: a reverse shift arm having a portion disposed adjacent the reverse idler gear and pivotally carried with respect to a transmission casing so that the portion rocks along a direction of axis of the reverse idler gear in response to shifting operation. The portion of the reverse shift arm is provided with a blind hole which is open at a first end toward the reverse idler gear and is closed at a second end away from the reverse idler gear; and a shift arm shoe carried by the portion of the reverse shift arm adjacent the reverse idler gear for pushing the reverse idler gear. The shift arm shoe has an end adapted to engage with a circumferential groove formed in the reverse idler gear and an opposing end shaped to fit in the blind hole of the reverse shift arm; whereby the shift arm shoe is prevented from coming off during assembly by virtue of a vacuum effect created by air confined in the blind hole by fitting engagement between the opposing end and the blind hole, and is held in place after assembly by being clamped between the groove of the reverse idler gear and the blind hole of the reverse shift arm.

  2. Benzothiadiazole oligoene fatty acids: fluorescent dyes with large Stokes shifts

    PubMed Central

    Patalag, Lukas J

    2016-01-01

    Herein, we report on the synthesis and characterization of novel fluorescent fatty acids with large Stokes shifts. Three examples consisting of the same number of carbon atoms and thus of similar chain length are presented differing in their degree of unsaturation. As major fluorogenic contributor at the terminus benzo[c][1,2,5]thiadiazole was used. Respective syntheses based on Wittig reactions followed by iodine-mediated isomerization are presented. The absorption properties are modulated by the number of conjugated C=C double bonds of the oligoene chain ranging from one to three. Large Stokes shifts of about 4900–5700 cm−1 and fluorescence quantum yields of up to 0.44 were observed. PMID:28144344

  3. Paradigm shift in lead design.

    PubMed

    Irnich, W

    1999-09-01

    During the past 30 years there has been a tremendous development in electrode technology from bulky (90 mm2) to pin-sized (1.0 mm2) electrodes. Simultaneously, impedance has increased from 110 Ohms to >1 kOhms, which has been termed a "paradigm shift" in lead design. If current is responsible for stimulation, why is its impedance a key factor in saving energy? Further, what mechanism is behind this development based on experimental findings and what conclusion can be drawn from it to optimize electrode size? If it is assumed that there is always a layer of nonexcitable tissue between the electrode surface and excitable myocardium and that the electric field (potential gradient) produced by the electrode at this boundary is reaching threshold level, then a formula can be derived for the voltage threshold that completely describes the electrophysiology and electrophysics of a hemispherical electrode. Assuming that the mean chronic threshold for porous steroid-eluting electrodes is 0.6 V with 0.5-ms pulse duration, thickness of nonexcitable tissue can be estimated to be 1.5 mm. Taking into account this measure and the relationship between chronaxie and electrode area, voltage threshold, impedance, and energy as a function of surface area can be calculated. The lowest voltage for 0.5-ms pulse duration is reached with r(o) = 0.5 d, yielding a surface area of 4 mm2 and a voltage threshold of 0.62 V, an impedance of 1 kOhms, and an energy level of 197 nJ. It can be deduced from our findings that a further reduction of surface areas below 1.6 mm2 will not diminish energy threshold substantially, if pulse duration remains at 0.5 ms. Lowest energy is reached with t = chronaxie, yielding an energy level <100 nJ with surface areas < or =1.5 mm2. It is striking to see how well the theoretically derived results correspond to the experimental findings. It is also surprising that the hemispheric model so accurately approximates experimental results with differently shaped

  4. Dealing with a Paradigm Shift

    PubMed Central

    Pack, Allan I.

    2015-01-01

    Recent changes in policies by insurance companies with respect to mandating home sleep apnea testing rather than in-laboratory studies have a large impact on the financial viability of clinical sleep centers. Coping with this disruptive change requires forward planning. First, it is important to be well positioned with respect to facilities so that these can be quickly downsized to control costs. There is also a need to develop, in advance, an accredited home sleep study program so that centers can respond to the rapidly changing environment. Following the change there is a need to control costs by rapidly downsizing the technology workforce. Technologists can be retrained for other essential roles. Centralizing the precertification process with knowledgeable, well-trained staff and a robust auditing process is an essential component. The approach taken at the University of Pennsylvania to this change is described as is how one can ensure continued financial viability of a comprehensive sleep center program in a major academic medical center. Citation: Pack AI. Dealing with a paradigm shift. J Clin Sleep Med 2015;11(8):925–929. PMID:26094918

  5. Shifting boundaries in professional care.

    PubMed

    Hopkins, A; Solomon, J; Abelson, J

    1996-07-01

    The nature of the work undertaken by different health professionals and inter-professional boundaries are constantly shifting. The greater knowledge of users of health care, and the increasing technical and organizational complexity of modern medicine, have partly eroded the control of health professionals over the substance of their work. The definition of a field of work as lying within the province of any one profession is culturally rather than scientifically determined. It is evident that care of good quality should be delivered at the lowest possible cost. This might include delivery of care by a less trained person than heretofore, or by someone with limited but focused training. Sharing of skills is a more sensible subject for discussion than transfer of tasks. We review a number of studies which show the effectiveness of inter-professional substitution in various care settings, and also the effectiveness of substitution by those other than health professionals. The views of users of health services on inter-professional substitution need to be considered. Health professionals and others need to work together to devise innovative ways of delivering effective health care. The legal issues need clarification.

  6. Shifting boundaries in professional care.

    PubMed Central

    Hopkins, A; Solomon, J; Abelson, J

    1996-01-01

    The nature of the work undertaken by different health professionals and inter-professional boundaries are constantly shifting. The greater knowledge of users of health care, and the increasing technical and organizational complexity of modern medicine, have partly eroded the control of health professionals over the substance of their work. The definition of a field of work as lying within the province of any one profession is culturally rather than scientifically determined. It is evident that care of good quality should be delivered at the lowest possible cost. This might include delivery of care by a less trained person than heretofore, or by someone with limited but focused training. Sharing of skills is a more sensible subject for discussion than transfer of tasks. We review a number of studies which show the effectiveness of inter-professional substitution in various care settings, and also the effectiveness of substitution by those other than health professionals. The views of users of health services on inter-professional substitution need to be considered. Health professionals and others need to work together to devise innovative ways of delivering effective health care. The legal issues need clarification. PMID:8774532

  7. Shifting Baselines, Science, and Society

    NASA Astrophysics Data System (ADS)

    Jackson, J. B.

    2006-12-01

    All of us have a deeply personal concept of nature based upon our childhood perceptions of the world around us, and of the subsequent degradation of nature by the experiences of our lifetimes. Yet even the most rudimentary knowledge of history clearly demonstrates that the modern rise of human population and consumption have wreaked havoc on global ecosystems to the extent that nowhere is close to natural or pristine and that most places have been increasingly degraded over many centuries. This disconnect between direct personal experience and abstract historical perspective is the problem of "shifting baselines" that is the fundamental impediment to basic scientific understanding and environmental policy, and affects scientists as much as the general public, business, and government. Scientists in particular suffer from the inability to directly observe and experimentally verify causes and effects of previous changes in ecosystems that now bear so little resemblance to their natural state. Under the circumstances, it is essential for scientists to draw scientific conclusions based on imperfect data and to publicly explain, defend, and discuss their conclusions as the best possible science given present information. The failure to do so makes science virtually irrelevant to social and environmental policy and government.

  8. Interpreting lateral dynamic weight shifts using a simple inverted pendulum model.

    PubMed

    Kennedy, Michael W; Bretl, Timothy; Schmiedeler, James P

    2014-01-01

    Seventy-five young, healthy adults completed a lateral weight-shifting activity in which each shifted his/her center of pressure (CoP) to visually displayed target locations with the aid of visual CoP feedback. Each subject's CoP data were modeled using a single-link inverted pendulum system with a spring-damper at the joint. This extends the simple inverted pendulum model of static balance in the sagittal plane to lateral weight-shifting balance. The model controlled pendulum angle using PD control and a ramp setpoint trajectory, and weight-shifting was characterized by both shift speed and a non-minimum phase (NMP) behavior metric. This NMP behavior metric examines the force magnitude at shift initiation and provides weight-shifting balance performance information that parallels the examination of peak ground reaction forces in gait analysis. Control parameters were optimized on a subject-by-subject basis to match balance metrics for modeled results to metric values calculated from experimental data. Overall, the model matches experimental data well (average percent error of 0.35% for shifting speed and 0.05% for NMP behavior). These results suggest that the single-link inverted pendulum model can be used effectively to capture lateral weight-shifting balance, as it has been shown to model static balance.

  9. Electromagnetic tracking of the pivot-shift.

    PubMed

    Kuroda, Ryosuke; Hoshino, Yuichi

    2016-06-01

    The pivot-shift test is an important examination to assess the rotational laxity in the anterior cruciate ligament (ACL) injured and reconstructed knees. Because this examination is related to subjective knee function, we may still see cases that have residual rotational laxity after ACL reconstruction. Quantitative evaluation of the pivot-shift test is preferable to the clinical pivot-shift test but is difficult to attain mainly due to complicated movements of the pivot-shift. The electromagnetic tracking system was developed to evaluate knee kinematics during the pivot-shift, providing information related to 6-degree-of-freedom knee kinematics with a high sampling rate. Through this device, the abnormal movement of the pivot-shift is characterized in two phases: an increased anterior tibial translation and a boosted acceleration of tibial posterior reduction. Since its invention, this system has been utilized to assess rotational laxity for clinical follow-up and research after the ACL reconstruction.

  10. Host shifts and evolutionary radiations of butterflies.

    PubMed

    Fordyce, James A

    2010-12-22

    Ehrlich and Raven proposed a model of coevolution where major host plant shifts of butterflies facilitate a burst of diversification driven by their arrival to a new adaptive zone. One prediction of this model is that reconstructions of historical diversification of butterflies should indicate an increase in diversification rate following major host shifts. Using reconstructed histories of 15 butterfly groups, I tested this prediction and found general agreement with Ehrlich and Raven's model. Butterfly lineages with an inferred major historical host shift showed evidence of diversification rate variation, with a significant acceleration following the host shift. Lineages without an inferred major host shift generally agreed with a constant-rate model of diversification. These results are consistent with the view that host plant associations have played a profound role in the evolutionary history of butterflies, and show that major shifts to chemically distinct plant groups leave a historical footprint that remains detectable today.

  11. EUVL alternating phase shift mask

    NASA Astrophysics Data System (ADS)

    Yan, Pei-Yang; Myers, Alan; Shroff, Yashesh; Chandhok, Manish; Zhang, Guojing; Gullikson, Eric; Salmassi, Farhad

    2011-04-01

    Extreme ultra-violet Lithography (EUVL) alternating phase shift mask (APSM) or other optical enhancement techniques are likely needed for 16nm (half pitch) technology generation and beyond. One possible option is the combination of EUVL and APSM. The fabrication of EUVL APSM is more difficult than either the fabrication of an EUVL binary mask or a conventional optical APSM mask. In the case of EUVL APSM, the phase difference in the two regions (0 and 180-degree phase regions) is created by a phase step in the substrate prior to the multilayer (ML) coating. The step height that induces 180-degree phase mismatch in the ML is determined by [λ/(4cosθ)](2m+1), where m are integers (0, 1, 2,...). In this experiment, we targeted for a step height with m=1. The same mask design also contains the standard binary structures so that the comparison between the EUVL APSM and the EUVL binary mask can be performed under the same illumination and wafer process conditions. The EUVL APSM mask was exposed using Nikon's EUV1 scanner in Kumagaya Japan. The wafer level results showed higher dense line resolution for EUVL APSM as compared to that of EUVL binary mask. APSM also showed improved line width roughness (LWR) and depth of focus (DoF) as compared to the best EUVL binary results obtained with C-dipole off-axis illumination (OAI). The wafer CD resolution improvement obtained by APSM in this experiment is partially limited by the resist resolution and the mask phase edge spread during ML deposition. We believe that wafer CD resolution and can further be improved with imaging imbalance compensation mask design and improvements in resist resolution and the phase generation portion of the mask fabrication process. In this paper, we will discuss in detail the mask fabrication process, wafer level data analysis, and our understanding of EUVL APSM related issues.

  12. Effects of Shift Work on Cognitive Performance, Sleep Quality, and Sleepiness among Petrochemical Control Room Operators

    PubMed Central

    Kazemi, Reza; Haidarimoghadam, Rashid; Golmohamadi, Rostam; Soltanian, Alireza; Zoghipaydar, Mohamad Reza

    2016-01-01

    Shift work is associated with both sleepiness and reduced performance. The aim of this study was to examine cognitive performance, sleepiness, and sleep quality among petrochemical control room shift workers. Sixty shift workers participated in this study. Cognitive performance was evaluated using a number of objective tests, including continuous performance test, n-back test, and simple reaction time test; sleepiness was measured using the subjective Karolinska Sleepiness Scale (KSS); and sleep quality was assessed using the Pittsburgh Sleep Quality Index (PSQI) questionnaire. ANCOVA, t-test, and repeated-measures ANOVA were applied for statistical analyses, and the significance level was set at p < 0.05. All variables related to cognitive performance, except for omission error, significantly decreased at the end of both day and night shifts (p < 0.0001). There were also significant differences between the day and night shifts in terms of the variables of omission error (p < 0.027) and commission error (p < 0.036). A significant difference was also observed between daily and nightly trends of sleepiness (p < 0.0001) so that sleepiness was higher for the night shift. Participants had low sleep quality on both day and night shifts, and there were significant differences between the day and night shifts in terms of subjective sleep quality and quantity (p < 0.01). Long working hours per shift result in fatigue, irregularities in the circadian rhythm and the cycle of sleep, induced cognitive performance decline at the end of both day and night shifts, and increased sleepiness in night shift. It, thus, seems necessary to take ergonomic measures such as planning for more appropriate shift work and reducing working hours. PMID:27103934

  13. Shift mechanism for engine starting apparatus

    SciTech Connect

    Colvin, J.A.; Colvill, R.G.; Smock, A.L.

    1986-04-01

    This patent describes a shift lever mechanism for translating axial movement of the plunger of a starter solenoid into axial movement of a pinion of an engine starting apparatus. This apparatus consists of, a starter solenoid having an axially shiftable plunger and a coil winding, a spring opposing pull-in movement of the plunger and a solenoid switch operated to a closed condition when the plunger is completely pulled-in, a shift lever actuator carried by the plunger for axial movement therewith. The actuator has a pair of spaced surfaces, a pivotally mounted shift lever one end of which is adapted to be coupled to the pinion. The opposite end of the shift lever has a pair of opposed shift lever surfaces that respectively engage the surfaces on the actuator. The actuator surfaces and the shift lever surfaces are substantially engaged when the shift lever is in an at rest postion. The surfaces on the shift lever are at different radial distances from the pivot point of the shift lever and are arranged relative to the surfaces on the actuator such that when the solenoid plunger pulls-in the surface on the shift lever that is at the greater radial distance from the pivot point is moved by a surface of the actuator and the other surface on the shift lever becomes separated by a predetermined amount from its cooperating surface on the actuator. The amount of separation is sufficient to allow the solenoid switch to be actuated to an open condition when the solenoid coil winding is deenergized and the spring shifts and plunger to reengage the separated surfaces.

  14. Shift multiplexing by planar waveguide referencing

    NASA Astrophysics Data System (ADS)

    Yi, Tao; Zhang, Jiasen; Yan, Lifen; Gong, Qihuang

    2005-09-01

    We present a new method with which to implement shift multiplexing by planar waveguide referencing. In this method, a planar waveguide is used to steer the reference beam, and we implement shift multiplexing by shifting the recording medium. A spatial selectivity as high as 1.1 μm is obtained. By using waveguide referencing we can make a compact and simple holographic system.

  15. Light shifts in atomic Bragg diffraction

    NASA Astrophysics Data System (ADS)

    Giese, E.; Friedrich, A.; Abend, S.; Rasel, E. M.; Schleich, W. P.

    2016-12-01

    Bragg diffraction of an atomic wave packet in a retroreflective geometry with two counterpropagating optical lattices exhibits a light shift induced phase. We show that the temporal shape of the light pulse determines the behavior of this phase shift: In contrast to Raman diffraction, Bragg diffraction with Gaussian pulses leads to a significant suppression of the intrinsic phase shift due to a scaling with the third power of the inverse Doppler frequency. However, for box-shaped laser pulses, the corresponding shift is twice as large as for Raman diffraction. Our results are based on approximate but analytical expressions as well as a numerical integration of the corresponding Schrödinger equation.

  16. Jet Lag and Shift Work Disorder.

    PubMed

    Reid, Kathryn J; Abbott, Sabra M

    2015-12-01

    Jet lag and shift work disorder are circadian rhythm sleep-wake disorders resulting from behaviorally altering the sleep-wake schedule in relation to the external environment. Not everyone who experiences trans-meridian travel or performs shift work has a disorder. The prevalence of jet lag disorder is unclear, approximately 5%-10% of shift workers have shift work disorder. Treatment aims to realign the internal circadian clock with the external environment. Behavioral therapies include sleep hygiene and management of the light-dark and sleep schedule. Pharmacologic agents are used to treat insomnia and excessive sleepiness, and melatonin is used to facilitate sleep and circadian realignment.

  17. Goos-Haenchen shift in complex crystals

    SciTech Connect

    Longhi, Stefano; Della Valle, Giuseppe; Staliunas, Kestutis

    2011-10-15

    The Goos-Haenchen (GH) effect for wave scattering from complex PT-symmetric periodic potentials (complex crystals) is theoretically investigated, with specific reference to optical GH shift in photonic crystal slabs with a sinusoidal periodic modulation of both real and imaginary parts of the dielectric constant. The analysis highlights some distinct and rather unique features as compared to the GH shift found in ordinary crystals. In particular, as opposed to GH shift in ordinary crystals, which is large at the band gap edges, in complex crystals the GH shift can be large inside the reflection (amplification) band and becomes extremely large as the PT symmetry-breaking threshold is approached.

  18. The second-order gravitational red shift

    NASA Technical Reports Server (NTRS)

    Jaffe, J.

    1973-01-01

    The direct measurement of the nonlinear term of the gravitational field equations by using very stable clocks is discussed along with measuring the perhelion advance of a planet or satellite. These are considered measurements of the second-order gravitational red shift. The exact expression for the frequency shift of light in a gravitational field is derived. Other topics discussed include: The Doppler-cancelling technique; the second-order red shift in a spherically symmetric gravitational field; finite signal transit time; and the reality and interpretation of coordinates in the second-order red shift experiment.

  19. Zero difference algorithm for phase shift extraction in blind phase-shifting holography.

    PubMed

    Guo, Cheng-Shan; Sha, Bei; Xie, Yi-Yan; Zhang, Xiu-Jiang

    2014-02-15

    A simple noniterative algorithm for retrieval of the unknown phase shifts in phase-shifting holography is proposed. In this algorithm, the phase shift value between two phase-shifting holograms can be calculated through a simple analytical formula that is derived according to the fact that there exist some points whose intensity difference between two phase-shifting holograms is equal to zero. Both the simulated and experimental results demonstrated the feasibility of this so-called zero difference algorithm over a wide range of phase shifts.

  20. Exercise, energy balance and the shift worker.

    PubMed

    Atkinson, Greg; Fullick, Sarah; Grindey, Charlotte; Maclaren, Don

    2008-01-01

    Shift work is now common in society and is not restricted to heavy industry or emergency services, but is increasingly found amongst 'white collar' occupations and the growing number of service industries. Participation in shift work is associated with increased body mass index, prevalence of obesity and other health problems. We review the behavioural and biological disturbances that occur during shift work and discuss their impact on leisure-time physical activity and energy balance. Shift work generally decreases opportunities for physical activity and participation in sports. For those shift workers who are able to exercise, subjective and biological responses can be altered if the exercise is taken at unusual times of day and/or if the shift worker is sleep deprived. These altered responses may in turn impact on the longer-term adherence to an exercise programme. The favourable effects of exercise on body mass control and sleep quality in shift workers have not been confirmed. Similarly, recent reports of relationships between sleep duration and obesity have not been examined in a shift work context. There is no evidence that exercise can mediate certain circadian rhythm characteristics (e.g. amplitude or timing) for improved tolerance to shift work. Total energy intake and meal composition do not seem to be affected by participation in shift work. Meal frequency is generally reduced but snacking is increased on the night shift. Unavailability of preferred foods in the workplace, a lack of time, and a reduced desire to eat at night explain these findings. 'Normal' eating habits with the family are also disrupted. The metabolic responses to food are also altered by shift work-mediated disruptions to sleep and circadian rhythms. Whether any interactions on human metabolism exist between timing or content of food intake and physical activity during shift work is not known at present. There are very few randomized controlled studies on the efficacy of physical

  1. In-line phase shift tomosynthesis

    SciTech Connect

    Hammonds, Jeffrey C.; Price, Ronald R.; Pickens, David R.; Donnelly, Edwin F.

    2013-08-15

    Purpose: The purpose of this work is to (1) demonstrate laboratory measurements of phase shift images derived from in-line phase-contrast radiographs using the attenuation-partition based algorithm (APBA) of Yan et al.[Opt. Express 18(15), 16074–16089 (2010)], (2) verify that the APBA reconstructed images obey the linearity principle, and (3) reconstruct tomosynthesis phase shift images from a collection of angularly sampled planar phase shift images.Methods: An unmodified, commercially available cabinet x-ray system (Faxitron LX-60) was used in this experiment. This system contains a tungsten anode x-ray tube with a nominal focal spot size of 10 μm. The digital detector uses CsI/CMOS with a pixel size of 50 × 50 μm. The phantoms used consisted of one acrylic plate, two polystyrene plates, and a habanero pepper. Tomosynthesis images were reconstructed from 51 images acquired over a ±25° arc. All phase shift images were reconstructed using the APBA.Results: Image contrast derived from the planar phase shift image of an acrylic plate of uniform thickness exceeded the contrast of the traditional attenuation image by an approximate factor of two. Comparison of the planar phase shift images from a single, uniform thickness polystyrene plate with two polystyrene plates demonstrated an approximate linearity of the estimated phase shift with plate thickness (−1600 rad vs −2970 rad). Tomographic phase shift images of the habanero pepper exhibited acceptable spatial resolution and contrast comparable to the corresponding attenuation image.Conclusions: This work demonstrated the feasibility of laboratory-based phase shift tomosynthesis and suggests that phase shift imaging could potentially provide a new imaging biomarker. Further investigation will be needed to determine if phase shift contrast will be able to provide new tissue contrast information or improved clinical performance.

  2. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  3. Anaphylaxis-Like Reactions

    MedlinePlus

    ... Home Conditions Anaphylaxis Anaphylaxis-Like Reactions Anaphylaxis-Like Reactions Make an Appointment Refer a Patient Ask a ... exposed to a foreign substance, some people suffer reactions identical to anaphylaxis, but no allergy (IgE antibody) ...

  4. Temperature effects on enzyme-catalyzed reactions within a cell: Monte Carlo simulations for coupled reaction and diffusion

    NASA Astrophysics Data System (ADS)

    Nangia, Shivangi; Anderson, James B.

    2013-01-01

    We report Monte Carlo simulations of temperature effects on single-step enzymatic reactions with varied rate constants and diffusion coefficients. For typical systems, where the intrinsic reaction rate is more sensitive to temperature than diffusion, the overall reaction is rate-limited at low temperatures and diffusion-limited at high temperatures. The effective activation energy shifts to a much lower value as temperature is increased. Our results show that the temperature dependence of enzyme-catalyzed reactions within a cell may be only loosely related to a potential energy barrier height. The effective activation energy may be strongly affected by coupling of reaction and diffusion.

  5. Effects of extended work shifts and shift work on patient safety, productivity, and employee health.

    PubMed

    Keller, Simone M

    2009-12-01

    It is estimated 1.3 million health care errors occur each year and of those errors 48,000 to 98,000 result in the deaths of patients (Barger et al., 2006). Errors occur for a variety of reasons, including the effects of extended work hours and shift work. The need for around-the-clock staff coverage has resulted in creative ways to maintain quality patient care, keep health care errors or adverse events to a minimum, and still meet the needs of the organization. One way organizations have attempted to alleviate staff shortages is to create extended work shifts. Instead of the standard 8-hour shift, workers are now working 10, 12, 16, or more hours to provide continuous patient care. Although literature does support these staffing patterns, it cannot be denied that shifts beyond the traditional 8 hours increase staff fatigue, health care errors, and adverse events and outcomes and decrease alertness and productivity. This article includes a review of current literature on shift work, the definition of shift work, error rates and adverse outcomes related to shift work, health effects on shift workers, shift work effects on older workers, recommended optimal shift length, positive and negative effects of shift work on the shift worker, hazards associated with driving after extended shifts, and implications for occupational health nurses.

  6. 29 CFR 102.171 - Cost shifting.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 2 2010-07-01 2010-07-01 false Cost shifting. 102.171 Section 102.171 Labor Regulations... By Federal Income Tax Refund Offset § 102.171 Cost shifting. Costs incurred by the Agency in... amount of the offset. Such costs may include administrative costs and attorneys fees....

  7. 29 CFR 102.165 - Cost shifting.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 2 2010-07-01 2010-07-01 false Cost shifting. 102.165 Section 102.165 Labor Regulations... by Administrative Offset § 102.165 Cost shifting. Costs incurred by the Agency in connection with... offset. Such costs may include administrative costs and attorneys fees....

  8. Gain Shift Corrections at Chi-Nu

    SciTech Connect

    Brown, Tristan Brooks; Devlin, Matthew James

    2016-08-30

    Ambient conditions have the potential to cause changes in liquid scintillator detector gain that vary with time and temperature. These gain shifts can lead to poor resolution in both energy as well as pulse shape discrimination. In order to correct for these shifts in the Chi-Nu high energy array, a laser system has been developed for calibration of the pulse height signals.

  9. A simplified, compact static shift register

    NASA Technical Reports Server (NTRS)

    Pryor, R. L.; Smith, A. M.

    1972-01-01

    Shift register was developed which uses only one D type flip-flop and improves packaging density by approximately 25% over the usual arrangement. Circuit is compromise between full master-slave arrangement and dynamic shift register, with limitation only of length of time that clock can be held high during new data entry.

  10. Set Shifting Among Adolescents with Anorexia Nervosa

    PubMed Central

    Fitzpatrick, Kathleen Kara; Darcy, Alison; Colborn, Danielle; Gudorf, Caroline; Lock, James

    2012-01-01

    Objective Set shifting difficulties are documented for adults with anorexia nervosa (AN). However, AN typically onsets in adolescents and it is unclear if set-shifting difficulties are a result of chronic AN or present earlier in its course. This study examined whether adolescents with short duration AN demonstrated set shifting difficulties compared to healthy controls (HC). Method Data on set shifting collected from the Delis-Kaplan Executive Functioning System (DKEFS) and Wisconsin Card Sort Task (WCST) as well as eating psychopathology were collected from 32 adolescent inpatients with AN and compared to those from 22 HCs. Results There were no differences in set-shifting in adolescents with AN compared to HCs on most measures. Conclusion The findings suggest that set-shifting difficulties in AN may be a consequence of AN. Future studies should explore set-shifting difficulties in a larger sample of adolescents with the AN to determine if there is sub-set of adolescents with these difficulties and determine any relationship of set-shifting to the development of a chronic from of AN. PMID:22692985

  11. A Short History of Three Chemical Shifts

    ERIC Educational Resources Information Center

    Nagaoka, Shin-ichi

    2007-01-01

    A short history of chemical shifts in nuclear magnetic resonance (NMR), electron spectroscopy for chemical analysis (ESCA) and Mossbauer spectroscopy, which are useful for chemical studies, is described. The term chemical shift is shown to have originated in the mistaken assumption that nuclei of a given element would all undergo resonance at the…

  12. Lamb Shift in Nonrelativistic Quantum Electrodynamics.

    ERIC Educational Resources Information Center

    Grotch, Howard

    1981-01-01

    The bound electron self-energy or Lamb shift is calculated in nonrelativistic quantum electrodynamics. Retardation is retained and also an interaction previously dropped in other nonrelativistic approaches is kept. Results are finite without introducing a cutoff and lead to a Lamb shift in hydrogen of 1030.9 MHz. (Author/JN)

  13. Social Change and Language Shift: South Africa.

    ERIC Educational Resources Information Center

    Kamwangamalu, Nkonko M.

    2003-01-01

    Examines language shift from majority African languages, such as Sotho, Xhosa, and Zulu to English in South Africa. Examines the extent to which sociopolitical changes that have taken place in South Africa have impacted everyday linguistic interaction and have contributed to language shift from the indigenous African language to English,…

  14. Apparatus for controlling transmission gear shift selection

    SciTech Connect

    Bailey, T.M.

    1986-07-29

    In an automotive engine having an electrical power source and an automatic or semi-automatic transmission including a manually operated transmission gear shift lever having at least two forward drive positions, an apparatus is described which consists of: (a) a speed sensing means for sensing the rotation speed of the engine and generating an output signal when the engine reaches a preselected rotational speed; and (b) a gear shifting means for changing the shift positions of the gear shift lever from a first drive position to a second drive position automatically in response to the output signal from the speed sensing means, the gear shifting means including (i) a latch actuable between open and closed positions, (ii) a normally de-energized solenoid having a plunger connected to the latch and operable to move the latch to the open position when the solenoid is energized by the electrical power source, (iii) a relay means for allowing the energizing of the solenoid by the power source in response to the output signal from the speed sensing means, and (iv) an actuating means, including a spring biased linkage mechanism operably connected to the gear shift lever and the latch, for actuating the movement of the gear shift lever from the first drive position to the second drive position in response to movement of the latch from the closed to the open position, thereby causing gear shifting to occur when the engine reaches the preselected rotational speed.

  15. Quality of life in shift work syndrome.

    PubMed

    Puca, F M; Perrucci, S; Prudenzano, M P; Savarese, M; Misceo, S; Perilli, S; Palumbo, M; Libro, G; Genco, S

    1996-01-01

    Air Force radar controllers represent an excellent example of night shift workers, as they are obliged to demonstrate perfect alertness during working hours. We set out: a) to assess the quality of life in these shift workers; b) to identify those with shift work syndrome and c) to evaluate the possible effects of triazolam both on their quality of life and sleep. The results reveal an impairment of the quality of life in shift workers, independently of the presence of a circadian rhythm sleep disorder. Quality of life was more severely impaired in subjects with circadian rhythm sleep disorder. Hypnotic therapy brought about an improvement both in the sleep disorder and in the quality of life of subjects affected by shift work syndrome. Selective alertness tests failed to demonstrate any "sedative carry-over" in the treated patients.

  16. Doppler interpretation of quasar red shifts.

    PubMed

    Zapolsky, H S

    1966-08-05

    The hypothesis that the quasistellar sources (quasars) are local objects moving with velocities close to the speed of light is examined. Provided there is no observational cutoff on apparent bolometric magnitude for the quasars, the transverse Doppler effect leads to the expectation of fewer blue shifts than red shifts for an isotropic distribution of velocities. Such a distribution also yields a function N(z), the number of objects with red shift less than z which is not inconsistent with the present data. On the basis of two extreme assumptions concerning the origin of such rapidly moving sources, we computed curves of red shift plotted against magnitude. In particular, the curve obtained on the assumption that the quasars originated from an explosion in or nearby our own galaxy is in as good agreement with the observations as the curve of cosmological red shift plotted against magnitude.

  17. Design principles for shift current photovoltaics

    PubMed Central

    Cook, Ashley M.; M. Fregoso, Benjamin; de Juan, Fernando; Coh, Sinisa; Moore, Joel E.

    2017-01-01

    While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. By analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. Our method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenides such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W−1. Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells. PMID:28120823

  18. Design principles for shift current photovoltaics

    NASA Astrophysics Data System (ADS)

    Cook, Ashley M.; M. Fregoso, Benjamin; de Juan, Fernando; Coh, Sinisa; Moore, Joel E.

    2017-01-01

    While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. By analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. Our method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenides such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W-1. Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells.

  19. Design principles for shift current photovoltaics.

    PubMed

    Cook, Ashley M; M Fregoso, Benjamin; de Juan, Fernando; Coh, Sinisa; Moore, Joel E

    2017-01-25

    While the basic principles of conventional solar cells are well understood, little attention has gone towards maximizing the efficiency of photovoltaic devices based on shift currents. By analysing effective models, here we outline simple design principles for the optimization of shift currents for frequencies near the band gap. Our method allows us to express the band edge shift current in terms of a few model parameters and to show it depends explicitly on wavefunctions in addition to standard band structure. We use our approach to identify two classes of shift current photovoltaics, ferroelectric polymer films and single-layer orthorhombic monochalcogenides such as GeS, which display the largest band edge responsivities reported so far. Moreover, exploring the parameter space of the tight-binding models that describe them we find photoresponsivities that can exceed 100 mA W(-1). Our results illustrate the great potential of shift current photovoltaics to compete with conventional solar cells.

  20. Equations for Bistatic Doppler Shift and Rate of Change of Doppler Shift of Dark Satellite Observations

    DTIC Science & Technology

    Equations are given for the doppler shift and rate of change of doppler shift for the bistatic case where an orbiting, nontransmitting earth... of change of doppler shift, satellite height, earth-center angle between the receiver and the satellite, and zenith angle from receiver to satellite are shown for a typical satellite, 1958 Alpha, Explorer I....have been computed, using transmitting and receiving sites of the Space Surveillance System. Plots of various relationships between doppler shift, rate

  1. Shifting Mindsets: The Changing Work Roles of Vocational Education and Training Practitioners

    ERIC Educational Resources Information Center

    Harris, Roger; Simons, Michele; Clayton, Berwyn

    2005-01-01

    Reforms to Australia's vocational education and training (VET) sector have had a significant impact on practitioners' work in public and private providers. This study analyses practitioners' perceptions of, and reactions to, the changes. The scope of these changes has been substantial and has required shifts to practitioners' habits, norms, skills…

  2. Visual sensitivities tuned by heterochronic shifts in opsin gene expression

    PubMed Central

    Carleton, Karen L; Spady, Tyrone C; Streelman, J Todd; Kidd, Michael R; McFarland, William N; Loew, Ellis R

    2008-01-01

    Background Cichlid fishes have radiated into hundreds of species in the Great Lakes of Africa. Brightly colored males display on leks and vie to be chosen by females as mates. Strong discrimination by females causes differential male mating success, rapid evolution of male color patterns and, possibly, speciation. In addition to differences in color pattern, Lake Malawi cichlids also show some of the largest known shifts in visual sensitivity among closely related species. These shifts result from modulated expression of seven cone opsin genes. However, the mechanisms for this modulated expression are unknown. Results In this work, we ask whether these differences might result from changes in developmental patterning of cone opsin genes. To test this, we compared the developmental pattern of cone opsin gene expression of the Nile tilapia, Oreochromis niloticus, with that of several cichlid species from Lake Malawi. In tilapia, quantitative polymerase chain reaction showed that opsin gene expression changes dynamically from a larval gene set through a juvenile set to a final adult set. In contrast, Lake Malawi species showed one of two developmental patterns. In some species, the expressed gene set changes slowly, either retaining the larval pattern or progressing only from larval to juvenile gene sets (neoteny). In the other species, the same genes are expressed in both larvae and adults but correspond to the tilapia adult genes (direct development). Conclusion Differences in visual sensitivities among species of Lake Malawi cichlids arise through heterochronic shifts relative to the ontogenetic pattern of the tilapia outgroup. Heterochrony has previously been shown to be a powerful mechanism for change in morphological evolution. We found that altering developmental expression patterns is also an important mechanism for altering sensory systems. These resulting sensory shifts will have major impacts on visual communication and could help drive cichlid speciation

  3. Skin reactions to sunscreens.

    PubMed

    Nixon, R L; Frowen, K E; Lewis, A E

    1997-06-01

    Sunscreen reactions are said not to be uncommon. A population referred to a patch testing clinic was evaluated for reactions to sunscreen by questionnaire initially and then, if relevant, by patch testing to sunscreen products and their components. Irritant reactions were more common than allergic contact dermatitis. Allergic reactions to sunscreens were less common than to non-sunscreen chemicals present in sunscreen products.

  4. The Glyoxal Clock Reaction

    ERIC Educational Resources Information Center

    Ealy, Julie B.; Negron, Alexandra Rodriguez; Stephens, Jessica; Stauffer, Rebecca; Furrow, Stanley D.

    2007-01-01

    Research on the glyoxal clock reaction has led to adaptation of the clock reaction to a general chemistry experiment. This particular reaction is just one of many that used formaldehyde in the past. The kinetics of the glyoxal clock makes the reaction suitable as a general chemistry lab using a Calculator Based Laboratory (CBL) or a LabPro. The…

  5. Two-stage coal liquefaction without gas-phase hydrogen

    DOEpatents

    Stephens, H.P.

    1986-06-05

    A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

  6. Mechanized pivot shift test achieves greater accuracy than manual pivot shift test.

    PubMed

    Musahl, Volker; Voos, James; O'Loughlin, Padhraig F; Stueber, Volker; Kendoff, Daniel; Pearle, Andrew D

    2010-09-01

    The objective of this study was to design a navigated mechanized pivot shift test setup and evaluate its repeatability in the ACL-deficient knee. It was hypothesized that translations and rotations measured with the mechanized pivot shift would be more repeatable when compared to those obtained with a manual pivot shift. Twelve fresh frozen cadaveric hip-to-toe whole lower extremities were used for this study. A manual pivot shift test was performed in the intact knee and in the ACL-deficient knee and was repeated three times. A navigation system simultaneously recorded tibial translation and rotation. The mechanized pivot shift test consists of a modified continuous passive motion (CPM) machine and a custom-made foot holder to allow for the application of internal rotation moments at the knee. Valgus moments were achieved by a 45 degrees tilt of the CPM machine with respect to the supine position and a Velcro strap secured across the proximal tibia. The mechanized pivot shift was repeated three times. Repeated measures ANOVA was used to compare manual and mechanized pivot shift testing. An intra-class correlation coefficient (ICC) was used to determine variability within each knee at each testing condition. In the ACL-deficient knee, translation with manual pivot shift testing (11.7 +/- 2.6 mm) was significantly higher than with mechanized pivot shift testing (7.4 +/- 2.5 mm; p < 0.05). Rotation with the manual pivot shift testing (18.6 +/- 5.4 degrees) was also significantly higher than with mechanized pivot shift testing (11.0 +/- 2.3 degrees; p < 0.05). The intra-class ICC for translations was 0.76 for manual pivot shift and 0.92 for the mechanized pivot shift test. The intra-class ICC for rotations was 0.89 for manual pivot shift and 0.82 for the mechanized pivot shift test. This study introduced a modified CPM for mechanized pivot shift testing. Although recorded translations and rotations with the mechanized pivot shift test were lower than with manual

  7. Selected reaction monitoring applied to quantitative proteomics.

    PubMed

    Kiyonami, Reiko; Domon, Bruno

    2010-01-01

    Proteomics is gradually shifting from pure qualitative studies (protein identification) to large-scale quantitative experiments, prompted by the growing need to analyze consistently and precisely a large set of proteins in biological samples. The selected reaction monitoring (SRM) technique is increasingly applied to quantitative proteomics because of its selectivity (two levels of mass selection), its sensitivity (non-scanning mode), and its wide dynamic range. This account describes the different steps in the design and the experimental setup of SRM experiments.

  8. Optical vortex phase-shifting digital holography.

    PubMed

    Guo, Cheng-Shan; Cheng, Xin; Ren, Xiu-Yun; Ding, Jian-Ping; Wang, Hui-Tian

    2004-10-18

    We report a new optical vortex phase-shifting method for digital holography, in which an optical vortex mode is taken as the reference beam for holographic recording, and the required phase shifts are directly generated by rotating the vortex mode. In digital reconstruction, the complex amplitude of the object wave can be retrieved by use of the conventional phase shifting algorithm on condition that the digital illumination beam is replaced by an vortex beam with the same topological charge as the reference used. Both the theoretical analysis and experimental results demonstrate the feasibility of this approach.

  9. Theory of the Helium Isotope Shift

    SciTech Connect

    Pachucki, Krzysztof; Yerokhin, V. A.

    2015-09-15

    Theory of the isotope shift of the centroid energies of light few-electron atoms is reviewed. Numerical results are presented for the isotope shift of the 2{sup 3}P-2{sup 3}S and 2{sup 1}S-2{sup 3}S transition energies of {sup 3}He and {sup 4}He. By comparing theoretical predictions for the isotope shift with the experimental results, the difference of the squares of the nuclear charge radii of {sup 3}He and {sup 4}He, δR{sup 2}, is determined with high accuracy.

  10. Search for Higgs shifts in white dwarfs

    SciTech Connect

    Onofrio, Roberto; Wegner, Gary A. E-mail: gary.a.wegner@dartmouth.edu

    2014-08-20

    We report on a search for differential shifts between electronic and vibronic transitions in carbon-rich white dwarfs BPM 27606 and Procyon B. The absence of differential shifts within the spectral resolution and taking into account systematic effects such as space motion and pressure shifts allows us to set the first upper bound of astrophysical origin on the coupling between the Higgs field and the Kreschmann curvature invariant. Our analysis provides the basis for a more general methodology to derive bounds to the coupling of long-range scalar fields to curvature invariants in an astrophysical setting complementary to the ones available from high-energy physics or table-top experiments.

  11. Giant lamb shift in photonic crystals.

    PubMed

    Wang, Xue-Hua; Kivshar, Yuri S; Gu, Ben-Yuan

    2004-08-13

    We obtain a general result for the Lamb shift of excited states of multilevel atoms in inhomogeneous electromagnetic structures and apply it to study atomic hydrogen in inverse-opal photonic crystals. We find that the photonic-crystal environment can lead to very large values of the Lamb shift, as compared to the case of vacuum. We also suggest that the position-dependent Lamb shift should extend from a single level to a miniband for an assembly of atoms with random distribution in space, similar to the velocity-dependent Doppler effect in atomic/molecular gases.

  12. Shift in Food Intake and Changes in Metabolic Regulation and Gene Expression during Simulated Night-Shift Work: A Rat Model

    PubMed Central

    Marti, Andrea Rørvik; Meerlo, Peter; Grønli, Janne; van Hasselt, Sjoerd Johan; Mrdalj, Jelena; Pallesen, Ståle; Pedersen, Torhild Thue; Henriksen, Tone Elise Gjøtterud; Skrede, Silje

    2016-01-01

    Night-shift work is linked to a shift in food intake toward the normal sleeping period, and to metabolic disturbance. We applied a rat model of night-shift work to assess the immediate effects of such a shift in food intake on metabolism. Male Wistar rats were subjected to 8 h of forced activity during their rest (ZT2-10) or active (ZT14-22) phase. Food intake, body weight, and body temperature were monitored across four work days and eight recovery days. Food intake gradually shifted toward rest-work hours, stabilizing on work day three. A subgroup of animals was euthanized after the third work session for analysis of metabolic gene expression in the liver by real-time polymerase chain reaction (PCR). Results show that work in the rest phase shifted food intake to rest-work hours. Moreover, liver genes related to energy storage and insulin metabolism were upregulated, and genes related to energy breakdown were downregulated compared to non-working time-matched controls. Both working groups lost weight during the protocol and regained weight during recovery, but animals that worked in the rest phase did not fully recover, even after eight days of recovery. In conclusion, three to four days of work in the rest phase is sufficient to induce disruption of several metabolic parameters, which requires more than eight days for full recovery. PMID:27834804

  13. Adaptation to shift work: physiologically based modeling of the effects of lighting and shifts' start time.

    PubMed

    Postnova, Svetlana; Robinson, Peter A; Postnov, Dmitry D

    2013-01-01

    Shift work has become an integral part of our life with almost 20% of the population being involved in different shift schedules in developed countries. However, the atypical work times, especially the night shifts, are associated with reduced quality and quantity of sleep that leads to increase of sleepiness often culminating in accidents. It has been demonstrated that shift workers' sleepiness can be improved by a proper scheduling of light exposure and optimizing shifts timing. Here, an integrated physiologically-based model of sleep-wake cycles is used to predict adaptation to shift work in different light conditions and for different shift start times for a schedule of four consecutive days of work. The integrated model combines a model of the ascending arousal system in the brain that controls the sleep-wake switch and a human circadian pacemaker model. To validate the application of the integrated model and demonstrate its utility, its dynamics are adjusted to achieve a fit to published experimental results showing adaptation of night shift workers (n = 8) in conditions of either bright or regular lighting. Further, the model is used to predict the shift workers' adaptation to the same shift schedule, but for conditions not considered in the experiment. The model demonstrates that the intensity of shift light can be reduced fourfold from that used in the experiment and still produce good adaptation to night work. The model predicts that sleepiness of the workers during night shifts on a protocol with either bright or regular lighting can be significantly improved by starting the shift earlier in the night, e.g.; at 21:00 instead of 00:00. Finally, the study predicts that people of the same chronotype, i.e. with identical sleep times in normal conditions, can have drastically different responses to shift work depending on their intrinsic circadian and homeostatic parameters.

  14. Postural Stability is Altered by Blood Shift

    NASA Astrophysics Data System (ADS)

    Marais, M.; Denise, P.; Guincetre, J. Y.; Normand, H.

    2008-06-01

    Non-vestibular influences as shift in blood volume changed perception of body posture. Then, factors affecting blood shift may alter postural control. The purpose of our study was to investigate the effects of leg venous contention on postural stability. Twelve subjects were studied on a balance plate for 5 minutes with the eyes closed, in 3 conditions: with no leg venous contention or grade 1 and 3 support stockings. Standard deviation of x and y position was calculated before and after the closure of the eyes. Strong venous contention altered postural stability, after the eyes were closed, during the first 10 s of standing. As support stockings prevent blood shift induced by upright posture, this result is in line with the hypothesis that blood shifts influence the perception of body orientation and postural control among others factors as vision, vestibular inputs... This strong venous contention could induce an increase of fall.

  15. Red Shifts with Obliquely Approaching Light Sources.

    ERIC Educational Resources Information Center

    Head, C. E.; Moore-Head, M. E.

    1988-01-01

    Refutes the Doppler effect as the explanation of large red shifts in the spectra of distant galaxies and explains the relativistic effects in which the light sources approach the observer obliquely. Provides several diagrams and graphs. (YP)

  16. Trends in adsorbate induced core level shifts

    NASA Astrophysics Data System (ADS)

    Nilsson, Viktor; Van den Bossche, Maxime; Hellman, Anders; Grönbeck, Henrik

    2015-10-01

    Photoelectron core level spectroscopy is commonly used to monitor atomic and molecular adsorption on metal surfaces. As changes in the electron binding energies are convoluted measures with different origins, calculations are often used to facilitate the decoding of experimental signatures. The interpretation could in this sense benefit from knowledge on trends in surface core level shifts for different metals and adsorbates. Here, density functional theory calculations have been used to systematically evaluate core level shifts for (111) and (100) surfaces of 3d, 4d, and 5d transition metals upon CO, H, O and S adsorption. The results reveal trends and several non-intuitive cases. Moreover, the difficulties correlating core level shifts with charging and d-band shifts are underlined.

  17. Gradual regime shifts in fairy circles.

    PubMed

    Zelnik, Yuval R; Meron, Ehud; Bel, Golan

    2015-10-06

    Large responses of ecosystems to small changes in the conditions--regime shifts--are of great interest and importance. In spatially extended ecosystems, these shifts may be local or global. Using empirical data and mathematical modeling, we investigated the dynamics of the Namibian fairy circle ecosystem as a case study of regime shifts in a pattern-forming ecosystem. Our results provide new support, based on the dynamics of the ecosystem, for the view of fairy circles as a self-organization phenomenon driven by water-vegetation interactions. The study further suggests that fairy circle birth and death processes correspond to spatially confined transitions between alternative stable states. Cascades of such transitions, possible in various pattern-forming systems, result in gradual rather than abrupt regime shifts.

  18. Prolonged instability prior to a regime shift.

    PubMed

    Spanbauer, Trisha L; Allen, Craig R; Angeler, David G; Eason, Tarsha; Fritz, Sherilyn C; Garmestani, Ahjond S; Nash, Kirsty L; Stone, Jeffery R

    2014-01-01

    Regime shifts are generally defined as the point of 'abrupt' change in the state of a system. However, a seemingly abrupt transition can be the product of a system reorganization that has been ongoing much longer than is evident in statistical analysis of a single component of the system. Using both univariate and multivariate statistical methods, we tested a long-term high-resolution paleoecological dataset with a known change in species assemblage for a regime shift. Analysis of this dataset with Fisher Information and multivariate time series modeling showed that there was a∼2000 year period of instability prior to the regime shift. This period of instability and the subsequent regime shift coincide with regional climate change, indicating that the system is undergoing extrinsic forcing. Paleoecological records offer a unique opportunity to test tools for the detection of thresholds and stable-states, and thus to examine the long-term stability of ecosystems over periods of multiple millennia.

  19. [Sleep disorders among physicians on shift work].

    PubMed

    Schlafer, O; Wenzel, V; Högl, B

    2014-11-01

    Sleep disorders in physicians who perform shift work can result in increased risks of health problems that negatively impact performance and patient safety. Even those who cope well with shift work are likely to suffer from sleep disorders. The aim of this manuscript is to discuss possible causes, contributing factors and consequences of sleep disorders in physicians and to identify measures that can improve adaptation to shift work and treatment strategies for shift work-associated sleep disorders. The risk factors that influence the development of sleep disorders in physicians are numerous and include genetic factors (15 % of the population), age (> 50 years), undiagnosed sleep apnea,, alcohol abuse as well as multiple stress factors inherent in clinical duties (including shift work), research, teaching and family obligations. Several studies have reported an increased risk for medical errors in sleep-deprived physicians. Shift workers have an increased risk for psychiatric and cardiovascular diseases and shift work may also be a contributing factor to cancer. A relationship has been reported not only with sleep deprivation and changes in food intake but also with diabetes mellitus, obesity, hypertension and coronary heart disease. Nicotine and alcohol consumption are more frequent among shift workers. Increased sickness and accident rates among physicians when commuting (especially after night shifts) have a socioeconomic impact. In order to reduce fatigue and to improve performance, short naps during shiftwork or naps plus caffeine, have been proposed as coping strategies; however, napping during adverse circadian phases is less effective, if not impossible when unable to fall asleep. Bright and blue light supports alertness during a night shift. After shiftwork, direct sunlight exposure to the retina can be avoided by using dark sunglasses or glasses with orange lenses for commuting home. The home environment for daytime sleeping after a night shift should be

  20. Nuclear waste vitrification efficiency: cold cap reactions

    SciTech Connect

    Hrma, Pavel R.; Kruger, Albert A.; Pokorny, Richard

    2012-12-15

    The cost and schedule of nuclear waste treatment and immobilization are greatly affected by the rate of glass production. Various factors influence the performance of a waste-glass melter. One of the most significant, and also one of the least understood, is the process of batch melting. Studies are being conducted to gain fundamental understanding of the batch reactions, particularly those that influence the rate of melting, and models are being developed to link batch makeup and melter operation to the melting rate. Batch melting takes place within the cold cap, i.e., a batch layer floating on the surface of molten glass. The conversion of batch to glass consists of various chemical reactions, phase transitions, and diffusion-controlled processes. These include water evaporation (slurry feed contains as high as 60% water), gas evolution, the melting of salts, the formation of borate melt, reactions of borate melt with molten salts and with amorphous oxides (Fe2O3 and Al2O3), the formation of intermediate crystalline phases, the formation of a continuous glass-forming melt, the growth and collapse of primary foam, and the dissolution of residual solids. To this list we also need to add the formation of secondary foam that originates from molten glass but accumulates on the bottom of the cold cap. This study presents relevant data obtained for a high-level-waste melter feed and introduces a one-dimensional (1D) mathematical model of the cold cap as a step toward an advanced three-dimensional (3D) version for a complete model of the waste glass melter. The 1D model describes the batch-to-glass conversion within the cold cap as it progresses in a vertical direction. With constitutive equations and key parameters based on measured data, and simplified boundary conditions on the cold-cap interfaces with the glass melt and the plenum space of the melter, the model provides sensitivity analysis of the response of the cold cap to the batch makeup and melter conditions

  1. NUCLEAR WASTE VITRIFICATION EFFICIENCY COLD CAP REACTIONS

    SciTech Connect

    KRUGER AA; HRMA PR; POKORNY R

    2011-07-29

    The cost and schedule of nuclear waste treatment and immobilization are greatly affected by the rate of glass production. Various factors influence the performance of a waste-glass melter. One of the most significant, and also one of the least understood, is the process of batch melting. Studies are being conducted to gain fundamental understanding of the batch reactions, particularly those that influence the rate of melting, and models are being developed to link batch makeup and melter operation to the melting rate. Batch melting takes place within the cold cap, i.e., a batch layer floating on the surface of molten glass. The conversion of batch to glass consists of various chemical reactions, phase transitions, and diffusion-controlled processes. These include water evaporation (slurry feed contains as high as 60% water), gas evolution, the melting of salts, the formation of borate melt, reactions of borate melt with molten salts and with amorphous oxides (Fe{sub 2}O{sub 3} and Al{sub 2}O{sub 3}), the formation of intermediate crystalline phases, the formation of a continuous glass-forming melt, the growth and collapse of primary foam, and the dissolution of residual solids. To this list we also need to add the formation of secondary foam that originates from molten glass but accumulates on the bottom of the cold cap. This study presents relevant data obtained for a high-level-waste melter feed and introduces a one-dimensional (1D) mathematical model of the cold cap as a step toward an advanced three-dimensional (3D) version for a complete model of the waste glass melter. The 1D model describes the batch-to-glass conversion within the cold cap as it progresses in a vertical direction. With constitutive equations and key parameters based on measured data, and simplified boundary conditions on the cold-cap interfaces with the glass melt and the plenum space of the melter, the model provides sensitivity analysis of the response of the cold cap to the batch makeup

  2. Phase shifts extraction based on time-domain orthogonal character of phase-shifting interferograms

    NASA Astrophysics Data System (ADS)

    Shou, Junwei; Zhong, Liyun; Zhou, Yunfei; Tian, Jindong; Lu, Xiaoxu

    2017-01-01

    Based on the time-domain orthogonal character of different pixel intensity variation of phase-shifting interferograms, a novel non-iterative algorithm is proposed to achieve the phase shifts in random phase-shifting interferometry. Due to there is no requirement for the fringe number of phase-shifting interferograms, the proposed algorithm can work well even in the case that the fringe number of interferogram is less than one, which is a difficult problem in interferometry. Moreover, only two one-dimensional vectors, achieved from the average intensity of several pixels of interferogram, are enough to perform the phase shifts extraction, the proposed algorithm reveals rapid processing speed. Specially, compared with the conventional phase shifts extraction algorithms, the proposed algorithm does not need to perform the pixel-pixel calculation or the iterative calculation, so its processing speed is greatly improved. Both the simulation and the experiment demonstrate the outstanding performance of the proposed algorithm.

  3. Increasing the Chemical‐Shift Dispersion of Unstructured Proteins with a Covalent Lanthanide Shift Reagent

    PubMed Central

    Göbl, Christoph; Resch, Moritz; Strickland, Madeleine; Hartlmüller, Christoph; Viertler, Martin

    2016-01-01

    Abstract The study of intrinsically disordered proteins (IDPs) by NMR often suffers from highly overlapped resonances that prevent unambiguous chemical‐shift assignments, and data analysis that relies on well‐separated resonances. We present a covalent paramagnetic lanthanide‐binding tag (LBT) for increasing the chemical‐shift dispersion and facilitating the chemical‐shift assignment of challenging, repeat‐containing IDPs. Linkage of the DOTA‐based LBT to a cysteine residue induces pseudo‐contact shifts (PCS) for resonances more than 20 residues from the spin‐labeling site. This leads to increased chemical‐shift dispersion and decreased signal overlap, thereby greatly facilitating chemical‐shift assignment. This approach is applicable to IDPs of varying sizes and complexity, and is particularly helpful for repeat‐containing IDPs and low‐complexity regions. This results in improved efficiency for IDP analysis and binding studies. PMID:27763708

  4. A holistic view of marine regime shifts

    PubMed Central

    Conversi, Alessandra; Dakos, Vasilis; Gårdmark, Anna; Ling, Scott; Folke, Carl; Mumby, Peter J.; Greene, Charles; Edwards, Martin; Blenckner, Thorsten; Casini, Michele; Pershing, Andrew; Möllmann, Christian

    2015-01-01

    Understanding marine regime shifts is important not only for ecology but also for developing marine management that assures the provision of ecosystem services to humanity. While regime shift theory is well developed, there is still no common understanding on drivers, mechanisms and characteristic of abrupt changes in real marine ecosystems. Based on contributions to the present theme issue, we highlight some general issues that need to be overcome for developing a more comprehensive understanding of marine ecosystem regime shifts. We find a great divide between benthic reef and pelagic ocean systems in how regime shift theory is linked to observed abrupt changes. Furthermore, we suggest that the long-lasting discussion on the prevalence of top-down trophic or bottom-up physical drivers in inducing regime shifts may be overcome by taking into consideration the synergistic interactions of multiple stressors, and the special characteristics of different ecosystem types. We present a framework for the holistic investigation of marine regime shifts that considers multiple exogenous drivers that interact with endogenous mechanisms to cause abrupt, catastrophic change. This framework takes into account the time-delayed synergies of these stressors, which erode the resilience of the ecosystem and eventually enable the crossing of ecological thresholds. Finally, considering that increased pressures in the marine environment are predicted by the current climate change assessments, in order to avoid major losses of ecosystem services, we suggest that marine management approaches should incorporate knowledge on environmental thresholds and develop tools that consider regime shift dynamics and characteristics. This grand challenge can only be achieved through a holistic view of marine ecosystem dynamics as evidenced by this theme issue.

  5. Microscale Thermite Reactions.

    ERIC Educational Resources Information Center

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana

    1998-01-01

    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  6. Microfluidic chemical reaction circuits

    SciTech Connect

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C; Huang, Jiang; Heath, James R; Phelps, Michael E; Quake, Stephen R; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  7. Allergic reactions (image)

    MedlinePlus

    Allergic reaction is a sensitivity to a specific substance, called an allergen, that is contacted through the skin, inhaled into the lungs, swallowed or injected. The body's reaction to an allergen can be mild, such as ...

  8. Allergic reactions (image)

    MedlinePlus

    Allergic reaction can be provoked by skin contact with poison plants, chemicals and animal scratches, as well as by ... dust, nuts and shellfish, may also cause allergic reaction. Medications such as penicillin and other antibiotics are ...

  9. Hash: a Program to Accurately Predict Protein Hα Shifts from Neighboring Backbone Shifts3

    PubMed Central

    Zeng, Jianyang; Zhou, Pei; Donald, Bruce Randall

    2012-01-01

    Chemical shifts provide not only peak identities for analyzing NMR data, but also an important source of conformational information for studying protein structures. Current structural studies requiring Hα chemical shifts suffer from the following limitations. (1) For large proteins, the Hα chemical shifts can be difficult to assign using conventional NMR triple-resonance experiments, mainly due to the fast transverse relaxation rate of Cα that restricts the signal sensitivity. (2) Previous chemical shift prediction approaches either require homologous models with high sequence similarity or rely heavily on accurate backbone and side-chain structural coordinates. When neither sequence homologues nor structural coordinates are available, we must resort to other information to predict Hα chemical shifts. Predicting accurate Hα chemical shifts using other obtainable information, such as the chemical shifts of nearby backbone atoms (i.e., adjacent atoms in the sequence), can remedy the above dilemmas, and hence advance NMR-based structural studies of proteins. By specifically exploiting the dependencies on chemical shifts of nearby backbone atoms, we propose a novel machine learning algorithm, called Hash, to predict Hα chemical shifts. Hash combines a new fragment-based chemical shift search approach with a non-parametric regression model, called the generalized additive model, to effectively solve the prediction problem. We demonstrate that the chemical shifts of nearby backbone atoms provide a reliable source of information for predicting accurate Hα chemical shifts. Our testing results on different possible combinations of input data indicate that Hash has a wide rage of potential NMR applications in structural and biological studies of proteins. PMID:23242797

  10. Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents

    DOE PAGES

    Matyushov, Dmitry V.; Newton, Marshall D.

    2017-03-09

    Solvent-induced shift of optical transition lines is traditionally described by the Lippert- McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. Here we have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for themore » reaction field of permanent dipoles in the Lippert-McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert- McRae equation equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, non-additive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. Finally, the main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert-McRae formula.« less

  11. Solvent-Induced Shift of Spectral Lines in Polar-Polarizable Solvents

    DOE PAGES

    Matyushov, Dmitry V.; Newton, Marshall D.

    2017-02-28

    Solvent-induced shift of optical transition lines is traditionally described by the Lippert- McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. Here we have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for themore » reaction field of permanent dipoles in the Lippert-McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert- McRae equation equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, non-additive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. Finally, the main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert-McRae formula.« less

  12. Influences on Dietary Choices during Day versus Night Shift in Shift Workers: A Mixed Methods Study.

    PubMed

    Bonnell, Emily K; Huggins, Catherine E; Huggins, Chris T; McCaffrey, Tracy A; Palermo, Claire; Bonham, Maxine P

    2017-02-26

    Shift work is associated with diet-related chronic conditions such as obesity and cardiovascular disease. This study aimed to explore factors influencing food choice and dietary intake in shift workers. A fixed mixed method study design was undertaken on a convenience sample of firefighters who continually work a rotating roster. Six focus groups (n = 41) were conducted to establish factors affecting dietary intake whilst at work. Dietary intake was assessed using repeated 24 h dietary recalls (n = 19). Interviews were audio recorded, transcribed verbatim, and interpreted using thematic analysis. Dietary data were entered into FoodWorks and analysed using Wilcoxon signed-rank test; p < 0.05 was considered significant. Thematic analysis highlighted four key themes influencing dietary intake: shift schedule; attitudes and decisions of co-workers; time and accessibility; and knowledge of the relationship between food and health. Participants reported consuming more discretionary foods and limited availability of healthy food choices on night shift. Energy intakes (kJ/day) did not differ between days that included a day or night shift but greater energy density (EDenergy, kJ/g/day) of the diet was observed on night shift compared with day shift. This study has identified a number of dietary-specific shift-related factors that may contribute to an increase in unhealthy behaviours in a shift-working population. Given the increased risk of developing chronic diseases, organisational change to support workers in this environment is warranted.

  13. Influences on Dietary Choices during Day versus Night Shift in Shift Workers: A Mixed Methods Study

    PubMed Central

    Bonnell, Emily K.; Huggins, Catherine E.; Huggins, Chris T.; McCaffrey, Tracy A.; Palermo, Claire; Bonham, Maxine P.

    2017-01-01

    Shift work is associated with diet-related chronic conditions such as obesity and cardiovascular disease. This study aimed to explore factors influencing food choice and dietary intake in shift workers. A fixed mixed method study design was undertaken on a convenience sample of firefighters who continually work a rotating roster. Six focus groups (n = 41) were conducted to establish factors affecting dietary intake whilst at work. Dietary intake was assessed using repeated 24 h dietary recalls (n = 19). Interviews were audio recorded, transcribed verbatim, and interpreted using thematic analysis. Dietary data were entered into FoodWorks and analysed using Wilcoxon signed-rank test; p < 0.05 was considered significant. Thematic analysis highlighted four key themes influencing dietary intake: shift schedule; attitudes and decisions of co-workers; time and accessibility; and knowledge of the relationship between food and health. Participants reported consuming more discretionary foods and limited availability of healthy food choices on night shift. Energy intakes (kJ/day) did not differ between days that included a day or night shift but greater energy density (EDenergy, kJ/g/day) of the diet was observed on night shift compared with day shift. This study has identified a number of dietary-specific shift-related factors that may contribute to an increase in unhealthy behaviours in a shift-working population. Given the increased risk of developing chronic diseases, organisational change to support workers in this environment is warranted. PMID:28245625

  14. Phase shifting interferometry from two normalized interferograms with random tilt phase-shift.

    PubMed

    Liu, Fengwei; Wu, Yongqian; Wu, Fan

    2015-07-27

    We propose a novel phase shifting interferometry from two normalized interferograms with random tilt phase-shift. The determination of tilt phase-shift is performed by extracting the tilted phase-shift plane from the phase difference of two normalized interferograms, and with the calculated tilt phase-shift value the phase distribution can be retrieved from the two normalized frames. By analyzing the distribution of phase difference and utilizing special points fitting method, the tilted phase-shift plane is extracted in three different cases, which relate to different magnitudes of tilts. Proposed method has been applied to simulations and experiments successfully and the satisfactory results manifest that proposed method is of high accuracy and high speed compared with the three step iterative method. Additionally, both open and closed fringe can be analyzed with proposed method. What's more, it cannot only eliminate the small tilt-shift error caused by slight vibration in phase-shifting interferometry, but also detect the large tilt phase-shift in phase-tilting interferometry. Thus, it will relaxes the requirements on the accuracy of phase shifter, and the costly phase shifter may even be useless by applying proposed method in high amplitude vibrated circumstance to achieve high-precision analysis.

  15. Nozzle Aerodynamic Stability During a Throat Shift

    NASA Technical Reports Server (NTRS)

    Kawecki, Edwin J.; Ribeiro, Gregg L.

    2005-01-01

    An experimental investigation was conducted on the internal aerodynamic stability of a family of two-dimensional (2-D) High Speed Civil Transport (HSCT) nozzle concepts. These nozzles function during takeoff as mixer-ejectors to meet acoustic requirements, and then convert to conventional high-performance convergent-divergent (CD) nozzles at cruise. The transition between takeoff mode and cruise mode results in the aerodynamic throat and the minimum cross-sectional area that controls the engine backpressure shifting location within the nozzle. The stability and steadiness of the nozzle aerodynamics during this so called throat shift process can directly affect the engine aerodynamic stability, and the mechanical design of the nozzle. The objective of the study was to determine if pressure spikes or other perturbations occurred during the throat shift process and, if so, identify the caused mechanisms for the perturbations. The two nozzle concepts modeled in the test program were the fixed chute (FC) and downstream mixer (DSM). These 2-D nozzles differ principally in that the FC has a large over-area between the forward throat and aft throat locations, while the DSM has an over-area of only about 10 percent. The conclusions were that engine mass flow and backpressure can be held constant simultaneously during nozzle throat shifts on this class of nozzles, and mode shifts can be accomplished at a constant mass flow and engine backpressure without upstream pressure perturbations.

  16. Chemical shift prediction for denatured proteins.

    PubMed

    Prestegard, James H; Sahu, Sarata C; Nkari, Wendy K; Morris, Laura C; Live, David; Gruta, Christian

    2013-02-01

    While chemical shift prediction has played an important role in aspects of protein NMR that include identification of secondary structure, generation of torsion angle constraints for structure determination, and assignment of resonances in spectra of intrinsically disordered proteins, interest has arisen more recently in using it in alternate assignment strategies for crosspeaks in (1)H-(15)N HSQC spectra of sparsely labeled proteins. One such approach involves correlation of crosspeaks in the spectrum of the native protein with those observed in the spectrum of the denatured protein, followed by assignment of the peaks in the latter spectrum. As in the case of disordered proteins, predicted chemical shifts can aid in these assignments. Some previously developed empirical formulas for chemical shift prediction have depended on basis data sets of 20 pentapeptides. In each case the central residue was varied among the 20 amino common acids, with the flanking residues held constant throughout the given series. However, previous choices of solvent conditions and flanking residues make the parameters in these formulas less than ideal for general application to denatured proteins. Here, we report (1)H and (15)N shifts for a set of alanine based pentapeptides under the low pH urea denaturing conditions that are more appropriate for sparse label assignments. New parameters have been derived and a Perl script was created to facilitate comparison with other parameter sets. A small, but significant, improvement in shift predictions for denatured ubiquitin is demonstrated.

  17. Attentional Set-Shifting Across Species.

    PubMed

    Brown, Verity J; Tait, David S

    Attentional set-shifting, as a measure of executive flexibility, has been a staple of investigations into human cognition for over six decades. Mediated by the frontal cortex in mammals, the cognitive processes involved in forming, maintaining and shifting an attentional set are vulnerable to dysfunction arising from a number of human neurodegenerative diseases (such as Alzheimer's, Parkinson's and Huntington's diseases) and other neurological disorders (such as schizophrenia, depression, and attention deficit/hyperactivity disorder). Our understanding of these diseases and disorders, and the cognitive impairments induced by them, continues to advance, in tandem with an increasing number of tools at our disposal. In this chapter, we review and compare commonly used attentional set-shifting tasks (the Wisconsin Card Sorting Task and Intradimensional/Extradimensional tasks) and their applicability across species. In addition to humans, attentional set-shifting has been observed in a number of other animals, with a substantial body of literature describing performance in monkeys and rodents. We consider the task designs used to investigate attentional set-shifting in these species and the methods used to model human diseases and disorders, and ultimately the comparisons and differences between species-specific tasks, and between performance across species.

  18. Choice Shift in Opinion Network Dynamics

    NASA Astrophysics Data System (ADS)

    Gabbay, Michael

    Choice shift is a phenomenon associated with small group dynamics whereby group discussion causes group members to shift their opinions in a more extreme direction so that the mean post-discussion opinion exceeds the mean pre-discussion opinion. Also known as group polarization, choice shift is a robust experimental phenomenon and has been well-studied within social psychology. In opinion network models, shifts toward extremism are typically produced by the presence of stubborn agents at the extremes of the opinion axis, whose opinions are much more resistant to change than moderate agents. However, we present a model in which choice shift can arise without the assumption of stubborn agents; the model evolves member opinions and uncertainties using coupled nonlinear differential equations. In addition, we briefly describe the results of a recent experiment conducted involving online group discussion concerning the outcome of National Football League games are described. The model predictions concerning the effects of network structure, disagreement level, and team choice (favorite or underdog) are in accord with the experimental results. This research was funded by the Office of Naval Research and the Defense Threat Reduction Agency.

  19. How automatic is manual gear shifting?

    PubMed

    Shinar, D; Meir, M; Ben-Shoham, I

    1998-12-01

    Manual gear shifting is often used as an example of an automated (vs. controlled) process in driving. The present study provided an empirical evaluation of this assumption by evaluating sign detection and recall performance of novice and experienced drivers driving manual shift and automatic transmission cars in a downtown area requiring frequent gear shifting. The results showed that manual gear shifting significantly impaired sign detection performance of novice drivers using manual gears compared with novice drivers using an automatic transmission, whereas no such differences existed between the two transmission types for experienced drivers. The results clearly demonstrate that manual gear shifting is a complex psychomotor skill that is not easily (or quickly) automated and that until it becomes automated, it is an attention-demanding task that may impair other monitoring aspects of driving performance. Actual or potential applications of this research include a reevaluation of the learning process in driving and the need for phased instruction in driving from automatic gears to manual gears.

  20. Doppler broadening induced spectral shift effects on reactor safety

    SciTech Connect

    Alapour, A.

    1980-01-01

    It is commonly accepted that the resonance reaction rate of any material increases when the temperature is raised. However, in a nuclear reactor the increase in resonance reaction rates with temperature at relatively high energy shifts the neutron spectrum in such a way that a net decrease in the neutron flux results at lower energies. This finding suggested that the spectral shift could significantly affect the Doppler reactivity change, warranting further investigations. The objective was to study the physical characteristics of this new phenomenon and its effects on reactor safety. The desirability of studying this effect was strengthened by the presence of discrepancies between the calculated and measured integral experiments. An exact Doppler broadening kernel, based on the Maxwellian distribution of nuclear velocities, and an accurate integral transport method NDCRAB, capable of including resonance overlap of all materials present in the reactor cell, were used in this study. The ZPR-6 Assembly 7 benchmark, a typical LMFBR reactor, was used to quantify the Doppler reactivity change for an increase in fuel temperature and to analyze the natural UO/sub 3/ sample Doppler worth in this assembly. The quantification of the various components of the Doppler reactivity change shows that the fissile material, /sup 239/Pu, has a large negative Doppler effect and contributes a large fraction to the total negative effect. The calculated Doppler effect of the natural UO/sub 3/ sample in this assembly was in good agreement with the measured value. The calculated and measured values for an increase in sample temperature from 293-0K to 1100/sup 0/K wre -0.887 Ih/kgU and -0.868 Ih/kgU.

  1. Gradual regime shifts in fairy circles

    PubMed Central

    Zelnik, Yuval R.; Meron, Ehud; Bel, Golan

    2015-01-01

    Large responses of ecosystems to small changes in the conditions—regime shifts—are of great interest and importance. In spatially extended ecosystems, these shifts may be local or global. Using empirical data and mathematical modeling, we investigated the dynamics of the Namibian fairy circle ecosystem as a case study of regime shifts in a pattern-forming ecosystem. Our results provide new support, based on the dynamics of the ecosystem, for the view of fairy circles as a self-organization phenomenon driven by water–vegetation interactions. The study further suggests that fairy circle birth and death processes correspond to spatially confined transitions between alternative stable states. Cascades of such transitions, possible in various pattern-forming systems, result in gradual rather than abrupt regime shifts. PMID:26362787

  2. Liquid crystal display for phase shifting

    NASA Astrophysics Data System (ADS)

    Villalobos-Mendoza, B.; Granados-Agustín, F. S.; Aguirre-Aguirre, D.; Cornejo-Rodríguez, A.

    2013-11-01

    This work arises based on the idea proposed by Millered et al. in 2004, where they show how to get in one shot interferograms with phase shift using a mask with micro-polarizers, in this work we pretend to obtain phase shift in localized areas of an interferogram using the properties of polarization and the pixelated configuration of a liquid crystal display (LCD) for testing optical surfaces. In this work we describes the process of characterization of a liquid crystal display CRL Opto and XGA2P01 model, which is introduced in one arm of a Twyman Green interferometer. Finally we show the experimental interferograms with phase shifts which are caused by different gray levels displayed in the LCD.

  3. Isotope shifts in spectra of molecular liquids

    NASA Astrophysics Data System (ADS)

    Dubrovskaya, E. V.; Kolomiitsova, T. D.; Shurukhina, A. V.; Shchepkin, D. N.

    2016-02-01

    In the IR absorption spectra of low-temperature molecular liquids, we have observed anomalously large isotope shifts of frequencies of vibrational bands that are strong in the dipole absorption. The same effect has also been observed in their Raman spectra. At the same time, in the spectra of cryosolutions, the isotope shifts of the same bands coincide with a high accuracy (±(0.1-0.5) cm-1) with the shifts that are observed in the spectra of the gas phase. The difference between the spectra of examined low-temperature systems is caused by the occurrence of resonant dipole-dipole interactions between spectrally active identical molecules. The calculation of the band contour in the spectrum of liquid freon that we have performed in this work taking into account the resonant interaction between states of simultaneous transitions in isotopically substituted molecules can explain this effect.

  4. Isotope shift measurements in titanium I

    NASA Astrophysics Data System (ADS)

    Azaroual, E. M.; Luc, P.; Vetter, R.

    1992-06-01

    The use of an effusive beam of titanium atoms crossed with a CW single-mode tunable dye laser has allowed the high-resolution, Doppler-free study of the isotope shifts between50Ti,48Ti and46Ti, for seven 3 d 2 4 s 2 a3 F J → 3 d 2 4 s 4 p z 5 D J , visible transitions of Ti I. The measurements show without ambiguity the existence of a non-negligible field shift. Using the values of the nuclear radii of titanium (coming from muonic X-ray measurements), it is possible to determine the respective values of the field and mass shifts.

  5. Multiscale regime shifts and planetary boundaries.

    PubMed

    Hughes, Terry P; Carpenter, Stephen; Rockström, Johan; Scheffer, Marten; Walker, Brian

    2013-07-01

    Life on Earth has repeatedly displayed abrupt and massive changes in the past, and there is no reason to expect that comparable planetary-scale regime shifts will not continue in the future. Different lines of evidence indicate that regime shifts occur when the climate or biosphere transgresses a tipping point. Whether human activities will trigger such a global event in the near future is uncertain, due to critical knowledge gaps. In particular, we lack understanding of how regime shifts propagate across scales, and whether local or regional tipping points can lead to global transitions. The ongoing disruption of ecosystems and climate, combined with unprecedented breakdown of isolation by human migration and trade, highlights the need to operate within safe planetary boundaries.

  6. Work function shifts of catalytic metals under hydrogen gas visualized by terahertz chemical microscopy.

    PubMed

    Kiwa, Toshihiko; Hagiwara, Takafumi; Shinomiya, Mitsuhiro; Sakai, Kenji; Tsukada, Keiji

    2012-05-21

    Terahertz chemical microscopy (TCM) was applied to visualize the distribution of the work function shift of catalytic metals under hydrogen gas. TCM measures the chemical potential on the surface of a SiO(2)/Si/sapphire sensing plate without any contact with the plate. By controlling the bias voltage between an electrode on the SiO(2)/ surface and the Si layer, the relationship between the voltage and the THz amplitude from the sensing plate can be obtained. As a demonstration, two types of structures were fabricated on the sensing plate, and the work function shifts due to catalytic reactions were visualized.

  7. Shift work in a security environment

    SciTech Connect

    Longhouser, G.A. Jr.

    1993-12-31

    Human beings are diurnal species, normally active by day and asleep by night. Yet over thirty million Americans struggle with work schedules that include an off-normal work effort. The railroads, law enforcement, health services, Department of Defense, factory workers, chemical plants and public services, communications and utility workers must provide some form of around-the-clock effort. Shift work has been around since the advent of recorded history. There has always been a need for some type of off-normal service and assistance. The impact of shift work is replete with tales and factual evidence of an increased personnel error rate; disorders, both personal and family, and of course, increased accident events. In recent memory, the Three Mile Island Nuclear Plant incident, Union Carbide`s explosion in Bhopal, and the Chernobyl Nuclear Plant catastrophe all occurred during off-normal working hours. Yet management overall has done little to correct the production-driven twelve hour, seven day week shift mentality of the nineteenth century. Most schedules in use today are nothing more than cosmetic variations of the old production schedules. This could be driven by a management consideration of the worker`s response to change coupled with a reluctant buy-in of responsibility for the effects of change. Florida Power Corporation has developed for its nuclear security force, a unique work schedule which attempts to employ the sound principles of circadian rhythms coupled with a comprehensive training program to counter the problems associated with shift work. The results over the last four years have seen a marked reduction in the generic problems of personnel errors, absenteeism, unscheduled overtime and turnover rates. Utilization and understanding of this scheduling process for rotational shift work needs to be assessed to determine if the benefits are site specific or provide an expected response to the problems of shift work.

  8. Gear shift controller for automatic transmission

    SciTech Connect

    Nishikawa, M.; Sakai, S.; Sakurai, T.

    1987-01-20

    A gear shift controller is described for an automatic transmission having a gear shift, comprising: a hydraulic torque converter; a gear change group, having a plurality of gears, each gear providing a different transmission ratio for the transmission of power from the hydraulic torque converter to the output of the transmission, each of the gears comprising a gear train; a one-way clutch interposed in at least one of the gear trains; a plurality of clutch means operatively connected with the gear trains for actuating each of the gear trains selectively; a gear change determination circuit operatively connected with the clutch means to control the operation of each of the clutch means according to a predetermined gear shifting program for engaging a gear train selected by the program; a coasting detection circuit for detecting a car in the coasting state; a gear shift limiting circuit, operatively connected with the gear change determination circuit and with the coasting detection circuit. The circuit is for actuating only the gear train in which the one-way clutch is interposed immediately, regardless of the selected gear train and of the operation of the gear change determination circuit, when the coasting detection circuit has determined the car to be coasting; and an operation transfer control system including a brake operation detecting means and a mode selector switch means for transferring the operation of the gear shift limiting circuit. The operation transfer control system is adapted to stop, upon detection of one of the brake operation and a reset state of the mode selector switch, the operation of the gear shift limiting circuit and to place the plurality of clutch means under the control of the gear change determination circuit.

  9. Nonphotic phase shifting in hamster clock mutants.

    PubMed

    Mrosovsky, N; Salmon, P A; Menaker, M; Ralph, M R

    1992-01-01

    Golden hamsters with the tau mutation were kept in the dark and induced to become active through confinement to a novel running wheel for 3 hr. The response of the mutants to this nonphotic phase-shifting stimulus differed from that of wild-type hamsters. The mutants showed larger phase shifts, and their phase response curves differed in shape, with an advance portion at about circadian time 24, a phase at which wild types show delays. The results establish that the tau mutation, in addition to its already known effects, alters the response of the circadian system to nonphotic events.

  10. Isotope shifts in methane near 6000/cm

    NASA Technical Reports Server (NTRS)

    Fox, K.; Halsey, G. W.; Jennings, D. E.

    1976-01-01

    Isotope shifts for cleanly resolved vibrational-rotational absorption lines of CH4-12 and CH4-13 were measured by a 5-m focal length Littrow spectrometer in the 6000/cm range. The methane isotopes were held in separate absorption cells: 20 torr of CH4-13 in a 1-m cell, and 5 torr of CH4-12 in a White cell of 4-m optical path length. Measured shifts for the cleanly resolved singlets R(0), R(1), Q(1) and P(1) are summarized in tabular form.

  11. Phase-shifting structures for isolated features

    NASA Astrophysics Data System (ADS)

    Garofalo, Joseph G.; Kostelak, Robert L.; Yang, Tungsheng

    1991-07-01

    The technique for improving optical projection-system resolution by phase-shifting alternate apertures of a periodic grating was introduced in 1982. This halves the frequency content of the image passing through the optics and should therefore double the effective resolution of such patterns. Unfortunately, as feature separation increases, the efficacy of this method diminishes. Previous work applying a similar approach to isolated features involves introducing minute, non-printable, phase-shifted assist slots around the desired feature. The diffraction side-lobes of these slots constructively interfere with the center lobe of the primary aperture. The resolution enhancement afforded be this technique is limited by the printability of the assist slots. This restraint also dictates 1X-size reticle feature dimensions and the employment of high contrast imaging resists. A new approach entails significantly oversizing the desired feature and introducing a phase-shifting region around the periphery. This type of structure affords substantial focus-exposure improvements and may either be fabricated in a single-level, self-aligned scheme or by a two-level exposure with conventional e-beam tools since the phase-shifting regions are on the order of 1 micrometers (reticle dimensions). Extensive modeling of this structure for isolated contact holes and spaces explores the myriad of trade- offs involved in an optimum design. Mask-fabrication tolerances, such as phase-shift uniformity, are also investigated. It is shown that the focus-exposure window enlarges as the overall structure dimensions increase. The degree of enhancement must therefore by weighed against packing density restrictions. Also, the structure suffers, to some degree, from the effect of side-lobes. However, for a given side-lobe intensity, this technique yields enhancements superior to the assist-slot approach. As is typical of phase-shifted systems, performance is improved as the partial coherence ((sigma

  12. What are 12-hour shifts good for?

    PubMed

    In the UK many hospitals use 12-hour shifts, believing it to be a cost-efficient means of providing 24-hour nursing care on wards. While healthcare organisations need to find ways to deliver nursing care around the clock and efficiency is a key consideration, nurse leaders have raised concerns about ' whether nurses can function effectively and safely when working long hours (Calkin, 2012; Rogers et al, 2004). In this Policy Plus, we focus specifically on what is known about the impact of shift length on patient safety, employee health and quality of care.

  13. Quadrature-Quadrature Phase Shift Keying.

    DTIC Science & Technology

    1986-09-01

    Q 2PSK for the data stream a (t) in Figure 3.1 ................................................ 27 3.3. Spectral densities of OQPSK , MSK and Q’PSK...Offset Quadrature Phase Shift Keying ( OQPSK ). Minimum Shift Keying ( vISK ), Quadrature Overlapped taised Cosine ( QOW signalling scheme, Tamed Frequency...orthogonal; hence the name %liniliur ’t Keving (AfSK) . The baseband power spectral densities S~.f) a1nd( o’,,, r QPSlK (or OQPSk . and NLSK are given by

  14. Shared Information Framework and Technology (SHIFT) Handbook

    DTIC Science & Technology

    2009-02-01

    Preferences‖ and click it . 29 The following page will show up: 4. Click the ―create a personal page‖ link. On following page the user...the ―Space‖ you want to view in the space listing and click it . You will end up to a folder view of the chosen space. For instance, a view of MNE5...tools) in SHIFT portal. Some of the items on the list are in form of an active link. If a link is clicked it will automatically open the SHIFT tool

  15. Shift-and-add for astronomical imaging

    NASA Technical Reports Server (NTRS)

    Ribak, Erez; Hege, E. Keith; Strobel, Nicolas V.; Christou, Julian C.

    1989-01-01

    Diffraction-limited astronomical images have been obtained utilizing a variant of the shift-and-add method. It is shown that the matched filter approach for extending the weighted shift-and-add method reduces specklegrams from extended objects and from an object dominated by photon noise. The method is aberration-insensitive and yields very high dynamic range results. The iterative method for arriving at the matched filter does not automatically converge in the case of photon-noisy specklegrams for objects with more than one maximum.

  16. Progress in speckle-shift strain measurement

    NASA Technical Reports Server (NTRS)

    Lant, Christian T.; Barranger, John P.; Oberle, Lawrence G.; Greer, Lawrence C., III

    1991-01-01

    The Instrumentation and Control Technology Division of the Lewis Research Center has been developing an in-house capability to make one dimensional and two dimensional optical strain measurements on high temperature test specimens. The measurements are based on a two-beam speckle-shift technique. The development of composite materials for use in high temperature applications is generating interest in using the speckle-shift technique to measure strains on small diameter fibers and wires of various compositions. The results of preliminary speckle correlation tests on wire and fiber specimens are covered, and the advanced system currently under development is described.

  17. Shifted Fresnel diffraction for computational holography.

    PubMed

    Muffoletto, Richard P; Tyler, John M; Tohline, Joel E

    2007-04-30

    Fourier-based approaches to calculate the Fresnel diffraction of light provide one of the most efficient algorithms for holographic computations because this permits the use of the fast Fourier transform (FFT). This research overcomes the limitations on sampling imposed by Fourier-based algorithms by the development of a fast shifted Fresnel transform. This fast shifted Fresnel transform is used to develop a tiling approach to hologram construction and reconstruction, which computes the Fresnel propagation of light between parallel planes having different resolutions.

  18. Lamb shift in the muonic helium ion

    SciTech Connect

    Martynenko, A. P.

    2007-07-15

    The Lamb shift (2P{sub 1/2}-2S{sub 1/2}) in the muonic helium ion ({mu}-{sub 2}{sup 4}He){sup +} is calculated with the account of contributions of orders {alpha}{sup 3}, {alpha}{sup 4}, {alpha}{sup 5}, and {alpha}{sup 6}. Special attention is given to corrections of the electron vacuum polarization, the nuclear structure, and recoil effects. The obtained numerical value of the Lamb shift 1381.72 meV can be considered as a reliable estimate for the comparison with experimental data.

  19. Lamb shift in the muonic deuterium atom

    SciTech Connect

    Krutov, A. A.; Martynenko, A. P.

    2011-11-15

    We present an investigation of the Lamb shift (2P{sub 1/2}-2S{sub 1/2}) in the muonic deuterium ({mu}D) atom using the three-dimensional quasipotential method in quantum electrodynamics. The vacuum polarization, nuclear-structure, and recoil effects are calculated with the account of contributions of orders {alpha}{sup 3}, {alpha}{sup 4}, {alpha}{sup 5}, and {alpha}{sup 6}. The results are compared with earlier performed calculations. The obtained numerical value of the Lamb shift at 202.4139 meV can be considered a reliable estimate for comparison with forthcoming experimental data.

  20. The Lamb shift in the hydrogen atom: Shift of s states

    SciTech Connect

    Karshenboim, S.G.

    1995-02-01

    A theoretical expression for the difference of the Lamb shifts of the 1s{sub 1/2} and 2s{sub 1/2} levels is obtained. The Lamb shift of the ground state in the hydrogen atom is recalculated and found to be 8172.898(26) MHz. 22 refs.

  1. Work shift duration: a review comparing eight hour and 12 hour shift systems

    PubMed Central

    Smith, L.; Folkard, S.; Tucker, P.; Macdonald, I.

    1998-01-01

    OBJECTIVES: Shiftwork is now a major feature of working life across a broad range of industries. The features of the shift systems operated can impact on the wellbeing, performance, and sleep of shiftworkers. This paper reviews the current state of knowledge on one major characteristic of shift rotas-namely, shift duration. Evidence comparing the relative effects of eight hour and 12 hour shifts on fatigue and job performance, safety, sleep, and physical and psychological health are considered. At the organisational level, factors such as the mode of system implementation, attitudes towards shift rotas, sickness absence and turnover, overtime, and moonlighting are discussed. METHODS: Manual and electronic searches of the shiftwork research literature were conducted to obtain information on comparisons between eight hour and 12 hour shifts. RESULTS: The research findings are largely equivocal. The bulk of the evidence suggests few differences between eight and 12 hour shifts in the way they affect people. There may even be advantages to 12 hour shifts in terms of lower stress levels, better physical and psychological wellbeing, improved durations and quality of off duty sleep as well as improvements in family relations. On the negative side, the main concerns are fatigue and safety. It is noted that a 12 hour shift does not equate with being active for only 12 hours. CONCLUSIONS: There can be considerable extension of the person's time awake either side of the shift. However, the effects of longer term exposure to extended work days have been relatively uncharted in any systematic way. Longitudinal comparative research into the chronic impact of the compressed working week is needed.   PMID:9624275

  2. Implications of Shifting Technology in Education

    ERIC Educational Resources Information Center

    Holland, Janet; Holland, John

    2014-01-01

    This article examines the implications of shifting technology trends by looking at what we've lost or are losing, where we are, and where we need to go for making the needed transitions in knowledge and skills. Areas of growth within new media and the tech industry are good indicators of our growing interests in mobility, improved quality,…

  3. Tilting and shifting modes in a spheromak

    SciTech Connect

    Jardin, S.C.; Chance, M.S.; Dewar, R.L.; Grimm, R.C.; Monticello, D.A.

    1981-04-01

    In the absence of a conducting wall, typical spheromak plasmas are unstable to tilting and/or shifting modes. The effects of the cross-sectional shape, aspect ratio, and the location of a conducting wall on the stability of these modes are investigated.

  4. Ambiguity Produces Attention Shifts in Category Learning

    ERIC Educational Resources Information Center

    Vadillo, Miguel A.; Orgaz, Cristina; Luque, David; Nelson, James Byron

    2016-01-01

    It has been suggested that people and nonhuman animals protect their knowledge from interference by shifting attention toward the context when presented with information that contradicts their previous beliefs. Despite that suggestion, no studies have directly measured changes in attention while participants are exposed to an interference…

  5. Shifting Context: A Better Approach to Training?

    ERIC Educational Resources Information Center

    Lefkoe, Morty

    1985-01-01

    Context shifting is an approach to training that aims to transform the participants' point of view, allowing them to create a new context in which to perform their jobs, a new way of defining their roles that motivates them to exhibit skills and use information. (SK)

  6. Blackbody radiation shifts in optical atomic clocks.

    PubMed

    Safronova, Marianna; Kozlov, Mikhail; Clark, Charles

    2012-03-01

    A review of recent theoretical calculations of blackbody radiation (BBR) shifts in optical atomic clocks is presented. We summarize previous results for monovalent ions that were obtained by a relativistic all-order single-double method, where all single and double excitations of the Dirac- Fock wave function are included to all orders of perturbation theory. A recently developed method for accurate calculations of BBR shifts in divalent atoms is then presented. This approach combines the relativistic all-order method and the configuration interaction method, which provides for accurate treatment of correlation corrections in atoms with two valence electrons. Calculations of the BBR shifts in B+, Al+, and In+ have enabled us to reduce the present fractional uncertainties in the frequencies of their clock transitions as measured at room temperature: to 4 × 10-19 for Al+ and 10-18 for B+ and In+. These uncertainties approach recent estimates of the limits of precision of currently proposed optical atomic clocks. We discuss directions of future theoretical developments for reducing clock uncertainties resulting from blackbody radiation shifts.

  7. Paradigmatic Shift or Tinkering at the Edges?

    ERIC Educational Resources Information Center

    Sutherland, Margaret

    2012-01-01

    In their target paper, "Towards a systemic theory of gifted education," A. Ziegler and S. N. Phillipson present a long awaited call for a paradigmatic shift in thinking within the field of gifted education. The paper considers how educators and researchers within the field could bring about such a change. They challenge the prevailing…

  8. Heart-rate pulse-shift detector

    NASA Technical Reports Server (NTRS)

    Anderson, M.

    1974-01-01

    Detector circuit accurately separates and counts phase-shift pulses over wide range of basic pulse-rate frequency, and also provides reasonable representation of full repetitive EKG waveform. Single telemeter implanted in small animal monitors not only body temperature but also animal movement and heart rate.

  9. Deindustrialization and the Shift to Services.

    ERIC Educational Resources Information Center

    Kutscher, Ronald E.; Personick, Valerie A.

    1986-01-01

    Bureau of Labor Statistics data show the industrial sector as a whole in healthy shape, but a few manufacturing industries in deep trouble. These industries include tobacco manufacturers, iron and steel foundries, leather products, and steel manufacturers. Also examines shifts in employment and output, job quality, and outlook for the future. (CT)

  10. Hispanics Find Jobs that Shift Migration

    ERIC Educational Resources Information Center

    Gilroy, Marilyn

    2007-01-01

    Economic opportunity, the force that has driven population shifts for years, is changing the face of migration as Hispanics move into parts of the nation beyond border states and traditional ports of entry. North Carolina, Tennessee, Georgia, and Indiana are experiencing a steady growth in Hispanic population. In addition, West Virginia, Ohio, and…

  11. Gender shifts in equine veterinary practice.

    PubMed

    Heinke, Marsha L; Sabo, Carol

    2009-12-01

    This article examines gender shifts in equine veterinary practice. A significant gender compensation gap continues across the spectrum of professions, including veterinary medicine. Many styles of practice serve the disparate and sometimes conflicting goals of financial well-being, patient care, and physical family presence.

  12. Attention-Shifting in Frederick Douglass.

    ERIC Educational Resources Information Center

    Leroux, Neil R.

    A study explored rhetorical strategies and dynamics within a single speech delivered by Frederick Douglass on July 5, l852 in Rochester, New York, which was considered by speaker and audience to be an Independence Day speech. An examination of the text suggests that Douglass embarked on a strategy of attention-shifting--turning the attention of…

  13. Has the Education Paradigm Begun to Shift?

    ERIC Educational Resources Information Center

    Chadwick, Clifton B.

    2014-01-01

    The author reviews various elements of what may be considered as evidence that the long-awaited shift in the education paradigm is actually happening. Concepts like student-centered learning, attainment-based evaluation, knowledge-based constructivism, and effort-based intelligence are growing, are being more widely recognized as important, and…

  14. A Paradigm Shift to Improve Academic Performance

    ERIC Educational Resources Information Center

    Rulloda, Rudolfo B.

    2009-01-01

    A shift to computer skills for improving academic performances was investigated. The No Child Left Behind Act of 2001 increased the amount of high school dropouts after the Act was enacted. At-risk students were included in this research study. Several models described using teachers for core subjects and mentors to built citizenship skills, along…

  15. The Phase Shift in the Jumping Ring

    ERIC Educational Resources Information Center

    Jeffery, Rondo N.; Amiri, Farhang

    2008-01-01

    The popular physics demonstration experiment known as Thomson's Jumping Ring (JR) has been variously explained as a simple example of Lenz's law, or as the result of a phase shift of the ring current relative to the induced emf. The failure of the first-quadrant Lenz's law explanation is shown by the time the ring takes to jump and by levitation.…

  16. Design principles of shift current photovoltaics

    NASA Astrophysics Data System (ADS)

    Cook, Ashley; Fregoso, Benjamin; de Juan, Fernando; Moore, Joel

    While the basic principles and limitations of conventional solar cells are well understood, relatively little attention has gone toward evaluating and maximizing the potential efficiency of photovoltaic devices based on shift currents. In this work, a sum rule approach is introduced and used to outline design principles for optimizing shift currents for photon energies near the band gap, which depend on wavefunctions via Berry connections as well as standard band structure. Using these we identify two new classes of shift current photovoltaics, ferroelectric polymer films and orthorhombic monochalcogenides, both of which exhibit peak photoresponsivities larger than predictions for previously-known photovoltaics of this type. Using physically-motivated tight-binding models, the full frequency dependent response of these materials is obtained. Exploring the phase space of these models, we find photoresponsivities that can exceed 100 mA/W. These results show that considering the microscopic origin of shift current via effective models allows one to improve the possible efficiency of devices using this mechanism and better grasp their potential to compete with conventional solar cells. This work was completed with the support of an NSERC Michael Smith Foreign Study Supplement.

  17. SHIFT: Shared Information Framework and Technology Concept

    DTIC Science & Technology

    2009-02-01

    awareness tools ................................................................29 4.5.1. Map interface and GIS services...information). The information in the SHIFT situational picture can also be exported to other services. 4.5.1. Map interface and GIS services...drawings. A metadata about map quality is essential information and it can be presented as well. Geographic Information System ( GIS ) services offered by

  18. RQL Fuel Shifting Sector Rig Test

    NASA Technical Reports Server (NTRS)

    Holdeman, James D. (Technical Monitor); Haid, Daniel A.; Koopman, Frederick S.; Peschke, William O. T.; Siskind, Kenneth S.

    2004-01-01

    The low emissions potential of a Rich-Quench-Lean (RQL) combustor for use in the HIgh Speed Civil transport (HSCT) application was evaluated as part of the NASA Critical Propulsion Components (CPC) Program. Fuel shifting as an approach to combustor control was evaluated in a multiple bank RQL combustor, utilizing reduced scale quench technology implemented in a convoluted linear with quench plate concept.

  19. Core level shifts of intercalated graphene

    NASA Astrophysics Data System (ADS)

    Schröder, Ulrike A.; Petrović, Marin; Gerber, Timm; Martínez-Galera, Antonio J.; Grånäs, Elin; Arman, Mohammad A.; Herbig, Charlotte; Schnadt, Joachim; Kralj, Marko; Knudsen, Jan; Michely, Thomas

    2017-03-01

    Through intercalation of metals and gases the Dirac cone of graphene on Ir(111) can be shifted with respect to the Fermi level without becoming destroyed by strong hybridization. Here, we use x-ray photoelectron spectroscopy to measure the C 1s core level shift (CLS) of graphene in contact with a number of structurally well-defined intercalation layers (O, H, Eu, and Cs). By analysis of our own and additional literature data for decoupled graphene, the C 1s CLS is found to be a non-monotonic function of the doping level. For small doping levels the shifts are well described by a rigid band model. However, at larger doping levels, a second effect comes into play which is proportional to the transferred charge and counteracts the rigid band shift. Moreover, not only the position, but also the C 1s peak shape displays a unique evolution as a function of doping level. Our conclusions are supported by intercalation experiments with Li, with which, due to the absence of phase separation, the doping level of graphene can be continuously tuned.

  20. Majors' Shift to Natural Gas, The

    EIA Publications

    2001-01-01

    The Majors' Shift to Natural Gas investigates the factors that have guided the United States' major energy producers' growth in U.S. natural gas production relative to oil production. The analysis draws heavily on financial and operating data from the Energy Information Administration's Financial Reporting System (FRS)

  1. Survey Detects Shifting Priorities of School Boards

    ERIC Educational Resources Information Center

    Samuels, Christina A.

    2011-01-01

    The author reports the results of a nationwide survey of school board members which show a shift in focus toward student achievement and away from district-management issues known as the "killer B's": buses, buildings, books, budgets, and bonds. But today's school board members appear not to be as interested in issues that many policy observers…

  2. Shifting responsibilities for food safety in Europe: an introduction.

    PubMed

    Halkier, Bente; Holm, Lotte

    2006-09-01

    Following the BSE crisis in 1996, the European food sector underwent profound regulatory and institutional change. The present introductory article introduces, and sketches the background to, seven studies of the institutional reactions and initiatives that were part of, or prompted by, this reorganisation. The studies analyse the way in which the division of responsibilities for food safety has changed both across the EU as a whole and, more specifically, in six European countries. Prepared as part of the comparative research project, Trust in Food, the studies attempt to go beyond traditional policy network analysis and work on regulation. They ask which constellations of societal actors and logics are important in the shifting responsibilities of public and private actors; and they treat this as an empirical question. It emerges that, at EU level, the main strategy for restoring consumer confidence in food was to enhance the institutional independence, transparency and consumer agency. In the countries covered by the remaining six studies, by contrast, institutional reactions in the food sector varied depending on the particular configurations of state, market and civil society.

  3. Noncanonical reactions of flavoenzymes.

    PubMed

    Sobrado, Pablo

    2012-11-05

    Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a "molecular scaffold" in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  4. Reaction spreading on graphs.

    PubMed

    Burioni, Raffaella; Chibbaro, Sergio; Vergni, Davide; Vulpiani, Angelo

    2012-11-01

    We study reaction-diffusion processes on graphs through an extension of the standard reaction-diffusion equation starting from first principles. We focus on reaction spreading, i.e., on the time evolution of the reaction product M(t). At variance with pure diffusive processes, characterized by the spectral dimension d{s}, the important quantity for reaction spreading is found to be the connectivity dimension d{l}. Numerical data, in agreement with analytical estimates based on the features of n independent random walkers on the graph, show that M(t)∼t{d{l}}. In the case of Erdös-Renyi random graphs, the reaction product is characterized by an exponential growth M(t)e{αt} with α proportional to ln(k), where (k) is the average degree of the graph.

  5. Systems analysis of electricity production from coal using fuel cells

    NASA Technical Reports Server (NTRS)

    Fleming, D. K.

    1983-01-01

    Gasifiers, heat transfer, gas stability, quench, water-gas shift reaction, reforming-methanation, other catalytic reactions, compressors and expanders, acid-gas removal, the fuel cell, and catalytic combustors are described. System pressure drops, efficiency of rotating power equipment, heat exchangers, chemical reactions, steam systems, and the fuel cell subsystems are discussed.

  6. Photoneutron Reactions in Nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Utsunomiya, Hiroaki

    Photoneutron reactions are discussed in the context of nucleosynthesis with emphasis on a unified understanding of (γ, n) and (n, γ) reactions for heavy nuclei through the γ-ray strength function and a revisit to explosive nucleosynthesis of 9Be through the reciprocity theorem. The role of photonuclear reactions in nucleosynthesis is supplemented by the photonuclear data project (IAEA-CRP F42032) and will be strengthened in the Extreme Light Infrastructure-Nuclear Physics (ELI-NP) in the future.

  7. Nuclear reaction studies

    SciTech Connect

    Alexander, J.M.; Lacey, R.A.

    1994-11-01

    Research focused on the statistical and dynamical properties of ``hot`` nuclei formed in symmetric heavy-ion reactions. Theses included ``flow`` measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study {sup 40}Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs.

  8. Sleep Loss and Fatigue in Shift Work and Shift Work Disorder

    PubMed Central

    Åkerstedt, Torbjörn; Wright, Kenneth P.

    2010-01-01

    Shift work is highly prevalent in industrialized societies (>20%) but, when it includes night work, it has pronounced negative effects on sleep, subjective and physiological sleepiness, performance, accident risk, as well as on health outcomes such as cardiovascular disease and certain forms of cancer. The reason is the conflict between the day oriented circadian physiology and the requirement for work and sleep at the “wrong” biological time of day. Other factors that negatively impact work shift sleepiness and accident risk include long duration shifts greater than 12 hours and individual vulnerability for phase intolerance that may lead to a diagnosis of shift work disorder; i.e., those shift workers with the greatest sleepiness and performance impairment during the biological night and insomnia during the biological day. Whereas some countermeasures may be used to ameliorate the negative impact of shift work on nighttime sleepiness and daytime insomnia (combined countermeasures may be the best available), there seems at present to be no way to eliminate most of the negative effects of shift work on human physiology and cognition. PMID:20640236

  9. Sleeve reaction chamber system

    DOEpatents

    Northrup, M. Allen; Beeman, Barton V.; Benett, William J.; Hadley, Dean R.; Landre, Phoebe; Lehew, Stacy L.; Krulevitch, Peter A.

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  10. Observation of hydroxymethyl hydroperoxide in a reaction system containing CH2OO and water vapor through pure rotational spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakajima, Masakazu; Endo, Yasuki

    2015-10-01

    Pure rotational transitions of hydroxymethyl hydroperoxide (HMHP) were observed in the discharged plasma of a CH2I2/O2/water gas mixture, where the water complex with the simplest Criegee intermediate CH2OO has been identified [M. Nakajima and Y. Endo, J. Chem. Phys. 140, 134302 (2014)]. Isotope experiments using heavy water support that the currently observed HMHP molecule was produced by the reaction of CH2OO with water vapor. The observed species was identified as the most stable conformer with the help of quantum chemical calculations. We also clarified that productions of formic acid and dioxirane are promoted by the existence of water vapor in the discharged reaction system.

  11. Moving attention - Evidence for time-invariant shifts of visual selective attention

    NASA Technical Reports Server (NTRS)

    Remington, R.; Pierce, L.

    1984-01-01

    Two experiments measured the time to shift spatial selective attention across the visual field to targets 2 or 10 deg from central fixation. A central arrow cued the most likely target location. The direction of attention was inferred from reaction times to expected, unexpected, and neutral locations. The development of a spatial attentional set with time was examined by presenting target probes at varying times after the cue. There were no effects of distance on the time course of the attentional set. Reaction times for far locations were slower than for near, but the effects of attention were evident by 150 msec in both cases. Spatial attention does not shift with a characteristic, fixed velocity. Rather, velocity is proportional to distance, resulting in a movement time that is invariant over the distances tested.

  12. A small high sensitivity neutron detector using a wavelength shifting fiber.

    PubMed

    Yagi, T; Misawa, T; Pyeon, C H; Shiroya, S

    2011-01-01

    A small neutron detector using an optical fiber was previously developed for reaction rate measurements at research reactors and accelerator facilities. This detector can be inserted into narrow spaces and its spatial resolution is less than 1mm; however, its neutron sensitivity is low because of the small size of its detector. The purpose of this study is to develop a new optical fiber detector with high neutron sensitivity by using a wavelength shifting fiber. Through the measurement of the reaction rate distribution in a reactor core, we found that it is possible to increase the effective length of the detector, resulting in increased neutron sensitivity compared with a conventional optical fiber detector. Additionally, using a longer wavelength shifting fiber, the sensitivity can be increased until it is as large as that of a typical small BF(3) proportional counter, which means that this detector can be used for even low neutron flux fields.

  13. Robust phase-shift estimation method for statistical generalized phase-shifting digital holography.

    PubMed

    Yoshikawa, Nobukazu; Shiratori, Takaaki; Kajihara, Kazuki

    2014-06-16

    We propose a robust phase-shift estimation method for statistical generalized phase-shifting digital holography using a slightly off-axis optical configuration. The phase randomness condition in the Fresnel diffraction field of an object can be sufficiently established by the linear phase factor of the oblique incident reference wave. Signed phase-shift values can be estimated with a statistical approach regardless of the statistical properties of the Fresnel diffraction field of the object. We present computer simulations and optical experiments to verify the proposed method.

  14. Doppler-shift attenuation method lifetime measurements of low-lying states in 111In

    NASA Astrophysics Data System (ADS)

    Bucurescu, D.; Căta-Danil, I.; Ilaş, G.; Ivaşcu, M.; Mărginean, N.; Stroe, L.; Ur, C. A.

    1996-11-01

    The lifetimes of nine low-lying excited states in 111In have been measured with the Doppler-shift attenuation method in the 111Cd(p,nγ) reaction. A comparison of experimental quantities with predictions based on the interacting boson-fermion model unravels the states due to the coupling of a g9/2 proton hole to the quadrupole vibrations of the core.

  15. Two-step phase-shifting SPIDER

    PubMed Central

    Zheng, Shuiqin; Cai, Yi; Pan, Xinjian; Zeng, Xuanke; Li, Jingzhen; Li, Ying; Zhu, Tianlong; Lin, Qinggang; Xu, Shixiang

    2016-01-01

    Comprehensive characterization of ultrafast optical field is critical for ultrashort pulse generation and its application. This paper combines two-step phase-shifting (TSPS) into the spectral phase interferometry for direct electric-field reconstruction (SPIDER) to improve the reconstruction of ultrafast optical-fields. This novel SPIDER can remove experimentally the dc portion occurring in traditional SPIDER method by recording two spectral interferograms with π phase-shifting. As a result, the reconstructed results are much less disturbed by the time delay between the test pulse replicas and the temporal widths of the filter window, thus more reliable. What is more, this SPIDER can work efficiently even the time delay is so small or the measured bandwidth is so narrow that strong overlap happens between the dc and ac portions, which allows it to be able to characterize the test pulses with complicated temporal/spectral structures or narrow bandwidths. PMID:27666528

  16. Shape-shifting colloids via stimulated dewetting

    PubMed Central

    Youssef, Mena; Hueckel, Theodore; Yi, Gi-Ra; Sacanna, Stefano

    2016-01-01

    The ability to reconfigure elementary building blocks from one structure to another is key to many biological systems. Bringing the intrinsic adaptability of biological systems to traditional synthetic materials is currently one of the biggest scientific challenges in material engineering. Here we introduce a new design concept for the experimental realization of self-assembling systems with built-in shape-shifting elements. We demonstrate that dewetting forces between an oil phase and solid colloidal substrates can be exploited to engineer shape-shifting particles whose geometry can be changed on demand by a chemical or optical signal. We find this approach to be quite general and applicable to a broad spectrum of materials, including polymers, semiconductors and magnetic materials. This synthetic methodology can be further adopted as a new experimental platform for designing and rapidly prototyping functional colloids, such as reconfigurable micro swimmers, colloidal surfactants and switchable building blocks for self-assembly. PMID:27426418

  17. Two-step phase-shifting SPIDER

    NASA Astrophysics Data System (ADS)

    Zheng, Shuiqin; Cai, Yi; Pan, Xinjian; Zeng, Xuanke; Li, Jingzhen; Li, Ying; Zhu, Tianlong; Lin, Qinggang; Xu, Shixiang

    2016-09-01

    Comprehensive characterization of ultrafast optical field is critical for ultrashort pulse generation and its application. This paper combines two-step phase-shifting (TSPS) into the spectral phase interferometry for direct electric-field reconstruction (SPIDER) to improve the reconstruction of ultrafast optical-fields. This novel SPIDER can remove experimentally the dc portion occurring in traditional SPIDER method by recording two spectral interferograms with π phase-shifting. As a result, the reconstructed results are much less disturbed by the time delay between the test pulse replicas and the temporal widths of the filter window, thus more reliable. What is more, this SPIDER can work efficiently even the time delay is so small or the measured bandwidth is so narrow that strong overlap happens between the dc and ac portions, which allows it to be able to characterize the test pulses with complicated temporal/spectral structures or narrow bandwidths.

  18. Phase-shifting color digital holography.

    PubMed

    Yamaguchi, Ichirou; Matsumura, Tatsuki; Kato, Jun-Ichi

    2002-07-01

    Digital holography with a three-wavelength laser and a color CCD has been demonstrated. With the phase shifting of the reference beam, in-line holograms for three wavelengths are recorded simultaneously for derivation of the complex amplitude at each wavelength, and then the three monochromatic images are reconstructed and combined into full-color images in the computer. Laser power variation for wavelengths can be compensated for in the reconstruction process. We have compared the images reconstructed by two algorithms using a single Fourier transformation and a convolution with each other by both experiments and numerical simulations. Phase-shifting errors arising at two of the three wavelengths have proved not to cause serious deterioration of the reconstructed images.

  19. Phase-Shifting Zernike Interferometer Wavefront Sensor

    NASA Technical Reports Server (NTRS)

    Wallace, J. Kent; Rao, Shanti; Jensen-Clemb, Rebecca M.; Serabyn, Gene

    2011-01-01

    The canonical Zernike phase-contrast technique1,2,3,4 transforms a phase object in one plane into an intensity object in the conjugate plane. This is done by applying a static pi/2 phase shift to the central core (approx. lambda/D) of the PSF which is intermediate between the input and output planes. Here we present a new architecture for this sensor. First, the optical system is simple and all reflective. Second, the phase shift in the central core of the PSF is dynamic and or arbitrary size. This common-path, all-reflective design makes it minimally sensitive to vibration, polarization and wavelength. We review the theory of operation, describe the optical system, summarize numerical simulations and sensitivities and review results from a laboratory demonstration of this novel instrument

  20. Phase-Shifting Zernike Interferometer Wavefront Sensor

    NASA Technical Reports Server (NTRS)

    Wallace, J. Kent; Rao, Shanti; Jensen-Clem, Rebecca M.

    2011-01-01

    The canonical Zernike phase-contrast technique transforms a phase object in one plane into an intensity object in the conjugate plane. This is done by applying a static pi/2 phase shift to the central core (approx. lambda/diameter) of the PSF which is intermediate between the input and output plane. Here we present a new architecture for this sensor. First, the optical system is simple and all reflective, and second the phase shift in the central core of the PSF is dynamic and can be made arbitrarily large. This common-path, all-reflective design makes it minimally sensitive to vibration, polarization and wavelength. We review the theory of operation, describe the optical system, summarize numerical simulations and sensitivities and review results from a laboratory demonstration of this novel instrument.

  1. Forensic voice comparison and the paradigm shift.

    PubMed

    Morrison, Geoffrey Stewart

    2009-12-01

    We are in the midst of a paradigm shift in the forensic comparison sciences. The new paradigm can be characterised as quantitative data-based implementation of the likelihood-ratio framework with quantitative evaluation of the reliability of results. The new paradigm was widely adopted for DNA profile comparison in the 1990s, and is gradually spreading to other branches of forensic science, including forensic voice comparison. The present paper first describes the new paradigm, then describes the history of its adoption for forensic voice comparison over approximately the last decade. The paradigm shift is incomplete and those working in the new paradigm still represent a minority within the forensic-voice-comparison community.

  2. Eliminating light shifts for single atom trapping

    NASA Astrophysics Data System (ADS)

    Hutzler, Nicholas R.; Liu, Lee R.; Yu, Yichao; Ni, Kang-Kuen

    2017-02-01

    Microscopically controlled neutral atoms in optical tweezers and lattices have led to exciting advances in the study of quantum information and quantum many-body systems. The light shifts of atomic levels from the trapping potential in these systems can result in detrimental effects such as fluctuating dipole force heating, inhomogeneous detunings, and inhibition of laser cooling, which limits the atomic species that can be manipulated. In particular, these light shifts can be large enough to prevent loading into optical tweezers directly from a magneto-optical trap. We implement a general solution to these limitations by loading, as well as cooling and imaging the atoms with temporally alternating beams, and present an analysis of the role of heating and required cooling for single atom tweezer loading. Because this technique does not depend on any specific spectral properties, it should enable the optical tweezer platform to be extended to nearly any atomic or molecular species that can be laser cooled and optically trapped.

  3. Protein structure determination from NMR chemical shifts.

    PubMed

    Cavalli, Andrea; Salvatella, Xavier; Dobson, Christopher M; Vendruscolo, Michele

    2007-06-05

    NMR spectroscopy plays a major role in the determination of the structures and dynamics of proteins and other biological macromolecules. Chemical shifts are the most readily and accurately measurable NMR parameters, and they reflect with great specificity the conformations of native and nonnative states of proteins. We show, using 11 examples of proteins representative of the major structural classes and containing up to 123 residues, that it is possible to use chemical shifts as structural restraints in combination with a conventional molecular mechanics force field to determine the conformations of proteins at a resolution of 2 angstroms or better. This strategy should be widely applicable and, subject to further development, will enable quantitative structural analysis to be carried out to address a range of complex biological problems not accessible to current structural techniques.

  4. Is the Lamb shift chemically significant?

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.; Bauschlicher, Charles W., Jr.; Schwenke, David W.; Pyykko, Pekka; Arnold, James (Technical Monitor)

    2001-01-01

    The contribution of the Lamb shift to the atomization energies of some prototype molecules, BF3, AlF3, and GaF3, is estimated by a perturbation procedure. It is found to be in the range of 3-5% of the one-electron scalar relativistic contribution to the atomization energy. The maximum absolute value is 0.2 kcal/mol for GaF3. These sample calculations indicate that the Lamb shift is probably small enough to be neglected for energetics of molecules containing light atoms if the target accuracy is 1 kcal/mol, but for higher accuracy calculations and for molecules containing heavy elements it must be considered.

  5. Shape-shifting colloids via stimulated dewetting

    NASA Astrophysics Data System (ADS)

    Youssef, Mena; Hueckel, Theodore; Yi, Gi-Ra; Sacanna, Stefano

    2016-07-01

    The ability to reconfigure elementary building blocks from one structure to another is key to many biological systems. Bringing the intrinsic adaptability of biological systems to traditional synthetic materials is currently one of the biggest scientific challenges in material engineering. Here we introduce a new design concept for the experimental realization of self-assembling systems with built-in shape-shifting elements. We demonstrate that dewetting forces between an oil phase and solid colloidal substrates can be exploited to engineer shape-shifting particles whose geometry can be changed on demand by a chemical or optical signal. We find this approach to be quite general and applicable to a broad spectrum of materials, including polymers, semiconductors and magnetic materials. This synthetic methodology can be further adopted as a new experimental platform for designing and rapidly prototyping functional colloids, such as reconfigurable micro swimmers, colloidal surfactants and switchable building blocks for self-assembly.

  6. Oscillating Reactions: Two Analogies

    ERIC Educational Resources Information Center

    Petruševski, Vladimir M.; Stojanovska, Marina I.; Šoptrajanov, Bojan T.

    2007-01-01

    Oscillating chemical reactions are truly spectacular phenomena, and demonstrations are always appreciated by the class. However, explaining such reactions to high school or first-year university students is problematic, because it may seem that no acceptable explanation is possible unless the students have profound knowledge of both physical…

  7. Degradations and Rearrangement Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Jianbo

    This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

  8. Photoinduced Multicomponent Reactions.

    PubMed

    Garbarino, Silvia; Ravelli, Davide; Protti, Stefano; Basso, Andrea

    2016-12-12

    The combination of multicomponent approaches with light-driven processes opens up new scenarios in the area of synthetic organic chemistry, where the need for sustainable, atom- and energy-efficient reactions is increasingly urgent. Photoinduced multicomponent reactions are still in their infancy, but significant developments in this area are expected in the near future.

  9. Lithium Cell Reactions.

    DTIC Science & Technology

    1983-12-01

    SUPPLEMENTARY NOTES It. KEY WORDS (Continue on reverse .,ide if necessary and Identify by block number) Batteries Thionyl Chloride Batteries Lithium ...Batteries Lithium Cells Primary Batteries Thionyl Chloride Cells Non Rechargeable Batteries Electrochemical Reactions 20. ABSTRACT (Continue on reverse...INVESTIGATION OF CHEMICAL, ELECTROCHEMICAL AND PARASITIC REACTIONS IN LITHIUM - THIONYL CHLORIDE CELLS .......................................... 1 1.0 IN TRO D UC

  10. Clock Reaction: Outreach Attraction

    ERIC Educational Resources Information Center

    Carpenter, Yuen-ying; Phillips, Heather A.; Jakubinek, Michael B.

    2010-01-01

    Chemistry students are often introduced to the concept of reaction rates through demonstrations or laboratory activities involving the well-known iodine clock reaction. For example, a laboratory experiment involving thiosulfate as an iodine scavenger is part of the first-year general chemistry laboratory curriculum at Dalhousie University. With…

  11. Hydrogen evolution reaction catalyst

    DOEpatents

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  12. REUSABLE REACTION VESSEL

    DOEpatents

    Soine, T.S.

    1963-02-26

    This patent shows a reusable reaction vessel for such high temperature reactions as the reduction of actinide metal chlorides by calcium metal. The vessel consists of an outer metal shell, an inner container of refractory material such as sintered magnesia, and between these, a bed of loose refractory material impregnated with thermally conductive inorganic salts. (AEC)

  13. Reactions to Attitudinal Deviancy.

    ERIC Educational Resources Information Center

    Levine, John M.; Allen, Vernon L.

    This paper presents a critical review of empirical and theoretical treatments of group reaction to attitudinal deviancy. Inspired by Festinger's (1950) ideas on resolution of attitudinal discrepancies in groups, Schachter (1951) conducted an experiment that has greatly influenced subsequent research and theory concerning reaction to attitudinal…

  14. Applications of Reaction Rate

    ERIC Educational Resources Information Center

    Cunningham, Kevin

    2007-01-01

    This article presents an assignment in which students are to research and report on a chemical reaction whose increased or decreased rate is of practical importance. Specifically, students are asked to represent the reaction they have chosen with an acceptable chemical equation, identify a factor that influences its rate and explain how and why it…

  15. Chemical Reaction Problem Solving.

    ERIC Educational Resources Information Center

    Veal, William

    1999-01-01

    Discusses the role of chemical-equation problem solving in helping students predict reaction products. Methods for helping students learn this process must be taught to students and future teachers by using pedagogical skills within the content of chemistry. Emphasizes that solving chemical reactions should involve creative cognition where…

  16. Parallel phase-shifting color digital holography using two phase shifts.

    PubMed

    Kakue, Takashi; Tahara, Tatsuki; Ito, Kenichi; Shimozato, Yuki; Awatsuji, Yasuhiro; Nishio, Kenzo; Ura, Shogo; Kubota, Toshihiro; Matoba, Osamu

    2009-12-01

    We propose parallel phase-shifting color digital holography using two phase shifts. This technique enables the instantaneous acquisition of three-dimensional information of a moving color object. The interference fringe image that contains six holograms with two phase shifts for three wavelengths is recorded by a single shot exposure. Decreasing the degree of space-division multiplexing of these holograms makes it possible to suppress the degradation of the image quality owing to the aliasing caused by the multiplexing. Numerical simulation and preliminary experiments demonstrate the validity of the proposed technique; the reconstructed images of the proposed technique are clearer than those of the previously reported single-shot phase-shifting color digital holography that uses four phase steps.

  17. Written Language Shift among Norwegian Youth

    ERIC Educational Resources Information Center

    Özerk, Kamil; Todal, Jon

    2013-01-01

    In Norway there are two written Norwegian languages, Bokmâl and Nynorsk. Of these two written languages Bokmâl is being used by the majority of the people, and Bokmâl has the highest prestige in the society. This article is about the shift of written language from Nynorsk to Bokmâl among young people in a traditional Nynorsk district in the…

  18. Exploring Insight: Focus on Shifts of Attention

    ERIC Educational Resources Information Center

    Palatnik, Alik; Koichu, Boris

    2015-01-01

    The paper presents and analyses a sequence of events that preceded an insight solution to a challenging problem in the context of numerical sequences. A three­week long solution process by a pair of ninth­-grade students is analysed by means of the theory of shifts of attention. The goal for this article is to reveal the potential of this theory…

  19. The Shifting Balance of Military Power

    DTIC Science & Technology

    1970-09-30

    shifting of the strategic military balance against the United States and in favor of the Soviet Union .** These trends include: (i) the growing Soviet...deployment thereof; (iii) the possibility that present U.S. technological superiority will be lost to the Soviet Union ; (iv) the convincing evidence...that the Soviet Union seeks a preemptive first-strike capability; (v) the rapidly ex- panding Soviet naval capability; and (vi) the mounting hostility

  20. Digital phase-shifting point diffraction interferometer.

    PubMed

    Akondi, Vyas; Jewel, A R; Vohnsen, Brian

    2014-03-15

    A digital phase-shifting (PS) point diffraction interferometer is demonstrated with a transmitting liquid crystal spatial light modulator. This novel wavefront sensor allows tunability in the choice of pinhole size and eliminates the need for mechanically moving parts to achieve PS. It is shown that this wavefront sensor is capable of sensing Zernike aberrations introduced with a deformable mirror. The results obtained are compared with those of a commercial Hartmann-Shack wavefront sensor.

  1. Collisionally induced atomic clock shifts and correlations

    SciTech Connect

    Band, Y. B.; Osherov, I.

    2011-07-15

    We develop a formalism to incorporate exchange symmetry considerations into the calculation of collisional frequency shifts for atomic clocks using a density-matrix formalism. The formalism is developed for both fermionic and bosonic atomic clocks. Numerical results for a finite-temperature {sup 87}Sr {sup 1}S{sub 0} (F=9/2) atomic clock in a magic wavelength optical lattice are presented.

  2. Simple phase-shifting lateral shearing interferometer.

    PubMed

    Mihaylova, Emilia; Whelan, Maurice; Toal, Vincent

    2004-06-01

    A phase-shifting electronic speckle pattern shearing interferometer with a very simple shearing device is proposed. Two partially reflective glass plates are used to introduce the shear in this new interferometer. The reflection coefficients of the coatings on the two plates are 0.3 and 0.7. The distance between the two glass plates controls the size of the shear. The proposed new interferometric system is simple, flexible, and low cost.

  3. Reactions and their management.

    PubMed

    Ganapati, R; Pai, V V

    2004-12-01

    The uneventful response to chemotherapy in leprosy is marked by clinically disturbing episodes encountered in 20-30% of patients and these phenomena are called "reactions". Generally they are classified as reversal reaction (type-1) and erythema nodosum leprosum (type-2). The cutaneous menifestations are: (1) Type-2 reactions in LL, BL types constituting erythema nodosum leprosum, erythema multiforme, erythema necroticans, subcutaneous nodules, lepromatous exacerbation. (2) Type-1 reactions in borderline and tuberculoid leprosy. The other manifestations include: Acute neuritis, lymphadenitis, arthritis, oedema of the hands and feet, ocular lesions, etc. Sequelae of reactions are: Paralytic deformities, non-paralytic deformities, extensive scarring and renal damage. A simple guideline to identify the risk-prone cases has been narrated. Prednisolone in standard dosage schedule as recommended by WHO is now being widely used in control programmes.

  4. A Shifted Double-Diamond Titania Scaffold.

    PubMed

    Li, Hong; Liu, Ye; Cao, Xin; Han, Lu; Jiang, Chun; Che, Shunai

    2017-01-16

    Photonic crystals are expected to be metamaterials because of their potential to control the propagation of light in the linear and nonlinear regimes. Biological single-network, triply periodic constant mean curvature surface structures are considered excellent candidates owing to their large complete band gap. However, the chemical construction of these relevant structures is rare and developing new structures from thermodynamically stable double-network self-organizing systems is challenging. Herein, we reveal that the shifted double-diamond titania scaffold can achieve a complete band gap. The largest (7.71 %) band gap is theoretically obtained by shifting 0.332 c with the dielectric contrast of titania (6.25). A titania scaffold with similar shifted double-diamond structure was fabricated using a reverse core-shell microphase-templating system with an amphiphilic diblock copolymer and a titania source in a mixture of tetrahydrofuran and water, which could result in a 2.05-3.78 % gap.

  5. Atomic clocks with suppressed blackbody radiation shift.

    PubMed

    Yudin, V I; Taichenachev, A V; Okhapkin, M V; Bagayev, S N; Tamm, Chr; Peik, E; Huntemann, N; Mehlstäubler, T E; Riehle, F

    2011-07-15

    We develop a concept of atomic clocks where the blackbody radiation shift and its fluctuations can be suppressed by 1-3 orders of magnitude independent of the environmental temperature. The suppression is based on the fact that in a system with two accessible clock transitions (with frequencies ν1 and ν2) which are exposed to the same thermal environment, there exists a "synthetic" frequency ν(syn) ∝ (ν1 - ε12ν2) largely immune to the blackbody radiation shift. For example, in the case of 171Yb+ it is possible to create a synthetic-frequency-based clock in which the fractional blackbody radiation shift can be suppressed to the level of 10(-18) in a broad interval near room temperature (300±15  K). We also propose a realization of our method with the use of an optical frequency comb generator stabilized to both frequencies ν1 and ν2, where the frequency ν(syn) is generated as one of the components of the comb spectrum.

  6. Thermal field theories and shifted boundary conditions

    NASA Astrophysics Data System (ADS)

    Giusti, L.; Meyer, H.

    The analytic continuation to an imaginary velocity of the canonical partition function of a thermal system expressed in a moving frame has a natural implementation in the Euclidean path-integral formulation in terms of shifted boundary conditions. The Poincare' invariance underlying a relativistic theory implies a dependence of the free-energy on the compact length L_0 and the shift xi only through the combination beta=L_0(1+xi^2)^(1/2). This in turn implies that the energy and the momentum distributions of the thermal theory are related, a fact which is encoded in a set of Ward identities among the correlators of the energy-momentum tensor. The latter have interesting applications in lattice field theory: they offer novel ways to compute thermodynamic potentials, and a set of identities to renormalize non-perturbatively the energy-momentum tensor. At fixed bare parameters the shifted boundary conditions also provide a simple method to vary the temperature in much smaller steps than with the standard procedure.

  7. Projecting the risk of future climate shifts

    NASA Astrophysics Data System (ADS)

    Enfield, David B.; Cid-Serrano, Luis

    2006-06-01

    Recent research has shown that decadal-to-multidecadal (D2M) climate variability is associated with environmental changes that have important consequences for human activities, such as public health, water availability, frequency of hurricanes, and so forth. As scientists, how do we convert these relationships into decision support products useful to water managers, insurance actuaries, and others, whose principal interest lies in knowing when future climate regime shifts will likely occur that affect long-horizon decisions? Unfortunately, numerical models are far from being able to make deterministic predictions for future D2M climate shifts. However, the recent development of paleoclimate reconstructions of the Atlantic Multidecadal Oscillation (AMO) (Gray et al., [2004]) and Pacific Decadal Oscillation (PDO); (MacDonald and Case, [2005]) give us a viable alternative: to estimate probability distribution functions from long climate index series that allow us to calculate the probability of future D2M regime shifts. In this paper, we show how probabilistic projections can be developed for a specific climate mode - the AMO as represented by the Gray et al. ([2004]) tree-ring reconstruction. The methods are robust and can be applied to any D2M climate mode for which a sufficiently long index series exists, as well as to the growing body of paleo-proxy reconstructions that have become available. The target index need not be a paleo-proxy calibrated against a climate index; it may profitably be calibrated against a specific resource of interest, such as stream flow or lake levels.

  8. Bashful ballerina: Southward shifted heliospheric current sheet

    NASA Astrophysics Data System (ADS)

    Mursula, K.; Hiltula, T.

    2003-11-01

    It is known since long [Rosenberg and Coleman, 1969] that one of the two sectors of the interplanetary magnetic field (IMF) observed at the Earth's orbit dominates at high heliographic latitudes during solar minimum times, reflecting the poloidal structure of the global solar magnetic field at these times. Here we find that while this latitudinal variation of the dominant IMF sector around the solar equator is valid for both solar hemispheres during the last four solar minima covered by direct observations, it is systematically more strongly developed in the northern heliographic hemisphere. This implies that the average heliospheric current sheet is shifted or coned southward during solar minimum times, suggesting that the temporary southward shift of the heliosheet found earlier by Ulysses observations in 1995 is a persistent pattern. This also implies that the open solar magnetic field is north-south asymmetric at these times, suggesting that the solar dynamo has an asymmetric component. Accordingly, the Sun with the heliosheet is like a bashful ballerina who is repeatedly trying to push her excessively high flaring skirt downward. However, the effective shift at 1 AU is only a few degrees, allowing the Rosenberg-Coleman rule to be valid, on an average, in both hemispheres during solar minima.

  9. Bashful Ballerina: Southward shifted Heliospheric Current Sheet

    NASA Astrophysics Data System (ADS)

    Mursula, K.; Hiltula, T.

    It is known since long (Rosenberg and Coleman, 1969) that one of the two sectors of the interplanetary magnetic field (IMF) observed at the Earth's orbit dominates at high heliographic latitudes during solar minimum times, reflecting the poloidal structure of the global solar magnetic field at these times. Here we find that while this latitudinal variation of the dominant IMF sector around the solar equator is valid for both solar hemispheres during the last four solar minima covered by direct observations, it is systematically more strongly developed in the northern heliographic hemisphere. This implies that the average heliospheric current sheet is shifted or coned southward during solar minimum times, suggesting that the temporary southward shift of the heliosheet found earlier by Ulysses observations in 1995 is a persistent pattern. This also implies that the open solar magnetic field is north-south asymmetric at these times, suggesting that the solar dynamo has an asymmetric component. Accordingly, the Sun with the heliosheet is like a bashful ballerina who is repeatedly trying to push her excessively high flaring skirt downward. However, the effective shift at 1 AU is only a few degrees, allowing the Rosenberg-Coleman rule to be valid, on an average, in both hemispheres during solar minima.

  10. Michelson interferometer based spatial phase shift shearography.

    PubMed

    Xie, Xin; Yang, Lianxiang; Xu, Nan; Chen, Xu

    2013-06-10

    This paper presents a simple spatial phase shift shearography based on the Michelson interferometer. The Michelson interferometer based shearographic system has been widely utilized in industry as a practical nondestructive test tool. In the system, the Michelson interferometer is used as a shearing device to generate a shearing distance by tilting a small angle in one of the two mirrors. In fact, tilting the mirror in the Michelson interferometer also generates spatial frequency shift. Based on this feature, we introduce a simple Michelson interferometer based spatial phase shift shearography. The Fourier transform (FT) method is applied to separate the spectrum on the spatial frequency domain. The phase change due to the loading can be evaluated using a properly selected windowed inverse-FT. This system can generate a phase map of shearography by using only a single image. The effects of shearing angle, spatial resolution of couple charge device camera, and filter methods are discussed in detail. The theory and the experimental results are presented.

  11. Is there a shift to "active nanostructures"?

    NASA Astrophysics Data System (ADS)

    Subramanian, Vrishali; Youtie, Jan; Porter, Alan L.; Shapira, Philip

    2010-01-01

    It has been suggested that an important transition in the long-run trajectory of nanotechnology development is a shift from passive to active nanostructures. Such a shift could present different or increased societal impacts and require new approaches for risk assessment. An active nanostructure "changes or evolves its state during its operation," according to the National Science Foundation's (2006) Active Nanostructures and Nanosystems grant solicitation. Active nanostructure examples include nanoelectromechanical systems (NEMS), nanomachines, self-healing materials, targeted drugs and chemicals, energy storage devices, and sensors. This article considers two questions: (a) Is there a "shift" to active nanostructures? (b) How can we characterize the prototypical areas into which active nanostructures may emerge? We build upon the NSF definition of active nanostructures to develop a research publication search strategy, with a particular intent to distinguish between passive and active nanotechnologies. We perform bibliometric analyses and describe the main publication trends from 1995 to 2008. We then describe the prototypes of research that emerge based on reading the abstracts and review papers encountered in our search. Preliminary results suggest that there is a sharp rise in active nanostructures publications in 2006, and this rise is maintained in 2007 and through to early 2008. We present a typology that can be used to describe the kind of active nanostructures that may be commercialized and regulated in the future.

  12. Experience with the shift technical advisor position

    SciTech Connect

    Melber, B.D.; Olson, J.; Schreiber, R.E.; Winges, L.

    1984-03-01

    The provision of engineering expertise on shift at commercial nuclear power plants has mainly taken the form of the Shift Technical Advisor (STA). This person, acting in a capacity that is part engineer and part operator, is expected to advise the operations crew in the event of an emergency and review plant operating experience during normal circumstances. The position was mandated by the Nuclear Regulatory Commission following the incident at Three Mile Island. This report expands on a growing body of knowledge regarding the effectiveness of the STA. The new data presented here come from interviews with plant personnel and utility officials from nine sites. Researchers from the Pacific Northwest Laboratory (PNL) interviewed plant personnel, including the STA and immediate management, the shift supervisor and management, the training department, and ancillary staff, all of whom affect the intended performance of the STA. The conclusions of the report are that the design of the STA position results in limited contribution during emergencies; more comprehensive ways should be sought to provide the variety and specificity of engineering expertise needed during such times.

  13. Stereoscopic watermarking by horizontal noise mean shifting

    NASA Astrophysics Data System (ADS)

    Lee, Ji-Won; Kim, Hee-Dong; Choi, Hak-Yeol; Choi, Sung-Hee; Lee, Heung-Kyu

    2012-03-01

    Depth-image-based rendering (DIBR) is a method to represent a stereoscopic content. The DIBR consists of a monoscopic center view and an associated per-pixel depth map. Using these two components and given depth condition from a user, the DIBR renders left and right views. The advantages of DIBR are numerous. The user can choose not only the monoscopic or stereoscopic view selectively, but also the depth condition what he prefers when he watches a stereoscopic content. However, in the view of copyright protection, since not only the center view but also each left or right view can be used as a monoscopic content when they are illegally distributed, the watermark signal which is embedded in the center view must have an ability to protect the respective three views. In this study, we solve this problem by exploiting the horizontal noise mean shifting (HNMS) technique. We exploit the fact that the objects in the view are shifted only to horizontal way when the center view renders to the left and right views. Using this fact, the proposed stereoscopic watermarking scheme moves the mean of horizontal noise histogram which is invariant to horizontal shifting, and we achieve good performance as shown in the experimental results.

  14. Concatenated shift registers generating maximally spaced phase shifts of PN-sequences

    NASA Technical Reports Server (NTRS)

    Hurd, W. J.; Welch, L. R.

    1977-01-01

    A large class of linearly concatenated shift registers is shown to generate approximately maximally spaced phase shifts of pn-sequences, for use in pseudorandom number generation. A constructive method is presented for finding members of this class, for almost all degrees for which primitive trinomials exist. The sequences which result are not normally characterized by trinomial recursions, which is desirable since trinomial sequences can have some undesirable randomness properties.

  15. Phase-shifting error and its elimination in phase-shifting digital holography.

    PubMed

    Guo, Cheng-Shan; Zhang, Li; Wang, Hui-Tian; Liao, Jun; Zhu, Y Y

    2002-10-01

    We investigate the influence of phase-shifting error on the quality of the reconstructed image in digital holography and propose a method of error elimination for a perfect image. In this method the summation of the intensity bit errors of the reconstructed image is taken as an evaluation function for an iterative algorithm to find the exact phase-shifting value. The feasibility of this method is demonstrated by computer simulation.

  16. Conversion reactions for sodium-ion batteries.

    PubMed

    Klein, Franziska; Jache, Birte; Bhide, Amrtha; Adelhelm, Philipp

    2013-10-14

    Research on sodium-ion batteries has recently been rediscovered and is currently mainly focused on finding suitable electrode materials that enable cell reactions of high energy densities combined with low cost. Naturally, an assessment of potential electrode materials requires a rational comparison with the analogue reaction in lithium-ion batteries. In this paper, we systematically discuss the broad range of different conversion reactions for sodium-ion batteries based on their basic thermodynamic properties and compare them with their lithium analogues. Capacities, voltages, energy densities and volume expansions are summarized to sketch out the scope for future studies in this research field. We show that for a given conversion electrode material, replacing lithium by sodium leads to a constant shift in cell potential ΔE°(Li-Na) depending on the material class. For chlorides ΔE°(Li-Na) equals nearly zero. The theoretical energy densities of conversion reactions of sodium with fluorides or chlorides as positive electrode materials typically reach values between 700 W h kg(-1) and 1000 W h kg(-1). Next to the thermodynamic assessment, results on several conversion reactions between copper compounds (CuS, CuO, CuCl, CuCl2) and sodium are being discussed. Reactions with CuS and CuO were chosen because these compounds are frequently studied for conversion reactions with lithium. Chlorides are interesting because of ΔE°(Li-Na)≈ 0 V. As a result of chloride solubility in the electrolyte, the conversion process proceeds at defined potentials under rather small kinetic limitations.

  17. Absolute surface metrology with a phase-shifting interferometer for incommensurate transverse spatial shifts.

    PubMed

    Bloemhof, E E

    2014-02-10

    We consider the detailed implementation and practical utility of a novel absolute optical metrology scheme recently proposed for use with a phase-shifting interferometer (PSI). This scheme extracts absolute phase differences between points on the surface of the optic under test by differencing phase maps made with slightly different transverse spatial shifts of that optic. These absolute phase (or height) differences, which for single-pixel shifts are automatically obtained in the well-known Hudgin geometry, yield the underlying absolute surface map by standard wavefront reconstruction techniques. The PSI by itself maps surface height only relative to that of a separate reference optic known or assumed to be flat. In practice, even relatively high-quality (and expensive) transmission flats or spheres used to reference a PSI are flat or spherical only to a few dozen nanometers peak to valley (P-V) over typical 4 in. apertures. The new technique for removing the effects of the reference surface is in principle accurate as well as simple, and may represent a significant advance in optical metrology. Here it is shown that transverse shifts need not match the pixel size; somewhat counterintuitively, the single-pixel spatial resolution of the PSI is retained even when transverse shifts are much coarser. Practical considerations for shifts not necessarily commensurate with pixel size, and broader applications, are discussed.

  18. Regime Shifts in the Anthropocene: Drivers, Risks, and Resilience

    PubMed Central

    Rocha, Juan Carlos; Peterson, Garry D.; Biggs, Reinette

    2015-01-01

    Many ecosystems can experience regime shifts: surprising, large and persistent changes in the function and structure of ecosystems. Assessing whether continued global change will lead to further regime shifts, or has the potential to trigger cascading regime shifts has been a central question in global change policy. Addressing this issue has, however, been hampered by the focus of regime shift research on specific cases and types of regime shifts. To systematically assess the global risk of regime shifts we conducted a comparative analysis of 25 generic types of regime shifts across marine, terrestrial and polar systems; identifying their drivers, and impacts on ecosystem services. Our results show that the drivers of regime shifts are diverse and co-occur strongly, which suggests that continued global change can be expected to synchronously increase the risk of multiple regime shifts. Furthermore, many regime shift drivers are related to climate change and food production, whose links to the continued expansion of human activities makes them difficult to limit. Because many regime shifts can amplify the drivers of other regime shifts, continued global change can also be expected to increase the risk of cascading regime shifts. Nevertheless, the variety of scales at which regime shift drivers operate provides opportunities for reducing the risk of many types of regime shifts by addressing local or regional drivers, even in the absence of rapid reduction of global drivers. PMID:26267896

  19. Regime shifts in the anthropocene: drivers, risks, and resilience.

    PubMed

    Rocha, Juan Carlos; Peterson, Garry D; Biggs, Reinette

    2015-01-01

    Many ecosystems can experience regime shifts: surprising, large and persistent changes in the function and structure of ecosystems. Assessing whether continued global change will lead to further regime shifts, or has the potential to trigger cascading regime shifts has been a central question in global change policy. Addressing this issue has, however, been hampered by the focus of regime shift research on specific cases and types of regime shifts. To systematically assess the global risk of regime shifts we conducted a comparative analysis of 25 generic types of regime shifts across marine, terrestrial and polar systems; identifying their drivers, and impacts on ecosystem services. Our results show that the drivers of regime shifts are diverse and co-occur strongly, which suggests that continued global change can be expected to synchronously increase the risk of multiple regime shifts. Furthermore, many regime shift drivers are related to climate change and food production, whose links to the continued expansion of human activities makes them difficult to limit. Because many regime shifts can amplify the drivers of other regime shifts, continued global change can also be expected to increase the risk of cascading regime shifts. Nevertheless, the variety of scales at which regime shift drivers operate provides opportunities for reducing the risk of many types of regime shifts by addressing local or regional drivers, even in the absence of rapid reduction of global drivers.

  20. Radiation reaction in quantum field theory

    NASA Astrophysics Data System (ADS)

    Higuchi, Atsushi

    2002-11-01

    We investigate radiation-reaction effects for a charged scalar particle accelerated by an external potential realized as a space-dependent mass term in quantum electrodynamics. In particular, we calculate the position shift of the final-state wave packet of the charged particle due to radiation at lowest order in the fine structure constant α and in the small ħ approximation. We show that it disagrees with the result obtained using the Lorentz-Dirac formula for the radiation-reaction force, and that it agrees with the classical theory if one assumes that the particle loses its energy to radiation at each moment of time according to the Larmor formula in the static frame of the potential. However, the discrepancy is much smaller than the Compton wavelength of the particle. We also point out that the electromagnetic correction to the potential has no classical limit.

  1. Pterandra pyroidea: a case of pollination shift within Neotropical Malpighiaceae

    PubMed Central

    Cappellari, Simone C.; Haleem, Muhammad A.; Marsaioli, Anita J.; Tidon, Rosana; Simpson, Beryl B.

    2011-01-01

    Background and Aims Most Neotropical species of Malpighiaceae produce floral fatty oils in calyx glands to attract pollinating oil-collecting bees, which depend on this resource for reproduction. This specialized type of pollination system tends to be lost in members of the family that occur outside the geographic distribution (e.g. Africa) of Neotropical oil-collecting bees. This study focused on the pollination ecology, chemical ecology and reproductive biology of an oil flower species, Pterandra pyroidea (Malpighiaceae) from the Brazilian Cerrado. Populations of this species consist of plants with oil-secreting (glandular) flowers, plants with non-oil-secreting flowers (eglandular) or a mix of both plant types. This study specifically aims to clarify the role of eglandular morphs in this species. Methods Data on pollinators were recorded by in situ observations. Breeding system experiments were conducted by isolating inflorescences and by enzymatic reactions. Floral resources, pollen and floral oils offered by this species were analysed by staining and a combination of various spectroscopic methods. Key Results Eglandular flowers of P. pyroidea do not act as mimics of their oil-producing conspecifics to attract pollinators. Instead, both oil-producing and oil-free flowers depend on pollen-collecting bees for reproduction, and their main pollinators are bumble-bees. Floral oils produced by glandular flowers are less complex than those described in closely related genera. Conclusions Eglandular flowers represent a shift in the pollination system in which oil is being lost and pollen is becoming the main reward of P. pyroidea flowers. Pollination shifts of this kind have hitherto not been demonstrated empirically within Neotropical Malpighiaceae and this species exhibits an unusual transition from a specialized towards a generalized pollination system in an area considered the hotspot of oil-collecting bee diversity in the Neotropics. Transitions of this type

  2. Enhancing chemical reactions

    DOEpatents

    Morrey, John R.

    1978-01-01

    Methods of enhancing selected chemical reactions. The population of a selected high vibrational energy state of a reactant molecule is increased substantially above its population at thermal equilibrium by directing onto the molecule a beam of radiant energy from a laser having a combination of frequency and intensity selected to pump the selected energy state, and the reaction is carried out with the temperature, pressure, and concentrations of reactants maintained at a combination of values selected to optimize the reaction in preference to thermal degradation by transforming the absorbed energy into translational motion. The reaction temperature is selected to optimize the reaction. Typically a laser and a frequency doubler emit radiant energy at frequencies of .nu. and 2.nu. into an optical dye within an optical cavity capable of being tuned to a wanted frequency .delta. or a parametric oscillator comprising a non-centrosymmetric crystal having two indices of refraction, to emit radiant energy at the frequencies of .nu., 2.nu., and .delta. (and, with a parametric oscillator, also at 2.nu.-.delta.). Each unwanted frequency is filtered out, and each desired frequency is focused to the desired radiation flux within a reaction chamber and is reflected repeatedly through the chamber while reactants are fed into the chamber and reaction products are removed therefrom.

  3. Algorithm for reaction classification.

    PubMed

    Kraut, Hans; Eiblmaier, Josef; Grethe, Guenter; Löw, Peter; Matuszczyk, Heinz; Saller, Heinz

    2013-11-25

    Reaction classification has important applications, and many approaches to classification have been applied. Our own algorithm tests all maximum common substructures (MCS) between all reactant and product molecules in order to find an atom mapping containing the minimum chemical distance (MCD). Recent publications have concluded that new MCS algorithms need to be compared with existing methods in a reproducible environment, preferably on a generalized test set, yet the number of test sets available is small, and they are not truly representative of the range of reactions that occur in real reaction databases. We have designed a challenging test set of reactions and are making it publicly available and usable with InfoChem's software or other classification algorithms. We supply a representative set of example reactions, grouped into different levels of difficulty, from a large number of reaction databases that chemists actually encounter in practice, in order to demonstrate the basic requirements for a mapping algorithm to detect the reaction centers in a consistent way. We invite the scientific community to contribute to the future extension and improvement of this data set, to achieve the goal of a common standard.

  4. Modeling of surface reactions

    SciTech Connect

    Ray, T.R.

    1993-01-01

    Mathematical models are used to elucidate properties of the monomer-monomer and monomer-dimer type chemical reactions on a two-dimensional surface. The authors use mean-field and lattice gas models, detailing similarities and differences due to correlations in the lattice gas model. The monomer-monomer, or AB surface reaction model, with no diffusion, is investigated for various reaction rates k. Study of the exact rate equations reveals that poisoning always occurs if the adsorption rates of the reactants are unequal. If the adsorption rates of the reactants are equal, simulations show slow poisoning, associated with clustering of reactants. This behavior is also shown for the two-dimensional voter model. The authors analyze precisely the slow poisoning kinetics by an analytic treatment for the AB reaction with infinitesimal reaction rate, and by direct comparison with the voter model. They extend the results to incorporate the effects of place-exchange diffusion, and they compare the AB reaction with infinitesimal reaction rate and no diffusion to the voter model with diffusion at rate 1/2. They also consider the relationship of the voter model to the monomer-dimer model, and investigate the latter model for small reaction rates. The monomer-dimer, or AB[sub 2] surface reaction model is also investigated. Specifically, they consider the ZGB-model for CO-oxidation, and in generalizations of this model which include adspecies diffusion. A theory of nucleation to describe properties of non-equilibrium first-order transitions, specifically the evolution between [open quote]reactive[close quote] steady states and trivial adsorbing states, is derived. The behavior of the [open quote]epidemic[close quote] survival probability, P[sub s], for a non-poisoned patch surrounded by a poisoned background is determined below the poisoning transition.

  5. Fundamental studies of retrograde reactions in direct liquefaction

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1991-12-17

    The overall objective of the program was to improve the understanding of retrograde reactions and their dependencies on coal rank and structure, and/or coal modifications and reaction conditions. Because retrograde reactions are competitive with bond breaking reactions, an understanding of both is required to shift the competition in favor of the latter. Related objectives were to clarify the conflicting observations reported in literature on such major topics as the role of oxygen groups in retrograde reactions and to provide a bridge from very fundamental studies on pure compounds to phenomenological studies on actual coal. This information was integrated into the FG-DVC model, which was improved and extended to the liquefaction context.

  6. Thermotolerance of apple tree leaves probed by chlorophyll a fluorescence and modulated 820 nm reflection during seasonal shift.

    PubMed

    Duan, Ying; Zhang, Mengxia; Gao, Jin; Li, Pengmin; Goltsev, Vasilij; Ma, Fengwang

    2015-11-01

    During the seasonal shift from June to August, air temperatures increase. To explore how apple trees improve their thermotolerance during this shift, we examined the photochemical reaction capacity of apple tree leaves by simultaneous measurement of prompt chlorophyll fluorescence, delayed chlorophyll fluorescence, and modulated 820 nm reflection at varying temperatures. It was found that the reaction centers and antennae of photosystem II (PSII) and photosystem I (PSI), the donor side of PSII, the electron transfer capacity from QA to QB, and the reoxidation capacity of plastoquinol were all sensitive to heat stress, particularly in June. As the season shifted, apple tree leaves improved in thermotolerance. Interestingly, the acclimation to seasonal shift enhanced the thermotolerance of PSII and PSI reaction centers more than that of their antennae, and the activity of PSII more than that of PSI. This may be a strategy for plant adaptation to changes in environmental temperatures. In addition, results from prompt and delayed fluorescence, as well as modulated 820 nm reflection corroborate each other. We suggest that the simultaneous measurement of the three independent signals may provide more information on thermal acclimation mechanisms of photochemical reactions in plant leaves.

  7. Cycloaddition reactions of ICNO

    NASA Astrophysics Data System (ADS)

    Pasinszki, Tibor; Krebsz, Melinda; Hajgató, Balázs

    2009-05-01

    The mechanism and selectivity of cycloaddition reactions of iodonitrile oxide, ICNO, have been studied with theoretical methods for the first time using MR-AQCC coupled-cluster and B3LYP DFT methods. Calculations have predicted that the favoured ICNO dimerisation process is a multi-step reaction to diiodofuroxan involving dinitrosoethylene-like intermediates. The ICNO cycloaddition with nitriles and ethynyl derivatives is a synchronous process favouring the formation of 1,2,4-oxadiazole and 1,2-oxazole derivatives, respectively. The cycloaddition reactions of ICNO have been studied experimentally by generating ICNO from AgCNO and iodine. Diiodofuroxan is obtained, however, even at the presence of nitriles.

  8. NEUTRONIC REACTION SYSTEM

    DOEpatents

    Wigner, E.P.

    1963-09-01

    A nuclear reactor system is described for breeding fissionable material, including a heat-exchange tank, a high- and a low-pressure chamber therein, heat- exchange tubes connecting these chambers, a solution of U/sup 233/ in heavy water in a reaction container within the tank, a slurry of thorium dioxide in heavy water in a second container surrounding the first container, an inlet conduit including a pump connecting the low pressure chamber to the reaction container, an outlet conduit connecting the high pressure chamber to the reaction container, and means of removing gaseous fission products released in both chambers. (AEC)

  9. Ecohydrology by thinking outside the bog: Shifting paradigms in an era of shifting peatland ecosystems

    NASA Astrophysics Data System (ADS)

    Waddington, James; Moore, Paul

    2016-04-01

    Large shifts in vegetation distributions are occurring worldwide and at unprecedented rates. The most extreme of these regime shifts are expected to occur at ecosystem boundaries of both semi-arid and semi-humid landscapes. Despite extensive hydrological research on the interactions between water and semi-arid ecosystems, research in peatlands on the wet end of ecosystem continuum has been "bogged down" (pun fully intended) by the traditional conceptual models (paradigms?) of peatland hydrology and ecology. The consequences of this "thinking" are large given that northern peatlands provide important global and regional ecosystem services (carbon storage, water storage, and biodiversity). This is especially true because peatlands face increases in the severity, areal extent, and frequency of climate-mediated (e.g., wildfire, drought) and land-use change (e.g., drainage, flooding, and mining) disturbances placing the future security of these critical ecosystem services in doubt. We use the word doubt because while numerical modelling studies predict peatland regime shifts and the demise of global peat stocks, there is growing evidence that peatlands are self-regulating ecosystems dominated by negative ecohydrological feedbacks that stabilize the aforementioned ecosystem services through high ecosystem resilience to disturbance. This raises several important hydrological questions? "Is there field evidence of peatland regime shifts? If so, what are the potential impacts of these shifts on water resources and watershed management? If not, are researchers actually looking in the right places (or times)? In this presentation we explore the need for a "thinking outside the bog" in order to understand the ecohydrological consequences of transformative landscape change caused by peatland regime shifts. With reference to over two decades of field research, recent advances with our Peatland Hydrological Impacts model and recent research examining primary peat formation, we

  10. Pressure Shift and Gravitational RedShift of Balmer Lines in White Dwarfs: Rediscussion

    NASA Astrophysics Data System (ADS)

    Halenka, Jacek; Olchawa, Wieslaw; Madej, Jerzy; Grabowski, Boleslaw

    2015-08-01

    The Stark-induced shift and asymmetry, the so-called pressure shift (PS) of Hα and Hβ Balmer lines in spectra of DA white dwarfs (WDs), have been examined in detail as masking effects in measurements of the gravitational redshift in WDs. The results are compared with our earlier ones from a quarter of a century ago. In these earlier papers, the standard, symmetrical Stark line profiles, as a dominant constituent of the Balmer line profiles but shifted as a whole by the PS effect, were applied to all spectrally active layers of the WD atmosphere. At present, in each of the WD layers, the Stark line profiles (especially of Hβ) are inherently asymmetrical and shifted due to the effects of strong inhomogeneity of the perturbing fields in plasma. To calculate the Stark line profiles in successive layers of the WD atmosphere we used the modified Full Computer Simulation Method, able to take adequately into account the complexity of local elementary quantum processes in plasma. In the case of the Hα line, the present value of Stark-induced shift of the synthetic Hα line profile is about half the previous one and it is negligible in comparison with the gravitational redshift. In the case of the Hβ line, the present value of Stark-induced shift of the synthetic Hβ line profile is about twice the previous one. The source of this extra shift is the asymmetry of Hβ peaks. In memory of Jan Jerzy Kubikowski (1927-1968)—one of the pioneers of plasma in astrophysics.

  11. Eye gaze triggers reflexive attention shifts: evidence from lateralised ERPs.

    PubMed

    Feng, Qing; Zhang, Xuemin

    2014-11-17

    Social cues, such as another individual׳s eye gaze, provide valuable information regarding the actions and intentions of others. Previous studies have suggested that seeing another׳s gaze automatically orients one׳s attention in the gaze direction. In this event-related potential (ERP) study, a spatial cuing paradigm was combined with a visual search task in which targets were defined by feature conjunctions in order to eliminate effects of target/distractor salience. Participants viewed centrally presented faces with neutral expressions in which eyes looked to the left or right. The participants׳ task was to identify a target object (with or without gap) defined by a combination of shape and orientation, which appeared in either the same (cued) or the opposite (uncued) location as the direction of the eye gaze. There was behavioural evidence of a gaze congruency effect, as reaction times (RTs) were faster when the eyes looked towards the target rather than away from the location of the target. The ERP data indicated the presence of significant gaze-congruent early directing attention negativity (EDAN) and anterior directing attention negativity (ADAN), reflecting attention shifts to the cued location in advance of the target presentation. ERP data did not show evidence of later orienting of attention triggered by gaze cues in the late attention-directing attention positivity (LDAP) at posterior sites. The results disclosed the neural response during reflexive attention shifting triggered by gazes and ascertained the relationship among EDAN, ADAN, LDAP and gaze-elicited attention shifts. After the presentation of the target array without salient stimuli, the presence of the N2-posterior-contralateral (N2pc) in the cued trials and the absence in the uncued trials further supported that attention had been directed to the possible target location prior to the target onset. The ERPs in response to the target array also extend our understanding of the neural

  12. Intrinsic Wavelength Shifts in Stellar Spectra

    NASA Astrophysics Data System (ADS)

    Dravins, D.; Lindegren, L.; Ludwig, H.-G.; Madsen, S.

    2004-12-01

    Wavelengths of stellar spectral lines do not have the precise values `naively' expected from laboratory wavelengths merely Doppler-shifted by stellar radial motion. Slight displacements may originate as convective shifts (correlated velocity and brightness patterns in the photosphere), as gravitational redshifts, or perhaps be induced by wave motions. Intrinsic lineshifts thus reveal stellar surface structure, while possible periodic changes (during a stellar activity cycle, say) need to be segregated from variability induced by orbiting exoplanets. Absolute lineshifts can now be studied also in some stars other than the Sun, thanks to astrometric determinations of stellar radial motion. Comparisons between spectroscopic apparent radial velocities and astrometrically determined radial motions reveal greater spectral blueshifts in F-type stars than in the Sun (as theoretically expected from their more vigorous convection), further increasing in A-type stars (possibly due to atmospheric shockwaves). Solar spectral atlases, and high-resolution spectra (from UVES on ESO VLT) of a dozen solar-type stars are being surveyed for `unblended' photospheric lines of most atomic species with accurate laboratory wavelengths available. One aim is to understand the ultimate information content of stellar spectra, and in what detail it will be feasible to verify models of stellar atmospheric hydrodynamics. These may predict line asymmetries (bisectors) and shifts for widely different classes of lines, but there will not result any comparison with observations if such lines do not exist in real spectra. An expected near-future development in stellar physics is spatially resolved spectroscopy across stellar disks, enabled by optical interferometry and adaptive optics on very large telescopes. Stellar surface structure manifests itself in the center-to-limb wavelength changes along a stellar diameter, and their spatially resolved time variability, diagnostics which already now can be

  13. Green binary and phase shifting mask

    NASA Astrophysics Data System (ADS)

    Shy, S. L.; Hong, Chao-Sin; Wu, Cheng-San; Chen, S. J.; Wu, Hung-Yu; Ting, Yung-Chiang

    2009-12-01

    SixNy/Ni thin film green mask blanks were developed , and are now going to be used to replace general chromium film used for binary mask as well as to replace molydium silicide embedded material for AttPSM for I-line (365 nm), KrF (248 nm), ArF (193 nm) and Contact/Proximity lithography. A bilayer structure of a 1 nm thick opaque, conductive nickel layer and a SixNy layer is proposed for binary and phase-shifting mask. With the good controlling of plasma CVD of SixNy under silane (50 sccm), ammonia (5 sccm) and nitrogen (100 sccm), the pressure is 250 mTorr. and RF frequency 13.56 MHz and power 50 W. SixNy has enough deposition latitude to meet the requirements as an embedded layer for required phase shift 180 degree, and the T% in 193, 248 and 365 nm can be adjusted between 2% to 20% for binary and phase shifting mask usage. Ni can be deposited by E-gun, its sheet resistance Rs is less than 1.435 kΩ/square. Jeol e-beam system and I-line stepper are used to evaluate these thin film green mask blanks, feature size less than 200 nm half pitch pattern and 0.558 μm pitch contact hole can be printed. Transmission spectrums of various thickness of SixNy film are inspected by using UV spectrometer and FTIR. Optical constants of the SixNy film are measured by n & k meter and surface roughness is inspected by using Atomic Force Microscope (AFM).

  14. Methane storage in dry water gas hydrates.

    PubMed

    Wang, Weixing; Bray, Christopher L; Adams, Dave J; Cooper, Andrew I

    2008-09-03

    Dry water stores 175 v(STP)/v methane at 2.7 MPa and 273.2 K in a hydrate form which is close to the Department of Energy volumetric target for methane storage. Dry water is a silica-stabilized free-flowing powder (95% wt water), and fast methane uptakes were observed (90% saturation uptake in 160 min with no mixing) as a result of the relatively large surface-to-volume ratio of this material.

  15. Bad Reaction to Cosmetics?

    MedlinePlus

    ... Devices Radiation-Emitting Products Vaccines, Blood & Biologics Animal & Veterinary Cosmetics Tobacco Products For Consumers Home For Consumers ... Reactions From Cosmetics More in Consumer Updates Animal & Veterinary Children's Health Cosmetics Dietary Supplements Drugs Food Medical ...

  16. Reactor for exothermic reactions

    DOEpatents

    Smith, Jr., Lawrence A.; Hearn, Dennis; Jones, Jr., Edward M.

    1993-01-01

    A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  17. Untoward penicillin reactions

    PubMed Central

    Guthe, T.; Idsöe, O.; Willcox, R. R.

    1958-01-01

    The literature on untoward reactions following the administration of penicillin is reviewed. These reactions, including a certain number of deaths which have been reported, are of particular interest to health administrations and to WHO in view of the large-scale programmes for controlling the treponematoses which are now under way—programmes affecting millions of people in many parts of the world. The most serious problems are anaphylactic sensitivity phenomena and superinfection or cross-infection with penicillin-resistant organisms, and the reactions involved range in intensity from the mildest to the fatal; the incidence of the latter is estimated at 0.1-0.3 per million injections. The authors point out that with increasing use of penicillin, more persons are likely to become sensitized and the number of reactions can therefore be expected to rise. The best prevention against such an increase is the restriction of the unnecessary use of penicillin. PMID:13596877

  18. Translated chemical reaction networks.

    PubMed

    Johnston, Matthew D

    2014-05-01

    Many biochemical and industrial applications involve complicated networks of simultaneously occurring chemical reactions. Under the assumption of mass action kinetics, the dynamics of these chemical reaction networks are governed by systems of polynomial ordinary differential equations. The steady states of these mass action systems have been analyzed via a variety of techniques, including stoichiometric network analysis, deficiency theory, and algebraic techniques (e.g., Gröbner bases). In this paper, we present a novel method for characterizing the steady states of mass action systems. Our method explicitly links a network's capacity to permit a particular class of steady states, called toric steady states, to topological properties of a generalized network called a translated chemical reaction network. These networks share their reaction vectors with their source network but are permitted to have different complex stoichiometries and different network topologies. We apply the results to examples drawn from the biochemical literature.

  19. Common Reactions After Trauma

    MedlinePlus

    ... Loss of intimacy or feeling detached Recovery from stress reactions Turn to your family and friends when ... someone is thinking about killing themselves, call the Suicide Prevention Lifeline 1-800-273-TALK (8255) http:// ...

  20. Reaction wheel assembly

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The fabrication and testing of three reaction wheels with associated drive and system monitoring electronics and brushless dc spin motors are discussed; the wheels are intended for use in a teleoperator simulator. Test results are included as graphs.

  1. Reactor for exothermic reactions

    DOEpatents

    Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

    1993-03-02

    A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  2. Oral Hypersensitivity Reactions

    MedlinePlus

    ... often flavored with agents like cinnamon, peppermint or menthol, which can trigger hypersensitivity reactions in susceptible individuals. ... potential allergens such as cinnamon, peppermint, eugenol and menthol. Even dental floss and denture cleansers may contain ...

  3. Iodine Clock Reaction.

    ERIC Educational Resources Information Center

    Mitchell, Richard S.

    1996-01-01

    Describes a combination of solutions that can be used in the study of kinetics using the iodine clock reaction. The combination slows down degradation of the prepared solutions and can be used successfully for several weeks. (JRH)

  4. Response reactions: equilibrium coupling.

    PubMed

    Hoffmann, Eufrozina A; Nagypal, Istvan

    2006-06-01

    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle.

  5. Skin Reactions to Cold

    PubMed Central

    Talpash, Orest

    1976-01-01

    Although skin reactions to cold are seen surprisingly infrequently in Canada, it is important to manage them correctly when they do occur. Frostbite, cold urticarias, Raynaud's disease and phenomenon, and several miscellaneous changes are discussed. PMID:21308019

  6. Chemisorption And Precipitation Reactions

    EPA Science Inventory

    The transport and bioavailability of chemical components within soils is, in part, controlled by partitioning between solids and solution. General terms used to describe these partitioning reactions include chemisorption and precipitation. Chemisorption is inclusive of the suit...

  7. An Illuminating Reaction.

    ERIC Educational Resources Information Center

    Matthews, Catherine E.

    1996-01-01

    Describes the use of carbide lights as an excellent mechanism for introducing or reviewing many basic chemistry concepts including elements and compounds, endothermic and exothermic reactions, physical and chemical changes, and balancing chemical equations. (JRH)

  8. Cost-shifting in the current medical environment

    NASA Astrophysics Data System (ADS)

    Gruber, William H.

    1994-12-01

    `Cost shifting' occurs when there is not a fair or accurate match of the payment and use of medical services. A common `cost shifting' occurs when an insured patient is charged more to cover free services provided to an uninsured patient. This paper documents the multiple negative consequences of the many categories of cost shifting, reviews forces which are leading both to an increase and decrease in the magnitude of cost shifting, and evaluates the consequences of cost shifting on the goals of U.S. health care reform and investment in medical technology. Policy to minimize the negative consequences of cost shifting is recommended.

  9. How orbital angular momentum affects beam shifts in optical reflection

    SciTech Connect

    Merano, M.; Hermosa, N.; Woerdman, J. P.; Aiello, A.

    2010-08-15

    It is well known that reflection of a Gaussian light beam (TEM{sub 00}) by a planar dielectric interface leads to four beam shifts when compared to the geometrical-optics prediction. These are the spatial Goos-Haenchen (GH) shift, the angular GH shift, the spatial Imbert-Fedorov (IF) shift, and the angular IF shift. We report here, theoretically and experimentally, that endowing the beam with orbital angular momentum leads to coupling of these four shifts; this is described by a 4x4 mixing matrix.

  10. Goos-Hänchen shifts in harmonic generation from metals.

    PubMed

    Yallapragada, V J; Gopal, Achanta Venu; Agarwal, G S

    2013-05-06

    We present the first calculation of the Goos-Hänchen shifts in the context of the nonlinear generation of fields. We specifically concentrate on shifts of second harmonic generated at metallic surfaces. At metallic surfaces the second harmonic primarily arises from discontinuities of the field at surfaces which not only result in large harmonic generation but also in significant Goos-Hänchen shifts of the generated second harmonic. Our results can be extended to other shifts like angular shifts and Fedorov-Imbert shifts.

  11. Pendulum Shifts, Context, Error, and Personal Accountability

    SciTech Connect

    Harold Blackman; Oren Hester

    2011-09-01

    This paper describes a series of tools that were developed to achieve a balance in under-standing LOWs and the human component of events (including accountability) as the INL continues its shift to a learning culture where people report, are accountable and interested in making a positive difference - and want to report because information is handled correctly and the result benefits both the reporting individual and the organization. We present our model for understanding these interrelationships; the initiatives that were undertaken to improve overall performance.

  12. Higher-order phase shift reconstruction approach

    SciTech Connect

    Cong Wenxiang; Wang Ge

    2010-10-15

    Purpose: Biological soft tissues encountered in clinical and preclinical imaging mainly consists of atoms of light elements with low atomic numbers and their elemental composition is nearly uniform with little density variation. Hence, x-ray attenuation contrast is relatively poor and cannot achieve satisfactory sensitivity and specificity. In contrast, x-ray phase-contrast provides a new mechanism for soft tissue imaging. The x-ray phase shift of soft tissues is about a thousand times greater than the x-ray absorption over the diagnostic x-ray energy range, yielding a higher signal-to-noise ratio than the attenuation contrast counterpart. Thus, phase-contrast imaging is a promising technique to reveal detailed structural variation in soft tissues, offering a high contrast resolution between healthy and malignant tissues. Here the authors develop a novel phase retrieval method to reconstruct the phase image on the object plane from the intensity measurements. The reconstructed phase image is a projection of the phase shift induced by an object and serves as input to reconstruct the 3D refractive index distribution inside the object using a tomographic reconstruction algorithm. Such x-ray refractive index images can reveal structural features in soft tissues, with excellent resolution differentiating healthy and malignant tissues. Methods: A novel phase retrieval approach is proposed to reconstruct an x-ray phase image of an object based on the paraxial Fresnel-Kirchhoff diffraction theory. A primary advantage of the authors' approach is higher-order accuracy over that with the conventional linear approximation models, relaxing the current restriction of slow phase variation. The nonlinear terms in the autocorrelation equation of the Fresnel diffraction pattern are eliminated using intensity images measured at different distances in the Fresnel diffraction region, simplifying the phase reconstruction to a linear inverse problem. Numerical experiments are performed

  13. Echelle Blaze Shift vs. MSM Monthly Offset

    NASA Astrophysics Data System (ADS)

    Valenti, Jeff

    2002-07-01

    In the near future, monthly MSM offsets will probably be disabled for STIS echelle gratings, alleviating to some extent calibration problems associated with the monthly offsets. The data from this program will be used to improve empirical and optical models relating wavelength and blaze function shifts. These models will in turn be used to improve the calibration of archival echelle data obtained while monthly MSM offsets were enabled. The flux standard HZ43 will be observed with the E230H echelle grating at a central wavelength of 2513 Angstroms. Five exposures will be obtained, each with a different monthly offset applied to the Mode Select Mechanism {MSM}.

  14. A partial differential equation for pseudocontact shift.

    PubMed

    Charnock, G T P; Kuprov, Ilya

    2014-10-07

    It is demonstrated that pseudocontact shift (PCS), viewed as a scalar or a tensor field in three dimensions, obeys an elliptic partial differential equation with a source term that depends on the Hessian of the unpaired electron probability density. The equation enables straightforward PCS prediction and analysis in systems with delocalized unpaired electrons, particularly for the nuclei located in their immediate vicinity. It is also shown that the probability density of the unpaired electron may be extracted, using a regularization procedure, from PCS data.

  15. Ambiguity produces attention shifts in category learning.

    PubMed

    Vadillo, Miguel A; Orgaz, Cristina; Luque, David; Nelson, James Byron

    2016-04-01

    It has been suggested that people and nonhuman animals protect their knowledge from interference by shifting attention toward the context when presented with information that contradicts their previous beliefs. Despite that suggestion, no studies have directly measured changes in attention while participants are exposed to an interference treatment. In the present experiments, we adapted a dot-probe task to track participants' attention to cues and contexts while they were completing a simple category learning task. The results support the hypothesis that interference produces a change in the allocation of attention to cues and contexts.

  16. Nonrelativistic Lamb shift for muonic molecules

    NASA Astrophysics Data System (ADS)

    Bukowski, Robert; Jeziorski, Bogumil

    1993-03-01

    A recently developed formula [R. Bukowski and B. Jeziorski, Phys. Rev. A46 (1992) 5437]. has been applied to estimate the soft-photon Lamb shift contribution to the energies of the muonic molecules ppμ, ddμ, ttμ, pdμ, ptμ and dtμ. The corresponding corrections to the dissociation energies for the excited P states of ddμ and dtμ have been found to be almost identical and equal to 0.048 meV. The magnitude of this stabilizing effect is too small to affect seriously the formation rates predictions.

  17. Resonance-shifting luminescent solar concentrators

    DOEpatents

    Giebink, Noel Christopher; Wiederrecht, Gary P; Wasielewski, Michael R

    2014-09-23

    An optical system and method to overcome luminescent solar concentrator inefficiencies by resonance-shifting, in which sharply directed emission from a bi-layer cavity into a glass substrate returns to interact with the cavity off-resonance at each subsequent reflection, significantly reducing reabsorption loss en route to the edges. In one embodiment, the system comprises a luminescent solar concentrator comprising a transparent substrate, a luminescent film having a variable thickness; and a low refractive index layer disposed between the transparent substrate and the luminescent film.

  18. Ambiguity produces attention shifts in category learning

    PubMed Central

    Orgaz, Cristina; Luque, David; Nelson, James Byron

    2016-01-01

    It has been suggested that people and nonhuman animals protect their knowledge from interference by shifting attention toward the context when presented with information that contradicts their previous beliefs. Despite that suggestion, no studies have directly measured changes in attention while participants are exposed to an interference treatment. In the present experiments, we adapted a dot-probe task to track participants’ attention to cues and contexts while they were completing a simple category learning task. The results support the hypothesis that interference produces a change in the allocation of attention to cues and contexts. PMID:26980780

  19. Solar Doppler shifts - Sources of continuous spectra

    NASA Technical Reports Server (NTRS)

    Duvall, T. L., Jr.; Harvey, J. W.

    1986-01-01

    Oscillation observations can be used to study nonoscillatory solar phenomena that exhibit Doppler shifts. The paper discusses several effects of these phenomena and their associated temporal and spatial power spectra: (1) they limit the signal-to-noise ratio and sometimes detectability of oscillation modes; (2) there is the potential for better understanding and/or detection of solar phenomena; (3) large-scale convection may spatially modulate oscillation modes, leading to a continuous background spectrum; and (4) in regions of the spectrum where the resolution to separate modes is lacking one can determine upper limits for the integrated effects of modes.

  20. In defence of the right shift theory.

    PubMed

    Annett, M

    1996-02-01

    The right shift (RS) theory of a gene for left-cerebral dominance which increases the probability of right-handedness is outlined, together with two proposed alternatives, the 1985a genetic theory of McManus and the 1993 developmental instability theory of Yeo and Gangestad. Similarities and differences among the three theories are reviewed. Both of the genetic theories can predict the distribution of handedness in families and in twins more efficiently than the developmental instability theory, and the RS theory better than the McManus theory.

  1. A tentative explanation of cosmological red shift

    NASA Technical Reports Server (NTRS)

    Chang, T.; Torr, D. G.

    1990-01-01

    The authors suggest a possible alternative explanation of cosmological red shift. They consider that there exists a background field in the universe, and that light (the photon) has an extremely weak interaction with this background, and as result, experiences an energy loss. By analogy with damped oscillations, the authors introduce a dumping term with the first derivative with respect to time in the wave equation. The solution yields a linearly reduced frequency of the light with travel distance. The purpose of this exercise is to demonstrate how a simple alternative interpretation of the Hubble relation can be generated.

  2. Differential-phase-shift quantum secret sharing.

    PubMed

    Inoue, K; Ohashi, T; Kukita, T; Watanebe, K; Hayashi, S; Honjo, T; Takesue, H

    2008-09-29

    A quantum secret sharing (QSS) protocol based on a differential-phase-shift scheme is proposed, which quantum mechanically provides a full secret key to one party and partial keys to two other parties. A weak coherent pulse train is utilized instead of individual photons as in conventional schemes. Compared with previous QSS protocols, the present one features a simple setup, is suitable for fiber transmission, and offers the possibility for a high key creation rate. An experiment is also carried out to demonstrate the operation.

  3. [Occurrence of drug reactions].

    PubMed

    Pastorello, E; Qualizza, R M; Luraghi, M T; Ispano, M; Villa, A M; Ortolani, C; Zanussi, C

    1986-01-01

    The aim of this prospective study was to evaluate the incidence of allergic reactions to drugs compared to other kinds of medical emergencies admitted to the main Hospital in Milan during a 6 months period. At the same time we drew a list of drugs most frequently involved in allergic reactions, and a list of the most frequent symptoms. Using special forms, the medical staff collected patients' data: age, history of atopy, identification of the drug causing the reaction, and any previous reactions. Among 11,407 cases of medical emergencies, we found 163 (1.43%) patients showing drug reactions: the mean age was 27.3; 58.90% were female; atopy was present in 16.56%. The drugs most frequently involved were: pyrazon group (22%); ASA (20.86%); penicillin and derivatives (9.20%); sulfa drugs (6.14%); group B vitamins (4.30%); tetanus toxoid (4.30%); hyposensitizing extracts (3.68%); propionic acid derivatives (2.46%); paracetamol (1.84%); indomethacin (1.23%); rifampicin (1.23%); erythromycin (1.23%); glafenine (1.23%); others (17.80%). Urticaria and/or angioedema were the most frequent symptoms (86.51%), then anaphylactic shock (9.81%) and asthma (3.68%) with regard to anaphylactic shock only 6.20% of the patients had had a previous reaction to the same drug. From these data we can see that the incidence of drug reactions is very low compared to other medical emergencies; penicillin evidenced fewer reactions than expected, while the pyrazon group and ASA confirmed the data from literature.

  4. Anaphylactoid reaction to ethanol.

    PubMed

    Kelso, J M; Keating, M U; Squillace, D L; O'Connell, E J; Yunginger, J W; Sachs, M I

    1990-05-01

    We studied a 14-year-old boy who developed a pruritic rash and facial swelling after ingestion of beer or wine. A blinded challenge with purified ethanol was positive demonstrating ethanol itself to be the offending agent. An IgE-mediated reaction to ethanol or one of its metabolites as a hapten is possible, or the reaction may involve unusual metabolism of ethanol with accumulation of acetaldehyde and/or direct mast cell degranulation.

  5. Oxygen evolution reaction catalysis

    DOEpatents

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

    2016-09-06

    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

  6. Automatic Detection of Attention Shifts in Infancy: Eye Tracking in the Fixation Shift Paradigm.

    PubMed

    Kulke, Louisa; Atkinson, Janette; Braddick, Oliver

    2015-01-01

    This study measured changes in switches of attention between 1 and 9 months of age in 67 typically developing infants. Remote eye-tracking (Tobii X120) was used to measure saccadic latencies, related to switches of fixation, as a measure of shifts of attention, from a central stimulus to a peripheral visual target, measured in the Fixation Shift Paradigm. Fixation shifts occur later if the central fixation stimulus stays visible when the peripheral target appears (competition condition), than if the central stimulus disappears as the peripheral target appears (non-competition condition). This difference decreases with age. Our results show significantly faster disengagement in infants over 4 months than in the younger group, and provide more precise measures of fixation shifts, than behavioural observation with the same paradigm. Reduced saccadic latencies in the course of a test session indicate a novel learning effect. The Fixation Shift Paradigm combined with remote eye-tracking measures showed improved temporal and spatial accuracy compared to direct observation by a trained observer, and allowed an increased number of trials in a short testing time. This makes it an infant-friendly non-invasive procedure, involving minimal observational training, suitable for use in future studies of clinical populations to detect early attentional abnormalities in the first few months of life.

  7. NMR characterization of cellulose acetate: chemical shift assignments, substituent effects, and chemical shift additivity.

    PubMed

    Kono, Hiroyuki; Hashimoto, Hisaho; Shimizu, Yuuichi

    2015-03-15

    A series of cellulose acetates (CA) with degrees of substitution (DS) ranging from 2.92-0.92 dissolved in dimethylsulfoxide (DMSO)-d6 and cellulose dissolved in tetrabutylammonium fluoride (TBAF)/DMSO-d6 were investigated by two-dimensional NMR spectroscopy. The NMR spectroscopic analysis allowed the determination of the (1)H and (13)C NMR chemical shifts of the eight anhydroglucose units (AGUs) that contain CA: 2,3,6-tri-, 2,3-di-, 2,6-di-, 3,6-di-, 2-mono-, 3-mono-, 6-mono-, and unacetylated AGUs. A comparative analysis of the chemical shift data revealed the substituent effect of acetyl groups at the 2-, 3-, and 6-positions on the (1)H and (13)C nuclei in the same AGU. In addition, chemical shift additivity could be applied to the (1)H and (13)C chemical shifts of CA because the chemical shifts of the diacetylated and triacetylated AGUs could be almost completely explained by the acetyl substituent effects at the 2-, 3-, and 6-positions.

  8. Pollen dispersal slows geographical range shift and accelerates ecological niche shift under climate change

    PubMed Central

    Aguilée, Robin; Raoul, Gaël; Rousset, François; Ronce, Ophélie

    2016-01-01

    Species may survive climate change by migrating to track favorable climates and/or adapting to different climates. Several quantitative genetics models predict that species escaping extinction will change their geographical distribution while keeping the same ecological niche. We introduce pollen dispersal in these models, which affects gene flow but not directly colonization. We show that plant populations may escape extinction because of both spatial range and ecological niche shifts. Exact analytical formulas predict that increasing pollen dispersal distance slows the expected spatial range shift and accelerates the ecological niche shift. There is an optimal distance of pollen dispersal, which maximizes the sustainable rate of climate change. These conclusions hold in simulations relaxing several strong assumptions of our analytical model. Our results imply that, for plants with long distance of pollen dispersal, models assuming niche conservatism may not accurately predict their future distribution under climate change. PMID:27621443

  9. Advantages of shift changeovers with meetings: ergonomic analysis of shift supervisors' activity in aircraft building.

    PubMed

    Le Bris, Valérie; Barthe, Béatrice; Marquié, Jean-Claude; Kerguelen, Alain; Aubert, Sophie; Bernadou, Bernadette

    2012-03-01

    Good shift changeovers contribute to ensuring continuity and reliability in shift work. In situations where production is not maintained 24 h a day, changeovers with meetings (SCM) between the two work teams (written plus oral face-to-face handovers) alternate with changeovers without meetings (SCnM; written handovers only). An ergonomic work analysis on an aircraft assembly line showed that (1) incoming and outgoing operators met during the overlap time allotted by the company, and (2) the content of the exchanges was richer for SCMs than for SCnMs. SCMs enabled the operators to pass on and process more aspects of their work than SCnMs did. SCMs also allowed incoming operators to validate their predictions, and enabled both outgoing and incoming operators to update their mental models and work together on peripheral aspects of the technical process over a greater time span. The findings highlight the importance of allowing overlap time in shift work.

  10. Edge technique for measurement of laser frequency shifts including the Doppler shift

    NASA Technical Reports Server (NTRS)

    Korb, Larry (Inventor)

    1991-01-01

    A method is disclosed for determining the frequency shift in a laser system by transmitting an outgoing laser beam. An incoming laser beam having a frequency shift is received. A first signal is acquired by transmitting a portion of the incoming laser beam to an energy monitor detector. A second signal is acquired by transmitting a portion of the incoming laser beam through an edge filter to an edge detector, which derives a first normalized signal which is proportional to the transmission of the edge filter at the frequency of the incoming laser beam. A second normalized signal is acquired which is proportional to the transmission of the edge filter at the frequency of the outgoing laser beam. The frequency shift is determined by processing the first and second normalized signals.

  11. Tachyons, Lamb shifts and superluminal chaos

    NASA Astrophysics Data System (ADS)

    Tomaschitz, R.

    2000-10-01

    An elementary account on the origins of cosmic chaos in an open and multiply connected universe is given; there is a finite region in the open 3-space in which the world-lines of galaxies are chaotic, and the mixing taking place in this chaotic nucleus of the universe provides a mechanism to create equidistribution. The galaxy background defines a distinguished frame of reference and a unique cosmic time order; in this context superluminal signal transfer is studied. Tachyons are described by a real Proca field with negative mass square, coupled to a current of subluminal matter. Estimates on tachyon mixing in the geometric optics limit are derived. The potential of a static point source in this field theory is a damped periodic function. We treat this tachyon potential as a perturbation of the Coulomb potential, and study its effects on energy levels in hydrogenic systems. By comparing the induced level shifts to high-precision Lamb shift measurements and QED calculations, we suggest a tachyon mass of 2.1 keV/c2 and estimate the tachyonic coupling strength to subluminal matter. The impact of the tachyon field on ground state hyperfine transitions in hydrogen and muonium is investigated. Bounds on atomic transition rates effected by tachyon radiation as well as estimates on the spectral energy density of a possible cosmic tachyon background radiation are derived.

  12. The Underlying Social Dynamics of Paradigm Shifts

    PubMed Central

    Claro, Francisco; Fuentes, Miguel Angel

    2015-01-01

    We develop here a multi-agent model of the creation of knowledge (scientific progress or technological evolution) within a community of researchers devoted to such endeavors. In the proposed model, agents learn in a physical-technological landscape, and weight is attached to both individual search and social influence. We find that the combination of these two forces together with random experimentation can account for both i) marginal change, that is, periods of normal science or refinements on the performance of a given technology (and in which the community stays in the neighborhood of the current paradigm); and ii) radical change, which takes the form of scientific paradigm shifts (or discontinuities in the structure of performance of a technology) that is observed as a swift migration of the knowledge community towards the new and superior paradigm. The efficiency of the search process is heavily dependent on the weight that agents posit on social influence. The occurrence of a paradigm shift becomes more likely when each member of the community attaches a small but positive weight to the experience of his/her peers. For this parameter region, nevertheless, a conservative force is exerted by the representatives of the current paradigm. However, social influence is not strong enough to seriously hamper individual discovery, and can act so as to empower successful individual pioneers who have conquered the new and superior paradigm. PMID:26418255

  13. Wright's shifting balance theory: an experimental study.

    PubMed

    Wade, M J; Goodnight, C J

    1991-08-30

    Experimental confirmation of Wright's shifting balance theory of evolution, one of the most comprehensive theories of adaptive evolution, is presented. The theory is regarded by many as a cornerstone of modern evolutionary thought, but there has been little direct empirical evidence supporting it. Some of its underlying assumptions are viewed as contradictory, and the existence and efficacy of the theory's fundamental adaptive process, interdemic selection, is the focus of controversy. Interdemic selection was imposed on large arrays of laboratory populations of the flour beetle Tribolium castaneum in the manner described by Wright: the differential dispersion of individuals from demes of high fitness into demes of low fitness. A significant increase in average fitness was observed in the experimental arrays when compared to control populations with equivalent but random migration rates. The response was not proportional to the selection differential: The largest response occurred with interdemic selection every two generations rather than every generation or every three generations. The results indicate that the interdemic phase of Wright's shifting balance theory can increase average fitness and suggest that gene interactions are involved in the observed response.

  14. Neural signals encoding shifts in beliefs

    PubMed Central

    Schwartenbeck, Philipp; FitzGerald, Thomas H.B.; Dolan, Ray

    2016-01-01

    Dopamine is implicated in a diverse range of cognitive functions including cognitive flexibility, task switching, signalling novel or unexpected stimuli as well as advance information. There is also longstanding line of thought that links dopamine with belief formation and, crucially, aberrant belief formation in psychosis. Integrating these strands of evidence would suggest that dopamine plays a central role in belief updating and more specifically in encoding of meaningful information content in observations. The precise nature of this relationship has remained unclear. To directly address this question we developed a paradigm that allowed us to decompose two distinct types of information content, information-theoretic surprise that reflects the unexpectedness of an observation, and epistemic value that induces shifts in beliefs or, more formally, Bayesian surprise. Using functional magnetic-resonance imaging in humans we show that dopamine-rich midbrain regions encode shifts in beliefs whereas surprise is encoded in prefrontal regions, including the pre-supplementary motor area and dorsal cingulate cortex. By linking putative dopaminergic activity to belief updating these data provide a link to false belief formation that characterises hyperdopaminergic states associated with idiopathic and drug induced psychosis. PMID:26520774

  15. Microstrip Antennas with Broadband Integrated Phase Shifting

    NASA Technical Reports Server (NTRS)

    Bernhard, Jennifer T.; Romanofsky, Robert R. (Technical Monitor)

    2001-01-01

    The goal of this research was to investigate the feasibility of using a spiral microstrip antenna that incorporates a thin ferroelectric layer to achieve both radiation and phase shifting. This material is placed between the conductive spiral antenna structure and the grounded substrate. Application of a DC bias between the two arms of the spiral antenna will change the effective permittivity of the radiating structure and the degree of coupling between contiguous spiral arms, therefore changing the phase of the RF signal transmitted or received by the antenna. This could eliminate the need for a separate phase shifter apart from the antenna structure. The potential benefits of such an antenna element compared to traditional phased array elements include: continuous, broadband phase shifting at the antenna, lower overall system losses, lighter, more efficient, and more compact phased arrays, and simpler control algorithms. Professor Jennifer Bernhard, graduate student Gregory Huff, and undergraduate student Brian Huang participated in this effort from March 1, 2000 to February 28, 2001. No inventions resulted from the research undertaken in this cooperative agreement.

  16. Language lateralization shifts with learning by adults.

    PubMed

    Plante, Elena; Almryde, Kyle; Patterson, Dianne K; Vance, Christopher J; Asbjørnsen, Arve E

    2015-05-01

    For the majority of the population, language is a left-hemisphere lateralized function. During childhood, a pattern of increasing left lateralization for language has been described in brain imaging studies, suggesting that this trait develops. This development could reflect change due to brain maturation or change due to skill acquisition, given that children acquire and refine language skills as they mature. We test the possibility that skill acquisition, independent of age-associated maturation can result in shifts in language lateralization in classic language cortex. We imaged adults exposed to an unfamiliar language during three successive fMRI scans. Participants were then asked to identify specific words embedded in Norwegian sentences. Exposure to these sentences, relative to complex tones, resulted in consistent activation in the left and right superior temporal gyrus. Activation in this region became increasingly left-lateralized with repeated exposure to the unfamiliar language. These results demonstrate that shifts in lateralization can be produced in the short term within a learning context, independent of maturation.

  17. Saturated Dispersive Extinction Theory of Red Shift

    NASA Astrophysics Data System (ADS)

    Wang, Ling Jun

    2012-03-01

    The Dispersive Extinction Theory (DET) proposed by WangfootnotetextWang, Ling Jun, Physics Essays, 18, No. 2, (2005). offers an alternative to the Big Bang. According to DET, the cosmic red shift is caused by the dispersive extinction of the star light during the propagation from the stars to the earth, instead of being caused by the Doppler shift due to the expansion of the universe.footnotetextHubble, E., Astrophys. J. 64, 321 (1926).^,footnotetextHubble, E., The Realm of the Nebulae, (Yale University Press, New Haven, 1936). DET allows an infinite, stable, non expanding universe, and is immune of the fundamental problems inherent to the Big Bang such as the horizon problem, the extreme violation of the conservation of mass, energy and charge, and the geocentric nature which violates the principle of relativity.footnotetextWang, Ling Jun, Physics Essays, 20, No. 2, (2007). The scenario dealt with in Reference (1) is a one in which the extinction by the space medium is not saturated. This work deals with a different scenario when the extinction is saturated. The saturated extinction causes limited energy loss, and the star light can travel a much greater distance than in the unsaturated scenario.

  18. Metabolic Shifts during Aging and Pathology

    PubMed Central

    Ma, Yina; Li, Ji

    2016-01-01

    The heart is a very special organ in the body and has a high requirement for metabolism due to its constant workload. As a consequence, to provide a consistent and sufficient energy a high steady-state demand of metabolism is required by the heart. When delicately balanced mechanisms are changed by physiological or pathophysiological conditions, the whole system’s homeostasis will be altered to a new balance, which contributes to the pathologic process. So it is no wonder that almost every heart disease is related to metabolic shift. Furthermore, aging is also found to be related to the reduction in mitochondrial function, insulin resistance, and dysregulated intracellular lipid metabolism. Adenosine monophosphate-activated protein kinase (AMPK) functions as an energy sensor to detect intracellular ATP/AMP ratio and plays a pivotal role in intracellular adaptation to energy stress. During different pathology (like myocardial ischemia and hypertension), the activation of cardiac AMPK appears to be essential for repairing cardiomyocyte’s function by accelerating ATP generation, attenuating ATP depletion, and protecting the myocardium against cardiac dysfunction and apoptosis. In this overview, we will talk about the normal heart’s metabolism, how metabolic shifts during aging and different pathologies, and how AMPK regulates metabolic changes during these conditions. PMID:25880509

  19. Shifting seasons, climate change and ecosystem consequences

    NASA Astrophysics Data System (ADS)

    Thackeray, Stephen; Henrys, Peter; Hemming, Deborah; Huntingford, Chris; Bell, James; Leech, David; Wanless, Sarah

    2014-05-01

    In recent decades, the seasonal timing of many biological events (e.g. flowering, breeding, migration) has shifted. These phenological changes are believed to be one of the most conspicuous biological indicators of climate change. Rates and directions of phenological change have differed markedly among species, potentially threatening the seasonal synchrony of key species interactions and ultimately ecosystem functioning. Differences in phenological change among-species at different trophic levels, and with respect to other broad species traits, are likely to be driven by variations in the climatic sensitivity of phenological events. However, as yet, inconsistencies in analytical methods have hampered broad-scale assessments of variation in climate sensitivity among taxonomic and functional groups of organisms. In this presentation, results will be presented from a current collaborative project (http://www.ceh.ac.uk/sci_programmes/shifting-seasons-uk.html) in which many UK long-term data sets are being integrated in order to assess relationships between temperature/precipitation, and the timing of seasonal events for a wide range of plants and animals. Our aim is to assess which organism groups (in which locations/habitats) are most sensitive to climate. Furthermore, the role of anthropogenic climate change as a driver of phenological change is being assessed.

  20. Theory of Lamb Shift in Muonic Hydrogen

    SciTech Connect

    Karshenboim, Savely G.; Korzinin, Evgeny Yu.; Shelyuto, Valery A.; Ivanov, Vladimir G.

    2015-09-15

    There has been for a while a large discrepancy between the values of the proton charge radius measured by the Lamb shift in muonic hydrogen and by other methods. It has already been clear that theory of muonic hydrogen is reliable at the level of this discrepancy and an error there cannot be a reason for the contradiction. Still the status of theory at the level of the uncertainty of the muonic-hydrogen experiment (which is two orders of magnitude below the discrepancy level) requires an additional clarification. Here, we revisit theory of the 2p − 2s Lamb shift in muonic hydrogen. We summarize all the theoretical contributions in order α{sup 5}m, including pure quantum electrodynamics (QED) ones as well as those which involve the proton-structure effects. Certain enhanced higher-order effects are also discussed. We basically confirm former QED calculations of other authors, present a review of recent calculations of the proton-structure effects, and treat self-consistently higher-order proton-finite-size corrections. We also overview theory of the 2p states. Eventually, we derive a value of the root-mean-square proton charge radius. It is found to be 0.840 29(55) fm, which is slightly different from that previously published in the literature (0.840 87(39) fm [Antognini et al., Science 339, 417 (2013)])