Sample records for catalytic mechanism operating

  1. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones


    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

  2. Propulsion Mechanism of Catalytic Microjet Engines (United States)

    Fomin, Vladimir M.; Hippler, Markus; Magdanz, Veronika; Soler, Lluís; Sanchez, Samuel; Schmidt, Oliver G.


    We describe the propulsion mechanism of the catalytic microjet engines that are fabricated using rolled-up nanotech. Microjets have recently shown numerous potential applications in nanorobotics but currently there is a lack of an accurate theoretical model that describes the origin of the motion as well as the mechanism of self-propulsion. The geometric asymmetry of a tubular microjet leads to the development of a capillary force, which tends to propel a bubble toward the larger opening of the tube. Because of this motion in an asymmetric tube, there emerges a momentum transfer to the fluid. In order to compensate this momentum transfer, a jet force acting on the tube occurs. This force, which is counterbalanced by the linear drag force, enables tube velocities of the order of 100 μm/s. This mechanism provides a fundamental explanation for the development of driving forces that are acting on bubbles in tubular microjets. PMID:25177214

  3. Short hydrogen bonds in the catalytic mechanism of serine proteases

    Directory of Open Access Journals (Sweden)



    Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.


    Directory of Open Access Journals (Sweden)

    Martin Lisý


    Full Text Available The paper focuses on the theoretical description of the cleaning of syngas from biomass and waste gasification using catalytic methods, and on the verification of the theory through experiments. The main obstruction to using syngas from fluid gasification of organic matter is the presence of various high-boiling point hydrocarbons (i.e., tar in the gas. The elimination of tar from the gas is a key factor in subsequent use of the gas in other technologies for cogeneration of electrical energy and heat. The application of a natural or artificial catalyst for catalytic destruction of tar is one of the methods of secondary elimination of tar from syngas. In our experiments, we used a natural catalyst (dolomite or calcium magnesium carbonate from Horní Lánov with great mechanical and catalytic properties, suitable for our purposes. The advantages of natural catalysts in contrast to artificial catalysts include their availability, low purchase prices and higher resilience to the so-called catalyst poison. Natural calcium catalysts may also capture undesired compounds of sulphure and chlorine. Our paper presents a theoretical description and analysis of catalytic destruction of tar into combustible gas components, and of the impact of dolomite calcination on its efficiency. The efficiency of the technology is verified in laboratories. The facility used for verification was a 150 kW pilot gasification unit with a laboratory catalytic filter. The efficiency of tar elimination reached 99.5%, the tar concentration complied with limits for use of the gas in combustion engines, and the tar content reached approximately 35 mg/mn3. The results of the measurements conducted in laboratories helped us design a pilot technology for catalytic gas cleaning.

  5. Solid catalytic growth mechanism of micro-coiled carbon fibers

    Institute of Scientific and Technical Information of China (English)


    Micro-coiled carbon fibers were prepared by catalytic pyrolysisof acetylene with nano-sized nickel powder catalyst using the substrate method. The morphology of micro-coiled carbon fibers was observed through field emission scanning electron microscopy. It was found that the fiber and coil diameter of the obtained micro-coiled carbon fibers is about 500—600 nm and 4—5 μm, respectively. Most of the micro-coiled carbon fibers obtained were regular double carbon coils, but a few irregular ones were also observed. On the basis of the experimental observation, a solid catalytic growth mechanism of micro-coiled carbon fibers was proposed.

  6. Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation (United States)

    Gone, Swapna; Alfonso-Prieto, Mercedes; Paudyal, Samridhdi; Nicholson, Allen W.


    Ribonuclease III (RNase III) is a conserved, gene-regulatory bacterial endonuclease that cleaves double-helical structures in diverse coding and noncoding RNAs. RNase III is subject to multiple levels of control, reflective of its global regulatory functions. Escherichia coli (Ec) RNase III catalytic activity is known to increase during bacteriophage T7 infection, reflecting the expression of the phage-encoded protein kinase, T7PK. However, the mechanism of catalytic enhancement is unknown. This study shows that Ec-RNase III is phosphorylated on serine in vitro by purified T7PK, and identifies the targets as Ser33 and Ser34 in the N-terminal catalytic domain. Kinetic experiments reveal a 5-fold increase in kcat and a 1.4-fold decrease in Km following phosphorylation, providing a 7.4–fold increase in catalytic efficiency. Phosphorylation does not change the rate of substrate cleavage under single-turnover conditions, indicating that phosphorylation enhances product release, which also is the rate-limiting step in the steady-state. Molecular dynamics simulations provide a mechanism for facilitated product release, in which the Ser33 phosphomonoester forms a salt bridge with the Arg95 guanidinium group, thereby weakening RNase III engagement of product. The simulations also show why glutamic acid substitution at either serine does not confer enhancement, thus underscoring the specific requirement for a phosphomonoester.

  7. Surface Catalytic Mechanism in Square-Wave Voltammetry


    Mirceski, Valentin; Gulaboski, Rubin


    A pseudo-first-order catalytic mechanism in which both reactant and product of the redox reaction are strongly immobilized on the electrode surface is theoretically analyzed under conditions of square-wave voltammetry (SWV). A mathematical procedure is developed for diffusionless conditions. The relationships between the properties of the voltammetric response and both the kinetic parameters of the redox reaction and the parameters of the excitement signal are studied. The phenomenon...

  8. Operator Formulation of Classical Mechanics. (United States)

    Cohn, Jack


    Discusses the construction of an operator formulation of classical mechanics which is directly concerned with wave packets in configuration space and is more similar to that of convential quantum theory than other extant operator formulations of classical mechanics. (Author/HM)

  9. Three-Dimensional Structure and Catalytic Mechanism of Cytosine Deaminase

    Energy Technology Data Exchange (ETDEWEB)

    R Hall; A Fedorov; C Xu; E Fedorov; S Almo; F Raushel


    Cytosine deaminase (CDA) from E. coli is a member of the amidohydrolase superfamily. The structure of the zinc-activated enzyme was determined in the presence of phosphonocytosine, a mimic of the tetrahedral reaction intermediate. This compound inhibits the deamination of cytosine with a K{sub i} of 52 nM. The zinc- and iron-containing enzymes were characterized to determine the effect of the divalent cations on activation of the hydrolytic water. Fe-CDA loses activity at low pH with a kinetic pKa of 6.0, and Zn-CDA has a kinetic pKa of 7.3. Mutation of Gln-156 decreased the catalytic activity by more than 5 orders of magnitude, supporting its role in substrate binding. Mutation of Glu-217, Asp-313, and His-246 significantly decreased catalytic activity supporting the role of these three residues in activation of the hydrolytic water molecule and facilitation of proton transfer reactions. A library of potential substrates was used to probe the structural determinants responsible for catalytic activity. CDA was able to catalyze the deamination of isocytosine and the hydrolysis of 3-oxauracil. Large inverse solvent isotope effects were obtained on k{sub cat} and k{sub cat}/K{sub m}, consistent with the formation of a low-barrier hydrogen bond during the conversion of cytosine to uracil. A chemical mechanism for substrate deamination by CDA was proposed.

  10. New aspects of the electrochemical-catalytic (EC’) mechanism in square-wave voltammetry


    Gulaboski, Rubin; Mirceski, Valentin


    Several new theoretical aspects of the electrocatalytic (regenerative) EC’ mechanism under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV) are presented. Elaborating the effect of the rate of the catalytic reaction in the diffusion-controlled catalytic mechanism (diffusional EC’ mechanism) and surface catalytic mechanism (surface EC’ mechanism), we refer to several phenomena related to the shift of the position and the half-peak width of the net peak in ...

  11. The catalytic mechanism of an aspartic proteinase explored with neutron and X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Kovalevsky, Andrey [Los Alamos National Laboratory (LANL); Erskine, Peter T. [University of Southampton, England; Cooper, Jon [University of Southampton, England


    Hydrogen atoms play key roles in enzyme mechanism, but as this study shows, even high-quality X-ray data to a resolution of 1 {angstrom} cannot directly visualize them. Neutron diffraction, however, can locate deuterium atoms even at resolutions around 2 {angstrom}. Both neutron and X-ray diffraction data have been used to investigate the transition state of the aspartic proteinase endothiapepsin. The different techniques reveal a different part of the story, revealing the clearest picture yet of the catalytic mechanism by which the enzyme operates. Room temperature neutron and X-ray diffraction data were used in a newly developed joint refinement software package to visualize deuterium atoms within the active site of the enzyme when a gem-diol transition state analogue inhibitor is bound at the active site. These data were also used to estimate their individual occupancy, while analysis of the differences between the bond lengths of the catalytic aspartates was performed using atomic resolution X-ray data. The two methods are in agreement on the protonation state of the active site with a transition state analogue inhibitor bound confirming the catalytic mechanism at which the enzyme operates.

  12. Linear operators for quantum mechanics

    CERN Document Server

    Jordan, Thomas F


    This compact treatment highlights the logic and simplicity of the mathematical structure of quantum mechanics. Suitable for advanced undergraduates and graduate students, it treats the language of quantum mechanics as expressed in the mathematics of linear operators.Originally oriented toward atomic physics, quantum mechanics became a basic language for solid-state, nuclear, and particle physics. Its grammar consists of the mathematics of linear operators, and with this text, students will find it easier to understand and use the language of physics. Topics include linear spaces and linear fun

  13. Theoretical insights into catalytic mechanism of protein arginine methyltransferase 1.

    Directory of Open Access Journals (Sweden)

    Ruihan Zhang

    Full Text Available Protein arginine methyltransferase 1 (PRMT1, the major arginine asymmetric dimethylation enzyme in mammals, is emerging as a potential drug target for cancer and cardiovascular disease. Understanding the catalytic mechanism of PRMT1 will facilitate inhibitor design. However, detailed mechanisms of the methyl transfer process and substrate deprotonation of PRMT1 remain unclear. In this study, we present a theoretical study on PRMT1 catalyzed arginine dimethylation by employing molecular dynamics (MD simulation and quantum mechanics/molecular mechanics (QM/MM calculation. Ternary complex models, composed of PRMT1, peptide substrate, and S-adenosyl-methionine (AdoMet as cofactor, were constructed and verified by 30-ns MD simulation. The snapshots selected from the MD trajectory were applied for the QM/MM calculation. The typical SN2-favored transition states of the first and second methyl transfers were identified from the potential energy profile. Deprotonation of substrate arginine occurs immediately after methyl transfer, and the carboxylate group of E144 acts as proton acceptor. Furthermore, natural bond orbital analysis and electrostatic potential calculation showed that E144 facilitates the charge redistribution during the reaction and reduces the energy barrier. In this study, we propose the detailed mechanism of PRMT1-catalyzed asymmetric dimethylation, which increases insight on the small-molecule effectors design, and enables further investigations into the physiological function of this family.

  14. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G


    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with

  15. [Mechanism of catalytic ozonation for the degradation of paracetamol by activated carbon]. (United States)

    Wang, Jia-Yu; Dai, Qi-Zhou; Yu, Jie; Yan, Yi-Zhou; Chen, Jian-Meng


    The degradation of paracetamol (APAP) in aqueous solution was studied with ozonation integrated with activated carbon (AC). The synergistic effect of ozonation/AC process was explored by comparing the degradation efficiency of APAP in three processes (ozonation alone, activated carbon alone and ozonation integrated with activated carbon). The operational parameters that affected the reaction rate were carefully optimized. Based on the intermediates detected, the possible pathway for catalytic degradation was discussed and the reaction mechanism was also investigated. The results showed that the TOC removal reached 55.11% at 60 min in the AC/O3 system, and was significantly better than the sum of ozonation alone (20.22%) and activated carbon alone (27.39%), showing the great synergistic effect. And the BOD5/COD ratio increased from 0.086 (before reaction) to 0.543 (after reaction), indicating that the biodegradability was also greatly improved. The effects of the initial concentration of APAP, pH value, ozone dosage and AC dosage on the variation of reaction rate were carefully discussed. The catalytic reaction mechanism was different at different pH values: the organic pollutions were removed by adsorption and direct ozone oxidation at acidic pH, and mainly by catalytic ozonation at alkaline pH.

  16. A biophysically based mathematical model for the catalytic mechanism of glutathione reductase. (United States)

    Pannala, Venkat R; Bazil, Jason N; Camara, Amadou K S; Dash, Ranjan K


    Glutathione reductase (GR) catalyzes the reduction of oxidized glutathione (GSSG) to reduced glutathione (GSH) using NADPH as the reducing cofactor, and thereby maintains a constant GSH level in the system. GSH scavenges superoxide (O2(*-)) and hydroxyl radicals (OH) nonenzymatically or by serving as an electron donor to several enzymes involved in reactive oxygen species (ROS) detoxification. In either case, GSH oxidizes to GSSG and is subsequently regenerated by the catalytic action of GR. Although the GR kinetic mechanism has been extensively studied under various experimental conditions with variable substrates and products, the catalytic mechanism has not been studied in terms of a mechanistic model that accounts for the effects of the substrates and products on the reaction kinetics. The aim of this study is therefore to develop a comprehensive mathematical model for the catalytic mechanism of GR. We use available experimental data on GR kinetics from various species/sources to develop the mathematical model and estimate the associated model parameters. The model simulations are consistent with the experimental observation that GR operates via both ping-pong and sequential branching mechanisms based on relevant concentrations of its reaction substrate GSSG. Furthermore, we show the observed pH-dependent substrate inhibition of GR activity by GSSG and bimodal behavior of GR activity with pH. The model presents a unique opportunity to understand the effects of products on the kinetics of GR. The model simulations show that under physiological conditions, where both substrates and products are present, the flux distribution depends on the concentrations of both GSSG and NADP(+), with ping-pong flux operating at low levels and sequential flux dominating at higher levels. The kinetic model of GR may serve as a key module for the development of integrated models for ROS-scavenging systems to understand protection of cells under normal and oxidative stress

  17. Operator methods in quantum mechanics

    CERN Document Server

    Schechter, Martin


    This advanced undergraduate and graduate-level text introduces the power of operator theory as a tool in the study of quantum mechanics, assuming only a working knowledge of advanced calculus and no background in physics. The author presents a few simple postulates describing quantum theory, gradually introducing the mathematical techniques that help answer questions important to the physical theory; in this way, readers see clearly the purpose of the method and understand the accomplishment. The entire book is devoted to the study of a single particle moving along a straight line. By posing q

  18. Data reconciliation and optimal operation of a Catalytic naphtha reformer

    Directory of Open Access Journals (Sweden)

    Tore Lid


    Full Text Available The naphtha reforming process converts low-octane gasoline blending components to high-octane components for use in high-performance gasoline fuels. The reformer also has an important function as the producer of hydrogen to the refinery hydrotreaters. A process model based on a unit model structure, is used for estimation of the process condition using data reconciliation. Measurements are classified as redundant or non redundant and the model variables are classified as observable, barely observable or unobservable. The computed uncertainty of the measured and unmeasured variables shows that even if a variable is observable it may have a very large uncertainty and may thereby be practically unobservable. The process condition at 21 data points, sampled from two years of operation, was reconciled and used to optimize the process operation. There are large seasonal variations in the reformer product price and two operational cases are studied. In case 1, the product price is high and throughput is maximized with respect to process and product quality constraints. In case 2, the product price is low and the throughput is minimized with respect to a low constraint on the hydrogen production. Based on the characteristics of the optimal operation, a "self optimizing" control structure is suggested for each of the two operational cases.

  19. Mechanism of Transition-Metal Nanoparticle Catalytic Graphene Cutting. (United States)

    Ma, Liang; Wang, Jinlan; Yip, Joanne; Ding, Feng


    Catalytic cutting by transition-metal (TM) particles is a promising method for the synthesizing of high-quality graphene quantum dots and nanoribbons with smooth edges. Experimentally, it is observed that the cutting always results in channels with zigzag (ZZ) or armchair (AC) edges. However, the driving force that is responsible for such a cutting behavior remains a puzzle. Here, by calculating the interfacial formation energies of the TM-graphene edges with ab initio method, we show that the surface of a catalyst particle tends to be aligned along either AC or ZZ direction of the graphene lattice, and thus the cutting of graphene is guided as such. The different cutting behaviors of various catalysts are well-explained based on the competition between TM-passivated graphene edges and the etching-agent-terminated ones. Furthermore, the kinetics of graphene catalytic cutting along ZZ and AC directions, respectively, are explored at the atomic level.

  20. Substrate binding and catalytic mechanism in phospholipase C from Bacillus cereus. a molecular mechanics and molecular dynamics study

    DEFF Research Database (Denmark)

    da Graça Thrige, D; Buur, J R; Jørgensen, Flemming Steen


    For the first time a consistent catalytic mechanism of phospholipase C from Bacillus cereus is reported based on molecular mechanics calculations. We have identified the position of the nucleophilic water molecule, which is directly involved in the hydrolysis of the natural substrate phosphatidyl...

  1. Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS) with Catalytic Intermediates and Substrate Analogues

    Energy Technology Data Exchange (ETDEWEB)

    Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; Bell, Charles E.; Pei, Dehua; (OSU); (FIU)


    S-Ribosylhomocysteinase (LuxS) cleaves the thioether bond in S-ribosylhomocysteine (SRH) to produce homocysteine (Hcys) and 4,5-dihydroxy-2,3-pentanedione (DPD), the precursor of the type II bacterial quorum sensing molecule (AI-2). The catalytic mechanism of LuxS comprises three distinct reaction steps. The first step involves carbonyl migration from the C1 carbon of ribose to C2 and the formation of a 2-ketone intermediate. The second step shifts the C=O group from the C2 to C3 position to produce a 3-ketone intermediate. In the final step, the 3-ketone intermediate undergoes a {beta}-elimination reaction resulting in the cleavage of the thioether bond. In this work, the 3-ketone intermediate was chemically synthesized and shown to be chemically and kinetically competent in the LuxS catalytic pathway. Substrate analogues halogenated at the C3 position of ribose were synthesized and reacted as time-dependent inhibitors of LuxS. The time dependence was caused by enzyme-catalyzed elimination of halide ions. Examination of the kinetics of halide release and decay of the 3-ketone intermediate catalyzed by wild-type and mutant LuxS enzymes revealed that Cys-84 is the general base responsible for proton abstraction in the three reaction steps, whereas Glu-57 likely facilitates substrate binding and proton transfer during catalysis.

  2. Substrate-enzyme interactions and catalytic mechanism in phospholipase C

    DEFF Research Database (Denmark)

    Byberg, J R; Jørgensen, Flemming Steen; Hansen, S;


    Based on the high-resolution X-ray crystallographic structure of phospholipase C from Bacillus cereus, the orientation of the phosphatidylcholine substrate in the active site of the enzyme is proposed. The proposal is based on extensive calculations using the GRID program and molecular mechanics ...

  3. Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling (United States)

    García, Andrés; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.


    Statistical mechanical modeling is developed to describe a catalytic conversion reaction A →Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Furthermore, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A .

  4. Catalytic mechanism of a retinoid isomerase essential for vertebrate vision. (United States)

    Kiser, Philip D; Zhang, Jianye; Badiee, Mohsen; Li, Qingjiang; Shi, Wuxian; Sui, Xuewu; Golczak, Marcin; Tochtrop, Gregory P; Palczewski, Krzysztof


    Visual function in vertebrates is dependent on the membrane-bound retinoid isomerase RPE65, an essential component of the retinoid cycle pathway that regenerates 11-cis-retinal for rod and cone opsins. The mechanism by which RPE65 catalyzes stereoselective retinoid isomerization has remained elusive because of uncertainty about how retinoids bind to its active site. Here we present crystal structures of RPE65 in complex with retinoid-mimetic compounds, one of which is in clinical trials for the treatment of age-related macular degeneration. The structures reveal the active site retinoid-binding cavity located near the membrane-interacting surface of the enzyme as well as an Fe-bound palmitate ligand positioned in an adjacent pocket. With the geometry of the RPE65-substrate complex clarified, we delineate a mechanism of catalysis that reconciles the extensive biochemical and structural research on this enzyme. These data provide molecular foundations for understanding a key process in vision and pharmacological inhibition of RPE65 with small molecules.

  5. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

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    Effendy Mohammad


    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  6. Catalytic mechanism investigation of lysine-specific demethylase 1 (LSD1: a computational study.

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    Xiangqian Kong

    Full Text Available Lysine-specific demethylase 1 (LSD1, the first identified histone demethylase, is a flavin-dependent amine oxidase which specifically demethylates mono- or dimethylated H3K4 and H3K9 via a redox process. It participates in a broad spectrum of biological processes and is of high importance in cell proliferation, adipogenesis, spermatogenesis, chromosome segregation and embryonic development. To date, as a potential drug target for discovering anti-tumor drugs, the medical significance of LSD1 has been greatly appreciated. However, the catalytic mechanism for the rate-limiting reductive half-reaction in demethylation remains controversial. By employing a combined computational approach including molecular modeling, molecular dynamics (MD simulations and quantum mechanics/molecular mechanics (QM/MM calculations, the catalytic mechanism of dimethylated H3K4 demethylation by LSD1 was characterized in details. The three-dimensional (3D model of the complex was composed of LSD1, CoREST, and histone substrate. A 30-ns MD simulation of the model highlights the pivotal role of the conserved Tyr761 and lysine-water-flavin motif in properly orienting flavin adenine dinucleotide (FAD with respect to substrate. The synergy of the two factors effectively stabilizes the catalytic environment and facilitated the demethylation reaction. On the basis of the reasonable consistence between simulation results and available mutagenesis data, QM/MM strategy was further employed to probe the catalytic mechanism of the reductive half-reaction in demethylation. The characteristics of the demethylation pathway determined by the potential energy surface and charge distribution analysis indicates that this reaction belongs to the direct hydride transfer mechanism. Our study provides insights into the LSD1 mechanism of reductive half-reaction in demethylation and has important implications for the discovery of regulators against LSD1 enzymes.

  7. Catalytic routes and oxidation mechanisms in photoreforming of polyols

    Energy Technology Data Exchange (ETDEWEB)

    Sanwald, Kai E.; Berto, Tobias F.; Eisenreich, Wolfgang; Gutiérrez, Oliver Y.; Lercher, Johannes A.


    Photocatalytic reforming of biomass-derived oxygenates leads to H2 generation and evolution of CO2 via parallel formation of organic intermediates through anodic oxidations on a Rh/TiO2 photocatalyst. The reaction pathways and kinetics in the photoreforming of C3–C6 polyols were explored. Polyols are converted via direct and indirect hole transfer pathways resulting in (i) oxidative rupture of C–C bonds, (ii) oxidation to a-oxygen functionalized aldoses and ketoses (carbonyl group formation) and (iii) light-driven dehydration. Direct hole transfer to chemisorbed oxygenates on terminal Ti(IV)-OH groups, generating alkoxy-radicals that undergo ß-C–C-cleavage, is proposed for the oxidative C–C rupture. Carbonyl group formation and dehydration are attributed to indirect hole transfer at surface lattice oxygen sites [Ti_ _ _O_ _ _Ti] followed by the generation of carbon-centered radicals. Polyol chain length impacts the contribution of the oxidation mechanisms favoring the C–C bond cleavage (internal preferred over terminal) as the dominant pathway with higher polyol carbon number.

  8. Unique kinase catalytic mechanism of AceK with a single magnesium ion.

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    Quanjie Li

    Full Text Available Isocitrate dehydrogenase kinase/phosphatase (AceK is the founding member of the protein phosphorylation system in prokaryotes. Based on the novel and unique structural characteristics of AceK recently uncovered, we sought to understand its kinase reaction mechanism, along with other features involved in the phosphotransfer process. Herein we report density functional theory QM calculations of the mechanism of the phosphotransfer reaction catalysed by AceK. The transition states located by the QM calculations indicate that the phosphorylation reaction, catalysed by AceK, follows a dissociative mechanism with Asp457 serving as the catalytic base to accept the proton delivered by the substrate. Our results also revealed that AceK prefers a single Mg(2+-containing active site in the phosphotransfer reaction. The catalytic roles of conserved residues in the active site are discussed.

  9. Evidence for the formation of a covalent thiosulfinate intermediate with peroxiredoxin in the catalytic mechanism of sulfiredoxin. (United States)

    Roussel, Xavier; Béchade, Guillaume; Kriznik, Alexandre; Van Dorsselaer, Alain; Sanglier-Cianferani, Sarah; Branlant, Guy; Rahuel-Clermont, Sophie


    The typical 2-Cys peroxiredoxins are thiol-peroxidases involved in the physiology of hydrogen peroxide not only as a toxic but also as a signaling molecule. Coordination of these functions depends on the sulfinylation of the catalytic Cys, a modification reversed by ATP-dependent sulfiredoxin, which specifically reduces the sulfinic acid group of overoxidized 2-Cys peroxiredoxins into a sulfenic acid. Sulfiredoxin was originally proposed to operate by covalent catalysis, with formation of a peroxiredoxin-sulfiredoxin intermediate linked by a thiosulfinate bond between the catalytic Cys of both partners, a hypothesis rejected by a study of the human enzyme. To settle the argument, we investigated the catalytic mechanism of Saccharomyces cerevisiae sulfiredoxin, by the characterization of the nature and kinetics of formation of the protein species formed between sulfiredoxin and its substrate in the presence of ATP, using mutants of the non-essential Cys residues of both proteins. We observed the formation of a dithiothreitol-reducible peroxiredoxin-sulfiredoxin species using SDS-PAGE and Western blot analysis, and its mass was shown to correspond to a thiosulfinate complex by high resolution mass spectrometry coupled to liquid chromatography. We next measured indirectly and directly a rate constant of formation of the thiosulfinate species of approximately 2 min(-1), for both wild-type and mutant sulfiredoxins, at least equal to the steady-state rate constant of the reaction, with a stoichiometry of 1:1 relative to peroxiredoxin. Taken altogether, our results strongly argue in favor of the formation of a covalent thiosulfinate peroxiredoxin-sulfiredoxin species as an intermediate on the catalytic pathway.

  10. Catalytic effect and reaction mechanism of Ti doped in NaAlH4: A review

    Institute of Scientific and Technical Information of China (English)

    WANG Qiang; CHEN YunGui; WU ChaoLing; TAO MingDa


    Catalytic effect and hydrogen reaction mechanism of Ti doped in NaAlH4 were elaborated in this paper, and current viewpoints about Ti active species in hydrogen reaction were discussed, in a further step, the possibility and practicality of the hydrogen reaction mechanism of Ti-doped NaAlH4 were elucidated. They could be summarized as follows: while the current theory about the hydrogen reaction mecha-nism of Ti-doped NaAlH4 should be further improved and modified, the research on Ti-doped NaAlH4 would be a recommendable pattern for the catalyst research in other metal complex hydrides.

  11. Theoretical modeling study for the phosphonylation mechanisms of the catalytic triad of acetylcholinesterase by sarin. (United States)

    Wang, Jing; Gu, Jiande; Leszczynski, Jerzy


    Potential energy surfaces for the process of phosphonylation of the catalytic triad of acetylcholinesterase by sarin have been explored at the B3LYP/6-311G(d,p) level of theory through a computational study. It is concluded that the phosphonylation process involves a critical addition-elimination mechanism. The first nucleophilic addition process is the rate-determining step. The following elimination process of the fluoride ion comprises a composite reaction that includes several steps, and it occurs rapidly by comparison with the rate-determining step. The mobility characteristics of histidine play an important role in the reaction. A double proton-transfer mechanism is proposed for the catalytic triad during the phosphonylation process of sarin on AChE. The effect of aqueous solvation has been considered via the polarizable continuum model (PCM). One concludes that the energy barriers are generally lowered in solvent, compared to the gas-phase reactions.

  12. Interagency mechanical operations group numerical systems group

    Energy Technology Data Exchange (ETDEWEB)



    This report consists of the minutes of the May 20-21, 1971 meeting of the Interagency Mechanical Operations Group (IMOG) Numerical Systems Group. This group looks at issues related to numerical control in the machining industry. Items discussed related to the use of CAD and CAM, EIA standards, data links, and numerical control.

  13. MnO2/CeO2 for catalytic ultrasonic decolorization of methyl orange: Process parameters and mechanisms. (United States)

    Zhao, He; Zhang, Guangming; Chong, Shan; Zhang, Nan; Liu, Yucai


    MnO2/CeO2 catalyst was prepared and characterized by means of Brunauer-Emmet-Teller (BET) method, X-ray diffraction (XRD) and scanning electron microscope (SEM). The characterization showed that MnO2/CeO2 had big specific surface area and MnO2 was dispersed homogeneously on the surface of CeO2. Excellent degradation efficiency of methyl orange was achieved by MnO2/CeO2 catalytic ultrasonic process. Operating parameters were studied and optimized. The optimal conditions were 10 min of ultrasonic irradiation, 1.0 g/L of catalyst dose, 2.6 of pH value and 1.3 W/ml of ultrasonic density. Under the optimal conditions, nearly 90% of methyl orange was removed. The mechanism of methyl orange degradation was further studied. The decolorization mechanism in the ultrasound-MnO2/CeO2 system was quite different with that in the ultrasound-MnO2 system. Effects of manganese and cerium in catalytic ultrasonic process were clarified. Manganese ions in solution contributed to generating hydroxyl free radical. MnO2/CeO2 catalyst strengthened the oxidation ability of ultrasound and realized complete decolorization of methyl orange.

  14. Discerning the catalytic mechanism of Staphylococcus aureus sortase A with QM/MM free energy calculations. (United States)

    Shrestha, Pooja; Wereszczynski, Jeff


    Sortases are key virulence factors in Gram-positive bacteria. These enzymes embed surface proteins in the cell wall through a transpeptidation reaction that involves recognizing a penta-peptide "sorting signal" in a target protein, cleaving it, and covalently attaching it to a second substrate that is later inserted into the cell wall. Although well studied, several aspects of the mechanism by which sortases perform these functions remains unclear. In particular, experiments have revealed two potential sorting signal binding motifs: a "Threonine-Out" (Thr-Out) structure in which the catalytically critical threonine residues protrudes into solution, and a "Threonine-In" (Thr-In) configuration in which this residue inserts into the binding site. To determine which of these is the biologically relevant state, we have performed a series of conventional and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations of the Staphylococcus aureus sortase A (SrtA) enzyme bound to a sorting signal substrate. Through the use of multi-dimensional metadynamics, our simulations were able to both map the acylation mechanism of SrtA in the Thr-In and Thr-Out states, as well as determine the free energy minima and barriers along these reactions. Results indicate that in both states the catalytic mechanisms are similar, however the free energy barriers are lower in the Thr-In configuration, suggesting that Thr-In is the catalytically relevant state. This has important implications for advancing our understanding of the mechanisms of sortase enzymes, as well we for future structure based drug design efforts aimed at inhibiting sortase function in vivo.

  15. Quantum Mechanics and Molecular Mechanics Study of the Catalytic Mechanism of Human AMSH-LP Domain Deubiquitinating Enzymes. (United States)

    Zhu, Wenyou; Liu, Yongjun; Ling, Baoping


    Deubiquitinating enzymes (DUBs) catalyze the cleavage of the isopeptide bond in polyubiquitin chains to control and regulate the deubiquitination process in all known eukaryotic cells. The human AMSH-LP DUB domain specifically cleaves the isopeptide bonds in the Lys63-linked polyubiquitin chains. In this article, the catalytic mechanism of AMSH-LP has been studied using a combined quantum mechanics and molecular mechanics method. Two possible hydrolysis processes (Path 1 and Path 2) have been considered. Our calculation results reveal that the activation of Zn(2+)-coordinated water molecule is the essential step for the hydrolysis of isopeptide bond. In Path 1, the generated hydroxyl first attacks the carbonyl group of Gly76, and then the amino group of Lys63 is protonated, which is calculated to be the rate limiting step with an energy barrier of 13.1 kcal/mol. The energy barrier of the rate limiting step and the structures of intermediate and product are in agreement with the experimental results. In Path 2, the protonation of amino group of Lys63 is prior to the nucleophilic attack of activated hydroxyl. The two proton transfer processes in Path 2 correspond to comparable overall barriers (33.4 and 36.1 kcal/mol), which are very high for an enzymatic reaction. Thus, Path 2 can be ruled out. During the reaction, Glu292 acts as a proton transfer mediator, and Ser357 mainly plays a role in stabilizing the negative charge of Gly76. Besides acting as a Lewis acid, Zn(2+) also influences the reaction by coordinating to the reaction substrates (W1 and Gly76).

  16. Catalytic mechanisms, basic roles, and biotechnological and environmental significance of halogenating enzymes

    Institute of Scientific and Technical Information of China (English)

    Xianping Chen; Karl-Heinz van Pée


    The understanding of enzymatic incorporation of halogen atoms into organic molecules has increased during the last few years. Two novel types of halogenating enzymes, flavindependent halogenases and α-ketoglutarate-dependent halogenases, are now known to play a significant role in enzyme-catalyzed halogenation. The recent advances on the halogenating enzymes RebH, SyrB2, and CytC3 have suggested some new mechanisms for enzymatic halogenations. This review concentrates on the occurrence, catalytic mechanisms, and biotechnological applications of the halogenating enzymes that are currently known.

  17. ALD Functionalized Nanoporous Gold: Thermal Stability, Mechanical Properties, and Catalytic Activity

    Energy Technology Data Exchange (ETDEWEB)

    Biener, M M; Biener, J; Wichmann, A; Wittstock, A; Baumann, T F; Baeumer, M; Hamza, A V


    Nanoporous metals have many technologically promising applications but their tendency to coarsen limits their long-term stability and excludes high temperature applications. Here, we demonstrate that atomic layer deposition (ALD) can be used to stabilize and functionalize nanoporous metals. Specifically, we studied the effect of nanometer-thick alumina and titania ALD films on thermal stability, mechanical properties, and catalytic activity of nanoporous gold (np-Au). Our results demonstrate that even only one-nm-thick oxide films can stabilize the nanoscale morphology of np-Au up to 1000 C, while simultaneously making the material stronger and stiffer. The catalytic activity of np-Au can be drastically increased by TiO{sub 2} ALD coatings. Our results open the door to high temperature sensor, actuator, and catalysis applications and functionalized electrodes for energy storage and harvesting applications.

  18. Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst (Ⅰ) Mechanism of Catalytic Decarboxylation

    Institute of Scientific and Technical Information of China (English)

    Fu Xiaoqin; Dai Zhenyu; Tian Songbai; Hou Suandi; Wang Xieqing


    In this paper, the charge distribution, the chemical bond order and the reactive performance of carboxylic acid model compounds on acidic catalyst were investigated by using molecular simulation technology. The simulation results showed that the bond order of C-O was higher than that of C-C,and C-C bond connected to the carbon atom in the carboxyl radical had the lowest bond order. The charge distributions of model naphthenic acids were similar in characteristics that the negative charges were concentrated on carboxyls. According to the simulation results, the mechanisms of catalytic decarboxylation over acidic solid catalyst were proposed, and a new route was put forward regarding removal of the naphthenic acid from crude oil through catalytic decarboxylation.

  19. Catalytic mechanism in cyclic voltammetry at disc electrodes: an analytical solution. (United States)

    Molina, Angela; González, Joaquín; Laborda, Eduardo; Wang, Yijun; Compton, Richard G


    The theory of cyclic voltammetry at disc electrodes and microelectrodes is developed for a system where the electroactive reactant is regenerated in solution using a catalyst. This catalytic process is of wide importance, not least in chemical sensing, and it can be characterized by the resulting peak current which is always larger than that of a simple electrochemical reaction; in contrast the reverse peak is always relatively diminished in size. From the theoretical point of view, the problem involves a complex physical situation with two-dimensional mass transport and non-uniform surface gradients. Because of this complexity, hitherto the treatment of this problem has been tackled mainly by means of numerical methods and so no analytical expression was available for the transient response of the catalytic mechanism in cyclic voltammetry when disc electrodes, the most popular practical geometry, are used. In this work, this gap is filled by presenting an analytical solution for the application of any sequence of potential pulses and, in particular, for cyclic voltammetry. The induction principle is applied to demonstrate mathematically that the superposition principle applies whatever the geometry of the electrode, which enabled us to obtain an analytical equation valid whatever the electrode size and the kinetics of the catalytic reaction. The theoretical results obtained are applied to the experimental study of the electrocatalytic Fenton reaction, determining the rate constant of the reduction of hydrogen peroxide by iron(II).

  20. The mechanism of selective catalytic reduction of NOx on Cu-SSZ-13 - a computational study. (United States)

    Crandell, Douglas W; Zhu, Haiyang; Yang, Xiaofan; Hochmuth, John; Baik, Mu-Hyun


    The copper-exchanged aluminosilicate zeolite SSZ-13 is a leading catalyst for the selective catalytic reduction of NO. Density functional theory calculations are used to construct a complete catalytic cycle of this process paying special attention to the coordination geometries and redox states of copper. N2 can be produced in the reduction half-cycle via a nitrosamine intermediate generated from the reaction of the additive reductant NH3 with a NO(+) intermediate stabilized by the zeolite lattice. The decomposition of this nitrosamine species can be assisted by incipient Brønsted acid sites generated during catalysis. Our calculations also suggest that the reoxidation of Cu(i) to Cu(ii) requires the addition of both NO and O2. The production of a second equivalent of N2 during the oxidation half-cycle proceeds through a peroxynitrite intermediate to form a Cu-nitrite intermediate, which may react with an acid, either HNO2 or NH4(+) to close the catalytic cycle. Models of copper neutralized by an external hydroxide ligand are also examined. These calculations form a key basis for understanding the mechanism of NO reduction in Cu-SSZ-13 in order to develop strategies for rationally optimizing the performance in future experiments.

  1. The Three-Dimensional Structure and Catalytic Mechanism of Cytosine Deaminase† (United States)

    Hall, Richard S.; Fedorov, Alexander A.; Xu, Chengfu; Fedorov, Elena V.; Almo, Steven C.; Raushel, Frank M.


    Cytosine deaminase (CDA) from E. coli is a member of the amidohydrolase superfamily. The structure of the zinc-activated enzyme was determined in the presence of phosphonocytosine, a mimic of the tetrahedral reaction intermediate. This compound inhibits the deamination of cytosine with a Ki of 52 nM. The zinc and iron containing enzymes were characterized to determine the effect of the divalent cations on activation of the hydrolytic water. Fe-CDA loses activity at low pH with a kinetic pKa of 6.0 and Zn-CDA has a kinetic pKa of 7.3. Mutation of Gln-156 decreased the catalytic activity by more than 5 orders of magnitude, supporting its role in substrate binding. Mutation of Glu-217, Asp-313, and His-246 significantly decreased catalytic activity supporting the role of these three residues in activation of the hydrolytic water molecule and facilitation of proton transfer reactions. A library of potential substrates was used to probe the structural determinants responsible for catalytic activity. CDA was able to catalyze the deamination of isocytosine and the hydrolysis of 3-oxauracil. Large inverse solvent isotope effects were obtained on kcat and kcat/Km, consistent with the formation of a low-barrier hydrogen bond during the conversion of cytosine to uracil. A chemical mechanism for substrate deamination by CDA was proposed. PMID:21545144

  2. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process (United States)

    Pura, Jarosław; Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna; Laskowski, Zbigniew; Gierej, Maciej


    The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800-900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic "cauliflower-shape protrusions". The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires' surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires' preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better understanding of the precious metals etching and deposition processes during oxidation.

  3. The roles of active site residues in the catalytic mechanism of methylaspartate ammonia-lyase. (United States)

    Raj, Hans; Poelarends, Gerrit J


    Methylaspartate ammonia-lyase (MAL; EC catalyzes the reversible addition of ammonia to mesaconate to yield l-threo-(2S,3S)-3-methylaspartate and l-erythro-(2S,3R)-3-methylaspartate as products. In the proposed minimal mechanism for MAL of Clostridium tetanomorphum, Lys-331 acts as the (S)-specific base catalyst and abstracts the 3S-proton from l-threo-3-methylaspartate, resulting in an enolate anion intermediate. This enolic intermediate is stabilized by coordination to the essential active site Mg(2+) ion and hydrogen bonding to the Gln-329 residue. Collapse of this intermediate results in the release of ammonia and the formation of mesaconate. His-194 likely acts as the (R)-specific base catalyst and abstracts the 3R-proton from the l-erythro isomer of 3-methylaspartate, yielding the enolic intermediate. In the present study, we have investigated the importance of the residues Gln-73, Phe-170, Gln-172, Tyr-356, Thr-360, Cys-361 and Leu-384 for the catalytic activity of C. tetanomorphum MAL. These residues, which are part of the enzyme surface lining the substrate binding pocket, were subjected to site-directed mutagenesis and the mutant enzymes were characterized for their structural integrity, ability to catalyze the amination of mesaconate, and regio- and diastereoselectivity. Based on the observed properties of the mutant enzymes, combined with previous structural studies and protein engineering work, we propose a detailed catalytic mechanism for the MAL-catalyzed reaction, in which the side chains of Gln-73, Gln-172, Tyr-356, Thr-360, and Leu-384 provide favorable interactions with the substrate, which are important for substrate binding and activation. This detailed knowledge of the catalytic mechanism of MAL can serve as a guide for future protein engineering experiments.

  4. Mechanism of store-operated calcium entry

    Indian Academy of Sciences (India)

    Devkanya Dutta


    Activation of receptors coupled to the phospholipase C/IP3 signalling pathway results in a rapid release of calcium from its intracellular stores, eventually leading to depletion of these stores. Calcium store depletion triggers an influx of extracellular calcium across the plasma membrane, a mechanism known as the store-operated calcium entry or capacitative calcium entry. Capacitative calcium current plays a key role in replenishing calcium stores and activating various physiological processes. Despite considerable efforts, very little is known about the molecular nature of the capacitative channel and the signalling pathway that activates it. This review summarizes our current knowledge about store operated calcium entry and suggests possible hypotheses for its mode of activation.

  5. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures (United States)

    Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.


    Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

  6. Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design. (United States)

    Madhavan, Nandita; Jones, Christopher W; Weck, Marcus


    Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst

  7. Crystal Structure of a Novel Viral Protease with a Serine/Lysine Catalytic Dyad Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Feldman,A.; Lee, J.; Delmas, B.; Paetzel, M.


    The blotched snakehead virus (BSNV), an aquatic birnavirus, encodes a polyprotein (NH2-pVP2-X-VP4-VP3-COOH) that is processed through the proteolytic activity of its own protease (VP4) to liberate itself and the viral proteins pVP2, X and VP3. The protein pVP2 is further processed by VP4 to give rise to the capsid protein VP2 and four structural peptides. We report here the crystal structure of a VP4 protease from BSNV, which displays a catalytic serine/lysine dyad in its active site. This is the first crystal structure of a birnavirus protease and the first crystal structure of a viral protease that utilizes a lysine general base in its catalytic mechanism. The topology of the VP4 substrate binding site is consistent with the enzymes substrate specificity and a nucleophilic attack from the si-face of the substrates scissile bond. Despite low levels of sequence identity, VP4 shows similarities in its active site to other characterized Ser/Lys proteases such as signal peptidase, LexA protease and Lon protease. Together, the structure of VP4 provides insights into the mechanism of a recently characterized clan of serine proteases that utilize a lysine general base and reveals the structure of potential targets for antiviral therapy, especially for other related and economically important viruses, such as infectious bursal disease virus in poultry and infectious pancreatic necrosis virus in aquaculture.

  8. Parkin mitochondrial translocation is achieved through a novel catalytic activity coupled mechanism

    Institute of Scientific and Technical Information of China (English)

    Xinde Zheng; Tony Hunter


    Pink1,a mitochondrial kinase,and Parkin,an E3 ubiquitin ligase,function in mitochondrial maintenance.Pink1 accumulates on depolarized mitochondria,where it recruits Parkin to mainly induce K63-1inked chain ubiquitination of outer membrane proteins and eventually mitophagy.Parkin belongs to the RBR E3 iigase family.Recently,it has been proposed that the RBR domain transfers ubiquitin to targets via a cysteine-ubiquitin enzyme intermediate,in a manner similar to HECT domain E3 ligases.However,direct evidence for a ubiquitin transfer mechanism and its importance for Parkin's in vivo function is still missing.Here,we report that Parkin E3 activity relies on cysteinemediated ubiquitin transfer during mitophagy.Mutating the putative catalytic cysteine to serine (Parkin C431S)traps ubiquitin,and surprisingly,also abrogates Parkin mitochondrial translocation,indicating that E3 activity is essential for Parkin translocation.We found that Parkin can bind to K63-1inked ubiquitin chains,and that targeting K63-mimicking ubiquitin chains to mitochondria restores Parkin C431S localization.We propose that Parkin translocation is achieved through a novel catalytic activity coupled mechanism.

  9. Parkin mitochondrial translocation is achieved through a novel catalytic activity coupled mechanism (United States)

    Zheng, Xinde; Hunter, Tony


    Pink1, a mitochondrial kinase, and Parkin, an E3 ubiquitin ligase, function in mitochondrial maintenance. Pink1 accumulates on depolarized mitochondria, where it recruits Parkin to mainly induce K63-linked chain ubiquitination of outer membrane proteins and eventually mitophagy. Parkin belongs to the RBR E3 ligase family. Recently, it has been proposed that the RBR domain transfers ubiquitin to targets via a cysteine∼ubiquitin enzyme intermediate, in a manner similar to HECT domain E3 ligases. However, direct evidence for a ubiquitin transfer mechanism and its importance for Parkin's in vivo function is still missing. Here, we report that Parkin E3 activity relies on cysteine-mediated ubiquitin transfer during mitophagy. Mutating the putative catalytic cysteine to serine (Parkin C431S) traps ubiquitin, and surprisingly, also abrogates Parkin mitochondrial translocation, indicating that E3 activity is essential for Parkin translocation. We found that Parkin can bind to K63-linked ubiquitin chains, and that targeting K63-mimicking ubiquitin chains to mitochondria restores Parkin C431S localization. We propose that Parkin translocation is achieved through a novel catalytic activity coupled mechanism. PMID:23670163

  10. Catalytic mechanism and allosteric regulation of an oligomeric (p)ppGpp synthetase by an alarmone. (United States)

    Steinchen, Wieland; Schuhmacher, Jan S; Altegoer, Florian; Fage, Christopher D; Srinivasan, Vasundara; Linne, Uwe; Marahiel, Mohamed A; Bange, Gert


    Nucleotide-based second messengers serve in the response of living organisms to environmental changes. In bacteria and plant chloroplasts, guanosine tetraphosphate (ppGpp) and guanosine pentaphosphate (pppGpp) [collectively named "(p)ppGpp"] act as alarmones that globally reprogram cellular physiology during various stress conditions. Enzymes of the RelA/SpoT homology (RSH) family synthesize (p)ppGpp by transferring pyrophosphate from ATP to GDP or GTP. Little is known about the catalytic mechanism and regulation of alarmone synthesis. It also is unclear whether ppGpp and pppGpp execute different functions. Here, we unravel the mechanism and allosteric regulation of the highly cooperative alarmone synthetase small alarmone synthetase 1 (SAS1) from Bacillus subtilis. We determine that the catalytic pathway of (p)ppGpp synthesis involves a sequentially ordered substrate binding, activation of ATP in a strained conformation, and transfer of pyrophosphate through a nucleophilic substitution (SN2) reaction. We show that pppGpp-but not ppGpp-positively regulates SAS1 at an allosteric site. Although the physiological significance remains to be elucidated, we establish the structural and mechanistic basis for a biological activity in which ppGpp and pppGpp execute different functional roles.

  11. Catalytic mechanism and product specificity of cyclodextrin glycosyltransferase, a prototypical transglycosylase from the α-amylase family

    NARCIS (Netherlands)

    Uitdehaag, Joost C.M.; Veen, Bart A. van der; Dijkhuizen, Lubbert; Dijkstra, Bauke W.


    The catalytic mechanism of cyclodextrin glycosyltransferase, a member of the α-amylase family, is reviewed. The focus is put on the bond cleavage mechanism, the nature of the transition state and of the covalent intermediate, and on the stereo-electronic and lateral protonation contributions to cata

  12. Catalytic mechanism and product specificity of cyclodextrin glycosyltransferase, a prototypical transglycosylase from the alpha-amylase family

    NARCIS (Netherlands)

    Uitdehaag, JCM; van der Veen, BA; Dijkhuizen, L; Dijkstra, BW


    The catalytic mechanism of cyclodextrin glycosyltransferase, a member of the a-amylase family, is reviewed. The focus is put on the bond cleavage mechanism, the nature of the transition state and of the covalent intermediate, and on the stereo-electronic and lateral protonation contributions to cata

  13. A Redox 2-Cys Mechanism Regulates the Catalytic Activity of Divergent Cyclophilins1[W (United States)

    Campos, Bruna Medéia; Sforça, Mauricio Luis; Ambrosio, Andre Luis Berteli; Domingues, Mariane Noronha; Brasil de Souza, Tatiana de Arruda Campos; Barbosa, João Alexandre Ribeiro Gonçalvez; Leme, Adriana Franco Paes; Perez, Carlos Alberto; Whittaker, Sara Britt-Marie; Murakami, Mario Tyago; Zeri, Ana Carolina de Matos; Benedetti, Celso Eduardo


    The citrus (Citrus sinensis) cyclophilin CsCyp is a target of the Xanthomonas citri transcription activator-like effector PthA, required to elicit cankers on citrus. CsCyp binds the citrus thioredoxin CsTdx and the carboxyl-terminal domain of RNA polymerase II and is a divergent cyclophilin that carries the additional loop KSGKPLH, invariable cysteine (Cys) residues Cys-40 and Cys-168, and the conserved glutamate (Glu) Glu-83. Despite the suggested roles in ATP and metal binding, the functions of these unique structural elements remain unknown. Here, we show that the conserved Cys residues form a disulfide bond that inactivates the enzyme, whereas Glu-83, which belongs to the catalytic loop and is also critical for enzyme activity, is anchored to the divergent loop to maintain the active site open. In addition, we demonstrate that Cys-40 and Cys-168 are required for the interaction with CsTdx and that CsCyp binds the citrus carboxyl-terminal domain of RNA polymerase II YSPSAP repeat. Our data support a model where formation of the Cys-40-Cys-168 disulfide bond induces a conformational change that disrupts the interaction of the divergent and catalytic loops, via Glu-83, causing the active site to close. This suggests a new type of allosteric regulation in divergent cyclophilins, involving disulfide bond formation and a loop-displacement mechanism. PMID:23709667

  14. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface (United States)

    Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.; Tilley, S. David; Francàs, Laia; Mesa, Camilo A.; Grätzel, Michael; Durrant, James R.


    Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

  15. Study on Mechanism for Formation of Carbon Oxides During Catalytic Cracking of High Acidic Crude

    Institute of Scientific and Technical Information of China (English)

    Wei Xiaoli; Mao Anguo; Xie Chaogang


    Based on the basis of analysis and interpretation of the products distribution of catalytic cracking of high acidic crude,the mechanism for decarboxylation of petroleum acids during FCC process was discussed.The protons originated from the Br(o)nsted acid sites can combine with oxygen of the carbonyl groups with more negative charges to form reaction intermediates that Call be subjected to cleavage at the weak bonds,leading to breaking of carboxylic groups from the carboxylic acids followed by its decomposition to form alkyl three-coordinated carbenium ions,CO and H2O.The Lewis acid as an electrophilic reagent can abstract carboxylic groups from carboxylic acids to subsequently release CO2.

  16. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface (United States)

    Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.; Tilley, S. David; Francàs, Laia; Mesa, Camilo A.; Grätzel, Michael; Durrant, James R.


    Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen. PMID:28233785

  17. Exploring the Catalytic Mechanism of Human Glutamine Synthetase by Computer Simulations. (United States)

    Issoglio, Federico M; Campolo, Nicolas; Zeida, Ari; Grune, Tilman; Radi, Rafael; Estrin, Dario A; Bartesaghi, Silvina


    Glutamine synthetase is an important enzyme that catalyzes the ATP-dependent formation of glutamine from glutamate and ammonia. In mammals, it plays a key role in preventing excitotoxicity in the brain and detoxifying ammonia in the liver. In plants and bacteria, it is fundamental for nitrogen metabolism, being critical for the survival of the organism. In this work, we show how the use of classical molecular dynamics simulations and multiscale quantum mechanics/molecular mechanics simulations allowed us to examine the structural properties and dynamics of human glutamine synthetase (HsGS), as well as the reaction mechanisms involved in the catalytic process with atomic level detail. Our results suggest that glutamine formation proceeds through a two-step mechanism that includes a first step in which the γ-glutamyl phosphate intermediate forms, with a 5 kcal/mol free energy barrier and a -8 kcal/mol reaction free energy, and then a second rate-limiting step involving the ammonia nucleophilic attack, with a free energy barrier of 19 kcal/mol and a reaction free energy of almost zero. A detailed analysis of structural features within each step exposed the relevance of the acid-base equilibrium related to protein residues and substrates in the thermodynamics and kinetics of the reactions. These results provide a comprehensive study of HsGS dynamics and establish the groundwork for further analysis regarding changes in HsGS activity, as occur in natural variants and post-translational modifications.

  18. NO-CO-O2 Reaction on a Metal Catalytic Surface using Eley-Rideal Mechanism

    Institute of Scientific and Technical Information of China (English)

    Waqar Ahmad


    Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal (ER) mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood (LH) thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.

  19. Analysis of the Staphylococcus aureus DgkB structure reveals a common catalytic mechanism for the soluble diacylglycerol kinases. (United States)

    Miller, Darcie J; Jerga, Agoston; Rock, Charles O; White, Stephen W


    Soluble diacylglycerol (DAG) kinases function as regulators of diacylglycerol metabolism in cell signaling and intermediary metabolism. We report the structure of a DAG kinase, DgkB from Staphylococcus aureus, both as the free enzyme and in complex with ADP. The molecule is a tight homodimer, and each monomer comprises two domains with the catalytic center located within the interdomain cleft. Two distinctive features of DkgB are a structural Mg2+ site and an associated Asp*water*Mg2+ network that extends toward the active site locale. Site-directed mutagenesis revealed that these features play important roles in the catalytic mechanism. The key active site residues and the components of the Asp*water*Mg2+ network are conserved in the catalytic cores of the mammalian signaling DAG kinases, indicating that these enzymes use the same mechanism and have similar structures as DgkB.

  20. Analysis of the Staphylococcus aureus DgkB Structure Reveals a Common Catalytic Mechanism for the Soluble Diacylglycerol Kinases

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Darcie J.; Jerga, Agoston; Rock, Charles O.; White, Stephen W. (SJCH)


    Soluble diacylglycerol (DAG) kinases function as regulators of diacylglycerol metabolism in cell signaling and intermediary metabolism. We report the structure of a DAG kinase, DgkB from Staphylococcus aureus, both as the free enzyme and in complex with ADP. The molecule is a tight homodimer, and each monomer comprises two domains with the catalytic center located within the interdomain cleft. Two distinctive features of DkgB are a structural Mg{sup 2+} site and an associated Asp{center_dot}water{center_dot}Mg{sup 2+} network that extends toward the active site locale. Site-directed mutagenesis revealed that these features play important roles in the catalytic mechanism. The key active site residues and the components of the Asp{center_dot}water{center_dot}Mg{sup 2+} network are conserved in the catalytic cores of the mammalian signaling DAG kinases, indicating that these enzymes use the same mechanism and have similar structures as DgkB.

  1. First-principles quantum-mechanical investigations: The role of water in catalytic conversion of furfural on Pd(111) (United States)

    Xue, Wenhua; Borja, Miguel Gonzalez; Resasco, Daniel E.; Wang, Sanwu


    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of water has attracted wide attention. Recent experiments showed that the proportion of alcohol product from catalytic reactions of furfural conversion with palladium in the presence of water is significantly increased, when compared with other solvent including dioxane, decalin, and ethanol. We investigated the microscopic mechanism of the reactions based on first-principles quantum-mechanical calculations. We particularly identified the important role of water and the liquid/solid interface in furfural conversion. Our results provide atomic-scale details for the catalytic reactions. Supported by DOE (DE-SC0004600). This research used the supercomputer resources at NERSC, of XSEDE, at TACC, and at the Tandy Supercomputing Center.

  2. Effect of Precursor Mechanism on CO-NO Catalytic Reaction on Body-Centred Cubic Structure: Monte Carlo Simulation

    Institute of Scientific and Technical Information of China (English)

    A. U. Qaisrani; M. Khalid; M. K.Khan


    @@ The CO-NO catalytic reaction on body-centred cubic (bcc) lattice is studied by Monte Carlo simulation. The simple Langmuir-Hinshelwood (LH) mechanism yields a steady reactive window, which is separated by continuous and discontinuous irreversible phase transitions. The effect of precursor mechanism on the phase diagram of the system is also studied. According to this mechanism, the precursor motion of CO molecules is considered only on the surface of bcc lattice. Some interesting observations are reported.

  3. Catalytic mechanism of Cu(p-OTs)2/ethanolamine as mimetic enzyme

    Institute of Scientific and Technical Information of China (English)

    宋继国; 沈培康


    The electrochemical behaviors of various copper salts complexes coordinated with equal molar ethanolamine were studied, and those of Cu(p-OTs)2 and Cu(p-OTs)2/ethanolamine(1:1) complex in CH3OH or DMF were characterized. The results show that the reduction of Cu( Ⅱ ) in Cu(p-OTs)2 is via one two-electron step mechanism both in CH3 OH and DMF. The reduction mechanism transforms to two one-electron steps in the case of Cu (p-OTs)2/ethanolamine(1:1) in DMF. However, it does not change in CH3 OH. All the Cu( Ⅱ )/ethanolamine(1:1) with the electrochemical reactions are through two one-electron steps, and can act as mimetic enzyme to oxidize 1, 1'-bi-2-naphthol. The Cu( Ⅱ )/ethanolamine(1:1) with electrochemical reactions through one two-electron step could not act as mimetic enzyme. It is concluded that the transformation between centre Cu( Ⅱ ) and Cu( Ⅰ ) is the crucial condition for the catalytic activity of copper-amine complex.

  4. Kinetic Mechanism of Uracil Phosphoribosyltransferase from Escherichia coli and Catalytic Importance of the Conserved Proline in the PRPP Binding Site

    DEFF Research Database (Denmark)

    Lundegaard, Claus; Jensen, Kaj Frank


    catalytic properties with the properties of the wild-type protein. We found that UPRTase of E. coli obeyed the kinetics of a sequential mechanism with the binding of PRPP preceding the binding of uracil. The basic kinetic constants were derived from initial velocity measurements, product inhibition......, and ligand binding assays. The change of Pro 131 to Asp caused a 50-60-fold reduction of the catalytic rate (kcat) in both directions of the reaction and approximately a 100-fold increase in the KM for uracil. The KM for PRPP was strongly diminished by the mutation, but kcat/KM,PRPP and the dissociation...... constant (KD,PRPP) were nearly unaffected. We conclude that the proline in the PRPP binding site of UPRTase is of only little importance for binding of PRPP to the free enzyme, but is critical for binding of uracil to the enzyme-PRPP complex and for the catalytic rate....

  5. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15. (United States)

    Sun, Qiangqiang; Wang, Yu; Li, Laisheng; Bing, Jishuai; Wang, Yingxin; Yan, Huihua


    Comparative experiments were conducted to investigate the catalytic ability of MnO(x)/SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O3/MnO(x)/SBA-15). Adsorption of CA and its intermediates by MnO(x)/SBA-15 was proved unimportant in O3/MnO(x)/SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO3) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO(x)/SBA-15 facilitated the generation of hydroxyl radicals (OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO(x) on SBA-15 were believed to be the main active component in MnO(x)/SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more OH.

  6. Catalytic reaction mechanism of L-lactate dehydrogenase: an ab initio study

    Institute of Scientific and Technical Information of China (English)

    侯若冰; 陈志达; 义祥辉; 卞江; 徐光宪


    Studies on the catalytic reaction mechanism of L-lactate dehydrogenase have been carried out by using quantum chemical ab initio calculation at HF/6-31G* level. It is found that the interconversion reaction of pyruvate to L-lactate is dominated by the hydride ion HR- transfer, and the transfers of the hydride ion HR and proton HR+ are a quasi-coupled process, in which the energy barrier of the transition state is about 168.37 kJ/mol. It is shown that the reactant complex is 87.61 kJ/mol lower, in energy, than the product complex. The most striking features in our calculated results are that pyridine ring of the model cofactor is a quasi-boat-like configuration in the transited state, which differs from a planar conformation in some previous semiempirical quantum chemical studies. On the other hand, the similarity in the structure and charge between the HR transfer process and the hydrogen bonding with lower barrier indicates that the HR transfer process occurs by means of an unusual manner. In addition,

  7. Catalytic mechanism of LENR in quasicrystals based on localized anharmonic vibrations and phasons

    CERN Document Server

    Dubinko, Volodymyr; Irwin, Klee


    Quasicrystals (QCs) are a novel form of matter, which are neither crystalline nor amorphous. Among many surprising properties of QCs is their high catalytic activity. We propose a mechanism explaining this peculiarity based on unusual dynamics of atoms at special sites in QCs, namely, localized anharmonic vibrations (LAVs) and phasons. In the former case, one deals with a large amplitude (~ fractions of an angstrom) time-periodic oscillations of a small group of atoms around their stable positions in the lattice, known also as discrete breathers, which can be excited in regular crystals as well as in QCs. On the other hand, phasons are a specific property of QCs, which are represented by very large amplitude (~angstrom) oscillations of atoms be-tween two quasi-stable positions determined by the geometry of a QC. Large amplitude atomic motion in LAVs and phasons results in time-periodic driving of adjacent potential wells occupied by hydrogen ions (protons or deuterons) in case of hydrogenated QCs. This drivin...

  8. Towards Understanding the Catalytic Mechanism of Human Paraoxonase 1: Experimental and In Silico Mutagenesis Studies. (United States)

    Tripathy, Rajan K; Aggarwal, Geetika; Bajaj, Priyanka; Kathuria, Deepika; Bharatam, Prasad V; Pande, Abhay H


    Human paraoxonase 1 (h-PON1) is a ~45-kDa serum enzyme that can hydrolyze a variety of substrates, including organophosphate (OP) compounds. It is a potential candidate for the development of antidote against OP poisoning in humans. However, insufficient OP-hydrolyzing activity of native enzyme affirms the urgent need to develop improved variant(s) having enhanced OP-hydrolyzing activity. The crystal structure of h-PON1 remains unsolved, and the molecular details of how the enzyme catalyses hydrolysis of different types of substrates are also not clear. Understanding the molecular details of the catalytic mechanism of h-PON1 is essential to engineer better variant(s) of enzyme. In this study, we have used a random mutagenesis approach to increase the OP-hydrolyzing activity of recombinant h-PON1. The mutants not only showed a 10-340-fold increased OP-hydrolyzing activity against different OP substrates but also exhibited differential lactonase and arylesterase activities. In order to investigate the mechanistic details of the effect of observed mutations on the hydrolytic activities of enzyme, molecular docking studies were performed with selected mutants. The results suggested that the observed mutations permit differential binding of substrate/inhibitor into the enzyme's active site. This may explain differential hydrolytic activities of the enzyme towards different substrates.

  9. Ire1 Has Distinct Catalytic Mechanisms for XBP1/HAC1 Splicing and RIDD

    Directory of Open Access Journals (Sweden)

    Arvin B. Tam


    Full Text Available An evolutionarily conserved unfolded protein response (UPR component, IRE1, cleaves XBP1/HAC1 introns in order to generate spliced mRNAs that are translated into potent transcription factors. IRE1 also cleaves endoplasmic-reticulum-associated RNAs leading to their decay, an activity termed regulated IRE1-dependent decay (RIDD; however, the mechanism by which IRE1 differentiates intron cleavage from RIDD is not well understood. Using in vitro experiments, we found that IRE1 has two different modes of action: XBP1/HAC1 is cleaved by IRE1 subunits acting cooperatively within IRE1 oligomers, whereas a single subunit of IRE1 performs RIDD without cooperativity. Furthermore, these distinct activities can be separated by complementation of catalytically inactive IRE1 RNase and mutations at oligomerization interfaces. Using an IRE1 RNase inhibitor, STF-083010, selective inhibition of XBP1 splicing indicates that XBP1 promotes cell survival, whereas RIDD leads to cell death, revealing modulation of IRE1 activities as a drug-development strategy.

  10. Integrating Programming Language and Operating System Information Security Mechanisms (United States)


    AFRL-AFOSR-VA-TR-2016-0306 Integrating Programming Language and Operating System Information Security Mechanisms Stephen Chong HARVARD COLLEGE...REPORT TYPE Final 3. DATES COVERED (From - To) 01-06-2013 - 31-05-2016 4. TITLE AND SUBTITLE Integrating Programming Language and Operating System ...improve the guarantees offered by both language-based information security mechanisms, and operating system information security mechanisms. It seeks to

  11. Cellular graphene aerogel combines ultralow weight and high mechanical strength: A highly efficient reactor for catalytic hydrogenation. (United States)

    Zhang, Bingxing; Zhang, Jianling; Sang, Xinxin; Liu, Chengcheng; Luo, Tian; Peng, Li; Han, Buxing; Tan, Xiuniang; Ma, Xue; Wang, Dong; Zhao, Ning


    The construction of three-dimensional graphene aerogels (GAs) is of great importance owing to their outstanding properties for various applications. Up to now, the combination of ultralow weight and super mechanical strength for GA remains a great challenge. Here we demonstrate the fabrication of cellular GAs by a facile, easily controlled and versatile route, i.e. the chemical reduction of graphene oxide assemblies at oil-water interface under a mild condition (70 °C). The GA is ultralight (with density <3 mg cm(-3)) yet mechanically resilient because the walls of the cell closely pack in a highly ordered manner to maximize mechanical strength. The GA has been utilized as an appealing reactor for catalytic hydrogenation, which exhibited great advantages such as large oil absorption capability, exceptional catalytic activity, ease of product separation and high stability.

  12. Structural functionality, catalytic mechanism modeling and molecular allergenicity of phenylcoumaran benzylic ether reductase, an olive pollen (Ole e 12) allergen (United States)

    Jimenez-Lopez, Jose C.; Kotchoni, Simeon O.; Hernandez-Soriano, Maria C.; Gachomo, Emma W.; Alché, Juan D.


    Isoflavone reductase-like proteins (IRLs) are enzymes with key roles in the metabolism of diverse flavonoids. Last identified olive pollen allergen (Ole e 12) is an IRL relevant for allergy amelioration, since it exhibits high prevalence among atopic patients. The goals of this study are the characterization of (A) the structural-functionality of Ole e 12 with a focus in its catalytic mechanism, and (B) its molecular allergenicity by extensive analysis using different molecular computer-aided approaches covering (1) physicochemical properties and functional-regulatory motifs, (2) sequence analysis, 2-D and 3D structural homology modeling comparative study and molecular docking, (3) conservational and evolutionary analysis, (4) catalytic mechanism modeling, and (5) sequence, structure-docking based B-cell epitopes prediction, while T-cell epitopes were predicted by inhibitory concentration and binding score methods. Structural-based detailed features, phylogenetic and sequences analysis have identified Ole e 12 as phenylcoumaran benzylic ether reductase. A catalytic mechanism has been proposed for Ole e 12 which display Lys133 as one of the conserved residues of the IRLs catalytic tetrad (Asn-Ser-Tyr-Lys). Structure characterization revealed a conserved protein folding among plants IRLs. However, sequence polymorphism significantly affected residues involved in the catalytic pocket structure and environment (cofactor and substrate interaction-recognition). It might also be responsible for IRLs isoforms functionality and regulation, since micro-heterogeneities affected physicochemical and posttranslational motifs. This polymorphism might have large implications for molecular differences in B- and T-cells epitopes of Ole e 12, and its identification may help designing strategies to improve the component-resolving diagnosis and immunotherapy of pollen and food allergy through development of molecular tools.

  13. Atomistic insight into the catalytic mechanism of glycosyltransferases by combined quantum mechanics/molecular mechanics (QM/MM) methods. (United States)

    Tvaroška, Igor


    Glycosyltransferases catalyze the formation of glycosidic bonds by assisting the transfer of a sugar residue from donors to specific acceptor molecules. Although structural and kinetic data have provided insight into mechanistic strategies employed by these enzymes, molecular modeling studies are essential for the understanding of glycosyltransferase catalyzed reactions at the atomistic level. For such modeling, combined quantum mechanics/molecular mechanics (QM/MM) methods have emerged as crucial. These methods allow the modeling of enzymatic reactions by using quantum mechanical methods for the calculation of the electronic structure of the active site models and treating the remaining enzyme environment by faster molecular mechanics methods. Herein, the application of QM/MM methods to glycosyltransferase catalyzed reactions is reviewed, and the insight from modeling of glycosyl transfer into the mechanisms and transition states structures of both inverting and retaining glycosyltransferases are discussed.

  14. Operation and uphold of area of liquid ammonia in Selective Catalytic Reduction%SCR氨区的运行维护

    Institute of Scientific and Technical Information of China (English)



    液氨是选择性催化还原脱硝法( SCR)工艺首选的脱硝反应剂,它属于危险化学品。氨区的安全运行是SCR系统安全运行的基础保障。从氨区的运行、维护、人员防护和事故处理等方面阐述了SCR系统运行维护中需要注意的一些关键点。%Liquid ammonia is the first choice of reductant in selective catalytic reduction,it is a sort of dangerous chemical. The safe operation in the area of liquid ammonia is foundation of SCR. lt describes take notice of SCR from the operation,uphold,physical protection and accident handling in the area of liquid ammonia.

  15. Functional MRI and NMR spectroscopy of an operating gas-liquid-solid catalytic reactor. (United States)

    Koptyug, Igor V; Lysova, Anna A; Kulikov, Alexander V; Kirillov, Valery A; Parmon, Valentin N; Sagdeev, Renad Z


    A dynamic in situ study of alpha-methylstyrene catalytic hydrogenation on a single catalyst pellet or in a granular bed is performed using 1H MRI and spatially resolved 1H NMR spectroscopy. Owing to reaction exothermicity, a reciprocating motion of the liquid front within the pellet accompanied by pellet temperature oscillations has been observed. Spatially resolved information on the reactant to product conversion within the catalyst bed has been obtained for a steady-state regime. Two-dimensional 27Al NMR images of alumina catalyst supports and other alumina-containing materials have been detected using moderate magnetic field gradients (80 G/cm) and a two-pulse spin-echo sequence. Temperature dependence of signal intensity and 27Al T1 time of alumina are considered as possible temperature sensors for NMR thermometry applications.

  16. Mechanism and substrate specificity of tRNA-guanine transglycosylases (TGTs): tRNA-modifying enzymes from the three different kingdoms of life share a common catalytic mechanism. (United States)

    Stengl, Bernhard; Reuter, Klaus; Klebe, Gerhard


    Transfer RNA-guanine transglycosylases (TGTs) are evolutionarily ancient enzymes, present in all kingdoms of life, catalyzing guanine exchange within their cognate tRNAs by modified 7-deazaguanine bases. Although distinct bases are incorporated into tRNA at different positions in a kingdom-specific manner, the catalytic subunits of TGTs are structurally well conserved. This review provides insight into the sequential steps along the reaction pathway, substrate specificity, and conformational adaptions of the binding pockets by comparison of TGT crystal structures in complex with RNA substrates of a eubacterial and an archaebacterial species. Substrate-binding modes indicate an evolutionarily conserved base-exchange mechanism with a conserved aspartate serving as a nucleophile through covalent binding to C1' of the guanosine ribose moiety in an intermediate state. A second conserved aspartate seems to control the spatial rearrangement of the ribose ring along the reaction pathway and supposedly operates as a general acid/base. Water molecules inside the binding pocket accommodating interaction sites subsequently occupied by polar atoms of substrates help to elucidate substrate-recognition and substrate-specificity features. This emphasizes the role of water molecules as general probes to map binding-site properties for structure-based drug design. Additionally, substrate-bound crystal structures allow the extraction of valuable information about the classification of the TGT superfamily into a subdivision of presumably homologous superfamilies adopting the triose-phosphate isomerase type barrel fold with a standard phosphate-binding motif.

  17. Thermal catalytic oxidation of octachloronaphthalene over anatase TiO2 nanomaterial and its hypothesized mechanism (United States)

    Su, Guijin; Li, Qianqian; Lu, Huijie; Zhang, Lixia; Huang, Linyan; Yan, Li; Zheng, Minghui


    As an environmentally-green technology, thermal catalytic oxidation of octachloronaphthalene (CN-75) over anatase TiO2 nanomaterials was investigated at 300 °C. A wide range of oxidation intermediates, which were investigated using various techniques, could be of three types: naphthalene-ring, single-benzene-ring, and completely ring-opened products. Reactive oxygen species on anatase TiO2 surface, such as O2-• and O2-, contributed to oxidative degradation. Based on these findings, a novel oxidation degradation mechanism was proposed. The reaction at (101) surface of anatase TiO2 was used as a model. The naphthalene-ring oxidative products with chloronaphthols and hydroxyl-pentachloronaphthalene-dione, could be formed via attacking the carbon of naphthalene ring at one or more positions by nucleophilic O2-. Lateral cleavage of the naphthalene ring at different C1-C10 and C4-C9, C1-C2 and C4-C9, C1-C2 or and C3-C4 bond positions by electrophilic O2-• could occur. This will lead to the formation of tetrachlorophenol, tetrachloro-benzoic acid, tetrachloro-phthalaldehyde, and tetrachloro-acrolein-benzoic acid, partially with further transformation into tetrachlorobenzene-dihydrodiol and tetrachloro-salicylic acid. Unexpectedly, the symmetric half section of CN-75 could be completely remained with generating the intricate oxidative intermediates characteristically containing tetrachlorobenzene structure. Complete cleavage of naphthalene ring could produce the ring-opened products, such as formic and acetic acids.

  18. Structural Insights into the Catalytic Mechanism of Escherichia coli Selenophosphate Synthetase

    Energy Technology Data Exchange (ETDEWEB)

    Noinaj, Nicholas; Wattanasak, Rut; Lee, Duck-Yeon; Wally, Jeremy L.; Piszczek, Grzegorz; Chock, P. Boon; Stadtman, Thressa C.; Buchanan, Susan K. (NIH)


    Selenophosphate synthetase (SPS) catalyzes the synthesis of selenophosphate, the selenium donor for the biosynthesis of selenocysteine and 2-selenouridine residues in seleno-tRNA. Selenocysteine, known as the 21st amino acid, is then incorporated into proteins during translation to form selenoproteins which serve a variety of cellular processes. SPS activity is dependent on both Mg{sup 2+} and K{sup +} and uses ATP, selenide, and water to catalyze the formation of AMP, orthophosphate, and selenophosphate. In this reaction, the gamma phosphate of ATP is transferred to the selenide to form selenophosphate, while ADP is hydrolyzed to form orthophosphate and AMP. Most of what is known about the function of SPS has derived from studies investigating Escherichia coli SPS (EcSPS) as a model system. Here we report the crystal structure of the C17S mutant of SPS from E. coli (EcSPS{sup C17S}) in apo form (without ATP bound). EcSPS{sup C17S} crystallizes as a homodimer, which was further characterized by analytical ultracentrifugation experiments. The glycine-rich N-terminal region (residues 1 through 47) was found in the open conformation and was mostly ordered in both structures, with a magnesium cofactor bound at the active site of each monomer involving conserved aspartate residues. Mutating these conserved residues (D51, D68, D91, and D227) along with N87, also found at the active site, to alanine completely abolished AMP production in our activity assays, highlighting their essential role for catalysis in EcSPS. Based on the structural and biochemical analysis of EcSPS reported here and using information obtained from similar studies done with SPS orthologs from Aquifex aeolicus and humans, we propose a catalytic mechanism for EcSPS-mediated selenophosphate synthesis.

  19. Effect of Operating Conditions on Catalytic Gasification of Bamboo in a Fluidized Bed

    Directory of Open Access Journals (Sweden)

    Thanasit Wongsiriamnuay


    Full Text Available Catalytic gasification of bamboo in a laboratory-scale, fluidized bed reactor was investigated. Experiments were performed to determine the effects of reactor temperature (400, 500, and 600°C, gasifying medium (air and air/steam, and catalyst to biomass ratio (0 : 1, 1 : 1, and 1.5 : 1 on product gas composition, H2/CO ratio, carbon conversion efficiency, heating value, and tar conversion. From the results obtained, it was shown that at 400°C with air/steam gasification, maximum hydrogen content of 16.5% v/v, carbon conversion efficiency of 98.5%, and tar conversion of 80% were obtained. The presence of catalyst was found to promote the tar reforming reaction and resulted in improvement of heating value, carbon conversion efficiency, and gas yield due to increases in H2, CO, and CH4. The presence of steam and dolomite had an effect on the increasing of tar conversion.

  20. Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

    Institute of Scientific and Technical Information of China (English)

    Shicheng XU; Junhua LI; Dong YANG; Jiming HAO


    The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH4)over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Bronsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Bronsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NOy species and the corresponding reaction routes were determined by the overall acidity strength of the support.The reaction routes where NO2 moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts,reactions between appropriate couples of active NOy species and activated hydrocarbon intermediates should be realized by modification of the support acidity.

  1. Human augmenter of liver regeneration: probing the catalytic mechanism of a flavin-dependent sulfhydryl oxidase. (United States)

    Schaefer-Ramadan, Stephanie; Gannon, Shawn A; Thorpe, Colin


    Augmenter of liver regeneration is a member of the ERV family of small flavin-dependent sulfhydryl oxidases that contain a redox-active CxxC disulfide bond in redox communication with the isoalloxazine ring of bound FAD. These enzymes catalyze the oxidation of thiol substrates with the reduction of molecular oxygen to hydrogen peroxide. This work studies the catalytic mechanism of the short, cytokine form of augmenter of liver regeneration (sfALR) using model thiol substrates of the enzyme. The redox potential of the proximal disulfide in sfALR was found to be approximately 57 mV more reducing than the flavin chromophore, in agreement with titration experiments. Rapid reaction studies show that dithiothreitol (DTT) generates a transient mixed disulfide intermediate with sfALR signaled by a weak charge-transfer interaction between the thiolate of C145 and the oxidized flavin. The subsequent transfer of reducing equivalents to the flavin ring is relatively slow, with a limiting apparent rate constant of 12.4 s(-1). However, reoxidation of the reduced flavin by molecular oxygen is even slower (2.3 s(-1) at air saturation) and thus largely limits turnover at 5 mM DTT. The nature of the charge-transfer complexes observed with DTT was explored using a range of simple monothiols to mimic the initial nucleophilic attack on the proximal disulfide. While β-mercaptoethanol is a very poor substrate of sfALR (∼0.3 min(-1) at 100 mM thiol), it rapidly generates a mixed disulfide intermediate allowing the thiolate of C145 to form a strong charge-transfer complex with the flavin. Unlike the other monothiols tested, glutathione is unable to form charge-transfer complexes and is an undetectable substrate of the oxidase. These data are rationalized on the basis of the stringent steric requirements for thiol-disulfide exchange reactions. The inability of the relatively bulky glutathione to attain the in-line geometry required for efficient disulfide exchange in sfALR may be

  2. New fundamental quantum mechanical operator-ordering identities for the coordinate and momentum operators

    Institute of Scientific and Technical Information of China (English)

    FAN HongYi


    In quantum mechanics theory one of the basic operator orderings is Q - P and P - Q ordering,where Q and P are the coordinate operator and the momentum operator,respectively.We derive some new fundamental operator identities about their mutual reordering.The technique of integration within Q - P ordering and P - Q ordering is introduced.The Q - P ordered and P - Q ordered formulas of the Wigner operator are also deduced which makes arranging the operators in either Q - P or P - Q ordering much more convenient.

  3. New insight in the microscopic mechanism of the catalytic synthesis of ammonia

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.


    Theoretical quantum calculations and molecular beam experiments of the dissociative chemisorption of N-2 molecules on catalytic active metal surfaces have given new insight in the fundamental process of the ammonia synthesis. This new approach to the study of catalytic process supplements...... to dissociation. Our analysis of the dissociation process suggests that it is not possible to define, in some well specified way, a precursor state at typical temperatures in the technical ammonia synthesis. The kinetic scheme for the complete ammonia synthesis without the precursor state can still account...... for the observed conversion to ammonia. We have constructed an empirical potential energy surface for N-2/Fe(111) which has barriers to dissociation even larger than for the previously studied N-2/Re system. It is shown that the presence of barriers is consistent with the observation that the activation energy...

  4. Electronic and catalytic properties of iron porphyrin complexes: Trends and reaction mechanisms.


    Mala, Alhaji


    ABSTRACTThe University of Manchester,School of Chemical Engineering and Analytical ScienceABSTRACT OF THESIS submitted by Mala Alhaji Sainna for the degree of Doctor of Philosophy (PhD) and entitled “Electronic and catalytic properties of iron porphyrin complexes: Trends and reaction mechanisms” The cytochrome P450s belong to the superfamily of proteins containing a heme cofactor and, thus, are termed hemoproteins. They perform important oxidation reactions in the body, and are, for instance,...

  5. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway. (United States)

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng


    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  6. Catalytic Thr or Ser Residue Modulates Structural Switches in 2-Cys Peroxiredoxin by Distinct Mechanisms (United States)

    Tairum, Carlos A.; Santos, Melina Cardoso; Breyer, Carlos A.; Geyer, R. Ryan; Nieves, Cecilia J.; Portillo-Ledesma, Stephanie; Ferrer-Sueta, Gerardo; Toledo, José Carlos; Toyama, Marcos H.; Augusto, Ohara; Netto, Luis E. S.; de Oliveira, Marcos A.


    Typical 2-Cys Peroxiredoxins (2-Cys Prxs) reduce hydroperoxides with extraordinary rates due to an active site composed of a catalytic triad, containing a peroxidatic cysteine (CP), an Arg, and a Thr (or Ser). 2-Cys Prx are involved in processes such as cancer; neurodegeneration and host-pathogen interactions. During catalysis, 2-Cys Prxs switch between decamers and dimers. Analysis of 2-Cys Prx structures in the fully folded (but not locally unfolded) form revealed a highly conserved, non-conventional hydrogen bond (CH-π) between the catalytic triad Thr of a dimer with an aromatic residue of an adjacent dimer. In contrast, structures of 2-Cys Prxs with a Ser in place of the Thr do not display this CH-π bond. Chromatographic and structural data indicate that the Thr (but not Ser) destabilizes the decamer structure in the oxidized state probably through steric hindrance. As a general trend, mutations in a yeast 2-Cys Prx (Tsa1) favoring the dimeric state also displayed a decreased catalytic activity. Remarkably, yeast naturally contains Thr-Ser variants (Tsa1 and Tsa2, respectively) with distinct oligomeric stabilities in their disulfide states. PMID:27629822

  7. Bell operator and Gaussian squeezed states in noncommutative quantum mechanics (United States)

    Bastos, Catarina; Bernardini, Alex E.; Bertolami, Orfeu; Dias, Nuno Costa; Prata, João Nuno


    We examine putative corrections to the Bell operator due to the noncommutativity in the phase space. Starting from a Gaussian squeezed envelope whose time evolution is driven by commutative (standard quantum mechanics) and noncommutative dynamics, respectively, we conclude that although the time-evolving covariance matrix in the noncommutative case is different from the standard case, the squeezing parameter dominates and there are no noticeable noncommutative corrections to the Bell operator. This indicates that, at least for squeezed states, the privileged states to test Bell correlations, noncommutativity versions of quantum mechanics remain as nonlocal as quantum mechanics itself.

  8. DNA repair mechanism by photolyase: electron transfer path from the photolyase catalytic cofactor FADH(-) to DNA thymine dimer. (United States)

    Medvedev, D; Stuchebrukhov, A A


    Photolyase is an enzyme that catalyses photorepair of thymine dimers in UV damaged DNA by electron transfer reaction. The structure of the photolyase/DNA complex is unknown at present. Using crystal structure coordinates of the substrate-free enzyme from E. coli, we have recently built a computer molecular model of a thymine dimer docked to photolyase catalytic site and studied molecular dynamics of the system. In this paper, we present analysis of the electronic coupling and electron transfer pathway between the catalytic cofactor FADH(-) and the pyrimidine dimer by the method of interatomic tunneling currents. Electronic structure is treated in the extended Hückel approximation. The root mean square transfer matrix element is about 6 cm(-1), which is consistent with the experimentally determined rate of transfer. We find that electron transfer mechanism responsible for the repair utilizes an unusual folded conformation of FADH(-) in photolyases, in which the isoalloxazine ring of the flavin and the adenine are in close proximity, and the peculiar features of the docked orientation of the dimer. The tunneling currents show explicitly that despite of the close proximity between the donor and acceptor complexes, the electron transfer mechanism between the flavin and the thymine bases is not direct, but indirect, with the adenine acting as an intermediate. These calculations confirm the previously made conclusion based on an indirect evidence for such mechanism.

  9. Model-based Derivation of the Safety Operating Limits of a Semi-batch Reactor for the Catalytic Acetoacetylation of Pyrrole Using a Generalized Sensitivity Criterion


    Maria, G; A Dan; Stefan, D.-N.


    The safe operation of a semi-batch catalytic reactor remains a sensitive issue when highly exothermic side reactions may occur, and various elements such as controllability, stability, safety, and economic aspects have to be considered in the process development. Nominal operating conditions are set to avoid excessive thermal sensitivity to variations in the process parameters. Several shortcuts or model-based methods are used to estimate the safety limits and runaway boundaries for the op...

  10. Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe–Co/Mg(Al)O derived from hydrotalcites

    KAUST Repository

    Tope, Balkrishna B.


    Catalytic mechanism of ethylbenzene dehydrogenation over Fe-Co/Mg(Al)O derived from hydrotalcites has been studied based on the XAFS and XPS catalyst characterization and the FTIR measurements of adsorbed species. Fe-Co/Mg(Al)O showed synergy, whereas Fe-Ni/Mg(Al)O showed no synergy, in the dehydrogenation of ethylbenzene. Ni species were stably incorporated as Ni2+ in the regular sites in periclase and spinel structure in the Fe-Ni/Mg(Al)O. Contrarily, Co species exists as a mixture of Co3+/Co2+ in the Fe-Co/Mg(Al)O and was partially isolated from the regular sites in the structures with increasing the Co content. Co addition enhanced Lewis acidity of Fe3+ active sites by forming Fe3+-O-Co 3+/2+(1/1) bond, resulting in an increase in the activity. FTIR of ethylbenzene adsorbed on the Fe-Co/Mg(Al)O clearly showed formations of C-O bond and π-adsorbed aromatic ring. This suggests that ethylbenzene was strongly adsorbed on the Fe3+ acid sites via π-bonding and the dehydrogenation was initiated by α-H+ abstraction from ethyl group on Mg2+-O2- basic sites, followed by C-O-Mg bond formation. The α-H+ abstraction by O2-(-Mg 2+) was likely followed by β-H abstraction, leading to the formations of styrene and H2. Such catalytic mechanism by the Fe 3+ acid-O2-(-Mg2+) base couple and the Fe 3+/Fe2+ reduction-oxidation cycle was further assisted by Co3+/Co2+, leading to a good catalytic activity for the dehydrogenation of ethylbenzene. © 2011 Elsevier B.V. All rights reserved.

  11. Bisubstrate analog probes for the insulin receptor protein tyrosine kinase: molecular yardsticks for analyzing catalytic mechanism and inhibitor design. (United States)

    Hines, Aliya C; Parang, Keykavous; Kohanski, Ronald A; Hubbard, Stevan R; Cole, Philip A


    Bisubstrate analogs have the potential to provide enhanced specificity for protein kinase inhibition and tools to understand catalytic mechanism. Previous efforts led to the design of a peptide-ATP conjugate bisubstrate analog utilizing aminophenylalanine in place of tyrosine and a thioacetyl linker to the gamma-phosphate of ATP which was a potent inhibitor of the insulin receptor kinase (IRK). In this study, we have examined the contributions of various electrostatic and structural elements in the bisubstrate analog to IRK binding affinity. Three types of changes (seven specific analogs in all) were introduced: a Tyr isostere of the previous aminophenylalanine moiety, modifications of the spacer between the adenine and the peptide, and deletions and substitutions within the peptide moiety. These studies allowed a direct evaluation of the hydrogen bond strength between the anilino nitrogen of the bisubstrate analog and the enzyme catalytic base Asp and showed that it contributes 2.5 kcal/mol of binding energy, in good agreement with previous predictions. Modifications of the linker length resulted in weakened inhibitory affinity, consistent with the geometric requirements of an enzyme-catalyzed dissociative transition state. Alterations in the peptide motif generally led to diminished inhibitory potency, and only some of these effects could be rationalized based on prior kinetic and structural studies. Taken together, these results suggest that a combination of mechanism-based design and empirical synthetic manipulation will be necessary in producing optimized protein kinase bisubstrate analog inhibitors.

  12. Structure of human aspartyl aminopeptidase complexed with substrate analogue: insight into catalytic mechanism, substrate specificity and M18 peptidase family

    Directory of Open Access Journals (Sweden)

    Chaikuad Apirat


    Full Text Available Abstract Backround Aspartyl aminopeptidase (DNPEP, with specificity towards an acidic amino acid at the N-terminus, is the only mammalian member among the poorly understood M18 peptidases. DNPEP has implicated roles in protein and peptide metabolism, as well as the renin-angiotensin system in blood pressure regulation. Despite previous enzyme and substrate characterization, structural details of DNPEP regarding ligand recognition and catalytic mechanism remain to be delineated. Results The crystal structure of human DNPEP complexed with zinc and a substrate analogue aspartate-β-hydroxamate reveals a dodecameric machinery built by domain-swapped dimers, in agreement with electron microscopy data. A structural comparison with bacterial homologues identifies unifying catalytic features among the poorly understood M18 enzymes. The bound ligands in the active site also reveal the coordination mode of the binuclear zinc centre and a substrate specificity pocket for acidic amino acids. Conclusions The DNPEP structure provides a molecular framework to understand its catalysis that is mediated by active site loop swapping, a mechanism likely adopted in other M18 and M42 metallopeptidases that form dodecameric complexes as a self-compartmentalization strategy. Small differences in the substrate binding pocket such as shape and positive charges, the latter conferred by a basic lysine residue, further provide the key to distinguishing substrate preference. Together, the structural knowledge will aid in the development of enzyme-/family-specific aminopeptidase inhibitors.

  13. Treatment of municipal landfill leachate by catalytic wet air oxidation: Assessment of the role of operating parameters by factorial design. (United States)

    Anglada, Angela; Urtiaga, Ane; Ortiz, Inmaculada; Mantzavinos, Dionissios; Diamadopoulos, Evan


    The wet air oxidation (WAO) of municipal landfill leachate catalyzed by cupric ions and promoted by hydrogen peroxide was investigated. The effect of operating conditions such as WAO treatment time (15-30min), temperature (160-200°C), Cu(2+) concentration (250-750mgL(-1)) and H(2)O(2) concentration (0-1500mgL(-1)) on chemical oxygen demand (COD) removal was investigated by factorial design considering a two-stage, sequential process comprising the heating-up of the reactor and the actual WAO. The leachate, at an initial COD of 4920mgL(-1), was acidified to pH 3 leading to 31% COD decrease presumably due to the coagulation/precipitation of colloidal and other organic matter. During the 45min long heating-up period of the WAO reactor under an inert atmosphere, COD removal values up to 35% (based on the initial COD value) were recorded as a result of the catalytic decomposition of H(2)O(2) to reactive hydroxyl radicals. WAO at 2.5MPa oxygen partial pressure advanced treatment further; for example, 22min of oxidation at 200°C, 250mgL(-1) Cu(2+) and 0-1500mgL(-1) H(2)O(2) resulted in an overall (i.e. including acidification and heating-up) COD reduction of 78%. Amongst the operating variables in question, temperature had the strongest influence on both the heating-up and WAO stages, while H(2)O(2) concentration strongly affected the former and reaction time the latter. Nonetheless, the effects of temperature and H(2)O(2) concentration were found to depend on the concentration levels of catalyst as suggested by the significance of their 3rd order interaction term.

  14. Pseudo-Hermitian quantum mechanics with unbounded metric operators. (United States)

    Mostafazadeh, Ali


    I extend the formulation of pseudo-Hermitian quantum mechanics to η(+)-pseudo-Hermitian Hamiltonian operators H with an unbounded metric operator η(+). In particular, I give the details of the construction of the physical Hilbert space, observables and equivalent Hermitian Hamiltonian for the case that H has a real and discrete spectrum and its eigenvectors belong to the domain of η(+) and consequently √η(+).

  15. Bell operator and Gaussian squeezed states in noncommutative quantum mechanics

    CERN Document Server

    Bastos, Catarina; Bertolami, Orfeu; Dias, Nuno Costa; Prata, João Nuno


    One examines putative corrections to the Bell operator due to the noncommutativity in the phase-space. Starting from a Gaussian squeezed envelop whose time evolution is driven by commutative (standard quantum mechanics) and noncommutative dynamics respectively, one concludes that, although the time evolving covariance matrix in the noncommutative case is different from the standard case, the squeezing parameter dominates and there are no noticeable noncommutative corrections to the Bell operator. This indicates that, at least for squeezed states, the privileged states to test Bell correlations, noncommutativity versions of quantum mechnics remains as non-local as quantum mechanics itself.

  16. Modal Testing of Mechanical Structures Subject to Operational Excitation Forces

    DEFF Research Database (Denmark)

    Møller, N.; Brincker, Rune; Herlufsen, H.;


    Operational Modal Analysis also known as Output Only Modal Analysis has in the recent years been used for extracting modal parameters of civil engineering structures and is now becoming popular for mechanical structures. The advantage of the method is that no artificial excitation need...... to the Operational Modal Analysis. For Operational Modal Analysis two different estimation techniques are used: a non-parametric technique based on Frequency Domain Decomposition (FDD), and a parametric technique working on the raw data in time domain, a data driven Stochastic Subspace Identification (SSI) algorithm....... These are compared to other methods such as traditional Modal Analysis....

  17. Gravitational Mass, Its Mechanics - What It Is; How It Operates


    Ellman, Roger


    The earlier paper, Inertial Mass, Its Mechanics - What It Is; How It Operates, developed the mechanics of inertial mass. The present paper is for the purpose of equivalently developing gravitation. The behavior of gravitation is well known, as described by Newton's Law of Gravitation. But just what gravitational mass is, how gravitational behavior comes about, what in material reality produces the effects of gravitational mass, has been little understood. The only extant hypotheses involve th...

  18. Fundamental Entangling Operators in Quantum Mechanics and Their Properties (United States)

    Dao-Ming, Lu


    For the first time, we introduce so-called fundamental entangling operators e^{iQ1 P2} and e^{iP1 Q2 } for composing bipartite entangled states of continuum variables, where Q i and P i ( i = 1, 2) are coordinate and momentum operator, respectively. We then analyze how these entangling operators naturally appear in the quantum image of classical quadratic coordinate transformation ( q 1, q 2) → ( A q 1 + B q 2, C q 1 + D q 2), where A D- B C = 1, which means even the basic coordinate transformation ( Q 1, Q 2) → ( A Q 1 + B Q 2, C Q 1 + D Q 2) involves entangling mechanism. We also analyse their Lie algebraic properties and use the integration technique within an ordered product of operators to show they are also one- and two- mode combinatorial squeezing operators.

  19. Syringomyelia after operation: diagnosis and its formational mechanism

    Institute of Scientific and Technical Information of China (English)

    Shi Jiangang; Xu Guohua; Jia Lianshun; Yuan Wen; Shi Guodong; Wu Jianfeng; Ye XiaoJian; Ni Bin; Xiao Jianru; Tan Junming


    Objective: To describe the MRI findings and discuss the pathogenesis formation mechanism of syringomyelia in the patients after spine surgical operation. Methods: Totally 13 patients were been enrolled in the study. Before operation, none of our patients presented with spinal cord syringomyelia. The mean follow-up duration was 6 years (range 2-10 months) by MRI. Four of the 13 patients after spinal cord tumor removed operation, 3 patients after spinal trauma operation, 2 cases had scoliosis before, 2 cases were cervical spondylotic myelopathy and 2 cases had tethered cord syndrome before operation. MR features of pre- and post-operation on all patients were been studied in contrast with surgical results and clinical symptoms. The radiology diagnostic was made by 3 different radiologists respectively. The characteristics of length, width, signals, shape of cavity and spinal cord position as well as subarachnoid shape were focused on. Results: All the patients had no syringomyelia on MRI before operation. The spinal cord of 7 patients showed persist compression and 2 patients had tethered cord before operation. MRI features of syringomyelia after operation in our cases showed longitudinal cavity with syrinx fluid had T1 and T2 relation characteristics of cerebrospinal fluid (CSF). The mean length was 5.5 spinal segment, 4 cord of 13 patients presented cord compressed from anterior materials, 4 occurred postoperative adhesion to the back of lumbar spinal canal and spinal cord of 1 cases clung to the front wall of cervical spinal canal. Conclusion: The mechanism of syringomyelia in the patients after spinal surgical intervention may be the persisting compression or intention of the spinal cord in the period of pre- or post-operation. The edema, cyst, malacia of spinal cord are the most important lesions and risk factors resulted in the syringomyelia.

  20. Mechanism of the catalytic ozonization of lignin in the presence of Mn(II) ions (United States)

    Mitrofanova, A. N.; Khudoshin, A. G.; Lunin, V. V.


    The reaction between ozone and lignin in aqueous solutions catalyzed by Mn(II) ions is studied. The rate of destruction for aromatic structures of lignin is found to increase in the presence of Mn(II) ions. However, the greatest catalytic effect is observed upon the transformation of aliphatic acids that are difficult to oxidize with ozone. The introduction of catalyst raises the total consumption of ozone from 3 to 7 mol per each structural unit of lignin. A scheme is proposed for the transformation of phenol fragments of lignin using ozone with the participation of Mn(II) ions: at the initial stage, we observe the ozone oxidation of lignin and Mn(II) to Mn(III) ions stabilized with products of lignin oxidation and accompanied by the formation of chelate complexes, and the Mn(III) chelate complexes act as low-molecular mediators, attacking phenol structures and initiating radical processes.

  1. Self-catalytic crystal growth, formation mechanism, and optical properties of indium tin oxide nanostructures. (United States)

    Liang, Yuan-Chang; Zhong, Hua


    In-Sn-O nanostructures with rectangular cross-sectional rod-like, sword-like, and bowling pin-like morphologies were successfully synthesized through self-catalytic growth. Mixed metallic In and Sn powders were used as source materials, and no catalyst layer was pre-coated on the substrates. The distance between the substrate and the source materials affected the size of the Sn-rich alloy particles during crystal growth in a quartz tube. This caused In-Sn-O nanostructures with various morphologies to form. An X-ray photoelectron spectroscope and a transmittance electron microscope with an energy-dispersive X-ray spectrometer were used to investigate the elemental binding states and compositions of the as-synthesized nanostructures. The Sn doping and oxygen vacancies in the In2O3 crystals corresponded to the blue-green and yellow-orange emission bands of the nanostructures, respectively.

  2. Structural Basis on the Catalytic Reaction Mechanism of Novel 1,2-Alpha L-Fucosidase (AFCA) From Bifidobacterium Bifidum

    Energy Technology Data Exchange (ETDEWEB)

    Nagae, M.; Tsuchiya, A.; Katayama, T.; Yamamoto, K.; Wakatsuki, S.; Kato, R.


    1,2-alpha-L-fucosidase (AfcA), which hydrolyzes the glycosidic linkage of Fucalpha1-2Gal via an inverting mechanism, was recently isolated from Bifidobacterium bifidum and classified as the first member of the novel glycoside hydrolase family 95. To better understand the molecular mechanism of this enzyme, we determined the x-ray crystal structures of the AfcA catalytic (Fuc) domain in unliganded and complexed forms with deoxyfuconojirimycin (inhibitor), 2'-fucosyllactose (substrate), and L-fucose and lactose (products) at 1.12-2.10 A resolution. The AfcA Fuc domain is composed of four regions, an N-terminal beta region, a helical linker, an (alpha/alpha)6 helical barrel domain, and a C-terminal beta region, and this arrangement is similar to bacterial phosphorylases. In the complex structures, the ligands were buried in the central cavity of the helical barrel domain. Structural analyses in combination with mutational experiments revealed that the highly conserved Glu566 probably acts as a general acid catalyst. However, no carboxylic acid residue is found at the appropriate position for a general base catalyst. Instead, a water molecule stabilized by Asn423 in the substrate-bound complex is suitably located to perform a nucleophilic attack on the C1 atom of L-fucose moiety in 2'-fucosyllactose, and its location is nearly identical near the O1 atom of beta-L-fucose in the products-bound complex. Based on these data, we propose and discuss a novel catalytic reaction mechanism of AfcA.

  3. Directed evolution of Tau class glutathione transferases reveals a site that regulates catalytic efficiency and masks co-operativity. (United States)

    Axarli, Irine; Muleta, Abdi W; Vlachakis, Dimitrios; Kossida, Sophia; Kotzia, Georgia; Maltezos, Anastasios; Dhavala, Prathusha; Papageorgiou, Anastassios C; Labrou, Nikolaos E


    A library of Tau class GSTs (glutathione transferases) was constructed by DNA shuffling using the DNA encoding the Glycine max GSTs GmGSTU2-2, GmGSTU4-4 and GmGSTU10-10. The parental GSTs are >88% identical at the sequence level; however, their specificity varies towards different substrates. The DNA library contained chimaeric structures of alternated segments of the parental sequences and point mutations. Chimaeric GST sequences were expressed in Escherichia coli and their enzymatic activities towards CDNB (1-chloro-2,4-dinitrobenzene) and the herbicide fluorodifen (4-nitrophenyl α,α,α-trifluoro-2-nitro-p-tolyl ether) were determined. A chimaeric clone (Sh14) with enhanced CDNB- and fluorodifen-detoxifying activities, and unusual co-operative kinetics towards CDNB and fluorodifen, but not towards GSH, was identified. The structure of Sh14 was determined at 1.75 Å (1 Å=0.1 nm) resolution in complex with S-(p-nitrobenzyl)-glutathione. Analysis of the Sh14 structure showed that a W114C point mutation is responsible for the altered kinetic properties. This was confirmed by the kinetic properties of the Sh14 C114W mutant. It is suggested that the replacement of the bulky tryptophan residue by a smaller amino acid (cysteine) results in conformational changes of the active-site cavity, leading to enhanced catalytic activity of Sh14. Moreover, the structural changes allow the strengthening of the two salt bridges between Glu(66) and Lys(104) at the dimer interface that triggers an allosteric effect and the communication between the hydrophobic sites.

  4. Protein engineering in the alpha-amylase family: catalytic mechanism, substrate specificity, and stability. (United States)

    Svensson, B


    Most starch hydrolases and related enzymes belong to the alpha-amylase family which contains a characteristic catalytic (beta/alpha)8-barrel domain. Currently known primary structures that have sequence similarities represent 18 different specificities, including starch branching enzyme. Crystal structures have been reported in three of these enzyme classes: the alpha-amylases, the cyclodextrin glucanotransferases, and the oligo-1,6-glucosidases. Throughout the alpha-amylase family, only eight amino acid residues are invariant, seven at the active site and a glycine in a short turn. However, comparison of three-dimensional models with a multiple sequence alignment suggests that the diversity in specificity arises by variation in substrate binding at the beta-->alpha loops. Designed mutations thus have enhanced transferase activity and altered the oligosaccharide product patterns of alpha-amylases, changed the distribution of alpha-, beta- and gamma-cyclodextrin production by cyclodextrin glucanotransferases, and shifted the relative alpha-1,4:alpha-1,6 dual-bond specificity of neopullulanase. Barley alpha-amylase isozyme hybrids and Bacillus alpha-amylases demonstrate the impact of a small domain B protruding from the (beta/alpha)8-scaffold on the function and stability. Prospects for rational engineering in this family include important members of plant origin, such as alpha-amylase, starch branching and debranching enzymes, and amylomaltase.

  5. Insight into the Catalytic Mechanism of Bimetallic Platinum–Copper Core–Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Lu; Luo, Xiangyi; Kropf, A. Jeremy; Wen, Jianguo; Wang, Xiaoping; Lee, Sungsik; Myers, Deborah J.; Miller, Dean; Wu, Tianpin; Lu, Jun; Amine, Khalil


    The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt–Cu core–shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li–O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt–Cu core–shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

  6. Catalytic degradation of gaseous benzene by using TiO2/goethite immobilized on palygorskite: Preparation, characterization and mechanism (United States)

    Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Liu, Haibo; Huang, Li; Chen, Tianhu; Chen, Dong


    The nano-TiO2/goethite/palygorskite catalysts were prepared by sol-gel method. The morphology and structure of the catalysts were analyzed by X-ray diffraction (XRD), UV-Vis reflection spectrometer, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and N2 adsorption-desorption measurement. The results indicated that the self-made catalysts had excellent catalytic performance on gaseous benzene degradation. In the case of benzene concentration at 30 mg/m3, the degradation efficiency, over TiO2/goethite/palygorskite composite with mass ratio of 10:5:5, reached 70.4% after 180 min 254 nm UV irradiation. The reaction mechanism and kinetics study showed that palygorskite/goethite/TiO2 composites photocatalytic degradation benzene was mainly caused by oxidizing property of electron-holes and oxygen synergy effect.

  7. Structures of the human poly (ADP-ribose glycohydrolase catalytic domain confirm catalytic mechanism and explain inhibition by ADP-HPD derivatives.

    Directory of Open Access Journals (Sweden)

    Julie A Tucker

    Full Text Available Poly(ADP-ribose glycohydrolase (PARG is the only enzyme known to catalyse hydrolysis of the O-glycosidic linkages of ADP-ribose polymers, thereby reversing the effects of poly(ADP-ribose polymerases. PARG deficiency leads to cell death whilst PARG depletion causes sensitisation to certain DNA damaging agents, implicating PARG as a potential therapeutic target in several disease areas. Efforts to develop small molecule inhibitors of PARG activity have until recently been hampered by a lack of structural information on PARG. We have used a combination of bio-informatic and experimental approaches to engineer a crystallisable, catalytically active fragment of human PARG (hPARG. Here, we present high-resolution structures of the catalytic domain of hPARG in unliganded form and in complex with three inhibitors: ADP-ribose (ADPR, adenosine 5'-diphosphate (hydroxymethylpyrrolidinediol (ADP-HPD and 8-n-octyl-amino-ADP-HPD. Our structures confirm conservation of overall fold amongst mammalian PARG glycohydrolase domains, whilst revealing additional flexible regions in the catalytic site. These new structures rationalise a body of published mutational data and the reported structure-activity relationship for ADP-HPD based PARG inhibitors. In addition, we have developed and used biochemical, isothermal titration calorimetry and surface plasmon resonance assays to characterise the binding of inhibitors to our PARG protein, thus providing a starting point for the design of new inhibitors.

  8. Investigation of the catalytic mechanism of Sir2 enzyme with QM/MM approach: SN1 vs SN2? (United States)

    Liang, Zhongjie; Shi, Ting; Ouyang, Sisheng; Li, Honglin; Yu, Kunqian; Zhu, Weiliang; Luo, Cheng; Jiang, Hualiang


    Sir2, the histone deacetylase III family, has been subjected to a wide range of studies because of their crucial roles in DNA repair, longevity, transcriptional silencing, genome stability, apoptosis, and fat mobilization. The enzyme binds NAD(+) and acetyllysine as substrates and generates lysine, 2'-O-acetyl-ADP-ribose, and nicotinamide as products. However, the mechanism of the first step in Sir2 deacetylation reaction from various studies is controversial. To characterize this catalytic mechanism of acetyllysine deacetylation by Sir2, we employed a combined computational approach to carry out molecular modeling, molecular dynamics (MD) simulations, quantum mechanics/molecular mechanics (QM/MM) calculations on catalysis by both yeast Hst2 (homologue of SIR two 2) and bacterial Sir2TM (Sir2 homologue from Thermatoga maritima). Our three-dimensional (3D) model of the complex is composed of Sir2 protein, NAD(+), and acetyllysine (ALY) substrate. A 15-ns MD simulation of the complex revealed that Gln115 and His135 play a determining role in deacetylation. These two residues can act as bases to facilitate the deprotonation of 2'-OH from N-ribose. The result is in great agreement with previous mutagenesis analysis data. QM/MM calculations were further performed to study the mechanism of the first step in deacetylation in the two systems. The predicted potential energy barriers for yHst2 and Sir2TM are 12.0 and 15.7 kcal/mol, respectively. The characteristics of the potential energy surface indicated this reaction belongs to a SN2-like mechanism. These results provide insights into the Sir2 mechanism of nicotinamide inhibition and have important implications for the discovery of effectors against Sir2 enzymes.

  9. Quantum Gravity and a Time Operator in Relativistic Quantum Mechanics

    CERN Document Server

    Bauer, M


    The problem of time in the quantization of gravity arises from the fact that time in Schroedinger's equation is a parameter. This sets time apart from the spatial coordinates, represented by operators in quantum mechanics (QM). Thus "time" in QM and "time" in General Relativity (GR) are seen as mutually incompatible notions. The introduction of a dy- namical time operator in relativistic quantum mechanics (RQM), that in the Heisenberg representation is also a function of the parameter t (iden- tifed as the laboratory time), prompts to examine whether it can help to solve the disfunction referred to above. In particular, its application to the conditional interpretation of the canonical quantization approach toquantum gravity is developed. 1

  10. Which computational mechanisms operate in the hippocampus during novelty detection? (United States)

    Kumaran, Dharshan; Maguire, Eleanor A


    A fundamental property of adaptive behavior is the ability to rapidly distinguish what is novel from what is familiar in our environment. Empirical evidence and computational work have provided biologically plausible models of the neural substrate and mechanisms underlying the coding of stimulus novelty in the perirhinal cortex. In this article, we highlight the importance of a different category of novelty, namely associative novelty, which has received relatively little attention, despite its clear ecological importance. While previous studies in both animals and humans have documented hippocampal responses in relation to associative novelty, a key issue concerning the computations underlying these novelty signals has not been previously addressed. We argue that this question has importance not only for our understanding of novelty processing, but also for advancing our knowledge of the fundamental computational operations performed by the hippocampus. We suggest a different approach to this problem, and discuss recent evidence supporting the hypothesis that the hippocampus operates as a comparator during the processing of associative novelty, generating mismatch/novelty signals when prior predictions are violated by sensory reality. We also draw on conceptual similarities between associative novelty and contextual novelty to suggest that empirical findings from these two seemingly distant research fields accord with the operation of a comparator mechanism during novelty detection more generally. We therefore conclude that a comparator mechanism may underlie the role of the hippocampus not only in detecting occurrences that are unexpected given specific associatively retrieved predictions, but also events that violate more abstract properties of the experimental context.

  11. Detailed characterization of the cooperative mechanism of Ca(2+) binding and catalytic activation in the Ca(2+) transport (SERCA) ATPase. (United States)

    Zhang, Z; Lewis, D; Strock, C; Inesi, G; Nakasako, M; Nomura, H; Toyoshima, C


    Expression of heterologous SERCA1a ATPase in Cos-1 cells was optimized to yield levels that account for 10-15% of the microsomal protein, as revealed by protein staining on electrophoretic gels. This high level of expression significantly improved our characterization of mutants, including direct measurements of Ca(2+) binding by the ATPase in the absence of ATP, and measurements of various enzyme functions in the presence of ATP or P(i). Mutational analysis distinguished two groups of amino acids within the transmembrane domain: The first group includes Glu771 (M5), Thr799 (M6), Asp800 (M6), and Glu908 (M8), whose individual mutations totally inhibit binding of the two Ca(2+) required for activation of one ATPase molecule. The second group includes Glu309 (M4) and Asn796 (M6), whose individual or combined mutations inhibit binding of only one and the same Ca(2+). The effects of mutations of these amino acids were interpreted in the light of recent information on the ATPase high-resolution structure, explaining the mechanism of Ca(2+) binding and catalytic activation in terms of two cooperative sites. The Glu771, Thr799, and Asp800 side chains contribute prominently to site 1, together with less prominent contributions by Asn768 and Glu908. The Glu309, Asn796, and Asp800 side chains, as well as the Ala305 (and possibly Val304 and Ile307) carbonyl oxygen, contribute to site 2. Sequential binding begins with Ca(2+) occupancy of site 1, followed by transition to a conformation (E') sensitive to Ca(2+) inhibition of enzyme phosphorylation by P(i), but still unable to utilize ATP. The E' conformation accepts the second Ca(2+) on site 2, producing then a conformation (E' ') which is able to utilize ATP. Mutations of residues (Asp813 and Asp818) in the M6/M7 loop reduce Ca(2+) affinity and catalytic turnover, suggesting a strong influence of this loop on the correct positioning of the M6 helix. Mutation of Asp351 (at the catalytic site within the cytosolic domain

  12. Operational Mechanism and Evaluation System for Emergency Logistics Risks

    Directory of Open Access Journals (Sweden)

    Qi Cheng


    Full Text Available Lots of risks existed in the operating process of emergency logistics especially when natural disasters happened. Both operating mechanism and evaluation system research on Emergency Logistics Risks (ELR are the basis of effective recognizing, preventing and responding to risks, so it’s of great theoretical and practical significance to study the formation and influence mechanism and to establish an evaluating index system for ELR. Firstly, some foundation research about ELR was carried out, including definition, characteristics and classification of ELR. The formation and influence mechanism of ELR were discussed. The research of questionnaire survey offered an objective support for theoretical mechanism and index system establishment. Then, the evaluating index system for ELR was established. This system was a multi-level index system, and mainly evaluated by the decision-making risk, dispatching and commanding risk, organizing and coordinating risk, executing and controlling risk, resources supporting risk and their sub index. The establishment principles and significance of the index system were discussed. Then, the fuzzy comprehensive evaluation and Delphi method were used to confirm the index weight and value. Finally, a case analysis on ELR of Yushu earthquake was conducted to demonstrate the evaluating index system and to evaluate the actual risk level.

  13. Catalyst Residence Time Distributions in Riser Reactors for Catalytic Fast Pyrolysis. Part 2: Pilot-Scale Simulations and Operational Parameter Study

    Energy Technology Data Exchange (ETDEWEB)

    Foust, Thomas D.; Ziegler, Jack L.; Pannala, Sreekanth; Ciesielski, Peter; Nimlos, Mark R.; Robichaud, David J.


    Using the validated simulation model developed in part one of this study for biomass catalytic fast pyrolysis (CFP), we assess the functional utility of using this validated model to assist in the development of CFP processes in fluidized catalytic cracking (FCC) reactors to a commercially viable state. Specifically, we examine the effects of mass flow rates, boundary conditions (BCs), pyrolysis vapor molecular weight variation, and the impact of the chemical cracking kinetics on the catalyst residence times. The factors that had the largest impact on the catalyst residence time included the feed stock molecular weight and the degree of chemical cracking as controlled by the catalyst activity. Because FCC reactors have primarily been developed and utilized for petroleum cracking, we perform a comparison analysis of CFP with petroleum and show the operating regimes are fundamentally different.

  14. Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(III) corrole 1-Fe. (United States)

    Avidan-Shlomovich, Shlomit; Gross, Zeev


    The amphipolar iron(III) corrole 1-Fe is one of the most efficient catalysts for the decomposition of peroxynitrite, the toxin involved in numerous diseases. This research focused on the mechanism of that reaction at physiological pH, where peroxynitrite is in equilibrium with its much more reactive conjugated acid, by focusing on the elementary steps involved in the catalytic cycle. Kinetic investigations uncovered the formation of a reaction intermediate in a process that is complete within a few milliseconds (k1 ∼ 3 × 10(7) M(-1) s(-1) at 5 °C, about 7 orders of magnitude larger than the first order rate constant for the non-catalyzed process). Multiple evidence points towards iron-catalyzed homolytic O-O bond cleavage to form nitrogen dioxide and hydroxo- or oxo-iron(iv) corrole. The iron(iv) intermediate was found to decay via multiple pathways that proceed at similar rates (k2 about 10(6) M(-1) s(-1)): reaction with nitrogen dioxide to form nitrate, nitration of the corrole macrocyclic, and dimerization to binuclear iron(iv) corrole. Catalysis in the presence of substrates affects the decay of the iron intermediate by either oxidative nitration (phenolic substrates) or reduction (ascorbate). A large enough excess of ascorbate accelerates the catalytic decomposition of PN by 1-Fe by orders of magnitude, prevents other decay routes of the iron intermediate, and eliminates nitration products as well. This suggests that the beneficial effect of the iron corrole under the reducing conditions present in most biological media might be even larger than in the purely chemical system. The acquired mechanistic insight is of prime importance for the design of optimally acting catalysts for the fast and safe decomposition of reactive oxygen and nitrogen species.

  15. Experimental research on catalysts and their catalytic mechanism for hydrogen production by gasification of peanut shell in supercritical water

    Institute of Scientific and Technical Information of China (English)

    PEI Aixia; GUO Liejin; JIN Hui


    Peanut shell,mixed with sodium carboxymethylcellulose,was gasified at a temperature of 450℃ and a pressure range from 24 to 27 MPa with the presence of different catalysts,including K2CO3,ZnCl2 and Raney-Ni.The experimental results show that different catalysts have greatly different effects on the reaction.Gasification efficiency (GE),hydrogen gasification efficiency (GHE),carbon gasification efficiency (GCE),yield of hydrogen production (YH2) and potential yield of hydrogen production (YPH2) are applied to describe the catalytic efficiency.From the result of gaseous components,ZnCl2 has the highest hydrogen selectivity,K2CO3 is lower,and Raney-Ni is the lowest,but Raney-Ni is the most favorable to gasify biomass among the three catalysts,and its GE,GHE,GcE reach 126.84%,185.71%,94.24%,respectively.As expected,hydrogen selectivity increased and CH4 reduced rapidly when the mixture of ZnCl2 and Raney-Ni is used under the same condition.The optimization mixture appeared when 0.2 g of ZnCl2 was added to 1 g of Raney-Ni,43.56 g·kg-1 of hydrogen production was obtained.In addition,the catalytic mechanisms of different catalysts were analyzed,and the possible reaction pathway was brought forward,which helped to explain the experiment phenomena and results correctly.

  16. The role of the active site Zn in the catalytic mechanism of the GH38 Golgi alpha-mannosidase II: Implications from noeuromycin inhibition

    DEFF Research Database (Denmark)

    Bols, Mikael; Kuntz, Douglas A.; Rose, David R.


    Golgi alpha-mannosidase II (GMII) is a Family 38 glycosyl hydrolase involved in the eukaryotic N-glycosylation pathway in protein synthesis. Understanding of its catalytic mechanism has been of interest for the development of specific inhibitors that could lead to novel anti-metastatic or anti...

  17. MOPITT Mechanisms 16 Years In-Orbit Operation on TERRA (United States)

    Gibson, Andrew S.; Nichitiu, Florian; Caldwell, Dwight


    The 16th anniversary of the launch of NASA's Terra Spacecraft was marked on December 18, 2015, with the Measurements of Pollution in the Troposphere (MOPITT) instrument being a successful contributor to the NASA EOS flagship. MOPITT has been enabled by a large suite of mechanisms, allowing the instrument to perform long-duration monitoring of atmospheric carbon monoxide, providing global measurements of this important greenhouse gas for 16 years. Mechanisms have been successfully employed for scanning, cooling of detectors, and to optically modulate the gas path length within the instrument by means of pressure and gas cell length variation. The instrument utilizes these devices to perform correlation spectroscopy, enabling measurements with vertical resolution from the nadir view, and has thereby furthered understanding of source and global transport effects of carbon monoxide. Given the design requirement for a 5.25-year lifetime, the stability and performance of the majority of mechanisms have far surpassed design goals. With 16 continuously operating mechanisms in service on MOPITT, including 12 rotating mechanisms and 4 with linear drive elements, the instrument was an ambitious undertaking. The long life requirements combined with demands for cleanliness and optical stability made for difficult design choices including that of the selection of new lubrication processes. Observations and lessons learned with regards to many aspects of the mechanisms and associated monitoring devices are discussed here. Mechanism behaviors are described, including anomalies, long-term drive current/power, fill pressure, vibration and cold-tip temperature trends. The effectiveness of particular lubrication formulations and the screening method implemented is discussed in relation to continuous rotating mechanisms and stepper motors, which have exceeded 15 billon rotations and 2.5 billion steps respectively. Aspects of gas cell hermeticity, optical cleanliness, heater problems

  18. The roles of active site residues in the catalytic mechanism of methylaspartate ammonia-lyase

    NARCIS (Netherlands)

    Raj, Hans; Poelarends, Gerrit J


    Methylaspartate ammonia-lyase (MAL; EC catalyzes the reversible addition of ammonia to mesaconate to yield l-threo-(2S,3S)-3-methylaspartate and l-erythro-(2S,3R)-3-methylaspartate as products. In the proposed minimal mechanism for MAL of Clostridium tetanomorphum, Lys-331 acts as the (S)-s

  19. Mechanisms for catalytic carbon nanofiber growth studied by ab initio density functional theory calculations

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Rostrup-Nielsen, Jens;


    Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported...

  20. Operators and representation theory canonical models for algebras of operators arising in quantum mechanics

    CERN Document Server

    Jorgensen, PET


    Historically, operator theory and representation theory both originated with the advent of quantum mechanics. The interplay between the subjects has been and still is active in a variety of areas.This volume focuses on representations of the universal enveloping algebra, covariant representations in general, and infinite-dimensional Lie algebras in particular. It also provides new applications of recent results on integrability of finite-dimensional Lie algebras. As a central theme, it is shown that a number of recent developments in operator algebras may be handled in a particularly e

  1. The mechanism of methane and dioxygen activation in the catalytic cycle of methane monooxygenase. (United States)

    Shteinman, A A


    The binuclear structure of the active center of methane monooxygenase plays a determining role in dioxygen activation and in selectivity and specificity of alkane oxidation with this enzyme. A new mechanism is suggested for binding and activation of O2, which involves side-on binding of O2-(2) to iron atoms followed by its conversion to the bis-mu-oxo complex considered as an alternative of ferryl in CH4 activation. This mechanism results in the sequence of the cleavage of the O-O bond of peroxide O/O2-instead of the opposite sequence O2-/O, which takes place in the case of heme monooxygenase cytochrome P-450. Therefore, in this case there is no necessity of the charge relay system [N.B. Gerber and S.G. Sligar, J. Am. Chem. Soc. 114 (1992) 8742] for the transformation of O2 to an active intermediate. The experiment for checking this hypothesis is suggested.

  2. Removal performance and mechanism of ibuprofen from water by catalytic ozonation using sludge-corncob activated carbon as catalyst. (United States)

    Wang, Hongjuan; Zhang, Liqiu; Qi, Fei; Wang, Xue; Li, Lu; Feng, Li


    To discover the catalytic activity of sludge-corncob activated carbon in catalytic ozonation of Ibuprofen, the performance of sludge-corncob activated carbon and three selected commercial activated carbons as catalysts in catalytic ozonation was investigated. The observation indicates the degradation rate of Ibuprofen increases significantly in the presence of sludge-corncob activated carbon and the catalytic activity of sludge-corncob activated carbon is much higher than that of the other three commercial activated carbons. Ibuprofen's removal rate follows pseudo-first order kinetics model well. It is also found that the adsorption removal of Ibuprofen by sludge-corncob activated carbon is less than 30% after 40 min. And the removal efficiency of Ibuprofen in the hybrid ozone/sludge-corncob activated carbon system is higher than the sum of sludge-corncob activated carbon adsorption and ozonation alone, which is a supportive evidence for catalytic reaction. In addition, the results of radical scavenger experiments demonstrate that catalytic ozonation of Ibuprofen by sludge-corncob activated carbon follows a hydroxyl radical reaction pathway. During ozonation of Ibuprofen in the presence of activated carbon, ozone could be catalytically decomposed to form hydrogen peroxide, which can promote the formation of hydroxyl radical. The maximum amount of hydrogen peroxide occurs in the presence of sludge-corncob activated carbon, which can explain why sludge-corncob activated carbon has the best catalytic activity among four different activated carbons.

  3. Mechanisms of renewal after the extinction of discriminated operant behavior. (United States)

    Todd, Travis P; Vurbic, Drina; Bouton, Mark E


    Three experiments demonstrated, and examined the mechanisms that underlie, the renewal of extinguished discriminated operant behavior. In Experiment 1, rats were trained to perform 1 response (lever press or chain pull) in the presence of one discriminative stimulus (S; light or tone) in Context A, and to perform the other response in the presence of the other S in Context B. Next, each of the original S/response combinations was extinguished in the alternate context. When the S/response combinations were tested back in the context in which they had been trained, responding in the presence of S returned (an ABA renewal effect was observed). This renewal could not be due to differential context-reinforcer associations, suggesting instead that the extinction context inhibits either the response and/or the effectiveness of the S. Consistent with the latter mechanism, in Experiment 2, ABA renewal was still observed when both the extinction and renewal contexts inhibited the same response. However, in Experiment 3, previous extinction of the response in the renewing context (occasioned by a different S) reduced AAB renewal more than did extinction of the different response. Taken together, the results suggest at least 2 mechanisms of renewal after instrumental extinction. First, extinction performance is at least partly controlled by a direct inhibitory association that is formed between the context and the response. Second, in the discriminated operant procedure, extinction performance can sometimes be partly controlled by a reduction in the effectiveness of the S in the extinction context. Renewal of discriminated operant behavior can be produced by a release from either of these forms of inhibition.

  4. The mechanism of catalytic methylation of 2-phenylpyridine using di-tert-butyl peroxide. (United States)

    Sharma, Akhilesh K; Roy, Dipankar; Sunoj, Raghavan B


    The mechanism of palladium chloride-catalyzed direct methylation of arenes with peroxides is elucidated by using the energetics computed at the M06 density functional theory. The introduction of a methyl group by tert-butyl peroxides at the ortho-position of a prototypical 2-phenyl pyridine, a commonly used substrate in directed C-H functionalization reactions, is examined in detail by identifying the key intermediates and transition states involved in the reaction sequence. Different possibilities that differ in terms of the site of catalyst coordination with the substrate and the ensuing mechanism are presented. The important mechanistic events involved are (a) an oxidative or a homolytic cleavage of the peroxide O-O bond, (b) C-H bond activation, (c) C-C bond activation, and (d) reductive elimination involving methyl transfer to the aromatic ring. We have examined both radical and non-radical pathways. In the non-radical pathway, the lowest energy pathway involves C-H bond activation prior to the coordination of the peroxide to palladium, which is subsequently followed by the O-O bond cleavage of the peroxide and the C-C bond activation. Reductive elimination in the resulting intermediate leads to the vital C-C bond formation between methyl and aryl carbon atoms. In the non-radical pathway, the C-C bond activation is higher in energy and has been identified as the rate-limiting step of this reaction. In the radical pathway, however, the activation barrier for the C-C bond cleavage is lower than for the peroxide O-O bond cleavage. A combination of a radical pathway up to the formation of a palladium methyl intermediate and a subsequent non-radical pathway has been identified as the most favored pathway for the title reaction. The predicted mechanism is in good agreement with the experimental observations on PdCl2 catalyzed methylation of 2-phenyl pyridine using tert-butyl peroxide.

  5. Operational dynamic modeling transcending quantum and classical mechanics. (United States)

    Bondar, Denys I; Cabrera, Renan; Lompay, Robert R; Ivanov, Misha Yu; Rabitz, Herschel A


    We introduce a general and systematic theoretical framework for operational dynamic modeling (ODM) by combining a kinematic description of a model with the evolution of the dynamical average values. The kinematics includes the algebra of the observables and their defined averages. The evolution of the average values is drawn in the form of Ehrenfest-like theorems. We show that ODM is capable of encompassing wide-ranging dynamics from classical non-relativistic mechanics to quantum field theory. The generality of ODM should provide a basis for formulating novel theories.

  6. Mechanism of catalytic functionalization of primary C-H bonds using a silylation strategy. (United States)

    Parija, Abhishek; Sunoj, Raghavan B


    The mechanism of Ir-catalyzed γ-functionalization of a primary sp(3)(C-H) bond in 2-methyl cyclohexanol is examined using the density functional theory (M06). The nature of the active catalyst for the initial silylation of alcohol is identified as the monomer derived from [Ir(cod)OMe]2 while that for γ-sp(3)(C-H) activation leading to oxasilolane is [IrH(nbe)(phen)]. The rate-determining step is found to involve Si-C coupling through reductive elimination.

  7. Molecular modeling of Mycobacterium tuberculosis dUTpase: docking and catalytic mechanism studies. (United States)

    Ramalho, Teodorico C; Caetano, Melissa S; Josa, Daniela; Luz, Gustavo P; Freitas, Elisangela A; da Cunha, Elaine F F


    Mycobacterium tuberculosis is a leading cause of infectious disease in the world today. This outlook is aggravated by a growing number of M. tuberculosis infections in individuals who are immunocompromised as a result of HIV infections. Thus, new and more potent anti-TB agents are necessary. Therefore, dUTpase was selected as a target enzyme to combat M. tuberculosis. In this work, molecular modeling methods involving docking and QM/MM calculations were carried out to investigate the binding orientation and predict binding affinities of some potential dUTpase inhibitors. Our results suggest that the best potential inhibitor investigated, among the compounds studied in this work, is the compound dUPNPP. Regarding the reaction mechanism, we concluded that the decisive stage for the reaction is the stage 1. Furthermore, it was also observed that the compounds with a -1 electrostatic charge presented lower activation energy in relation to the compounds with a -2 charge.

  8. Cloning, functional characterization and catalytic mechanism of a bergaptol O-methyltransferase from Peucedanum praeruptorum Dunn

    Directory of Open Access Journals (Sweden)

    Yucheng eZhao


    Full Text Available Coumarins are main active components of Peucedanum praeruptorum Dunn. Among them, methoxylated coumarin compound, such as bergapten, xanthotoxin and isopimpinellin, has high officinal value and plays an important role in medicinal field. However, major issues associated with the biosynthesis mechanism of coumarins remain unsolved and no corresponding enzyme has been cloned from P. praeruptorum. In this study, a local BLASTN program was conducted to find the candidate genes from P. praeruptorum transcriptome database using the nucleotide sequence of Ammi majus bergaptol O-methyltransferase (AmBMT, GenBank accession No: AY443006 as a template. As a result, a 1335 bp full-length of cDNA sequence which contains an open reading frame of 1080 bp encoding a BMT polypeptide of 359 amino acids was obtained. The recombinant protein was functionally expressed in Escherichia coli and displayed an observed activity to bergaptol. In vitro experiments show that the protein has narrow substrate specificity for bergaptol. Expression profile indicated that the cloned gene had a higher expression level in roots and can be induced by methyl jasmonate (MeJA. Subcellular localization analysis showed that the BMT protein was located in cytoplasm in planta. Homology modeling and docking based site-directed mutagenesis have been employed to investigate the amino acid residues in BMT required for substrate binding and catalysis. Conservative amino acid substitutions at residue H264 affected BMT catalysis, whereas substitutions at residues F171, M175, D226 and L312 affected substrate binding. The systemic study summarized here will enlarge our knowledge on OMTs and provide useful information in investigating the coumarins biosynthesis mechanism in P. praeruptorum.

  9. Piezo-Operated Shutter Mechanism Moves 1.5 cm (United States)

    Glaser, Robert; Bamford, Robert


    The figure shows parts of a shutter mechanism designed to satisfy a number of requirements specific to its original intended application as a component of an atomic clock to be flown in outer space. The mechanism may also be suitable for use in laboratory and industrial vacuum systems on Earth for which there are similar requirements. The requirements include the following: a) To alternately close, then open, a 1.5-cm-diameter optical aperture twice per second, with a stroke time of no more than 15 ms, during a total operational lifetime of at least a year; b) To attenuate light by a factor of at least 1012 when in the closed position; c) To generate little or no magnetic field; d) To be capable of withstanding bakeout at a temperature of 200 C to minimize outgassing during subsequent operation in an ultrahigh vacuum; and e) To fit within a diameter of 12 in. (=305 mm) a size limit dictated by the size of an associated magnetic shield. The light-attenuation requirement is satisfied by use of overlapping shutter blades. The closure of the aperture involves, among other things, insertion of a single shutter blade between a pair of shutter blades. The requirement to minimize the magnetic field is satisfied by use of piezoelectric actuators. Because piezoelectric actuators cannot withstand bakeout, they must be mounted outside the vacuum chamber, and, hence, motion must be transmitted from the actuators to the shutter levers via a vacuum-chamber-wall diaphragm.

  10. Crystal Structure and Catalytic Mechanism of CouO, a Versatile C-Methyltransferase from Streptomyces rishiriensis (United States)

    Pavkov-Keller, Tea; Steiner, Kerstin; Faber, Mario; Tengg, Martin; Schwab, Helmut; Gruber-Khadjawi, Mandana


    Friedel–Crafts alkylation of aromatic systems is a classic reaction in organic chemistry, for which regiospecific mono-alkylation, however, is generally difficult to achieve. In nature, methyltransferases catalyze the addition of methyl groups to a wide range of biomolecules thereby modulating the physico-chemical properties of these compounds. Specifically, S-adenosyl-L-methionine dependent C-methyltransferases possess a high potential to serve as biocatalysts in environmentally benign organic syntheses. Here, we report on the high resolution crystal structure of CouO, a C-methyltransferase from Streptomyces rishiriensis involved in the biosynthesis of the antibiotic coumermycin A1. Through molecular docking calculations, site-directed mutagenesis and the comparison with homologous enzymes we identified His120 and Arg121 as key functional residues for the enzymatic activity of this group of C-methyltransferases. The elucidation of the atomic structure and the insight into the catalytic mechanism provide the basis for the (semi)-rational engineering of the enzyme in order to increase the substrate scope as well as to facilitate the acceptance of SAM-analogues as alternative cofactors. PMID:28152088

  11. The regulation and catalytic mechanism of the NADP-malic enzyme from tobacco leaves

    Directory of Open Access Journals (Sweden)



    Full Text Available The non-photosynthetic NADP-malic enzyme EC (NADP-ME, which catalyzes the oxidative decarboxylation of L-malate and NADP+ to produce pyruvate and NADPH, respectively, and which could be involved in plant defense responses, was isolated from Nicotiana tabacum L. leaves. The mechanism of the enzyme reaction was studied by the initial rate method and was found to be an ordered sequential one. Regulation possibilities of purified cytosolic NADP-ME by cell metabolites were tested. Intermediates of the citric acid cycle (a-ketoglutarate, succinate, fumarate, metabolites of glycolysis (pyruvate, phosphoenolpyruvate, glucose-6-phosphate, compounds connected with lipogenesis (coenzyme A, acetyl-CoA, palmitoyl-CoA and some amino acids (glutamate, glutamine, aspartate did not significantly affect the NADP-ME activity from tobacco leaves. In contrast, macroergic compounds (GTP, ATP and ADP were strong inhibitors of NADP-ME; the type of inhibition and the inhibition constants were determined in the presence of the most effective cofactors (Mn2+ or Mg2+, required by NADP-ME. Predominantly non-competitive type of inhibitions of NADP-ME with respect to NADP+ and mixed type to L-malate were found.

  12. Effect of biomass ash in catalytic fast pyrolysis of pine wood

    NARCIS (Netherlands)

    Yildiz, G.; Ronsse, F.; Venderbosch, R.H.; Duren, van R.; Kersten, S.R.A.; Prins, W.


    Fast pyrolysis experiments of pine wood have been performed in a continuously operated mechanically stirred bed reactor at 500 °C. The effects of the pine wood ash were studied by comparing non-catalytic and catalytic experiments (using a ZSM-5 based catalyst) with their ash-added counterparts. To s

  13. New insights into the catalytic mechanism of vitamin K epoxide reductase (VKORC1) - The catalytic properties of the major mutations of rVKORC1 explain the biological cost associated to mutations. (United States)

    Matagrin, Benjamin; Hodroge, Ahmed; Montagut-Romans, Adrien; Andru, Julie; Fourel, Isabelle; Besse, Stéphane; Benoit, Etienne; Lattard, Virginie


    The systematic use of antivitamin K anticoagulants (AVK) as rodenticides caused the selection of rats resistant to AVKs. The resistance is mainly associated to genetic polymorphisms in the Vkorc1 gene encoding the VKORC1 enzyme responsible for the reduction of vitamin K 2,3-epoxide to vitamin K. Five major mutations, which are responsible for AVK resistance, have been described. Possible explanations for the biological cost of these mutations have been suggested. This biological cost might be linked to an increase in the vitamin K requirements. To analyze the possible involvement of VKORC1 in this biological cost, rVKORC1 and its major mutants were expressed in Pichia pastoris as membrane-bound proteins and their catalytic properties were determined for vitamin K and 3-OH-vitamin K production. In this report, we showed that mutations at Leu-120 and Tyr-139 dramatically affect the vitamin K epoxide reductase activity. Moreover, this study allowed the detection of an additional production of 3-hydroxyvitamin K for all the mutants in position 139. This result suggests the involvement of Tyr-139 residue in the second half-step of the catalytic mechanism corresponding to the dehydration of vitamin K epoxide. As a consequence, the biological cost observed in Y139C and Y139S resistant rat strains is at least partially explained by the catalytic properties of the mutated VKORC1 involving a loss of vitamin K from the vitamin K cycle through the formation of 3-hydroxyvitamin K and a very low catalytic efficiency of the VKOR activity.

  14. Quantitative comparison of catalytic mechanisms and overall reactions in convergently evolved enzymes: implications for classification of enzyme function.

    Directory of Open Access Journals (Sweden)

    Daniel E Almonacid


    Full Text Available Functionally analogous enzymes are those that catalyze similar reactions on similar substrates but do not share common ancestry, providing a window on the different structural strategies nature has used to evolve required catalysts. Identification and use of this information to improve reaction classification and computational annotation of enzymes newly discovered in the genome projects would benefit from systematic determination of reaction similarities. Here, we quantified similarity in bond changes for overall reactions and catalytic mechanisms for 95 pairs of functionally analogous enzymes (non-homologous enzymes with identical first three numbers of their EC codes from the MACiE database. Similarity of overall reactions was computed by comparing the sets of bond changes in the transformations from substrates to products. For similarity of mechanisms, sets of bond changes occurring in each mechanistic step were compared; these similarities were then used to guide global and local alignments of mechanistic steps. Using this metric, only 44% of pairs of functionally analogous enzymes in the dataset had significantly similar overall reactions. For these enzymes, convergence to the same mechanism occurred in 33% of cases, with most pairs having at least one identical mechanistic step. Using our metric, overall reaction similarity serves as an upper bound for mechanistic similarity in functional analogs. For example, the four carbon-oxygen lyases acting on phosphates (EC 4.2.3 show neither significant overall reaction similarity nor significant mechanistic similarity. By contrast, the three carboxylic-ester hydrolases (EC 3.1.1 catalyze overall reactions with identical bond changes and have converged to almost identical mechanisms. The large proportion of enzyme pairs that do not show significant overall reaction similarity (56% suggests that at least for the functionally analogous enzymes studied here, more stringent criteria could be used to

  15. Catalytic hydropyrolysis of microalgae: influence of operating variables on the formation and composition of bio-oil. (United States)

    Chang, Zhoufan; Duan, Peigao; Xu, Yuping


    Catalytic hydropyrolysis of microalgae has been studied by using a batch reactor. Nine different heterogenous catalysts of Pd/C, Pt/C, Ru/C, Rh/C, CoMo/γ-Al2O3, Mo2C, MoS2, and activated carbon were screened. Mo2C was identified as the most suitable catalyst. With Mo2C catalyst, influence of reaction conditions on the yield and properties of the hydropyrolysis oil (HPO) was examined. Temperature was the most influential factor affecting the yield and quality of the HPO. Higher temperature will produce HPO with higher C and H content and lower N and O content but at the cost of lowering the yield of HPO. Mo2C promoted the in situ deoxygenation and desulfurization of the HPO which has a HHVs varying between 35.3 and 39.3 MJ/kg. The highest energy recovery of 87.5% was achieved. Thus, this work shows that the catalytic hydropyrolysis is an effective way to produce high quality bio-oil from microalgae.

  16. Mechanisms of Extending Operation Regionin the HL-1M Tokamak

    Institute of Scientific and Technical Information of China (English)


    Stable operating region in the HL-1M tokamak has been extended by means ofwall conditioning, core fuelling and current control techniques. The mechanisms of the extensionare analyzed in this paper. Lithiumization diminishes the impurities and hydrogen recycling tothe lowest level. After lithiumization a high density up to 7×1019 m-3 was obtained easily bystrong gas puffing with ordinary ohmic discharge alone. More attractively we found that metalLi-coating exhibited the effects of wall stabilization. The low qa limit with higher density wasextended by a factor of 1.5~2 in comparison with that for boronization, and 1.2 for siliconization.Siliconization not only extended stable operating region significantly by itself, but also provideda good target plasma for other experiments of raising density limit. Core fuelling schemes arefavourable especially for siliconized wall with a higher level of medium-Z impurity (Z=14).After siliconization the maximum density near to 1020 m-3 was achieved by a combination ofsupersonic molecule beam injection and multipellet injection. The new defined slope of Hugilllimit illustrating more clearly the situation under low qa and high ne discharges was created toindicate the new region extended by combining Ip ramp-up with core fuelling. The slope with alarge Murakami coefficient increased by a factor of 50~60 %.

  17. About the velocity operator for spinning particles in quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Salesi, Giovanni [Universita Statale di Catania (Italy). Dipt. di Fisica]|[Istituto Nazionale di Fisica Nucleare, Catania (Italy); Recami, Erasmo; Rodrigues Junior, Waldyr A. [Universidade Estadual de Campinas, SP (Brazil). Dept. de Matematica Aplicada


    Starting from the formal expressions of the hydrodynamical (or local) quantities employed in the applications of Clifford Algebras to quantum mechanics, we introduce - in terms of the ordinary tensorial framework - a new definition for the field of a generic quantity. By translating from Clifford into sensor algebra, we also propose a new (non-relativistic) velocity operator for a spin 1/2 particle. This operator is the sum of the ordinary part p/m describing the mean motion (the motion of the center-of-mass), and of a second part associated with the so-called Zitterbewegung, which is the spin internal motion observed in the center-of-mass frame. This spin component of the velocity operator is non-zero not only in the Pauli theoretical framework in presence of external magnetic fields and spin precession, but also in the Schroedinger case, when the wave-function is a spin eigenstate. In the latter case, one gets a decomposition of the velocity field for the Madelueng fluid into two distinct parts: which constitutes the non-relativistic analogue of the Gordon decomposition for the Dirac current. We find furthermore that the Zitterbewegung motion involves a velocity field which is solenoidal, and that the local angular velocity is parallel to the spin vector. In presence of a non-constant spin vector (Pauli case) we have, besides the component normal to spin present even in the Schroedinger theory, also a component of the local velocity which is parallel to the rotor of the spin vector. (author). 19 refs.

  18. A QM/MM investigation of the catalytic mechanism of metal-ion-independent core 2 β1,6-N-acetylglucosaminyltransferase. (United States)

    Tvaroška, Igor; Kozmon, Stanislav; Wimmerová, Michaela; Koča, Jaroslav


    β1,6-GlcNAc-transferase (C2GnT) is an important controlling factor of biological functions for many glycoproteins and its activity has been found to be altered in breast, colon, and lung cancer cells, in leukemia cells, in the lymhomonocytes of multiple sclerosis patients, leukocytes from diabetes patients, and in conditions causing an immune deficiency. The result of the action of C2GnT is the core 2 structure that is essential for the further elongation of the carbohydrate chains of O-glycans. The catalytic mechanism of this metal-ion-independent glycosyltransferase is of paramount importance and is investigated here by using quantum mechanical (QM) (density functional theory (DFT))/molecular modeling (MM) methods with different levels of theory. The structural model of the reaction site used in this report is based on the crystal structures of C2GnT. The entire enzyme-substrate system was subdivided into two different subsystems: the QM subsystem containing 206 atoms and the MM region containing 5914 atoms. Three predefined reaction coordinates were employed to investigate the catalytic mechanism. The calculated potential energy surfaces discovered the existence of a concerted SN 2-like mechanism. In this mechanism, a nucleophilic attack by O6 facilitated by proton transfer to the catalytic base and the separation of the leaving group all occur almost simultaneously. The transition state for the proposed reaction mechanism at the M06-2X/6-31G** (with diffuse functions on the O1', O5', OGlu , and O6 atoms) level was located at C1-O6=1.74 Å and C1-O1=2.86 Å. The activation energy for this mechanism was estimated to be between 20 and 29 kcal mol⁻¹, depending on the method used. These calculations also identified a low-barrier hydrogen bond between the nucleophile O6H and the catalytic base Glu320, and a hydrogen bond between the N-acetamino group and the glycosidic oxygen of the donor in the TS. It is proposed that these interactions contribute to a


    Institute of Scientific and Technical Information of China (English)


    Hydrogen transfer is an important secondary reaction of catalytic cracking reactions, which affects product yield distribution and product quality. It is an exothermic reaction with low activation energy around 43.3 kJ/mol. Catalyst properties and operation parameters in catalytic cracking greatly influence the hydrogen transfer reaction. Satisfactory results are expected through careful selection of proper catalysts and operation conditions.

  20. Comparison of Efficiencies and Mechanisms of Catalytic Ozonation of Recalcitrant Petroleum Refinery Wastewater by Ce, Mg, and Ce-Mg Oxides Loaded Al2O3

    Directory of Open Access Journals (Sweden)

    Chunmao Chen


    Full Text Available The use of catalytic ozonation processes (COPs for the advanced treatment of recalcitrant petroleum refinery wastewater (RPRW is rapidly expanding. In this study, magnesium (Mg, cerium (Ce, and Mg-Ce oxide-loaded alumina (Al2O3 were developed as cost efficient catalysts for ozonation treatment of RPRW, having performance metrics that meet new discharge standards. Interactions between the metal oxides and the Al2O3 support influence the catalytic properties, as well as the efficiency and mechanism. Mg-Ce/Al2O3 (Mg-Ce/Al2O3-COP reduced the chemical oxygen demand by 4.7%, 4.1%, 6.0%, and 17.5% relative to Mg/Al2O3-COP, Ce/Al2O3-COP, Al2O3-COP, and single ozonation, respectively. The loaded composite metal oxides significantly increased the hydroxyl radical-mediated oxidation. Surface hydroxyl groups (–OHs are the dominant catalytic active sites on Al2O3. These active surface –OHs along with the deposited metal oxides (Mg2+ and/or Ce4+ increased the catalytic activity. The Mg-Ce/Al2O3 catalyst can be economically produced, has high efficiency, and is stable under acidic and alkaline conditions.

  1. Selective catalytic reduction (SCR) of NO by urea loaded on activated carbon fibre (ACF) and CeO2/ACF at 30 degrees C: the SCR mechanism. (United States)

    Zeng, Zheng; Lu, Pei; Li, Caiting; Zeng, Guangming; Jiang, Xiao; Zhai, Yunbo; Fan, Xiaopeng


    Selective catalytic reduction (SCR) of NO by urea loaded on rayon-based activated carbon fibre (ACF) and CeO2/ACF (CA) was studied at ambient temperature (30 degrees C) to establish a basic scheme for its reduction. Nitric oxide was found to be reduced to N2 with urea deposited on the ACF and CA. When oxygen was present, the greater the amount of loaded urea (20-60%), the greater the NO(x) conversions, which were between 72.03% and 77.30%, whereas the NO(x) conversions were about 50% when oxygen was absent. Moreover, when the urea was loaded on CA, a catalyst containing 40% urea/ACF loaded with 10% CeO2 (UCA4) could yield a NO(x) conversion of about 80% for 24.5 h. Based on the experimental results, the catalytic mechanisms of SCR with and without oxygen are discussed. The enhancing effect of oxygen resulted from the oxidation of NO to NO2, and urea was the main reducing agent in the SCR of loaded catalysts. ACF-C was the catalytic centre in the SCR of NO of ACF, while CeO2 of urea-loaded CA was the catalytic centre.

  2. Ergonomics applications of a mechanical model of the human operator in power hand tool operation. (United States)

    Lin, Jia-Hua; Radwin, Robert; Nembhard, David


    Applications of a new model for predicting power threaded-fastener-driving tool operator response and capacity to react against impulsive torque reaction forces are explored for use in tool selection and ergonomic workplace design. The model is based on a mechanical analog of the human operator, with parameters dependent on work location (horizontal and vertical distances); work orientation (horizontal and vertical); and tool shape (in-line, pistol grip, and right angle); and is stratified by gender. This model enables prediction of group means and variances of handle displacement and force for a given tool configuration. Response percentiles can be ascertained for specific tool operations. For example, a sample pistol grip nutrunner used on a horizontal surface at 30 cm in front of the ankles and 140 cm above the floor results in a predicted mean handle reaction displacement of 39.0 (SD=28.1) mm for males. Consequently 63%of the male users exceed a 30 mm handle displacement limit. When a right angle tool of similar torque output is used instead, the model predicted that only 4.6%of the male tool users exceed a 30 mm handle displacement. A method is described for interpolating individual subject model parameters at any given work location using linear combinations in relation to the range of modeled factors. Additional examples pertinent to ergonomic workstation design and tool selection are provided to demonstrate how the model can be used to aid tool selection and workstation design.

  3. Catalytic Mechanism of Perosamine N-Acetyltransferase Revealed by High-Resolution X-ray Crystallographic Studies and Kinetic Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Thoden, James B.; Reinhardt, Laurie A.; Cook, Paul D.; Menden, Patrick; Cleland, W.W.; Holden, Hazel M. (UW); (Mount Union); (UW-MED)


    N-Acetylperosamine is an unusual dideoxysugar found in the O-antigens of some Gram-negative bacteria, including the pathogenic Escherichia coli strain O157:H7. The last step in its biosynthesis is catalyzed by PerB, an N-acetyltransferase belonging to the left-handed {beta}-helix superfamily of proteins. Here we describe a combined structural and functional investigation of PerB from Caulobacter crescentus. For this study, three structures were determined to 1.0 {angstrom} resolution or better: the enzyme in complex with CoA and GDP-perosamine, the protein with bound CoA and GDP-N-acetylperosamine, and the enzyme containing a tetrahedral transition state mimic bound in the active site. Each subunit of the trimeric enzyme folds into two distinct regions. The N-terminal domain is globular and dominated by a six-stranded mainly parallel {beta}-sheet. It provides most of the interactions between the protein and GDP-perosamine. The C-terminal domain consists of a left-handed {beta}-helix, which has nearly seven turns. This region provides the scaffold for CoA binding. On the basis of these high-resolution structures, site-directed mutant proteins were constructed to test the roles of His 141 and Asp 142 in the catalytic mechanism. Kinetic data and pH-rate profiles are indicative of His 141 serving as a general base. In addition, the backbone amide group of Gly 159 provides an oxyanion hole for stabilization of the tetrahedral transition state. The pH-rate profiles are also consistent with the GDP-linked amino sugar substrate entering the active site in its unprotonated form. Finally, for this investigation, we show that PerB can accept GDP-3-deoxyperosamine as an alternative substrate, thus representing the production of a novel trideoxysugar.

  4. Dissecting the Catalytic Mechanism of Betaine-Homocysteine S-Methyltransferase Using Intrinsic Tryptophan Fluorescence and Site-Directed Mutagenesis

    Energy Technology Data Exchange (ETDEWEB)

    Castro, C.; Gratson, A.A.; Evans, J.C.; Jiracek, J.; Collinsova, M.; Ludwig, M.L.; Garrow, T.A. (ASCR); (UIUC); (Michigan)


    Betaine-homocysteine S-methyltransferase (BHMT) is a zinc-dependent enzyme that catalyzes the transfer of a methyl group from glycine betaine (Bet) to homocysteine (Hcy) to form dimethylglycine (DMG) and methionine (Met). Previous studies in other laboratories have indicated that catalysis proceeds through the formation of a ternary complex, with a transition state mimicked by the inhibitor S-({delta}-carboxybutyl)-l-homocysteine (CBHcy). Using changes in intrinsic tryptophan fluorescence to determine the affinity of human BHMT for substrates, products, or CBHcy, we now demonstrate that the enzyme-substrate complex reaches its transition state through an ordered bi-bi mechanism in which Hcy is the first substrate to bind and Met is the last product released. Hcy, Met, and CBHcy bind to the enzyme to form binary complexes with K{sub d} values of 7.9, 6.9, and 0.28 {micro}M, respectively. Binary complexes with Bet and DMG cannot be detected with fluorescence as a probe, but Bet and DMG bind tightly to BHMT-Hcy to form ternary complexes with K{sub d} values of 1.1 and 0.73 {micro}M, respectively. Mutation of each of the seven tryptophan residues in human BHMT provides evidence that the enzyme undergoes two distinct conformational changes that are reflected in the fluorescence of the enzyme. The first is induced when Hcy binds, and the second, when Bet binds. As predicted by the crystal structure of BHMT, the amino acids Trp44 and Tyr160 are involved in binding Bet, and Glu159 in binding Hcy. Replacing these residues by site-directed mutagenesis significantly reduces the catalytic efficiency (V{sub max}/K{sub m}) of the enzyme. Replacing Tyr77 with Phe abolishes enzyme activity.

  5. Mechanical grading in PGI Tropea red onion post harvest operations

    Directory of Open Access Journals (Sweden)

    Bruno Bernardi


    Full Text Available The growing interest expressed by consumers toward food products quality as well as toward their linkage to the territory, has led producers to fit to the continuous rising demand for “typical products”, and to look for new and more efficient production and marketing strategies. An emblematic case is represented by Tropea red onion that, as a typical product, plays an important role in economical and rural development of the territory to which it is linked. The organoleptic features offered by “Tropea Red Onion”, PGI certified (Calabria, have to be associated as well to the quality of services that accompanies its processing. Technology application in post-harvest operations, has certainly contributed to make faster and less tiring all processing tasks. The main problem related to the mechanization of Tropea red onion post-harvest operations lies in the removal of the various layers of the external tunic, making it impossible for optical or electronic grader to achieve this task in a satisfactory way since the sensors are not able yet to separate the “bulb” from its involucre. In this context, the current study aims to assess the productivity of three different machines used for round Tropea red onion grading, and determine their work efficiency. The carried out analysis highlighted the ability of the studied machines to ensure a high work capacity, while maintaining a high level of precision during calibration process. Such precision allows to decrease laborer employment and increase processing chain speed, rising as well the annual use of the machines, allowing consequently processing cost savings. For a more profitable employment of such graders, it is, however, necessary from one hand, to properly form the technicians responsible of processing plants management, and from the other hand, to be able to take advantage of a technical assistance network, able to serve users in a short time.

  6. β-Molybdenum nitride: synthesis mechanism and catalytic response in the gas phase hydrogenation of p-chloronitrobenzene

    NARCIS (Netherlands)

    Cárdenas-Lizana, F.; Gómez-Quero, S.; Perret, N.; Kiwi-Minsker, L.; Keane, M.A.


    A temperature programmed treatment of MoO3 in flowing N2 + H2 has been employed to prepare β-phase molybdenum nitride (β-Mo2N) which has been used to promote, for the first time, the catalytic hydrogenation of p-chloronitrobenzene. The reduction/nitridation synthesis steps have been monitored in sit

  7. Thermodynamic analysis of ionizable groups involved in the catalytic mechanism of human matrix metalloproteinase 7 (MMP-7). (United States)

    Takeharu, Hitoshi; Yasukawa, Kiyoshi; Inouye, Kuniyo


    Human matrix metalloproteinase 7 (MMP-7) exhibits a broad bell-shaped pH-dependence with the acidic and alkaline pK(e) (pK(e1) and pK(e2)) values of about 4 and 10. In this study, we estimated the ionizable groups involved in its catalytic mechanism by thermodynamic analysis. pK(a) of side chains of L-Asp, L-Glu, L-His, L-Cys, L-Tyr, L-Lys, and L-Arg at 25-45°C were determined by the pH titration of amino-acid solutions, from which their enthalpy changes, ∆H°, of deprotonation were calculated. pK(e1) and pK(e2) of MMP-7 at 15-45°C were determined in the hydrolysis of (7-methoxycoumarin-4-yl)acetyl-L-Pro-L-Leu-Gly-L-Leu-[N(3)-(2,4-dinitrophenyl)-L-2,3-diaminopropionyl]-L-Ala-L-Arg-NH(2), from which ∆H(o) for pK(e1) and pK(e2) was calculated. The ∆H(o) for pK(e1) (-20.6±6.1kJmol(-1)) was similar to that for L-Glu (-23.6±5.8kJmol(-1)), and the ∆H(o) for pK(e2) (89.9±4.0kJmol(-1)) was similar to those for L-Arg (87.6±5.5kJmol(-1)) and L-Lys (70.4±4.4kJmol(-1)). The mutation of the active-site residue Glu198 into Ala completely abolished the activity, suggesting that Glu198 is the ionizable group for pK(e1). On the other hand, no arginine or lysine residues are found in the active site of MMP-7. We proposed a possibility that a protein-bound water is the ionizable group for pK(e2).

  8. Insights into the catalytic mechanisms of phenylalanine and tryptophan hydroxylase from kinetic isotope effects on aromatic hydroxylation. (United States)

    Pavon, Jorge Alex; Fitzpatrick, Paul F


    Phenylalanine hydroxylase (PheH) and tryptophan hydroxylase (TrpH) catalyze the aromatic hydroxylation of phenylalanine and tryptophan, forming tyrosine and 5-hydroxytryptophan, respectively. The reactions of PheH and TrpH have been investigated with [4-(2)H]-, [3,5-(2)H(2)]-, and (2)H(5)-phenylalanine as substrates. All (D)k(cat) values are normal with Delta117PheH, the catalytic core of rat phenylalanine hydroxylase, ranging from 1.12-1.41. In contrast, for Delta117PheH V379D, a mutant protein in which the stoichiometry between tetrahydropterin oxidation and amino acid hydroxylation is altered, the (D)k(cat) value with [4-(2)H]-phenylalanine is 0.92 but is normal with [3,5-(2)H(2)]-phenylalanine. The ratio of tetrahydropterin oxidation to amino acid hydroxylation for Delta117PheH V379D shows a similar inverse isotope effect with [4-(2)H]-phenylalanine. Intramolecular isotope effects, determined from the deuterium contents of the tyrosine formed from [4-(2)H]-and [3,5(2)H(2)]-phenylalanine, are identical for Delta117PheH and Delta117PheH V379D, suggesting that steps subsequent to oxygen addition are unaffected in the mutant protein. The inverse effects are consistent with the reaction of an activated ferryl-oxo species at the para position of the side chain of the amino acid to form a cationic intermediate. The normal effects on the (D)k(cat) value for the wild-type enzyme are attributed to an isotope effect of 5.1 on the tautomerization of a dienone intermediate to tyrosine with a rate constant 6- to7-fold that for hydroxylation. In addition, there is a slight ( approximately 34%) preference for the loss of the hydrogen originally at C4 of phenylalanine. With (2)H(5)-indole-tryptophan as a substrate for Delta117PheH, the (D)k(cat) value is 0.89, consistent with hydroxylation being rate-limiting in this case. When deuterated phenylalanines are used as substrates for TrpH, the (D)k(cat) values are within error of those for Delta117PheH V379D. Overall, these results

  9. Sequence analysis and structure prediction of type II Pseudomonas sp. USM 4–55 PHA synthase and an insight into its catalytic mechanism

    Directory of Open Access Journals (Sweden)

    Ahmad Khairudin Nurul


    Full Text Available Abstract Background Polyhydroxyalkanoates (PHA, are biodegradable polyesters derived from many microorganisms such as the pseudomonads. These polyesters are in great demand especially in the packaging industries, the medical line as well as the paint industries. The enzyme responsible in catalyzing the formation of PHA is PHA synthase. Due to the limited structural information, its functional properties including catalysis are lacking. Therefore, this study seeks to investigate the structural properties as well as its catalytic mechanism by predicting the three-dimensional (3D model of the Type II Pseudomonas sp. USM 4–55 PHA synthase 1 (PhaC1P.sp USM 4–55. Results Sequence analysis demonstrated that PhaC1P.sp USM 4–55 lacked similarity with all known structures in databases. PSI-BLAST and HMM Superfamily analyses demonstrated that this enzyme belongs to the alpha/beta hydrolase fold family. Threading approach revealed that the most suitable template to use was the human gastric lipase (PDB ID: 1HLG. The superimposition of the predicted PhaC1P.sp USM 4–55 model with 1HLG covering 86.2% of the backbone atoms showed an RMSD of 1.15 Å. The catalytic residues comprising of Cys296, Asp451 and His479 were found to be conserved and located adjacent to each other. In addition to this, an extension to the catalytic mechanism was also proposed whereby two tetrahedral intermediates were believed to form during the PHA biosynthesis. These transition state intermediates were further postulated to be stabilized by the formation of oxyanion holes. Based on the sequence analysis and the deduced model, Ser297 was postulated to contribute to the formation of the oxyanion hole. Conclusion The 3D model of the core region of PhaC1P.sp USM 4–55 from residue 267 to residue 484 was developed using computational techniques and the locations of the catalytic residues were identified. Results from this study for the first time highlighted Ser297 potentially

  10. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnO{sub x}/SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Qiangqiang; Wang, Yu [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China); Li, Laisheng, E-mail: [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China); Bing, Jishuai [Key Laboratory of Aquatic Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Wang, Yingxin; Yan, Huihua [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China)


    Highlights: • Clofibric acid (CA) is efficiently mineralized by O{sub 3}/MnO{sub x}/SBA-15. • Adsorption of CA and its intermediates on MnO{sub x}/SBA-15 is proved unimportant. • Initiation of hydroxyl radicals (·OH) is enhanced in O{sub 3}/MnO{sub x}/SBA-15. • Uniformly distributed MnO{sub x} accounts for the high activity of MnO{sub x}/SBA-15. • Degradation routes of CA in ozonation alone and catalytic ozonation are proposed. - Abstract: Comparative experiments were conducted to investigate the catalytic ability of MnO{sub x}/SBA-15 for the ozonation of clofibric acid (CA) and its reaction mechanism. Compared with ozonation alone, the degradation of CA was barely enhanced, while the removal of TOC was significantly improved by catalytic ozonation (O{sub 3}/MnO{sub x}/SBA-15). Adsorption of CA and its intermediates by MnO{sub x}/SBA-15 was proved unimportant in O{sub 3}/MnO{sub x}/SBA-15 due to the insignificant adsorption of CA and little TOC variation after ceasing ozone in stopped-flow experiment. The more remarkably inhibition effect of sodium bisulfite (NaHSO{sub 3}) on the removal of TOC in catalytic ozonation than in ozonation alone elucidated that MnO{sub x}/SBA-15 facilitated the generation of hydroxyl radicals (·OH), which was further verified by electron spin-resonance spectroscopy (ESR). Highly dispersed MnO{sub x} on SBA-15 were believed to be the main active component in MnO{sub x}/SBA-15. Some intermediates were indentified and different degradation routes of CA were proposed in both ozonation alone and catalytic ozonation. The amounts of small molecular carboxylic acids (i.e., formic acid (FA), acetic acid (AA) and oxalic acid (OA)) generated in catalytic ozonation were lower than in ozonation alone, resulting from the generation of more ·OH.

  11. SOFC system with integrated catalytic fuel processing (United States)

    Finnerty, Caine; Tompsett, Geoff. A.; Kendall, Kevin; Ormerod, R. Mark

    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm -2 at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H 2/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack.

  12. SOFC system with integrated catalytic fuel processing

    Energy Technology Data Exchange (ETDEWEB)

    Finnerty, C.; Tompsett, G.A.; Kendall, K.; Ormerod, R.M. [Birchall Centre for Inorganic Chemistry and Materials Science, Keele Univ. (United Kingdom)


    In recent years, there has been much interest in the development of solid oxide fuel cell technology operating directly on hydrocarbon fuels. The development of a catalytic fuel processing system, which is integrated with the solid oxide fuel cell (SOFC) power source is outlined here. The catalytic device utilises a novel three-way catalytic system consisting of an in situ pre-reformer catalyst, the fuel cell anode catalyst and a platinum-based combustion catalyst. The three individual catalytic stages have been tested in a model catalytic microreactor. Both temperature-programmed and isothermal reaction techniques have been applied. Results from these experiments were used to design the demonstration SOFC unit. The apparatus used for catalytic characterisation can also perform in situ electrochemical measurements as described in previous papers [C.M. Finnerty, R.H. Cunningham, K. Kendall, R.M. Ormerod, Chem. Commun. (1998) 915-916; C.M. Finnerty, N.J. Coe, R.H. Cunningham, R.M. Ormerod, Catal. Today 46 (1998) 137-145]. This enabled the performance of the SOFC to be determined at a range of temperatures and reaction conditions, with current output of 290 mA cm{sup -2} at 0.5 V, being recorded. Methane and butane have been evaluated as fuels. Thus, optimisation of the in situ partial oxidation pre-reforming catalyst was essential, with catalysts producing high H{sub 2}/CO ratios at reaction temperatures between 873 K and 1173 K being chosen. These included Ru and Ni/Mo-based catalysts. Hydrocarbon fuels were directly injected into the catalytic SOFC system. Microreactor measurements revealed the reaction mechanisms as the fuel was transported through the three-catalyst device. The demonstration system showed that the fuel processing could be successfully integrated with the SOFC stack. (orig.)

  13. Modal Testing of Mechanical Structures subject to Operational Excitation Forces

    DEFF Research Database (Denmark)

    Møller, N.; Brincker, Rune; Herlufsen, H.;


    to the Operational Modal Analysis. For Operational Modal Analysis two different estimation techniques are used: a non-parametric technique based on Frequency Domain Decomposition (FDD), and a parametric technique working on the raw data in time domain, a data driven Stochastic Subspace Identification (SSI) algorithm...

  14. Modal Testing of Mechanical Structures Subject to Operational Excitation Forces

    DEFF Research Database (Denmark)

    Møller, N.; Brincker, Rune; Herlufsen, H.;


    to the Operational Modal Analysis. For Operational Modal Analysis two different estimation techniques are used: a non-parametric technique based on Frequency Domain Decomposition (FDD), and a parametric technique working on the raw data in time domain, a data driven Stochastic Subspace Identification (SSI) algorithm...

  15. A flexible loop as a functional element in the catalytic mechanism of nucleoside hydrolase from Trypanosoma vivax. (United States)

    Vandemeulebroucke, An; De Vos, Stefan; Van Holsbeke, Els; Steyaert, Jan; Versées, Wim


    The nucleoside hydrolase of Trypanosoma vivax hydrolyzes the N-glycosidic bond of purine nucleosides. Structural and kinetic studies on this enzyme have suggested a catalytic role for a flexible loop in the vicinity of the active sites. Here we present the analysis of the role of this flexible loop via the combination of a proline scan of the loop, loop deletion mutagenesis, steady state and pre-steady state analysis, and x-ray crystallography. Our analysis reveals that this loop has an important role in leaving group activation and product release. The catalytic role involves the entire loop and could only be perturbed by deletion of the entire loop and not by single site mutagenesis. We present evidence that the loop closes over the active site during catalysis, thereby ordering a water channel that is involved in leaving group activation. Once chemistry has taken place, the loop dynamics determine the rate of product release.

  16. 46 CFR 113.35-13 - Mechanical engine order telegraph systems; operation. (United States)


    ... 46 Shipping 4 2010-10-01 2010-10-01 false Mechanical engine order telegraph systems; operation...) ELECTRICAL ENGINEERING COMMUNICATION AND ALARM SYSTEMS AND EQUIPMENT Engine Order Telegraph Systems § 113.35-13 Mechanical engine order telegraph systems; operation. If more than one transmitter operates...


    Directory of Open Access Journals (Sweden)



    Full Text Available Micro-scale catalytic combustion characteristics and heat transfer processes of preheated methane-air mixtures (φ = 0.4 in the plane channel were investigated numerically with detailed chemical kinetic mechanisms. The plane channel of length L = 10.0 mm, height H =1.0 mm and wall thickness δ = 0.1 mm, which inner horizontal surfaces contained Pt/γ-Al2O3 catalyst washcoat. The computational results indicate that the presence of the gas phase reactions extends mildly the micro-combustion stability limits at low and moderate inlet velocities due to the strong flames establishment, and have a more profound effect on extending the high-velocity blowout limits by allowing for additional heat release originating mainly from the incomplete CH4 gas phase oxidation in the plane channel. When the same mass flow rate (ρin × Vin is considered, the micro-combustion stability limits at p: 0.1 MPa are much narrower than at p: 0.6 MPa due to both gas phase and catalytic reaction activities decline with decreasing pressure. Catalytic micro-combustor can achieve stable combustion at low solid thermal conductivity ks < 0.1 W∙m-1•K-1, while the micro-combustion extinction limits reach their larger extent for the higher thermal conductivity ks = 20.0-100.0 W∙m-1•K-1. The existence of surface radiation heat transfers significantly effects on the micro-combustion stability limits and micro-combustors energy balance. Finally, gas phase combustion in catalytic micro-combustors can be sustained at the sub-millimeter scale (plane channel height of 0.25 mm.

  18. Influencing mechanism of temperature on the degradation of nitrobenzene in aqueous solution by ceramic honeycomb catalytic ozonation. (United States)

    Zhao, Lei; Ma, Jun; Sun, Zhizhong; Liu, Huiling


    The heterogeneous catalytic ozonation of nitrobenzene in aqueous solution has been carried out at different reaction temperatures in a semi-continuous batch reactor where ceramic honeycomb has been used as a catalyst. The experimental results indicated that the presence of ceramic honeycomb catalyst significantly improved the degradation efficiency of nitrobenzene compared to the results from non-catalytic ozonation, and the adsorption of nitrobenzene on the catalytic surface has no significant effect on its degradation efficiency. The degradation of nitrobenzene followed the pseudo-first-order kinetic model in both the processes of ozone alone and ozone/ceramic honeycomb. With the increase of reaction temperature from 278K to 328K, the degradation efficiency of nitrobenzene, the reaction rate constants, the utilization efficiency of ozone, the formation of hydroxyl radicals (*OH) and the removal of total organic carbon (TOC) all increased in the process of ozone/ceramic honeycomb. The enhancement of reaction rate constant and the enhancement of *OH formation exhibited a good correlation in the reaction temperature scope of 278-328K.

  19. Low-temperature catalytic oxidation of aldehyde mixtures using wood fly ash: kinetics, mechanism, and effect of ozone. (United States)

    Kolar, Praveen; Kastner, James R


    Poultry rendering emissions contain volatile organic compounds (VOCs) that are nuisance, odorous, and smog and particulate matter precursors. Present treatment options, such as wet scrubbers, do not eliminate a significant fraction of the VOCs emitted including, 2-methylbutanal (2-MB), 3-methylbutanal, and hexanal. This research investigated the low-temperature (25-160 degrees C) catalytic oxidation of 2-MB and hexanal vapors in a differential, plug flow reactor using wood fly ash (WFA) as a catalyst and oxygen and ozone as oxidants. The oxidation rates of 2-MB and hexanal ranged between 3.0 and 3.5 x 10(-9)mol g(-1)s(-1) at 25 degrees C and the activation energies were 2.2 and 1.9 kcal mol(-1), respectively. The catalytic activity of WFA was comparable to other commercially available metal and metal oxide catalysts. We theorize that WFA catalyzed a free radical reaction in which 2-butanone and CO(2) were formed as end products of 2-MB oxidation, while CO(2), pentanal, and butanal were formed as end products of hexanal oxidation. When tested as a binary mixture at 25 and 160 degrees C, no inhibition was observed. Additionally, when ozone was tested as an oxidant at 160 degrees C, 100% removal was achieved within a 2-s reaction time. These results may be used to design catalytic oxidation processes for VOC removal at poultry rendering facilities and potentially replace energy and water intensive air pollution treatment technologies currently in use.

  20. High-Resolution Crystal Structures of Streptococcus pneumoniae Nicotinamidase with Trapped Intermediates Provide Insights into the Catalytic Mechanism and Inhibition by Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    French, Jarrod B.; Cen, Yana; Sauve, Anthony A.; Ealick, Steven E. (Cornell); (Weill-Med)


    Nicotinamidases are salvage enzymes that convert nicotinamide to nicotinic acid. These enzymes are essential for the recycling of nicotinamide into NAD{sup +} in most prokaryotes and most single-cell and multicellular eukaryotes, but not in mammals. The significance of these enzymes for nicotinamide salvage and for NAD{sup +} homeostasis has stimulated interest in nicotinamidases as possible antibiotic targets. Nicotinamidases are also regulators of intracellular nicotinamide concentrations, thereby regulating signaling of downstream NAD{sup +}-consuming enzymes, such as the NAD{sup +}-dependent deacetylases (sirtuins). Here, we report several high-resolution crystal structures of the nicotinamidase from Streptococcus pneumoniae (SpNic) in unliganded and ligand-bound forms. The structure of the C136S mutant in complex with nicotinamide provides details about substrate binding, while a trapped nicotinoyl thioester in a complex with SpNic reveals the structure of the proposed thioester reaction intermediate. Examination of the active site of SpNic reveals several important features, including a metal ion that coordinates the substrate and the catalytically relevant water molecule and an oxyanion hole that both orients the substrate and offsets the negative charge that builds up during catalysis. Structures of this enzyme with bound nicotinaldehyde inhibitors elucidate the mechanism of inhibition and provide further details about the catalytic mechanism. In addition, we provide a biochemical analysis of the identity and role of the metal ion that orients the ligand in the active site and activates the water molecule responsible for hydrolysis of the substrate. These data provide structural evidence of several proposed reaction intermediates and allow for a more complete understanding of the catalytic mechanism of this enzyme.

  1. In situ FT-IR studies on the mechanism of selective catalytic reduction of NOx by propene over SnO2/Al2O3 catalyst. (United States)

    Liu, Zhiming; Woo, Seong Ihl; Lee, Won Su


    The mechanism of the selective catalytic reduction (SCR) of NOx by propene over SnO2/Al2O3 catalyst in the presence of oxygen has been investigated using in situ Fourier transform infrared (FT-IR) spectroscopy. In situ IR measurements indicate that acetate and formate, which are the derivatives of the partial oxidation of propene, play a crucial role in the formation of NCO by reacting with the reactive monodentate nitrate species. The resulting NCO species subsequently reacts with NOx to form N2. The presence of oxygen substantially contributes to the partial oxidation of propene and thus shows a promoting effect for the NOx reduction.

  2. Operation analysis of a Chebyshev-Pantograph leg mechanism for a single DOF biped robot (United States)

    Liang, Conghui; Ceccarelli, Marco; Takeda, Yukio


    In this paper, operation analysis of a Chebyshev-Pantograph leg mechanism is presented for a single degree of freedom (DOF) biped robot. The proposed leg mechanism is composed of a Chebyshev four-bar linkage and a pantograph mechanism. In contrast to general fully actuated anthropomorphic leg mechanisms, the proposed leg mechanism has peculiar features like compactness, low-cost, and easy-operation. Kinematic equations of the proposed leg mechanism are formulated for a computer oriented simulation. Simulation results show the operation performance of the proposed leg mechanism with suitable characteristics. A parametric study has been carried out to evaluate the operation performance as function of design parameters. A prototype of a single DOF biped robot equipped with two proposed leg mechanisms has been built at LARM (Laboratory of Robotics and Mechatronics). Experimental test shows practical feasible walking ability of the prototype, as well as drawbacks are discussed for the mechanical design.

  3. Generalized space and linear momentum operators in quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Bruno G. da, E-mail: [Instituto Federal de Educação, Ciência e Tecnologia do Sertão Pernambucano, Campus Petrolina, BR 407, km 08, 56314-520 Petrolina, Pernambuco (Brazil); Instituto de Física, Universidade Federal da Bahia, R. Barão de Jeremoabo s/n, 40170-115 Salvador, Bahia (Brazil); Borges, Ernesto P., E-mail: [Instituto de Física, Universidade Federal da Bahia, R. Barão de Jeremoabo s/n, 40170-115 Salvador, Bahia (Brazil)


    We propose a modification of a recently introduced generalized translation operator, by including a q-exponential factor, which implies in the definition of a Hermitian deformed linear momentum operator p{sup ^}{sub q}, and its canonically conjugate deformed position operator x{sup ^}{sub q}. A canonical transformation leads the Hamiltonian of a position-dependent mass particle to another Hamiltonian of a particle with constant mass in a conservative force field of a deformed phase space. The equation of motion for the classical phase space may be expressed in terms of the generalized dual q-derivative. A position-dependent mass confined in an infinite square potential well is shown as an instance. Uncertainty and correspondence principles are analyzed.

  4. First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface (United States)

    Xue, Wenhua

    Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL

  5. Renormalizing the Kinetic Energy Operator in Elementary Quantum Mechanics (United States)

    Coutinho, F. A. B.; Amaku, M.


    In this paper, we consider solutions to the three-dimensional Schrodinger equation of the form [psi](r) = u(r)/r, where u(0) [is not equal to] 0. The expectation value of the kinetic energy operator for such wavefunctions diverges. We show that it is possible to introduce a potential energy with an expectation value that also diverges, exactly…

  6. Quantum chemical study on the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process

    Institute of Scientific and Technical Information of China (English)

    Zheng-cheng WEN; Zhi-hua WANG; Jun-hu ZHOU; Ke-fa CEN


    Quantum chemical simulation was used to investigate the catalytic mechanism of Na/K on NO-char heterogeneous reactions during the coal reburning process. Both NO-char and NO-NaYK reactions were considered as three-step processes in this calculation. Based on geometry optimizations made using the UB3LYP/6-31 G(d) method, the activation energies of NO-char and NO-Na/K reactions were calculated using the QC1SD(T)/6-3 i 1G(d, p) method; Results showed that the activation energy of the NO-Na/K reaction (107.9/82.0 kJ/mol) was much lower than that of the NO-char reaction (245.1 kJ/mol). The reactions of NaO/KO and Na2P/K2O reduced by char were also studied, and their thermodynamics were calculated using the UB3LYP/6-31G(d) method; Results showed that both Na and K can be refreshed easily and rapidly by char at high temperature during the coal rebuming process. Based on the calculations and analyses, the catalytic mechanism of Na/K on NO-char het-erogeneous reactions during the coal reburning process was clarified.

  7. New insights into the catalytic mechanism of Bombyx mori prostaglandin E synthase gained from structure–function analysis

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Kohji, E-mail: [Faculty of Agriculture, Kyushu University Graduate School, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Suzuki, Mamoru; Higashiura, Akifumi [Institute for Protein Research, Osaka University, Suita 565-0871 (Japan); Aritake, Kosuke; Urade, Yoshihiro; Uodome, Nobuko [Department of Molecular Behavioral Biology, Osaka Bioscience Institute, 6-2-4 Furuedai, Suita, Osaka 565-0874 (Japan); Hossain, MD. Tofazzal [Faculty of Agriculture, Kyushu University Graduate School, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Nakagawa, Atsushi [Institute for Protein Research, Osaka University, Suita 565-0871 (Japan)


    Highlights: •Structure of Bombyx mori prostaglandin E synthase is determined. •Bound glutathione sulfonic acid is located at the glutathione-binding site. •Electron-sharing network is present in this protein. •This network includes Asn95, Asp96, and Arg98. •Site-directed mutagenesis reveals that the residues contribute to the catalytic activity. -- Abstract: Prostaglandin E synthase (PGES) catalyzes the isomerization of PGH{sub 2} to PGE{sub 2}. We previously reported the identification and structural characterization of Bombyx mori PGES (bmPGES), which belongs to Sigma-class glutathione transferase. Here, we extend these studies by determining the structure of bmPGES in complex with glutathione sulfonic acid (GTS) at a resolution of 1.37 Å using X-ray crystallography. GTS localized to the glutathione-binding site. We found that electron-sharing network of bmPGES includes Asn95, Asp96, and Arg98. Site-directed mutagenesis of these residues to create mutant forms of bmPGES mutants indicate that they contribute to catalytic activity. These results are, to our knowledge, the first to reveal the presence of an electron-sharing network in bmPGES.

  8. Catalyst performance and mechanism of catalytic combustion of dichloromethane (CH2Cl2) over Ce doped TiO2. (United States)

    Cao, Shuang; Wang, Haiqiang; Yu, Feixiang; Shi, Mengpa; Chen, Shuang; Weng, Xiaole; Liu, Yue; Wu, Zhongbiao


    TiO2 and Ce/TiO2 were synthesized and subsequently used for the catalytic combustion of DCM. TiO2 had abundant Lewis acid sites and was responsible for the adsorption and the rupture of C-Cl bonds. However, TiO2 tended to be inactivated because of chloride poisoning due to the adsorption and accumulation of Cl species over the surface. While, Ce/TiO2 obtained total oxidation of CH2Cl2 at 335°C and exhibited stable DCM removal activity on 100h long-time stability tests at 330°C without any catalyst deactivation. The doped cerium generated Ce(3+) chemical states and surface active oxygen, and therefore played important roles from two aspects as follows. First of all, the poisoning of Cl for Ce/TiO2 was inhibited to some extent by CeO2 due to the rapid removal of Cl on the surface of CeO2, which has been verified by NH3-IR characterization. In the other hand, CeO2 enhanced the further deep oxidation of C-H from byproducts and retained the certain oxidation of CO to CO2. Based on the DRIFT characterization and the catalysts activity tests, a two-step reaction pathway for the catalytic combustion of DCM on Ce/TiO2 catalyst was proposed.

  9. Mechanism of N2O formation during the low-temperature selective catalytic reduction of NO with NH3 over Mn-Fe spinel. (United States)

    Yang, Shijian; Xiong, Shangchao; Liao, Yong; Xiao, Xin; Qi, Feihong; Peng, Yue; Fu, Yuwu; Shan, Wenpo; Li, Junhua


    The mechanism of N2O formation during the low-temperature selective catalytic reduction reaction (SCR) over Mn-Fe spinel was studied. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and transient reaction studies demonstrated that the Eley-Rideal mechanism (i.e., the reaction of adsorbed NH3 species with gaseous NO) and the Langmuir-Hinshelwood mechanism (i.e., the reaction of adsorbed NH3 species with adsorbed NOx species) both contributed to N2O formation. However, N2O selectivity of NO reduction over Mn-Fe spinel through the Langmuir-Hinshelwood mechanism was much less than that through the Eley-Rideal mechanism. The ratio of NO reduction over Mn-Fe spinel through the Langmuir-Hinshelwood mechanism remarkably increased; therefore, N2O selectivity of NO reduction over Mn-Fe spinel decreased with the decrease of the gas hourly space velocity (GHSV). As the gaseous NH3 concentration increased, N2O selectivity of NO reduction over Mn-Fe spinel increased because of the promotion of NO reduction through the Eley-Rideal mechanism. Meanwhile, N2O selectivity of NO reduction over Mn-Fe spinel decreased with the increase of the gaseous NO concentration because the formation of NH on Mn-Fe spinel was restrained. Therefore, N2O selectivity of NO reduction over Mn-Fe spinel was related to the GHSV and concentrations of reactants.

  10. Arcsecond grating drive mechanism for operation at 4 K (United States)

    Downey, C. H.; Kubitschek, M. J.; Tarde, R. W.; Houck, J. R.


    A grating drive mechanism that achieves arcsecond positional control at both room temperature and 4 K is described. The mechanism accommodates eight equally spaced facets on a 360-deg drum, with each facet having arcsecond control over an angular range of +/-3 deg. The cryogenic portion consists of dry lubricated angular contact bearings, a dc brushless torque motor, and a compact magnetic position sensor capable of less than 1 arcsec rms resolution. Test results demonstrate angular repeatability of less than 2 arcsec rms at 4 K and static power dissipation to the helium bath of less than 100 microW.

  11. Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study. (United States)

    Han, You; Sun, Mengxia; Li, Wei; Zhang, Jinli


    The catalytic mechanism of Ru-based catalysts in the acetylene hydrochlorination reaction has been investigated via the density functional theory (DFT) method. To study the effect of the chlorine coordination number on the catalytic mechanism, Ru3Cl9, Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 clusters were chosen as the catalytic models. Our results show that the energy barrier for acetylene hydrochlorination on Ru3Cl9 was as high as 1.51 eV at 458 K. When the chlorine coordination number decreased, the energy barriers on Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 were 1.29, 0.89, 1.01 and 1.42 eV, respectively. On Ru3Cl9, the H and Cl atoms of HCl were simultaneously added to C2H2 to form C2H3Cl, while the reaction was divided into two steps on Ru3Cl7, Ru3Cl3 and Ru3 clusters. The first step was the addition of H atom of HCl to C2H2 to form C2H3˙, and the second step was the addition of Cl atom to C2H3˙ to form C2H3Cl. The step involving the addition of Cl was the rate-controlling step during the whole reaction. On Ru5Cl7 cluster, there was an additional step before the steps involving the addition of H and Cl: the transfer of H atom from HCl to Ru atom. This step was the rate-controlling step during the reaction of acetylene hydrochlorination on Ru5Cl7 and its energy barrier was the lowest among all the above-mentioned catalytic models. Therefore, the Ru5Cl7 cluster played the most predominant role in acetylene hydrochlorination with the largest reaction rate constant kTST of 10(3).

  12. Mechanical Transformation of Task Heuristics into Operational Procedures (United States)


    specified form. Given a mechanism for performing such a search, the ability to solve a particula kind of problem can be dramatically improved just by...oIStRIBUTE by RULE1A2) ---> (OR f, IDE OS) DECK] (. (tOC QS) POT] (, (LOC OS) HOLE] E’ (LOC QS) ( NANO ME)]) (OR (OR (I (LOC OS) DECE] Et (LOC QS

  13. 16 CFR 703.5 - Operation of the Mechanism. (United States)


    ... consumer that: (i) The dispute has been settled to the consumer's satisfaction; and (ii) The settlement... of a dispute, the Mechanism shall immediately inform both the warrantor and the consumer of receipt..., and to what extent, warrantor will abide by its decision; and (4) Disclose to the consumer...

  14. The operational mechanism of ferroelectric-driven organic resistive switches

    NARCIS (Netherlands)

    Kemerink, M.; Asadi, K.; Blom, P.W.M.; Leeuw, D.M. de


    The availability of a reliable memory element is crucial for the fabrication of 'plastic' logic circuits. We use numerical simulations to show that the switching mechanism of ferroelectric-driven organic resistive switches is the stray field of the polarized ferroelectric phase. The stray field modu

  15. Bond dissociation mechanism of ethanol during carbon nanotube synthesis via alcohol catalytic CVD technique: Ab initio molecular dynamics simulation (United States)

    Oguri, Tomoya; Shimamura, Kohei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu


    Dissociation of ethanol on a nickel cluster is investigated by ab initio molecular dynamics simulation to reveal the bond dissociation mechanism of carbon source molecules during carbon nanotube synthesis. C-C bonds in only CHxCO fragments are dissociated on the nickel cluster, whereas there is no preferential structure among the fragments for C-O bond dissociation. The dissociation preference is uncorrelated with the bond dissociation energy of corresponding bonds in freestanding molecules but is correlated with the energy difference between fragment molecules before and after dissociation on the nickel surface. Moreover, carbon-chain formation occurs after C-C bond dissociation in a continuous simulation. What determines the chirality of CNTs? What happens at the dissociation stage of carbon source molecules? Regarding the former question, many researchers have pointed out the good epitaxial relationship between a graphite network and a close-packed facet (i.e., fcc(1 1 1) or hcp(0 0 0 1)) of transition metals [17-19]. Therefore, the correlation between the chirality of CNTs and the angle of the step edge on metal (or metal carbide) surfaces has been closely investigated [20-22]. In association with this geometric matching, the epitaxial growth of graphene on Cu(1 1 1) and Ni(1 1 1) surfaces has recently been achieved via CCVD technique [23-25], which is a promising technique for the synthesis of large-area and monolayer graphene.Regarding the latter question, it is empirically known that the yield and quality of CNT products strongly depend on the choice of carbon source molecules and additives. For example, it is well known that the use of ethanol as carbon source molecules yields a large amount of SWNTs without amorphous carbons (called the alcohol CCVD (ACCVD) technique) compared with the CCVD process using hydrocarbons [4]. Moreover, the addition of a small amount of water dramatically enhances the activity and lifetime of the catalytic metal (called the

  16. mTOR Ser-2481 Autophosphorylation Monitors mTORC-specific Catalytic Activity and Clarifies Rapamycin Mechanism of Action* (United States)

    Soliman, Ghada A.; Acosta-Jaquez, Hugo A.; Dunlop, Elaine A.; Ekim, Bilgen; Maj, Nicole E.; Tee, Andrew R.; Fingar, Diane C.


    The mammalian target of rapamycin (mTOR) Ser/Thr kinase signals in at least two multiprotein complexes distinguished by their different partners and sensitivities to rapamycin. Acute rapamycin inhibits signaling by mTOR complex 1 (mTORC1) but not mTOR complex 2 (mTORC2), which both promote cell growth, proliferation, and survival. Although mTORC2 regulation remains poorly defined, diverse cellular mitogens activate mTORC1 signaling in a manner that requires sufficient levels of amino acids and cellular energy. Before the identification of distinct mTOR complexes, mTOR was reported to autophosphorylate on Ser-2481 in vivo in a rapamycin- and amino acid-insensitive manner. These results suggested that modulation of mTOR intrinsic catalytic activity does not universally underlie mTOR regulation. Here we re-examine the regulation of mTOR Ser-2481 autophosphorylation (Ser(P)-2481) in vivo by studying mTORC-specific Ser(P)-2481 in mTORC1 and mTORC2, with a primary focus on mTORC1. In contrast to previous work, we find that acute rapamycin and amino acid withdrawal markedly attenuate mTORC1-associated mTOR Ser(P)-2481 in cycling cells. Although insulin stimulates both mTORC1- and mTORC2-associated mTOR Ser(P)-2481 in a phosphatidylinositol 3-kinase-dependent manner, rapamycin acutely inhibits insulin-stimulated mTOR Ser(P)-2481 in mTORC1 but not mTORC2. By interrogating diverse mTORC1 regulatory input, we find that without exception mTORC1-activating signals promote, whereas mTORC1-inhibitory signals decrease mTORC1-associated mTOR Ser(P)-2481. These data suggest that mTORC1- and likely mTORC2-associated mTOR Ser-2481 autophosphorylation directly monitors intrinsic mTORC-specific catalytic activity and reveal that rapamycin inhibits mTORC1 signaling in vivo by reducing mTORC1 catalytic activity. PMID:20022946

  17. Intelligent Control Mechanism of Part Picking Operations of Automated Warehouse

    Institute of Scientific and Technical Information of China (English)

    Chwen-Tzeng; Su


    This paper studies the part picking operations of a ut omated warehouse. It assumed the demand of picking orders of automated warehouse are dynamic generated. Once the picking orders of certain period of time are kn own, it is necessary to decide an efficient order picking sequence and routing t o minimize the total travel distance to complete those orders. Assumed there are n i items to be picked in order O i. Each item in the picking ord er is located in different locations in the warehouse. Since i...

  18. Renormalizing the kinetic energy operator in elementary quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, F A B [Faculdade de Medicina, Universidade de Sao Paulo e LIM 01-HCFMUSP, 05405-000 Sao Paulo (Brazil); Amaku, M [Faculdade de Medicina Veterinaria e Zootecnia, Universidade de Sao Paulo, 05508-970 Sao Paulo (Brazil)], E-mail:


    In this paper, we consider solutions to the three-dimensional Schroedinger equation of the form {psi}(r) = u(r)/r, where u(0) {ne} 0. The expectation value of the kinetic energy operator for such wavefunctions diverges. We show that it is possible to introduce a potential energy with an expectation value that also diverges, exactly cancelling the kinetic energy divergence. This renormalization procedure produces a self-adjoint Hamiltonian. We solve some problems with this new Hamiltonian to illustrate its usefulness.

  19. Structural and Biochemical Characterization of a Cyanobacterial PP2C Phosphatase Reveals Insights into Catalytic Mechanism and Substrate Recognition

    Directory of Open Access Journals (Sweden)

    Yunlong Si


    Full Text Available PP2C-type phosphatases play roles in signal transduction pathways related to abiotic stress. The cyanobacterial PP2C-type phosphatase tPphA specifically dephosphorylates the PII protein, which is a key regulator in cyanobacteria adapting to nitrogen-deficient environments. Previous studies have shown that residue His39 of tPphA is critical for the enzyme’s recognition of the PII protein; however, the manner in which this residue determines tPphA substrate specificity is unknown. Here, we solved the crystal structure of H39A, a tPphA variant. The structure revealed that the mutation of residue His39 to alanine changes the conformation and the flexibility of the loop in which residue His39 is located, and these changes affect the substrate specificity of tPphA. Moreover, previous studies have assumed that the FLAP subdomain and the third metal (M3 of tPphA could mutually influence each other to regulate PP2C catalytic activity and substrate specificity. However, despite the variable conformations adopted by the FLAP subdomain, the position of M3 was consistent in the tPphA structure. These results indicate that the FLAP subdomain does not influence M3 and vice versa. In addition, a small screen of tPphA inhibitors was performed. Sanguinarine and Ni2+ were found to be the most effective inhibitors among the assayed chemicals. Finally, the dimeric form of tPphA was stabilized by cross-linkers and still exhibited catalytic activity towards p-nitrophenyl phosphate.

  20. Multiple cathodic reaction mechanisms in seawater cathodic biofilms operating in sediment microbial fuel cells. (United States)

    Babauta, Jerome T; Hsu, Lewis; Atci, Erhan; Kagan, Jeff; Chadwick, Bart; Beyenal, Haluk


    In this study, multiple reaction mechanisms in cathodes of sediment microbial fuel cells (SMFCs) were characterized by using cyclic voltammetry and microelectrode measurements of dissolved oxygen and pH. The cathodes were acclimated in SMFCs with sediment and seawater from San Diego Bay. Two limiting current regions were observed with onset potentials of approximately +400 mVAg/AgCl for limiting current I and -120 mVAg/AgCl for limiting current II. The appearance of two catalytic waves suggests that multiple cathodic reaction mechanisms influence cathodic performance. Microscale oxygen concentration measurements showed a zero surface concentration at the electrode surface for limiting current II but not for limiting current I, which allowed us to distinguish limiting current II as the conventional oxygen reduction reaction and limiting current I as a currently unidentified cathodic reaction mechanism. Microscale pH measurements further confirmed these results.

  1. Study on the control mechanism of China aerospace enterprises' binary multinational operation

    Institute of Scientific and Technical Information of China (English)

    Wang Jian; Li Hanling; Wu Weiwei


    China's aerospace enterprises carry on the multinational operation and participate in the international competition and the international division of labor and cooperation positively.This article first analyzs China aerospace enterprises' binary multinational business control objective and constructes its model.Then the article analyzes the tangible and intangible control mechanism of China aerospace enterprises' binary multinational operation respectively.Finally,the article constructs the model of China aerospace enterprises' binary multinational operation mechanisms.

  2. SPENCER OPERATOR AND APPLICATIONS: From Continuum Mechanics to Mathematical physics


    Pommaret, J.F.


    Though a few of the results presented are proved in the recent references provided, the way they are combined with others and patched together around the three books quoted is new. In view of the importance of the full paper, the present version is only a summary of the definitive version to appear later on. Finally, the reader must not forget that "each formula" appearing in this new general framework has been used explicitly or implicitly in (C), (M) and (W) for a mechanical, mathematical o...

  3. Catalytic mechanism of cationic red GTL at wide pH using the Mo-Zn-Al-O nanocatalyst under room conditions. (United States)

    Xu, Yin; Li, Xiaoyi; Sun, Dezhi


    Catalytic mechanism of cationic red GTL at wide pH using the Mo-Zn-Al-O nanocatalyst under room conditions was investigated. The experimental results indicate that initial pH significantly affected the removal of cationic red GTL, the removal of COD, the pH value and residual oxygen in the reaction. In the range of pH value from 4 to 10, decolorization of cationic red GTL was almost above 90%. COD removal efficiency was enhanced with the decrease of pH in CWAO process and 79% of the COD was removed at pH 4.0, whereas only 57% COD removal was observed at pH 10.0. The terminal pH was in the range of 5.0-6.0 and the highest terminal concentrations of aqueous oxygen with 5.5 mg/L were observed at pH = 4.0. The radical inhibition experiments also carried out and the generation of *OH and 1O2 in catalytic wet air oxidation process were detected. It was found that the degradation of cationic red GTL occurs mainly via oxidation by 1O2 radical generated by Mo-Zn-Al-O nanocatalyst under acid conditions and *OH radical under alkaline conditions.

  4. Structures of the Bacillus subtilis glutamine synthetase dodecamer reveal large intersubunit catalytic conformational changes linked to a unique feedback inhibition mechanism. (United States)

    Murray, David S; Chinnam, Nagababu; Tonthat, Nam Ky; Whitfill, Travis; Wray, Lewis V; Fisher, Susan H; Schumacher, Maria A


    Glutamine synthetase (GS), which catalyzes the production of glutamine, plays essential roles in nitrogen metabolism. There are two main bacterial GS isoenzymes, GSI-α and GSI-β. GSI-α enzymes, which have not been structurally characterized, are uniquely feedback-inhibited by Gln. To gain insight into GSI-α function, we performed biochemical and cellular studies and obtained structures for all GSI-α catalytic and regulatory states. GSI-α forms a massive 600-kDa dodecameric machine. Unlike other characterized GS, the Bacillus subtilis enzyme undergoes dramatic intersubunit conformational alterations during formation of the transition state. Remarkably, these changes are required for active site construction. Feedback inhibition arises from a hydrogen bond network between Gln, the catalytic glutamate, and the GSI-α-specific residue, Arg(62), from an adjacent subunit. Notably, Arg(62) must be ejected for proper active site reorganization. Consistent with these findings, an R62A mutation abrogates Gln feedback inhibition but does not affect catalysis. Thus, these data reveal a heretofore unseen restructuring of an enzyme active site that is coupled with an isoenzyme-specific regulatory mechanism. This GSI-α-specific regulatory network could be exploited for inhibitor design against Gram-positive pathogens.

  5. Newton Leibniz integration for ket bra operators in quantum mechanics and derivation of entangled state representations (United States)

    Fan, Hong-yi; Lu, Hai-liang; Fan, Yue


    Newton-Leibniz integration rule only applies to commuting functions of continuum variables, while operators made of Dirac's symbols (ket versus bra, e.g., | q>mechanics are usually not commutative. Therefore, integrations over the operators of type |>mathematical gap between classical mechanics and quantum mechanics, and further reveals the beauty and elegance of Dirac's symbolic method and transformation theory. Various applications of the IWOP technique, including constructing the entangled state representations and their applications, are presented.

  6. Cobalt-Catalyzed [2π + 2π] Cycloadditions of Alkenes: Scope, Mechanism, and Elucidation of Electronic Structure of Catalytic Intermediates. (United States)

    Schmidt, Valerie A; Hoyt, Jordan M; Margulieux, Grant W; Chirik, Paul J


    Aryl-substituted bis(imino)pyridine cobalt dinitrogen compounds, ((R)PDI)CoN2, are effective precatalysts for the intramolecular [2π + 2π] cycloaddition of α,ω-dienes to yield the corresponding bicyclo[3.2.0]heptane derivatives. The reactions proceed under mild thermal conditions with unactivated alkenes, tolerating both amine and ether functional groups. The overall second order rate law for the reaction, first order with respect to both the cobalt precatalyst and the substrate, in combination with electron paramagnetic resonance (EPR) spectroscopic studies established the catalyst resting state as dependent on the identity of the precatalyst and diene substrate. Planar S = ½ κ(3)-bis(imino)pyridine cobalt alkene and tetrahedral κ(2)-bis(imino)pyridine cobalt diene complexes were observed by EPR spectroscopy and in the latter case structurally characterized. The hemilabile chelate facilitates conversion of a principally ligand-based singly occupied molecular orbital (SOMO) in the cobalt dinitrogen and alkene compounds to a metal-based SOMO in the diene intermediates, promoting C-C bond-forming oxidative cyclization. Structure-activity relationships on bis(imino)pyridine substitution were also established with 2,4,6-tricyclopentyl-substituted aryl groups, resulting in optimized catalytic [2π + 2π] cycloaddition. The cyclopentyl groups provide a sufficiently open metal coordination sphere that encourages substrate coordination while remaining large enough to promote a challenging, turnover-limiting C(sp(3))-C(sp(3)) reductive elimination.

  7. Detection of Operator Performance Breakdown as an Automation Triggering Mechanism (United States)

    Yoo, Hyo-Sang; Lee, Paul U.; Landry, Steven J.


    Performance breakdown (PB) has been anecdotally described as a state where the human operator "loses control of context" and "cannot maintain required task performance." Preventing such a decline in performance is critical to assure the safety and reliability of human-integrated systems, and therefore PB could be useful as a point at which automation can be applied to support human performance. However, PB has never been scientifically defined or empirically demonstrated. Moreover, there is no validated objective way of detecting such a state or the transition to that state. The purpose of this work is: 1) to empirically demonstrate a PB state, and 2) to develop an objective way of detecting such a state. This paper defines PB and proposes an objective method for its detection. A human-in-the-loop study was conducted: 1) to demonstrate PB by increasing workload until the subject reported being in a state of PB, and 2) to identify possible parameters of a detection method for objectively identifying the subjectively-reported PB point, and 3) to determine if the parameters are idiosyncratic to an individual/context or are more generally applicable. In the experiment, fifteen participants were asked to manage three concurrent tasks (one primary and two secondary) for 18 minutes. The difficulty of the primary task was manipulated over time to induce PB while the difficulty of the secondary tasks remained static. The participants' task performance data was collected. Three hypotheses were constructed: 1) increasing workload will induce subjectively-identified PB, 2) there exists criteria that identifies the threshold parameters that best matches the subjectively-identified PB point, and 3) the criteria for choosing the threshold parameters is consistent across individuals. The results show that increasing workload can induce subjectively-identified PB, although it might not be generalizable-only 12 out of 15 participants declared PB. The PB detection method based on

  8. The catalytic mechanism of indole-3-glycerol phosphate synthase: crystal structures of complexes of the enzyme from Sulfolobus solfataricus with substrate analogue, substrate, and product. (United States)

    Hennig, Michael; Darimont, B D; Jansonius, J N; Kirschner, K


    Indoleglycerol phosphate synthase catalyzes the ring closure of an N-alkylated anthranilate to a 3-alkyl indole derivative, a reaction requiring Lewis acid catalysis in vitro. Here, we investigated the enzymatic reaction mechanism through X-ray crystallography of complexes of the hyperthermostable enzyme from Sulfolobus solfataricus with the substrate 1-(o-carboxyphenylamino) 1-deoxyribulose 5-phosphate, a substrate analogue and the product indole-3-glycerol phosphate. The substrate and the substrate analogue are bound to the active site in a similar, extended conformation between the previously identified phosphate binding site and a hydrophobic pocket for the anthranilate moiety. This binding mode is unproductive, because the carbon atoms that are to be joined are too far apart. The indole ring of the bound product resides in a second hydrophobic pocket adjacent to that of the anthranilate moiety of the substrate. Although the hydrophobic moiety of the substrate moves during catalysis from one hydrophobic pocket to the other, the triosephosphate moiety remains rigidly bound to the same set of hydrogen-bonding residues. Simultaneously, the catalytically important residues Lys53, Lys110 and Glu159 maintain favourable distances to the atoms of the ligand undergoing covalent changes. On the basis of these data, the structures of two putative catalytic intermediates were modelled into the active site. This new structural information and the modelling studies provide further insight into the mechanism of enzyme-catalyzed indole synthesis. The charged epsilon-amino group of Lys110 is the general acid, and the carboxylate group of Glu159 is the general base. Lys53 guides the substrate undergoing conformational transitions during catalysis, by forming a salt-bridge to the carboxylate group of its anthranilate moiety.

  9. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya


    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  10. Unified Theory of Annihilation-Creation Operators for Solvable (`Discrete') Quantum Mechanics


    Odake, Satoru; Sasaki, Ryu


    The annihilation-creation operators $a^{(\\pm)}$ are defined as the positive/negative frequency parts of the exact Heisenberg operator solution for the `sinusoidal coordinate'. Thus $a^{(\\pm)}$ are hermitian conjugate to each other and the relative weights of various terms in them are solely determined by the energy spectrum. This unified method applies to most of the solvable quantum mechanics of single degree of freedom including those belonging to the `discrete' quantum mechanics.

  11. Action Mechanism of Relation Skills of Villager Autonomy Organizations on Operation Performance of Farmer Households

    Institute of Scientific and Technical Information of China (English)

    Jianhui; WU; Jintao; HE; Huazhong; LI


    Through building " relation skills- knowledge acquisition- operation performance",this paper discussed action mechanism of relation skills of villager autonomy organizations on operation performance of farmer households. On the basis of questionnaire survey of 208 farmer households in Guangdong,it studied influence of relation skills of villager autonomy organizations on operation performance of farmer households from hierarchical relation skills and market relation skills,and introduced knowledge acquisition as mediator variables to discuss the influence mechanism. Results indicate that relation skills and knowledge acquisition have positive influence on operation performance of farmer households,knowledge acquisition takes intermediate action on market relation skills and operation performance,while hierarchical relation skills promote improvement of operation performance only through acquisition of explicit knowledge.

  12. Structure and Catalytic Mechanism of Laccase%漆酶的结构与催化反应机理

    Institute of Scientific and Technical Information of China (English)

    靳蓉; 张飞龙


    漆酶是一种广泛分布的多酚氧化酶,主要由单一多肽、铜离子活性中心、糖配基组成。多肽链一般含有18种氨基酸,构成漆酶的结构主体;糖配基因漆酶的来源不同而异,是漆酶多样性的标志之一。漆酶活性中心的铜离子依据光学和磁学特性被分为3种类型:Ⅰ型或蓝型铜,Ⅱ型或通常型铜,Ⅲ型或偶联的双核型铜。漆酶的催化反应机理主要包括酶对底物的电子提取、电子的传递和氧分子对酶的还原三步,是一个通过电子转移发生氧化还原反应的过程。%Laccase is one kind of polyphenol-oxidase distributed widely. It is mainly composed of single peptide,copper ions active center and sugar genin. There are 18 kinds of amino acid in the peptide generally,making up the structure body; sugar genin,as one of the signs of diversity,differs in laccases. The copper ions in the acticve center are divided into 3 types based on optical and magnetic properties: type Ⅰor blue type copper,type Ⅱor usually type copper,typeⅢ or coupling double-core copper. The catalysis of laccase is redox reaction through electron transfer,generally including the electronic extraction of substrate, the transmission of electrons ,enzyme reduction by O 2 . Factors like temperature,pH,buffer system,acid, inhibitors,etc. all have an effect on the catalytic ability of laccase.

  13. Bessel equation as an operator identity's matrix element in quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Fan Hongyi; Li Chao


    We study the well-known Bessel equation itself in the framework of quantum mechanics. We show that the Bessel equation is a spontaneous result of an operator identity's matrix element in some definite entangled state representations, which is a fresh look. Application of this operator formalism in the Hankel transform of Laplace equation is presented.

  14. The human operator transfer function: Identification of the limb mechanics subsystem (United States)

    Jones, Lynette A.; Hunter, Ian W.


    The objective of our research is to decompose the performance of the human operator in terms of the subsystems that determine the operator's responses in order to establish how the dynamics of these component subsystems influence the operator's performance. In the present experiment, the dynamic stiffness of the human elbow joint was measured at rest and under different levels of biceps muscle activation; this work forms part of the analysis of the limb mechanics subsystem.

  15. Diversity in mechanisms of substrate oxidation by cytochrome P450 2D6. Lack of an allosteric role of NADPH-cytochrome P450 reductase in catalytic regioselectivity. (United States)

    Hanna, I H; Krauser, J A; Cai, H; Kim, M S; Guengerich, F P


    Cytochrome P450 (P450) 2D6 was first identified as the polymorphic human debrisoquine hydroxylase and subsequently shown to catalyze the oxidation of a variety of drugs containing a basic nitrogen. Differences in the regioselectivity of oxidation products formed in systems containing NADPH-P450 reductase/NADPH and the model oxidant cumene hydroperoxide have been proposed by others to be due to an allosteric influence of the reductase on P450 2D6 (Modi, S., Gilham, D. E., Sutcliffe, M. J., Lian, L.-Y., Primrose, W. U., Wolf, C. R., and Roberts, G. C. K. (1997) Biochemistry 36, 4461-4470). We examined the differences in the formation of oxidation products of N-methyl-4-phenyl-1,2,5,6-tetrahydropyridine, metoprolol, and bufuralol between reductase-, cumene hydroperoxide-, and iodosylbenzene-supported systems. Catalytic regioselectivity was not influenced by the presence of the reductase in any of the systems supported by model oxidants, ruling out allosteric influences. The presence of the reductase had little effect on the affinity of P450 2D6 for any of these three substrates. The addition of the reaction remnants of the model oxidants (cumyl alcohol and iodobenzene) to the reductase-supported system did not affect reaction patterns, arguing against steric influences of these products on catalytic regioselectivity. Label from H(2)18O was quantitatively incorporated into 1'-hydroxybufuralol in the iodosylbenzene- but not in the reductase- or cumene hydroperoxide-supported reactions. We conclude that the P450 systems utilizing NADPH-P450 reductase, cumene hydroperoxide, and iodosylbenzene use similar but distinct chemical mechanisms. These differences are the basis for the variable product distributions, not an allosteric influence of the reductase.

  16. Insights into the catalytic mechanism of 16S rRNA methyltransferase RsmE (m³U1498) from crystal and solution structures. (United States)

    Zhang, Heng; Wan, Hua; Gao, Zeng-Qiang; Wei, Yong; Wang, Wen-Jia; Liu, Guang-Feng; Shtykova, Eleonora V; Xu, Jian-Hua; Dong, Yu-Hui


    RsmE is the founding member of a new RNA methyltransferase (MTase) family responsible for methylation of U1498 in 16S ribosomal RNA in Escherichia coli. It is well conserved across bacteria and plants and may play an important role in ribosomal intersubunit communication. The crystal structure in monomer showed that it consists of two distinct but structurally related domains: the PUA (pseudouridine synthases and archaeosine-specific transglycosylases)-like RNA recognition and binding domain and the conserved MTase domain with a deep trefoil knot. Analysis of small-angle X-ray scattering data revealed that RsmE forms a flexible dimeric conformation that may be essential for substrate binding. The S-adenosyl-l-methionine (AdoMet)-binding characteristic determined by isothermal titration calorimetry suggested that there is only one AdoMet molecule bound in the subunit of the homodimer. In vitro methylation assay of the mutants based on the RsmE-AdoMet-uridylic acid complex model showed key residues involved in substrate binding and catalysis. Comprehensive comparisons of RsmE with closely related MTases, combined with the biochemical experiments, indicated that the MTase domain of one subunit in dimeric RsmE is responsible for binding of one AdoMet molecule and catalytic process while the PUA-like domain in the other subunit is mainly responsible for recognition of one substrate molecule (the ribosomal RNA fragment and ribosomal protein complex). The methylation process is required by collaboration of both subunits, and dimerization is functionally critical for catalysis. In general, our study provides new information on the structure-function relationship of RsmE and thereby suggests a novel catalytic mechanism.

  17. Poisoning of bubble propelled catalytic micromotors: the chemical environment matters (United States)

    Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G.; Pumera, Martin


    Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing -SH, -SSR, and -SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered.

  18. 42 CFR 433.116 - FFP for operation of mechanized claims processing and information retrieval systems. (United States)


    ... FISCAL ADMINISTRATION Mechanized Claims Processing and Information Retrieval Systems § 433.116 FFP for operation of mechanized claims processing and information retrieval systems. (a) Subject to 42 CFR 433.113(c... and information retrieval systems. 433.116 Section 433.116 Public Health CENTERS FOR...

  19. The role of mechanization and integration of manufacturing processes in achieving operational performance

    DEFF Research Database (Denmark)

    Naqvi, Syed Turab Haider; Farooq, Sami; Johansen, John


    Small manufacturing firms are the dominant organization type for most of the developed countries. However, these firms have not been the focus of research and their strategic and operational needs are not extensively addressed by the academic community. Therefore, this research aims at empirically...... finding the impact of mechanization and integration of manufacturing processes and systems on operational performance in small Danish manufacturing firms. We use data of 357 small Danish manufacturing firms and empirically found distinct impact of mechanization and integration of systems on operational...... performance in context of production to order (PTO) and production to stock (PTS) strategies....

  20. Determination of the structure and catalytic mechanism of sorghum bicolor caffeoyl-CoA O-methyltransferase (United States)

    Although cold acclimation is a key process in plants from temperate climates, the mechanisms sensing low temperature remain obscure. Here, we show that the accumulation of the organic acid fumaric acid, mediated by the cytosolic fumarase FUM2, is essential for cold acclimation of metabolism in the c...

  1. Research Advances in Methanation Catalysts and Their Catalytic Mechanisms%甲烷化催化剂及反应机理的研究进展

    Institute of Scientific and Technical Information of China (English)

    胡大成; 高加俭; 贾春苗; 平原; 贾丽华; 王莹利; 许光文; 古芳娜; 苏发兵


    Recent advances in methanantion catalysts and catalytic mechanism together with the wide applications of methanation in industry were reviewed, focusing on the effects of catalyst supports, promoters, active components as well as preparation methods on the performance of methanation catalysts. In addition, the catalytic deactivation and mechanism of methanation reaction for carbon oxides are critically analysed based on the reported work. It is pointed out that the temperature rising derived from exothermic methanation reactions in the catalyst bed and carbon deposition on the catalyst surface are the key factors for catalyst deactivation, which can be avoided considering both catalyst and process. Finally, outlook for the future development of methanation catalyst and further investigation of mechanism is provided in light of the current research status, regarding composite support with the high surface area, catalyst modified with the rare earth elements, sulfur- and heat-resistant catalysts, as well as fluidized bed reactor.%概述了甲烷化反应在工业生产中的应用,重点介绍了甲烷化催化剂中活性组分、载体、助剂的种类及催化剂制备方法、条件对其催化性能的影响;分析了甲烷化催化剂失活的原因及甲烷化反应的机理,指出床层飞温和积碳是造成催化剂失活的主要因素,必须从甲烷化催化剂和工艺技术两方面予以改进;并对甲烷化催化剂研究进行了展望,提出高比表面复合载体的研制、稀土元素的添加、新型耐硫、高热稳定性甲烷化催化剂的开发及流化床甲烷化工艺技术的改进是甲烷化研究的主要方向.


    Directory of Open Access Journals (Sweden)

    Jaroslav HOMIŠIN


    Full Text Available The main purpose of this paper is to inform the technical community about new tuning methods of torsional oscillating mechanical systems (TOMS during operation in a steady state by means of application of pneumatic flexible shaft couplings. It is possible to change the torsional stiffness of pneumatic couplings by means of a change of gaseous medium pressure either out of operation or during operation. There are two possibilities how to tune the torsional oscillating mechanical systems: - tuning of torsion oscillating mechanical systems out of operation, what fulfils condition of given system tuning, - tuning of torsion oscillating mechanical systems during operation in a steady state, what fulfils condition of given system continual tuning. The basic principle of TOMS tuning during operation in the steady state consists in an adjustment of basic dynamical properties of pneumatic coupling according to the system dynamics. This adjustment can be made by means of a regulation system working in regulation circuit arrangement with a feedback. In this way it is possible to change dynamical properties of pneumatic coupling continuously with regard to dynamic of mechanical system, so that it can be eliminated dangerous torsional oscillation of given system in the working mode.

  3. A combined experimental and computational study of the catalytic dehydration of glycerol on microporous zeolites: an investigation of the reaction mechanism and acrolein selectivity. (United States)

    Lin, Xufeng; Lv, Yanhong; Qu, Yuanyuan; Zhang, Guodong; Xi, Yanyan; Phillips, David L; Liu, Chenguang


    The catalytic activity and the acrolein selectivity for liquid phase glycerol dehydration on β zeolites (HNa-β-k) were found to be dependent on the reaction temperature as well as on the amount of acid sites on the zeolites. An increase in the reaction temperature favors the acrolein selectivity. The acrolein selectivity increases with the Na(+)/H(+) ratio and the glycerol conversion decreases with it so that a maximum acrolein yield is obtained when a certain amount of acidic sites are replaced by non-active Na(+) sites. The computational results indicate that 3-hydoxylpropanal (HPA) is an important intermediate that determines the final product selectivity. The relative rates of the different reaction pathways for HAP can be affected by the amount of water molecules involved in its homogeneous reaction. Based on the reaction mechanism proposed, it was hypothesized that smaller pores reduce activity but increase selectivity to acrolein, and results of the H-MFI zeolite were consistent with this hypothesis. Our work provides important insight into the overall landscape of the reaction mechanism and can be used to help design reaction systems that have good acrolein selectivity for the liquid phase glycerol dehydration reactions.

  4. Spectroscopic investigation of the reaction mechanism of CopB-B, the catalytic fragment from an archaeal thermophilic ATP-driven heavy metal transporter. (United States)

    Völlmecke, Christian; Kötting, Carsten; Gerwert, Klaus; Lübben, Mathias


    The mechanism of ATP hydrolysis of a shortened variant of the heavy metal-translocating P-type ATPase CopB of Sulfolobus solfataricus was studied. The catalytic fragment, named CopB-B, comprises the nucleotide binding and phosphorylation domains. We demonstrated stoichiometric high-affinity binding of one nucleotide to the protein (K(diss) 1-20 microm). Mg is not necessary for nucleotide association but is essential for the phosphatase activity. Binding and hydrolysis of ATP released photolytically from the caged precursor nitrophenylethyl-ATP was measured at 30 degrees C by infrared spectroscopy, demonstrating that phosphate groups are not involved in nucleotide binding. The hydrolytic kinetics was biphasic, and provides evidence for at least one reaction intermediate. Modelling of the forward reaction gave rise to three kinetic states connected by two intrinsic rate constants. The lower kinetic constant (k(1) = 4.7 x 10(-3) s(-1) at 30 degrees C) represents the first and rate-limiting reaction, probably reflecting the transition between the open and closed conformations of the domain pair. The subsequent step has a faster rate (k(2) = 17 x 10(-3) s(-1) at 30 degrees C), leading to product formation. Although the latter appears to be a single step, it probably comprises several reactions with presently unresolved intermediates. Based on these data, we suggest a model of the hydrolytic mechanism.

  5. Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1-x/TiO2 (United States)

    Chen, Xujuan; Sun, Xiaoliang; Gong, Cairong; Lv, Gang; Song, Chonglin


    Copper-cerium-zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brønsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4 + (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature ( 200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.

  6. Electro-catalytic oxidation of phenacetin with a three-dimensional reactor: Degradation pathway and removal mechanism. (United States)

    Xiao, Mengshi; Zhang, Yonggang


    Phenacetin is a common analgesic, anti-arthritic and anti-rheumatic drug. This study dealt with the degradation of phenacetin in alkaline media using a three-dimensional reactor with particle electrodes. Particular attention was paid to the degradation pathway and the reaction mechanism in the system. Liquid chromatography coupled with time-of-flight mass spectrometry was used to identify the intermediates. The phenacetin was observed to be firstly cut off the branch chains main by direct oxidation, and then the intermediates further degraded to ring opening products by hydroxyl radical resulting from indirect oxidation and finally mineralized to CO2, H2O. A possible removal mechanism was proposed that direct and indirect oxidation together did effect on the pollutants with oxygen.


    NARCIS (Netherlands)



    A pilot plant study on propane catalytic combustion in a membrane reactor with separate reactant feeds is presented. The membrane consisted of a porous alumina tube activated by insertion into its pores of a Pt/gamma-Al2O3 catalyst. The role of reactants concentration and of the feed flow rates were

  8. Experimental demonstration of the reverse flow catalytic membrane reactor concept for energy efficient syngas production. Part 1: Influence of operating conditions

    NARCIS (Netherlands)

    Smit, J.; Bekink, G.J.; Sint Annaland, van M.; Kuipers, J.A.M.


    In this contribution the technical feasibility of the reverse flow catalytic membrane reactor (RFCMR) concept with porous membranes for energy efficient syngas production is investigated. In earlier work an experimental proof of principle was already provided [Smit, J., Bekink, G.J., van Sint Annala

  9. Effect of the operating variables of a fluid catalytic cracking unit (FCC) on the naphtha gum formation; Efeito das variaveis operacionais de uma unidade de craqueamento catalitico (FCC) na formacao da goma na nafta

    Energy Technology Data Exchange (ETDEWEB)

    Mattos, Leandro Generoso de [PETROBRAS, Betim, MG (Brazil). Unidade de Negocio Refinaria Gabriel Passos (REGAP). Gerencia de Hidrotratamento e Coque]. E-mail:; Almeida, Gustavo Matheus de [Universidade de Sao Paulo (USP), SP (Brazil). Escola Politecnica. Dept. de Engenharia Quimica]. E-mail:; Oliveira, Eder Domingos de; Cardoso, Marcelo [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Engenharia Quimica]. E-mails:;


    One of the main problems brought by gasoline combustion in vehicles is the deposition of gum in the fuel system. Gum, though soluble in gasoline, appears in the form of a viscous residue after gasoline has evaporated. The carbon deposits coating carburetors, nozzles, collector pipes, intake valves and combustion chambers affect the car's steering capacity, lower the engine's performance and increase the emission of exhaust gas. Given the sort of refining used in Brazil, the content of naphtha resulting from catalytic cracking in gasoline coming from refineries is quite significant. The chains resulting from catalytic or thermal cracking processes have a strong tendency to form gum. In Fluid Catalytic Cracking (FCC), a complex network of chemical reactions takes place, which can either be catalytic or thermal. Principal Component Analysis techniques (PCA), stepwise regression and genetic algorithms have been used to select the operating variables of FCC that will bear the most influence on gum formation. An ARN (Artificial Neural Networks) software tool was also used to anticipate gum forming from operating variables selected by means of the above mentioned techniques. The results achieved in forecasting gum forming in cracked naphtha lead us to believe that the data analysis methodology used was suitable. It is possible to forecast potential gum through seven variables with a 10% Mean Relative Error (MRE) and a 1.75 g/100 mL Mean Absolute Error (MAE) with a linear correlation coefficient of 0.844; or through eight variables with an 11% MRE and a 1.93 g/100 mL MAE with a linear correlation coefficient of 0.829. In the first case, the methodology employed to reduce variables was stepwise regression, and in the second, genetic algorithms. (author)

  10. Explicit expressions of quantum mechanical rotation operators for spins 1 to 2 (United States)

    Kocakoç, Mehpeyker; Tapramaz, Recep


    Quantum mechanical rotation operators are the subject of quantum mechanics, mathematics and pulsed magnetic resonance spectroscopies, namely NMR, EPR and ENDOR. They are also necessary for spin based quantum information systems. The rotation operators of spin 1/2 are well known and can be found in related textbooks. But rotation operators of other spins greater than 1/2 can be found numerically by evaluating the series expansions of exponential operator obtained from Schrödinger equation, or by evaluating Wigner-d formula or by evaluating recently established expressions in polynomial forms discussed in the text. In this work, explicit symbolic expressions of x, y and z components of rotation operators for spins 1 to 2 are worked out by evaluating series expansion of exponential operator for each element of operators and utilizing linear curve fitting process. The procedures gave out exact expressions of each element of the rotation operators. The operators of spins greater than 2 are under study and will be published in a separate paper.

  11. Catalytic Mechanism and Efficiency of Methane Oxidation by Hg(II) in Sulfuric Acid and Comparison to Radical Initiated Conditions


    Fuller, Jack T.; Butler, Steven; Devarajan, Deepa; Jacobs, Austin; Hashiguchi, Brian G.; Konnick, Michael M.; Goddard, William A.; Gonzales, Jason M.; Periana, Roy A.; Ess, Daniel H.


    Methane conversion to methyl bisulfate by Hg^(II)(SO_4) in sulfuric acid is an example of fast and selective alkane oxidation catalysis. Dichotomous mechanisms involving C–H activation and electron transfer have been proposed based on experiments. Radical oxidation pathways have also been proposed for some reaction conditions. Hg^(II) is also of significant interest because as a d^(10) transition metal it is similar to d^(10) main-group metals that also oxidize alkanes. Density-functional cal...

  12. Some Aspects of the Catalytic Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Anil; K.Saikia


    1 Results Catalytic reactions are gaining importance due to its low cost, operational simplicity, high efficiency and selectivity. It is also getting much attention in green synthesis. Many useful organic reactions, including the acylation of alcohols and aldehydes, carbon-carbon, carbon-nitrogen, carbon-sulfur bond forming and oxidation reactions are carried out by catalyst. We are exploring the catalytic acylation of alcohols and aldehydes in a simple and efficient manner. Catalytic activation of unr...

  13. Stepwise catalytic mechanism via short-lived intermediate inferred from combined QM/MM MERP and PES calculations on retaining glycosyltransferase ppGalNAcT2. (United States)

    Trnka, Tomáš; Kozmon, Stanislav; Tvaroška, Igor; Koča, Jaroslav


    The glycosylation of cell surface proteins plays a crucial role in a multitude of biological processes, such as cell adhesion and recognition. To understand the process of protein glycosylation, the reaction mechanisms of the participating enzymes need to be known. However, the reaction mechanism of retaining glycosyltransferases has not yet been sufficiently explained. Here we investigated the catalytic mechanism of human isoform 2 of the retaining glycosyltransferase polypeptide UDP-GalNAc transferase by coupling two different QM/MM-based approaches, namely a potential energy surface scan in two distance difference dimensions and a minimum energy reaction path optimisation using the Nudged Elastic Band method. Potential energy scan studies often suffer from inadequate sampling of reactive processes due to a predefined scan coordinate system. At the same time, path optimisation methods enable the sampling of a virtually unlimited number of dimensions, but their results cannot be unambiguously interpreted without knowledge of the potential energy surface. By combining these methods, we have been able to eliminate the most significant sources of potential errors inherent to each of these approaches. The structural model is based on the crystal structure of human isoform 2. In the QM/MM method, the QM region consists of 275 atoms, the remaining 5776 atoms were in the MM region. We found that ppGalNAcT2 catalyzes a same-face nucleophilic substitution with internal return (SNi). The optimized transition state for the reaction is 13.8 kcal/mol higher in energy than the reactant while the energy of the product complex is 6.7 kcal/mol lower. During the process of nucleophilic attack, a proton is synchronously transferred to the leaving phosphate. The presence of a short-lived metastable oxocarbenium intermediate is likely, as indicated by the reaction energy profiles obtained using high-level density functionals.

  14. Stepwise catalytic mechanism via short-lived intermediate inferred from combined QM/MM MERP and PES calculations on retaining glycosyltransferase ppGalNAcT2.

    Directory of Open Access Journals (Sweden)

    Tomáš Trnka


    Full Text Available The glycosylation of cell surface proteins plays a crucial role in a multitude of biological processes, such as cell adhesion and recognition. To understand the process of protein glycosylation, the reaction mechanisms of the participating enzymes need to be known. However, the reaction mechanism of retaining glycosyltransferases has not yet been sufficiently explained. Here we investigated the catalytic mechanism of human isoform 2 of the retaining glycosyltransferase polypeptide UDP-GalNAc transferase by coupling two different QM/MM-based approaches, namely a potential energy surface scan in two distance difference dimensions and a minimum energy reaction path optimisation using the Nudged Elastic Band method. Potential energy scan studies often suffer from inadequate sampling of reactive processes due to a predefined scan coordinate system. At the same time, path optimisation methods enable the sampling of a virtually unlimited number of dimensions, but their results cannot be unambiguously interpreted without knowledge of the potential energy surface. By combining these methods, we have been able to eliminate the most significant sources of potential errors inherent to each of these approaches. The structural model is based on the crystal structure of human isoform 2. In the QM/MM method, the QM region consists of 275 atoms, the remaining 5776 atoms were in the MM region. We found that ppGalNAcT2 catalyzes a same-face nucleophilic substitution with internal return (SNi. The optimized transition state for the reaction is 13.8 kcal/mol higher in energy than the reactant while the energy of the product complex is 6.7 kcal/mol lower. During the process of nucleophilic attack, a proton is synchronously transferred to the leaving phosphate. The presence of a short-lived metastable oxocarbenium intermediate is likely, as indicated by the reaction energy profiles obtained using high-level density functionals.

  15. Degradation and healing mechanisms of carbon fibers during the catalytic growth of carbon nanotubes on their surfaces. (United States)

    Kim, Kyoung Ju; Yu, Woong-Ryeol; Youk, Ji Ho; Lee, Jinyong


    This study reports on the main cause of the reduced tensile strength of carbon fibers (CFs) by investigating the microstructural changes in the CFs that are undergoing mainly two processes: catalyst nanoparticle formation and chemical vapor deposition (CVD). Interestingly, the two processes oppositely influenced the tensile strength of the CFs: the former negatively and the latter positively. The catalysts coating and nanoparticle formation degraded the CF surface by inducing amorphous carbons and severing graphitic layers, while those defects were healed by both the injected carbons and interfaced CNTs during the CVD process. The revealed degradation and healing mechanisms can serve as a fundamental engineering basis for exploring optimized processes in the manufacturing of hierarchical reinforcements without sacrificing the tensile strength of the substrate CFs.

  16. Exploratory study of mechanical kinematic innovation design based on gene recombination operation

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Yixiong; Gao, Yicong; Tan, Jianrong [Zhejiang University, Hangzhou (China); Hagiwara, Ichiro [Tokyo Institute of Technology, Tokyo (Korea, Republic of)


    This paper analyzes the influencing factor of motion output of the inspired mechanism under the premise that the motion input is invariant. These factors are respectively expressed as kinematic pair chromosome number, kinematic pair feature gene and distance relationship vector gene by virtue of several concepts and principles in genetics, and then they are encoded. Mechanism chromosome model is established, which is constituted by mechanism chromosome relationship graph and mechanism chromosome matrix. Three kinematic pair chromosome gene recombination operations on mechanism chromosome model (dominance, translocation and metastasis), are proposed by using meiosis and chromosome variance in genetics for reference. Finally the paper takes shaper as the original mechanism and acquires its inspired mechanism, which proves the convenience and practicality of the methods.

  17. [Study on mechanism of ceramic honeycomb-catalytic ozonation for the decomposition of trace nitrobenzene in aqueous solution]. (United States)

    Zhao, Lei; Ma, Jun; Sun, Zhi-Zhong; Liu, Zheng-Qian; Yang, Yi-Xin; Lu, Wei


    The experiment investigated effects of the presence of hydroxyl radical inhibitor on degradation efficiency of trace nitrobenzene in aqueous solution in the processes of ozonation alone and ceramic honeycomb-catalyzed ozonation, including HCO3-, CO3(2-), HPO4(2-), H2PO4- and tert-butanol, and studied preliminarily on their mechanism. The results indicated that degradation rate of the two processes both increased firstly and decreased subsequently with the increase of the concentration of HCO3- (0 - 200 mg x L(-1)), and reached the climax at the concentration of bicarbonate ion 50 mg x L(-1) under the same experimental condition. The degradation rates of ozonation alone and ozonation/ ceramic honeycomb both declined by 16.57% and 27.52% with the increase of the concentration of CO3(2-) (0 - 20 mg x L(-1)), respectively, and decreased by 13.61% and 17.52% with the addition of the concentration of HPO4(2-) (0 - 12 mg x L(-1)), and reduced by 6.61% and 12.52% with the enhancement of the concentration of H2PO4- (0 - 120 mg x L(-1)), and dropped by 30.06% and 46.09% with the increasing of the concentration of tert-butanol (0 - 10 mg x L(-1)). The experimental results indicated that decomposition of nitrobenzene in both processes all followed the mechanism of oxidization by OH free radical, and tert-butanol is a more suitable indicator for the radical type reaction. The removal rate of ozonation alone rose with the increase of the concentration of pH (3.02 - 10.96), but that of ozonation/ceramic honeycomb process reached the maximum at pH = 9.23.

  18. Amino acid residues involved in the catalytic mechanism of NAD-dependent glutamate dehydrogenase from Halobacterium salinarum. (United States)

    Pérez-Pomares, F; Ferrer, J; Camacho, M; Pire, C; LLorca, F; Bonete, M J


    The pH dependence of kinetic parameters for a competitive inhibitor (glutarate) was determined in order to obtain information on the chemical mechanism for NAD-dependent glutamate dehydrogenase from Halobacterium salinarum. The maximum velocity is pH dependent, decreasing at low pHs giving a pK value of 7.19+/-0.13, while the V/K for l-glutamate at 30 degrees C decreases at low and high pHs, yielding pK values of 7.9+/-0.2 and 9.8+/-0.2, respectively. The glutarate pKis profile decreases at high pHs, yielding a pK of 9. 59+/-0.09 at 30 degrees C. The values of ionization heat calculated from the change in pK with temperature are: 1.19 x 10(4), 5.7 x 10(3), 7 x 10(3), 6.6 x 10(3) cal mol-1, for the residues involved. All these data suggest that the groups required for catalysis and/or binding are lysine, histidine and tyrosine. The enzyme shows a time-dependent loss in glutamate oxidation activity when incubated with diethyl pyrocarbonate (DEPC). Inactivation follows pseudo-first-order kinetics with a second-order rate constant of 53 M-1min-1. The pKa of the titratable group was pK1=6.6+/-0.6. Inactivation with ethyl acetimidate also shows pseudo-first-order kinetics as well as inactivation with TNM yielding second-order constants of 1.2 M-1min-1 and 2.8 M-1min-1, and pKas of 8.36 and 9.0, respectively. The proposed mechanism involves hydrogen binding of each of the two carboxylic groups to tyrosyl residues; histidine interacts with one of the N-hydrogens of the l-glutamate amino group. We also corroborate the presence of a conservative lysine that has a remarkable ability to coordinate a water molecule that would act as general base.

  19. Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism. (United States)

    Rossin, Andrea; Bottari, Giovanni; Lozano-Vila, Ana M; Paneque, Margarita; Peruzzini, Maurizio; Rossi, Andrea; Zanobini, Fabrizio


    Catalytic dehydrogenation of ammonia-borane (NH(3)·BH(3), AB) and dimethylamine borane (NHMe(2)·BH(3), DMAB) by the Pd(II) complex [((tBu)PCP)Pd(H(2)O)]PF(6) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] leads to oligomerization and formation of spent fuels of general formula cyclo-[BH(2)-NR(2)](n) (n = 2,3; R = H, Me) as reaction byproducts, while one equivalent of H(2) is released per amine-borane equivalent. The processes were followed through multinuclear ((31)P, (1)H, (11)B) variable temperature NMR spectroscopy; kinetic measurements on the hydrogen production rate and the relative rate constants were also carried out. One non-hydridic intermediate could be detected at low temperature, whose chemical nature was explored through a DFT modeling of the reaction mechanism, at the M06//6-31+G(d,p) computational level. The computational output was of help to propose a reliable mechanistic picture of the process.

  20. Structural and catalytic characterization of mechanical mixtures of Pt/WOx-ZrO{sub 2} and Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, J.L., E-mail: jlcl@correo.azc.uam.m [Universidad Autonoma Metropolitana-Azcapotzalco, CBI, Dpto. Energia, Av. Sn. Pablo 180, Col. Reynosa, C.P. 02200, Mexico, DF (Mexico); Fuentes, G.A. [Universidad Autonoma Metropolitana-Iztapalapa, CBI, Depto. de IPH C.P. 09340, Mexico, DF (Mexico); Navarrete, J.; Vazquez, A. [Instituto Mexicano del Petroleo, IBP, Ger. de Catalizadores, Eje Central Lazaro Cardenas No. 152, C.P. 07300, Mexico, DF (Mexico); Zeifert, B.; Salmones, J. [Instituto Politecnico Nacional Mexico, ESIQIE, Laboratorio de Catalisis y Materiales, C.P. 07738, Mexico, DF (Mexico); Nuno, L. [Universidad Autonoma Metropolitana-Azcapotzalco, CBI, Dpto. Energia, Av. Sn. Pablo 180, Col. Reynosa, C.P. 02200, Mexico, DF (Mexico)


    The effect of the Bronsted/Lewis acid ratio on isomerization of n-heptane using Al{sub 2}O{sub 3} as a source of Lewis acidity and WOx/ZrO{sub 2} as a source of Bronsted and Lewis acidity was studied and controlled using mechanical mixtures of these solids. These mixtures were characterized by surface area, infrared spectroscopy of pyridine, X-ray diffraction and Raman spectroscopy. It was found that the presence of W=O stretching mode which was consistent with the presence of oxotungstate species which were the precursors of the acid sites. It was found out that as the oxotungstate structures increased, the selectivity to n-heptane isomers increased while the hydrocracking and dehydrocyclization selectivity decreased. The presence of Bronsted acidity of the WOx/ZrO{sub 2} domains, the increase of Knudsen diffusivity and the loss of Pt metallic area by strong interaction of the Pt with the WOx/ZrO{sub 2} explain this catalytic behavior.

  1. Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles. (United States)

    Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A


    We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

  2. Valance electron structure of carbide-diamond interface and catalytic mechanism for diamond synthesis under high-pressure and high-temperature

    Institute of Scientific and Technical Information of China (English)

    GONG Jianhong; XU Bin; YIN Longwei; QI Yongxin; LI Li; SU Qingcai; LI Musen


    The metallic films surrounding a synthetic diamond formed under high-pressure and high-temperature (HPHT) in the presence of Fe-based and Ni-based catalysts were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). It was showed that the carbide was the primary carbon source for the nucleation and growth of diamond. Based on the EET (empirical electron theory in solid and molecules) theory, the valence electron structure of interface between carbide (Fe3C, Ni3C, (Fe, Ni)3C) and diamond was calculated using the bonding length difference (BLD) method. The boundary criterion of Thomas-Fermi-Dirac-Cheng (TFDC): "the electron density being equal on the contacting surfaces of atoms" was applied to analyze the valence structure of carbide-diamond interface. The result based on the calculation valance electron structure is in good accordance with the experimental result. This study is very helpful to reveal the catalytic mechanism of diamond nucleation and growth and design the new catalyst for diamond synthesis.

  3. Catalytic effect of nanoparticle 3d-transition metals on hydrogen storage properties in magnesium hydride MgH2 prepared by mechanical milling. (United States)

    Hanada, Nobuko; Ichikawa, Takayuki; Fujii, Hironobu


    We examined the catalytic effect of nanoparticle 3d-transition metals on hydrogen desorption (HD) properties of MgH(2) prepared by mechanical ball milling method. All the MgH(2) composites prepared by adding a small amount of nanoparticle Fe(nano), Co(nano), Ni(nano), and Cu(nano) metals and by ball milling for 2 h showed much better HD properties than the pure ball-milled MgH(2) itself. In particular, the 2 mol % Ni(nano)-doped MgH(2) composite prepared by soft milling for a short milling time of 15 min under a slow milling revolution speed of 200 rpm shows the most superior hydrogen storage properties: A large amount of hydrogen ( approximately 6.5 wt %) is desorbed in the temperature range from 150 to 250 degrees C at a heating rate of 5 degrees C/min under He gas flow with no partial pressure of hydrogen. The EDX micrographs corresponding to Mg and Ni elemental profiles indicated that nanoparticle Ni metals as catalyst homogeneously dispersed on the surface of MgH(2). In addition, it was confirmed that the product revealed good reversible hydriding/dehydriding cycles even at 150 degrees C. The hydrogen desorption kinetics of catalyzed and noncatalyzed MgH(2) could be understood by a modified first-order reaction model, in which the surface condition was taken into account.

  4. Study of a self-adjoint operator indicating the direction of time within standard quantum mechanics

    CERN Document Server

    Strauss, Y; Machnes, S; Horwitz, L P


    In [J. Math. Phys. 51 (2010) 022104] a self-adjoint operator was introduced that has the property that it indicates the direction of time within the framework of standard quantum mechanics, in the sense that as a function of time its expectation value decreases monotonically for any initial state. In this paper we study some of this operator's properties. In particular, we derive its spectrum and generalized eigenstates, and treat the example of the free particle.

  5. Quantum Mechanical Version of z-Transform Related to Eigenkets of Boson Creation Operator

    Institute of Scientific and Technical Information of China (English)

    FANHong-Yi; FULiang; A.Wiinsche


    Using the completeness relation composed of the coherent state and of the eigenket of bosonic creation operator, we establish a one-to-one correspondence between the z-transform and the quantum-mechanical transform from the representation by number states |n) to the representation by coherent states |(z)) (Bargmann representation).In this way, the quantum-mechanical version of the various properties of z-transform are obtained and the operators for embodying these properties in the Fock space are derived, which may find applications in quantum states engineering.

  6. Mechanical Properties of a Unidirectional Basalt-Fiber-Reinforced Plastic Under a Loading Simulating Operation Conditions (United States)

    Lobanov, D. S.; Slovikov, S. V.


    The results of experimental investigations of unidirectional composites based on basalt fibers and different marks of epoxy resins are presented. Uniaxial tensile tests were carried out using a specimen fixation technique simulating the operation conditions of structures. The mechanical properties of the basalt-fiber-reinforced plastics (BFRPs) were determined. The diagrams of loading and deformation of BFRP specimens were obtain. The formulations of the composites with the highest mechanical properties were revealed.

  7. Catalytic mechanism of MraY and WecA, two paralogues of the polyprenyl-phosphate N-acetylhexosamine 1-phosphate transferase superfamily. (United States)

    Al-Dabbagh, Bayan; Olatunji, Samir; Crouvoisier, Muriel; El Ghachi, Meriem; Blanot, Didier; Mengin-Lecreulx, Dominique; Bouhss, Ahmed


    The MraY transferase catalyzes the first membrane step of bacterial cell wall peptidoglycan biosynthesis, namely the transfer of the N-acetylmuramoyl-pentapeptide moiety of the cytoplasmic precursor UDP-MurNAc-pentapeptide to the membrane transporter undecaprenyl phosphate (C55P), yielding C55-PP-MurNAc-pentapeptide (lipid I). A paralogue of MraY, WecA, catalyzes the transfer of the phospho-GlcNAc moiety of UDP-N-acetylglucosamine onto the same lipid carrier, leading to the formation of C55-PP-GlcNAc that is essential for the synthesis of various bacterial cell envelope components. These two enzymes are members of the polyprenyl-phosphate N-acetylhexosamine 1-phosphate transferase superfamily, which are essential for bacterial envelope biogenesis. Despite the availability of detailed biochemical information on the MraY enzyme, and the recently published crystal structure of MraY of Aquifex aeolicus, the molecular basis for its catalysis remains poorly understood. This knowledge can contribute to the design of potential inhibitors. Here, we report a detailed catalytic study of the Bacillus subtilis MraY and Thermotoga maritima WecA transferases. Both forward and reverse exchange reactions required the presence of the second substrate, C55P and uridine monophosphate (UMP), respectively. Both enzymes did not display any pyrophosphatase activity on the nucleotide substrate. Moreover, we showed that the nucleotide substrate UDP-MurNAc-pentapeptide, as well as the nucleotide product UMP, can bind to MraY in the absence of lipid ligands. Therefore, our data are in favour of a single displacement mechanism. During this "one-step" mechanism, the oxyanion of the polyprenyl-phosphate attacks the β-phosphate of the nucleotide substrate, leading to the formation of lipid product and the liberation of UMP. The involvement of an invariant aspartyl residue in the deprotonation of the lipid substrate is discussed.

  8. 催化重整装置提高安稳运行方案探讨%Discussion on improving safe and stable operation scheme of catalytic reforming Unit

    Institute of Scientific and Technical Information of China (English)



    A catalytic reforming unit has been running for 50 years,the aging phenomenon of some equipment in this unit was severe. Many problems exited during equipment management,maintenance and operation. In this paper,problems existed in operation was analyzed,strategy and method for solving equipment problem were put forward,which ensured safe and stable operation of equipment in the Unit.%某催化重整装置已经运行了50 a,装置中的部分设备老化现象严重。在设备管理、维护、运行过程中出现了诸多问题,文中提出了解决设备问题的策略及方法,确保了装置设备安稳运行。

  9. 活性炭催化臭氧氧化扑热息痛的机制研究%Mechanism of Catalytic Ozonation for the Degradation of Paracetamol by Activated Carbon

    Institute of Scientific and Technical Information of China (English)

    王佳裕; 戴启洲; 鱼杰; 颜亦舟; 陈建孟


    The degradation of paracetamol (APAP) in aqueous solution was studied with ozonation integrated with activated carbon ( AC). The synergistic effect of ozonation/AC process was explored by comparing the degradation efficiency of APAP in three processes (ozonation alone, activated carbon alone and ozonation integrated with activated carbon). The operational parameters that affected the reaction rate were carefully optimized. Based on the intermediates detected, the possible pathway for catalytic degradation was discussed and the reaction mechanism was also investigated. The results showed that the TOC removal reached 55. 11% at 60 min in the AC/O3 system, and was significantly better than the sum of ozonation alone (20. 22% ) and activated carbon alone (27. 39% ) , showing the great synergistic effect. And the BOD5/COD ratio increased from 0.086 (before reaction) to 0.543 (after reaction) , indicating that the biodegradability was also greatly improved. The effects of the initial concentration of APAP, pH value, ozone dosage and AC dosage on the variation of reaction rate were carefully discussed. The catalytic reaction mechanism was different at different pH values; the organic pollutions were removed by adsorption and direct ozone oxidation at acidic pH, and mainly by catalytic ozonation at alkaline pH.%采用活性炭催化臭氧处理典型解热镇痛药扑热息痛,研究了活性炭/臭氧体系的协同效应,优化了工艺参数,分析了降解产物并探讨了降解机制.结果表明:在臭氧活性炭体系下,反应60 min后,TOC的去除率为55.11%,效果明显优于臭氧体系的20.22%和活性炭体系的27.39%之和,具有明显的协同作用,并且BOD5/COD比值从反应前的0.086提高到反应后的0.543,可生化性显著提高.研究了pH、臭氧投加量、污染物初始浓度和活性炭投加量等操作参数的作用规律.在此基础上,探讨了臭氧活性炭体系在不同pH下的催化反应机制,发现在酸性条件

  10. Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries. (United States)

    Kim, Ki Jae; Park, Min-Sik; Kim, Jae-Hun; Hwang, Uk; Lee, Nam Jin; Jeong, Goojin; Kim, Young-Jun


    A new approach for enhancing the electrochemical performance of carbon felt electrodes by employing non-precious metal oxides is designed. The outstanding electro-catalytic activity and mechanical stability of Mn(3)O(4) are advantageous in facilitating the redox reaction of vanadium ions, leading to efficient operation of a vanadium redox flow battery.

  11. Feeding Behavior of Aplysia: A Model System for Comparing Cellular Mechanisms of Classical and Operant Conditioning (United States)

    Baxter, Douglas A.; Byrne, John H.


    Feeding behavior of Aplysia provides an excellent model system for analyzing and comparing mechanisms underlying appetitive classical conditioning and reward operant conditioning. Behavioral protocols have been developed for both forms of associative learning, both of which increase the occurrence of biting following training. Because the neural…

  12. Difference of operation mechanisms in SWNTs network FETs studied via scanning gate microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xiaojun; Matsunaga, Masahiro; Yahagi, Tatsurou; Maeda, Kenji; Ochiai, Yuichi; Aoki, Nobuyuki [Graduate School of Advanced Integration Science, Chiba University, Chiba 263-8522 (Japan); Bird, Jonathan P. [Department of Electrical Engineering, University at Buffalo, the State University of New York, Buffalo, NY 14260-1920 (United States); Ishibashi, Koji [Advanced Device Laboratory, RIKEN, Wako, Saitama 351-0198 (Japan)


    Field effect transistors (FETs) whose channel is composed of a network of single wall carbon nanotubes (SWNTs) have been studied to investigate the mechanism of the device operation via scanning gate microscopy (SGM) at room temperature. We observed different SGM response in networks of SWNTs either synthesized by CoMoCAT process or semiconducting enriched by density gradient ultracentrifuge process. In the former case, SGM response was observed at specific inter-tube junctions suggesting a Schottky junction formed with semiconducting and metallic SWNTs in the network. In contrast, multiple concentric rings in the SGM response are observed within the tubes in a network of the latter SWNTs suggesting a possibility of quantum mechanical transport at room-temperature. Different type of SGM responses are confirmed in the two kinds of SWNTs networks, nevertheless such active positions would likely have an important role in the FET operation mechanism in each network.

  13. Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid-base catalysis. (United States)

    Schultz, Eric P; Vasquez, Ernesto E; Scott, William G


    The hammerhead ribozyme catalyzes RNA cleavage via acid-base catalysis. Whether it does so by general acid-base catalysis, in which the RNA itself donates and abstracts protons in the transition state, as is typically assumed, or by specific acid-base catalysis, in which the RNA plays a structural role and proton transfer is mediated by active-site water molecules, is unknown. Previous biochemical and crystallographic experiments implicate an invariant purine in the active site, G12, as the general base. However, G12 may play a structural role consistent with specific base catalysis. To better understand the role of G12 in the mechanism of hammerhead catalysis, a 2.2 Å resolution crystal structure of a hammerhead ribozyme from Schistosoma mansoni with a purine substituted for G12 in the active site of the ribozyme was obtained. Comparison of this structure (PDB entry 3zd4), in which A12 is substituted for G, with three previously determined structures that now serve as important experimental controls, allows the identification of structural perturbations that are owing to the purine substitution itself. Kinetic measurements for G12 purine-substituted schistosomal hammerheads confirm a previously observed dependence of rate on the pK(a) of the substituted purine; in both cases inosine, which is similar to G in pK(a) and hydrogen-bonding properties, is unexpectedly inactive. Structural comparisons indicate that this may primarily be owing to the lack of the exocyclic 2-amino group in the G12A and G12I substitutions and its structural effect upon both the nucleotide base and phosphate of A9. The latter involves the perturbation of a previously identified and well characterized metal ion-binding site known to be catalytically important in both minimal and full-length hammerhead ribozyme sequences. The results permit it to be suggested that G12 plays an important role in stabilizing the active-site structure. This result, although not inconsistent with the potential

  14. O-GlcNAcylation of protein kinase A catalytic subunits enhances its activity: a mechanism linked to learning and memory deficits in Alzheimer's disease. (United States)

    Xie, Shutao; Jin, Nana; Gu, Jianlan; Shi, Jianhua; Sun, Jianming; Chu, Dandan; Zhang, Liang; Dai, Chun-Ling; Gu, Jin-Hua; Gong, Cheng-Xin; Iqbal, Khalid; Liu, Fei


    Alzheimer's disease (AD) is characterized clinically by memory loss and cognitive decline. Protein kinase A (PKA)-CREB signaling plays a critical role in learning and memory. It is known that glucose uptake and O-GlcNAcylation are reduced in AD brain. In this study, we found that PKA catalytic subunits (PKAcs) were posttranslationally modified by O-linked N-acetylglucosamine (O-GlcNAc). O-GlcNAcylation regulated the subcellular location of PKAcα and PKAcβ and enhanced their kinase activity. Upregulation of O-GlcNAcylation in metabolically active rat brain slices by O-(2-acetamido-2-deoxy-d-glucopyranosylidenamino) N-phenylcarbamate (PUGNAc), an inhibitor of N-acetylglucosaminidase, increased the phosphorylation of tau at the PKA site, Ser214, but not at the non-PKA site, Thr205. In contrast, in rat and mouse brains, downregulation of O-GlcNAcylation caused decreases in the phosphorylation of CREB at Ser133 and of tau at Ser214, but not at Thr205. Reduction in O-GlcNAcylation through intracerebroventricular injection of 6-diazo-5-oxo-l-norleucine (DON), the inhibitor of glutamine fructose-6-phosphate amidotransferase, suppressed PKA-CREB signaling and impaired learning and memory in mice. These results indicate that in addition to cAMP and phosphorylation, O-GlcNAcylation is a novel mechanism that regulates PKA-CREB signaling. Downregulation of O-GlcNAcylation suppresses PKA-CREB signaling and consequently causes learning and memory deficits in AD.

  15. Mechanism of catalytic ozonation in Fe ₂O₃/Al ₂O₃@SBA-15 aqueous suspension for destruction of ibuprofen. (United States)

    Bing, Jishuai; Hu, Chun; Nie, Yulun; Yang, Min; Qu, Jiuhui


    Fe2O3 and/or Al2O3 were supported on mesoporous SBA-15 by wet impregnation and calcinations with AlCl3 and FeCl3 as the metal precursor and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectra (FTIR) of adsorbed pyridine. Fe2O3/Al2O3@SBA-15 was found to be highly effective for the mineralization of ibuprofen aqueous solution with ozone. The characterization studies showed that Al-O-Si was formed by the substitution of Al(3+) for the hydrogen of surface Si-OH groups, not only resulting in high dispersion of Al2O3 and Fe2O3 on SBA-15, but also inducing the greatest amount of surface Lewis acid sites. By studies of in situ attenuated total reflection FTIR (ATR-FTIR), in situ Raman, and electron spin resonance (ESR) spectra, the chemisorbed ozone was decomposed into surface atomic oxygen species at the Lewis acid sites of Al(3+) while it was converted into surface adsorbed (•)OHads and O2(•-) radicals at the Lewis acid sites of Fe(3+). The combination of both Lewis acid sites of iron and aluminum onto Fe2O3/Al2O3@SBA-15 enhanced the formation of (•)OHads and O2(•-) radicals, leading to highest reactivity. Mechanisms of catalytic ozonation were proposed for the tested catalysts on the basis of all the experimental information.

  16. [The operative cystoscope with joystick control mechanism of flexible tools inserted into the urinary bladder and the ureter]. (United States)

    Komiakov, B K; Topuzov, M É; Zubarev, V A; Stetsik, O V


    The authors developed an operative cystoscope with joystick control mechanism of ureter catheters and other flexible tools. This construction allowed control of flexible tools inserted into the bladder and the ureter in various directions, thus providing a necessary observation of the operative field at endoscopic operations on the bladder and ureter. This was one of the factors, which determined the operation success.

  17. Mechanical behaviour of PEM fuel cell catalyst layers during regular cell operation

    Directory of Open Access Journals (Sweden)

    Maher A.R. Sadiq Al-Baghdadi


    Full Text Available Damage mechanisms in a proton exchange membrane fuel cell are accelerated by mechanical stresses arising during fuel cell assembly (bolt assembling, and the stresses arise during fuel cell running, because it consists of the materials with different thermal expansion and swelling coefficients. Therefore, in order to acquire a complete understanding of the mechanical behaviour of the catalyst layers during regular cell operation, mechanical response under steady-state hygro-thermal stresses should be studied under real cell operating conditions and in real cell geometry (three-dimensional. In this work, full three-dimensional, non-isothermal computational fluid dynamics model of a PEM fuel cell has been developed to investigate the behaviour of the cathode and anode catalyst layers during the cell operation. A unique feature of the present model is to incorporate the effect of hygro and thermal stresses into actual three-dimensional fuel cell model. In addition, the temperature and humidity dependent material properties are utilize in the simulation for the membrane. The model is shown to be able to understand the many interacting, complex electrochemical, transport phenomena, and deformation that have limited experimental data.

  18. Optimal mechanical harvester route planning for sugarcane f ield operations using particle swarm optimization

    Directory of Open Access Journals (Sweden)

    Woraya Neungmatcha


    Full Text Available Since current agricultural production systems such as the sugarcane supply system in the sugar industry are developing towards larger and more complicated systems, there is consequently increasing use of agricultural machinery. Even though mechanization can help to increase the sugarcane yield, if the mechanical operation efficiency is low, then higher harvest costs and machinery shortages will occur. Global route planning for mechanical harvesters is one of the most important problems in the field of sugarcane harvesting and transporting operations. Improved efficiency and realistic implementation can be achieved by applying advanced planning methods for the execution of field operations, especially considering the field accessibility aspect. To address this issue, participative research was undertaken with a sugar milling company to produce and implement a mixed integer programming model that represents the mechanical harvester route plan. Particle swarm optimization was applied to find a solution to the model, leading to potential cost savings versus schedules produced manually by the mill officer. The model was also applied to explore regional planning options for a more integrated harvesting and transport system.

  19. 催化干气制乙苯装置工业操作方案优化与应用%Optimization and Application of the Industrial Operation Scheme for Catalytic Dry Gas-to-Ethylbenzene Plant

    Institute of Scientific and Technical Information of China (English)

    申永贵; 郑长有; 孟令猛


      介绍了干气制乙苯装置两台烃化反应器并联运行的可行性、操作方案及运行数据。大庆炼化公司干气制乙苯装置两个阶段的烃化反应器并联的实践证明:无论是采用调和汽油生产方案,还是乙苯生产方案,烃化反应器的并联,解决了在不开干气压缩机条件下束缚装置提高干气进料量的瓶颈,有效提高了原料干气中的乙烯转化率、以及产品产量,且不影响产品质量;同时,还可以有效降低反应器压降,为催化干气制乙苯装置工业操作方案优化及节能降耗提供参考和借鉴。%  The feasibility, operation scheme and running results of parallel operation of two alkylation reactors in catalytic dry gas-to-ethylbenzene plant were discussed. The running results in Daqing Refining & Chemical Company(DRCC) show that the parallel operation of two alkylation reactors is feasibility, and the parallel operation can break the bottleneck that restrict the increasing of the catalytic dry gas feed rate, improve ethylene conversion and product output, and dose not affect product quality. At the same time, the pressure drop of reactors can be effectively decreased.

  20. Digital monitoring and health diagnosis for mechanical equipment operation safety based on fiber Bragg grating sensor

    Institute of Scientific and Technical Information of China (English)

    Zude ZHOU; Desheng JIANG; Quan LIU


    This paper introduces fiber Bragg grating (FBG) based on a fiber optic grating sensor developed to be embedded on mechanical equipment for digital monitoring and health diagnosis. The theoretical and experimental researches on the new-style FBG sensor (FBGS) technology, high-speed demodulation, and data transmission are discussed. The transmission characteristics between the FBG and the detection interface, modeling and compensation method for online distributed multi-parameter digital monitoring and methods for data processing, synchronous sampling, and long-term dynamic digital monitoring using embedded technology are also presented. The acquired information by an FBGS can be used for the optimization of maintenance schedules and refinement of mechanical equipment design. It is a chal-lenge to gather real-time data from components working at high speed and in a severe environment of high temperature, high pressure, and high rotation speed. Currently, there are no sensors or technologies available for digital monitoring and health diagnosis under this rigorous situation for use in mechanical engineering operation safety. As a result, this paper introduces an online distributed and integrated digital monitoring system and health diagnosis. The new principle and new method will contribute to modem measurements in science and technology, mechanical engineering, and large mechanical equipment operation safety.

  1. Main mechanisms of material properties degradation under reactor pressure vessel operating conditions

    Energy Technology Data Exchange (ETDEWEB)

    Karzov, Georgy; Timofeev, Boris [Central Research Inst. of Structural Materials ' prometey' , St. Petersburg (Russian Federation)


    In the process of NPP equipment operation materials are subjected to a prolonged influence of loads, associated with the variation of inner pressure and temperature under various conditions. Each equipment element damage is associated with some material fracture mechanism. For NPP equipment the mechanisms of irreversible damage accumulation are related with: irradiation embrittlement, thermal and strain aging, fatigue damages from mechanical and thermal loading, stress corrosion and fatigue corrosion, creep and thermal relaxation stresses, erosion and weak, thermal shock. The basic tasks of specialists working in the sphere of the provision of reliability and service life of nuclear power equipment are not only the determination of the main mechanisms of damages and reasons of their appearance, but also the study of methods which would permit to control these properties completely. By giving some examples of Russian NPP equipment with VVER-440 and VVER-1000 reactors the paper presents most typical degradation mechanisms of equipment material properties, including weldments, in the process of operation and methods to recover by using various technological means. (author)

  2. Operation Mechanism of Farmers’ Professional Cooperatives from the Point of Low-Carbon Agricultural Products

    Institute of Scientific and Technical Information of China (English)


    We firstly take a look at internal logic of cluster development of low-carbon agricultural products.In combination with operation features of farmers’ professional cooperatives and actual requirements for cluster development of low-carbon agricultural products;we elaborate establishing benefit allocation mechanism,bearing education and training functions,forming low-carbon value,building low-carbon identification system,as well as realizing low-carbon value.According to these situations,we systematically analyze operation mechanism of farmers’ professional cooperatives suitable for cluster development of low-carbon agricultural products.To promote cluster development of low-carbon agricultural products,we put forward following suggestions,including government guidance and encouragement,social acceptance and active cooperation,and integration into global low-carbon development system to share benefit of low-carbon development.

  3. Optimal Manoeuvres of Underactuated Linear Mechanical Systems: The Case of Controlling Gantry Crane Operations

    Directory of Open Access Journals (Sweden)

    S. Woods


    Full Text Available A method of solving optimal manoeuvre control of linear underactuated mechanical systems is presented. The nonintegrable constraints present in such systems are handled by adding dummy actuators and then by applying Lagrange multipliers to reduce their action to zero. The open- and closed-loop control schemes can be analyzed. The method, referred to as the constrained modal space optimal control (CMSOC, is illustrated in the examples of gantry crane operations.

  4. Optimal Manoeuvres of Underactuated Linear Mechanical Systems: The Case of Controlling Gantry Crane Operations


    Woods, S; Szyszkowski, W.


    A method of solving optimal manoeuvre control of linear underactuated mechanical systems is presented. The nonintegrable constraints present in such systems are handled by adding dummy actuators and then by applying Lagrange multipliers to reduce their action to zero. The open- and closed-loop control schemes can be analyzed. The method, referred to as the constrained modal space optimal control (CMSOC), is illustrated in the examples of gantry crane operations.

  5. Microwave power transmission system studies. Volume 3, section 8: Mechanical systems and flight operations (United States)

    Maynard, O. E.; Brown, W. C.; Edwards, A.; Haley, J. T.; Meltz, G.; Howell, J. M.; Nathan, A.


    The efforts and recommendations associated with preliminary design and concept definition for mechanical systems and flight operations are presented. Technical discussion in the areas of mission analysis, antenna structural concept, configuration analysis, assembly and packaging with associated costs are presented. Technology issues for the control system, structural system, thermal system and assembly including cost and man's role in assembly and maintenance are identified. Background and desired outputs for future efforts are discussed.

  6. Jamming Transition of Point-To Traffic Through Co-Operative Mechanisms (United States)

    Fang, Jun; Qin, Zheng; Chen, Xiqun; Xu, Zhaohui


    We study the jamming transition of two-dimensional point-to-point traffic through co-operative mechanisms (DCM) using computer simulation. We propose two decentralized co-operative mechanisms CM which are incorporated into the point-to-point traffic models: stepping aside (CM-SA) and choosing alternative routes (CM-CAR). Incorporating CM-SA is to prevent a type of ping-pong jumps from happening when two objects standing face-to-face want to move in opposite directions. Incorporating CM-CAR is to handle the conflict when more than one object competes for the same point in parallel update. We investigate and compare four models mainly from fundamental diagrams, jam patterns and the distribution of co-operation probability. It is found that although it decreases the average velocity a little, the CM-SA increases the critical density and the average flow. Despite increasing the average velocity, the CM-CAR decreases the average flow by creating substantially vacant areas inside jam clusters. We investigate the jam patterns of four models carefully and explain this result qualitatively. In addition, we discuss the advantage and applicability of decentralized co-operation modeling.

  7. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD


    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  8. Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

    NARCIS (Netherlands)

    Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP


    The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and X-ra

  9. Catalytic oxidation of volatile organic compounds (VOCs) - A review (United States)

    Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.


    Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

  10. Understanding mechanisms of enzyme co-operativity: The importance of not being at equilibrium

    Directory of Open Access Journals (Sweden)

    María Luz Cárdenas


    Full Text Available The discovery at the end of the 1950s and the beginning of the 1960s that there were enzymes like threonine deaminase and aspartate transcarbamoylase that failed to follow the expected hyperbolic behaviour predicted by the Michaelis–Menten equation, raised several questions and induced the development of mechanisms to explain this peculiar behaviour. At that time it was already known that the binding of oxygen to haemoglobin did not follow a hyperbolic curve, but a sigmoidal one, and it was thought that a similar situation probably existed for enzymes with sigmoidal kinetics. In other words, the observed kinetic behaviour was a consequence of co-operativity in the substrate binding. Two main models were postulated: those of Monod, Wyman and Changeux in 1965 and of Koshland, Némethy and Filmer in 1966. Both consider that the different conformations are in equilibrium and that there is a rapid equilibrium in the binding, which implies that co-operativity could only exist if there is more than one substrate binding site per enzyme molecule, that is, if the enzyme is an oligomer. What about monomeric enzymes, could they show kinetic co-operativity? Yes, but only through mechanisms that imply the existence of enzyme conformations that are not in equilibrium, and have different kinetic parameters. There are, in fact, very few examples of monomeric enzymes showing kinetic co-operativity with a natural substrate. The case of “glucokinase” (hexokinase D or hexokinase IV, a monomeric enzyme with co-operativity with respect to glucose, will be discussed.

  11. The Operation Mechanisms of External Quality Assurance Frameworks of Foreign Higher Education and Implications for Graduate Education (United States)

    Lin, Mengquan; Chang, Kai; Gong, Le


    The higher education quality evaluation and assurance frameworks and their operating mechanisms of countries such as the United Kingdom, France, and the United States show that higher education systems, traditional culture, and social background all impact quality assurance operating mechanisms. A model analysis of these higher education quality…

  12. VOCs催化反应过程与反应机理研究现状%Research Status of Volatile Organic Compounds(VOCs)Catalytic Oxidation Process and Mechanism

    Institute of Scientific and Technical Information of China (English)



    Reviews the research status of volatile organic compounds catalytic oxidation process and mechanism,such as catalyst characterization,research methods of catalytic process,and different research systems. In-situ technology and X-ray absorption fine structure (XAFS) in catalyst characterization can preferably elucidate the catalytic process and mechanism. The research of catalytic oxidation process mainly include reaction kinetic models (the Power-rate Law, the Mars-van Krevelen Model, and the Langmuir-Hinshelwood), reaction monitoring technology (In-situ FTIR, In-situ NMR, transient technique, isotopic tracing) , quantum chemical calculation, et al. Generally, reaction kinetics is one of the most widely techniques for the mechanism research of catalytic oxidation. The reaction products can be directly detected,which adsorb more attention. The research of quantum chemical calculation is just used for proof.%论述了挥发性有机污染物(VOCs)催化反应过程机理研究的现状,包括催化剂的表征、催化过程研究方法以及不同的研究体系。催化剂表征使用原位技术以及X射线吸收精细结构(XAFS)方法可以更好地阐述催化剂在催化过程中的作用与机制。催化过程研究主要包括催化反应动力学模拟(Power-rate Law、Mars-van Krevelen Model、Langmuir-Hinshelwood),反应产物监测(原位红外技术、原位核磁技术、暂态技术、同位素示踪技术),量子化学计算等。其中,反应动力学是使用较为广泛的研究催化反应机制的技术之一。反应产物监测可以得到直观的认识,获得了广大学者的关注。量子化学计算只作为论证。

  13. Flight Performance Handbook for Orbital Operations: Orbital Mechanics and Astrodynamics Formulae, Theorems, Techniques, and Applications (United States)

    Ambrosio, Alphonso; Blitzer, Leon; Conte, S.D.; Cooper, Donald H.; Dergarabedian, P.; Dethlefsen, D.G.; Lunn, Richard L.; Ireland, Richard O.; Jensen, Arnold A.; Kang, Garfield; Levy, Ezra C.; Liu, Anthony; Marcus, Silvia R.; Mickelwait, A.B.; Moe, Kenneth; Moe, Mildred M.; Pitton, A.R.; Scheuer, Ernest M.; Tompkins, E.H.; Weiser, Peter B.; Whitford, R.K.; Wolverton, R.W.


    This handbook provides parametric data useful both to the space vehicle designer and mission analyst. It provides numerical and analytical relationships between missions and gross vehicle characteristics as a function of performance parameters. The effects of missile constraints and gross guidance limitations plus operational constraints such as launch site location, tracking net location, orbit visibility and mission on trajectory and orbit design parameters are exhibited. The influence of state-of- the-art applications of solar power as compared to future applications of nuclear power on orbit design parameters, such as eclipse time, are among the parameters included in the study. The principal aim, however, is in providing the analyst with useful parametric design information to cover the general area of earth satellite missions in the region of near-earth to cislunar space and beyond and from injection to atmospheric entry and controlled descent. The chapters are organized around the central idea of orbital operations in the 1961-1969 era with emphasis on parametric flight mechanics studies for ascent phase and parking orbits, transfer maneuvers, rendezvous maneuver, operational orbit considerations, and operational orbit control. The results are based almost entirely on the principles of flight and celestial mechanics. Numerous practical examples have been worked out in detail. This is especially important where it has been difficult or impossible to represent all possible variations of the parameters. The handbook contains analytical formulae and sufficient textual material to permit their proper use. The analytic methods consist of both exact and rapid, approximate methods. Scores of tables, working graphs and illustrations amplify the mathematical models which, together with important facts and data, cover the engineering and scientific applications of orbital mechanics. Each of the five major chapters are arranged to provide a rapid review of an entire


    Institute of Scientific and Technical Information of China (English)


    The special subject"research on life prediction technology of important in-service pressure vessels" mainly analyzes the failure mechanism of large-sized important and critical in-service pressure vessels under the action of working medium and investigates safety assessment and life prediction technology with a view to enhance the operation reliability of in-service pressure vessels in China. Based on a series of accident investigation and test & measuring research, the cause of cracking of catalytic regenerator is analyzed and the in-line non-destructive examination method and failure prevention measures for the cracking of catalytic regenerator are proposed.

  15. High power operation with beam of a CLIC pets equipped with on/off mechanism

    CERN Document Server

    Syratchev, I; Dubrovskiy, A; Skowronski, P; Ruber, R


    One of the feasibility issues of the CLIC two-beam scheme, is the possibility of rapidly switching off the rf power production in an individual Power Extraction and Transfer Structures (PETS) in case of breakdowns, either in the PETS or one of the main beam accelerating structures. The proposed solution is to use a variable external reflector connected to the PETS. When activated, this scheme allows us to gradually manipulate the rf power transfer to the accelerating structure and to reduce the rf power production in the PETS itself by a factor of 4. Recently the first operation of the Two Beam Test Stand (TBTS) PETS equipped with an ON/OFF mechanism was performed in CTF3. In this paper we will present the results of the PETS operation when powered by the drive beam up to high peak power levels (>100 MW) and compare them to expectations.

  16. Coordinate Systems, Numerical Objects and Algorithmic Operations of Computational Experiment in Fluid Mechanics

    Directory of Open Access Journals (Sweden)

    Degtyarev Alexander


    Full Text Available The paper deals with the computer implementation of direct computational experiments in fluid mechanics, constructed on the basis of the approach developed by the authors. The proposed approach allows the use of explicit numerical scheme, which is an important condition for increasing the effciency of the algorithms developed by numerical procedures with natural parallelism. The paper examines the main objects and operations that let you manage computational experiments and monitor the status of the computation process. Special attention is given to a realization of tensor representations of numerical schemes for direct simulation; b realization of representation of large particles of a continuous medium motion in two coordinate systems (global and mobile; c computing operations in the projections of coordinate systems, direct and inverse transformation in these systems. Particular attention is paid to the use of hardware and software of modern computer systems.

  17. Mathematics for quantum mechanics an introductory survey of operators, eigenvalues, and linear vector spaces

    CERN Document Server

    Jackson, John David


    Advanced undergraduates and graduate students studying quantum mechanics will find this text a valuable guide to mathematical methods. Emphasizing the unity of a variety of different techniques, it is enduringly relevant to many physical systems outside the domain of quantum theory.Concise in its presentation, this text covers eigenvalue problems in classical physics, orthogonal functions and expansions, the Sturm-Liouville theory and linear operators on functions, and linear vector spaces. Appendixes offer useful information on Bessel functions and Legendre functions and spherical harmonics.

  18. Analysis of Information Sharing Mechanism in the Food Industry Green Supply Chain Management and Operation Process

    Institute of Scientific and Technical Information of China (English)


    In order to effectively address the issues of environmental pollution and food safety in food industry,the green supply chain management should be used in the food industry.However,information sharing is the basis of supply chain management.For this purpose,on the basis of describing the connotation of food industry green supply chain management,the paper introduces the contents and the effects of information sharing mode in detail.It focuses on the barriers of the implementation of information-sharing mechanisms in the food industry green supply chain management and operation process and analyzes the necessity of using information sharing mechanism among the members of the food industry green supply chain management mode by game theory,so as to strengthen the competitiveness of enterprises through supply chain management.

  19. Foamy oil flow : a laboratory curiosity or a real drive mechanism in field operations?

    Energy Technology Data Exchange (ETDEWEB)

    Maini, B.B. [Calgary Univ., AB (Canada)


    The exceptional performance of primary depletion in many Canadian and Venezuelan heavy oil reservoirs can be attributed to the mechanism of foamy oil flow. It is has been speculated that the solution gas released during depletion remains dispersed in the oil and flows towards the production well in the form of gas-in-oil dispersion. However, most laboratory studies of foamy-oil-flow reveal that the depletion rates required for generating dispersed flow are completely unrealistic in field operations. This study examined whether foamy oil flow is merely a laboratory aberration. The paper defines foamy oil flow and explains how it evolved. A brief review of Canadian field practices was presented along with observations from cold production of heavy oil. The pore-scale mechanisms involved and the interplay between capillary and viscous forces were also discussed along with the conditions under which dispersed flow is generated in field operations. The strengths and weaknesses of several mathematical models proposed for numerical simulation of foamy oil flow were described.

  20. Multidimensional Generalized Functions in Aeroacoustics and Fluid Mechanics. Part 1; Basic Concepts and Operations (United States)

    Farassat, Fereidoun; Myers, Michael K.


    This paper is the first part of a three part tutorial on multidimensional generalized functions (GFs) and their applications in aeroacoustics and fluid mechanics. The subject is highly fascinating and essential in many areas of science and, in particular, wave propagation problems. In this tutorial, we strive to present rigorously and clearly the basic concepts and the tools that are needed to use GFs in applications effectively and with ease. We give many examples to help the readers in understanding the mathematical ideas presented here. The first part of the tutorial is on the basic concepts of GFs. Here we define GFs, their properties and some common operations on them. We define the important concept of generalized differentiation and then give some interesting elementary and advanced examples on Green's functions and wave propagation problems. Here, the analytic power of GFs in applications is demonstrated with ease and elegance. Part 2 of this tutorial is on the diverse applications of generalized derivatives (GDs). Part 3 is on generalized Fourier transformations and some more advanced topics. One goal of writing this tutorial is to convince readers that, because of their powerful operational properties, GFs are absolutely essential and useful in engineering and physics, particularly in aeroacoustics and fluid mechanics.

  1. Crystal structure of the ternary complex of the catalytic domain of human phenylalanine hydroxylase with tetrahydrobiopterin and 3-(2-thienyl)-L-alanine, and its implications for the mechanism of catalysis and substrate activation. (United States)

    Andersen, Ole Andreas; Flatmark, Torgeir; Hough, Edward


    Phenylalanine hydroxylase catalyzes the stereospecific hydroxylation of L-phenylalanine, the committed step in the degradation of this amino acid. We have solved the crystal structure of the ternary complex (hPheOH-Fe(II).BH(4).THA) of the catalytically active Fe(II) form of a truncated form (DeltaN1-102/DeltaC428-452) of human phenylalanine hydroxylase (hPheOH), using the catalytically active reduced cofactor 6(R)-L-erythro-5,6,7,8-tetrahydrobiopterin (BH(4)) and 3-(2-thienyl)-L-alanine (THA) as a substrate analogue. The analogue is bound in the second coordination sphere of the catalytic iron atom with the thiophene ring stacking against the imidazole group of His285 (average interplanar distance 3.8A) and with a network of hydrogen bonds and hydrophobic contacts. Binding of the analogue to the binary complex hPheOH-Fe(II).BH(4) triggers structural changes throughout the entire molecule, which adopts a slightly more compact structure. The largest change occurs in the loop region comprising residues 131-155, where the maximum r.m.s. displacement (9.6A) is at Tyr138. This loop is refolded, bringing the hydroxyl oxygen atom of Tyr138 18.5A closer to the iron atom and into the active site. The iron geometry is highly distorted square pyramidal, and Glu330 adopts a conformation different from that observed in the hPheOH-Fe(II).BH(4) structure, with bidentate iron coordination. BH(4) binds in the second coordination sphere of the catalytic iron atom, and is displaced 2.6A in the direction of Glu286 and the iron atom, relative to the hPheOH-Fe(II).BH(4) structure, thus changing its hydrogen bonding network. The active-site structure of the ternary complex gives new insight into the substrate specificity of the enzyme, notably the low affinity for L-tyrosine. Furthermore, the structure has implications both for the catalytic mechanism and the molecular basis for the activation of the full-length tetrameric enzyme by its substrate. The large conformational change, moving

  2. Cathepsin G Induces Cell Aggregation of Human Breast Cancer MCF-7 Cells via a 2-Step Mechanism: Catalytic Site-Independent Binding to the Cell Surface and Enzymatic Activity-Dependent Induction of the Cell Aggregation

    Directory of Open Access Journals (Sweden)

    Riyo Morimoto-Kamata


    Full Text Available Neutrophils often invade various tumor tissues and affect tumor progression and metastasis. Cathepsin G (CG is a serine protease secreted from activated neutrophils. Previously, we have shown that CG induces the formation of E-cadherin-mediated multicellular spheroids of human breast cancer MCF-7 cells; however, the molecular mechanisms involved in this process are unknown. In this study, we investigated whether CG required its enzymatic activity to induce MCF-7 cell aggregation. The cell aggregation-inducing activity of CG was inhibited by pretreatment of CG with the serine protease inhibitors chymostatin and phenylmethylsulfonyl fluoride. In addition, an enzymatically inactive S195G (chymotrypsinogen numbering CG did not induce cell aggregation. Furthermore, CG specifically bound to the cell surface of MCF-7 cells via a catalytic site-independent mechanism because the binding was not affected by pretreatment of CG with serine protease inhibitors, and cell surface binding was also detected with S195G CG. Therefore, we propose that the CG-induced aggregation of MCF-7 cells occurs via a 2-step process, in which CG binds to the cell surface, independently of its catalytic site, and then induces cell aggregation, which is dependent on its enzymatic activity.

  3. Interfacial effect of the nanostructured Ag2S/Co3O4 and its catalytic mechanism for the dye photodegradation under visible light (United States)

    Qiu, X. P.; Yu, J. S.; Xu, H. M.; Chen, W. X.; Hu, W.; Bai, H. Y.; Chen, G. L.


    In this study, the synthesis of a highly hybrid, heterogeneously structured nanocomposite catalyst consisting of Ag2S nanoparticles dotted on a Co3O4 microrod array is reported. The average diameter and length of the Co3O4 microrods was optimized to be approximately 300 nm and 20 μm, respectively, and the average size of the Ag2S nanoparticles was approximately 10 nm. When the Ag2S nanoparticles were deposited on the Co3O4 microrods, the characteristic optical band gap energy of Co3O4 decreased from 1.26 eV to 1.23 eV, and the intensity of the absorbance peak at 650 nm increased significantly. The catalytic activity of nanosized Ag2S/Co3O4 for the photodegradation of organic contaminants with potassium hydrogen persulfate (PMS) or ozone (O3) was evaluated using basic green 1 dye (BG1) as a model pollutant. In the presence of the hybrid Ag2S/Co3O4 catalyst developed in this study, the complete photodegradation of the BG1 solution was achieved in 20 min and 6 min when PMS and O3 were used, respectively. In addition, the experimental results suggest that the catalytic photodegradation of BG1 using the Ag2S/Co3O4/PMS and Ag2S/Co3O4/O3 processes was dominated by the rad OH and rad O2- radicals, respectively.

  4. Kinetics and mechanism of catalytic hydroprocessing of components of coal-derived liquids. Twentieth quarterly report, February 16, 1984-May 15, 1984

    Energy Technology Data Exchange (ETDEWEB)

    Gates, B.C.; Olson, J.H.; Schuit, G.C.A.; Stiles, A.B.; Petrakis, L.


    Kinetics data have been determined for the catalytic hydroprocessing of the acidic fractions of a heavy distillate of a liquid derived from Powhatan No. 5 coal. A commercial, sulfided Ni-Mo/..gamma..-Al/sub 2/O/sub 3/ catalyst was used in the experiments, carried out at 350/sup 0/C and 120 atm with the coal liquid fractions dissolved in cyclohexane. The feed and hydrotreated products were analyzed by gas chromatography/mass spectrometry. The data were analyzed with group-type methods for compound classes, and results were also obtained for some individual organooxygen compounds. Catalytic hydroprocessing leads to a large increase in the number of compounds and a shift to lower boiling ranges. The data are broadly consistent with reaction networks determined with pure compounds; the most important reactions include aromatic ring hydrogenation, hydrodeoxygenation, and hydrodemethylation. Pseudo first-order rate constants for conversion of the predominant organooxygen compounds are on the order of 10/sup -4/ L/(g of catalyst.s); the reactivity decreases in the order cyclohexylphenol > dimethylhydroxyindane > tetrahydronaphthol > phenylphenol > 1-naphthol. 12 references, 15 figures, 5 tables.

  5. The operation of stochastic heating mechanisms in an electromagnetic standing wave configuration

    Energy Technology Data Exchange (ETDEWEB)

    Gell, Y.; Nakach, R.


    The possibility of the operation of stochastic heating mechanisms of charged particles in a configuration consisting of a left-handed circularly polarized standing electromagnetic wave and a uniform magnetic field, has been studied numerically and theoretically. It is found that such a configuration induces stochasticity, the threshold of which is dependent on two independent parameters, determined by the frequency and the amplitude of the wave and the strength of the magnetic field. From the theoretical analysis, it emerges that the origin of onset of large scale stochasticity is the destabilization of fixed points associated with an equation describing the motion of the particles in an electrostatic-type potential having standing wave characteristics. The comparison of the theoretical predictions with the numerical results is found to be quite satisfactory. Possible applications to realistic plasmas have been discussed.

  6. Reaction Mechanism of Thiophene on Vanadium Oxides under FCC Operating Conditions

    Institute of Scientific and Technical Information of China (English)

    Wang Peng; Zheng Aiguo; Tian Huiping; Long Jun


    The reaction mechanism of thiophene on vanadium oxides under FCC operating conditions had been preliminary studied using in-situ FT-IR analysis of thiophene and atmospheric pressure continuous fixed-bed reaction, followed by characterization via pyridine adsorption-temperature programmed desorption method, and FT-IR and XPS spectra. The research had discovered that, under 500C thiophene could undergo the redox reaction with V2O5, while being converted into CO, CO2 as well as SO2 with its conversion rate reaching 41.2%. At the same time the oxidation number of vanadium decreased. The existence of a few Bronsted acid centers on V2O5 could lead to an increase of H2S yield among the products derived from the reaction with thiophene.

  7. How to Derive the Hilbert-Space Formulation of Quantum Mechanics From Purely Operational Axioms

    CERN Document Server

    D'Ariano, G M


    In the present paper I show how it is possible to derive the Hilbert space formulation of Quantum Mechanics from a comprehensive definition of "physical experiment" and assuming "experimental accessibility and simplicity" as specified by five simple Postulates. This accomplishes the program presented in form of conjectures in the previous paper quant-ph/0506034. Pivotal roles are played by the "local observability principle", which reconciles the holism of nonlocality with the reductionism of local observation, and by the postulated existence of "informationally complete observables" and of a "symmetric faithful state". This last notion allows one to introduce an operational definition for the real version of the "adjoint"--i. e. the transposition--from which one can derive a real Hilbert-space structure via either the Mackey-Kakutani or the Gelfand-Naimark-Segal constructions. Here I analyze in detail only the Gelfand-Naimark-Segal construction, which leads to a real Hilbert space structure analogous to that...

  8. Mechanism and operation parameters of a plasma-driven micro-particle accelerator

    Institute of Scientific and Technical Information of China (English)

    HUANG JianGuo; FENG ChunHua; HAN dianWei; LI HongWei; CAI MingHui; LI XiaoYin; ZHANG ZhenLong; CHEN ZhaoFeng; WANG Long; YANG XuanZong


    There is a large amount of micro debris ranging between millimeters and micrometers in space, which has significant influence on the reliability and life of spacecrafts through long-duration integrated im-pacts and has to be considered in designing a vehicle's suitability to the space environment. In order to simulate the micro-impacts on exposed materials, a plasma-driven micro-particle accelerator was de-veloped. The major processes, including the acceleration, compression and ejection of plasmas, were modeled. By comparing the theoretical simulations with the experimental results, the acceleration mechanism was clarified. Moreover, through a series of experiments, the optimum operation range was investigated, and the acceleration ability was primarily determined.


    DEFF Research Database (Denmark)

    Saleem, Arshad; Lind, Morten


    among electric power utilities to utilize modern information and communication technologies (ICT) in order to improve the automation of the distribution system. In this paper we present our work for the implementation of a dynamic multi-agent based distributed reinforcement learning mechanism......The Electric Power system of Denmark exhibits some unique characteristics. An increasing part of the electricity is produced by local generators called distributed generators DGs. Most of these DGs are connected to network through the distribution system. This situation has created an incentive...... for the islanding operation of the distribution system. Purpose of this system is to dynamically divide the distribution network in different sections (islands), in a fault scenario when they are separated from main utility system, and make them survive on local DGs....

  10. Quantum-mechanical tunneling differential operators, zeta-functions and determinants

    CERN Document Server

    Casahorrán, J


    We consider in detail the quantum-mechanical problem associated with the motion of a one-dimensional particle under the action of the double-well potential. Our main tool will be the euclidean (imaginary time) version of the path-integral method. Once we perform the Wick rotation, the euclidean equation of motion is the same as the usual one for the point particle in real time, except that the potential at issue is turned upside down. In doing so, our double-well potential becomes a two-humped potential. As required by the semiclassical approximation we may study the quadratic fluctuations over the instanton which represents in this context the localised finite-action solutions of the euclidean equation of motion. The determinants of the quadratic differential operators are evaluated by means of the zeta-function method. We write in closed form the eigenfunctions as well as the energy eigenvalues corresponding to such operators by using the shape-invariance symmetry. The effect of the multi-instantons configu...

  11. Quantum mechanics 1. Path-integral formulation and operator formalism; Quantenmechanik 1. Pfadintegralformulierung und Operatorformalismus

    Energy Technology Data Exchange (ETDEWEB)

    Reinhardt, Hugo [Tuebingen Univ. (Germany). Inst. fuer Theoretische Physik


    The first volume of this two-volume textbook gives a modern introduction to the quantum theory, which connects Feynman's path-integral formulation with the traditional operator formalism. In easily understandable form starting from the double-slit experiment the characteristic features and foundations of quantum theory are made accessible by means of the functional-integral approach. Just this approach makes a ''derivation'' of the Schroedinger equation from the principle of the interfering alternatives possible. In the following the author developes the traditional operator formulation of quantum mechanics, which is better suited for practical solution of elementary problems. However he then refers to the functional-integral approach, when this contributes to a better understanding. A further advance of this concept: The functional-integral approach facilitates essentially the later access to quantum field theory. The work is in like manner suited for the self-study as for the deepening accompanying of the course.

  12. Efficient Sustainable Operation Mechanism of Distributed Desktop Integration Storage Based on Virtualization with Ubiquitous Computing

    Directory of Open Access Journals (Sweden)

    Hyun-Woo Kim


    Full Text Available Following the rapid growth of ubiquitous computing, many jobs that were previously manual have now been automated. This automation has increased the amount of time available for leisure; diverse services are now being developed for this leisure time. In addition, the development of small and portable devices like smartphones, diverse Internet services can be used regardless of time and place. Studies regarding diverse virtualization are currently in progress. These studies aim to determine ways to efficiently store and process the big data generated by the multitude of devices and services in use. One topic of such studies is desktop storage virtualization, which integrates distributed desktop resources and provides these resources to users to integrate into distributed legacy desktops via virtualization. In the case of desktop storage virtualization, high availability of virtualization is necessary and important for providing reliability to users. Studies regarding hierarchical structures and resource integration are currently in progress. These studies aim to create efficient data distribution and storage for distributed desktops based on resource integration environments. However, studies regarding efficient responses to server faults occurring in desktop-based resource integration environments have been insufficient. This paper proposes a mechanism for the sustainable operation of desktop storage (SODS for high operational availability. It allows for the easy addition and removal of desktops in desktop-based integration environments. It also activates alternative servers when a fault occurs within a system.

  13. Understanding physiological and degenerative natural vision mechanisms to define contrast and contour operators.

    Directory of Open Access Journals (Sweden)

    Jacques Demongeot

    Full Text Available BACKGROUND: Dynamical systems like neural networks based on lateral inhibition have a large field of applications in image processing, robotics and morphogenesis modeling. In this paper, we will propose some examples of dynamical flows used in image contrasting and contouring. METHODOLOGY: First we present the physiological basis of the retina function by showing the role of the lateral inhibition in the optical illusions and pathologic processes generation. Then, based on these biological considerations about the real vision mechanisms, we study an enhancement method for contrasting medical images, using either a discrete neural network approach, or its continuous version, i.e. a non-isotropic diffusion reaction partial differential system. Following this, we introduce other continuous operators based on similar biomimetic approaches: a chemotactic contrasting method, a viability contouring algorithm and an attentional focus operator. Then, we introduce the new notion of mixed potential Hamiltonian flows; we compare it with the watershed method and we use it for contouring. CONCLUSIONS: We conclude by showing the utility of these biomimetic methods with some examples of application in medical imaging and computed assisted surgery.

  14. Standard guide for mechanical drive systems for remote operation in hot cell facilities

    CERN Document Server

    American Society for Testing and Materials. Philadelphia


    1.1 Intent: 1.1.1 The intent of this standard is to provide general guidelines for the design, selection, quality assurance, installation, operation, and maintenance of mechanical drive systems used in remote hot cell environments. The term mechanical drive systems used herein, encompasses all individual components used for imparting motion to equipment systems, subsystems, assemblies, and other components. It also includes complete positioning systems and individual units that provide motive power and any position indicators necessary to monitor the motion. 1.2 Applicability: 1.2.1 This standard is intended to be applicable to equipment used under one or more of the following conditions: The materials handled or processed constitute a significant radiation hazard to man or to the environment. The equipment will generally be used over a long-term life cycle (for example, in excess of two years), but equipment intended for use over a shorter life cycle is not excluded. The ...

  15. Whole body vibration exposures in forklift operators: comparison of a mechanical and air suspension seat. (United States)

    Blood, Ryan P; Ploger, James D; Johnson, Peter W


    Using a repeated measures design, this study compared differences in whole body vibration (WBV) exposures when 12 forklift operators drove the same forklift with a mechanical suspension and an air suspension seat. A portable PDA-based WBV data acquisition system collected and analysed time-weighted and raw WBV data per ISO 2631-1 and 2631-5 WBV measurement standards. Tri-axial measurements of weighted vibration (A(w)), crest factor, vibration dose values, time-weighted average-peak, raw (+) peak, raw (-) peak and static compression dose (S(ed)) were compared between seats. There were significant differences in z-axis WBV exposures with the air suspension seat, yielding lower WBV exposures. In addition, there were differences between seats in how they attenuated WBV exposures based on the driver's weight. In the mechanical suspension seat, WBV exposures were weight-dependent, with lighter drivers having higher WBV exposures, whereas with the air suspension seat, the same trends were not as prevalent. STATEMENT OF RELEVANCE: This study contributes to the understanding of how different seat suspensions can influence WBV transmission and how some components of vibration transmission are dependent on the weight of the driver. Additional systematic studies are needed to quantify how various factors can influence WBV exposures.

  16. Catalytic combustor for hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Mercea, J.; Grecu, E.; Fodor, T.; Kreibik, S.


    The performance of catalytic combustors for hydrogen using platinum-supported catalysts is described. Catalytic plates of different sizes were constructed using fibrous and ceramic supports. The temperature distribution as well as the reaction efficiency as a function of the fuel input rate was determined, and a comparison between the performances of different plates is discussed.

  17. Adsorption and Catalytic Oxidation of Methane by Indium Oxide Sensors Doped with Platinum

    Directory of Open Access Journals (Sweden)

    V.V. Golovanov


    Full Text Available Differential scanning calorimetry and X-ray photoelectron spectroscopy were used to investigate the mechanism of methane interaction with platinum-doped indium oxide surface. It was shown that sorption processes have a significant impact on the sensor response at the operating temperatures below 370 С for doped Pt/In2O3 and below 500 С for In2O3-based sensors. Above the critical temperatures the sensor response is dominated by the catalytic oxidation of methane. The operating temperature of sensors was decreased on 80 С by doping of the material with Pt 0.5 wt.%. Thus formed PtxIny clusters have a significant effect on the In¬2O3 catalytic properties. The developed sensors demonstrated high sensitivity, small operating parameters range, and low consuming power together with simple production technology.

  18. Intermediate processes and critical phenomena: Theory, method and progress of fractional operators and their applications to modern mechanics

    Institute of Scientific and Technical Information of China (English)

    XU; Mingyu; TAN; Wenchang


    From point of view of physics, especially of mechanics, we briefly introduce fractional operators (with emphasis on fractional calculus and fractional differential equations) used for describing intermediate processes and critical phenomena in physics and mechanics, their progress in theory and methods and their applications to modern mechanics. Some authors' researches in this area in recent years are included. Finally, prospects and evaluation for this subject are made.

  19. Comparison of Carbonyls and BTEX Emissions from a Light Duty Vehicle Fuelled with Gasoline and Ethanol-Gasoline Blend, and Operated without 3-Way Catalytic Converter

    Directory of Open Access Journals (Sweden)

    Asad Naeem Shah


    Full Text Available This paper presents the comparison of unregulated emissions such as carbonyls and BTEX (Benzene, Toluene, Ethyl Benzene, and Xylenes species emanated from a light duty SI (Spark Ignition vehicle E-0 (fuelled on gasoline and E-10 (ethanol-gasoline blend. Meanwhile, the ozone forming potential of these pollutants based on their ozone SR (Specific Reactivity has also been addressed in this study. The experiments were performed on transient as well as steady-state modes in accordance with the standard protocols recommended for light duty vehicle emissions. Carbonyls and BTEX were analyzed by HPLC (High Performance Liquid Chromatography with UV detector and GC/MS (Gas Chromatography/Mass Spectroscopy, respectively. Formaldehyde and acetaldehyde were the predominant components of the carbonyls for E-0 and E-10, respectively. During transient mode, formaldehyde, acrolein + acetone, and tolualdehyde pollutants were decreased but, acetaldehyde emissions increased with E-10 as compared to E-0. The BTEX emissions were also decreased with E-10, relative to E-0. During the steady-state modes, formaldehyde, acrolein + acetone and propionaldehyde were lower, aromatic aldehydes were absent, but acetaldehyde pollutants were higher with E-10 compared to E-0. The BTEX emissions were decreased at medium and higher speed modes however, increased at lower speed mode with E-10 as compared to E-0. Total BTEX emissions were maximal at lower speed mode but, least at medium speed mode for both the fuels. SR of the pollutants was higher over transient cycle of operation, compared with steady-state mode. Relative to E-0, E-10 displayed lower SR during both transient as well as steady-state mode.

  20. Study and Analysis on Naphtha Catalytic Reforming Reactor Simulation

    Institute of Scientific and Technical Information of China (English)

    Liang Ke min; Song Yongji; Pan Shiwei


    A naphtha catalytic reforming unit with four reactors connected in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reaction characteristics based on idealizing the complex naphtha mixture to represent the paraffin, naphthene, and aromatic groups with individual compounds. The simulation results based on above models agree very well with actual operating data of process unit.

  1. A study on naphtha catalytic reforming reactor simulation and analysis

    Institute of Scientific and Technical Information of China (English)

    LIANG Ke-min; GUO Hai-yan; PAN Shi-wei


    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

  2. Quantum dynamics of a macroscopic magnet operating as an environment of a mechanical oscillator (United States)

    Foti, C.; Cuccoli, A.; Verrucchi, P.


    We study the dynamics of a bipartite quantum system in a way such that its formal description keeps holding even if one of its parts becomes macroscopic; the problem is related to the analysis of the quantum-to-classical crossover, but our approach implies that the whole system stays genuinely quantum. The aim of the work is to understand (1) if, (2) to what extent, and possibly (3) how the evolution of a macroscopic environment testifies to the coupling with its microscopic quantum companion. To this purpose we consider a magnetic environment made of a large number of spin-1/2 particles, coupled with a quantum mechanical oscillator, possibly in the presence of an external magnetic field. We take the value of the total environmental spin S constant and large, which allows us to consider the environment as one single macroscopic system, and further deal with the hurdles of the spin-algebra via approximations that are valid in the large-S limit. We find an insightful expression for the propagator of the whole system, where we identify an effective "back-action" term, i.e., an operator acting on the magnetic environment only, and yet missing in the absence of the quantum principal system. This operator emerges as a time-dependent magnetic anisotropy whose character, whether uniaxial or planar, also depends on the detuning between the frequency of the oscillator and the level splitting in the spectrum of the free magnetic system, induced by the possible presence of the external field. The time dependence of the anisotropy is analyzed, and its effects on the dynamics of the magnet, as well as its relation to the entangling evolution of the overall system, are discussed.

  3. Search for an onset mechanism that operates for both CMEs and substorms

    Directory of Open Access Journals (Sweden)

    G. L. Siscoe


    Full Text Available Substorms and coronal mass ejections have been cited as the most accessible examples of the explosive energy conversion phenomenon that seems to characterize one of the behavior modes of cosmic plasmas. This paper addresses the question of whether these two examples – substorms and CMEs – support or otherwise the idea that explosive energy conversion is the result of a single process operating in different places and under different conditions. As a candidate mechanism that might be common to both substorms and CMEs we use the Forbes catastrophe model for CMEs because before testing it appears to have the potential, suitably modified, to operate also for substorms. The essence of the FCM is a sudden onset of an imbalance of the forces acting on an incipient CME. The imbalance of forces causes the CME to start to rise. Beneath the rising CME conditions develop that favor the onset of magnetic reconnection which then releases the CME and assists its expulsion. Thus the signature of the FCM is a temporally ordered sequence in which there is first the appearance of force imbalance which leads to upward (or outward motion of the CME which leads to magnetic reconnection under it which expedites rapid expulsion. We look for the FCM signature in the output of two global magnetospheric MHD simulations that produce substorm-like events. We find the ordered sequence of events as stated but with a significant difference: there is no plasmoid prior to the onset of rapid reconnection, that is, there is no counterpart to the incipient CME on which an imbalance of forces acts to initiate the action in the FCM. If this result – that rapid tailward motion precedes the rapid reconnection of substorm expansion – is ultimately verified by other studies, it suggests that a description of the cause of substorm expansion should identify the cause of the preceding rapid tailward motion, since this leads necessarily to rapid reconnection, whatever the

  4. Crystal Structures of Two Bacterial 3-Hydroxy-3-methylglutaryl-CoA Lyases Suggest a Common Catalytic Mechanism among a Family of TIM Barrel Metalloenzymes Cleaving Carbon-Carbon Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Forouhar,F.; Hussain, M.; Farid, R.; Benach, J.; Abashidze, M.; Edstrom, W.; Vorobiev, S.; Montelione, G.; Hunt, J.; et al.


    The enzyme 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) lyase catalyzes the terminal steps in ketone body generation and leucine degradation. Mutations in this enzyme cause a human autosomal recessive disorder called primary metabolic aciduria, which typically kills victims because of an inability to tolerate hypoglycemia. Here we present crystal structures of the HMG-CoA lyases from Bacillus subtilis and Brucella melitensis at 2.7 and 2.3 {angstrom} resolution, respectively. These enzymes share greater than 45% sequence identity with the human orthologue. Although the enzyme has the anticipated triose-phosphate isomerase (TIM) barrel fold, the catalytic center contains a divalent cation-binding site formed by a cluster of invariant residues that cap the core of the barrel, contrary to the predictions of homology models. Surprisingly, the residues forming this cation-binding site and most of their interaction partners are shared with three other TIM barrel enzymes that catalyze diverse carbon-carbon bond cleavage reactions believed to proceed through enolate intermediates (4-hydroxy-2-ketovalerate aldolase, 2-isopropylmalate synthase, and transcarboxylase 5S). We propose the name 'DRE-TIM metallolyases' for this newly identified enzyme family likely to employ a common catalytic reaction mechanism involving an invariant Asp-Arg-Glu (DRE) triplet. The Asp ligates the divalent cation, while the Arg probably stabilizes charge accumulation in the enolate intermediate, and the Glu maintains the precise structural alignment of the Asp and Arg. We propose a detailed model for the catalytic reaction mechanism of HMG-CoA lyase based on the examination of previously reported product complexes of other DRE-TIM metallolyases and induced fit substrate docking studies conducted using the crystal structure of human HMG-CoA lyase (reported in the accompanying paper by Fu, et al. (2006) J. Biol. Chem. 281, 7526-7532). Our model is consistent with extensive mutagenesis


    Institute of Scientific and Technical Information of China (English)

    朱长健; 姚孝胜


    介绍了中国石化安庆分公司蜡油加氢装置与催化裂解装置的生产运行情况,分析了蜡油加氢精制后对催化裂解装置运行的影响.结果表明:混合蜡油经加氢精制后可以作为优质的催化裂解原料;催化裂解装置产物分布得到显著优化,轻质油收率提高2.89百分点,干气、焦炭等低附加值产物收率下降明显;产品质量显著改善,催化裂解汽油的硫含量、诱导期、烯烃含量、芳烃含量均能达到国Ⅲ排放标准对汽油的要求.%The operation of gas oil hydrotreating unit and deep catalytic cracking (DCC) unit of SINOPEC Anqing Branch is introduced and the influence of hydrotreated feedstock on the operation of DCC unit is analyzed.Results show that the hydrotreated mixed gas oil can be used as a high quality feedstock for DCC unit.The product distributions of DCC unit is improved remarkably: light oil yield increases by 2.89 percentage point, and the yields of dry gas, coke and low value products decrease significantly.Meanwhile, the quality of products is improved greatly as well, items including sulfur content, induction period, olefins content and aromatics content of DCC gasoline can meet the specifications of gasoline for national emission standard Ⅲ.

  6. Unsteady processes in catalytic reactors

    Energy Technology Data Exchange (ETDEWEB)

    Matros, Yu.Sh.


    In recent years a realization has occurred that reaction and reactor dynamics must be considered when designing and operating catalytic reactors. In this book, the author has focussed on both the processes occurring on individual porous-catalyst particles as well as the phenomena displayed by collections of these particles in fixed-bed reactors. The major topics discussed include the effects of unsteady-state heat and mass transfer, the influence of inhomogeneities and stagnant regions in fixed beds, and reactor operation during forced cycling of operating conditions. Despite the title of the book, attention is also paid to the determination of the number and stability of fixed-bed steady states, with the aim of describing the possibility of controlling reactors at unstable steady states. However, this development is somewhat dated, given the recent literature on multiplicity phenomena and process control.

  7. Self-correction coil: operation mechanism of self-correction coil

    Energy Technology Data Exchange (ETDEWEB)

    Hosoyama, K.


    We discuss here the operation mechanism of self-correction coil with a simple model. At the first stage, for the ideal self-correction coil case we calculate the self-inductance L of self-correction coil, the mutual inductance M between the error field coil and the self-correction coil, and using the model the induced curent in the self-correction coil by the external magnetic error field and induced magnetic field by the self-correction coil. And at the second stage, we extend this calculation method to non-ideal self-correction coil case, there we realize that the wire distribution of self-correction coil is important to get the high enough self-correction effect. For measure of completeness of self-correction effect, we introduce the efficiency eta of self-correction coil by the ratio of induced magnetic field by the self-correction coil and error field. As for the examples, we calculate L, M and eta for two cases; one is a single block approximation of self-correction coil winding and the other is a two block approximation case. By choosing the adequate angles of self-correction coil winding, we can get about 98% efficiency for single block approximation case and 99.8% for two block approximation case. This means that by using the self-correction coil we can improve the field quality about two orders.

  8. Helium-filled proportional counter and its operation mechanism at low temperatures

    CERN Document Server

    Isozumi, Y; Kishimoto, S


    The operation mechanism of helium-filled proportional counter (HFPC) at about 4.2 K is explained. Unstable behavior of HFPC is caused by releasing secondary-electron from the cathode by four kinds of active particles such as He sub n sup + , non-resonance photon from excited helium atom, non-resonance photon from He sub 2 sup * (A sup 1 Su sup +) and He sub 2 sup m (a sup 3 Su sup +). On experiments of HFPC behavior at low temperature, the following facts were observed; 1) main charge formation process in the electron avalanche is direct ionization by electron without Hornbeck-Molnar process. Accordingly, the gas amplification factor becomes small at low temperature. 2) Stable helium cation is He sub 2 sup + at room temperature, but cluster at low temperature. Large after-pulse is observed in output signal depends on cluster ion. The probability of secondary-electron emission decreased. The gas gain increased with increasing anode voltage. 3) By decreasing reaction rate of atom and molecule collision at low t...

  9. LBNF Hadron Absorber: Mechanical Design and Analysis for 2.4MW Operation

    Energy Technology Data Exchange (ETDEWEB)

    Hartsell, B. [Fermilab; Anderson, K. [Fermilab; Hylen, J. [Fermilab; Sidorov, V. [Fermilab; Tariq, S. [Fermilab


    Fermilab’s Long-Baseline Neutrino Facility (LBNF) requires an absorber, essentially a large beam dump consisting of actively cooled aluminum and steel blocks, at the end of the decay pipe to stop leftover beam particles and provide radiation protection to people and groundwater. At LBNF’s final beam power of 2.4 MW and assuming the worst case condition of a 204 m long helium filled decay pipe, the absorber is required to handle a heat load of about 750 kW. This results in significant thermal management challenges which have been mitigated by the addition of an aluminum ‘spoiler’ and ‘sculpting’ the central portion of the aluminum core blocks. These thermal effects induce structural stresses which can lead to fatigue and creep considerations. Various accident conditions are considered and safety systems are planned to monitor operation and any accident pulses. Results from these thermal and structural analyses will be presented as well as the mechanical design of the absorber. The design allows each of the core blocks to be remotely removed and replaced if necessary. A shielded remote handling structure is incorporated to hold the hadron monitor when it is removed from the beam.

  10. Custos operacionais da colheita mecanizada do cafeeiro Operational costs of mechanized harvest of coffee

    Directory of Open Access Journals (Sweden)

    Ezequiel de Oliveira


    Full Text Available O objetivo desse trabalho foi avaliar os custos operacionais da colheita mecanizada do cafeeiro em duas passadas da colhedora. O trabalho foi desenvolvido na Fazenda Capetinga, Município de Boa Esperança, MG. Os experimentos foram realizados com duas passadas da colhedora, definidas de acordo com o índice de ocorrência de grãos verdes na planta. Na primeira passada, com média de 30% de grãos verdes, a velocidade foi fixada em torno de 0,45 m s-1, tendo-se variado as vibrações em 10,83, 12,50, 14,17 e 15 Hz (tratamentos T1, T2, T3 e T4, respectivamente. Na segunda passada, realizada sobre as mesmas parcelas da primeira passada, com média de 10% de grãos verdes, a vibração foi fixada em 16,67 Hz, tendo-se variado as velocidades em 0,60, 0,72, 0,29 e 0,45 m s-1 (tratamentos T1, T2, T3 e T4, respectivamente. Utilizou-se delineamento inteiramente casualizado, com quatro repetições, em parcelas aleatórias com 40 plantas por linha, em média. Para a análise dos custos de colheita, comparou-se a colheita mecanizada com a manual. A redução do custo total da colheita mecanizada é de 62,36% em relação à colheita manual, colhendo com a velocidade operacional de 0,45 m s-1 nas duas passadas.The objective of this work was to evaluate the operational costs of mechanized harvest of coffee in two passes of the harvester. The work was carried out in the Capetinga Farm, Boa Esperança City, State of Minas Gerais, Brazil. The experiments were made with two passes of the harvester, defined according to the green grain index. In the first pass, with average of 30% green grains, velocity was fixed around 0.45 m s-1, and vibration varied at 10.85, 12.50 14.17 and 15 Hz (treatments T1, T2, T3 and T4. In the second pass, carried out in the same plots of the first pass, with average of 10% green grains, vibration was fixed in 16.67 Hz, and velocity varied at 0.60, 0.72, 0.29 and 0.45 m s-1 (treatments T1, T2, T3 and T4. It was utilized a completely

  11. Shape and catalytic mechanism of RuO{sub 2} particles at CO oxidation reaction conditions. First-principles based multi-scale modeling

    Energy Technology Data Exchange (ETDEWEB)

    Reuter, Karsten [TU Muenchen (Germany). Lehrstuhl fuer Theoretische Chemie


    For model catalyst studies on low-index single-crystal surfaces close agreement between detailed measurements and quantitative microkinetic modeling can increasingly be achieved. However, for 'real' catalyst particles, such structure-morphology-activity relationships are only scarcely established. This is prototypically reflected by the situation for RuO{sub 2}, as a most active catalyst for CO oxidation. Here, existing first-principles kinetic modeling is restricted to just one facet, namely the RuO{sub 2}(110) surface, which is not able to fully account for activity data obtained from polycrystalline RuO{sub 2} powder catalysts. The overarching objective of this project was correspondingly to close this gap and demonstrate that similarly close agreement as for individual single-crystal model catalysts can also be achieved for catalyst particles. Specifically, we addressed experiments where an intact RuO{sub 2} bulk structure is conserved, and establish the atomic-scale structure and reactivity of other RuO{sub 2} low-index facets under the gas-phase conditions characteristic for catalytic CO oxidation.

  12. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism (United States)

    Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong


    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.

  13. Comparing the catalytic oxidation of ethanol at the solid-gas and solid-liquid interfaces over size-controlled Pt nanoparticles: striking differences in kinetics and mechanism. (United States)

    Sapi, Andras; Liu, Fudong; Cai, Xiaojun; Thompson, Christopher M; Wang, Hailiang; An, Kwangjin; Krier, James M; Somorjai, Gabor A


    Pt nanoparticles with controlled size (2, 4, and 6 nm) are synthesized and tested in ethanol oxidation by molecular oxygen at 60 °C to acetaldehyde and carbon dioxide both in the gas and liquid phases. The turnover frequency of the reaction is ∼80 times faster, and the activation energy is ∼5 times higher at the gas-solid interface compared to the liquid-solid interface. The catalytic activity is highly dependent on the size of the Pt nanoparticles; however, the selectivity is not size sensitive. Acetaldehyde is the main product in both media, while twice as much carbon dioxide was observed in the gas phase compared to the liquid phase. Added water boosts the reaction in the liquid phase; however, it acts as an inhibitor in the gas phase. The more water vapor was added, the more carbon dioxide was formed in the gas phase, while the selectivity was not affected by the concentration of the water in the liquid phase. The differences in the reaction kinetics of the solid-gas and solid-liquid interfaces can be attributed to the molecular orientation deviation of the ethanol molecules on the Pt surface in the gas and liquid phases as evidenced by sum frequency generation vibrational spectroscopy.

  14. DRIFT studies on promotion mechanism of H3PW12O40 in selective catalytic reduction of NO with NH3. (United States)

    Weng, Xiaole; Dai, Xiaoxia; Zeng, Qingshan; Liu, Yue; Wu, Zhongbiao


    Heteropoly acids (HPAs) have been effectively utilized in selective catalytic reduction (SCR) of NO to improve the NH3 absorption capacity and alkaline/alkali metal resistance for SCR catalysts. However, despite the promise on super-acidities, their other properties that would work on SCR process are still lack of exploration. In this study, a 12-tungstaphosphoric acid (H3PW12O40, HPW) was selected to modify a well-reported CeO2 catalyst. The resulted CeO2/HPW catalyst was subsequently utilized for SCR of NO with excess NH3, which revealed a significantly promoted performance in SCR reaction. DRIFT analyses showed that the unique NO2 absorption capacity of HPW could prevent the NO2 being further oxidized into nitrate species and the abundant Brønsted acid sites could effectively retain the NH3, avoiding them being over-oxidized at evaluated temperatures. The presence of NO2 was demonstrated able to induce a so called "fast SCR" reaction over the CeO2/HPW catalyst, which effectively facilitated the SCR reaction. Furthermore, we have also constructed a CeO2@HPW catalyst, which showed an enhanced SO2 poisoning resistance in SCR reaction.

  15. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)


    textabstractThe three different areas and the examples have illustrated several catalytic functions of standards for innovation. First, the standardisation process reduces the time to market of inventions, research results and innovative technologies. Second, standards themselves promote the diffusi

  16. Catalytic Synthesis Lactobionic Acid

    Directory of Open Access Journals (Sweden)

    V.G. Borodina


    Full Text Available Gold nanoparticles are obtained, characterized and deposited on the carrier. Conducted catalytic synthesis of lactobionic acid from lactose. Received lactobionic acid identify on the IR spectrum.

  17. Catalytic distillation process (United States)

    Smith, Jr., Lawrence A.


    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  18. Catalytic distillation process (United States)

    Smith, L.A. Jr.


    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  19. Catalytic distillation structure (United States)

    Smith, L.A. Jr.


    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.


    Directory of Open Access Journals (Sweden)

    F. Panteleenko


    Full Text Available The paper presents results of investigations on structure and mechanical properties of technological equipment elements made of heat-resistant steels. A scale of chrome and molybdenum steel microstructure degradation based on evaluation of  coagulated carbide size and material mechanical properties (a point from 0-operation without time limits, up to 4-operation prohibition has been proposed in the paper. It has been  established that an analysis of  steel microstructure directly on equipment elements by means of a portable microscope is an efficient express method for evaluation of equipment condition and structures due to control of material structure degradation rate of a diagnosed object.

  1. Effects of aggregating forests, establishing forest road networks, and mechanization on operational efficiency and costs in a mountainous re-gion in Japan

    Institute of Scientific and Technical Information of China (English)

    Kazuhiro Aruga; Gyo Hiyamizu; Chikara Nakahata; Masashi Saito


    We investigated forest road networks and forestry operations before and after mechanization on aggregated forestry operation sites. We developed equations to estimate densities of road networks with average slope angles, operational efficiency of bunching operations with road network density, and average forwarding distances with operation site areas. Subsequently, we analyzed the effects of aggregating forests, establishing forest road networks, and mechanization on operational efficiency and costs. Six ha proved to be an appropriate operation site area with minimum operation expenses. The operation site areas of the forest owners’ cooperative in this region aggregated approximately 6 ha and the cooperative conducted forestry operations on aggregated sites. Therefore, 6 ha would be an appropriate operation site area in this region. Regarding road network density, higher-density road networks increased operational expenses due to the higher direct operational expenses of strip road establishment. Therefore, road network density should be reduced to approximately 200 m⋅ha-1 within average pre-yarding dis-tances on which a grapple loader could conduct bunching without winching. With larger stem volumes a larger reduction in operational expenses occurred for the mechanized operation system compared to the conventional operation system. However, with smaller stem volumes, the operational expenses for the mechanized operation system were higher than for the conventional operation system. Therefore, the appropriate operation system and machine sizes should be determined based on stem volumes.

  2. The optimization, kinetics and mechanism of m-cresol degradation via catalytic wet peroxide oxidation with sludge-derived carbon catalyst. (United States)

    Wang, Yamin; Wei, Huangzhao; Zhao, Ying; Sun, Wenjing; Sun, Chenglin


    The sludge-derived carbon catalyst modified with 0°C HNO3 solution was tested in catalytic wet peroxide oxidation of m-cresol (100mgL(-1)) with systematical mathematical models and theoretical calculation for the first time. The reaction conditions were optimized by response surface methodology (RSM) as T=60°C, initial pH=3.0, C0,H2O2(30%)=1.20gL(-1) (lower than the stoichiometric amount of 1.80gL(-1)) and Ccat=0.80gL(-1), with 96% of m-cresol and 47% of TOC converted after 16min and 120min of reaction, respectively, and ξ (mg TOC/g H2O2 fed)=83.6mg/g. The end time of the first kinetic period in m-cresol model was disclosed to be correlated with the fixed residue m-cresol concentration of about 33%. Furthermore, the kinetic constants in models of TOC and H2O2 exactly provide convincing proof of three-dimensional response surfaces analysis by RSM, which showed the influence of the interaction between organics and H2O2 on effective H2O2 utilization. The reaction intermediates over time were identified by gas chromatography-mass spectrometer based on kinetics analysis. Four degradation pathways for m-cresol were proposed, of which the possibility and feasibility were well proven by frontier molecule orbital theory and atomic charge distribution via density functional theory method.

  3. Degradation of atenolol by UV/peroxymonosulfate: kinetics, effect of operational parameters and mechanism. (United States)

    Liu, Xiaowei; Zhang, Tuqiao; Zhou, Yongchao; Fang, Lei; Shao, Yu


    Photoactivation of peroxymonosulfate (PMS) with UV (254nm) irradiation was used to generate the SO4(-)-based advanced oxidation process, which was adopted to degrade atenolol (ATL) in water. The second-order reaction rate constants of ATL with HO and SO4(-) were determined, and the effects of operational parameters (dose of PMS, solution pH, HCO3(-), humic acids (HA), and N2 bubbling) were evaluated as well. Finally the main transformation intermediates were identified and possible degradation pathways were proposed. The results showed that there was a linear positive correlation between the degradation rate of ATL and specific dose of PMS (1-16M PMS/M ATL). Increasing solution pH from 3 to 9 promoted elimination of ATL due to the pH-dependent effect of PMS photodecomposition, while further pH increase from 9 to 11 caused slowing down of degradation because of apparent conversion of HO to SO4(-). 1-8mM HCO3(-) exerted no more than 5.3% inhibition effect on ATL destruction, suggesting HCO3(-) was a weak inhibitor. Absorption (or complexation) and photosensitized oxidation induced by HA improved ATL degradation during the first minute of degradation process, whereas photon competition and radical scavenging effects became the leading role afterward. Bubbling with nitrogen enhanced the degradation rate due to the stripping of dissolved oxygen. Hydroxylation of aromatic ring, cleavage of ether bond, oxidation of primary and secondary amine moieties, and dimerization were involved in the degradation mechanism of ATL by UV/PMS.

  4. Degradation mechanism of AlInGaP light emitting diodes during PMMA encapsulation and operation

    Energy Technology Data Exchange (ETDEWEB)

    Preuss, S.


    In this thesis we investigate the degradation mechanism of AlInGaP light emitting diodes (LEDs) during encapsulation and operation. The AlInGaP LEDs are encapsulated using an injection moulding tool. The molded part acts as physical housing as well as tailors the radiation pattern. Thus a narrow light beam with a spread angle of {alpha}=10 has been observed. The LED temperature has been measured by the voltage variation of the LED which is caused by the temperature change at a constant current. Thus the thermal load of the LED chips during the encapsulation process is investigated. To verify the temperature measurement a simulation based on the finite element method has been carried out. The experimental and theoretical data are in good agreement. The LED properties are investigated before and after the encapsulation. The results are compared and we found a reduction of the serial resistance and an enhanced luminous efficiency. The peak emission energy remained constant, but a peak broadening of {delta}E=9meV has been observed. A slight polarisation of the emitted light is an indication for a polarization effect of the polymethylmethacrylat (PMMA) housing. Accelerated degradation experiments using high forward currents are performed to estimate the lifetime of the PMMA encapsulated LEDs. A diffusion model is presented to explain the decay in luminous flux versus degradation time and degradation current. We believe that the reduction of quantum efficiency is caused by p-type dopant diffusion into the active layer where it acts as a non-radiative recombination centre. Using this model we determine the lifetime under the recommended drive current of I=20mA. The resulting lifetime is t=1.5.10{sup 6}h using a reduction of 50% in the luminous flux as failure criteria. (orig.)

  5. Numerical and experimental investigation on the performance of lean burn catalytic combustion for gas turbine application (United States)

    Yin, Juan; Weng, Yi-wu; Zhu, Jun-qiang


    This manuscript presents our numerical and experimental results regarding the performance characteristics of lean burn catalytic combustion for gas turbine application. The reactant transport was assumed to be controlled by both bulk diffusion as well as surface kinetics, implemented by means of an approximate reaction rate equation and empirical coefficients to incorporate reaction mechanism. Experimental and numerical results were compared to examine the effects of methane mole fraction, inlet temperature, operating pressure, velocity and hydrogen species on combustion intensity. The results indicate that inlet temperature is the most significant parameter that impacts operation of the catalytic combustor and the most effective methods for improving the methane conversion are increasing the inlet temperature and increasing the methane mole fraction. Simulations from 1D heterogeneous plug flow model can capture the trend of catalytic combustion and describe the behavior of the catalytic monolith in detail. The addition of hydrogen will provide heat release by the exothermic combustion reaction so that the reactants reach a temperature at which methane oxidation can light-off.

  6. Effect of operating frequency and phase angle on performance of Alpha Stirling cryocooler driven by a novel compact mechanism (United States)

    Sant, K. D.; Bapat, S. L.


    Amongst the mechanical cryocoolers in use, Stirling cycle cryocoolers exhibit the desirable features such as high efficiency, low specific power consumption, small size and mass and large mean time before failure. Stirling cycle cryocooler of Alpha configuration exhibits better theoretical performance as compared to Gamma. However, the theory could not be put into practice due to unavailability of compatible drive mechanism for Alpha cryocooler providing large stroke to diameter ratio. The concept of novel compact drive mechanism can be made functional to operate miniature Alpha Stirling cryocoolers. It allows the use of multicylinder system while converting rotary motion to reciprocating. This permits the drive mechanism to be employed for driving different configurations of Stirling cryocooler simultaneously. This drive is capable of providing large stroke to diameter ratio compared to other drive mechanisms generally in use for the purpose. A stroke to diameter ratio of three is chosen in the present work and the drive dimensions are calculated for four piston-cylinder arrangements with 90° phase difference between adjacent arrangements providing two Alpha Stirling cryocoolers working simultaneously. It has to be noted that the coolers operate at half the frequency of the motor used. As the two coolers operate at phase difference of 180°, during compression stroke of one unit, the suction stroke occurs for the other unit. Due to power output of second unit, the combined peak torque requirement falls by 26.81% below the peak torque needed when one unit is operated separately. This allows for use of a comparatively lower torque motor. The practicability of the drive ensuring smooth operation of the system is decided based on comparison between torque availability from the motor and torque requirement of the complete unit. The second order method of cyclic (or thermodynamic) analysis provides a simple computational procedure useful for the design of Stirling

  7. Studies on the function and catalytic mechanism of O-methyltransferases SviOMT02, SviOMT03 and SviOMT06 from Streptomyces virginiae IBL14. (United States)

    Zhang, Yan; Han, Mao-Zhen; Zhu, Shu-Liang; Li, Man; Dong, Xiang; Luo, Xue-Cai; Kong, Zhe; Lu, Yun-Xia; Wang, Shu-Yan; Tong, Wang-Yu


    To identify the fuctions of the nine putative O-methyltransferase genes in Streptomyces virginiae IBL14, the evolutionary and functional relationship of these genes in its 8.0 Mb linear chromosome was set up via sequence comparison with those of other Streptomyces species. Further, the functions and catalytic mechanism of the three genes sviOMT02, sviOMT03 and sviOMT06 from this strain were studied through experimental and computational approaches. As a result, the nine putative O-methyltransferases belong to methyltransf_2 superfamily, amdomet-MTases superfamily, and leucine carboxyl methyltransferase superfamily, and are phylogenetically close to those of Streptomyces sp. C. The products of genes sviOMT03 and sviOMT06 could catalyze O-methylation of caffeic acid to form ferulic acid. Computational analysis indicated that the O-methylation mechanism of SviOMT03 and SviOMT06 proceeds from a direct transfer of the SAM-methyl group to caffeic acid with inversion of symmetry aided by a divalent metal ion in a SN2-like mechanism. Particularly, the conservative polar amino acid residues in SviOMT03 and SviOMT06, including Lys143 that reacts with caffeic acid, Ser74, Asp140 and Tyr149 that react with S-adenosyl methionine, and His142 (SviOMT03) or His171 (SviOMT06) that transfers the 3-hydroxyl proton of substrate caffeic acid, probably be essential in their O-methylation.

  8. Possible involvement of membrane lipids peroxidation and oxidation of catalytically essential thiols of the cerebral transmembrane sodium pump as component mechanisms of iron-mediated oxidative stress-linked dysfunction of the pump's activity

    Directory of Open Access Journals (Sweden)

    T.I. Omotayo


    Full Text Available The precise molecular events defining the complex role of oxidative stress in the inactivation of the cerebral sodium pump in radical-induced neurodegenerative diseases is yet to be fully clarified and thus still open. Herein we investigated the modulation of the activity of the cerebral transmembrane electrogenic enzyme in Fe2+-mediated in vitro oxidative stress model. The results show that Fe2+ inhibited the transmembrane enzyme in a concentration dependent manner and this effect was accompanied by a biphasic generation of aldehydic product of lipid peroxidation. While dithiothreitol prevented both Fe2+ inhibitory effect on the pump and lipid peroxidation, vitamin E prevented only lipid peroxidation but not inhibition of the pump. Besides, malondialdehyde (MDA inhibited the pump by a mechanism not related to oxidation of its critical thiols. Apparently, the low activity of the pump in degenerative diseases mediated by Fe2+ may involve complex multi-component mechanisms which may partly involve an initial oxidation of the critical thiols of the enzyme directly mediated by Fe2+ and during severe progression of such diseases; aldehydic products of lipid peroxidation such as MDA may further exacerbate this inhibitory effect by a mechanism that is likely not related to the oxidation of the catalytically essential thiols of the ouabain-sensitive cerebral electrogenic pump.

  9. Catalytic reforming feed characterisation technique

    Energy Technology Data Exchange (ETDEWEB)

    Larraz Mora, R.; Arvelo Alvarez, R. [Univ. of La Laguna, Chemical Engineering Dept., La Laguna (Spain)


    The catalytic reforming of naphtha is one of the major refinery processes, designed to increase the octane number of naphtha or to produce aromatics. The naphtha used as catalytic reformer feedstock usually contains a mixture of paraffins, naphthenes, and aromatics in the carbon number range C{sub 6} to C{sub 10}. The detailed chemical composition of the feed is necessary to predict the aromatics and hydrogen production as well as the operation severity. The analysis of feed naphtha is usually reported in terms of its ASTM distillation curve and API or specific gravity. Since reforming reactions are described in terms of lumped chemical species (paraffins, naphthenes and aromatics), a feed characterisation technique should be useful in order to predict reforming operating conditions and detect feed quality changes. Unfortunately online analyzer applications as cromatography or recently introduced naphtha NMR [1] are scarce in most of refineries. This work proposes an algorithmic characterisation method focusing on its main steps description. The method could help on the subjects previously described, finally a calculation example is shown. (orig.)

  10. Investigation of switching mechanism in HfOx-ReRAM under low power and conventional operation modes (United States)

    Feng, Wei; Shima, Hisashi; Ohmori, Kenji; Akinaga, Hiroyuki


    Low-power resistive random access memory (LP-ReRAM) devices have attracted increasing attention owing to their advantages of low operation power. In this study, a vertical-type LP-ReRAM consisting of TiN/Ti/HfO2/TiN structure was fabricated. The switching mechanism for LP-ReRAM was elucidated as the conductive filament mechanism for conventional mode, and an interface-type switching mechanism for low power mode was proposed. The analysis of low frequency noise shows that power spectral density (PSD) is approximately proportional to 1/f for conventional operation mode. Nevertheless, for low power mode, the PSD of low resistance state (LRS) is proportional to 1/f, while that of high resistance state (HRS) is clear proportional to 1/f2. The envelope of multiple Lorentzian spectra of 1/f2 characteristics due to different traps reveals the characteristics of 1/f. For HRS of low power mode, a limited number of traps results in a characteristic of 1/f2. During the set process, the number of oxygen vacancies increases for LRS. Therefore, the PSD value is proportional to 1/f. Owing to the increase in the number of traps when the operation mode changes to conventional mode, the PSD value is proportional to 1/f. To the best of our knowledge, this is the first study that reveals the different noise characteristics in the low power operation mode from that in the conventional operation mode.

  11. Reductive removal of nitrate by electrochemistry/catalytic hydrogenation coupling process: kinetics and mechanism%电化学/催化加氢工艺去除硝酸盐的动力学及机理

    Institute of Scientific and Technical Information of China (English)

    张志强; 徐勇鹏; 时文歆; 张瑞君; 鲍现; 崔福义


    为解决地下水硝酸盐(NO3--N)污染问题,采用电化学/催化加氢耦合工艺对其进行去除,重点考察该工艺对NO3--N的降解动力学及反应机理.结果表明,电化学/催化加氢耦合工艺在厌氧条件下能够在短时间内将NO3--N完全去除,去除速率(以N计)可达72.6 mg.L-1.h-1 ,反应符合二级反应动力学规律,常数k=0.005 5 cm2.mA-1.min-1 . 水中NO3--N一部分由电化学反硝化降解去除,另一部分由催化加氢还原去除,两种反应通过电解水产H2反应耦联成为一个整体,宏观上符合电化学反硝化机理.%The kinetics and mechanism in the electrochemistry/catalytic hydrogenation ( E/C ) coupling process, which was employed to remove nitrate ( NO3--N ) from groundwater, was investigated in this paper. The results demonstrated that the NO3--N could be rapidly removed by E/C under anoxic conditions, and the degradation efficiency of NO3--N followed the increasing current density(ID) with observed second order reaction rate and the constant( k ) value of 0. 005 5 cm2·mA-1·min-1 . The NO3--N reductive by E/C with two kinds of reactions, electrochemistry denitrification and catalytic reduction, both of which aggregated by the reaction of brine electrolysis.

  12. The Catalytic Mechanism of Sorbitol Dehydrogenase and Its Role in the Process of Diapause of Different Species%山梨醇脱氢酶作用机制及其与滞育的关系

    Institute of Scientific and Technical Information of China (English)



    Sorbitol dehydrogenase is a key enzyme in the polyol pathway,which oxidizes D-sorbitol,L-iditol,D-glucitol,D-xylitol,D-galactitol into fructose.The catalytic process needs the combination of Zinc and NADH.The Sorbitol dehydrogenase inhibitor binds to the SDH-NADH complex and competitive with fructose.SDH plays a key role in the process of termination of diapause,and of redevelopment of embryo of many different species.This review summarizes the structure and catalytic mechanism of SDH,and its role in the process of diapause of different species.%山梨醇脱氢酶(sorbitol dehydrogenase或SDH)是多元醇代谢通路中的关键酶,可将底物D-山梨醇、L-艾杜淳、D-木糖醇、D-半乳糖醇等氧化成果糖。催化需要金属离子Zinc和辅酶NAD+。SDH特异性抑制剂直接作用于SDH-NADH复合体,通过阻止产物的释放而抑制酶反应。在近些年对于不同生物打破滞育的研究中发现SDH是滞育胚胎再度开始发育的关键酶。对SDH结构,催化机制以及其与不同物种滞育之间关系的研究进展进行综述。

  13. New insights into the activation mechanism of store-operated calcium channels:roles of STIM and Orai

    Institute of Scientific and Technical Information of China (English)

    Rui-wei GUO; Lan HUANG


    The activation of Ca2+ entry through store-operated channels by agonists that deplete Ca2+ from the endoplasmic reticulum (ER)is a ubiquitous signaling mechanism,the molecular basis of which has remained elusive for the past two decades.Store-operated Ca2+-release-activated Ca2+(CRAC)channels constitute the sole pathway for Ca2+ entry following antigen-receptor engagement.In a set of breakthrough studies over the past two years,stromal interaction molecule l(STIM1,tbe ER Ca2+ sensor) and Orail(a pore-forming subunit of the CRAC channel)have been identified.Here we review these recent studies and the insights they provide into the mechanism of store-operated Ca2+ channels(SOCCs).

  14. The deactivation mechanism of Cl on Ce/TiO2 catalyst for selective catalytic reduction of NO with NH3 (United States)

    Yang, Ning-zhi; Guo, Rui-tang; Pan, Wei-guo; Chen, Qi-lin; Wang, Qing-shan; Lu, Chen-zi; Wang, Shu-xian


    The poisoning mechanism of Cl on Ce/TiO2 catalyst was investigated based on temperature programmed desorption (TPD) and the in situ diffuse reflectance infrared transform spectroscopy (DRIFT) studies. The results of NH3-TPD and NO-TPD indicated that the addition of Cl on Ce/TiO2 catalyst would inhibit the adsorption of NH3 species and NOx species on it. As can be seen from the results of in situ DRIFT study, the NH3-SCR reaction over Ce/TiO2 and Ce/TiO2-Cl were all followed both the Eley-Rideal mechanism and the Langmuir-Hinshelwood mechanism. And the decreased adsorption ability of NH3 species and NOx species on the surface of Ce/TiO2-Cl should be mainly responsible for its low SCR activity.

  15. Design Optimization of Mechanical Components Using an Enhanced Teaching-Learning Based Optimization Algorithm with Differential Operator

    Directory of Open Access Journals (Sweden)

    B. Thamaraikannan


    Full Text Available This paper studies in detail the background and implementation of a teaching-learning based optimization (TLBO algorithm with differential operator for optimization task of a few mechanical components, which are essential for most of the mechanical engineering applications. Like most of the other heuristic techniques, TLBO is also a population-based method and uses a population of solutions to proceed to the global solution. A differential operator is incorporated into the TLBO for effective search of better solutions. To validate the effectiveness of the proposed method, three typical optimization problems are considered in this research: firstly, to optimize the weight in a belt-pulley drive, secondly, to optimize the volume in a closed coil helical spring, and finally to optimize the weight in a hollow shaft. have been demonstrated. Simulation result on the optimization (mechanical components problems reveals the ability of the proposed methodology to find better optimal solutions compared to other optimization algorithms.


    Institute of Scientific and Technical Information of China (English)

    刘化章; 李小年; 胡樟能; 岑亚青; 傅冠平


    用高压氨合成催化剂性能评价装置,研究了反应温度、压力、空速、惰性气体含量、氢氮比和催化剂粒度对A301催化剂活性的影响。A301催化剂在15 MPa下的最适反应温度在430~480℃,在7 MPa下在376~450℃,比A110-2低15~35℃。A301催化剂的最佳H2,N2摩尔比nm在450℃时为2.55~3.0,在400℃时为2.23~2.55,在350℃时为1.76~2.22, 并可用nm =1.50+1.49(cNH3/c*NH3)来表示。惰性气体含量会使催化剂活性大幅度降低,每当惰性气体含量增加1%,出口氨浓度(氨净值)平均降低0.2%~0.35%。颗粒大小对活性或反应速率有严重的影响,其内表面利用率受反应温度和催化效率两个因素的影响,对于高活性的A301催化剂,催化效率的因素起主要作用。根据实验结果和合成氨反应的基本理论,讨论并提出了A301催化剂在合成氨生产中的最佳操作工艺条件。%The influences of temperature, pressure, space velocity, concentration of inert gas, ratio of hydrogen to nitrogen and particle size on the activity of A301 catalyst were investigated. The optimal reaction temperatures for A301 catalyst are in the range of 430~480℃ at 15MPa of pressure and 376~450℃ at 7MPa of pressure, 15~35℃ lower than A110-2 catalyst. The optimal ratios of hydrogen to nitrogen nm for A301 catalyst are 2.55~3.0, 2.23~2.55 and 1.76~2.22 at temperature of 450, 400 and 350℃ respectively, and may be expressed by equation of nm =1.50+1.49(cNH3/cNH3*). The more the content of inert gas (CH4+Ar), the lower the outlet ammonia concentration. When the content of inert gas increased by one percent, the outlet ammonia concentration lowered 0.2%~0.35%. The use ratio of inner face of a catalyst is not only related to the particle size but also to temperature and catalytic efficiency. But the catalytic efficiency acts mainly for high active A301 catalyst. According to the experiment results and the

  17. Catalytic Amination of Alcohols, Aldehydes, and Ketones (United States)

    Klyuev, M. V.; Khidekel', M. L.


    Data on the catalytic amination of alcohols and carbonyl compounds are examined, the catalysts for these processes are described, and the problems of their effectiveness, selectivity, and stability are discussed. The possible mechanisms of the reactions indicated are presented. The bibliography includes 266 references.

  18. Determination of the structure and catalytic mechanism of Sorghum bicolor caffeic acid O-methyltransferase and the structural impact of three brown midrib12 mutations (United States)

    With S-adenosylmethionine (SAM) acting as the methyl donor, caffeic acid O-methyltransferase from Sorghum bicolor (SbCOMT) methylates the 5-hydroxyl group of its preferred substrate, 5-hydroxyconiferaldehyde, to form sinapaldehyde. In order to determine the mechanism of SbCOMT and understand the red...

  19. The deactivation mechanism of Pb on the Ce/TiO2 catalyst for the selective catalytic reduction of NOx with NH3: TPD and DRIFT studies. (United States)

    Wang, Shu-Xian; Guo, Rui-Tang; Pan, Wei-Guo; Li, Ming-Yuan; Sun, Peng; Liu, Shu-Ming; Liu, Shuai-Wei; Sun, Xiao; Liu, Jian


    It was well recognized that Pb had a poisoning effect on a SCR catalyst. In this study, the deactivation mechanism of Pb on the Ce/TiO2 catalyst was investigated based on the characterization results of TPD and in situ DRIFT studies. It was found that the addition of Pb on the Ce/TiO2 catalyst not only inhibited the adsorption and activation of NH3 species, but also led to the decrease of the activity of adsorbed NH3 species in the SCR reaction. The adsorption of NOx species and the oxidation of NO by O2 over the Ce/TiO2 catalyst were also suppressed by the addition of Pb, while the reactivity of adsorbed NO2 species did not decrease. Moreover, the results revealed that the NH3-SCR reaction over the Ce/TiO2 catalyst followed both the E-R and L-H mechanisms, while the NH3-SCR reaction over Ce/TiO2-Pb was mainly controlled by the L-H mechanism. The contributions of the L-H mechanism to the SCR reactions over Ce/TiO2 and Ce/TiO2-Pb decreased with increasing reaction temperature. The deactivation of Ce/TiO2-Pb was mainly attributed to the suppressed NH3 adsorption and activation, accompanied by the inhibited NO oxidation and the decrease of Brønsted acid sites.

  20. Adsorption and Catalytic Oxidation of Methane by Indium Oxide Sensors Doped with Platinum


    V.V. Golovanov; B.V. Nazarchuk; V.V.  Golovanova


    Differential scanning calorimetry and X-ray photoelectron spectroscopy were used to investigate the mechanism of methane interaction with platinum-doped indium oxide surface. It was shown that sorption processes have a significant impact on the sensor response at the operating temperatures below 370 С for doped Pt/In2O3 and below 500 С for In2O3-based sensors. Above the critical temperatures the sensor response is dominated by the catalytic oxidation of methane. The operating temperature of...

  1. Catalytic hydrotreating process (United States)

    Karr, Jr., Clarence; McCaskill, Kenneth B.


    Carbonaceous liquids boiling above about C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of to C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  2. Measurement of the Operating Parameters and Numerical Analysis of the Mechanical Subsystem (United States)

    Božek, Pavol; Turygin, Yuri


    Submission is focused on completing the information system about quality, operation, automatic testing and new evaluating method of vehicle subsystem. Numeric analysis is carried out on the base of automatic collection and systematic recording of commercial car operation. Proposed new information system about operation and trial process allows verification according to the proposed method. Critical components verified in laboratory conditions are detected by numeric analysis of reliability. Quality level increasing not only for final product, but also related automatic test laboratory for cars is the result of respecting these principles.

  3. Measurement of the Operating Parameters and Numerical Analysis of the Mechanical Subsystem

    Directory of Open Access Journals (Sweden)

    Božek Pavol


    Full Text Available Submission is focused on completing the information system about quality, operation, automatic testing and new evaluating method of vehicle subsystem. Numeric analysis is carried out on the base of automatic collection and systematic recording of commercial car operation. Proposed new information system about operation and trial process allows verification according to the proposed method. Critical components verified in laboratory conditions are detected by numeric analysis of reliability. Quality level increasing not only for final product, but also related automatic test laboratory for cars is the result of respecting these principles.

  4. Thermo-mechanical and damage analyses of EAST carbon divertor under type-I ELMy H-mode operation

    Energy Technology Data Exchange (ETDEWEB)

    Li, W.X. [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026 (China); Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); Song, Y.T. [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026 (China); Ye, M.Y. [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026 (China); Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); Peng, X.B., E-mail: [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); Wu, S.T. [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026 (China); Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); Qian, X.Y.; Zhu, C.C. [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230026 (China)


    Highlights: • Type-I ELMy H-mode is one of the most severe operating environment in tokamak. • An actual time-history heat load has been used in thermo-mechanical analysis. • The analysis results are time-dependent during the whole discharge process. • The analysis could be very useful in evaluating the operational capability of the divertor. - Abstract: The lower carbon divertor has been used since 2008 in EAST, and many significant physical results, like the 410 s long pulse discharge and the 32 s H-mode operation, have been achieved. As the carbon divertor will still be used in the next few years while the injected auxiliary heating power would be increased gradually, it’s necessary to evaluate the operational capability of the carbon divertor under the heat loads during future operation. In this paper, an actual time-history heat load during type-I ELMy H-mode from EAST experiment, as one of the most severe operating environment in tokamak, has been used in the calculation and analysis. The finite element (FE) thermal and mechanical calculations have been carried out to analysis the stress and deformation of the carbon divertor during the heat loads. According to the results, the main impact on the overall temperature comes from the relative stable phase before and after the type-I ELMs and local peak load, and the transient thermal load such as type-I ELMy only has a significant effect on the surface temperature of the graphite tiles. The carbon divertor would work with high stress near the screw bolts in the current operational conditions, because of high preload and conservative frictional coefficient between the bolts and heatsink. For the future operation, new plasma facing materials (PFM) and divertor technology should be developed.

  5. Catalytic activity of ruthenium(III) on the oxidation of an anticholinergic drug-atropine sulfate monohydrate by copper(III) periodate complex in aqueous alkaline medium - decarboxylation and free radical mechanism. (United States)

    Byadagi, Kirthi S; Nandibewoor, Sharanappa T; Chimatadar, Shivamurti A


    Atropine sulfate monohydrate (ASM) is an anticholinergic drug, having a wide spectrum of activity. Hence, the kinetics of oxidation of ASM by diperiodatocuperate (DPC) in the presence of micro (10-6) amounts of Ru(III) catalyst has been investigated spectrophotometrically in aqueous alkaline medium at I = 0.50 mol dm-3. The reaction between DPC and ASM exhibits 1:2 stoichiometry (ASM:DPC) i. e., one mole of ASM require two moles of DPC to give products. The main oxidation products were confirmed by spectral studies. The reaction is first order with respect to [DPC] and [Ru(III)], while the order with respect to [ASM] and [OH-] was less than unity. The rates decreased with increase in periodate concentration. The reaction rates revealed that Ru(III) catalyzed reaction was about seven-fold faster than the uncatalyzed reaction. The catalytic constant (KC) was also determined at different temperatures. A plausible mechanism is proposed. The activation parameters with respect to slow step of the mechanism were calculated and the thermodynamic quantities were also determined. Kinetic experiments suggest that [Cu(H2IO6)(H2O)2] is the reactive Cu(III) species and [Ru(H2O)5OH]2+ is the reactive Ru(III) species.

  6. Insight into the mechanism of selective catalytic reduction of NO(x) by propene over the Cu/Ti(0.7)Zr(0.3)O2 catalyst by Fourier transform infrared spectroscopy and density functional theory calculations. (United States)

    Liu, Jie; Li, Xinyong; Zhao, Qidong; Hao, Ce; Zhang, Dongke


    The mechanism of selective catalytic reduction of NOx by propene (C3H6-SCR) over the Cu/Ti0.7Zr0.3O2 catalyst was studied by in situ Fourier transform infrared (FTIR) spectroscopy and density functional theory (DFT) calculations. Especially, the formation and transformation of cyanide (-CN species) during the reaction was discussed. According to FTIR results, the excellent performance of the Cu/Ti0.7Zr0.3O2 catalyst in C3H6-SCR was attributed to the coexistence of two parallel pathways to produce N2 by the isocyanate (-NCO species) and -CN species intermediates. Besides the hydrolysis of the -NCO species, the reaction between the -CN species and nitrates and/or NO2 was also a crucial pathway for the NO reduction. On the basis of the DFT calculations on the energy of possible intermediates and transition states at the B3LYP/6-311 G (d, p) level of theory, the reaction channel of -CN species in the SCR reaction was identified and the role of -CN species as a crucial intermediate to generate N2 was also confirmed from the thermodynamics view. In combination of the FTIR and DFT results, a modified mechanism with two parallel pathways to produce N2 by the reaction of -NCO and -CN species over the Cu/Ti0.7Zr0.3O2 catalyst was proposed.

  7. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    Laster, W. R.; Anoshkina, E.


    Under the sponsorship of the U. S. Department of Energy’s National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1- Implementation Plan, Phase 2- Validation Testing and Phase 3 – Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  8. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    W. R. Laster; E. Anoshkina


    Under the sponsorship of the U. S. Department of Energy's National Energy Technology Laboratory, Siemens Westinghouse has conducted a three-year program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine application in IGCC. The program is defined in three phases: Phase 1 - Implementation Plan, Phase 2 - Validation Testing and Phase 3 - Field Testing. Both Phase 1 and Phase 2 of the program have been completed. In IGCC power plants, the gas turbine must be capable of operating on syngas as a primary fuel and an available back-up fuel such as natural gas. In this program the Rich Catalytic Lean (RCLTM) technology is being developed as an ultra low NOx combustor. In this concept, ultra low NOx is achieved by stabilizing a lean premix combustion process by using a catalytic reactor to oxidize a portion of the fuel, increasing the temperature of fuel/air mixture prior to the main combustion zone. In Phase 1, the feasibility of the catalytic concept for syngas application has been evaluated and the key technology issues identified. In Phase II the technology necessary for the application of the catalytic concept to IGCC fuels was developed through detailed design and subscale testing. Phase III (currently not funded) will consist of full-scale combustor basket testing on natural gas and syngas.

  9. Preparation and mechanism of Fe-K/AC for catalytic oxidation of hydrogen sulfide%Fe-K/AC催化氧化脱硫剂制备及反应机理研究

    Institute of Scientific and Technical Information of China (English)

    方惠斌; 赵建涛; 王胜; 黄戒介; 房倚天


    Modified activated carbon Fe-K/AC (activated carbon supported iron and potassium) was used as an oxidation catalyst for low concentration hydrogen sulfide (H2S) removed. The orthogonal design method was introduced in the research of Fe-K/AC preparation to determine the optimum condition and to measure the impact of different factors. Then, catalytic activity and mechanism on Fe-K/AC catalyst for oxidation of hydrogen sulfide was investigated. The optimum preparation condition of Fe-K/AC with high sulfur capacity and selectivity is that the iron and potassium content is 0. 5% and 5. 0% , respectively; and the calcination temperature and the Fe2VFe3+ atomic ratio is 600°C and 0. 5, respectively. The order of their influences is potassium content > iron content > calcination temperature > Fe2+/Fe3+ atomic ratio. Results from structural parameters and surface morphology of sorbents reveal that iron metal oxide loaded on the surface of activated carbon has the selective catalytic oxidation activity of hydrogen sulfide to element sulfur. Alkali metal oxide, which changes basic surface groups, has a synergistic effect on the catalytic oxidation of hydrogen sulfide. However,the catalytic activity decreases due to excessive metal oxides loadings that may block the accessibility of micropores and reduce the surface area.%采用正交实验法制备了负载铁、钾的活性炭(Fe-K/AC)热煤气催化氧化脱硫剂,考察了活性组分铁、钾含量、二价铁和三价铁比例、煅烧温度对催化氧化脱硫反应活性的影响.由正交实验极差分析可知,各因素影响程度依次为:钾含量>铁含量>煅烧温度> Fe2+/Fe3+,最优制备条件为,铁含量0.5%、钾含量5.0%、煅烧温度600℃、Fe2+/Fe3+比0.5.通过对脱硫剂的孔隙结构和表面形貌分析可知,活性炭表面负载的铁金属氧化物具有催化氧化硫化氢生成单质硫的活性,碱金属氧化物具有协同作用,可以改变表面酸碱性,促进硫化

  10. Model-based analysis of the effect of different operating conditions on fouling mechanisms in a membrane bioreactor. (United States)

    Sabia, Gianpaolo; Ferraris, Marco; Spagni, Alessandro


    This study proposes a model-based evaluation of the effect of different operating conditions with and without pre-denitrification treatment and applying three different solids retention times on the fouling mechanisms involved in membrane bioreactors (MBRs). A total of 11 fouling models obtained from literature were used to fit the transmembrane pressure variations measured in a pilot-scale MBR treating real wastewater for more than 1 year. The results showed that all the models represent reasonable descriptions of the fouling processes in the MBR tested. The model-based analysis confirmed that membrane fouling started by pore blocking (complete blocking model) and by a reduction of the pore diameter (standard blocking) while cake filtration became the dominant fouling mechanism over long-term operation. However, the different fouling mechanisms occurred almost simultaneously making it rather difficult to identify each one. The membrane "history" (i.e. age, lifespan, etc.) seems the most important factor affecting the fouling mechanism more than the applied operating conditions. Nonlinear regression of the most complex models (combined models) evaluated in this study sometimes demonstrated unreliable parameter estimates suggesting that the four basic fouling models (complete, standard, intermediate blocking and cake filtration) contain enough details to represent a reasonable description of the main fouling processes occurring in MBRs.

  11. Study on the thermal deactivation of motorcycle catalytic converters by laboratory aging tests. (United States)

    Chen, Yi-Chi; Chen, Lu-Yen; Yu, Yi-Hsien; Jeng, Fu-Tien


    Catalytic converters are used to curb exhaust pollution from motorcycles in Taiwan. A number of factors, including the length of time the converter is used for and driving conditions, affect the catalysts' properties during periods of use. The goal of this study is to resolve the thermal deactivation mechanism of motorcycle catalytic converters. Fresh catalysts were treated under different aging conditions by laboratory-scale aging tests to simulate the operation conditions of motorcycle catalytic converters. The aged catalysts were characterized by analytical techniques in order to provide information for investigating deactivation phenomena. The time-dependent data of specific surface areas were subsequently used to construct kinetics of sintering at the specific temperature. According to the analytical results of the catalysts' properties, the increase in aging temperature causes an increase in pore size of the catalysts and a decrease in the specific surface area. The aged catalysts all exhibited lower performances than the fresh ones. The reduction in catalytic activity is consistent with the reduction in the loss of specific surface area. The finding of catalytic properties' dependence on temperature is consistent with the thermally activated theory. In contrast, the effect of the aging time on the specific surface area was only significant during the initial few hours. The high correlation between specific surface areas measured by the Brunauer-Emmett-Teller (BET) method and predicted by the constructed model verifies that the prediction models can predict the sintering rate reasonably under the aging conditions discussed in this study. As compared to automobile catalytic converters, the differences of structures and aging conditions are made less obvious by the deactivation phenomena of motorcycles.

  12. Catalytic microreactors for portable power generation

    Energy Technology Data Exchange (ETDEWEB)

    Karagiannidis, Symeon [Paul Scherer Institute, Villigen (Switzerland)


    ''Catalytic Microreactors for Portable Power Generation'' addresses a problem of high relevance and increased complexity in energy technology. This thesis outlines an investigation into catalytic and gas-phase combustion characteristics in channel-flow, platinum-coated microreactors. The emphasis of the study is on microreactor/microturbine concepts for portable power generation and the fuels of interest are methane and propane. The author carefully describes numerical and experimental techniques, providing a new insight into the complex interactions between chemical kinetics and molecular transport processes, as well as giving the first detailed report of hetero-/homogeneous chemical reaction mechanisms for catalytic propane combustion. The outcome of this work will be widely applied to the industrial design of micro- and mesoscale combustors. (orig.)

  13. A computational study of detoxification of lewisite warfare agents by British anti-lewisite: catalytic effects of water and ammonia on reaction mechanism and kinetics. (United States)

    Sahu, Chandan; Pakhira, Srimanta; Sen, Kaushik; Das, Abhijit K


    trans-2-Chlorovinyldichloroarsine (lewisite, L agent, Lew-I) acts as a blistering agents. British anti-lewisite (BAL, 2,3-dimercaptopropanol) has long been used as an L-agent antidote. The main reaction channels for the detoxification proceed via breaking of As-Cl bonds and formation of As-S bonds, producing stable, nontoxic ring product [(2-methyl-1,3,2-dithiarsolan-4-yl)methanol]. M06-2X/GENECP calculations have been carried out to establish the enhanced rate of detoxification mechanism in the presence of NH3 and H2O catalysts in both gas and solvent phases, which has been modeled by use of the polarized continuum model (PCM). In addition, natural bond orbital (NBO) and atoms in molecules (AIM) analysis have been performed to characterize the intermolecular hydrogen bonding in the transition states. Transition-state theory (TST) calculation establishes that the rates of NH3-catalyzed (2.88 × 10(-11) s(-1)) and H2O-catalyzed (2.42 × 10(-11) s(-1)) reactions are reasonably faster than the uncatalyzed detoxification (5.44 × 10(-13) s(-1)). The results obtained by these techniques give new insight into the mechanism of the detoxification process, identification and thermodynamic characterization of the relevant stationary species, the proposal of alternative paths on modeled potential energy surfaces for uncatalyzed reaction, and the rationalization of the mechanistic role played by catalysts and solvents.

  14. The characterization of magnetic and photo-catalytic properties of nanocrystalline Ni-doped TiO{sub 2} powder synthesized by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Uhm, Young Rang [Nuclear Nano Materials Developmen Lab., Korea Atomic Energy Research Institute, KAERI, Daejeon 305-600 (Korea, Republic of); Woo, Seung Hee [Nuclear Nano Materials Developmen Lab., Korea Atomic Energy Research Institute, KAERI, Daejeon 305-600 (Korea, Republic of); Kim, Whung Whoe [Nuclear Nano Materials Developmen Lab., Korea Atomic Energy Research Institute, KAERI, Daejeon 305-600 (Korea, Republic of); Kim, Sun Jae [Department of Advanced Materials Engineering, Sejong University, Seoul 143-747 (Korea, Republic of); Rhee, Chang Kyu [Nuclear Nano Materials Developmen Lab., Korea Atomic Energy Research Institute, KAERI, Daejeon 305-600 (Korea, Republic of)]. E-mail:


    Nanocrystalline Ni-doped TiO{sub 2} powders were prepared by mechanical alloying. The X-ray patterns for samples showed three phases of TiO{sub 2} such as rutile, anatase and brookhite. Transmission electron microscopy analyses were carried out to clarify morphologies and position of Ni within the mechanically alloyed powders. The Ni-doped powder consisted of spherical particles and average grain size was less than 10 nm. For the Ni-doped TiO{sub 2}, the colour of powders changes from white to bright yellow with increasing concentration of Ni. The UV-vis absorption showed that the UV absorption for the Ni-doped powder shifted to a longer wavelength (red shift) and the photo-efficiency was enhanced. The absorption threshold depends on the concentration of nano-sized Ni dopant. Ferromagnetic behaviour such as the magnetic hysteresis loops was observed at room temperature. The coercivity (H {sub c}) changed from 40 to 60 Oe with increasing Ni concentration. Based on the UV absorption and magnetization, the dopant level is localized to the valence band of TiO{sub 2}.

  15. Catalytic efficiency of designed catalytic proteins. (United States)

    Korendovych, Ivan V; DeGrado, William F


    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution.

  16. Catalytic Phosphination and Arsination

    Institute of Scientific and Technical Information of China (English)

    Kwong Fuk Yee; Chan Kin Shing


    The catalytic, user-friendly phosphination and arsination of aryl halides and triflates by triphenylphosphine and triphenylarsine using palladium catalysts have provided a facile synthesis of functionalized aryl phosphines and arsines in neutral media. Modification of the cynaoarisne yielded optically active N, As ligands which will be screened in various asymmetric catalysis.

  17. Operation Mechanism of Farmers’ Professional Cooperatives from the Point of Low-Carbon Agricultural Products



    We firstly take a look at internal logic of cluster development of low-carbon agricultural products. In combination with operation features of farmers’ professional cooperatives and actual requirements for cluster development of low-carbon agricultural products; we elaborate establishing benefit allocation mechanism, bearing education and training functions, forming low-carbon value, building low-carbon identification system, as well as realizing low-carbon value. According to these situati...

  18. Research of Mechanical Properties of Piping Yards in the Assessment of their Safe Operation

    Directory of Open Access Journals (Sweden)

    Trebuňa, F.


    Full Text Available Working life of piping yards of compressor stations is mainly influenced by material parameters of particular structural members. In the paper are given the results of static and dynamic tests of basic as well as welded joint material of pipe of compressor station for which were determined conditions for safe operation.

  19. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System. (United States)

    Buonomo, Joseph A; Aldrich, Courtney C


    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

  20. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)


    works include: i) Effects of ligand, cluster charge state, and size on the catalytic reactivity in CO oxidation, semihydrogenation of alkynes; ii) Size-controlled synthesis of Au-n clusters and structural elucidation; iii) Catalytic mechanisms and correlation with structures of cluster catalyst; iv) Catalytic properties of Au nanorods in chemoselective hydrogenation of nitrobenzaldehyde and visible light driven photocatalytic reactions.

  1. Increasing nuclear safety and operational reliability by upgrading the charging pump mechanical sealing system

    Energy Technology Data Exchange (ETDEWEB)

    Loenhout, Gerard van [Flowserve Corporation, Etten-Leur (Netherlands); Nilsson, Peter [Flowsys Technologies AB, Moelndal (Sweden); Jehander, Magnus [Ringhals AB, Vaeroebacka (Sweden)


    For the Ringhals-2 nuclear power plant, three installed centrifugal pumps were designated to have a combined High Head Safety Injection function, as well as a Chemical Volume Control System function. The pumps were originally installed with rubber bellow type mechanical seals, which over time had demonstrated an unreliable sealing performance by displaying high leakages. In 2002, the Ringhals Maintenance engineers initiated to identify a more reliable and robust shaft sealing solution. In 2007, the project was launched and the installation of the first, new mechanical sealing solution took place in the autumn of 2011. In October 2014, these mechanical seals were dismantled and inspected. The inspection confirmed the expected reliability of the new solution.

  2. Increasing nuclear safety and operational reliability by upgrading the charging pump mechanical sealing system

    Energy Technology Data Exchange (ETDEWEB)

    Loenhout, Gerard van [Flowserve Corporation, Etten-Leur (Netherlands); Nilsson, Peter [Flowsys Technologies AB, Moelndal (Sweden); Jehander, Magnus [Ringhals AB, Vaeroebacka (Sweden)


    For the Ringhals-2 nuclear power plant, three installed centrifugal pumps were designated to have a combined High Head Safety Injection function, as well as a Chemical Volume Control System function. The pumps were originally installed with rubber bellow type mechanical seals, which over time had demonstrated an unreliable sealing performance by displaying high leakages. In 2002, the Ringhals Maintenance engineers initiated to identify a more reliable and robust shaft sealing solution. In 2007, the project was launched and the installation of the first, new mechanical sealing solution took place in the autumn of 2011. In October 2014, these mechanical seals were dismantled and inspected. The inspection confirmed the expected reliability of the new solution.

  3. Research on Operation Mechanism of Civil-military Integration Equipment Support Supply Chain

    Directory of Open Access Journals (Sweden)

    Zhou Chang Feng


    Full Text Available High-tech local wars under conditions of informatization is becoming increasingly dependent on the security of weapons and equipment, and civil-military integration equipment support has become a trend. Civil-military integration equipment support chain construction vigorously, must be starting from the strengthening of the top-level planning decisions, building the civil-military coordination and restraint mechanisms and establishing efficient incentives and effective oversight mechanisms to ensure the performance of various support tasks, and to enhance the equipment support ability to achieve “fast, accurate, and efficient” goals.

  4. Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Ye Wang


    Full Text Available The ethanol oxidation reaction (EOR has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to CO2. This mini review is aimed at presenting an overview of the advances in the study of reaction mechanisms and electrocatalytic materials for EOR over the past two decades with a focus on Pt- and Pd-based catalysts. We start with discussion on the mechanistic understanding of EOR on Pt and Pd surfaces using selected publications as examples. Consensuses from the mechanistic studies are that sufficient active surface sites to facilitate the cleavage of the C–C bond and the adsorption of water or its residue are critical for obtaining a higher electro-oxidation activity. We then show how this understanding has been applied to achieve improved performance on various Pt- and Pd-based catalysts through optimizing electronic and bifunctional effects, as well as by tuning their surface composition and structure. Finally we point out the remaining key problems in the development of anode electrocatalysts for EOR.

  5. Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane. (United States)

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia


    LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

  6. Two-Swim Operators in the Modified Bacterial Foraging Algorithm for the Optimal Synthesis of Four-Bar Mechanisms

    Directory of Open Access Journals (Sweden)

    Betania Hernández-Ocaña


    Full Text Available This paper presents two-swim operators to be added to the chemotaxis process of the modified bacterial foraging optimization algorithm to solve three instances of the synthesis of four-bar planar mechanisms. One swim favors exploration while the second one promotes fine movements in the neighborhood of each bacterium. The combined effect of the new operators looks to increase the production of better solutions during the search. As a consequence, the ability of the algorithm to escape from local optimum solutions is enhanced. The algorithm is tested through four experiments and its results are compared against two BFOA-based algorithms and also against a differential evolution algorithm designed for mechanical design problems. The overall results indicate that the proposed algorithm outperforms other BFOA-based approaches and finds highly competitive mechanisms, with a single set of parameter values and with less evaluations in the first synthesis problem, with respect to those mechanisms obtained by the differential evolution algorithm, which needed a parameter fine-tuning process for each optimization problem.

  7. Operational effectiveness and quality assurance mechanisms with stochastic demand of blood supply: blood bank case study. (United States)

    Smith, Alan D


    A general overview of various blood products operational effectiveness and related strategies that can be utilised by service providers (in particular, healthcare providers) is presented in the present study. In terms of the massive volumes of blood products, the North American blood centres collect more than eight million units of whole blood, which represents appropriately 50% of the US and Quebec, Canada?s volunteer donor blood supply. A case study of the quality inspection and inventory control concerns of the Central Blood Bank, located in the metropolitan area of Pittsburgh, PA, is presented. Initially, brief introduction to its general operating environment is followed by sections describing its general situation, quality-service initiatives, and followed by a fairly detailed discussion of the practical applications of lessons learned from the case study.


    Directory of Open Access Journals (Sweden)

    A. A. Sukhotsky


    Full Text Available The paper describes development of the methodology for optimization of parameters for an additional operating force mechanism in a device for pneumo-centrifugal machining of glass balls. Specific feature in manufacturing glass balls for micro-optics in accordance with technological process for obtaining ball-shaped workpieces is grinding and polishing of spherical surface in a free state. In this case component billets of future balls are made in the form of cubes and the billets are given preliminary a form of ball with the help of rough grinding. An advanced method for obtaining ball-shaped work-pieces from brittle materials is a pneumocentrifugal machining. This method presupposes an application of two conic rings with abrasive working surfaces which are set coaxially with large diameters to each other and the billets are rolled along these rings. Rotation of the billets is conveyed by means of pressure medium.The present devices for pneumo-centrifugal machining are suitable for obtaining balls up to 6 mm. Machining of the work-pieces with full spherical surfaces and large diameter is non-productive due to impossibility to ensure a sufficient force on the billet in the working zone. For this reason the paper proposes a modified device where an additional force on the machined billet is created by upper working disc that is making a reciprocating motion along an axis of abrasive conic rings. The motion is realized with the help of a cylindrical camshaft mechanism in the form of a ring with a profile working end face and the purpose of present paper is to optimize parameters of the proposed device.The paper presents expressions for calculation of constitutive parameters of the additional operating force mechanism including parameters of loading element motion, main dimensions of the additional operating force mechanism and parameters of a profile element in the additional operating force mechanism.Investigation method is a mathematical


    Directory of Open Access Journals (Sweden)

    Marin NEACSA


    Full Text Available In this paper is presented the way we can use the thermovision in detecting of the degradationprocesses of the mobile mechanical systems. It is also presented a method for establishing of theprofitableness in using thermovision to identify priority applications of this technology

  10. Operation mechanism of a molecular machine revealed using time-resolved vibrational spectroscopy

    NARCIS (Netherlands)

    M.R. Panman; P. Bodis; D.J. Shaw; B.H. Bakker; A.C. Newton; E.R. Kay; A.M. Brouwer; W.J. Buma; D.A. Leigh; S. Woutersen


    Rotaxanes comprise macrocycles that can shuttle between docking stations along an axle. We explored the nanosecond shuttling mechanism by reversing the relative binding affinities of two stations through ultraviolet-induced transient reduction. We monitored the ensuing changes in the CO-stretching b

  11. Modeling and analysis of hydraulic dashpot for impact free operation in a shut-off rod drive mechanism

    Directory of Open Access Journals (Sweden)

    Narendra K. Singh


    Full Text Available Rotary hydraulic dashpot used for shut-off rod drive mechanism application of a nuclear reactor has been studied in this paper for impact free operation. The rotary hydraulic dashpot has been modeled as a system with 1 degree of freedom (DOF and the simulation results are experimentally validated. The dashpot is modeled as a hinge joint with moving and fixed vanes as rigid bodies. Shut-off rods are used to shut-down a nuclear reactor and hydraulic dashpot absorbs the energy of freely falling shut-off rod at the end of rod travel. With the increase in the environmental temperature the dashpot becomes underdamped at a point because of reduction in the viscosity of oil and results into impact on mechanism components. Hydraulic dashpot designs are finalized with an optimum combination of dashpot clearances and oil viscosity to meet the drop time criterion and impact free operation at room temperature as well as at elevated temperature. Also with the change in mechanical loads the dashpot becomes underdamped. So the study is further extended to see the effects of various parameters such as moment of inertia, constraint angle and applied moment on the dashpot. Study is focused on obtaining dashpot responses in terms of relative rotation, relative angular velocity and relative angular acceleration at various environmental temperatures. Finite element commercial code COMSOL Multiphysics 5.1 has been used for numerical simulations. Equations for both rigid body dynamics and heat transfer in solids are solved simultaneously. Thus, energy absorbed and local temperature rise in the dashpot operation is also obtained. Both simulation and experimental results at wide range of environmental temperature are presented and compared in this paper. This study forms a good tool to design a hydraulic dashpot, which gives impact free operation in a shut-off rod free fall.

  12. Low temperature selective catalytic reduction of NOx with NH3 over Mn-based catalyst: A review


    TsungYu Lee; Hsunling Bai


    The removals of NOx by catalytic technology at low temperatures (100–300 °C) for industrial flue gas treatment have received increasing attention. However, the development of low temperature catalysts for selective catalytic reduction (SCR) of NOx with ammonia is still a challenge especially in the presence of SO2. The current status of using Mn-based catalysts for low temperature SCR of NOx with ammonia (NH3-SCR) is reviewed. Reaction mechanisms and effects of operating factors on low temper...

  13. Quantum dot heterojunction solar cells: the mechanism of device operation and impacts of quantum dot oxidation


    Ihly, Rachelle


    This thesis explores the understanding of the chemistry and physics of colloidal quantum dots for practical solar energy photoconversion. Solar cell devices that make use of PbS quantum dots generally rely on constant and unchanged optical properties such that band gap energies remain tuned within the device. The design and development of unique experiments to ascertain mechanisms of optical band gap shifts occurring in PbS quantum dot thin-films exposed to air are discussed. The systematic s...

  14. CO2催化氢化催化剂及其反应机理综述%Review on Catalysts and Its Mechanisms for Catalytic Hydrogenation of Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    张自丽; 赵毅


    研究二氧化碳资源化利用技术将对电厂CO2减排工作具有重要意义.综述了基于催化氢化思想的CO2转化催化剂及其反应机理,其主要涉及铜、镍、锌等过渡金属和钌、铱、钯等贵金属.现有催化氢化CO2转化技术研究主要集中于研究与开发高活性催化剂,分析与推测反应机理,提高产物产率及选择性,优化反应体系结构与条件等方面.高活性催化剂如双金属合金,过渡金属催化体系将是未来CO2催化氢化领域主要的研究方向之一.各催化剂催化氢化CO2反应机理较为复杂,值得深入研究.随着经济、环保、节能等新型CO2催化氢化技术的开发及研究的深入,电厂CO2减排及资源化工业应用也将成为可能.%Researches about carbon dioxide utilization technologies will have great significances for the emission reduction of carbon dioxide from power plants.Based on the theory about catalytic hydrogenation,the mechanisms of the catalysts such as transition metals,namely copper,nickel and zinc,and noble metals including ruthenium,iridium and palladium for carbon dioxide conversion were reviewed.Current researches about the catalytic hydrogenation of CO2 mainly focus on the studying and development of highly active catalysts,the analysis and conjecture of reaction mechanism,the improvement of productivity and selectivity,and the optimization of reaction system structure and condition,etc..The highly active catalysts,for example thermometal alloy,and the transition metal catalyst system will be one of the primary issues in the field of CO2 hydrogenation in the future.The reaction mechanism which is complicated with diverse catalysts in carbon dioxide conversion,is worth being researched deeply.As the development of new technics with the characteristics of economy,green and energy saving and the deep researches,it may be possible for the emission reduction and resource industry utilization of CO2 from power plants.

  15. Bring into Full Play the Role of Catalytic Reforming Unit

    Institute of Scientific and Technical Information of China (English)


    This article after analyzing the current status of catalytic reforming technology in China puts forward a host of problems related with catalytic reforming capacity, feedstock, size and techno-economic indicators. To solve these problems it is proposed to properly increase the catalytic reforming capacity,extend the feedstock source, and eliminate the bottlenecks to boost the capacity of existing units, improve the operating and management level, as well as speed up R&D work, disseminate new technologies, new processes and novel catalysts.

  16. Mechanical operation and intersubunit coordination of ring-shaped molecular motors: insights from single-molecule studies. (United States)

    Liu, Shixin; Chistol, Gheorghe; Bustamante, Carlos


    Ring NTPases represent a large and diverse group of proteins that couple their nucleotide hydrolysis activity to a mechanical task involving force generation and some type of transport process in the cell. Because of their shape, these enzymes often operate as gates that separate distinct cellular compartments to control and regulate the passage of chemical species across them. In this manner, ions and small molecules are moved across membranes, biopolymer substrates are segregated between cells or moved into confined spaces, double-stranded nucleic acids are separated into single strands to provide access to the genetic information, and polypeptides are unfolded and processed for recycling. Here we review the recent advances in the characterization of these motors using single-molecule manipulation and detection approaches. We describe the various mechanisms by which ring motors convert chemical energy to mechanical force or torque and coordinate the activities of individual subunits that constitute the ring. We also examine how single-molecule studies have contributed to a better understanding of the structural elements involved in motor-substrate interaction, mechanochemical coupling, and intersubunit coordination. Finally, we discuss how these molecular motors tailor their operation-often through regulation by other cofactors-to suit their unique biological functions.

  17. Sectoral crediting mechanisms for greenhouse gas mitigation. Institutional and operational issues

    Energy Technology Data Exchange (ETDEWEB)

    Baron, R. [International Energy Agency IEA, Paris (France); Ellis, J. [Environment Directorate, International Energy Agency IEA, Organisation for Economic Co-operation and Development OECD, Paris (France)


    Guiding policy choices requires a systematic comparison of options. In the case of a hypothetical policy instrument, e.g. sectoral crediting, such systematic comparison is difficult as different options may not be strictly comparable. For instance, not all options may be easily applied to a given sector (e.g. an intensity-based crediting may hardly be implemented to a government policy seeking to substitute public transport for personal vehicles); the policy-based SCM may be the only practical option in this case and comparison is therefore moot. Also, not all countries may have the institutional capacity to implement all three options at the same scale. Last, the ability of each option to deliver real reductions hinges on the 'additionality' of the sector's efforts and on the stringency of the baseline. Unfortunately, there is no universally recognised method to define additionality and to determine a baseline. This paper nonetheless offers some insights on how each potential SCM option may fare with respect to the following criteria: Environmental effectiveness: can this option trigger real reductions where implemented?; Addressing competitiveness concerns; Administrative cost and feasibility: how demanding is the mechanism in terms of monitoring, review and, possibly enforcement policy?; Economic efficiency: to what extent does the mechanism lead to the adoption of the least-cost mitigation options in the sector? An initial assessment of each option along these criteria is provided in the conclusion section. This paper explores potential SCMs along several lines. Section 2 draws lessons from existing mechanisms; section 3 considers several dimensions to be considered for baselines; section 4 discusses how SCM could be implemented to provide effective incentives to mitigation; section 5 explores international governance issues. Concluding remarks are presented in section 6.

  18. Catalytic Hydrothermal Gasification

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.


    The term “hydrothermal” used here refers to the processing of biomass in water slurries at elevated temperature and pressure to facilitate the chemical conversion of the organic structures in biomass into useful fuels. The process is meant to provide a means for treating wet biomass materials without drying and to access ionic reaction conditions by maintaining a liquid water processing medium. Typical hydrothermal processing conditions are 523-647K of temperature and operating pressures from 4-22 MPa of pressure. The temperature is sufficient to initiate pyrolytic mechanisms in the biopolymers while the pressure is sufficient to maintain a liquid water processing phase. Hydrothermal gasification is accomplished at the upper end of the process temperature range. It can be considered an extension of the hydrothermal liquefaction mechanisms that begin at the lowest hydrothermal conditions with subsequent decomposition of biopolymer fragments formed in liquefaction to smaller molecules and eventually to gas. Typically, hydrothermal gasification requires an active catalyst to accomplish reasonable rates of gas formation from biomass.

  19. Monitoring Local Strain in a Thermal Barrier Coating System Under Thermal Mechanical Gas Turbine Operating Conditions (United States)

    Manero, Albert; Sofronsky, Stephen; Knipe, Kevin; Meid, Carla; Wischek, Janine; Okasinski, John; Almer, Jonathan; Karlsson, Anette M.; Raghavan, Seetha; Bartsch, Marion


    Advances in aircraft and land-based turbine engines have been increasing the extreme loading conditions on traditional engine components and have incited the need for improved performance with the use of protective coatings. These protective coatings shield the load-bearing super alloy blades from the high-temperature combustion gases by creating a thermal gradient over their thickness. This addition extends the life and performance of blades. A more complete understanding of the behavior, failure mechanics, and life expectancy for turbine blades and their coatings is needed to enhance and validate simulation models. As new thermal-barrier-coated materials and deposition methods are developed, strides to effectively test, evaluate, and prepare the technology for industry deployment are of paramount interest. Coupling the experience and expertise of researchers at the University of Central Florida, The German Aerospace Center, and Cleveland State University with the world-class synchrotron x-ray beam at the Advanced Photon Source in Argonne National Laboratory, the synergistic collaboration has yielded previously unseen measurements to look inside the coating layer system for in situ strain measurements during representative service loading. These findings quantify the in situ strain response on multilayer thermal barrier coatings and shed light on the elastic and nonelastic properties of the layers and the role of mechanical load and internal cooling variations on the response. The article discusses the experimental configuration and development of equipment to perform in situ strain measurements on multilayer thin coatings and provides an overview of the achievements thus far.

  20. Polymer lattices as mechanically tunable 3-dimensional photonic crystals operating in the infrared

    Energy Technology Data Exchange (ETDEWEB)

    Chernow, V. F., E-mail: [Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena, California 91125 (United States); Alaeian, H. [Department of Electrical Engineering, Stanford University, Stanford, California 94305 (United States); Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States); Dionne, J. A. [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States); Greer, J. R. [Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena, California 91125 (United States); The Kavli Nanoscience Institute, California Institute of Technology, Pasadena, California 91125 (United States)


    Broadly tunable photonic crystals in the near- to mid-infrared region could find use in spectroscopy, non-invasive medical diagnosis, chemical and biological sensing, and military applications, but so far have not been widely realized. We report the fabrication and characterization of three-dimensional tunable photonic crystals composed of polymer nanolattices with an octahedron unit-cell geometry. These photonic crystals exhibit a strong peak in reflection in the mid-infrared that shifts substantially and reversibly with application of compressive uniaxial strain. A strain of ∼40% results in a 2.2 μm wavelength shift in the pseudo-stop band, from 7.3 μm for the as-fabricated nanolattice to 5.1 μm when strained. We found a linear relationship between the overall compressive strain in the photonic crystal and the resulting stopband shift, with a ∼50 nm blueshift in the reflection peak position per percent increase in strain. These results suggest that architected nanolattices can serve as efficient three-dimensional mechanically tunable photonic crystals, providing a foundation for new opto-mechanical components and devices across infrared and possibly visible frequencies.


    Directory of Open Access Journals (Sweden)

    S. V. Belokurov


    Full Text Available The article presents the list of facilities and necessary procedures to protect against threats of violation of information availability in terms of exposure to malware in ICT systems and principles conceptual design of mechanisms, antivirus protection, implemented in the form of a component of a software complex for protection of information. This development allows us to formulate the principles of conceptual design of mechanisms, antivirus protection, implemented in the form of a component of a complex of software tools of information security. Special this valuable development for the implementation of procedures for the management of complex organizationaltechnical systems. Streamlining usually has one or any combination of the following objectives (attitudes: rationality, efficiency, improvement of the system. The aim of good governance (e.g. anti-malware is the preservation of the existing structure and system parameters under certain constraints (e.g., constraints on computing resources. If you cannot provide the management on a rational basis, it becomes necessary to change the parameters (parametric synthesis or search for and select the set of admissible structures effective on the criteria of structure (structural synthesis. Note that in this case we are talking about effectiveness for a given period of time, as social and scientific progress inevitably lead to a change of criteria effectiveness evaluation.

  2. Anisotropic and Mechanical Behavior of 22MnB5 in Hot Stamping Operations (United States)

    Turetta, A.; Bruschi, S.; Ghiotti, A.


    The hot stamping of quenchable High Strength Steels offers the possibility of weight reduction in structural components maintaining the safety requirements together with enhanced accuracy and formability of sheets. The proper design of this technology requires a deep understanding of material behavior during the entire process chain, in terms of microstructural evolution and mechanical properties at elevated temperatures, in order to perform reliable FE simulations and obtain the desired characteristic on final parts. In particular, the analysis of technical-scientific literature shows that accurate data on material rheological behavior are difficult to find; while the lack of knowledge about anisotropic behavior at elevated temperatures is even more evident. To overcome these difficulties, a new experimental set-up was developed to reproduce the thermo-mechanical conditions of the industrial process and evaluate the influence of temperature and strain rate on 22MnB5 flow curves through uniaxial tensile tests; an optical strain measurement system was utilized to evaluate the effective strain after necking. From the same data, plastic anisotropy evolution was determined by means of a specially developed procedure. The influence of different cooling rates was taken into account and the rheological properties were correlated with microstructural changes occurring during deformation, previously evaluated through a dilatometric analysis performed in the same range of temperatures.

  3. A transient fault-valve mechanism operating in upper crustal level, Sierras Pampeanas, Argentina (United States)

    Japas, María Silvia; Urbina, Nilda Esther; Sruoga, Patricia; Garro, José Matías; Ibañes, Oscar


    Located in the Sierras Pampeanas (the broken-foreland of the Pampean flat slab segment in the southern Central Andes), the Cerro Tiporco volcanic field shows Neogene hydrothermal activity linked to migration of arc-magmatism into the foreland. Late Neogene deposits comprise epithermal vein systems emplaced in Precambrian-Early Palaeozoic igneous-metamorphic basement, Late Miocene sedimentary rocks and Early Pliocene volcaniclastic rocks. Mineralization consists of calcareous onyx, aragonite and calcite veins as well as travertine deposits. Onyx and aragonite occur as fill of low-displacement nearly vertical reverse-sinistral faults striking NW, and nearly horizontal dilatant fractures. The latter consist of load-removal induced fractures affecting the igneous-metamorphic rocks, as well as bedding planes in the Late Miocene sediments. The presence of veins recording multiple fracture episodes and crack-and-seal growth of veins suggests relatively low differential stress and supralithostatic fluid pressure, as well as cyclic changes in pore pressure and high mineral-deposition/fracture-opening ratio. These conditions support a mechanism of fault-valve behaviour during onyx and aragonite vein emplacement. The fault-valve mechanism involves fractures associated with impermeable barriers between environments with different fluid pressure. Faulting generated an appreciable directional permeability triggering fluid migration from the highest to the lowest pressure region, with subsequent deposition and sealing that started a new pressurization-faulting-sealing cycle. Late aragonite and calcite veins suggest a change in kinematics indicating the onset of tectonic-load conditions.

  4. Hydrogen production by catalytic partial oxidation of methane


    Enger, Bjørn Christian


    Hydrogen production by catalytic partial oxidation of natural gas was investigated using tools ranging from theoretical calculations to experimental work and sophisticated characterization techniques.Catalytic partial oxidation (CPO) was carried out in a conventional continuous flow experimental apparatus using a xed-bed reactor, and operating at 1 atm and furnace temperatures in the range from ambient to 1073 K. The feed typically consisted of a mixture of methane and air, with a CH4/O2 rati...

  5. Passive hybrid force-position control for tele-operation based on real-time simulation of a virtual mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Joly, L.; Andriot, C.


    Hybrid force-position control aims at controlling position and force in separate directions. It is particularly useful to perform certain robotic tasks. In tele-operation context, passivity is important because it ensures stability when the system interacts with any passive environment. In this paper, we propose an original approach to hybrid force-position control of a force reflecting tele-robot system. It is based on real-time simulation of a virtual mechanism corresponding to the task. the resulting control law is passive. Experiments on a 6 degrees of freedom tele-operation system consisting in following a bent pipe under several control modes validate the approach. (authors). 12 refs., 6 figs.

  6. A Mechanism Supporting the Client/Server Relationship in the Operating System of Distributed System “THUDS”

    Institute of Scientific and Technical Information of China (English)

    廖先Zhi; 金兰


    This paper presents a distributed operating system modeled as an abstract machine that provides all the distributed processes with the same set of services.The kernel of our operating system supports services which are achieved by a remote procedure call on requests by parallel processes.Therefore,a scheme for solving the client-server relationship is required.In our system there are more than one clients and,at least,a receive would be required for each.Similarly,there are more than one servers such that the send in a client should produce a message that can be received by every server.Consequently,a mechanism well suited for programming multiple-clients/single-server and single-client/multiple-servers interactions is proposed.

  7. 一种新的生产计划与催化裂化装置过程操作集成的闭环策略%A novel close-loop strategy for Integrating Process Operations of Fluidized Catalytic Cracking Unit with Production Planning Optimization

    Institute of Scientific and Technical Information of China (English)

    王如强; 李初福; 何小荣; 陈丙珍


    Production planning models generated by common modeling systems do not involve constraints for process operations, and a solution optimized by these models is called a quasi-optimal plan. The quasi-optimal plan cannot be executed in practice some time for no corresponding operating conditions. In order to determine a practically feasible optimal plan and corresponding operating conditions of fluidized catalytic cracking unit (FCCU), a novel close-loop integrated strategy, including determination of a quasi-optimal plan, search of operating conditions of FCCU and revision of the production planning model, was proposed in this article. In the strategy, a generalized genetic algorithm (GA) coupled with a sequential process simulator of FCCU was applied to search operating conditions implementing the quasi-optimal plan of FCCU and output the optimal individual in the GA search as a final genetic individual. When no corresponding operating conditions were found, the final genetic individual based correction (FGIC) method was presented to revise the production planning model, and then a new quasi-optimal production plan was determined. The above steps were repeated until a practically feasible optimal plan and corresponding operating conditions of FCCU were obtained. The close-loop integrated strategy was validated by two cases, and it was indicated that the strategy was efficient in determining a practically executed optimal plan and corresponding operating conditions of FCCU.

  8. Mechanical chest compressions in an avalanche victim with cardiac arrest: an option for extreme mountain rescue operations. (United States)

    Pietsch, Urs; Lischke, Volker; Pietsch, Christine; Kopp, Karl-Heinz


    Mountain rescue operations often present helicopter emergency medical service crews with unique challenges. One of the most challenging problems is the prehospital care of cardiac arrest patients during evacuation and transport. In this paper we outline a case in which we successfully performed a cardiopulmonary resuscitation of an avalanche victim. A mechanical chest-compression device proved to be a good way of minimizing hands-off time and providing high-quality chest compressions while the patient was evacuated from the site of the accident.

  9. Qualitative model of the operating mechanism of the protective coating for low pressure Hg lamps

    Energy Technology Data Exchange (ETDEWEB)

    Krasnochub, A V [DECO Ltd, PO Box 40, 141701 Dolgoprudnyi (Russian Federation); Vasiliev, A I [LIT Technology Ltd, Krasnobogatyrskaya 44, 107076 Moscow (Russian Federation)


    Interaction between the plasma and protective coating on the inner side of low pressure mercury lamp bulbs is considered. Under the assumption that the main way of decreasing the transmission of the bulb wall is the implantation of Hg ions within the fused quartz and formation of complexes [HgO] therein, a qualitative model of the attenuation mechanism is offered. The influence of the characteristics of a coating (thickness, close-packed structures, the lattice parameter, mass of atoms) on the transmission of the bulb walls is analysed. On the basis of the suggested model, estimates of the change in minimum transmission of bulb walls were made for lamps with and without protective coating. It is shown that in spite of approximations, the proposed model is in good agreement with experimental data.

  10. Novel sensing approach for LPG leakage detection: Part I: Operating Mechanism and Preliminary Results

    KAUST Repository

    Mukhopadhyay, Subhas


    Gas sensing technology has been among the topical research work for quite some time. This paper showcases the research done on the detection mechanism of leakage of domestic cooking gas at ambient conditions. MEMS-based interdigital sensors were fabricated on oxidized single crystal silicon surfaces by maskless photolithography technique. The electrochemical impedance analysis of these sensors was done to detect liquefied petroleum gas (LPG) with and without coated particles of tin oxide (SnO2) in form of thin layer.A thin-film of SnO2 was spin-coated on the sensing surface of the interdigital sensor to induce selectivity to LPG that consists of a 60/40 mixture of propane and butane respectively. The paper reports a novel strategy for gas detection under ambient temperature and humidity conditions. The response time of the coated sensor was encouraging and own a promising potential to the development of a complete efficient gas sensing system.

  11. 碳五烃催化裂解制取低碳烯烃反应性能及机理%Reaction Performance and Mechanism for Production of Propylene and Ethylene from C5 Hydrocarbon by Catalytic Cracking

    Institute of Scientific and Technical Information of China (English)

    刘俊涛; 滕加伟


    A catalytic cracking process for production of propylene and ethylene from C5 hydrocarbon with a catalyst of the ZSM-5 molecular sieve was investigated, especially the influence of reaction temperature and dilution ratio on product distribution was researched. The results showed that conversion of both C5 alkane and C5 olefins increased constantly with reaction temperature increasing, while the conversion of C5 olefins was much higher than that of C5 alkane. The yield of propylene and ethylene increased continuously from 8.84 % and 2.38 % at 450℃ to 19.67% and 13.86 % at 620℃ under reaction conditions of weight hourly space velocity of 3.06 h-1 and reaction partial pressure of 23.24 kPa. On the other hand, the conversion of C5 olefins, yield of ethylene, propylene and butene all decreased with dilution ratio increasing, while the yield of C6 hydrocarbon increased continuously. The mechanism of C5 hydrocarbon catalytic cracking was discussed. It was assumed that direct cracking of C5 olefins into ethylene and propylene and dimerisation of C5 olefins to C10 intermediate proceeded simultaneously. Then the cracking was carried out from the C10 intermediate. The above-mentioned mechanism can be used to explain experimental data satisfactorily.%以 ZSM-5分子筛为催化剂,碳五烃混合物为裂解原料,考察温度及稀释比对碳五烃催化裂解制丙烯/乙烯反应性能的影响。结果表明:随温度升高碳五烷烃及烯烃的转化率均不断升高,但碳五烯烃的转化率远高于碳五烷烃的转化率。同时乙烯及丙烯的收率也随温度的升高而升高,空速3.06 h-1,分压23.24 kPa时,分别由450℃的2.38%,8.84%升高到620℃时的13.86%和19.67%。另外,随稀释比的增加,碳五烯烃转化率,乙烯、丙烯及丁烯的收率不断下降,但 C6烃的收率随稀释比的增加而升高。碳五烯烃催化裂解机理分析指出:碳五烯烃催化裂解过程中碳五烯烃在直接裂解

  12. 25th anniversary article: Bulk heterojunction solar cells: understanding the mechanism of operation. (United States)

    Heeger, Alan J


    The status of understanding of the operation of bulk heterojunction (BHJ) solar cells is reviewed. Because the carrier photoexcitation recombination lengths are typically 10 nm in these disordered materials, the length scale for self-assembly must be of order 10-20 nm. Experiments have verified the existence of the BHJ nanostructure, but the morphology remains complex and a limiting factor. Three steps are required for generation of electrical power: i) absorption of photons from the sun; ii) photoinduced charge separation and the generation of mobile carriers; iii) collection of electrons and holes at opposite electrodes. The ultrafast charge transfer process arises from fundamental quantum uncertainty; mobile carriers are directly generated (electrons in the acceptor domains and holes in the donor domains) by the ultrafast charge transfer (≈70%) with ≈30% generated by exciton diffusion to a charge separating heterojunction. Sweep-out of the mobile carriers by the internal field prior to recombination is essential for high performance. Bimolecular recombination dominates in materials where the donor and acceptor phases are pure. Impurities degrade performance by introducing Shockly-Read-Hall decay. The review concludes with a summary of the problems to be solved to achieve the predicted power conversion efficiencies of >20% for a single cell.

  13. Mechanisms and Kinetics of Catalytic Reactions (United States)


    Microemulsions", PhD Thesis, Drexel University, Phil ., PA, 1980. 2. R.A. Mackay, F.R. Longo, B.L. Knier, H.D. Durst, J. Phys. Chem. 1987, 91, 861-864. 3. N.J...Am. Chem. Soc. 1978, 100, 117-122. 54. G.D. Hager, G.A. Crosby , J. Am. Chem. Soc. 1975, 97, 7031-7037. 55. S. Oishi, K. Tajime, I. Shiojima, J. Mol...Cat. 1982, 14, 383-386. 56. D.M. Klassen, G.A. Crosby , J. Chem. Phys. 1968, 48, 1853- 1858. 57. J.N. Braddock, T.J. Meyer, J. Am. Chem. Soc. 1973, 95

  14. Final Report of a CRADA Between Pacific Northwest National Laboratory and the General Motors Company (CRADA No. PNNL/271): “Degradation Mechanisms of Urea Selective Catalytic Reduction Technology”

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Do Heui; Lee, Jong H.; Peden, Charles HF; Howden, Ken; Kim, Chang H.; Oh, Se H.; Schmieg, Steven J.; Wiebenga, Michelle H.


    Diesel engines can offer substantially higher fuel efficiency, good driving performance characteristics, and reduced carbon dioxide (CO2) emission compared to stoichiometric gasoline engines. Despite the increasing public demand for higher fuel economy and reduced dependency on imported oil, however, meeting the stringent emission standards with affordable methods has been a major challenge for the wide application of these fuel-efficient engines in the US market. The selective catalytic reduction of NOx by urea (urea-SCR) is one of the most promising technologies for NOx emission control for diesel engine exhausts. To ensure successful NOx emission control in the urea-SCR technology, both a diesel oxidation catalyst (DOC) and a urea-SCR catalyst with high activity and durability are critical for the emission control system. Because the use of this technology for light-duty diesel vehicle applications is new, the relative lack of experience makes it especially challenging to satisfy the durability requirements. Of particular concern is being able to realistically simulate actual field aging of the catalyst systems under laboratory conditions, which is necessary both as a rapid assessment tool for verifying improved performance and certifiability of new catalyst formulations. In addition, it is imperative to develop a good understanding of deactivation mechanisms to help develop improved catalyst materials. In this CRADA program, General Motors Company and PNNL have investigated fresh, laboratory- and vehicle-aged DOC and SCR catalysts. The studies have led to a better understanding of various aging factors that impact the long-term performance of catalysts used in the urea-SCR technology, and have improved the correlation between laboratory and vehicle aging for reduced development time and cost. This Final Report briefly highlights many of the technical accomplishments and documents the productivity of the program in terms of peer-reviewed scientific publications

  15. The antitumor mechanism of di-2-pyridylketone 2-pyridine carboxylic acid hydrazone and its copper complex in ROS generation and topoisomerase inhibition, and hydrazone involvement in oxygen-catalytic iron mobilization. (United States)

    Huang, Tengfei; Li, Cuiping; Sun, Xingzhi; Zhu, Zhenfu; Fu, Yun; Liu, Youxun; Yuan, Yanbin; Li, Shaoshan; Li, Changzheng


    Iron depletion and stimulation of iron-dependent free radical damage is a rapidly developing field for chelation therapy, but the iron mobilization from ferritin by chelators has received less attention. In this study, the di-2-pyridylketone 2-pyridine carboxylic acid hydrazone (DPPCAH) and its copper complex was prepared and characterized by NMR and MS spectra. The proliferation inhibition assay showed that both DPPCAH and its copper complex exhibited selectively proliferation inhibition for HepG2 (IC50, 4.6 ± 0.2 µM for DPPACH and 1.3 ± 0.2 µM for its copper complex), but less inhibition for HCT-116 cell line (IC50, >100 µM for DPPACH and 7.8 ± 0.4 µM for its copper complex). The mechanistic studies revealed that DPPACH could remove iron from ferritin in a oxygen-catalytic manner, and contributed to redox activity of labile iron pool (LIP), that is less reported for the chelators that possess significant biological activity. The reactive oxygen species (ROS) generation and DNA cleavage assay in vitro and in vivo showed that both DPPACH-Fe(II) and DPPACH-Cu were redox-active species, indicating that ROS may mediate their antitumor activity. Further study revealed that both DPPACH and its copper complex displayed certain degree of inhibition of type II topoisomerase (Top) which contributed to their antitumor activity. Thus, the mechanism that iron mobilization by DPPACH from ferritin contributed to LIP was proposed, and both DPPACH and its copper complex were involved in ROS generation and Top II inhibition for their antitumor activities.

  16. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin


    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  17. Selective Catalytic Reduction of NO with Methane

    Institute of Scientific and Technical Information of China (English)

    Xiang Gao; Qi Yu; Limin Chen


    The removal of nitrogen oxides from exhaust gases has attracted great attention in recent years, and many approaches have been developed depending on the application. Methane, the main component of natural gas, has great potential as a NO reductant. In this paper, a number of catalysts previous reported for this catalytic reduction of NO have been reviewed, including a direct comparison of the relative activities and effective factors of the catalysts. Reaction mechanisms have also been explored preliminarily.

  18. Theoretical comparison, equivalent transformation, and conjunction operations of electromagnetic induction generator and triboelectric nanogenerator for harvesting mechanical energy. (United States)

    Zhang, Chi; Tang, Wei; Han, Changbao; Fan, Fengru; Wang, Zhong Lin


    Triboelectric nanogenerator (TENG) is a newly invented technology that is effective using conventional organic materials with functionalized surfaces for converting mechanical energy into electricity, which is light weight, cost-effective and easy scalable. Here, we present the first systematic analysis and comparison of EMIG and TENG from their working mechanisms, governing equations and output characteristics, aiming at establishing complementary applications of the two technologies for harvesting various mechanical energies. The equivalent transformation and conjunction operations of the two power sources for the external circuit are also explored, which provide appropriate evidences that the TENG can be considered as a current source with a large internal resistance, while the EMIG is equivalent to a voltage source with a small internal resistance. The theoretical comparison and experimental validations presented in this paper establish the basis of using the TENG as a new energy technology that could be parallel or possibly equivalently important as the EMIG for general power application at large-scale. It opens a field of organic nanogenerator for chemists and materials scientists who can be first time using conventional organic materials for converting mechanical energy into electricity at a high efficiency.

  19. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)


    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  20. Optimization of Operating Parameters for Minimum Mechanical Specific Energy in Drilling

    Energy Technology Data Exchange (ETDEWEB)

    Hamrick, Todd [West Virginia Univ., Morgantown, WV (United States)


    Efficiency in drilling is measured by Mechanical Specific Energy (MSE). MSE is the measure of the amount of energy input required to remove a unit volume of rock, expressed in units of energy input divided by volume removed. It can be expressed mathematically in terms of controllable parameters; Weight on Bit, Torque, Rate of Penetration, and RPM. It is well documented that minimizing MSE by optimizing controllable factors results in maximum Rate of Penetration. Current methods for computing MSE make it possible to minimize MSE in the field only through a trial-and-error process. This work makes it possible to compute the optimum drilling parameters that result in minimum MSE. The parameters that have been traditionally used to compute MSE are interdependent. Mathematical relationships between the parameters were established, and the conventional MSE equation was rewritten in terms of a single parameter, Weight on Bit, establishing a form that can be minimized mathematically. Once the optimum Weight on Bit was determined, the interdependent relationship that Weight on Bit has with Torque and Penetration per Revolution was used to determine optimum values for those parameters for a given drilling situation. The improved method was validated through laboratory experimentation and analysis of published data. Two rock types were subjected to four treatments each, and drilled in a controlled laboratory environment. The method was applied in each case, and the optimum parameters for minimum MSE were computed. The method demonstrated an accurate means to determine optimum drilling parameters of Weight on Bit, Torque, and Penetration per Revolution. A unique application of micro-cracking is also presented, which demonstrates that rock failure ahead of the bit is related to axial force more than to rotation speed.

  1. A novel multi-objective electromagnetism-like mechanism algorithm with applications in reservoir flood control operation. (United States)

    Ouyang, Shuo; Zhou, Jianzhong; Qin, Hui; Liao, Xiang; Wang, Hao


    Reservoir flood control operation (RFCO) is a complex problem that involves various constraints and purposes, which include the safety of the dam, watershed flood control and navigation. These objectives often conflict with each other. Thus, traditional methods have difficulty in solving the multi-objective problem efficiently. In this paper, a multi-objective self-adaptive electromagnetism-like mechanism (MOSEM) algorithm is introduced in the local searching operation of the proposed method. To enhance the optimization ability of EM, a self-adaptive parameter is applied in the local search operation of MOSEM for adjusting the values of parameters dynamically. Moreover, MOSEM is tested by several benchmark test problems and compared with some well-known multi-objective evolutionary algorithms. A case study is also used for solving RFCO problems of the Three Georges Reservoir by using the multi-objective cultured differential evolution (MOCDE), non-dominated sorting genetic algorithm-II (NSGA-II) and proposed MOSEM methods. The study results reveal that MOSEM can provide alternative Pareto-optimal solutions (POS) with better convergence properties and diversification.

  2. Reaction mechanism and degradation course of azo dyes by catalytic wet peroxide oxidation(CWPO)%催化湿式过氧化(CWPO)偶氮染料反应机理及降解历程研究

    Institute of Scientific and Technical Information of China (English)

    张蕾; 马宏瑞


    采用浸渍法制备出具有较高催化活性的催化剂CuO/γ-Al2O3,通过XRD、电镜等手段对催化剂进行了表征。降解了几种不同结构的偶氮染料,并通过改变CWPO的反应条件推断了其催化反应机理。采用紫外/可见分光光度计(UV-Vis)和傅里叶红外光谱仪(IR)等手段对染料降解过程进行跟踪和分析,对比染料处理前后紫外可见光谱与红外光谱图的变化,说明染料分子结构中的偶氮键发生断裂,破坏了分子结构的偶氮-苯环共轭发色体系,从而达到了脱色的目的。并借助水杨酸验证了CWPO体系中.OH的产生及CWPO反应机理。%The catalyst CuO/γ-Al2O3 with high catalytic activity by impregnation was prepared,and were examined by XRD、SEM to characterize the catalyst.Azo dyes of several different structures were degraded,and the reaction conditions were changed to study the reaction mechanism of CWPO.The UV/Visible spectrophotometer(UV-Vis) and the Fourier transform infrared spectrometer(IR) were used to track and analyze the degradation process of the dyes.Compared the UV-Vis and IR spectra before and after wastewater treatment,indicating the structure of the azo dye molecules bond was broken,destroyed azo benzene conjugated chromophoric system of the molecular structure,so as to achieve the purpose of bleaching.The salicylic acid was used to infer the ·OH generation and reaction mechanism in the CWPO system.

  3. 正辛烷热裂化和催化裂化生成甲烷反应机理%Mechanism of methane formation in thermal and catalytic cracking of n-octane

    Institute of Scientific and Technical Information of China (English)

    李福超; 张久顺; 袁起民


    The thermal and catalytic cracking reactions of n-octane were carried out in a temperature range of 550~650℃ with low conversions ( x<15%) in a pulse micro-reactor over quartz and ZRP zeolite. Reaction mechanism of methane formation was analyzed. The results showed that ethylene, propylene and n-butylene were primary products and four paths contributed to methane formation in thermal cracking of n-octane. At 600 ℃, dehydrogenation of terminal C-H bond in the chain attacked by methyl radical led to methane production. Due to higher activation energy of cleavage of terminal C-C bond in octyl radical formed via dehydrogenation of central C-C bond, only methane can form at higher temperature. Protolytic cracking was predominant with relatively remarkable yield of normal paraffin in catalytic cracking of n-octane over ZRP zeolite. Methane was produced by protolytic cracking route as well. By comparison of methane formation between thermal and protolytic cracking, it revealed that methane formed through protolytic cracking below 600℃ while thermal cracking dominated the selectivity of methane at higher reaction temperatures.%采用脉冲微反装置,在反应温度为550~650℃,低转化率(小于15%)下,研究了正辛烷在石英砂和ZRP分子筛上的热裂化和催化裂化反应,分析了甲烷的生成机理。结果表明,正辛烷热裂化时,乙烯、丙烯和正丁烯是初始产物,甲烷由4种反应路径生成。当反应温度为600℃时,甲基自由基攻击碳链端部C-H键生成甲烷。中部C-H键脱氢形成的辛基自由基在端部C-C键断裂的活化能较高,仅在高温下生成甲烷。正辛烷在ZRP分子筛上主要发生质子化裂化反应,正构烷烃占有相当比重,甲烷由质子化裂化步骤生成。热裂化与质子化裂化对甲烷贡献的对比可知,当反应温度低于600℃时,甲烷由质子化裂化反应生成;在高温下,热裂化反应决定甲烷选择性。

  4. The Synthesis of Silver Nanowires and Studies on Its Catalytic Mechanism of ECL%银纳米线的制备及其对电化学发光催化研究

    Institute of Scientific and Technical Information of China (English)

    朱岩; 向艳秋; 吴志博; 杨丽娟


    Silver nanowires were successfully synthesized by hydrothermal method using a small amount copper chloride as removing oxygen agent, ethylene glycol as reducing agent, in which poly(vinylpyrrolidone, PVP) was used as stabilizer and structure-directing agent, silver nitrate was used as predecessor. The effects of reaction temperature, reaction time and concentration of copper chloride on the sample morphology were investigeted. The structure and performance of the as-prepared silver nanowires were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). Meanwhile, the as-prepared silver nanowires were used as work electrode to the electrochemical luminescence (ECL) of Ru(bpy)32+for research its catalytic mechanism. The results show that the as-prepared silver nanowires had face-centered cubic structure, with length up to 13μm and the ratio of length-diameter was 75 under the temperature of 165 ℃ ,the reaction time of 1 h and the concentration of CuCl2 of 4 mmol/L. Compared with Ag bulk electrode, the silver nanowires e-lectrode was more suitable for the work electrode of ECL of Ru(bpy)32+ because of the high specific surface area and u-nique catalytic properties.%采用水热法,在反应体系中加入微量的CuCl2作为去氧剂,以AgNO3为前驱物,聚乙烯吡咯烷酮(PVP)为稳定剂和结构导向剂,乙二醇为还原剂和溶剂制备银纳米线.研究了反应温度、反应时间及CuCl2浓度对产物微观形貌的影响.通过X-射线衍射(XRD)、扫描电子显微镜(SEM)等检测手段表征了其结构和性能.同时,将所制得的银纳米线作为联吡啶钌[Ru(bpy)2+3]电化学发光(ECL)的工作电极对其催化机理进行研究.结果表明:在反应温度为165℃、反应时间为1h、CuCl2浓度为4 mmol/L时制备出了具有面心立方结构的,长度为13 μm,长径比约为75的银纳米线;与普通银丝电极相比,由于具有较高的比表面积和较独特的催化特性,银纳米线

  5. Structural basis unifying diverse GTP hydrolysis mechanisms. (United States)

    Anand, Baskaran; Majumdar, Soneya; Prakash, Balaji


    Central to biological processes is the regulation rendered by GTPases. Until recently, the GTP hydrolysis mechanism, exemplified by Ras-family (and G-α) GTPases, was thought to be universal. This mechanism utilizes a conserved catalytic Gln supplied "in cis" from the GTPase and an arginine finger "in trans" from a GAP (GTPase activating protein) to stabilize the transition state. However, intriguingly different mechanisms are operative in structurally similar GTPases. MnmE and dynamin like cation-dependent GTPases lack the catalytic Gln and instead employ a Glu/Asp/Ser situated elsewhere and in place of the arginine finger use a K(+) or Na(+) ion. In contrast, Rab33 possesses the Gln but does not utilize it for catalysis; instead, the GAP supplies both a catalytic Gln and an arginine finger in trans. Deciphering the underlying principles that unify seemingly unrelated mechanisms is central to understanding how diverse mechanisms evolve. Here, we recognize that steric hindrance between active site residues is a criterion governing the mechanism employed by a given GTPase. The Arf-ArfGAP structure is testimony to this concept of spatial (in)compatibility of active site residues. This understanding allows us to predict an as yet unreported hydrolysis mechanism and clarifies unexplained observations about catalysis by Rab11 and the need for HAS-GTPases to employ a different mechanism. This understanding would be valuable for experiments in which abolishing GTP hydrolysis or generating constitutively active forms of a GTPase is important.

  6. Analysis on the Load Carrying Mechanism Integrated as Heterogeneous Co-operative Manipulator in a Walking Wheelchair (United States)

    Rajay Vedaraj, I. S.; Jain, Ritika; Rao, B. V. A.


    After industrial robots came into existence during 1960, the technology of robotics with the design and analysis of robots in various forms in industries as well as in domestic applications were developed. Nowadays, along with the automotive sector the robots are producing a great impact in the form of quality and production rate to register their existence reliable in various other sectors also. Robotic technology has undergone various phase translations from being tortured as humanoids to the present day manipulators. Depending upon the various forms of its existence, robot manipulators are designed as serial manipulators and parallel manipulators. Individually both types can be proved effective though both have various drawbacks in design and the kinematic analysis. The versatility of robots can be increased by making them work in an environment where the same work volume is shared by more than one manipulator. This work volume can be identified as co-operative work volume of those manipulators. Here the interference of manipulators in the work volume of other manipulators is possible and is made obstacle free. The main advantage of co-operative manipulators is that when a number of independent manipulators are put together in a cooperative work envelope the efficiency and ability to perform tasks is greatly enhanced. The main disadvantage of the co-operative manipulators lies in the complication of its design even for a simple application, in almost all fields. In this paper, a cooperative design of robot manipulators to work in co-operative work environment is done and analysed for its efficacy. In the industrial applications when robotic manipulators are put together in more numbers, the trajectory planning becomes the tough task in the work cell. Proper design can remove the design defects of the cooperative manipulators and can be utilized in a more efficient way. In the proposed research paper an analysis is made on such a type of cooperative manipulator

  7. 克氏锥虫唾液酸转移酶催化机理的理论研究%Theoretical study on the catalytical mechanism of trans-sialidases from trypanosoma cruzi

    Institute of Scientific and Technical Information of China (English)

    冯燕; 管航敏


    克氏锥虫唾液酸转移酶(TcTs)是恰加斯病的致病原,它具有由6个β片构成的桶状催化结构域.该催化结构域集中在酶N端的边缘.本文利用量子力学/分子力学( QM/MM)联用的模型研究了克氏锥虫唾液酸转移酶的催化机理.初始酶和底物复合物模型由蛋白质晶体数据库得到(PDB ID:1SOI).其中QM部分在半经验模型中由AM1描述,在从头算模型中由B3LYP/6-31G*描述.MM部分只取酶的N端结构域,并始终由AMBER力场来描述.QM部分与MM部分成键相互作用边界用pseudo-bond方法处理,将3个重要的氨基酸残基(Glu230,Asp59,Tyr342)的Cα-Cβ键作为QM/MM模型中的pseudo-bond.由Nudged Elastic Band (NEB)路径优化方法得到的TcTs半经验的最低能量反应路径中,关键原子间距离沿最低能量路径的变化表明:反应开始后Glu230开始靠近Tyr342,当它们之间的氢键距离由2.9(A)缩短为2.4(A)时,Tyr342将质子转移给Glu230,增强了Tyr342酚氧负离子的碱性,更有利于Tyr342亲核进攻糖苷键.同时,Asp59作为酸,提供质子给糖苷键断裂后的离去基团.过程中,伴随着唾液酸的单糖糖环从扭曲的船式构象向松弛的椅式构象的转变,从而更有利于稳定生成的共价唾液酸-酶中间产物.对得到的半经验的最低能量反应路径再做B3LYP/6-31G*/MM模型下的优化,得到反应的能垒约为13.53 kcal/mol,说明该反应路径是合理的.研究结果与实验上通过突变的TcTSD59A推测的乒乓双置换酸碱催化的机理一致,是对实验结论的有力支持,为TcTs抑制剂的设计和结构修饰提供了理论参考,有助于预防和抗恰加斯病的新药物研发.%Trans-sialidases from Trypanosoma cruzi (TcTs) is the etiological agent of Chagas disease. It has a catalytic domain with a six-bladed β propeller topology on one side of the N-terminal domain. We investigated the catalytic mechanism of TcTs by Quantum Mechanical / Molecular Mechanical (QM

  8. Catalytic wet oxidation of black liquor


    Viader Riera, Gerard


    The major aspects of wet air oxidation and catalytic wet air oxidation have been reviewed in this work paying special attention to the reaction mechanisms, kinetics and the industrial process. In the experimental section a set of heterogeneous catalysts have been tested in the wet oxidation of non-wood black liquor. The oxidation runs were performed batchwise in a laboratory-scale mechanically stirred slurry reactor for 1 h at a temperature of 170°C and total pressure of 12 bar. Pure oxygen w...

  9. Method and apparatus for monitoring a hydrocarbon-selective catalytic reduction device (United States)

    Schmieg, Steven J; Viola, Michael B; Cheng, Shi-Wai S; Mulawa, Patricia A; Hilden, David L; Sloane, Thompson M; Lee, Jong H


    A method for monitoring a hydrocarbon-selective catalytic reactor device of an exhaust aftertreatment system of an internal combustion engine operating lean of stoichiometry includes injecting a reductant into an exhaust gas feedstream upstream of the hydrocarbon-selective catalytic reactor device at a predetermined mass flowrate of the reductant, and determining a space velocity associated with a predetermined forward portion of the hydrocarbon-selective catalytic reactor device. When the space velocity exceeds a predetermined threshold space velocity, a temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is determined, and a threshold temperature as a function of the space velocity and the mass flowrate of the reductant is determined. If the temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is below the threshold temperature, operation of the engine is controlled to regenerate the hydrocarbon-selective catalytic reactor device.

  10. Operation of Silicon-on-Insulator (SOI) Micro-ElectroMechanical Systems (MEMS) Gyroscopic Sensor as a Two-Axis Accelerometer (United States)


    TECHNICAL REPORT RDMR-WS-12-02 OPERATION OF SILICON-ON-INSULATOR (SOI) MICRO-ELECTROMECHANICAL SYSTEMS ( MEMS ) GYROSCOPIC SENSOR...DATES COVERED Final 4. TITLE AND SUBTITLE Operation of Silicon-on-Insulator (SOI) Micro-ElectroMechanical Systems ( MEMS ) Gyroscopic Sensor as a...existing Silicon-on-Insulator (SOI) Micro- ElectroMechanical Systems ( MEMS ) gyroscopic sensor previously developed in the early-2000s under MEMS

  11. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis

    Energy Technology Data Exchange (ETDEWEB)

    Greenwood, Alexander I.; Rogals, Monique J.; De, Soumya [Cornell University, Department of Molecular Biology and Genetics (United States); Lu, Kun Ping [Cancer Biology Program and Biology of Aging Program, Beth Israel Deaconess Medical Center, Harvard Medical School (United States); Kovrigin, Evgenii L. [Marquette University, Chemistry Department (United States); Nicholson, Linda K., E-mail: [Cornell University, Department of Molecular Biology and Genetics (United States)


    The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, k{sub cat}{sup cis} and apparent Michaelis constants, K{sub M}{sup App}. By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific {sup 13}C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide {sup 13}C-{sup 1}H constant time HSQC spectra to determine k{sub cat}{sup cis}, k{sub cat}{sup trans}, K{sub D}{sup cis}, and K{sub D}{sup trans} for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E{center_dot}trans]/[E{center_dot}cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

  12. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis. (United States)

    Greenwood, Alexander I; Rogals, Monique J; De, Soumya; Lu, Kun Ping; Kovrigin, Evgenii L; Nicholson, Linda K


    The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, [Formula: see text] and apparent Michaelis constants, [Formula: see text]. By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific (13)C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide (13)C-(1)H constant time HSQC spectra to determine [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E·trans]/[E·cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

  13. Revolutionary systems for catalytic combustion and diesel catalytic particulate traps.

    Energy Technology Data Exchange (ETDEWEB)

    Stuecker, John Nicholas; Witze, Peter O.; Ferrizz, Robert Matthew; Cesarano, Joseph, III; Miller, James Edward


    This report is a summary of an LDRD project completed for the development of materials and structures conducive to advancing the state of the art for catalyst supports and diesel particulate traps. An ancillary development for bio-medical bone scaffolding was also realized. Traditionally, a low-pressure drop catalyst support, such as a ceramic honeycomb monolith, is used for catalytic reactions that require high flow rates of gases at high-temperatures. A drawback to the traditional honeycomb monoliths under these operating conditions is poor mass transfer to the catalyst surface in the straight-through channels. ''Robocasting'' is a unique process developed at Sandia National Laboratories that can be used to manufacture ceramic monoliths with alternative 3-dimensional geometries, providing tortuous pathways to increase mass transfer while maintaining low-pressure drops. These alternative 3-dimensional geometries may also provide a foundation for the development of self-regenerating supports capable of trapping and combusting soot particles from a diesel engine exhaust stream. This report describes the structures developed and characterizes the improved catalytic performance that can result. The results show that, relative to honeycomb monolith supports, considerable improvement in mass transfer efficiency is observed for robocast samples synthesized using an FCC-like geometry of alternating rods. Also, there is clearly a trade-off between enhanced mass transfer and increased pressure drop, which can be optimized depending on the particular demands of a given application. Practical applications include the combustion of natural gas for power generation, production of syngas, and hydrogen reforming reactions. The robocast lattice structures also show practicality for diesel particulate trapping. Preliminary results for trapping efficiency are reported as well as the development of electrically resistive lattices that can regenerate the structure

  14. Catalytic quantum error correction

    CERN Document Server

    Brun, T; Hsieh, M H; Brun, Todd; Devetak, Igor; Hsieh, Min-Hsiu


    We develop the theory of entanglement-assisted quantum error correcting (EAQEC) codes, a generalization of the stabilizer formalism to the setting in which the sender and receiver have access to pre-shared entanglement. Conventional stabilizer codes are equivalent to dual-containing symplectic codes. In contrast, EAQEC codes do not require the dual-containing condition, which greatly simplifies their construction. We show how any quaternary classical code can be made into a EAQEC code. In particular, efficient modern codes, like LDPC codes, which attain the Shannon capacity, can be made into EAQEC codes attaining the hashing bound. In a quantum computation setting, EAQEC codes give rise to catalytic quantum codes which maintain a region of inherited noiseless qubits. We also give an alternative construction of EAQEC codes by making classical entanglement assisted codes coherent.

  15. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik


    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  16. Mechanized farming in the humid tropics with special reference to soil tillage, workability and timeliness of farm operations. A case study for the Zanderij area of Suriname

    NARCIS (Netherlands)

    Goense, D.


    The reported investigations concern aspects of mechanized farming for the production of rainfed crops on the loamy soils of the Zanderij formation in Suriname and in particular, the effect of tillage on crop yield and soil properties, workability of field operations and timeliness of field operation

  17. Preparation of catalytic ozonation membrane and analysis of humic acid removal mechanism%催化臭氧分离膜制备及去除腐殖酸机理分析

    Institute of Scientific and Technical Information of China (English)

    张海丰; 柴慧建; 赵贵龙; 张兰河; Song L


    To further improve the effectiveness of membrane process and reduce membrane fouling, catalytic membranes were prepared with the phase transfer method in order to realize microfiltration coupling and catalytic ozonation for micro-polluted water treatment. The sol-gel method was used to prepare TiO2,and nano-sized particles at different heat treatment temperatures were added into the casting solution. The characteristics of catalytic membranes were investigated with X-ray diffraction (XRD),scanning electron microscopy(SEM),water flux,porosity,and contact angle. The membranes catalytic efficiency and membrane separation processes were also investigated. Rutile TiO2 (namely PVDF/ TiO2-600) membrane achieved above 70% and 65% removal rate of humic acid (HA) and total organic carbon (TOC),respectively. The novel catalytic membrane exhibited good catalytic ozonation activity and anti-fouling property for HA removal,which demonstrated that catalytic ozonation membrane an emerging technique for water treatment.%以微污染水为处理对象,考察了新型催化膜的过滤性能及抗污染行为。实验过程中采用溶胶凝胶法制备纳米 TiO2粉体,将不同焙烧温度的纳米 TiO2颗粒加入铸膜液中,利用相转换法制备催化膜。采用 X 射线衍射(XRD)及扫描电子显微镜(SEM)对膜进行表征,对膜的纯水通量、孔隙率、接触角、膜的催化性能及分离特性进行了系统地测定。实验结果表明,金红石型TiO2催化膜对腐殖酸(humic acid,HA)及总有机碳(total organic carbon,TOC)的去除效率分别为70%及65%以上,说明金红石型 TiO2催化膜具有较高的污染物去除及抗污染特性。实验结果证实新型多功能膜对于水处理的实际应用具有较大的发展潜力。

  18. Upgrading of Intermediate Bio-Oil Produced by Catalytic Pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, Zia [Battelle Memorial Inst., Columbus, OH (United States); Chadwell, Brad [Battelle Memorial Inst., Columbus, OH (United States); Taha, Rachid [Battelle Memorial Inst., Columbus, OH (United States); Hindin, Barry [Battelle Memorial Inst., Columbus, OH (United States); Ralston, Kevin [Battelle Memorial Inst., Columbus, OH (United States)


    The objectives of this project were to (1) develop a process to upgrade catalytic pyrolysis bio-oil, (2) investigate new upgrading catalysts suited for upgrading catalytic pyrolysis bio-oil, (3) demonstrate upgrading system operation for more than 1,000 hours using a single catalyst charge, and (4) produce a final upgraded product that can be blended to 30 percent by weight with petroleum fuels or that is compatible with existing petroleum refining operations. This project has, to the best of our knowledge, for the first time enabled a commercially viable bio-oil hydrotreatment process to produce renewable blend stock for transportation fuels.

  19. Research on new type of fast-opening mechanism in steam turbine regulating system and optimization of operation tactic

    Institute of Scientific and Technical Information of China (English)

    Xiao-xiao LI; Xuan-yin WANG; Fu-shang LI


    With the analysis on regulating system in 200 MW steam turbine, the necessity of appending the fast-opening function to the original system is set forth and a new type of fast-opening mechanism is devised. The mathematical model of system is built up. With the use of AMESIM software, the displacement curve of the piston, the force curve of the cartridge valve spool, the pressure curve and the flux curve in the regulation process are obtained based on simulation. The performances of three fast-opening systems composed of cartridge valves with different diameters are compared. Based on the analysis on factors that affect the execution time of fast-opening, the dead zone of the fast-opening system is put forward, To overcome the defect, different operation modes are adopted for different zones. The result shows that with the increase of the valve diameter, the regulating time in the dead zone significantly exceeds the fast-opening time in the whole journey. Accordingly, the optimization operation tactic in the dead zone and the qualification conditions are brought forward. The fast-opening system composed of 32 mm cartridge valves is taken as an example with use of the tactic. The simulation result shows that the maximum regulating time is shortened by 509 ms.

  20. Unsteady catalytic processes and sorption-catalytic technologies

    Energy Technology Data Exchange (ETDEWEB)

    Zagoruiko, A N [G.K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)


    Catalytic processes that occur under conditions of the targeted unsteady state of the catalyst are considered. The highest efficiency of catalytic processes was found to be ensured by a controlled combination of thermal non-stationarity and unsteady composition of the catalyst surface. The processes based on this principle are analysed, in particular, catalytic selective reduction of nitrogen oxides, deep oxidation of volatile organic impurities, production of sulfur by the Claus process and by hydrogen sulfide decomposition, oxidation of sulfur dioxide, methane steam reforming and anaerobic combustion, selective oxidation of hydrocarbons, etc.

  1. Material characterisation and preliminary mechanical design for the HL-LHC shielded beam screens operating at cryogenic temperatures. (United States)

    Garion, C.; Dufay-Chanat, L.; Koettig, T.; Machiocha, W.; Morrone, M.


    The High Luminosity LHC project (HL-LHC) aims at increasing the luminosity (rate of collisions) in the Large Hadron Collider (LHC) experiments by a factor of 10 beyond the original design value (from 300 to 3000 fb-1). It relies on new superconducting magnets, installed close to the interaction points, equipped with new beam screen. This component has to ensure the vacuum performance together with shielding the cold mass from physics debris and screening the cold bore cryogenic system from beam induced heating. The beam screen operates in the range 40-60 K whereas the magnet cold bore temperature is 1.9 K. A tungsten-based material is used to absorb the energy of particles. In this paper, measurements of the mechanical and physical properties of such tungsten material are shown at room and cryogenic temperature. In addition, the design and the thermal mechanical behaviour of the beam screen assembly are presented also. They include the heat transfer from the tungsten absorbers to the cooling pipes and the supporting system that has to minimise the heat inleak into the cold mass. The behaviour during a magnet quench is also presented.

  2. Failure Mechanisms and Color Stability in Light-Emitting Diodes during Operation in High- Temperature Environments in Presence of Contamination

    Energy Technology Data Exchange (ETDEWEB)

    Lall, Pradeep; Zhang, Hao; Davis, J Lynn


    The energy efficiency of light-emitting diode (LED) technology compared to incandescent light bulbs has triggered an increased focus on solid state luminaries for a variety of lighting applications. Solid-state lighting (SSL) utilizes LEDs, for illumination through the process of electroluminescence instead of heating a wire filament as seen with traditional lighting. The fundamental differences in the construction of LED and the incandescent lamp results in different failure modes including lumen degradation, chromaticity shift and drift in the correlated color temperature. The use of LED-based products for safety-critical and harsh environment applications necessitates the characterization of the failure mechanisms and modes. In this paper, failure mechanisms and color stability has been studied for commercially available vertical structured thin film LED (VLED) under harsh environment conditions with and without the presence of contaminants. The VLED used for the study was mounted on a ceramic starboard in order to connect it to the current source. Contamination sources studied include operation in the vicinity of vulcanized rubber and adhesive epoxies in the presence of temperature and humidity. Performance of the VLEDs has been quantified using the measured luminous flux and color shift of the VLEDs subjected to both thermal and humidity stresses under a forward current bias of 350 mA. Results indicate that contamination can result in pre-mature luminous flux degradation and color shift in LEDs.

  3. Material characterisation and preliminary mechanical design for the HL-LHC shielded beam screens operating at cryogenic temperatures

    CERN Document Server

    Garion, C; Koettig, T; Machiocha, W; Morrone, M


    The High Luminosity LHC project (HL-LHC) aims at increasing the luminosity (rate of collisions) in the Large Hadron Collider (LHC) experiments by a factor of 10 beyond the original design value (from 300 to 3000 fb-1). It relies on new superconducting magnets, installed close to the interaction points, equipped with new beam screen. This component has to ensure the vacuum performance together with shielding the cold mass from physics debris and screening the cold bore cryogenic system from beam induced heating. The beam screen operates in the range 40-60 K whereas the magnet cold bore temperature is 1.9 K. A tungsten-based material is used to absorb the energy of particles. In this paper, measurements of the mechanical and physical properties of such tungsten material are shown at room and cryogenic temperature. In addition, the design and the thermal mechanical behaviour of the beam screen assembly are presented also. They include the heat transfer from the tungsten absorbers to the cooling pipes and the sup...


    Directory of Open Access Journals (Sweden)

    A. V. Pavlov


    Full Text Available A mechanism of cognitive dissonance reducing is demonstrated with approach for non-monotonic fuzzy-valued logics by Fourier-holography technique implementation developing. Cognitive dissonance occurs under perceiving of new information that contradicts to the existing subjective pattern of the outside world, represented by double Fourier-transform cascade with a hologram – neural layers interconnections matrix of inner information representation and logical conclusion. The hologram implements monotonic logic according to “General Modus Ponens” rule. New information is represented by a hologram of exclusion that implements interconnections of logical conclusion and exclusion for neural layers. The latter are linked by Fourier transform that determines duality of the algebra forming operations of conjunction and disjunction. Hologram of exclusion forms conclusion that is dual to the “General Modus Ponens” conclusion. It is shown, that trained for the main rule and exclusion system can be represented by two-layered neural network with separate interconnection matrixes for direct and inverse iterations. The network energy function is involved determining the cyclic dynamics character; dissipative factor causing convergence type of the dynamics is analyzed. Both “General Modus Ponens” and exclusion holograms recording conditions on the dynamics and convergence of the system are demonstrated. The system converges to a stable status, in which logical conclusion doesn’t depend on the inner information. Such kind of dynamics, leading to tolerance forming, is typical for ordinary kind of thinking, aimed at inner pattern of outside world stability. For scientific kind of thinking, aimed at adequacy of the inner pattern of the world, a mechanism is needed to stop the net relaxation; the mechanism has to be external relative to the model of logic. Computer simulation results for the learning conditions adequate to real holograms recording are

  5. Differential clearance mechanisms, neutrophil extracellular trap degradation and phagocytosis, are operative in systemic lupus erythematosus patients with distinct autoantibody specificities. (United States)

    Chauhan, Sudhir Kumar; Rai, Richa; Singh, Vikas Vikram; Rai, Madhukar; Rai, Geeta


    Systemic lupus erythematosus (SLE) patients are generally presented with autoantibodies against either dsDNA or RNA-associated antigens (also known as extractable nuclear antigens, ENA) or both. However, the mechanisms and processes that lead to this distinctive autoantibody profile are not well understood. Defects in clearance mechanism i.e. phagocytosis may lead to enhanced microbial and cellular debris of immunogenic potential. In addition to defective phagocytosis, impaired neutrophil extracellular trap (NET) degradation has been recently reported in SLE patients. However, the extent to which both these clearance processes (NET-degradation and phagocytosis) are operative in serologically distinguished subsets of SLE patients is not established. Therefore, in this report, we evaluated NET-degradation and phagocytosis efficiency among SLE patients with different autoantibody specificities. SLE patients were classified into three subsets based on their autoantibody profile (anti-dsDNA, anti-ENA or both) as determined by ELISA. NET-degradation by SLE and control sera was assessed by sytox orange-based fluorescence assay. Neutrophil-mediated phagocytosis in the presence of SLE and control sera was determined by flowcytometry. The segregation of SLE patients revealed significant differences in NET-degradation and phagocytosis in SLE patients with autoantibodies against dsDNA and ENA. We report that NET-degradation efficiency was significantly impaired in SLE patients with anti-dsDNA autoantibodies and not in those with anti-ENA autoantibodies. In contrast to NET-degradation, neutrophil-mediated phagocytosis was impaired in all three subsets independent of autoantibody specificity. These observations suggest that varying clearance mechanisms are operative in SLE subsets with anti-dsDNA or anti-ENA autoantibodies. The results outlined in this manuscript also suggest that sub-grouping of SLE patients could be useful in delineating the molecular and pathological

  6. Development of Catalytic Cooking Plates

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin; Silversand, Fredrik [CATATOR AB, Lund (Sweden); Tena, Emmanuel; Berger, Marc [Gaz de France (France)


    Gas catalytic combustion for gas stoves or cooking plates (closed catalytic burner system with ceramic plates) is a very promising technique in terms of ease of cleaning, power modulation and emissions. Previous investigations show that wire mesh catalysts, prepared and supplied by Catator AB (CAT), seem to be very well suited for such applications. Beside significantly reducing the NOx-emissions, these catalysts offer important advantages such as good design flexibility, low pressure drop and high heat transfer capacity, where the latter leads to a quick thermal response. Prior to this project, Gaz de France (GdF) made a series of measurements with CAT's wire mesh catalysts in their gas cooking plates and compared the measured performance with similar results obtained with theirs cordierite monolith catalysts. Compared to the monolith catalyst, the wire mesh catalyst was found to enable very promising results with respect to both emission levels (<10 mg NO{sub x} /kWh, <5 mg CO/kWh) and life-time (>8000 h vs. 700 h at 200 kW/m{sup 2}). It was however established that the radiation and hence, the thermal efficiency of the cooking plate, was significantly less than is usually measured in combination with the monolith (15 % vs. 32 %). It was believed that the latter could be improved by developing new burner designs based on CAT's wire mesh concept. As a consequence, a collaboration project between GdF, CAT and the Swedish Gas Technology AB was created. This study reports on the design, the construction and the evaluation of new catalytic burners, based on CAT's wire mesh catalysts, used for the combustion of natural gas in gas cooking stoves. The evaluation of the burners was performed with respect to key factors such as thermal efficiency, emission quality and pressure drop, etc, by the use of theoretical simulations and experimental tests. Impacts of parameters such as the the wire mesh number, the wire mesh structure (planar or folded), the

  7. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.


    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  8. Lipoprotein lipase-catalyzed hydrolysis of phosphatidylcholine of guinea pig very low density lipoproteins and discoidal complexes of phospholipid and apolipoprotein: effect of apolipoprotein C-II on the catalytic mechanism. (United States)

    Shirai, K; Fitzharris, T J; Shinomiya, M; Muntz, H G; Harmony, J A; Jackson, R L; Quinn, D M


    that apoC-II enhances phospholipid hydrolysis by LpL in apoC-III-DPPC discoidal complexes and VLDL(p) mainly by increasing the V(max) of the enzyme for the substrates, whereas the activator protein primarily causes a decrease in the apparent K(m) for triacylglycerol hydrolysis.-Shirai, K., T. J. Fitzharris, M. Shinomiya, H. G. Muntz, J. A. K. Harmony, R. L. Jackson and D. M. Quinn. Lipoprotein lipase-catalyzed hydrolysis of phosphatidylcholine of guinea pig very low density lipoproteins and discoidal complexes of phospholipid and apolipoprotein: effect of apolipoprotein C-II on the catalytic mechanism.

  9. A catalytic distillation process for light gas oil hydrodesulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Vargas-Villamil, F.D.; Marroquin, J.O.; Paz, C. de la; Rodriguez, E. [Prog. de Matematicas Aplicadas y Computacion, Prog. de Tratamiento de Crudo Maya, Instituto Mexicano del Petroleo, Mexico City, DF (Mexico)


    A light gas oil hydrodesulfurization process via catalytic distillation is developed and compared to a conventional process. By integrating the separation and reaction into a single unit, the catalytic distillation may produce a diesel with low concentration of sulfur compounds at a lower cost than the traditional reaction/separation process. The process proposed in this work is compared to an optimised conventional hydrodesulfurization unit which represents fairly well a plant that belongs to the National System of Refineries. During the optimisation of the conventional process, a compromise is established among the production of diesel and naphtha and the operating costs. The results show that the light gas oil hydrodesulfurization via catalytic distillation is as or more efficient than the conventional process. However, the removal of the sulfur compounds is carried out under less rigorous conditions. This design reduces the fix and operational costs. (author)

  10. Catalytic Membrane Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.


    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  11. Catalytic gasification of biomass (United States)

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


    Methane and methanol synthesis gas can be produced by steam gasification of biomass in the presence of appropriate catalysts. This concept is to use catalysts in a fluidized bed reactor which is heated indirectly. The objective is to determine the technical and economic feasibility of the concept. Technically the concept has been demonstrated on a 50 lb per hr scale. Potential advantages over conventional processes include: no oxygen plant is needed, little tar is produced so gas and water treatment are simplified, and yields and efficiencies are greater than obtained by conventional gasification. Economic studies for a plant processing 2000 T/per day dry wood show that the cost of methanol from wood by catalytic gasification is competitive with the current price of methanol. Similar studies show the cost of methane from wood is competitive with projected future costs of synthetic natural gas. When the plant capacity is decreased to 200 T per day dry wood, neither product is very attractive in today's market.

  12. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)


    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  13. A new exact quantum mechanical rovibrational kinetic energy operator for penta-atomic systems in internal coordinates

    Institute of Scientific and Technical Information of China (English)

    陈光巨; 李玉学


    The concrete molecule-fixed (MF) kinetic energy operator for penta-atomic molecules is expressed in terms of the parameterδ, the matrix element G?, and angular momentum operator (?). The applications of the operator are also discussed. Finally, a general compact form of kinetic energy operator suitable for calculating the rovibrational spectra of polyatomie molecules is presented.

  14. Geo-mechanical Model Testing for Stability of Underground Gas Storage in Halite During the Operational Period (United States)

    Chen, Xuguang; Zhang, Qiangyong; Li, Shucai; Liu, Dejun


    A 3D geo-mechanical model test is conducted to study the stability of underground gas storage in halite, modeled after the Jintan gas storage constructed in bedded salt rock in China. A testing apparatus is developed to generate long-term stable trapezoid geostresses onto the model cavity, corresponding to the actual gas storage cavern. The time-depending character of the material is simulated using a rheological material, which was tested using a self-developed apparatus. The model cavern is built using an ellipsoid wooden mold divided into small blocks which are assembled and placed into the designed position during the model construction. They are then pulled out one by one to form the cavern. The ellipsoid cavern wall is then lined within a latex balloon. Gas is injected into the cavity and extracted to simulate the operational process of gas injection and recovery. Optical sensors embedded into the model to measure the displacement around the cavity showed that the largest deformation occurs in the middle section of the cavity. The deformation rate increases with increasing gas pressure. At 11 MPa the cavity is in equilibrium with the geostress. The pressure is highest during the gas recovery stages, indicating that gas recovery can threaten the cavern's operational stability, while high gas injection causes rock mass compression and deformation outward from the cavern. The deformation is the combination of cavern convergence and gas-induced rebound which leads to tensile and compression during gas injection and recovery. Hence, the fatigue properties of salt rock should be studied further.

  15. 开放教育下的MOOCs运营机制研究%MOOCs Operational Mechanism in Open Education

    Institute of Scientific and Technical Information of China (English)

    肖君; 胡艺龄; 陈婧雅; 吴忭


    随着开放教育与互联网深度整合的第三次浪潮来袭,开放教育资源(OER)运动持续发酵。大规模开放网络课程(MOOCs)以其独特的开放特性为终身学习者及学习型社会提供了发展机会,在不断拓展教育疆域、吸引新学生、改善学习体验的基础上,逐步将在线课程纳入常规教学途径和企业培训之中,但在这变革之中却缺乏有效的运营机制和相关设计。该文立足于开放教育模式下的MOOCs发展,形成对其运营机制的思考,在分析全球范围内具有一定影响力的平台运营特征基础上,为我国开放教育下的MOOCs运营及发展提供支撑。%With the third wave of deep integration of open education and Internet, the Open Educational Resources (OER) movement is continually developing. Massive Open Online Courses (MOOCs) provide chances for the development of lifelong learners and our learning society with its unique openness characteristics. Which can expand educational area, attract new students, improve learning experience, and gradually integrate online courses into both school education and workplace training. But the lack of effective design to support MOOCs operating and development in open education makes the outcome not distinct. This paper focused on the operating mechanism of MOOCs from the perspective of open education. And some relevant mechanisms are proposed on the basis of analyzing features of MOOCs platform that have a certain inlfuence around the world.

  16. Catalytic partial oxidation of pyrolysis oils (United States)

    Rennard, David Carl


    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

  17. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)

    洪文明; 王梓坤


    The longtime behavior of the immigration process associated with a catalytic super-Brown-ian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d = 3.

  18. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)


    The longtime behavior of the immigration process associated with a catalytic super-Brownian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d=3.

  19. Operating mechanism and molecular dynamics of pheromone-binding protein ASP1 as influenced by pH.

    Directory of Open Access Journals (Sweden)

    Lei Han

    Full Text Available Odorant binding protein (OBP is a vital component of the olfactory sensation system. It performs the specific role of ferrying odorant molecules to odorant receptors. OBP helps insects and types of animal to sense and transport stimuli molecules. However, the molecular details about how OBPs bind or release its odorant ligands are unclear. For some OBPs, the systems' pH level is reported to impact on the ligands' binding or unbinding capability. In this work we investigated the operating mechanism and molecular dynamics in bee antennal pheromone-binding protein ASP1 under varying pH conditions. We found that conformational flexibility is the key factor for regulating the interaction of ASP1 and its ligands, and the odorant binds to ASP1 at low pH conditions. Dynamics, once triggered by pH changes, play the key roles in coupling the global conformational changes with the odorant release. In ASP1, the C-terminus, the N-terminus, helix α2 and the region ranging from helices α4 to α5 form a cavity with a novel 'entrance' of binding. These are the major regions that respond to pH change and regulate the ligand release. Clearly there are processes of dynamics and hydrogen bond network propagation in ASP1 in response to pH stimuli. These findings lead to an understanding of the mechanism and dynamics of odorant-OBP interaction in OBP, and will benefit chemsensory-related biotech and agriculture research and development.

  20. An empirical determination of upper operational frequency limits of transferred electron mechanism in bulk GaAs and GaN through ensemble Monte Carlo particle simulations (United States)

    Francis, S.; van Zyl, R. R.; Perold, W. J.


    The ensemble Monte Carlo particle simulation technique is used to determine the upper operational frequency limit of the transferred electron mechanism in bulk GaAs and GaN empirically. This mechanism manifests as a decrease in the average velocity of the electrons in the bulk material with an increase in the electric field bias, which yields the characteristic negative slope in the velocity-field curves of these materials. A novel approach is proposed whereby the hysteresis in the simulated dynamic, high-frequency velocity-field curves is exploited. The upper operational frequency limit supported by the material is defined as that frequency, where the average gradient of the dynamic characteristic curve over a radio frequency cycle approaches zero. Effects of temperature and doping level on the operational frequency limit are reported. The frequency limit thus obtained is also useful to predict the highest fundamental frequency of operation of transferred electron devices, such as Gunn diodes, which are based on materials that support the transferred electron mechanism. Based on the method presented here, the upper operational frequency limits of the transferred electron mechanism in bulk GaAs and GaN are 80 and 255 GHz, respectively, at typical doping levels and operating temperatures of Gunn diodes.

  1. Mechanically exfoliated black phosphorus as a new saturable absorber for both Q-switching and Mode-locking laser operation. (United States)

    Chen, Yu; Jiang, Guobao; Chen, Shuqing; Guo, Zhinan; Yu, Xuefeng; Zhao, Chujun; Zhang, Han; Bao, Qiaoliang; Wen, Shuangchun; Tang, Dingyuan; Fan, Dianyuan


    Black phosphorus (BP), an emerging narrow direct band-gap two-dimensional (2D) layered material that can fill the gap between the semi-metallic graphene and the wide-bandgap transition metal dichalcogenides (TMDs), had been experimentally found to exhibit the saturation of optical absorption if under strong light illumination. By taking advantage of this saturable absorption property, we could fabricate a new type of optical saturable absorber (SA) based on mechanically exfoliated BPs, and further demonstrate the applications for ultra-fast laser photonics. Based on the balanced synchronous twin-detector measurement method, we have characterized the saturable absorption property of the fabricated BP-SAs at the telecommunication band. By incorporating the BP-based SAs device into the all-fiber Erbium-doped fiber laser cavities, we are able to obtain either the passive Q-switching (with maximum pulse energy of 94.3 nJ) or the passive mode-locking operation (with pulse duration down to 946 fs). Our results show that BP could also be developed as an effective SA for pulsed fiber or solid-state lasers.

  2. 高负荷下臭氧催化氧化深度处理丙烯腈废水运行特性%Operation characteristics of catalytic ozonation under the high load condition for the treatment of acrylonitrile wastewater

    Institute of Scientific and Technical Information of China (English)



    采用臭氧催化氧化技术对大庆炼化公司丙烯腈废水进行深度处理,处理能力为20 m3/h。在实际进水COD远远高于设计进水浓度条件下,臭氧催化氧化装置对COD的去除总量大大高于设计值(1 kg/h),平均为1.88 kg/h。在高负荷条件下,该装置处理效果优于预期,但同时也存在催化剂污染等问题。通过每周1次的定期气水联合反洗,可保证装置稳定运行并维持良好的处理效果。%Catalytic ozo nation technology has been used for the advanced treatment of the acrylonitrile wastewater from Daqing Branch,Oil Refinery Chemical Co.,CNPC,whose treatment capacity is 20 m3/h. Under the condition that the COD of actual influent is much higher than the designed influent concentration ,the total amount of COD removing capacity is averagely 1.88 kg/h,much higher than the initially designed value,1 kg/h. Under the high load condition,the treatment effect of this system is better than what was expected,but in the meanwhile,problems,such as catalyst pollution,etc.,have occurred. By means of periodic air-water backwashing once a week,the system can run steadily and keep good treatment effect.

  3. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  4. Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    Yongki Choi


    Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

  5. Biofuel from fast pyrolysis and catalytic hydrodeoxygenation.

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.


    This review addresses recent developments in biomass fast pyrolysis bio-oil upgrading by catalytic hydrotreating. The research in the field has expanded dramatically in the past few years with numerous new research groups entering the field while existing efforts from others expand. The issues revolve around the catalyst formulation and operating conditions. Much work in batch reactor tests with precious metal catalysts needs further validation to verify long-term operability in continuous flow systems. The effect of the low level of sulfur in bio-oil needs more study to be better understood. Utilization of the upgraded bio-oil for feedstock to finished fuels is still in an early stage of understanding.

  6. Modified Decomposition Method with New Inverse Differential Operators for Solving Singular Nonlinear IVPs in First- and Second-Order PDEs Arising in Fluid Mechanics

    Directory of Open Access Journals (Sweden)

    Nemat Dalir


    Full Text Available Singular nonlinear initial-value problems (IVPs in first-order and second-order partial differential equations (PDEs arising in fluid mechanics are semianalytically solved. To achieve this, the modified decomposition method (MDM is used in conjunction with some new inverse differential operators. In other words, new inverse differential operators are developed for the MDM and used with the MDM to solve first- and second-order singular nonlinear PDEs. The results of the solutions by the MDM together with new inverse operators are compared with the existing exact analytical solutions. The comparisons show excellent agreement.

  7. Mechanics

    CERN Document Server

    Hartog, J P Den


    First published over 40 years ago, this work has achieved the status of a classic among introductory texts on mechanics. Den Hartog is known for his lively, discursive and often witty presentations of all the fundamental material of both statics and dynamics (and considerable more advanced material) in new, original ways that provide students with insights into mechanical relationships that other books do not always succeed in conveying. On the other hand, the work is so replete with engineering applications and actual design problems that it is as valuable as a reference to the practicing e

  8. Catalytic control over the formation of supramolecular materials

    NARCIS (Netherlands)

    Eelkema, R; Esch, van J.H.


    In this Perspective, we will discuss how the rate of formation of supramolecular materials can be drastically enhanced by catalytically controlling the rate of formation of their molecular building blocks, resulting in the formation of out-of-equilibrium soft materials with enhanced mechanical prope

  9. In situ DRIFTs investigation of the reaction mechanism over MnOx-MOy/Ce0.75Zr0.25O2 (M = Fe, Co, Ni, Cu) for the selective catalytic reduction of NOx with NH3 (United States)

    Hu, Hang; Zha, Kaiwen; Li, Hongrui; Shi, Liyi; Zhang, Dengsong


    A series of MnOx-MOy/Ce0.75Zr0.25O2 (M = Fe, Co, Ni, Cu) catalysts were synthesized by an impregnation method and used for selective catalytic reduction (SCR) of NOx with NH3. The catalytic performances of various MnOx-MOy/Ce0.75Zr0.25O2 catalysts were studied. It was found that MnOx-FeOy/Ce0.75Zr0.25O2 catalyst showed excellent low-temperature activity and a broad temperature window. The catalysts were characterized by N2 adsorption/desorption, X-ray diffraction, X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared transform spectroscopy (DRIFTS). Characterization of the catalyst confirmed the addition of iron oxide can enhance the NO oxidation ability of the catalyst which results in the outstanding low-temperature SCR activity. Meanwhile, iron oxides were well dispersed on catalyst surface which could avoid the agglomeration of active species, contributing to the strong interaction between active species and the support. More importantly, in situ DRIFTS results confirmed that bidentate nitrates are general active species on these catalysts, whereas the reactivity of gaseous NO2 and bridged nitrates got improved because of the addition of Fe.

  10. Hydrogen production via catalytic processing of renewable feedstocks

    Energy Technology Data Exchange (ETDEWEB)

    Nazim Muradov; Franklyn Smith; Ali T-Raissi [Florida Solar Energy Center, University of Central Florida, Cocoa, Florida, (United States)


    Landfill gas (LFG) and biogas can potentially become important feedstocks for renewable hydrogen production. The objectives of this work were: (1) to develop a catalytic process for direct reforming of CH{sub 4}-CO{sub 2} gaseous mixture mimicking LFG, (2) perform thermodynamic analysis of the reforming process using AspenPlus chemical process simulator, (3) determine operational conditions for auto-thermal (or thermo-neutral) reforming of a model CH{sub 4}-CO{sub 2} feedstock, and (4) fabricate and test a bench-scale hydrogen production unit. Experimental data obtained from catalytic reformation of the CH{sub 4}-CO{sub 2} and CH{sub 4}-CO{sub 2}-O{sub 2} gaseous mixtures using Ni-catalyst were in a good agreement with the simulation results. It was demonstrated that catalytic reforming of LFG-mimicking gas produced hydrogen with the purity of 99.9 vol.%. (authors)

  11. Exact quantum mechanical vibration-rotation kinetic energy operator of four-particle system in various coordinates

    Institute of Scientific and Technical Information of China (English)

    陈光巨; 刘若庄


    The vibration-rotational kinetic energy operators of four-particle system in various coordinates are derived using a new and simple angular momentum method. The operators are respectively suitable for studying the systems described by scattering coordinate, valence coordinate, Radau coordinate, Radau/Jacobi and Jacobi/valence hybrid coordinates and so on. Certain properties of these operators and their possible applications are discussed.

  12. Development of integrated, zero-G pneumatic transporter/rotating paddle incinerator/catalytic afterburner subsystem for processing human wastes on board spacecraft (United States)

    Fields, S. F.; Labak, L. J.; Honegger, R. J.


    A four component system was developed which consists of a particle size reduction mechanism, a pneumatic waste transport system, a rotating-paddle incinerator, and a catalytic afterburner to be integrated into a six-man, zero-g subsystem for processing human wastes on board spacecraft. The study included the development of different concepts or functions, the establishment of operational specifications, and a critical evaluation for each of the four components. A series of laboratory tests was run, and a baseline subsystem design was established. An operational specification was also written in preparation for detailed design and testing of this baseline subsystem.

  13. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Vivek V Ranade


    Catalytic reactions are ubiquitous in chemical and allied industries. A homogeneous or heterogeneous catalyst which provides an alternative route of reaction with lower activation energy and better control on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach.

  14. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne;


    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  15. Final Report of a CRADA Between Pacific Northwest National Laboratory and the Ford Motor Company (CRADA No. PNNL/265): “Deactivation Mechanisms of Base Metal/Zeolite Urea Selective Catalytic Reduction Materials, and Development of Zeolite-Based Hydrocarbon Adsorber Materials”

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Kwak, Ja Hun; Lee, Jong H.; Tran, Diana N.; Peden, Charles HF; Howden, Ken; Cheng, Yisun; Lupescu, Jason; Cavattaio, Giovanni; Lambert, Christine; McCabe, Robert W.


    Reducing NOx emissions and particulate matter (PM) are primary concerns for diesel vehicles required to meet current LEV II and future LEV III emission standards which require 90+% NOx conversion. Currently, urea SCR as the NOx reductant and a Catalyzed Diesel Particulate Filter (CDPF) are being used for emission control system components by Ford Motor Company for 2010 and beyond diesel vehicles. Because the use of this technology for vehicle applications is new, the relative lack of experience makes it especially challenging to satisfy durability requirements. Of particular concern is being able to realistically simulate actual field aging of the catalyst systems under laboratory conditions. This is necessary both as a rapid assessment tool for verifying improved performance and certifiability of new catalyst formulations, and to develop a good understanding of deactivation mechanisms that can be used to develop improved catalyst materials. In addition to NOx and PM, the hydrocarbon (HC) emission standards are expected to become much more stringent during the next few years. Meanwhile, the engine-out HC emissions are expected to increase and/or be more difficult to remove. Since HC can be removed only when the catalyst becomes warm enough for its oxidation, three-way catalyst (TWC) and diesel oxidation catalyst (DOC) formulations often contain proprietary zeolite materials to hold the HC produced during the cold start period until the catalyst reaches its operating temperature (e.g., >200°C). Unfortunately, much of trapped HC tends to be released before the catalyst reaches the operating temperature. Among materials effective for trapping HC during the catalyst warm-up period, siliceous zeolites are commonly used because of their high surface area and high stability under typical operating conditions. However, there has been little research on the physical properties of these materials related to the adsorption and release of various hydrocarbon species found in

  16. 小型断路器操作机构的动作可靠性分析%Action Reliability Analysis of Operating Mechanism in Miniature Circuit Breaker

    Institute of Scientific and Technical Information of China (English)

    陈文华; 张文; 潘骏; 张廷秀; 陈丽丽


    The operating mechanism action reliability of miniature circuit breaker was studied.The action reliability of miniature circuit breaker was investigated and the mechanism action reliability model was built at the overload breaking moment by using Monte Carlo method of mechanism reliabilG ity design theory.Meanwhile,the action reliability sensitivity of mechanism was analyzed,which gave out the variation laws of random parameters reliability sensitivity and the impacts of random parameG ter changes to operating mechanism action reliability.The analytical results indicate that the method used herein can analyze action reliability of miniature circuit breaker operating mechanism effectively and provide a basis for the design of miniature circuit breaker operating mechanism as well.%对小型断路器操作机构的动作可靠性灵敏度进行探讨。运用机构可靠性设计理论中的Monte Carlo 法分析了操作机构在过载分断时的动作可靠性,构建了操作机构在过载分断时的动作可靠性模型;同时,利用 Monte Carlo 法分析了操作机构的动作可靠性灵敏度,给出了操作机构随机参数可靠性灵敏度的变化规律,研究了随机参数的改变对操作机构动作可靠性的影响。结果表明,该方法能够有效地分析小型断路器操作机构的动作可靠性,同时也可为小型断路器操作机构的可靠性设计提供参考。

  17. Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

    Energy Technology Data Exchange (ETDEWEB)

    Eteman, Shahrokh


    Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

  18. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric


    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations...... and quantum state merging, and leads to a resource theory of decoupling....

  19. Progress of catalytic wet air oxidation technology

    Directory of Open Access Journals (Sweden)

    Guolin Jing


    Full Text Available Catalytic wet air oxidation (CWAO is one of the most economical and environmental-friendly advanced oxidation process for high strength, toxic, hazardous and non-biodegradable contaminants under milder conditions, which is developed on the basic of wet air oxidation. Various heterogeneous catalysts including noble metals and metal oxides have been extensively studied to enhance the efficiency of CWAO. The advances in the research on wastewater treatment by CWAO process are summarized in aspects of reaction mechanism investigation, reaction kinetics study and catalyst development. It is pointed out that the preparation of active and stable catalysts, the investigation on reaction mechanisms and the study on reaction kinetics models are very important for the promotion of CWAO application.

  20. Electro-catalytic degradation of sulfisoxazole by using graphene anode. (United States)

    Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng


    Graphite and graphene electrodes were prepared by using pure graphite as precursor. The electrode materials were characterized by a scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) measurements. The electro-catalytic activity for degradation of sulfisoxazole (SIZ) was investigated by using prepared graphene or graphite anode. The results showed that the degradation of SIZ was much more rapid on the graphene than that on the graphite electrode. Moreover, the graphene electrode exhibited good stability and recyclability. The analysis on the intermediate products and the measurement of active species during the SIZ degradation demonstrated that indirect oxidation is the dominant mechanism, involving the electro-catalytic generation of OH and O2(-) as the main active oxygen species. This study implies that graphene is a promising potential electrode material for long-term application to electro-catalytic degradation of organic pollutants.

  1. Complex Wall Boundary Conditions for Modeling Combustion in Catalytic Channels (United States)

    Zhu, Huayang; Jackson, Gregory


    Monolith catalytic reactors for exothermic oxidation are being used in automobile exhaust clean-up and ultra-low emissions combustion systems. The reactors present a unique coupling between mass, heat, and momentum transport in a channel flow configuration. The use of porous catalytic coatings along the channel wall presents a complex boundary condition when modeled with the two-dimensional channel flow. This current work presents a 2-D transient model for predicting the performance of catalytic combustion systems for methane oxidation on Pd catalysts. The model solves the 2-D compressible transport equations for momentum, species, and energy, which are solved with a porous washcoat model for the wall boundary conditions. A time-splitting algorithm is used to separate the stiff chemical reactions from the convective/diffusive equations for the channel flow. A detailed surface chemistry mechanism is incorporated for the catalytic wall model and is used to predict transient ignition and steady-state conversion of CH4-air flows in the catalytic reactor.

  2. Simple, chemoselective, catalytic olefin isomerization. (United States)

    Crossley, Steven W M; Barabé, Francis; Shenvi, Ryan A


    Catalytic amounts of Co(Sal(tBu,tBu))Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.

  3. Catalytic Asymmetric Bromocyclization of Polyenes. (United States)

    Samanta, Ramesh C; Yamamoto, Hisashi


    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  4. 管道爬行机器人机构设计%Operating principle of a pipeline robot crawling mechanism

    Institute of Scientific and Technical Information of China (English)

    李杰; 郭瑞杰; 王忠


    采用对称分布的两组曲柄滑块机构,设计了管道爬行机器人机构,既保持了机构的对称性,又增加了滑块的移动距离.其防逆方法采用楔形块挤压自锁.该机构成功地解决了管道爬行机器人的双向自锁和双向移动问题.采用棘轮机构对曲柄实施单向运动控制,通过电机的正转和反转来控制机器人的前进和倒退,使机器人能在管道内平稳移动.%Regarding the pipeline of the West-East Natural Gas Transmission Project as parameter background, this paper presents a pipeline robot crawling mechanism and makes a detailed illustration on the principle that the link mechanism crawling in the pipeline. This crawling mechanism takes the simple crank mechanism and the parallelogram linkage as the basic mechanism, though simple variation and combination, the forward walking and direction changing for the mechanism in the pipeline has been achieved, and also has good function of self-locking and reducing. The result shows that the mechanism has a good application prospect.

  5. Mechanics

    CERN Document Server

    Chester, W


    When I began to write this book, I originally had in mind the needs of university students in their first year. May aim was to keep the mathematics simple. No advanced techniques are used and there are no complicated applications. The emphasis is on an understanding of the basic ideas and problems which require expertise but do not contribute to this understanding are not discussed. How­ ever, the presentation is more sophisticated than might be considered appropri­ ate for someone with no previous knowledge of the subject so that, although it is developed from the beginning, some previous acquaintance with the elements of the subject would be an advantage. In addition, some familiarity with element­ ary calculus is assumed but not with the elementary theory of differential equations, although knowledge of the latter would again be an advantage. It is my opinion that mechanics is best introduced through the motion of a particle, with rigid body problems left until the subject is more fully developed. Howev...

  6. On the Operation Mechanism of the University Culture Construction%大学文化建设运行机制分析

    Institute of Scientific and Technical Information of China (English)



    大学文化建设运行机制是一个有机体系,在大学文化建设中起着基础性作用。其中,核心价值体系的引导机制是大学文化建设的灵魂,切实有效的组织调控机制是大学文化建设的核心架构,文化互动机制是大学文化建设共融互动、协同发展的基础,创新激励机制是大学文化建设的动力源泉,舆情反馈机制是对大学文化建设的基本策略和必要补充。大学文化建设运行机制只有实现整体性的结合,才能发挥出调控大学文化建设的集合效应。%The operation mechanism of the university culture construction is an organic system, it plays a fundamen tal role in the cultural construction of the university. Among them, the guiding mechanism of the core value system is the soul of the university culture building, the effective and organizational control mechanism is the core architec ture of the building of the university culture, the cultural interaction mechanism is the basis for the interactive and collaborative development of university culture, the innovative and incentives operation mechanism is the power source of the university cultural construction, the public opinion feedback mechanism is the basic strategy and a necessary complement to the construction of university culture. University culture construction and operation mecha nism is the organic combination in order to play out the collection effect of regulation of the university cultural con struction.

  7. Catalytic Kinetics of the Schiff Base Metal Complexes Bearing Side Chain of Cyclic morpholine in Carboxylic Ester Hydrolysis

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Shu-Lin; LI,Min-Jiao; OU,Zhong-Wen; CHEN,Guo-Xu; LIU,Fu-An; XIE,Jia-Qing


    It has been reported that two Schiff base transition metal complexes bearing the side chain of the morpholine ring were synthesized and characterized, and two complexes with the same base agent but different metal ions were used as a simulant hydrolase in the catalytic hydrolysis of p-nitrophenyl picolinate in this paper. The mechanism of PNPP catalytic hydrolysis is proposed and supported by the results of the spectral analysis and the kinetic calculation. A kinetic mathematical model, applied to the calculation of the kinetic and thermodynamics parameters of PNPP catalytic hydrolysis, has been established on the foundation of the mechanism proposed. The result of the study shows that the two complexes have a good catalytic activity in PNPP catalytic hydrolysis, and the rate of the PNPP catalytic hydrolysis was increased with the increase of the pH values in the buffer solution and affected by the polarization effect of metal ion of the complexes.

  8. 基于油藏实际的稠油层内水热催化裂解机理研究%Mechanism of underground heavy oil catalytic aquathermolysis

    Institute of Scientific and Technical Information of China (English)

    许洪星; 蒲春生; 吴飞鹏


    Field tests of underground heavy oil catalytic aquathermolysis were carried out in Shengli oilfield, the average period oil increment for 5 test wells reached to 653 t, and the viscosity of heavy oil was reduced by 79. 8% , and still decreased by more than 62% after 14 weeks. The chemical and physical properties of heavy oil before and after the reaction were investigated using DV-Ⅲ Ultra-Brookfield rheometers, Elementar Vario EL in elemental analyzer, Knauer K-700 Vapor permeability tester, Agilent 6890N gas chromatograph and EQUINOX 55 Fourier transform infrared spectrometer, etc. The results indicate that the heavy oil viscosity and average molecular weight are decreased and the content of resin and asphaltene is reduced after the reaction. The H/C ratio of heavy oil and the content of saturate and aromatic are increased. The amount of heteroatom in heavy oil is also decreased after the treatment. The reaction of underground heavy oil catalytic aquathermolysis is mainly affected by the catalyst system, high temperature water and reservoir mineral, in which the catalyst is the key control factor, and the hydrogen donating accelerator and dispersing agent can improve the cracking. In addition, the acid-base properties of water under high temperature and the reservoir mineral can promote the reaction. During the aquathermolysis, many reactions including the removal of alkyl side chain, the molecular chain isomerization, the hydrogenation, the ring opening, the ring closing and the desulfuration are involved, which can lead to the reduction of viscosity and improvement of heavy oil quality. The results suggest that the underground heavy oil catalytic aquathermolysis is feasible in field use.%开展了稠油层内水热催化裂解技术在胜利油田的先导实验,五口井平均周期单井增油653 t,稠油初期降黏率达79.8%,措施14周后降黏率仍大于62%.利用Brookfield DV-Ⅲ黏度计、ElementarVario ELⅢ元素分析仪、Knauer K-700

  9. 金陵分公司IFP和UOP连续重整技术比较与运行分析%Comparisons of different continuous catalytic reforming processes and operation analysis

    Institute of Scientific and Technical Information of China (English)



    Two CCR units in Sinopec Jinling Company are designed with IFP and UOP process design packages.The main differences between the two processes are in the reforming reaction section and catalyst regeneration section.The two processes are different in operation reaction performance.UOP' s process offers a slightly better reaction performance.The aromatics in the reaction product oil is higher and naphthene is 0.5% lower.There is no obvious pressure drop of the reactor in operation cycle.But low-purity reduction hydrogen will cause the coking in the inlet electric heater.Since the regeneration system of UOP' s process has adopted valveless catalyst transfer process,there is little catalyst abrasion.The regenerator Johnson screen has been deformed many times because the peak temperature of catalyst coking burning bed is as high as 565 ℃.The oxygen content of UOP catalyst calcination is controlled at 20% which is 4% ~ 6% higher than of that of IFP.UOP catalyst has a better dispersion.Whereas,the surface area decreases rapidly.The increasing speed of iron content of IFP catalyst is two times that of UOP' s.%中国石油化工股份有限公司金陵分公司两套连续重整装置分别使用IFP和UOP的工艺包,两种工艺最大的不同在于重整反应部分和催化剂再生部分,运行中反应性能有所区别,UOP反应器两主流道之间压差分布均匀,反应性能稍好,生成油中芳烃含量稍高,而环烷烃质量分数低0.5%.UOP运行周期内反应器压力降变化不明显,而再生部分低纯度的还原氢气引起入口电加热器结焦现象.UOP再生部分为无阀输送,催化剂磨损小,催化剂烧焦床层峰温565℃,引起再生器约翰逊网多次变形.催化剂焙烧UOP氧质量分数控制在20%,大于IFP的4%~6%,分散效果好,催化剂比表面积下降较快,而IFP催化剂铁含量上升速度较UOP快了1倍.

  10. Measurement of mechanical properties of a reactor operated Zr–2.5Nb pressure tube using an in situ cyclic ball indentation system

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, S., E-mail:; Panwar, Sanjay; Madhusoodanan, K.


    Highlights: • Measurement of mechanical properties of pressure tube is required for its fitness assessment. • Pressure tube removal from the core consumes large amount of radiation for laboratory test. • A remotely operable In situProperty Measurement System has been designed in house. • The tool head is capable to carry out in situ ball indentation trials inside pressure tube. • The paper describes the theory and results of the trials conducted on irradiated pressure tube. - Abstract: Periodic measurement of mechanical properties of pressure tubes of Indian Pressurised Heavy Water Reactors is required for assessment of their fitness for continued operation. Removal of pressure tube from the core for preparation of specimens to test for mechanical properties in laboratories consumes large amounts of radiation and hence is to be avoided as far as possible. In the field of in situ estimation of properties of materials, cyclic ball indentation is an emerging technique. Presently, commercial systems are available for doing indentation test either on outside surface of a component at site or on a test piece in a laboratory. However, these systems cannot be used inside a pressure tube for carrying out ball indentation trials under in situ condition. Considering this, a remotely operable hydraulic In situProperty Measurement System (IProMS) based on cyclic ball indentation technique has been designed and developed in house. The tool head of IProMS can be located inside a pressure tube at any axial location under in situ condition and the properties can be estimated from an analysis of the data on load and depth of indentation, recorded during the test. In order to qualify the system, a number of experimental trials have been conducted on spool pieces and specimens prepared from Zr–2.5Nb pressure tube having different mechanical properties. Based on the encouraging results obtained from the qualification trials, IProMS has been used inside a reactor operated

  11. Industrial Gas Turbine Engine Catalytic Pilot Combustor-Prototype Testing

    Energy Technology Data Exchange (ETDEWEB)

    Etemad, Shahrokh [Precision Combustion, Inc., North Haven, CT (United States); Baird, Benjamin [Precision Combustion, Inc., North Haven, CT (United States); Alavandi, Sandeep [Precision Combustion, Inc., North Haven, CT (United States); Pfefferle, William [Precision Combustion, Inc., North Haven, CT (United States)


    PCI has developed and demonstrated its Rich Catalytic Lean-burn (RCL®) technology for industrial and utility gas turbines to meet DOE's goals of low single digit emissions. The technology offers stable combustion with extended turndown allowing ultra-low emissions without the cost of exhaust after-treatment and further increasing overall efficiency (avoidance of after-treatment losses). The objective of the work was to develop and demonstrate emission benefits of the catalytic technology to meet strict emissions regulations. Two different applications of the RCL® concept were demonstrated: RCL® catalytic pilot and Full RCL®. The RCL® catalytic pilot was designed to replace the existing pilot (a typical source of high NOx production) in the existing Dry Low NOx (DLN) injector, providing benefit of catalytic combustion while minimizing engine modification. This report discusses the development and single injector and engine testing of a set of T70 injectors equipped with RCL® pilots for natural gas applications. The overall (catalytic pilot plus main injector) program NOx target of less than 5 ppm (corrected to 15% oxygen) was achieved in the T70 engine for the complete set of conditions with engine CO emissions less than 10 ppm. Combustor acoustics were low (at or below 0.1 psi RMS) during testing. The RCL® catalytic pilot supported engine startup and shutdown process without major modification of existing engine controls. During high pressure testing, the catalytic pilot showed no incidence of flashback or autoignition while operating over a wide range of flame temperatures. In applications where lower NOx production is required (i.e. less than 3 ppm), in parallel, a Full RCL® combustor was developed that replaces the existing DLN injector providing potential for maximum emissions reduction. This concept was tested at industrial gas turbine conditions in a Solar Turbines, Incorporated high-pressure (17 atm.) combustion rig and in a modified Solar

  12. Template electrodeposition of catalytic nanomotors. (United States)

    Wang, Joseph


    The combination of nanomaterials with electrode materials has opened new horizons in electroanalytical chemistry, and in electrochemistry in general. Over the past two decades we have witnessed an enormous activity aimed at designing new electrochemical devices based on nanoparticles, nanotubes or nanowires, and towards the use of electrochemical routes--particularly template-assisted electrodeposition--for preparing nanostructured materials. The power of template-assisted electrochemical synthesis is demonstrated in this article towards the preparation and the realization of self-propelled catalytic nanomotors, ranging from Pt-Au nanowire motors to polymer/Pt microtube engines. Design considerations affecting the propulsion behavior of such catalytic nanomotors are discussed along with recent bioanalytical and environmental applications. Despite recent major advances, artificial nanomotors have a low efficiency compared to their natural counterparts. Hopefully, the present Faraday Discussion will stimulate other electrochemistry teams to contribute to the fascinating area of artificial nanomachines.

  13. Nitrogenase on Structure and Catalytic Mechanism and Factors Influencing Its Activity in Agriculture Production%固氮酶的结构和催化机制及在农业生产实践中影响其活性的因素

    Institute of Scientific and Technical Information of China (English)



    The structure and catalytic mechanism of nitrogenase were introduced,and research of factors which affected the activity of nitrogenase in agriculture were summarized,including species of nitrogen-fixing bacteria,species of crops,types of soil,nitrogenous fertilizer,methods of cultiyation,and different phases of fertilization.%介绍了固氮酶的结构和催化机制,并综述了近几年在农业生产中对固氮酶活性有影响的几个因素的研究进展.这些因素包括固氮菌的品种、作物的品种、土壤类型、氮肥的类型、耕作方式和氮肥的施用时期.

  14. Catalytic control of enzymatic fluorine specificity. (United States)

    Weeks, Amy M; Chang, Michelle C Y


    The investigation of unique chemical phenotypes has led to the discovery of enzymes with interesting behaviors that allow us to explore unusual function. The organofluorine-producing microbe Streptomyces cattleya has evolved a fluoroacetyl-CoA thioesterase (FlK) that demonstrates a surprisingly high level of discrimination for a single fluorine substituent on its substrate compared with the cellularly abundant hydrogen analog, acetyl-CoA. In this report, we show that the high selectivity of FlK is achieved through catalysis rather than molecular recognition, where deprotonation at the C(α) position to form a putative ketene intermediate only occurs on the fluorinated substrate, thereby accelerating the rate of hydrolysis 10(4)-fold compared with the nonfluorinated congener. These studies provide insight into mechanisms of catalytic selectivity in a native system where the existence of two reaction pathways determines substrate rather than product selection.

  15. Study on catalytic oxidation of planar binuclear copper phthalocyanine on 2-mercaptoethanol

    Institute of Scientific and Technical Information of China (English)

    CHEN Wenxing; WEI Lili; WANG Jinqian; YAO Yuyuan; L(U) Shenshui; CHEN Shiliang


    Mononuclear copper phthalocyanine (CuPc) and binuclear copper phthalocyanine (Cu2Pc2) were synthesized by the phenylanhydride-urea route, and their catalytic oxidation activity on 2-mercaptoethanol was studied. Based on the experimental results, a catalytic mechanism of Cu2Pc2 on 2-mercaptoethanol has been proposed. Furthermore, the effects of pH, Cu2Pc2 concentration, and temperature on the catalytic oxidation activity were evaluated. The results showed that CuPc has no catalytic activity, while Cu2Pc2 has high catalytic oxidation activity towards 2-mercaptoethanol with the optimal activity at pH 11. The reaction can further be enhanced by increasing Cu2Pc2 concentration and temperature, due to its endothermic characteristics.

  16. Radiation/Catalytic Augmented Combustion. (United States)


    NATIO& NAk H(fJI At tl TANUAHTOb 19 A ~omm.81-0287 LVL RADIATION/CATALYTIC AUGMENTED COMBUST ION MOSHE LAVID CORPORATE RESEARCH-TECHNOLOGY FEASIBILITY...refinements as necessary. i. Perform cannular combustor experiments to Investigate ignition and flame attachment in flowing, liquid -fuel, unpremixed...stabilizer, with a sintered metal disk on the downstream side through which hot gases or products of partial fuel oxidation can be passed. Experimental

  17. VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu2(μ-O2)], [Fe2(μ-O2)] and Fe(IV)-O cores based on DFT potential energy surfaces. (United States)

    Kim, Yongho; Mai, Binh Khanh; Park, Sumin


    High-valent Cu and Fe species, which are generated from dioxygen activation in metalloenzymes, carry out the functionalization of strong C-H bonds. Understanding the atomic details of the catalytic mechanism has long been one of the main objectives of bioinorganic chemistry. Large H/D kinetic isotope effects (KIEs) were observed in the C-H activation by high-valent non-heme Cu or Fe complexes in enzymes and their synthetic models. The H/D KIE depends significantly on the transition state properties, such as structure, energies, frequencies, and shape of the potential energy surface, when the tunneling effect is large. Therefore, theoretical predictions of kinetic parameters such as rate constants and KIEs can provide a reliable link between atomic-level quantum mechanical mechanisms and experiments. The accurate prediction of the tunneling effect is essential to reproduce the kinetic parameters. The rate constants and HD/KIE have been calculated using the variational transition-state theory including multidimensional tunneling based on DFT potential energy surfaces along the reaction coordinate. Excellent agreement was observed between the predicted and experimental results, which assures the validity of the DFT potential energy surfaces and, therefore, the proposed atomic-level mechanisms. The [Cu2(μ-O)2], [Fe2(μ-O)2], and Fe(IV)-oxo species were employed for C-H activation, and their role as catalysts was discussed at an atomic level.

  18. H2CAP - Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Arndal, Trine Marie Hartmann; Høj, Martin; Jensen, Peter Arendt


    that can be used to upgrade the crude bio-oil to fuel-grade oil. The development of the HDO process is challenged by rapid catalyst deactivation, instability of the pyrolysis oil, poorly investigated reaction conditions and a high complexity and variability of the input oil composition. However, continuous...... catalytic hydropyrolysis coupled with downstream HDO of the pyrolysis vapors before condensation shows promise (Figure 1). A bench scale experimental setup will be constructed for the continuous conversion of solid biomass (100g /h) to low oxygen, fuel-grade bio-oil. The aim is to provide a proof......-of-concept for the proposed process(Figure 1), to understand the reaction mechanisms of HDO, to develop highly active and durable catalysts for hydropyrolysis and HDO and to optimize the operating conditions; all in order to develop a sustainable production of green transportation fuels from biomass.To support the process...

  19. Thermodynamics of catalytic nanoparticle morphology (United States)

    Zwolak, Michael; Sharma, Renu; Lin, Pin Ann

    Metallic nanoparticles are an important class of industrial catalysts. The variability of their properties and the environment in which they act, from their chemical nature & surface modification to their dispersion and support, allows their performance to be optimized for many chemical processes useful in, e.g., energy applications and other areas. Their large surface area to volume ratio, as well as varying sizes and faceting, in particular, makes them an efficient source for catalytically active sites. These characteristics of nanoparticles - i.e., their morphology - can often display intriguing behavior as a catalytic process progresses. We develop a thermodynamic model of nanoparticle morphology, one that captures the competition of surface energy with other interactions, to predict structural changes during catalytic processes. Comparing the model to environmental transmission electron microscope images of nickel nanoparticles during carbon nanotube (and other product) growth demonstrates that nickel deformation in response to the nanotube growth is due to a favorable interaction with carbon. Moreover, this deformation is halted due to insufficient volume of the particles. We will discuss the factors that influence morphology and also how the model can be used to extract interaction strengths from experimental observations.

  20. Catalytic polarographic currents of oxidizers

    Energy Technology Data Exchange (ETDEWEB)

    Zajtsev, P.M.; Zhdanov, S.I.; Nikolaeva, T.D. (Vsesoyuznyj Nauchno-Issledovatel' skij Inst. Khimicheskikh Reaktivov i Osobo Chistykh Veshchestv, Moscow (USSR))


    The state of theory and practice of an important direction in polarography, i.e. catalytic currents of oxidizers-substrates that have found a wide application in the development of highly sensitive methods of determination of a large number of substrates, catalysts and polarographically nonactive ligands, is considered. Transition and some non-transition elements serve as catalysts of reactions that cause catalytic polarographic currents of substrates. Catalytic activity of an inorganic catalyst increases with the increase in the number of its d-orbit. Complex formation in most cases leads to the increase of catalyst activity, however, sometimes a reverse phenomenon takes place. For many catalysts the maximum activity is observed at pH values close to pK value of their hydrolysis. The properties of oxidizers-substrates is revealed by H/sub 2/O/sub 2/, ClO/sub 3//sup -/, BrO/sub 3//sup -/, IO/sub 3//sup -/, ClO/sub 4//sup -/, IO/sub 4//sup -/, NO/sub 2//sup -/, NO/sub 3//sup -/, NH/sub 2/OH, V(5), V(4), S/sub 2/O/sub 8//sup 2 -/, H/sub 2/SO/sub 4/, H/sub 2/C/sub 2/O/sub 4/, COHCOOH, alkenes compounds, organic halogen , sulfur- and amine-containing compounds.

  1. Catalytically active nanomaterials: a promising candidate for artificial enzymes. (United States)

    Lin, Youhui; Ren, Jinsong; Qu, Xiaogang


    Natural enzymes, exquisite biocatalysts mediating every biological process in living organisms, are able to accelerate the rate of chemical reactions up to 10(19) times for specific substrates and reactions. However, the practical application of enzymes is often hampered by their intrinsic drawbacks, such as low operational stability, sensitivity of catalytic activity to environmental conditions, and high costs in preparation and purification. Therefore, the discovery and development of artificial enzymes is highly desired. Recently, the merging of nanotechnology with biology has ignited extensive research efforts for designing functional nanomaterials that exhibit various properties intrinsic to enzymes. As a promising candidate for artificial enzymes, catalytically active nanomaterials (nanozymes) show several advantages over natural enzymes, such as controlled synthesis in low cost, tunability in catalytic activities, as well as high stability against stringent conditions. In this Account, we focus on our recent progress in exploring and constructing such nanoparticulate artificial enzymes, including graphene oxide, graphene-hemin nanocomposites, carbon nanotubes, carbon nanodots, mesoporous silica-encapsulated gold nanoparticles, gold nanoclusters, and nanoceria. According to their structural characteristics, these enzyme mimics are categorized into three classes: carbon-, metal-, and metal-oxide-based nanomaterials. We aim to highlight the important role of catalytic nanomaterials in the fields of biomimetics. First, we provide a practical introduction to the identification of these nanozymes, the source of the enzyme-like activities, and the enhancement of activities via rational design and engineering. Then we briefly describe new or enhanced applications of certain nanozymes in biomedical diagnosis, environmental monitoring, and therapeutics. For instance, we have successfully used these biomimetic catalysts as colorimetric probes for the detection of


    Energy Technology Data Exchange (ETDEWEB)



    The growing concerns for the environment and increasingly stringent standards for NO emission have presented a major challenge to control NO emissions from electric utility plants and automobiles. Catalytic decomposition of NO is the most attractive approach for the control of NO emission for its simplicity. Successful development of an effective catalyst for NO decomposition will greatly decrease the equipment and operation cost of NO control. Due to lack of understanding of the mechanism of NO decomposition, efforts on the search of an effective catalyst have been unsuccessful. Scientific development of an effective catalyst requires fundamental understanding of the nature of active site, the rate-limiting step, and an approach to prolong the life of the catalyst. The authors have investigated the feasibility of two novel approaches for improving catalyst activity and resistance to sintering. The first approach is the use of silanation to stabilize metal crystallites and supports for Cu-ZSM-5 and promoted Pt catalysts; the second is utilization of oxygen spillover and desorption to enhance NO decomposition activity. The silanation approach failed to stabilize Cu-ZSM-5 activity under hydrothermal condition. Silanation blocked the oxygen migration and inhibited oxygen desorption. Oxygen spillover was found to be an effective approach for promoting NO decomposition activity on Pt-based catalysts. Detailed mechanistic study revealed the oxygen inhibition in NO decomposition and reduction as the most critical issue in developing an effective catalytic approach for controlling NO emission.

  3. Technique Key Points of Deep Tillage Land Preparation Mechanization Operation%深松整地机械化作业技术要领

    Institute of Scientific and Technical Information of China (English)



    The technique of deep tillage land preparation mechanization is expanded each year, and is becoming one of main agricultural mechanization techniques in Liaoning province and even nationwide. In the article, it introduced implementing effect and operation mode of deep tillage land preparation mechanization technique, set up implementation key points and using points, in order to provide technical guidance for applying deep tillage technique for farmers.%深松整地机械化技术的推广应用面积逐年扩大,成为辽宁乃至全国范围内主推的农机化技术之一. 介绍深松整地机械化技术的实施效果和作业方式,制定实施要点和使用要领,以期为农户科学使用深松作业技术提供指导.

  4. Android操作系统的安全机制研究%Research of the Android Operating System's Security Mechanism

    Institute of Scientific and Technical Information of China (English)

    朱长江; 杨一平


    Android system since its introduction, with regard to the obvious advantage of the gradual expansion of market share. Android is an open system, much favored by developers, its security is essential. Studied the Android system user ID mechanism, an application signature mechanism, isolated sandbox security policy mechanism ,analyzed Android security risks exist in terms of hardware, Linux kernel and itself permission mechanism.%Android系统自推出以来,就以明显的优势逐渐扩大市场占有份额。Android是一个开放性的系统,备受开发者的青睐,其安全性至关重要。研究了Android系统的用户ID机制、应用程序签名机制、沙箱隔离机制等安全策略,分析了它在硬件方面、Linux内核方面及Android自身权限机制方面存在的安全隐患。

  5. Discussion on the Operating Mechanisms of Social Services of University Library%高校图书馆社会化服务运行机制探讨

    Institute of Scientific and Technical Information of China (English)



    With the development of social economy and network technology,the social service of university library has already been inevitable.The development of social service of university library needs the good operating mechanisms for indemnification.This paper analyses the advantages of social service in university library,discuss the development mechanism,management mechanism,motivation mechanism,harmonious mechanism and favorable balance mechanism.%随着社会经济和网络技术的发展,高校图书馆社会化服务已成为大势所趋。高校图书馆社会化服务的开展,需要良好的运行机制作保障。分析高校图书馆开展社会化服务的优势,探讨高校图书馆社会化服务的发展机制、管理机制、动力机制、协调机制、平衡机制。

  6. Crystal structure of Glycine max glutathione transferase in complex with glutathione: investigation of the mechanism operating by the Tau class glutathione transferases. (United States)

    Axarli, Irene; Dhavala, Prathusha; Papageorgiou, Anastassios C; Labrou, Nikolaos E


    Cytosolic GSTs (glutathione transferases) are a multifunctional group of enzymes widely distributed in Nature and involved in cellular detoxification processes. The three-dimensional structure of GmGSTU4-4 (Glycine max GST Tau 4-4) complexed with GSH was determined by the molecular replacement method at 2.7 A (1 A=0.1 nm) resolution. The bound GSH is located in a region formed by the beginning of alpha-helices H1, H2 and H3 in the N-terminal domain of the enzyme. Significant differences in the G-site (GSH-binding site) as compared with the structure determined in complex with Nb-GSH [S-(p-nitrobenzyl)-glutathione] were found. These differences were identified in the hydrogen-bonding and electrostatic interaction pattern and, consequently, GSH was found bound in two different conformations. In one subunit, the enzyme forms a complex with the ionized form of GSH, whereas in the other subunit it can form a complex with the non-ionized form. However, only the ionized form of GSH may form a productive and catalytically competent complex. Furthermore, a comparison of the GSH-bound structure with the Nb-GSH-bound structure shows a significant movement of the upper part of alpha-helix H4 and the C-terminal. This indicates an intrasubunit modulation between the G-site and the H-site (electrophile-binding site), suggesting that the enzyme recognizes the xenobiotic substrates by an induced-fit mechanism. The reorganization of Arg111 and Tyr107 upon xenobiotic substrate binding appears to govern the intrasubunit structural communication between the G- and H-site and the binding of GSH. The structural observations were further verified by steady-state kinetic analysis and site-directed mutagenesis studies.

  7. High-Temperature Compatible Nickel Silicide Thermometer And Heater For Catalytic Chemical Microreactors

    DEFF Research Database (Denmark)

    Jensen, Søren; Quaade, U.J.; Hansen, Ole


    Integration of heaters and thermometers is important for agile and accurate control and measurement of the thermal reaction conditions in microfabricated chemical reactors (microreactors). This paper describes development and operation of nickel silicide heaters and temperature sensors...... for temperatures exceeding 700 °C. The heaters and thermometers are integrated with chemical microreactors for heterogeneous catalytic conversion of gasses, and thermally activated catalytic conversion of CO to CO2 in the reactors is demonstrated. The heaters and thermometers are shown to be compatible...

  8. Catalytic hot gas cleaning of gasification gas

    Energy Technology Data Exchange (ETDEWEB)

    Simell, P. [VTT Energy, Espoo (Finland). Energy Production Technologies


    The aim of this work was to study the catalytic cleaning of gasification gas from tars and ammonia. In addition, factors influencing catalytic activity in industrial applications were studied, as well as the effects of different operation conditions and limits. Also the catalytic reactions of tar and ammonia with gasification gas components were studied. The activities of different catalyst materials were measured with laboratory-scale reactors fed by slip streams taken from updraft and fluid bed gasifiers. Carbonate rocks and nickel catalysts proved to be active tar decomposing catalysts. Ammonia decomposition was in turn facilitated by nickel catalysts and iron materials like iron sinter and iron dolomite. Temperatures over 850 deg C were required at 2000{sup -1} space velocity at ambient pressure to achieve almost complete conversions. During catalytic reactions H{sub 2} and CO were formed and H{sub 2}O was consumed in addition to decomposing hydrocarbons and ammonia. Equilibrium gas composition was almost achieved with nickel catalysts at 900 deg C. No deactivation by H{sub 2}S or carbon took place in these conditions. Catalyst blocking by particulates was avoided by using a monolith type of catalyst. The apparent first order kinetic parameters were determined for the most active materials. The activities of dolomite, nickel catalyst and reference materials were measured in different gas atmospheres using laboratory apparatus. This consisted of nitrogen carrier, toluene as tar model compound, ammonia and one of the components H{sub 2}, H{sub 2}O, CO, CO{sub 2}, CO{sub 2}+H{sub 2}O or CO+CO{sub 2}. Also synthetic gasification gas was used. With the dolomite and nickel catalyst the highest toluene decomposition rates were measured with CO{sub 2} and H{sub 2}O. In gasification gas, however, the rate was retarded due to inhibition by reaction products (CO, H{sub 2}, CO{sub 2}). Tar decomposition over dolomite was modelled by benzene reactions with CO{sub 2}, H

  9. The Realization of Command Channel-Mechanism in a System for Human to Human Interaction and Co-operative%人人交互与协作系统中命令通道机制的实现

    Institute of Scientific and Technical Information of China (English)

    田友胜; 侯义斌


    The concept of command channel-mechanism has been introduced into the command channelmechanism system for human to human interaction and co-operative over the Internet/Intranet.A new type of interaction and co-operative environment has been built up.This paper discusses the running mechanism and software realization of the command channel.

  10. Evaluation and application of data sources for assessing operating costs for mechanical drive gas turbines in pipeline service

    Energy Technology Data Exchange (ETDEWEB)

    Smalley, A.J.; Mauney, D.A. [Southwest Research Inst., San Antonio, TX (United States); Ash, D.I. [Conoco Inc., Ponca City, OK (United States)


    The use of regression analysis of public domain data provided by interstate pipeline companies to the Federal Energy Regulatory Commission (FERC), combined with individual company equipment lists to generate information on cost of operations, maintenance, fuel gas used and the cost of fuel and power, is demonstrated. Methods of analysis and limitations are identified, and results of such regression analysis as average and variance of cost and fuel usage for industrial gas turbines and aeroderivative gas turbines are discussed. Comparison between gas turbine prime movers, reciprocating engine prime movers and electric motor drives are made, and annual costs per installed horsepower as a function of turbine size are calculated. 1 ref., 6 figs.

  11. Robotic Materials Handling in Space: Mechanical Design of the Robot Operated Materials Processing System HitchHiker Experiment (United States)

    Voellmer, George


    The Goddard Space Flight Center has developed the Robot Operated Materials Processing System (ROMPS) that flew aboard STS-64 in September, 1994. The ROMPS robot transported pallets containing wafers of different materials from their storage racks to a furnace for thermal processing. A system of tapered guides and compliant springs was designed to deal with the potential misalignments. The robot and all the sample pallets were locked down for launch and landing. The design of the passive lockdown system, and the interplay between it and the alignment system are presented.

  12. Enhanced efficiency in the excitation of higher modes for atomic force microscopy and mechanical sensors operated in liquids

    Energy Technology Data Exchange (ETDEWEB)

    Penedo, M., E-mail:; Hormeño, S.; Fernández-Martínez, I.; Luna, M.; Briones, F. [IMM-Instituto de Microelectrónica de Madrid (CNM-CSIC), Isaac Newton 8, PTM, E-28760 Tres Cantos, Madrid (Spain); Raman, A. [Birck Nanotechnology Center and School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47904 (United States)


    Recent developments in dynamic Atomic Force Microscopy where several eigenmodes are simultaneously excited in liquid media are proving to be an excellent tool in biological studies. Despite its relevance, the search for a reliable, efficient, and strong cantilever excitation method is still in progress. Herein, we present a theoretical modeling and experimental results of different actuation methods compatible with the operation of Atomic Force Microscopy in liquid environments: ideal acoustic, homogeneously distributed force, distributed applied torque (MAC Mode™), photothermal and magnetostrictive excitation. From the analysis of the results, it can be concluded that magnetostriction is the strongest and most efficient technique for higher eigenmode excitation when using soft cantilevers in liquid media.

  13. Mechanisms of Low-Energy Operation of XCT-SOI CMOS Devices—Prospect of Sub-20-nm Regime

    Directory of Open Access Journals (Sweden)

    Yasuhisa Omura


    Full Text Available This paper describes the performance prospect of scaled cross-current tetrode (XCT CMOS devices and demonstrates the outstanding low-energy aspects of sub-30-nm-long gate XCT-SOI CMOS by analyzing device operations. The energy efficiency improvement of such scaled XCT CMOS circuits (two orders higher stems from the “source potential floating effect”, which offers the dynamic reduction of effective gate capacitance. It is expected that this feature will be very important in many medical implant applications that demand a long device lifetime without recharging the battery.

  14. Challenges in Mechanization Efforts of Small Diameter Eucalyptus Harvesting Operations with a Low Capacity Running Skyline Yarder in Southern China

    Directory of Open Access Journals (Sweden)

    Stephan Hoffmann


    Full Text Available This case study examines the performance of the Igland Hauler employed in small diameter Eucalyptus clear-cut operations in Guangxi, China. A yarding crew of eight persons was monitored by a snap back elemental time study for 19.23 SMH (scheduled machine hours, with 159 yarding cycles and a yarded log volume at landing of 49.4 m³ solid over bark. A gross-productivity of 2.50 m³/SMH and net-productivity of 5.06 m³/PMH0 (productive machine hours excluding delay times was achieved, leading to a machine utilization rate of 49.5%. The costs of the yarder and associated overhead as well as the personnel costs of a large crew with eight people sum up to extraction costs of 50.24 USD/m³. The high costs make it difficult to compete economically with the locally common manual extraction system as long as abundant labor at a low hourly rate is available in the region. Further performance improvement through skill development, but also technical and organizational system modification in conjunction with rising wages and decreasing labor force in rural primary production will determine the justification of employing such yarding systems. However, new silvicultural regimes with extended rotations and supply requirements of the forest products industry in China demand new operational systems.

  15. Catalytic Combustion for Ultra-Low NOx Hydrogen Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Etemad, Shahrokh; Baird, Benjamin; Alavandi, Sandeep


    Precision Combustion, Inc., (PCI) in close collaboration with Solar Turbines, Incorporated, has developed and demonstrated a combustion system for hydrogen fueled turbines that reduces NOx to low single digit level while maintaining or improving current levels of efficiency and eliminating emissions of carbon dioxide. Full scale Rich Catalytic Hydrogen (RCH1) injector was developed and successfully tested at Solar Turbines, Incorporated high pressure test facility demonstrating low single digit NOx emissions for hydrogen fuel in the range of 2200F-2750F. This development work was based on initial subscale development for faster turnaround and reduced cost. Subscale testing provided promising results for 42% and 52% H2 with NOx emissions of less than 2 ppm with improved flame stability. In addition, catalytic reactor element testing for substrate oxidation, thermal cyclic injector testing to simulate start-stop operation in a gas turbine environment, and steady state 15 atm. operation testing were performed successfully. The testing demonstrated stable and robust catalytic element component life for gas turbine conditions. The benefit of the catalytic hydrogen combustor technology includes capability of delivering near-zero NOx without costly post-combustion controls and without requirement for added sulfur control. In addition, reduced acoustics increase gas turbine component life. These advantages advances Department of Energy (DOE’s) objectives for achievement of low single digit NOx emissions, improvement in efficiency vs. postcombustion controls, fuel flexibility, a significant net reduction in Integrated Gasification Combined Cycle (IGCC) system net capital and operating costs, and a route to commercialization across the power generation field from micro turbines to industrial and utility turbines.

  16. Catalytic Tubular Microjet Propulsion Model for Endovascular Navigation


    Sarkis, Bruno; Folio, David; Ferreira, Antoine


    International audience; This paper describes the propulsion of the catalytic tubular microjet using Navier-Stokes equations. Especially , the thrust capability of the microjet is outstanding compared with the other microsystems, but remains only partially understood. Studies have identified the internal precursory mechanisms of the propulsion of the microjet: its inner wall catalyzes the dismutation of aqueous hydrogen peroxide, and an oxygen bubble is then formed and migrates towards its wid...

  17. First-principles investigations for the catalytic dissociation and oxidation of methane on the Cu surfaces (United States)

    Li, Ying; Mahadevan, Jagan; Wang, Sanwu


    The catalytic reactions of dissociation and oxidation of methane on the copper surfaces play a key role in, for example, the development of high-performance solid oxide fuel cells. We used first-principles quantum theory and large-scale parallel calculations to investigate the atomic-scale mechanism of the catalytic chemical reactions. We report the calculated results, which provide fundamental information and understanding about the atomic-scale dynamics and electronic structures pertinent to the reactions and specifically the catalytic role of the Cu(100) and Cu(111) surfaces. We also report comparison of our results with available experimental data and previous theoretical investigations.


    Institute of Scientific and Technical Information of China (English)

    Wei-xia Tu; Bao-lin He; Han-fan Liu; Xue-lan Luo; Xun Liang


    Catalytic properties of polymer-stabilized colloidal metal nanoparticles synthesized by microwave irradiation were studied in the selective hydrogenation of unsaturated aldehydes, o-chloronitrobenzene and the hydrogenation of alkenes. The results show that nanosized metal particles synthesized by microwave irradiation have similar catalytic performance in selective hydrogenation of unsaturated aldehydes, better selectivity to o-chloroaniline in hydrogenation of o-chloronitrobenzene and higher catalytic activities in hydrogenation of alkenes, compared with metal clusters prepared by conventional heating. The same apparent activation energy (Ea = 29 kJ mol-1) for hydrogenation of 1-heptene catalyzed with platinum nanoparticles prepared by both heating modes implied that the reaction followed the same mechanism.

  19. Mechanical ventilation and the total artificial heart: optimal ventilator trigger to avoid post-operative autocycling - a case series and literature review

    Directory of Open Access Journals (Sweden)

    Arabia Francisco A


    Full Text Available Abstract Many patients with end-stage cardiomyopathy are now being implanted with Total Artificial Hearts (TAHs. We have observed individual cases of post-operative mechanical ventilator autocycling with a flow trigger, and subsequent loss of autocycling after switching to a pressure trigger. These observations prompted us to do a retrospective review of all TAH devices placed at our institution between August 2007 and May 2009. We found that in the immediate post-operative period following TAH placement, autocycling was present in 50% (5/10 of cases. There was immediate cessation of autocycling in all patients after being changed from a flow trigger of 2 L/minute to a pressure trigger of 2 cm H2O. The autocycling group was found to have significantly higher CVP values than the non-autocycling group (P = 0.012. Our data suggest that mechanical ventilator autocycling may be resolved or prevented by the use of a pressure trigger rather than a flow trigger setting in patients with TAHs who require mechanical ventilation.

  20. A review on nitrogen and organics removal mechanisms in subsurface flow constructed wetlands: dependency on environmental parameters, operating conditions and supporting media. (United States)

    Saeed, Tanveer; Sun, Guangzhi


    With the unique advantages of lower operational and maintenance cost, the applications of subsurface flow constructed wetlands for the treatment of wastewater have been increasing rapidly throughout the world. The removal of nitrogen and organics by such systems has gained substantial attention in recent years. In subsurface flow wetlands, the removal of pollutants often relies on a diverse range of co-existing physical, chemical and biological routes, which are vitally dependent on numerous environmental and operational parameters. This paper provides a comprehensive review of wetland structures, classic and novel nitrogen and organics removal mechanisms along with the key environmental parameters and operational conditions that enhance removal in subsurface flow wetland systems. The critical exploration identifies the major environmental parameters such as: pH, DO, and temperature, operational factors i.e. organic carbon availability, loading, feed mode, retention time, recirculation, harvesting, and the complex role (of both parameters) on classical nitrogen and organics removal pathways. Subsequently, the necessity of further extensive research on such factors, for promoting novel nitrogen removal routes in wetland systems has also been highlighted. The expansion of the review on the influence of the unconventional wetland matrix indicates that, the structural differences and inherent properties of these media can support substantial nitrogen and organics removal from wastewater, under optimal operating conditions. Overall, the critical review illustrates the necessity of a profound knowledge on the complicated inter-relationship between nitrogen and organics removal routes, governing environmental and operational parameters, and wetland matrix for improving the treatment performances of subsurface flow wetlands.

  1. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel


    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  2. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)


    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  3. Adaptive Model Predictive Control of Diesel Engine Selective Catalytic Reduction (SCR) Systems (United States)

    McKinley, Thomas L.


    Selective catalytic reduction or SCR is coming into worldwide use for diesel engine emissions reduction for on- and off-highway vehicles. These applications are characterized by broad operating range as well as rapid and unpredictable changes in operating conditions. Significant nonlinearity, input and output constraints, and stringent performance…

  4. Activity prediction of substrates in NADH-dependent carbonyl reductase by docking requires catalytic constraints and charge parameterization of catalytic zinc environment. (United States)

    Dhoke, Gaurao V; Loderer, Christoph; Davari, Mehdi D; Ansorge-Schumacher, Marion; Schwaneberg, Ulrich; Bocola, Marco


    Molecular docking of substrates is more challenging compared to inhibitors as the reaction mechanism has to be considered. This becomes more pronounced for zinc-dependent enzymes since the coordination state of the catalytic zinc ion is of greater importance. In order to develop a predictive substrate docking protocol, we have performed molecular docking studies of diketone substrates using the catalytic state of carbonyl reductase 2 from Candida parapsilosis (CPCR2). Different docking protocols using two docking methods (AutoDock Vina and AutoDock4.2) with two different sets of atomic charges (AM1-BCC and HF-RESP) for catalytic zinc environment and substrates as well as two sets of vdW parameters for zinc ion were examined. We have selected the catalytic binding pose of each substrate by applying mechanism based distance criteria. To compare the performance of the docking protocols, the correlation plots for the binding energies of these catalytic poses were obtained against experimental Vmax values of the 11 diketone substrates for CPCR2. The best correlation of 0.73 was achieved with AutoDock4.2 while treating catalytic zinc ion in optimized non-bonded (NBopt) state with +1.01 charge on the zinc ion, compared to 0.36 in non-bonded (+2.00 charge on the zinc ion) state. These results indicate the importance of catalytic constraints and charge parameterization of catalytic zinc environment for the prediction of substrate activity in zinc-dependent enzymes by molecular docking. The developed predictive docking protocol described here is in principle generally applicable for the efficient in silico substrate spectra characterization of zinc-dependent ADH.

  5. Research on Micro-operation Mechanism of Enterprise Cultural Capital%企业文化资本化的微观运行机制研究

    Institute of Scientific and Technical Information of China (English)



    Micro-operation mechanism of enterprise cultural capital takes innovation as the driving force, marketing as a means, image as the contents and platform for the protection. Operation of enterprise cultural capital should have the appropriate cultural environment, which can stimulate vitality, expand thinking space and create an environment for enterprise culture innovation.%企业文化资本化的微观运行机制是以创新为动力、以营销为手段、以意象为内容,以平台为保障.企业文化资本运营要有适宜的文化环境,可以激发企业文化创新的活力,拓展文化创新的思维空间,创造文化创新的环境.

  6. Study on the Operating Mechanism and Practice concerning Undergraduate Teaching Quality Assurance in the Chinese Agriculture-related Colleges and Universities

    Institute of Scientific and Technical Information of China (English)

    Zhongming; SHEN


    This paper analyzes the connotation of the undergraduate teaching quality assurance system in agriculture-related colleges and universities,and takes Southwest University Rongchang Campus for example to probe into the long-term operating mechanism of multidimensional integrated quality assurance system as well as the sound teaching quality monitoring and management system building assurance system and operational practice effect involving personnel training programs,teaching element control,supervision and control of the teaching process,supervision and control of teaching effectiveness,teaching assurance policy and system,teaching funding system,teaching technical support guarantee,and teaching environment building guarantee,with the purpose of providing a reference for the Chinese universities and colleges to improve the teaching quality.

  7. Monopropellant engine investigation for space shuttle reaction control. Volume 2: Design, fabrication, and demonstration test of a catalytic gas generator for the space shuttle APU (United States)


    The capability of a catalytic gas generator to meet the requirement specified for the space shuttle APU is established. A full-scale gas generator, designed to operate at a chamber pressure of 750 psia and a flow rate of 0.36 lbm/sec, was fabricated and subjected to three separate life test series. The nickel foam metal used for catalyst retention was investigated. Inspection of the foam metal following the first life test revealed significant degradation. Consequently an investigation was conducted to determine the mechanism of degradation and to provide an improved foam metal.

  8. The Analysis of Operating Mechanism Innovation in Science and Technology Museum%浅论科技博物馆运行机制的创新

    Institute of Scientific and Technical Information of China (English)



    通过关注国内外科技博物馆的现状,以及世界科技博物馆的发展趋势,且从管理体制、运行经费筹建机制、人才使用机制、评估监督制度等诸方面阐述世界科技博物馆的运行机制,并借鉴发达国家的先进理念与成功经验,分析影响国内科技博物馆运行机制的关键问题,寻找存在的差距,寻求从中的启示,提出符合我国运行机制实况的对策建议。%By analyzing the current situation of the science and technology museum both in china and abroad ,and the trends of science technology museum all of the world, from management system ,funds, developing system, human re-sources, supervision system, to explain the operating mechanism of science and technology museum all of the world. As well as Learn from the advanced concept and experience of developed countries, discussing the question which affects operating mechanism of science and technology museum in China. Seeking the difference between the domestic and o-verseas and the revelation .to give suggestions for fitting the operating mechanism in our country.

  9. Catalytic microrotor driven by geometrical asymmetry (United States)

    Yang, Mingcheng; Ripoll, Marisol; Chen, Ke


    An asymmetric gear with homogeneous surface properties is, here, presented as a prototype to fabricate catalytic microrotors. The driving torque arises from the diffusiophoretic effect induced by the concentration gradients generated by catalytic chemical reactions at the gear surface. This torque produces a spontaneous and unidirectional rotation of the asymmetric gear. By means of mesoscopic simulations, we prove and characterize this scenario. The gear rotational velocity is determined by the gear-solvent interactions, the gear geometry, the solvent viscosity, and the catalytic reaction ratio. Our work presents a simple way to design self-propelled microrotors, alternative to existing catalytic bi-component, or thermophoretic ones.

  10. Nanostructured Catalytic Reactors for Air Purification Project (United States)

    National Aeronautics and Space Administration — This SBIR Phase I project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  11. Nanostructured Catalytic Reactors for Air Purification Project (United States)

    National Aeronautics and Space Administration — This SBIR Phase II project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  12. Solubility of cerium in LaCoO3-influence on catalytic activity. (United States)

    French, S A; Catlow, C R A; Oldman, R J; Rogers, S C; Axon, S A


    The recent interest in the catalytic properties of lanthanum perovskites for methane combustion and three way catalysis has led to considerable debate as to their structure and defect chemistry. We have investigated the doping of LaCoO3 with the tetravalent cerium cation using atomistic simulation techniques. We have compared three routes for cerium insertion and identified the favoured doping mechanism, which explain experimental observations relating to the effect of cerium on catalytic activity.

  13. Electrical bistabilities and operating mechanisms of memory devices fabricated utilizing ZnO quantum dot-multi-walled carbon nanotube nanocomposites (United States)

    Li, Fushan; Son, Dong Ick; Cho, Sung Hwan; Kim, Tae Whan


    Transmission electron microscopy images showed that the ZnO quantum dots (QDs) were conjugated with multi-walled carbon nanotubes (MWCNTs). Bistable memories utilizing an ensemble of the ZnO QD-MWCNT heterostructures were developed and the storage capability of the devices was significantly enhanced due to the conjugation of the ZnO QDs and the MWCNTs. Operating mechanisms of memory devices fabricated utilizing the ZnO QD-MWCNT heterostructures are described on the basis of the current-voltage results. The memory devices exhibited excellent environmental stability at ambient conditions.

  14. Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins (United States)

    Al-Sabawi, Mustafa N.

    The limited availability of high value light hydrocarbon feedstocks along with the rise in crude prices has resulted in the international recognition of the vast potential of Canada's oil sands. With the recent expansion of Canadian bitumen production come, however, many technical challenges, one of which is the significant presence of aromatics and cycloparaffins in bitumen-derived feedstocks. In addition to their negative environmental impact, aromatics limit fluid catalytic cracking (FCC) feedstock conversion, decrease the yield and quality of valuable products such as gasoline and middle distillates, increase levels of polyaromatic hydrocarbons prone to form coke on the catalyst, and ultimately compromise the FCC unit performance. Although cycloparaffins do not have such negative impacts, they are precursors of aromatics as they frequently undergo hydrogen transfer reactions. However, cycloparaffin cracking chemistry involves other competing reactions that are complex and need much investigation. This dissertation provides insights and understanding of the fundamentals of the catalytic cracking of cycloparaffins using carefully selected model compounds such as methylcyclohexane (MCH) and decalin. Thermal and catalytic cracking of these cycloparaffins on FCC-type catalysts are carried out using the CREC Riser Simulator under operating conditions similar to those of the industrial FCC units in terms of temperature, reaction time, reactant partial pressure and catalyst-to-hydrocarbon ratio. The crystallite size of the supported zeolites is varied between 0.4 and 0.9 microns, with both activity and selectivity being monitored. Catalytic conversions ranged between 4 to 16 wt% for MCH and between 8 to 27 wt% for decalin. Reaction pathways of cycloparaffins are determined, and these include ring-opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. The yields and selectivities of over 60 and 140 products, formed during MCH and decalin

  15. Spontaneous emission and the operation of invisibility cloaks: Can the invisibility cloaks render objects invisible in quantum mechanic domain?

    CERN Document Server

    Behbahani, Mina Morshed; Mahdifar, Ali


    As a probe to explore the ability of invisibility cloaks to conceal objects in the quantum mechanics domain, we study the spontaneous emission rate of an excited two-level atom in the vicinity of an ideal invisibility cloaking. On this base, first, a canonical quantization scheme is presented for the electromagnetic field interacting with atomic systems in an anisotropic, inhomogeneous and absorbing magnetodielectric medium which can suitably be used for studying the influence of arbitrary invisibility cloak on the atomic radiative properties. The time dependence of the atomic subsystem is obtained in the Schrodinger picture. By introducing a modified set of the spherical wave vector functions, the Green tensor of the system is calculated via the continuous and discrete methods. In this formalism, the decay rate and as well the emission pattern of the aforementioned atom are computed analytically for both weak and strong coupling interaction, and then numerically calculations are done to demonstrate the perfo...

  16. Catalytic Reaction Synthesis for the Partial Oxidation of Methane to Formaldehyde. (United States)

    Cardenas-Galindo, Maria-Guadalupe

    Catalytic reaction synthesis for the partial oxidation of methane to formaldehyde has been studied by combining microkinetic analysis with molecular orbital calculations. This strategy is used to establish microscopic correlations between the structure and composition of the active site and the kinetic parameters of the reaction mechanism. Using atom clusters to represent the active site of transition metal oxide catalysts, the relationship was probed between coordination number, oxidation state, and ionization potential of the active cation and the reaction steps of methane activation and surface reactions leading to formaldehyde formation. The analysis suggests that in transition metal oxide catalysts, the d-band orbitals of the metal cation should be empty, since otherwise CO_2 formation from CO oxidation will be excessive. Furthermore, the transition metal oxide d-band must be located at sufficiently low energy that it may accept electrons during methane activation. Oxygen O- species, representing vacancies in the 2p cluster band, will favor methane activation. However, clusters with fully occupied 2p bands (O^ {2-}^ecies) will favor formaldehyde production. Such inferences illustrate how experimental and theoretical information already incorporated into an existing microkinetic model for the reaction over V _2O_5 and MoO _3 catalysts can be extended to describe the reaction over new materials in the search for more active and selective catalysts. Using parameters estimated from the molecular orbital calculations, microkinetic reaction simulations were also shown to be useful to identify reactor operating conditions that may favor the production of formaldehyde. The simulation can be used to identify key experiments necessary to test the performance of postulated catalytic materials. The economic evaluation of the process design sets important target goals for methane conversion and formaldehyde selectivity that a catalytic material must satisfy to create a new

  17. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.


    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  18. Phosphorus doped TiO{sub 2} as oxygen sensor with low operating temperature and sensing mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Han, Zhizhong; Wang, Jiejie; Liao, Lan [Institute of Research on the Functional Materials, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); College of Chemistry and Chemical Engineering, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China); Pan, Haibo, E-mail: [Institute of Research on the Functional Materials, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); College of Chemistry and Chemical Engineering, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China); Shen, Shuifa [Institute of Research on the Functional Materials, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); College of Chemistry and Chemical Engineering, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China); Chen, Jianzhong, E-mail: [College of Chemistry and Chemical Engineering, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China)


    Nano-scale TiO{sub 2} powders doped with phosphorus were prepared by sol–gel method. The characterization of the materials was performed by XRD, BET, FT-IR spectroscopy, Zeta potential measurement and XPS analysis. The results indicate that the phosphorus suppresses the crystal growth and phase transformation and, at the same time, increases the surface area and enhances the sensitivity and selectivity for the P-doped TiO{sub 2} oxygen sensors. In this system, the operating temperature is low, only 116 °C, and the response time is short. The spectra of FT-IR and XPS show that the phosphorus dopant presents as the pentavalent-oxidation state in TiO{sub 2}, further phosphorus can connect with Ti{sup 4+} through the bond of Ti-O-P. The positive shifts of XPS peaks indicate that electron depleted layer of P-doped TiO{sub 2} is narrowed compared with that of pure TiO{sub 2}, and the results of Zeta potential illuminate that the density of surface charge carrier is intensified. The adsorptive active site and Lewis acid characteristics of the surface are reinforced by phosphorus doping, where phosphorus ions act as a new active site. Thus, the sensitivity of P-doped TiO{sub 2} is improved, and the 5 mol% P-doped sample has the optimal oxygen sensing properties.

  19. Catalytic Potential of Nano-Magnesium Oxide on Degradation of Humic Acids From Aquatic Solutions

    Directory of Open Access Journals (Sweden)

    Ghorban Asgari


    Full Text Available Catalytic ozonation is a new and promising process used to remove the contaminants from drinking water and wastewater. This study aimed to evaluate the catalytic potential of nano-magnesium oxide (nano-MgO for the removal of humic acids (HA from water. Mg (NO32 solution was used to prepare MgO powder by the calcination method. In a semi-batch reactor, the catalytic ozonation was carried out. The effects of the various operating parameters, including pH, reaction time, T-butyl alcohol (TBA and phosphate on HA degradation were evaluated. Experimental results indicated that degradation of HA was increased as the pH solution and reaction time were increased. Maximum HA degradation was obtained at pH = 10 and the reaction time of 10 minutes in the catalytic process. The calculated catalytic potential of nano-MgO on ozonation of HA was 60%. Moreover, catalytic ozonation process was not affected by TBA and the main reaction on HA degradation HA have effect take place on MgO surface. According to the results of this study, the developed MgO catalyst is the active and proficient catalyst in HA degradation using the catalytic ozonation process.

  20. A catalytic burner using propane and toluene alternately for the drying of textile coatings

    Energy Technology Data Exchange (ETDEWEB)

    Yongseog Seo; Sungkyu Kang [Korea Inst. of Energy Research, Taejon (Korea); Hyundong Shin [Korea Advanced Inst. of Science and Technology (KAIST), Taejon (Korea)


    This study aims to develop a low-temperature catalytic burner using propane and toluene alternately as a fuel and to apply it to the drying of acrylic coatings on textiles. Pt catalysts deposited on ceramic fibres (Al{sub 2}O{sub 3}) were employed. For propane, the diffusive catalytic burner was used. The combustion efficiency of the diffusive catalytic burner deteriorated rapidly when it was installed in downward position. Two concepts of forced diffusion combustion and premixed combustion were introduced to improve the downward placed diffusive catalytic burner. The combustion efficiency was enhanced with these modifications, but the forced diffusion was preferred since premixed combustion raised the temperature of the catalyst above 700degC leading to sintering of the catalysts. For the toluene catalytic burner the premixed combustion mode was adopted. Its optimum operation conditions were obtained by analysing the temperature within the catalyst layer and by adjustment of the toluene mixture. Field tests were performed on the drying acrylic coatings using the catalytic burners. The results showed that the use of catalytic burners had several benefits such as energy savings and less pollutant emissions. (Author)