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Sample records for catalytic mechanism operating

  1. Reaction mechanisms and evaluation of effective process operation for catalytic oxidation and coagulation by ferrous solution and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Moon, H.J.; Kim, Y.M. [Dept. of Environmental Engineering, Sangmyung Univ., Cheonan (Korea); Bae, W.K. [Dept. of Civil and Environmental Engineering, Hanyang Univ., Ansan, Kyounggi (Korea)

    2003-07-01

    This research was carried out to evaluate the removal efficiencies of COD{sub cr} and colour for the dyeing wastewater by ferrous solution and the different dosage of H{sub 2}O{sub 2} in Fenton process. In the case of H{sub 2}O{sub 2} divided dosage, 7:3 was more effective than 3:7 to remove COD{sub cr} and colour. The results showed that COD was mainly removed by Fenton coagulation, where the ferric ions are formed in the initial step of Fenton reaction. On the other hand colour was removed by Fenton oxidation rather than Fenton coagulation. This paper also aims at pursuing to investigate the effective removal mechanisms using ferrous ion coagulation, ferric ion coagulation and Fenton oxidation process. The removal mechanism of COD{sub cr} and colour was mainly coagulation by ferrous ion, ferric ion and Fenton oxidation. The removal efficiencies were dependent on the ferric ion amount at the beginning of the reaction. However the final removal efficiency of COD and colour was in the order of Fenton oxidation, ferric ion coagulation and ferrous ion coagulation. The reason of the highest removal efficiency by Fenton oxidation can be explained by the chain reactions with ferrous solution, ferric ion and hydrogen peroxide. (orig.)

  2. Propulsion Mechanism of Catalytic Microjet Engines.

    Science.gov (United States)

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

    2014-02-01

    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 μ m/s. This mechanism provides a fundamental explanation for the development of driving forces that are acting on bubbles in tubular microjets.

  3. Turning goals into results: the power of catalytic mechanisms.

    Science.gov (United States)

    Collins, J

    1999-01-01

    Most executives have a big, hairy, audacious goal. They write vision statements, formalize procedures, and develop complicated incentive programs--all in pursuit of that goal. In other words, with the best of intentions, they install layers of stultifying bureaucracy. But it doesn't have to be that way. In this article, Jim Collins introduces the catalytic mechanism, a simple yet powerful managerial tool that helps translate lofty aspirations into concrete reality. Catalytic mechanisms are the crucial link between objectives and performance; they are a galvanizing, nonbureaucratic means to turn one into the other. What's the difference between catalytic mechanisms and most traditional managerial controls? Catalytic mechanisms share five characteristics. First, they produce desired results in unpredictable ways. Second, they distribute power for the benefit of the overall system, often to the discomfort of those who traditionally hold power. Third, catalytic mechanisms have teeth. Fourth, they eject "viruses"--those people who don't share the company's core values. Finally, they produce an ongoing effect. Catalytic mechanisms are just as effective for reaching individual goals as they are for corporate ones. To illustrate how catalytic mechanisms work, the author draws on examples of individuals and organizations that have relied on such mechanisms to achieve their goals. The same catalytic mechanism that works in one organization, however, will not necessarily work in another. Catalytic mechanisms must be tailored to specific goals and situations. To help readers get started, the author offers some general principles that support the process of building catalytic mechanisms effectively.

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

    Directory of Open Access Journals (Sweden)

    VLADIMIR LESKOVAC

    2008-04-01

    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.

  5. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.

    2006-01-01

    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  6. OPERATING SPECIFICATIONS OF CATALYTIC CLEANING OF GAS FROM BIOMASS GASIFICATION

    Directory of Open Access Journals (Sweden)

    Martin Lisý

    2015-12-01

    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.

  7. The catalytic cracking mechanism of lignite pyrolysis char on tar

    International Nuclear Information System (INIS)

    Lei, Z.; Huibin, H.; Xiangling, S.; Zhenhua, M.; Lei, Z.

    2017-01-01

    The influence of different pyrolysis conditions for tar catalytic cracking will be analyzed according to the lignite pyrolysis char as catalyst on pyrolytic tar in this paper. The pyrolysis char what is the by-product of the cracking of coal has an abundant of pore structure and it has good catalytic activity. On this basis, making the modified catalyst when the pyrolysis char is activation and loads Fe by impregnation method. The cracking mechanism of lignite pyrolytic tar is explored by applying gas chromatograph to analyze splitting products of tar. The experimental results showed that: (1) The effect of tar cracking as the pyrolysis temperature, the heating rate, the volatilization of pyrolysis char and particle size increasing is better and better. The effect of the catalytic and cracking of lignite pyrolysis char in tar is best when the heating rate, the pyrolysis temperature, the volatiles of pyrolysis char, particle size is in specific conditions.(2) The activation of pyrolysis char can improve the catalytic effect of pyrolysis char on the tar cracking. But it reduces the effect of the tar cracking when the pyrolysis char is activation loading Fe. (author)

  8. 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

    2011-12-31

    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.

  9. Cytochromes P450: History, Classes, Catalytic Mechanism, and Industrial Application.

    Science.gov (United States)

    Cook, D J; Finnigan, J D; Cook, K; Black, G W; Charnock, S J

    Cytochromes P450, a family of heme-containing monooxygenases that catalyze a diverse range of oxidative reactions, are so-called due to their maximum absorbance at 450nm, ie, "Pigment-450nm," when bound to carbon monoxide. They have appeal both academically and commercially due to their high degree of regio- and stereoselectivity, for example, in the area of active pharmaceutical ingredient synthesis. Despite this potential, they often exhibit poor stability, low turnover numbers and typically require electron transport protein(s) for catalysis. P450 systems exist in a variety of functional domain architectures, organized into 10 classes. P450s are also divided into families, each of which is based solely on amino acid sequence homology. Their catalytic mechanism employs a very complex, multistep catalytic cycle involving a range of transient intermediates. Mutagenesis is a powerful tool for the development of improved biocatalysts and has been used extensively with the archetypal Class VIII P450, BM3, from Bacillus megaterium, but with the increasing scale of genomic sequencing, a huge resource is now available for the discovery of novel P450s. © 2016 Elsevier Inc. All rights reserved.

  10. Catalytic membrane in reduction of aqueous nitrates: operational principles and catalytic performance

    NARCIS (Netherlands)

    Ilinitch, O.M.; Cuperus, F.P.; Nosova, L.V.; Gribov, E.N.

    2000-01-01

    The catalytic membrane with palladium-copper active component supported over the macroporous ceramic membrane, and a series of γ-Al 2O 3 supported Pd-Cu catalysts were prepared and investigated. In reduction of nitrate ions by hydrogen in water at ambient temperature, pronounced internal diffusion

  11. [Mechanism of catalytic ozonation for the degradation of paracetamol by activated carbon].

    Science.gov (United States)

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

    2013-04-01

    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.

  12. 40 CFR 60.105a - Monitoring of emissions and operations for fluid catalytic cracking units (FCCU) and fluid coking...

    Science.gov (United States)

    2010-07-01

    ..., Catalytic Reforming Units, and Sulfur Recovery Units. (iii) The owner or operator shall install, operate... for fluid catalytic cracking units (FCCU) and fluid coking units (FCU). 60.105a Section 60.105a... and operations for fluid catalytic cracking units (FCCU) and fluid coking units (FCU). (a) FCCU and...

  13. Reaction mechanisms of CO2 activation and catalytic reduction

    International Nuclear Information System (INIS)

    Wolff, Niklas von

    2016-01-01

    The use of CO 2 as a C1 chemical feedstock for the fine chemical industry is interesting both economically and ecologically, as CO 2 is non-toxic, abundant and cheap. Nevertheless, transformations of CO 2 into value-added products is hampered by its high thermodynamic stability and its inertness toward reduction. In order to design new catalysts able to overcome this kinetic challenge, a profound understanding of the reaction mechanisms at play in CO 2 reduction is needed. Using novel N/Si+ frustrated Lewis pairs (FLPs), the influence of CO 2 adducts and different hydro-borane reducing agents on the reaction mechanism in the catalytic hydroboration of CO 2 were investigated, both by DFT calculations and experiments. In a second step, the reaction mechanism of a novel reaction for the creation of C-C bonds from CO 2 and pyridyl-silanes (C 5 H 4 N-SiMe 3 ) was analyzed by DFT calculations. It was shown that CO 2 plays a double role in this transformation, acting both as a catalyst and a C1-building block. The fine understanding of this transformation then led to the development of a novel approach for the synthesis of sulfones and sulfonamides. Starting from SO 2 and aromatic silanes/amine silanes, these products were obtained in a single step under metal-free conditions. Noteworthy, sulfones and sulfonamides are common motifs in organic chemistry and found in a variety of highly important drugs. Finally, this concept was extended to aromatic halides as coupling partners, and it was thus shown for the first time that a sulfonylative Hiyama reaction is a possible approach to the synthesis of sulfones. (author) [fr

  14. A QM/MM–Based Computational Investigation on the Catalytic Mechanism of Saccharopine Reductase

    OpenAIRE

    Almasi, Joel N.; Bushnell, Eric A.C.; Gauld, James W.

    2011-01-01

    Saccharopine reductase from Magnaporthe grisea, an NADPH-containing enzyme in the α-aminoadipate pathway, catalyses the formation of saccharopine, a precursor to L-lysine, from the substrates glutamate and α-aminoadipate-δ-semialdehyde. Its catalytic mechanism has been investigated using quantum mechanics/molecular mechanics (QM/MM) ONIOM-based approaches. In particular, the overall catalytic pathway has been elucidated and the effects of electron correlation and the anisotropic polar protein...

  15. Catalytic Mechanism and Three-Dimensional Structure of Adenine Deaminase

    Energy Technology Data Exchange (ETDEWEB)

    S Kamat; A Bagaria; D Kumaran; G Holmes-Hampton; H Fan; A Sali; J Sauder; S Burley; P Lindahl; et. al.

    2011-12-31

    Adenine deaminase (ADE) catalyzes the conversion of adenine to hypoxanthine and ammonia. The enzyme isolated from Escherichia coli using standard expression conditions was low for the deamination of adenine (k{sub cat} = 2.0 s{sup -1}; k{sub cat}/K{sub m} = 2.5 x 10{sup 3} M{sup -1} s{sup -1}). However, when iron was sequestered with a metal chelator and the growth medium was supplemented with Mn{sup 2+} prior to induction, the purified enzyme was substantially more active for the deamination of adenine with k{sub cat} and k{sub cat}/K{sub m} values of 200 s{sup -1} and 5 x 10{sup 5} M{sup -1} s{sup -1}, respectively. The apoenzyme was prepared and reconstituted with Fe{sup 2+}, Zn{sup 2+}, or Mn{sup 2+}. In each case, two enzyme equivalents of metal were necessary for reconstitution of the deaminase activity. This work provides the first example of any member of the deaminase subfamily of the amidohydrolase superfamily to utilize a binuclear metal center for the catalysis of a deamination reaction. [Fe{sup II}/Fe{sup II}]-ADE was oxidized to [Fe{sup III}/Fe{sup III}]-ADE with ferricyanide with inactivation of the deaminase activity. Reducing [Fe{sup III}/Fe{sup III}]-ADE with dithionite restored the deaminase activity, and thus, the diferrous form of the enzyme is essential for catalytic activity. No evidence of spin coupling between metal ions was evident by electron paramagnetic resonance or Moessbauer spectroscopy. The three-dimensional structure of adenine deaminase from Agrobacterium tumefaciens (Atu4426) was determined by X-ray crystallography at 2.2 {angstrom} resolution, and adenine was modeled into the active site on the basis of homology to other members of the amidohydrolase superfamily. On the basis of the model of the adenine-ADE complex and subsequent mutagenesis experiments, the roles for each of the highly conserved residues were proposed. Solvent isotope effects, pH-rate profiles, and solvent viscosity were utilized to propose a chemical reaction

  16. Catalytic Mechanism and Three-Dimensional Structure of Adenine Deaminase

    Energy Technology Data Exchange (ETDEWEB)

    Kamat, S.S.; Swaminathan, S.; Bagaria, A.; Kumaran, D.; Holmes-Hampton, G. P.; Fan, H.; Sali, A.; Sauder, J. M.; Burley, S. K.; Lindahl, P. A.; Raushel, F. M.

    2011-03-22

    Adenine deaminase (ADE) catalyzes the conversion of adenine to hypoxanthine and ammonia. The enzyme isolated from Escherichia coli using standard expression conditions was low for the deamination of adenine (k{sub cat} = 2.0 s{sup -1}; k{sub cat}/K{sub m} = 2.5 x 10{sup 3} M{sup -1} s{sup -1}). However, when iron was sequestered with a metal chelator and the growth medium was supplemented with Mn{sup 2+} prior to induction, the purified enzyme was substantially more active for the deamination of adenine with kcat and kcat/Km values of 200 s{sup -1} and 5 x 10{sup 5} M{sup -1} s{sup -1}, respectively. The apoenzyme was prepared and reconstituted with Fe{sup 2+}, Zn{sup 2+}, or Mn{sup 2+}. In each case, two enzyme equivalents of metal were necessary for reconstitution of the deaminase activity. This work provides the first example of any member of the deaminase subfamily of the amidohydrolase superfamily to utilize a binuclear metal center for the catalysis of a deamination reaction. [Fe{sup II}/Fe{sup II}]-ADE was oxidized to [Fe{sup III}/Fe{sup III}]-ADE with ferricyanide with inactivation of the deaminase activity. Reducing [Fe{sup III}/Fe{sup III}]-ADE with dithionite restored the deaminase activity, and thus, the diferrous form of the enzyme is essential for catalytic activity. No evidence of spin coupling between metal ions was evident by electron paramagnetic resonance or Moessbauer spectroscopy. The three-dimensional structure of adenine deaminase from Agrobacterium tumefaciens (Atu4426) was determined by X-ray crystallography at 2.2 {angstrom} resolution, and adenine was modeled into the active site on the basis of homology to other members of the amidohydrolase superfamily. On the basis of the model of the adenine-ADE complex and subsequent mutagenesis experiments, the roles for each of the highly conserved residues were proposed. Solvent isotope effects, pH-rate profiles, and solvent viscosity were utilized to propose a chemical reaction mechanism and the

  17. Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

    2008-01-15

    Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

  18. Catalytic performance improvement of styrene hydrogenation in trickle bed reactor by using periodic operation

    International Nuclear Information System (INIS)

    Wongkia, Atittahn; Praserthdam, Piyasan; Assabumrungrat, Suttichai; Suriye, Kongkiat; Nonkhamwong, Anuwat

    2013-01-01

    We investigated the catalytic performance improvement of styrene hydrogenation in a trickle bed reactor by using periodic operation. The effects of cycle period and split on relative conversion, which is defined as styrene conversion obtained from periodic operation over that from steady state operation, were examined at various operating conditions including gas and average liquid flow rates, pressure and temperature. The experimental results reveal that both cycle period and split have strong influence on the catalytic performance. The fast mode (short cycle period) is a favorable condition. The improvement by the periodic operation becomes less pronounced for operations at high average liquid flow rate, pressure and temperature. From this study, a maximum improvement of styrene conversion of 18% is observed

  19. Catalytic performance improvement of styrene hydrogenation in trickle bed reactor by using periodic operation

    Energy Technology Data Exchange (ETDEWEB)

    Wongkia, Atittahn; Praserthdam, Piyasan; Assabumrungrat, Suttichai [Chulalongkorn University, Bangkok (Thailand); Suriye, Kongkiat; Nonkhamwong, Anuwat [SCG Chemicals Co. Ltd., Bangkok (Thailand)

    2013-03-15

    We investigated the catalytic performance improvement of styrene hydrogenation in a trickle bed reactor by using periodic operation. The effects of cycle period and split on relative conversion, which is defined as styrene conversion obtained from periodic operation over that from steady state operation, were examined at various operating conditions including gas and average liquid flow rates, pressure and temperature. The experimental results reveal that both cycle period and split have strong influence on the catalytic performance. The fast mode (short cycle period) is a favorable condition. The improvement by the periodic operation becomes less pronounced for operations at high average liquid flow rate, pressure and temperature. From this study, a maximum improvement of styrene conversion of 18% is observed.

  20. Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

    Science.gov (United States)

    Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

    2017-06-01

    Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

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

    Directory of Open Access Journals (Sweden)

    Tore Lid

    2008-10-01

    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.

  2. Differences in the catalytic mechanisms of mesophilic and thermophilic indole-3-glycerol phosphate synthase enzymes at their adaptive temperatures.

    Science.gov (United States)

    Zaccardi, Margot J; Mannweiler, Olga; Boehr, David D

    2012-02-10

    Thermophilic enzymes tend to be less catalytically-active at lower temperatures relative to their mesophilic counterparts, despite having very similar crystal structures. An often cited hypothesis for this general observation is that thermostable enzymes have evolved a more rigid tertiary structure in order to cope with their more extreme, natural environment, but they are also less flexible at lower temperatures, leading to their lower catalytic activity under mesophilic conditions. An alternative hypothesis, however, is that complementary thermophilic-mesophilic enzyme pairs simply operate through different evolutionary-optimized catalytic mechanisms. In this communication, we present evidence that while the steps of the catalytic mechanisms for mesophilic and thermophilic indole-3-glycerol phosphate synthase (IGPS) enzymes are fundamentally similar, the identity of the rate-determining step changes as a function of temperature. Our findings indicate that while product release is rate-determining at 25°C for thermophilic IGPS, near its adaptive temperature (75°C), a proton transfer event, involving a general acid, becomes rate-determining. The rate-determining steps for thermophilic and mesophilic IGPS enzymes are also different at their respective, adaptive temperatures with the mesophilic IGPS-catalyzed reaction being rate-limited before irreversible CO2 release, and the thermophilic IGPS-catalyzed reaction being rate limited afterwards. Copyright © 2012 Elsevier Inc. All rights reserved.

  3. Periodic Operation of Three-Phase Catalytic Reactors

    Czech Academy of Sciences Publication Activity Database

    Silveston, P.T.; Hanika, Jiří

    2005-01-01

    Roč. 82, č. 6 (2005), s. 1105-1142 ISSN 0008-4034 Institutional research plan: CEZ:AV0Z4072921 Keywords : three-phase reactors * trickle bed * periodic operation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.574, year: 2005

  4. Differences in the catalytic mechanisms of mesophilic and thermophilic indole-3-glycerol phosphate synthase enzymes at their adaptive temperatures

    International Nuclear Information System (INIS)

    Zaccardi, Margot J.; Mannweiler, Olga; Boehr, David D.

    2012-01-01

    Highlights: ► Catalytic mechanisms of thermophilic–mesophilic enzymes may differ. ► Product release is rate-determining for thermophilic IGPS at low temperatures. ► But at higher temperatures, proton transfer from the general acid is rate-limiting. ► Rate-determining step is different still for mesophilic IGPS. ► Both chemical and physical steps of catalysis are important for temperature adaptation. -- Abstract: Thermophilic enzymes tend to be less catalytically-active at lower temperatures relative to their mesophilic counterparts, despite having very similar crystal structures. An often cited hypothesis for this general observation is that thermostable enzymes have evolved a more rigid tertiary structure in order to cope with their more extreme, natural environment, but they are also less flexible at lower temperatures, leading to their lower catalytic activity under mesophilic conditions. An alternative hypothesis, however, is that complementary thermophilic–mesophilic enzyme pairs simply operate through different evolutionary-optimized catalytic mechanisms. In this communication, we present evidence that while the steps of the catalytic mechanisms for mesophilic and thermophilic indole-3-glycerol phosphate synthase (IGPS) enzymes are fundamentally similar, the identity of the rate-determining step changes as a function of temperature. Our findings indicate that while product release is rate-determining at 25 °C for thermophilic IGPS, near its adaptive temperature (75 °C), a proton transfer event, involving a general acid, becomes rate-determining. The rate-determining steps for thermophilic and mesophilic IGPS enzymes are also different at their respective, adaptive temperatures with the mesophilic IGPS-catalyzed reaction being rate-limited before irreversible CO 2 release, and the thermophilic IGPS-catalyzed reaction being rate limited afterwards.

  5. Operator methods in quantum mechanics

    CERN Document Server

    Schechter, Martin

    2003-01-01

    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

  6. 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)

    2009-05-12

    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.

  7. Catalytic Mechanisms and Biocatalytic Applications of Aspartate and Methylaspartate Ammonia Lyases

    NARCIS (Netherlands)

    de Villiers, Marianne; Veetil, Vinod Puthan; Raj, Hans; de Villiers, Jandre; Poelarends, Gerrit J.

    2012-01-01

    Ammonia lyases catalyze the formation of alpha-beta-unsaturated bonds by the elimination of ammonia from their substrates. This conceptually straightforward reaction has been the emphasis of many studies, with the main focus on the catalytic mechanism of these enzymes and/or the use of these enzymes

  8. Structural basis for the catalytic mechanism of a proficient enzyme: Orotidine 5'-Monophosphate Decarboxylase

    DEFF Research Database (Denmark)

    Harris, Pernille Hanne; Poulsen, Jens-Christian Navarro; Jensen, Kaj Frank

    2000-01-01

    /ß-barrels with two shared active sites. The orientation of the orotate moiety of the substrate is unambiguously deduced from the structure, and previously proposed catalytic mechanisms involving protonation of O2 or O4 can be ruled out. The proximity of the OMP carboxylate group with Asp71 appears to be instrumental...

  9. Further investigation on boric acid catalytic graphitization of polyacrylonitrile carbon fibers: Mechanism and mechanical properties

    International Nuclear Information System (INIS)

    Wen, Ya; Lu, Yonggen; Xiao, Hao; Qin, Xianying

    2012-01-01

    Highlights: ► The modulus of carbon fiber was improved by boric acid at the temperature range of 1500–2900 °C. ► 2300 °C is a key temperature degree from which the boron began to benefit fiber strength. ► The fiber strength was affected by the boron reaction and related to the boron states. -- Abstract: Catalytic graphitization of polyacrylonitrile based carbon fibers by boric acid doping was studied and the dependence of fiber tensile strength on the boron content and temperature was discussed. It was found that there existed a key temperature point for the boron to take effect. When the fibers were modified with 7.0 wt.% boric acid solution, with increasing temperature, the tensile strength was lower than that of the unmodified ones below 2300 °C, but a reverse thing happened above 2300 °C. Moreover, when being heated at 2500 °C, the modified fibers showed an increasing tensile modulus and strength with increasing boron content till maximums of 404 GPa and 2.46 GPa, 26% and 16% higher than those of unmodified ones. The mechanical properties of the fibers were affected by the interaction of carbon and boron, and also related with boron states. The decomposition of boron acid and its interaction with carbon brought defects on fiber surface, degrading the mechanical properties below 1300 °C. With further heat treatment, the boron diffused into the fibers and divided into two states: substitutional and interstitial. At a temperature over 2300 °C with an appreciate boron content, the substitutional would be formed predominantly, which removed the structural defects and relaxed the distortions, so as to benefit the mechanical properties.

  10. Density operators in quantum mechanics

    International Nuclear Information System (INIS)

    Burzynski, A.

    1979-01-01

    A brief discussion and resume of density operator formalism in the way it occurs in modern physics (in quantum optics, quantum statistical physics, quantum theory of radiation) is presented. Particularly we emphasize the projection operator method, application of spectral theorems and superoperators formalism in operator Hilbert spaces (Hilbert-Schmidt type). The paper includes an appendix on direct sums and direct products of spaces and operators, and problems of reducibility for operator class by using the projection operators. (author)

  11. 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.

    2016-12-01

    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.

  12. Insights into the catalytic mechanism of dehydrogenase BphB: A quantum mechanics/molecular mechanics study.

    Science.gov (United States)

    Zhang, Ruiming; Shi, Xiangli; Sun, Yanhui; Zhang, Qingzhu; Wang, Wenxing

    2018-05-17

    The present study delineated the dehydrogenation mechanism of cis-2,3-dihydro-2,3-dihydroxybiphenyl (2,3-DDBPH) and cis-2,3-dihydro-2,3-dihydroxy-4,4'-dichlorobiphenyl (2,3-DD-4,4'-DBPH) by Pandoraea pnomenusa strain B-356 cis-2,3-dihydro-2,3-dihydroxybiphenyl dehydrogenase (BphB) in atomistic detail. The enzymatic process was investigated by a combined quantum mechanics/molecular mechanics (QM/MM) approach. Five different snapshots were extracted and calculated, which revealed that the Boltzmann-weighted average barriers of 2,3-DDBPH and 2,3-DD-4,4'-DBPH dehydrogenation processes are 10.7 and 11.5 kcal mol -1 , respectively. The established dehydrogenation mechanism provides new insight into the degradation processes of other chlorinated 2,3-DDBPH. In addition to Asn115, Ser142, and Lys149, the importance of Ile 89, Asn143, Pro184, Met 187, Thr189, and Lue 191 during the dehydrogenation process of 2,3-DDBPH and 2,3-DD-4,4'-DBPH were also highlighted to search for promising mutation targets for improving the catalytic efficiency of BphB. Copyright © 2018. Published by Elsevier Ltd.

  13. A QM/MM–Based Computational Investigation on the Catalytic Mechanism of Saccharopine Reductase

    Directory of Open Access Journals (Sweden)

    James W. Gauld

    2011-10-01

    Full Text Available Saccharopine reductase from Magnaporthe grisea, an NADPH-containing enzyme in the α-aminoadipate pathway, catalyses the formation of saccharopine, a precursor to L-lysine, from the substrates glutamate and α-aminoadipate-δ-semialdehyde. Its catalytic mechanism has been investigated using quantum mechanics/molecular mechanics (QM/MM ONIOM-based approaches. In particular, the overall catalytic pathway has been elucidated and the effects of electron correlation and the anisotropic polar protein environment have been examined via the use of the ONIOM(HF/6-31G(d:AMBER94 and ONIOM(MP2/6-31G(d//HF/6-31G(d:AMBER94 methods within the mechanical embedding formulism and ONIOM(MP2/6-31G(d//HF/6-31G(d:AMBER94 and ONIOM(MP2/6-311G(d,p//HF/6-31G(d:AMBER94 within the electronic embedding formulism. The results of the present study suggest that saccharopine reductase utilises a substrate-assisted catalytic pathway in which acid/base groups within the cosubstrates themselves facilitate the mechanistically required proton transfers. Thus, the enzyme appears to act most likely by binding the three required reactant molecules glutamate, α-aminoadipate-δ-semialdehyde and NADPH in a manner and polar environment conducive to reaction.

  14. Characterization of nicotinamidases: steady state kinetic parameters, classwide inhibition by nicotinaldehydes, and catalytic mechanism.

    Science.gov (United States)

    French, Jarrod B; Cen, Yana; Vrablik, Tracy L; Xu, Ping; Allen, Eleanor; Hanna-Rose, Wendy; Sauve, Anthony A

    2010-12-14

    Nicotinamidases are metabolic enzymes that hydrolyze nicotinamide to nicotinic acid. These enzymes are widely distributed across biology, with examples found encoded in the genomes of Mycobacteria, Archaea, Eubacteria, Protozoa, yeast, and invertebrates, but there are none found in mammals. Although recent structural work has improved our understanding of these enzymes, their catalytic mechanism is still not well understood. Recent data show that nicotinamidases are required for the growth and virulence of several pathogenic microbes. The enzymes of Saccharomyces cerevisiae, Drosophila melanogaster, and Caenorhabditis elegans regulate life span in their respective organisms, consistent with proposed roles in the regulation of NAD(+) metabolism and organismal aging. In this work, the steady state kinetic parameters of nicotinamidase enzymes from C. elegans, Sa. cerevisiae, Streptococcus pneumoniae (a pathogen responsible for human pneumonia), Borrelia burgdorferi (the pathogen that causes Lyme disease), and Plasmodium falciparum (responsible for most human malaria) are reported. Nicotinamidases are generally efficient catalysts with steady state k(cat) values typically exceeding 1 s(-1). The K(m) values for nicotinamide are low and in the range of 2 -110 μM. Nicotinaldehyde was determined to be a potent competitive inhibitor of these enzymes, binding in the low micromolar to low nanomolar range for all nicotinamidases tested. A variety of nicotinaldehyde derivatives were synthesized and evaluated as inhibitors in kinetic assays. Inhibitions are consistent with reaction of the universally conserved catalytic Cys on each enzyme with the aldehyde carbonyl carbon to form a thiohemiacetal complex that is stabilized by a conserved oxyanion hole. The S. pneumoniae nicotinamidase can catalyze exchange of (18)O into the carboxy oxygens of nicotinic acid with H(2)(18)O. The collected data, along with kinetic analysis of several mutants, allowed us to propose a catalytic

  15. Significance of the enzymatic properties of yeast S39A enolase to the catalytic mechanism.

    Science.gov (United States)

    Brewer, J M; Glover, C V; Holland, M J; Lebioda, L

    1998-04-02

    The S39A mutant of yeast enolase (isozyme 1), prepared by site-directed mutagenesis, has a relative Vmax of 0.01% and an activation constant for Mg2+ ca. 10-fold higher, compared with native enzyme. It is correctly folded. There is little effect of solvent viscosity on activity. We think that the loop Ser36-His43 fails to move to the 'closed' position upon catalytic Mg2+ binding, weakening several electrostatic interactions involved in the mechanism.

  16. Synergetic mechanism of methanol–steam reforming reaction in a catalytic reactor with electric discharges

    International Nuclear Information System (INIS)

    Kim, Taegyu; Jo, Sungkwon; Song, Young-Hoon; Lee, Dae Hoon

    2014-01-01

    Highlights: • Methanol–steam reforming was performed on Cu catalysts under an electric discharge. • Discharge had a synergetic effect on the catalytic reaction for methanol conversion. • Discharge lowered the temperature for catalyst activation or light off. • Discharge controlled the yield and selectivity of species in a reforming process. • Adsorption triggered by a discharge was a possible mechanism for a synergetic effect. - Abstract: Methanol–steam reforming was performed on Cu/ZnO/Al 2 O 3 catalysts under an electric discharge. The discharge occurred between the electrodes where the catalysts were packed. The electric discharge was characterized by the discharge voltage and electric power to generate the discharge. The existence of a discharge had a synergetic effect on the catalytic reaction for methanol conversion. The electric discharge provided modified reaction paths resulting in a lower temperature for catalyst activation or light off. The discharge partially controlled the yield and selectivity of species in a reforming process. The aspect of control was examined in view of the reaction kinetics. The possible mechanisms for the synergetic effect between the catalytic reaction and electric discharge on methanol–steam reforming were addressed. A discrete reaction path, particularly adsorption triggered by an electric discharge, was suggested to be the most likely mechanism for the synergetic effect. These results are expected to provide a guide for understanding the plasma–catalyst hybrid reaction

  17. A QM/MM study of the catalytic mechanism of nicotinamidase.

    Science.gov (United States)

    Sheng, Xiang; Liu, Yongjun

    2014-02-28

    Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications.

  18. Quantum Mechanics and Molecular Mechanics Study of the Catalytic Mechanism of Human AMSH-LP Domain Deubiquitinating Enzymes.

    Science.gov (United States)

    Zhu, Wenyou; Liu, Yongjun; Ling, Baoping

    2015-08-25

    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).

  19. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    Science.gov (United States)

    Habershon, Scott

    2016-04-12

    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

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

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    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

  1. Catalytic mechanism of phenylacetone monooxygenases for non-native linear substrates.

    Science.gov (United States)

    Carvalho, Alexandra T P; Dourado, Daniel F A R; Skvortsov, Timofey; de Abreu, Miguel; Ferguson, Lyndsey J; Quinn, Derek J; Moody, Thomas S; Huang, Meilan

    2017-10-11

    Phenylacetone monooxygenase (PAMO) is the most stable and thermo-tolerant member of the Baeyer-Villiger monooxygenase family, and therefore it is an ideal candidate for the synthesis of industrially relevant compounds. However, its limited substrate scope has largely limited its industrial applications. In the present work, we provide, for the first time, the catalytic mechanism of PAMO for the native substrate phenylacetone as well as for a linear non-native substrate 2-octanone, using molecular dynamics simulations, quantum mechanics and quantum mechanics/molecular mechanics calculations. We provide a theoretical basis for the preference of the enzyme for the native aromatic substrate over non-native linear substrates. Our study provides fundamental atomic-level insights that can be employed in the rational engineering of PAMO for wide applications in industrial biocatalysis, in particular, in the biotransformation of long-chain aliphatic oils into potential biodiesels.

  2. 40 CFR Table 9 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment..., Subpt. UUU, Table 9 Table 9 to Subpart UUU of Part 63—Operating Limits for Organic HAP Emissions From...

  3. 40 CFR Table 16 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Reforming Units

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Operating Limits for Organic HAP Emissions From Catalytic Reforming Units 16 Table 16 to Subpart UUU of Part 63 Protection of Environment..., Subpt. UUU, Table 16 Table 16 to Subpart UUU of Part 63—Operating Limits for Organic HAP Emissions From...

  4. A novel approach to the design and operation scheduling of heterogeneous catalytic reactors

    International Nuclear Information System (INIS)

    Ghodasara, Kamlesh; Smith, Robin; Hwang, Sungwon

    2014-01-01

    A number of studies have been conducted to reduce the overall level of catalyst deactivation in heterogeneous catalytic reactors, and improve the performance of reactors, such as yield, conversion or selectivity. The methodology generally includes optimization of the following: (1) operating conditions of the reaction system, such as feed temperature, normal operating temperature, pressure, and composition of feed streams; (2) reactor design parameters, such as dimension of the reactor, side stream distribution along the axis of the reactor beds, the mixing ratio of inert catalyst at each bed; and (3) catalyst design parameters, such as the pore size distribution across the pellet, active material distribution, size and shape of the catalyst, etc. Few studies have examined optimization of the overall catalyst reactor performance throughout the catalyst lifetime, considering catalyst deactivation. Furthermore, little attention has been given to the impact of various configurations of reactor networks and scheduling of the reactor operation (i.e., online and offline-regeneration) on the overall reactor performance throughout the catalyst lifetime. Therefore, we developed a range of feasible sequences of reactors and scheduling of reactors for operation and regeneration, and compared the overall reactor performance of multiple cases. Furthermore, a superstructure of reactor networks was developed and optimized to determine the optimum reactor network that shows the maximum overall reactor performance. The operating schedule of each reactor in the network was considered further. Lastly, the methodology was illustrated using a case study of the MTO (methanol to olefin) process

  5. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

    International Nuclear Information System (INIS)

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

    2016-01-01

    Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: 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

  6. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

    Energy Technology Data Exchange (ETDEWEB)

    Pura, Jarosław, E-mail: jaroslawpura@gmail.com [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Laskowski, Zbigniew; Gierej, Maciej [Precious Metal Mint, Weteranów 95, 05-250 Radzymin (Poland)

    2016-12-01

    Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: 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

  7. Study on modeling of operator's learning mechanism

    International Nuclear Information System (INIS)

    Yoshimura, Seichi; Hasegawa, Naoko

    1998-01-01

    One effective method to analyze the causes of human errors is to model the behavior of human and to simulate it. The Central Research Institute of Electric Power Industry (CRIEPI) has developed an operator team behavior simulation system called SYBORG (Simulation System for the Behavior of an Operating Group) to analyze the human errors and to establish the countermeasures for them. As an operator behavior model which composes SYBORG has no learning mechanism and the knowledge of a plant is fixed, it cannot take suitable actions when unknown situations occur nor learn anything from the experience. However, considering actual operators, learning is an essential human factor to enhance their abilities to diagnose plant anomalies. In this paper, Q learning with 1/f fluctuation was proposed as a learning mechanism of an operator and simulation using the mechanism was conducted. The results showed the effectiveness of the learning mechanism. (author)

  8. Hydrodynamics and propulsion mechanism of self-propelled catalytic micromotors: model and experiment.

    Science.gov (United States)

    Li, Longqiu; Wang, Jiyuan; Li, Tianlong; Song, Wenping; Zhang, Guangyu

    2014-10-14

    The hydrodynamic behavior and propulsion mechanism of self-propelled micromotors are studied theoretically and experimentally. A hydrodynamic model to describe bubble growth and detachment is proposed to investigate the mechanism of a self-propelled conical tubular catalytic micromotor considering bubble geometric asymmetry and buoyancy force. The growth force caused by the growth of the bubble surface against the fluid is the driving force for micromotor motion. Also, the buoyancy force plays a primary role in bubble detachment. The effect of geometrical parameters on the micromotor velocity and drag force is presented. The bubble radius ratio is investigated for different micromotor radii to determine its hydrodynamic behavior during bubble ejection. The average micromotor velocity is found to be strongly dependent on the semi-cone angle, expelling frequency and bubble radius ratio. The semi-cone angle has a significant effect on the expelling frequency for conical tubular micromotors. The predicted results are compared to already existing experimental data for cylindrical micromotors (semi-cone angle δ = 0°) and conical micromotors. A good agreement is found between the theoretical calculation and experimental results. This model provides a profound explanation for the propulsion mechanism of a catalytic micromotor and can be used to optimize the micromotor design for its biomedical and environmental applications.

  9. New insights into the binding and catalytic mechanisms of Bacillus thuringiensis lactonase: insights into B. thuringiensis AiiA mechanism.

    Directory of Open Access Journals (Sweden)

    Marc N Charendoff

    Full Text Available The lactonase enzyme (AiiA produced by Bacillus thuringiensis serves to degrade autoinducer-1 (AI-1 signaling molecules in what is an evolved mechanism by which to compete with other bacteria. Bioassays have been previously performed to determine whether the AI-1 aliphatic tail lengths have any effect on AiiA's bioactivity, however, data to date are conflicting. Additionally, specific residue contributions to the catalytic activity of AiiA provide for some interesting questions. For example, it has been proposed that Y194 serves to provide an oxyanion hole to AI-1 which is curious given the fact the substrate spans two Zn(2+ ions. These ions might conceivably provide enough charge to promote both ligand stability and the carbonyl activation necessary to drive a nucleophilic attack. To investigate these questions, multiple molecular dynamics simulations were performed across a family of seven acylated homoserine lactones (AHL along with their associated intermediate and product states. Distance analyses and interaction energy analyses were performed to investigate current bioassay data. Our simulations are consistent with experimental studies showing that AiiA degrades AHLs in a tail length independent manner. However, the presence of the tail is required for activity. Also, the putative oxyanion hole function of Y194 toward the substrate is not observed in any of the reactant or product state simulation trajectories, but does seem to show efficacy in stabilizing the intermediate state. Last, we argue through ionization state analyses, that the proton shuttling necessary for catalytic activity might be mediated by both water and substrate-based intra-molecular proton transfer. Based on this argument, an alternate catalytic mechanism is proposed.

  10. Projection operator techniques in nonequilibrium statistical mechanics

    International Nuclear Information System (INIS)

    Grabert, H.

    1982-01-01

    This book is an introduction to the application of the projection operator technique to the statistical mechanics of irreversible processes. After a general introduction to the projection operator technique and statistical thermodynamics the Fokker-Planck and the master equation approach are described together with the response theory. Then, as applications the damped harmonic oscillator, simple fluids, and the spin relaxation are considered. (HSI)

  11. Operation of a catalytic reverse flow reactor for the purification of air contamined with volatile organic compounds

    NARCIS (Netherlands)

    van de Beld, L.; van de Beld, L.; Westerterp, K.R.

    1997-01-01

    Catalytic oxidation in a reverse flow reactor is an attractive process for the decontamination of air polluted with volatile organic compounds (VOCs). In this paper several aspects of operating this type of reactor for air purification under strongly varying conditions will be discussed. For a

  12. ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

    Energy Technology Data Exchange (ETDEWEB)

    Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

    1977-12-11

    The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

  13. Structural basis and catalytic mechanism for the dual functional endo-beta-N-acetylglucosaminidase A.

    Directory of Open Access Journals (Sweden)

    Jie Yin

    Full Text Available Endo-beta-N-acetylglucosaminidases (ENGases are dual specificity enzymes with an ability to catalyze hydrolysis and transglycosylation reactions. Recently, these enzymes have become the focus of intense research because of their potential for synthesis of glycopeptides. We have determined the 3D structures of an ENGase from Arthrobacter protophormiae (Endo-A in 3 forms, one in native form, one in complex with Man(3GlcNAc-thiazoline and another in complex with GlcNAc-Asn. The carbohydrate moiety sits above the TIM-barrel in a cleft region surrounded by aromatic residues. The conserved essential catalytic residues - E173, N171 and Y205 are within hydrogen bonding distance of the substrate. W216 and W244 regulate access to the active site during transglycosylation by serving as "gate-keepers". Interestingly, Y299F mutation resulted in a 3 fold increase in the transglycosylation activity. The structure provides insights into the catalytic mechanism of GH85 family of glycoside hydrolases at molecular level and could assist rational engineering of ENGases.

  14. Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

    Energy Technology Data Exchange (ETDEWEB)

    He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-03-01

    Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO2, the selective hydrogenolysis dominates for cleaving the Caliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

  15. 40 CFR Table 21 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Reforming Units

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Reforming Units 21 Table 21 to Subpart UUU of Part 63... Compliance With Operating Limits for Organic HAP Emissions From Catalytic Reforming Units As stated in § 63...

  16. 40 CFR Table 7 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 7 Table 7 to Subpart UUU of Part 63... With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units As stated in § 63.1564(c)(1...

  17. 40 CFR Table 14 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 14 Table 14 to Subpart UUU of Part 63... Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units As stated in § 63...

  18. Mechanisms of mono- and poly-ubiquitination: Ubiquitination specificity depends on compatibility between the E2 catalytic core and amino acid residues proximal to the lysine

    Directory of Open Access Journals (Sweden)

    Sadowski Martin

    2010-08-01

    Full Text Available Abstract Ubiquitination involves the attachment of ubiquitin to lysine residues on substrate proteins or itself, which can result in protein monoubiquitination or polyubiquitination. Ubiquitin attachment to different lysine residues can generate diverse substrate-ubiquitin structures, targeting proteins to different fates. The mechanisms of lysine selection are not well understood. Ubiquitination by the largest group of E3 ligases, the RING-family E3 s, is catalyzed through co-operation between the non-catalytic ubiquitin-ligase (E3 and the ubiquitin-conjugating enzyme (E2, where the RING E3 binds the substrate and the E2 catalyzes ubiquitin transfer. Previous studies suggest that ubiquitination sites are selected by E3-mediated positioning of the lysine toward the E2 active site. Ultimately, at a catalytic level, ubiquitination of lysine residues within the substrate or ubiquitin occurs by nucleophilic attack of the lysine residue on the thioester bond linking the E2 catalytic cysteine to ubiquitin. One of the best studied RING E3/E2 complexes is the Skp1/Cul1/F box protein complex, SCFCdc4, and its cognate E2, Cdc34, which target the CDK inhibitor Sic1 for K48-linked polyubiquitination, leading to its proteasomal degradation. Our recent studies of this model system demonstrated that residues surrounding Sic1 lysines or lysine 48 in ubiquitin are critical for ubiquitination. This sequence-dependence is linked to evolutionarily conserved key residues in the catalytic region of Cdc34 and can determine if Sic1 is mono- or poly-ubiquitinated. Our studies indicate that amino acid determinants in the Cdc34 catalytic region and their compatibility to those surrounding acceptor lysine residues play important roles in lysine selection. This may represent a general mechanism in directing the mode of ubiquitination in E2 s.

  19. The catalytic mechanism of mouse renin studied with QM/MM calculations.

    Science.gov (United States)

    Brás, Natércia F; Ramos, Maria J; Fernandes, Pedro A

    2012-09-28

    Hypertension is a chronic condition that affects nearly 25% of adults worldwide. As the Renin-Angiotensin-Aldosterone System is implicated in the control of blood pressure and body fluid homeostasis, its combined blockage is an attractive therapeutic strategy currently in use for the treatment of several cardiovascular conditions. We have performed QM/MM calculations to study the mouse renin catalytic mechanism in atomistic detail, using the N-terminal His6-Asn14 segment of angiotensinogen as substrate. The enzymatic reaction (hydrolysis of the peptidic bond between residues in the 10th and 11th positions) occurs through a general acid/base mechanism and, surprisingly, it is characterized by three mechanistic steps: it begins with the creation of a first very stable tetrahedral gem-diol intermediate, followed by protonation of the peptidic bond nitrogen, giving rise to a second intermediate. In a final step the peptidic bond is completely cleaved and both gem-diol hydroxyl protons are transferred to the catalytic dyad (Asp32 and Asp215). The final reaction products are two separate peptides with carboxylic acid and amine extremities. The activation energy for the formation of the gem-diol intermediate was calculated as 23.68 kcal mol(-1), whereas for the other steps the values were 15.51 kcal mol(-1) and 14.40 kcal mol(-1), respectively. The rate limiting states were the reactants and the first transition state. The associated barrier (23.68 kcal mol(-1)) is close to the experimental values for the angiotensinogen substrate (19.6 kcal mol(-1)). We have also tested the influence of the density functional on the activation and reaction energies. All eight density functionals tested (B3LYP, B3LYP-D3, X3LYP, M06, B1B95, BMK, mPWB1K and B2PLYP) gave very similar results.

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

    Science.gov (United States)

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

    2015-03-01

    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.

  1. Interagency mechanical operations group numerical systems group

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-09-01

    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.

  2. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

    Science.gov (United States)

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

    2016-06-01

    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.

  3. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp [Department of Hydrogen Energy Systems, Faculty of Engineering, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp [International Research Center for Hydrogen Energy, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp [Department of Hydrogen Energy Systems, Faculty of Engineering, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); International Research Center for Hydrogen Energy, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan)

    2016-06-03

    Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} 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. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–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 CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} 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 CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

  4. Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

    Science.gov (United States)

    Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

    2018-04-01

    The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

  5. Surface spintronics enhanced photo-catalytic hydrogen evolution: Mechanisms, strategies, challenges and future

    Science.gov (United States)

    Zhang, Wenyan; Gao, Wei; Zhang, Xuqiang; Li, Zhen; Lu, Gongxuan

    2018-03-01

    Hydrogen is a green energy carrier with high enthalpy and zero environmental pollution emission characteristics. Photocatalytic hydrogen evolution (HER) is a sustainable and promising way to generate hydrogen. Despite of great achievements in photocatalytic HER research, its efficiency is still limited due to undesirable electron transfer loss, high HER over-potential and low stability of some photocatalysts, which lead to their unsatisfied performance in HER and anti-photocorrosion properties. In recent years, many spintronics works have shown their enhancing effects on photo-catalytic HER. For example, it was reported that spin polarized photo-electrons could result in higher photocurrents and HER turn-over frequency (up to 200%) in photocatalytic system. Two strategies have been developed for electron spin polarizing, which resort to heavy atom effect and magnetic induction respectively. Both theoretical and experimental studies show that controlling spin state of OHrad radicals in photocatalytic reaction can not only decrease OER over-potential (even to 0 eV) of water splitting, but improve stability and charge lifetime of photocatalysts. A convenient strategy have been developed for aligning spin state of OHrad by utilizing chiral molecules to spin filter photo-electrons. By chiral-induced spin filtering, electron polarization can approach to 74%, which is significantly larger than some traditional transition metal devices. Those achievements demonstrate bright future of spintronics in enhancing photocatalytic HER, nevertheless, there is little work systematically reviewing and analysis this topic. This review focuses on recent achievements of spintronics in photocatalytic HER study, and systematically summarizes the related mechanisms and important strategies proposed. Besides, the challenges and developing trends of spintronics enhanced photo-catalytic HER research are discussed, expecting to comprehend and explore such interdisciplinary research in

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

    KAUST Repository

    Tope, Balkrishna B.; Balasamy, Rabindran J.; Khurshid, Alam; Atanda, Luqman A.; Yahiro, Hidenori; Shishido, Tetsuya; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

    2011-01-01

    -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-(-Mg

  7. Catalytic zinc site and mechanism of the metalloenzyme PR-AMP cyclohydrolase.

    Science.gov (United States)

    D'Ordine, Robert L; Linger, Rebecca S; Thai, Carolyn J; Davisson, V Jo

    2012-07-24

    The enzyme N(1)-(5'-phosphoribosyl) adenosine-5'-monophosphate cyclohydrolase (PR-AMP cyclohydrolase) is a Zn(2+) metalloprotein encoded by the hisI gene. It catalyzes the third step of histidine biosynthesis, an uncommon ring-opening of a purine heterocycle for use in primary metabolism. A three-dimensional structure of the enzyme from Methanobacterium thermoautotrophicum has revealed that three conserved cysteine residues occur at the dimer interface and likely form the catalytic site. To investigate the functions of these cysteines in the enzyme from Methanococcus vannielii, a series of biochemical studies were pursued to test the basic hypothesis regarding their roles in catalysis. Inactivation of the enzyme activity by methyl methane thiosulfonate (MMTS) or 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) also compromised the Zn(2+) binding properties of the protein inducing loss of up to 90% of the metal. Overall reaction stoichiometry and the potassium cyanide (KCN) induced cleavage of the protein suggested that all three cysteines were modified in the process. The enzyme was protected from DTNB-induced inactivation by inclusion of the substrate N(1)-(5'-phosphoribosyl)adenosine 5'-monophosphate; (PR-AMP), while Mg(2+), a metal required for catalytic activity, enhanced the rate of inactivation. Site-directed mutations of the conserved C93, C109, C116 and the double mutant C109/C116 were prepared and analyzed for catalytic activity, Zn(2+) content, and reactivity with DTNB. Substitution of alanine for each of the conserved cysteines showed no measurable catalytic activity, and only the C116A was still capable of binding Zn(2+). Reactions of DTNB with the C109A/C116A double mutant showed that C93 is completely modified within 0.5 s. A model consistent with these data involves a DTNB-induced mixed disulfide linkage between C93 and C109 or C116, followed by ejection of the active site Zn(2+) and provides further evidence that the Zn(2+) coordination site involves the

  8. Possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime

    Energy Technology Data Exchange (ETDEWEB)

    Chumakov, G A; Slinko, M G

    1979-05-01

    The possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime was demonstrated by analyzing a kinetic model of hydrogen interaction with oxygen over a metallic catalyst. Within a certain interval of partial pressures of oxygen, the average reaction rate over a period of oscillation may be over five times that of the steady-state reaction.

  9. 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.

    1995-01-01

    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 the con...

  10. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15.

    Science.gov (United States)

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

    2015-04-09

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Time Operator in Relativistic Quantum Mechanics

    Science.gov (United States)

    Khorasani, Sina

    2017-07-01

    It is first shown that the Dirac’s equation in a relativistic frame could be modified to allow discrete time, in agreement to a recently published upper bound. Next, an exact self-adjoint 4 × 4 relativistic time operator for spin-1/2 particles is found and the time eigenstates for the non-relativistic case are obtained and discussed. Results confirm the quantum mechanical speculation that particles can indeed occupy negative energy levels with vanishingly small but non-zero probablity, contrary to the general expectation from classical physics. Hence, Wolfgang Pauli’s objection regarding the existence of a self-adjoint time operator is fully resolved. It is shown that using the time operator, a bosonic field referred here to as energons may be created, whose number state representations in non-relativistic momentum space can be explicitly found.

  12. Towards Understanding the Catalytic Mechanism of Human Paraoxonase 1: Experimental and In Silico Mutagenesis Studies.

    Science.gov (United States)

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

    2017-08-01

    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.

  13. Mechanism of 3,4-dihydroxybenzaldehyde electropolymerization at carbon paste electrodes : catalytic detection of NADH

    Directory of Open Access Journals (Sweden)

    Delbem Maria Flávia

    2002-01-01

    Full Text Available Cyclic voltammetry was used to study 3,4-dihydroxybenzaldehyde (3,4-DHB electropolymerization processes on carbon paste electrodes. The characteristics of the electropolymerized films were highly dependent on pH, anodic switching potential, scan rate, 3,4-DHB concentrations and number of cycles. Film stability was determined in citrate/phosphate buffer solutions at the same pH used during the electropolymerization process. The best conditions to prepare carbon paste modified electrodes were pH 7.8; 0.0 <= Eapl <= 0.25 V; 10 mV s-1; 0.25 mmol L-1 3,4-DHB and 10 scans. These carbon paste modified electrodes were used for NADH catalytic detection at 0.23 V in the range 0.015 <= [NADH] <= 0.21 mmol L-1. Experimental data were used to propose a mechanism for the 3,4--DHB electropolymerization processes, which involves initial phenoxyl radical formation.

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

    Directory of Open Access Journals (Sweden)

    Arvin B. Tam

    2014-11-01

    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.

  15. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnOx/SBA-15

    International Nuclear Information System (INIS)

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

    2015-01-01

    Highlights: • Clofibric acid (CA) is efficiently mineralized by O 3 /MnO x /SBA-15. • Adsorption of CA and its intermediates on MnO x /SBA-15 is proved unimportant. • Initiation of hydroxyl radicals (·OH) is enhanced in O 3 /MnO x /SBA-15. • Uniformly distributed MnO x accounts for the high activity of MnO 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 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 3 /MnO x /SBA-15). Adsorption of CA and its intermediates by MnO x /SBA-15 was proved unimportant in O 3 /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 (NaHSO 3 ) 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

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

    Science.gov (United States)

    Tvaroška, Igor

    2015-02-11

    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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Thermal catalytic oxidation of octachloronaphthalene over anatase TiO2 nanomaterial and its hypothesized mechanism

    Science.gov (United States)

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

    2015-12-01

    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. Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

    Science.gov (United States)

    Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

    2014-01-09

    Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

  19. Catalytic Mechanism and Mode of Action of the Periplasmic Alginate Epimerase AlgG

    NARCIS (Netherlands)

    Wolfram, Francis; Kitova, Elena N.; Robinson, Howard; Walvoort, Marthe T. C.; Codee, Jeroen D. C.; Klassen, John S.; Howell, P. Lynne

    2014-01-01

    Background: The alginate epimerase AlgG converts mannuronate to its C5 epimer guluronate at the polymer level. Results: The structure of Pseudomonas syringae AlgG has been determined, and the protein has been functionally characterized. Conclusion: His(319) acts as the catalytic base, whereas

  20. Critical Role of Interdomain Interactions in the Conformational Change and Catalytic Mechanism of Endoplasmic Reticulum Aminopeptidase 1.

    Science.gov (United States)

    Stamogiannos, Athanasios; Maben, Zachary; Papakyriakou, Athanasios; Mpakali, Anastasia; Kokkala, Paraskevi; Georgiadis, Dimitris; Stern, Lawrence J; Stratikos, Efstratios

    2017-03-14

    Endoplasmic reticulum aminopeptidase 1 (ERAP1) is an intracellular enzyme that is important for the generation of antigenic epitopes and major histocompatibility class I-restricted adaptive immune responses. ERAP1 processes a vast variety of different peptides but still shows length and sequence selectivity, although the mechanism behind these properties is poorly understood. X-ray crystallographic analysis has revealed that ERAP1 can assume at least two distinct conformations in which C-terminal domain IV is either proximal or distal to active site domain II. To improve our understanding of the role of this conformational change in the catalytic mechanism of ERAP1, we used site-directed mutagenesis to perturb key salt bridges between domains II and IV. Enzymatic analysis revealed that these mutations, although located away from the catalytic site, greatly reduce the catalytic efficiency and change the allosteric kinetic behavior. The variants were more efficiently activated by small peptides and bound a competitive inhibitor with weaker affinity and faster dissociation kinetics. Molecular dynamics analysis suggested that the mutations affect the conformational distribution of ERAP1, reducing the population of closed states. Small-angle X-ray scattering indicated that both the wild type and the ERAP1 variants are predominantly in an open conformational state in solution. Overall, our findings suggest that electrostatic interactions between domains II and IV in ERAP1 are crucial for driving a conformational change that regulates the structural integrity of the catalytic site. The extent of domain opening in ERAP1 probably underlies its specialization for antigenic peptide precursors and should be taken into account in inhibitor development efforts.

  1. Theoretical Proposal for the Whole Phosphate Diester Hydrolysis Mechanism Promoted by a Catalytic Promiscuous Dinuclear Copper(II) Complex.

    Science.gov (United States)

    Esteves, Lucas F; Rey, Nicolás A; Dos Santos, Hélio F; Costa, Luiz Antônio S

    2016-03-21

    The catalytic mechanism that involves the cleavage of the phosphate diester model BDNPP (bis(2,4-dinitrophenyl) phosphate) catalyzed through a dinuclear copper complex is investigated in the current study. The metal complex was originally designed to catalyze catechol oxidation, and it showed an interesting catalytic promiscuity case in biomimetic systems. The current study investigates two different reaction mechanisms through quantum mechanics calculations in the gas phase, and it also includes the solvent effect through PCM (polarizable continuum model) single-point calculations using water as solvent. Two mechanisms are presented in order to fully describe the phosphate diester hydrolysis. Mechanism 1 is of the S(N)2 type, which involves the direct attack of the μ-OH bridge between the two copper(II) ions toward the phosphorus center, whereas mechanism 2 is the process in which hydrolysis takes place through proton transfer between the oxygen atom in the bridging hydroxo ligand and the other oxygen atom in the phosphate model. Actually, the present theoretical study shows two possible reaction paths in mechanism 1. Its first reaction path (p1) involves a proton transfer that occurs immediately after the hydrolytic cleavage, so that the proton transfer is the rate-determining step, which is followed by the entry of two water molecules. Its second reaction path (p2) consists of the entry of two water molecules right after the hydrolytic cleavage, but with no proton transfer; thus, hydrolytic cleavage is the rate-limiting step. The most likely catalytic path occurs in mechanism 1, following the second reaction path (p2), since it involves the lowest free energy activation barrier (ΔG(⧧) = 23.7 kcal mol(-1), in aqueous solution). A kinetic analysis showed that the experimental k(obs) value of 1.7 × 10(-5) s(-1) agrees with the calculated value k1 = 2.6 × 10(-5) s(-1); the concerted mechanism is kinetically favorable. The KIE (kinetic isotope effect) analysis

  2. The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

    NARCIS (Netherlands)

    Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

    1976-01-01

    The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

  3. Large-Scale Analysis Exploring Evolution of Catalytic Machineries and Mechanisms in Enzyme Superfamilies.

    Science.gov (United States)

    Furnham, Nicholas; Dawson, Natalie L; Rahman, Syed A; Thornton, Janet M; Orengo, Christine A

    2016-01-29

    Enzymes, as biological catalysts, form the basis of all forms of life. How these proteins have evolved their functions remains a fundamental question in biology. Over 100 years of detailed biochemistry studies, combined with the large volumes of sequence and protein structural data now available, means that we are able to perform large-scale analyses to address this question. Using a range of computational tools and resources, we have compiled information on all experimentally annotated changes in enzyme function within 379 structurally defined protein domain superfamilies, linking the changes observed in functions during evolution to changes in reaction chemistry. Many superfamilies show changes in function at some level, although one function often dominates one superfamily. We use quantitative measures of changes in reaction chemistry to reveal the various types of chemical changes occurring during evolution and to exemplify these by detailed examples. Additionally, we use structural information of the enzymes active site to examine how different superfamilies have changed their catalytic machinery during evolution. Some superfamilies have changed the reactions they perform without changing catalytic machinery. In others, large changes of enzyme function, in terms of both overall chemistry and substrate specificity, have been brought about by significant changes in catalytic machinery. Interestingly, in some superfamilies, relatives perform similar functions but with different catalytic machineries. This analysis highlights characteristics of functional evolution across a wide range of superfamilies, providing insights that will be useful in predicting the function of uncharacterised sequences and the design of new synthetic enzymes. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  4. PCI. Mechanism, measures, rules for reactor operation

    International Nuclear Information System (INIS)

    Bender, D.; Bender, G.; Dewes, P.; Wensauer, A.

    2009-01-01

    Though modern and advanced fuel assembly designs for BWR as AREVA's ATRIUM trademark 10 fuel assemblies show a high reliability, fuel failures are still encountered. The ZTF (Zero Tolerance for Failures) initiative was launched by AREVA to further upgrade BWR fuel assembly reliability towards failure free fuel. The introduction of the zirconium liner cladding has greatly reduced pellet cladding interaction (PCI) failures. However the phenomenon of PCI in reactor operation was not completely eliminated. There were failures in AREVA's BWR fuel with liner cladding attributed to PCI, but when subject to hot cell examinations, all these have been attributed to ''non-classical'' PCI, where local cladding stress is amplified due to missing pellet surface (MPS). However, in order to support the efforts to eliminate all possible root causes for fuel failures, AREVA NP addresses PCI with a ''multi-track'' strategy. First, and most important, the development of chromia doped pellets and more favorable pellet geometries aim at fuel that by design is protected as much as possible against PCI. A high pellet quality is further assured by the final assessment of the pellet appearance by an automatic visual inspection system in the pellet manufacturing lines. In order to support these hardware improvements, AREVA NP provides software aimed to minimize PCI risks. Two main approaches are described in this paper: - The ''classical'' PCI operation and maneuvering guidelines restrict power maneuvering and limit the ramping rates with the goal to control the stress level of the cladding. AREVA's guidelines are based on ramp tests as well as on extensive power plant experience, and are updated to reflect the performance of liner cladding. - Additional effort is made to further understand the PCI phenomenon, e.g. by the use of detailed fuel rod thermal-mechanical codes that provide far better insight of the state variables that control the process of rupture due to stress corrosion

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

    Directory of Open Access Journals (Sweden)

    Thanasit Wongsiriamnuay

    2013-01-01

    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.

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

    KAUST Repository

    Tope, Balkrishna B.

    2011-11-01

    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.

  7. Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

    Science.gov (United States)

    Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.; Naik, Rajesh R.; Knecht, Marc R.

    2011-05-01

    To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.

  8. Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts.

    Science.gov (United States)

    Pacardo, Dennis B; Slocik, Joseph M; Kirk, Kyle C; Naik, Rajesh R; Knecht, Marc R

    2011-05-01

    To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions. © The Royal Society of Chemistry 2011

  9. Catalytic mechanism of sodium compounds in black liquor during gasification of coal black liquor slurry

    International Nuclear Information System (INIS)

    Kuang Jianping; Zhou Junhu; Zhou Zhijun; Liu Jianzhong; Cen Kefa

    2008-01-01

    The coal black liquor slurry (CBLS) was composed of coal and black pulping liquor, which has plenty of sodium compounds, lignin and cellulose. The sodium compounds have a catalytic effect on the gasification process of coal black liquor slurry, while lignin and cellulose enhance the heat value. Alkali-catalyzed gasification experiments of CBLS and CWS (coal water slurry) are investigated on the thermobalance and fixed bed reactor. The residues of the gasification of CBLS and CWS are analyzed by XRD, SEM and FT-IR. It is found that many micro- and mesopores and zigzag faces exist in the surface of the CBLS coke, which play a key role in the catalytic gasification. Sodium can enhance the reaction potential, weaken the bond of C-O and improve the gasification reaction rate. XRD results show that sodium aluminum silicate and nepheline are the main crystal components of the CBLS and CWS. The C-O stretching vibration peak in the 1060 cm -1 band in the CBLS shifts to 995.65 cm -1 in the CBLS coke after partial gasification. This means that the energy of the C-O stretching vibration in the CBLS carbon matrix decreases, so the structure of the carbon matrix is more liable to react with an oxygen ion or hydroxide ion. The amplitude of the C-O stretching vibration peak is augmented step by step due to the ground-excited level jump of the C-O band

  10. Catalytic oxidation of dibromomethane over Ti-modified Co3O4 catalysts: Structure, activity and mechanism.

    Science.gov (United States)

    Mei, Jian; Huang, Wenjun; Qu, Zan; Hu, Xiaofang; Yan, Naiqiang

    2017-11-01

    Ti-modified Co 3 O 4 catalysts with various Co/Ti ratios were synthesized using the co-precipitation method and were used in catalytic oxidation of dibromomethane (CH 2 Br 2 ), which was selected as the model molecule for brominated volatile organic compounds (BVOCs). Addition of Ti distorted the crystal structure and led to the formation of a Co-O-Ti solid solution. Co 4 Ti 1 (Co/Ti molar ratio was 4) achieved higher catalytic activity with a T 90 (the temperature needed for 90% conversion) of approximately 245°C for CH 2 Br 2 oxidation and higher selectivity to CO 2 at a low temperature than the other investigated catalysts. In addition, Co 4 Ti 1 was stable for at least 30h at 500ppm CH 2 Br 2 , 0 or 2vol% H 2 O, 0 or 500ppm p-xylene (PX), and 10% O 2 at a gas hourly space velocity of 60,000h -1 . The final products were CO x , Br 2 , and HBr, without the formation of other Br-containing organic byproducts. The high catalytic activity was attributed to the high Co 3+ /Co 2+ ratio and high surface acidity. Additionally, the synergistic effect of Co and Ti made it superior for CH 2 Br 2 oxidation. Furthermore, based on the analysis of products and in situ DRIFTs studies, a receivable reaction mechanism for CH 2 Br 2 oxidation over Ti-modified Co 3 O 4 catalysts was proposed. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Synthesis of hydrophobic gold nanoclusters: growth mechanism study, luminescence property and catalytic application

    International Nuclear Information System (INIS)

    Selvam, Tamil Selvi; Chi, Kai-Ming

    2011-01-01

    One-pot synthesis of well dispersed, size-controlled gold nanoparticles with the average size of 10–15 nm and luminescent gold nanoclusters with average size of 1.7–2.0 nm were successfully achieved by thermal decomposition of gold organometallic precursor CH 3 AuPPh 3 in the presence of thiol surfactants in o-xylene. Only difference between the preparations of two types of Au nanoparticles is the amount of thiol surfactant employed. The mechanistic study of formation of gold nanoparticles was carried out by analyzing the samples at different reaction time intervals and revealed that two-staged growth process was involved. The nanoclusters showed strong red emission with the maximum intensity at about 600 nm. The maximum room temperature photoluminescence quantum yield was measured as 1.2%. The catalytic ability of the Au nanoclusters to promote Suzuki–Miyaura coupling involving the C–C bond formation was also investigated.

  12. Mechanism of store-operated calcium entry

    Indian Academy of Sciences (India)

    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 ...

  13. CO-Bridged H-Cluster Intermediates in the Catalytic Mechanism of [FeFe]-Hydrogenase CaI.

    Science.gov (United States)

    Ratzloff, Michael W; Artz, Jacob H; Mulder, David W; Collins, Reuben T; Furtak, Thomas E; King, Paul W

    2018-06-20

    The [FeFe]-hydrogenases ([FeFe] H 2 ases) catalyze reversible H 2 activation at the H-cluster, which is composed of a [4Fe-4S] H subsite linked by a cysteine thiolate to a bridged, organometallic [2Fe-2S] ([2Fe] H ) subsite. Profoundly different geometric models of the H-cluster redox states that orchestrate the electron/proton transfer steps of H 2 bond activation have been proposed. We have examined this question in the [FeFe] H 2 ase I from Clostridium acetobutylicum (CaI) by Fourier-transform infrared (FTIR) spectroscopy with temperature annealing and H/D isotope exchange to identify the relevant redox states and define catalytic transitions. One-electron reduction of H ox led to formation of H red H + ([4Fe-4S] H 2+ -Fe I -Fe I ) and H red ' ([4Fe-4S] H 1+ -Fe II -Fe I ), with both states characterized by low frequency μ-CO IR modes consistent with a fully bridged [2Fe] H . Similar μ-CO IR modes were also identified for H red H + of the [FeFe] H 2 ase from Chlamydomonas reinhardtii (CrHydA1). The CaI proton-transfer variant C298S showed enrichment of an H/D isotope-sensitive μ-CO mode, a component of the hydride bound H-cluster IR signal, H hyd . Equilibrating CaI with increasing amounts of NaDT, and probed at cryogenic temperatures, showed H red H + was converted to H hyd . Over an increasing temperature range from 10 to 260 K catalytic turnover led to loss of H hyd and appearance of H ox , consistent with enzymatic turnover and H 2 formation. The results show for CaI that the μ-CO of [2Fe] H remains bridging for all of the "H red " states and that H red H + is on pathway to H hyd and H 2 evolution in the catalytic mechanism. These results provide a blueprint for designing small molecule catalytic analogs.

  14. Theoretical study for pyridinium-based ionic liquid 1-ethylpyridinium trifluoroacetate: synthesis mechanism, electronic structure, and catalytic reactivity.

    Science.gov (United States)

    Zhu, Xueying; Cui, Peng; Zhang, Dongju; Liu, Chengbu

    2011-07-28

    By performing density functional theory calculations, we have studied the synthesis mechanism, electronic structure, and catalytic reactivity of a pyridinium-based ionic liquid, 1-ethylpyridinium trifluoroacetate ([epy](+)[CF(3)COO](-)). It is found that the synthesis of the pyridinium salt follows a S(N)2 mechanism. The electronic structural analyses show that multiple H bonds are generally involved in the pyridinium-based ionic liquid, which may play a decisive role for stabilizing the ionic liquid. The cation-anion interaction mainly involves electron transfer between the lone pair of the oxygen atom in the anion and the antibonding orbital of the C*-H bond (C* denotes the carbon atom at the ortho-position of nitrogen atom in the cation). This present work has also given clearly the catalytic mechanism of [epy](+)[CF(3)COO](-) toward to the Diels-Alder (D-A) reaction of acrylonitrile with 2-methyl-1,3-butadiene. Both the cation and anion are shown to play important roles in promoting the D-A reaction. The cation [epy](+), as a Lewis acid, associates the C≡N group by C≡N···H H bond to increase the polarity of the C═C double bond in acrylonitrile, while the anion CF(3)COO(-) links with the methyl group in 2-methyl-1,3-butadiene by C-H···O H bond, which weakens the electron-donating capability of methyl and thereby lowers the energy barrier of the D-A reaction. The present results are expected to provide valuable information for the design and application of pyridinium-based ionic liquids. © 2011 American Chemical Society

  15. Antiunitary symmetry operators in quantum mechanics

    International Nuclear Information System (INIS)

    Carinena, J.F.; Santander, M.

    1981-01-01

    A criterion to decide that some symmetries of a quantum system must be realized as antiunitary operators is given. It is based on some mathematical theorems about the second cohomology group of the symmetry group when expressed in terms of those of a normal subgroup and the corresponding factor group. It is also shown that this criterion implies that the only possibility for the unitary subgroup in the Galilean case is that generated by the space reflection and the connected component containing the identity; otherwise only massless systems would arise. (author)

  16. On the definition of time operator in quantum mechanics

    International Nuclear Information System (INIS)

    Nowicki, A.A.

    1974-01-01

    Different approaches to the quantum-mechanical definition of time operator T are briefly discussed. In particular we define the analytic continuation of the time operator and show that one can construct its exact eigenstates. We consider also the case of a relativistic free scalar particle and discuss the notion of proper time operator S. (author)

  17. Removal of elemental mercury by TiO₂doped with WO₃ and V₂O₅ for their photo- and thermo-catalytic removal mechanisms.

    Science.gov (United States)

    Shen, Huazhen; Ie, Iau-Ren; Yuan, Chung-Shin; Hung, Chung-Hsuang; Chen, Wei-Hsiang

    2016-03-01

    The catalytic removal of Hg(0) was investigated to ascertain whether the catalysts could simultaneously possess both thermo- and photo-catalytic reactivity. The immobilized V2O5/TiO2 and WO3/TiO2 catalysts were synthesized by sol-gel method and then coated on the surface of glass beads for catalytic removal of Hg(0). They were also characterized by SEM, BET, XRD, UV-visible, and XPS analysis, and their catalytic reactivity was tested under 100-160 °C under the near-UV irradiation. The results indicated that V2O5/TiO2 solely possessed the thermo-catalytic reactivity while WO3/TiO2 only had photo-catalytic reactivity. Although the synthesis catalytic reactivity has not been found for these catalysts up to date, but compared with TiO2, the removal efficiencies of Hg(0) at 140 and 160 °C were enhanced; particularly, the efficiency was improved from 20 % at 160 °C by TiO2 to nearly 90 % by WO3/TiO2 under the same operating conditions. The effects of doping amount of V2O5 and WO3 were also investigated, and the results showed that 10 % V2O5 and 5 % WO3/TiO2 were the best immobilized catalysts for thermo- and photo-catalytic reactivity, respectively. The effect of different influent concentrations of Hg(0) was demonstrated that the highest concentration of Hg(0) led to the best removal efficiencies for V2O5/TiO2 and WO3/TiO2 at 140 and 160 °C, because high Hg(0) concentration increased the mass transfer rate of Hg(0) toward the surface of catalysts and drove the reaction to proceed. At last, the effect of single gas component on the removal of Hg(0) was also investigated.

  18. Interdisciplinary study of the influence on effectiveness of catalytic hydrogen recombiners of operating conditions in the reactor containment

    International Nuclear Information System (INIS)

    Kelm, S.; Reinecke, E.A.; Schoppe, L.; Dornseiffer, J.; Leistner, F.; Juehe, S.

    2008-01-01

    At the Emsland nuclear power station, a total of 58 autocatalytic hydrogen recombiners were backfitted in 1999 as an additional measure of risk reduction in connection with major hydrogen releases after events going beyond the design basis. Annual in-service inspections after 2002 revealed that some of the catalyst sheets developed startup delays and marked evolutions of smoke and smell. Recombiners not meeting the inspection criterion were completely regenerated as a measure of precaution. A preventive study was conducted jointly with institutes of the Juelich Research Center and the Aachen Technical University to analyze the composition of the deposits, which was then compared with the chemical characteristics of potential sources in the reactor containment. At the same time, the influence on effectiveness of the catalyst sheets was examined. On the basis of a random evaluation of the in-service inspection logs of the past few years, representative samples were taken whose startup behavior and operating characteristics were studied in a test rig alongside chemical analyses so as to allow a correlation to be established between the analytical findings and the catalytic activity of the samples. The findings made allowed internal sources of the catalyst deposits to be excluded. The impurities are introduced with the outside air. As a consequence, the air ducts in the vicinity of the respective recombiners were inspected and optimization steps were taken in connection with in-service inspections and regeneration procedures. (orig.)

  19. DNA gyrase with a single catalytic tyrosine can catalyze DNA supercoiling by a nicking-closing mechanism

    Science.gov (United States)

    Gubaev, Airat; Weidlich, Daniela; Klostermeier, Dagmar

    2016-01-01

    The topological state of DNA is important for replication, recombination and transcription, and is regulated in vivo by DNA topoisomerases. Gyrase introduces negative supercoils into DNA at the expense of ATP hydrolysis. It is the accepted view that gyrase achieves supercoiling by a strand passage mechanism, in which double-stranded DNA is cleaved, and a second double-stranded segment is passed through the gap, converting a positive DNA node into a negative node. We show here that gyrase with only one catalytic tyrosine that cleaves a single strand of its DNA substrate can catalyze DNA supercoiling without strand passage. We propose an alternative mechanism for DNA supercoiling via nicking and closing of DNA that involves trapping, segregation and relaxation of two positive supercoils. In contrast to DNA supercoiling, ATP-dependent relaxation and decatenation of DNA by gyrase lacking the C-terminal domains require both tyrosines and strand passage. Our results point towards mechanistic plasticity of gyrase and might pave the way for finding novel and specific mechanism-based gyrase inhibitors. PMID:27557712

  20. Third-order differential ladder operators and supersymmetric quantum mechanics

    International Nuclear Information System (INIS)

    Mateo, J; Negro, J

    2008-01-01

    Hierarchies of one-dimensional Hamiltonians in quantum mechanics admitting third-order differential ladder operators are studied. Each Hamiltonian has associated three-step Darboux (pseudo)-cycles and Painleve IV equations as a closure condition. The whole hierarchy is generated applying some operations on the cycles. These operations are investigated in the frame of supersymmetric quantum mechanics and mainly involve algebraic manipulations. A consistent geometric representation for the hierarchy and cycles is built that also helps in understanding the operations. Three kinds of hierarchies are distinguished and a realization based on the harmonic oscillator Hamiltonian is supplied, giving an interpretation for the spectral properties of the Hamiltonians of each hierarchy

  1. Implementation of an operator model with error mechanisms for nuclear power plant control room operation

    International Nuclear Information System (INIS)

    Suh, Sang Moon; Cheon, Se Woo; Lee, Yong Hee; Lee, Jung Woon; Park, Young Taek

    1996-01-01

    SACOM(Simulation Analyser with Cognitive Operator Model) is being developed at Korea Atomic Energy Research Institute to simulate human operator's cognitive characteristics during the emergency situations of nuclear power plans. An operator model with error mechanisms has been developed and combined into SACOM to simulate human operator's cognitive information process based on the Rasmussen's decision ladder model. The operational logic for five different cognitive activities (Agents), operator's attentional control (Controller), short-term memory (Blackboard), and long-term memory (Knowledge Base) have been developed and implemented on blackboard architecture. A trial simulation with a scenario for emergency operation has been performed to verify the operational logic. It was found that the operator model with error mechanisms is suitable for the simulation of operator's cognitive behavior in emergency situation

  2. Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.

    1997-01-01

    Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

  3. 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.

    2006-01-01

    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-in...

  4. The catalytic mechanism of cyclic GMP-AMP synthase (cGAS) and implications for innate immunity and inhibition.

    Science.gov (United States)

    Hall, Justin; Ralph, Erik C; Shanker, Suman; Wang, Hong; Byrnes, Laura J; Horst, Reto; Wong, Jimson; Brault, Amy; Dumlao, Darren; Smith, James F; Dakin, Leslie A; Schmitt, Daniel C; Trujillo, John; Vincent, Fabien; Griffor, Matt; Aulabaugh, Ann E

    2017-12-01

    Cyclic GMP-AMP synthase (cGAS) is activated by ds-DNA binding to produce the secondary messenger 2',3'-cGAMP. cGAS is an important control point in the innate immune response; dysregulation of the cGAS pathway is linked to autoimmune diseases while targeted stimulation may be of benefit in immunoncology. We report here the structure of cGAS with dinucleotides and small molecule inhibitors, and kinetic studies of the cGAS mechanism. Our structural work supports the understanding of how ds-DNA activates cGAS, suggesting a site for small molecule binders that may cause cGAS activation at physiological ATP concentrations, and an apparent hotspot for inhibitor binding. Mechanistic studies of cGAS provide the first kinetic constants for 2',3'-cGAMP formation, and interestingly, describe a catalytic mechanism where 2',3'-cGAMP may be a minor product of cGAS compared with linear nucleotides. © 2017 The Authors Protein Science published by Wiley Periodicals, Inc. on behalf of The Protein Society.

  5. 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

    2006-01-01

    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......, and it is argued how these processes may lead to different nanofiber structures. The proposed growth model is found to be in good agreement with previous findings....

  6. New insights into the catalytic mechanism of human glycine N-acyltransferase.

    Science.gov (United States)

    van der Sluis, Rencia; Ungerer, Vida; Nortje, Carla; A van Dijk, Alberdina; Erasmus, Elardus

    2017-11-01

    Even though the glycine conjugation pathway was one of the first metabolic pathways to be discovered, this pathway remains very poorly characterized. The bi-substrate kinetic parameters of a recombinant human glycine N-acyltransferase (GLYAT, E.C. 2.3.1.13) were determined using the traditional colorimetric method and a newly developed HPLC-ESI-MS/MS method. Previous studies analyzing the kinetic parameters of GLYAT, indicated a random Bi-Bi and/or ping-pong mechanism. In this study, the hippuric acid concentrations produced by the GLYAT enzyme reaction were analyzed using the allosteric sigmoidal enzyme kinetic module. Analyses of the initial rate (v) against substrate concentration plots, produced a sigmoidal curve (substrate activation) when the benzoyl-CoA concentrations was kept constant, whereas the plot with glycine concentrations kept constant, passed through a maximum (substrate inhibition). Thus, human GLYAT exhibits mechanistic kinetic cooperativity as described by the Ferdinand enzyme mechanism rather than the previously assumed Michaelis-Menten reaction mechanism. © 2017 Wiley Periodicals, Inc.

  7. Safety relevant failure mechanisms in the post-operational phase

    International Nuclear Information System (INIS)

    Mayer, Gerhard; Stiller, Jan Christopher; Roemer, Sarah

    2017-03-01

    When the 13"t"h amendment of the Atomic Energy Act came into force, eight Germ an nuclear power plant units had their power operating licences revoked and are now in the so-called post operation phase. Of the remaining nuclear power plants, one have by now also entered the post operation phase, with those left in operation bound for entering this phase sometime between now and the end of 2022. Therefore, failure mechanisms that are particularly relevant for post operation were to be identified and described in the frame of the present project. To do so, three major steps were taken: Firstly, recent national and international pertinent literature was evaluated to obtain indications of failure mechanisms in the post operation phase. It turned out that most of the national and international literature deals with the general procedure of the transition from power operation to decommissioning and dismantling. However, there were also some documents providing detailed indications of possible failure mechanisms in post operation. This includes e.g. the release of radioactive materials caused by the drop of containers, chemical impacts on systems important to safety in connection with decontamination work, and corrosion in connection with the storage of the core in the spent fuel pool, with the latter leading to the jamming of the fuel assemblies in the storage racks and a possible reduction of coolant circulation. In a second step, three safety analyses of pressurised water reactors prepared by the respective plant operators were evaluated to identify failure mechanisms based on systems engineering. The failure mechanisms that were found here include e.g. faults in the boric acid concentration of the reactor coolant, damage to the equipment airlock upon the unloading of Castor casks, leakages in connection with primary system decontamination, and the drop of packages holding radioactive residual materials or waste with subsequent mobilisation of radioactive aerosols

  8. 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

    1997-01-01

    cereus including a docked substrate molecule was subjected to a stepwise molecular mechanics energy minimization. Second, the location of the nucleophilic water molecule in the active site of the fully relaxed enzyme-substrate complex was determined by evaluation of nonbonded interaction energies between...... water molecule was verified during a 100 ps molecular dynamics simulation. During the simulation the substrate undergoes a conformational change, but retains its localization in the active site. The contacts between the enzyme, the substrate, and the nucleophilic water molecule display some fluctuations...... the strong electrostatic interactions in the active site realistically during energy minimization, delocalization of the charges from the three zinc ions was considered. Therefore, quantum mechanics calculations on the zinc ions and the zinc-coordinating residues were carried out prior to the molecular...

  9. Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

    Science.gov (United States)

    Zhang, Lei; Wen, Xin; Lei, Zhang; Gao, Long; Sha, Xiangling; Ma, Zhenhua; He, Huibin; Wang, Yusu; Jia, Yang; Li, Yonghui

    2018-04-01

    Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction) was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction), SEM (scanning electron microscope), BET test and transient test. The experiments show that: * The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. * The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. * The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

  10. Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

    Directory of Open Access Journals (Sweden)

    Lei Zhang

    2018-04-01

    Full Text Available Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction, SEM (scanning electron microscope, BET test and transient test. The experiments show that: ① The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. ② The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. ③ The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

  11. Kinetic investigation of the catalytic mechanism for bovine liver mitochondrial monoamine oxidase

    International Nuclear Information System (INIS)

    Walker, M.C.

    1988-01-01

    The kinetic behavior of the oxidative deamination reaction catalyzed by bovine liver mitochondrial monoamine oxidase was investigated with a series of ring-substituted benzylamines. Oxidation rates were fastest with the meta isomers. Dalziel coefficients were consistent with a mechanism involving a ternary complex for all substrates tested. Alterations in the Michaelis constant for oxygen were similar in magnitude to those for the rate of catalysis. Deuterium and tritium isotope effects were determined to obtain more detailed information on the mechanism of catalysis. Large deuterium isotope effects expressed on k cat were obtained for all substrates. Determination of the tritium isotope effect for benzylamine allowed the calculation of an intrinsic isotope effect of 6.5 and a secondary isotope effect of 1.17. Steady-state experiments were supplemented with pre-steady-state kinetic techniques. Rates of flavin reduction were faster than that of turnover. The deuterium isotope effect obtained for the rate of flavin reduction was 7-15 for the various substrates. The observed isotope effect was found to be an appropriate estimate for the intrinsic isotope effect

  12. Calculating the C operator in PT-symmetric quantum mechanics

    International Nuclear Information System (INIS)

    Bender, C.M.

    2004-01-01

    It has recently been shown that a non-Hermitian Hamiltonian H possessing an unbroken PT-symmetry (i) has a real spectrum that is bounded below, and (ii) defines a unitary theory of quantum mechanics with positive norm. The proof of unitarity requires a linear operator C, which was originally defined as a sum over the eigenfunctions of H. However, using this definition it is cumbersome to calculate C in quantum mechanics and impossible in quantum field theory. An alternative method is devised here for calculating C directly in terms of the operator dynamical variables of the quantum theory. This new method is general and applies to a variety of quantum mechanical systems having several degrees of freedom. More importantly, this method can be used to calculate the C operator in quantum field theory. The C operator is a new time-independent observable in PT-symmetric quantum field theory. (author)

  13. Factor VII deficiency: Unveiling the cellular and molecular mechanisms underlying three model alterations of the enzyme catalytic domain.

    Science.gov (United States)

    Chollet, Maria Eugenia; Andersen, Elisabeth; Skarpen, Ellen; Myklebust, Christiane F; Koehler, Christian; Morth, Jens Preben; Chuansumrit, Ampaiwan; Pinotti, Mirko; Bernardi, Francesco; Thiede, Bernd; Sandset, Per Morten; Skretting, Grethe

    2018-03-01

    Activated factor (F) VII is a vitamin K-dependent glycoprotein that initiates blood coagulation upon interaction with tissue factor. FVII deficiency is the most common of the rare congenital bleeding disorders. While the mutational pattern has been extensively characterized, the pathogenic molecular mechanisms of mutations, particularly at the intracellular level, have been poorly defined. Here, we aimed at elucidating the mechanisms underlying altered FVII biosynthesis in the presence of three mutation types in the catalytic domain: a missense change, a microdeletion and a frameshift/elongation, associated with severe or moderate to severe phenotypes. Using CHO-K1 cells transiently transfected with expression vectors containing the wild-type FVII cDNA (FVIIwt) or harboring the p.I289del, p.G420V or p.A354V-p.P464Hfs mutations, we found that the secretion of the FVII mutants was severely decreased compared to FVIIwt. The synthesis rate of the mutants was slower than the FVIIwt and delayed, and no degradation of the FVII mutants by proteasomes, lysosomes or cysteine proteases was observed. Confocal immunofluorescence microscopy studies showed that FVII variants were localized into the endoplasmic reticulum (ER) but were not detectable within the Golgi apparatus. These findings suggested that a common pathogenic mechanism, possibly a defective folding of the mutant proteins, was triggered by the FVII mutations. The misfolded state led to impaired trafficking of these proteins causing ER retention, which would explain the low to very low FVII plasma levels observed in patients carrying these mutations. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Yucheng eZhao

    2016-05-01

    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.

  15. Catalytic mechanism and inhibition of tRNA (Uracil-5-)methyltransferase: evidence for covalent catalysis

    International Nuclear Information System (INIS)

    Santi, D.V.; Hardy, L.W.

    1987-01-01

    tRNA (Ura-5-) methyltransferase catalyzes the transfer of a methyl group from S-adenosylmethionine (AdoMet) to the 5-carbon of a specific Urd residue in tRNA. This results in stoichiometric release of tritium from [5- 3 H] Urd-labeled substrate tRNA isolated from methyltransferase-deficient Escherichia coli. The enzyme also catalyzes an AdoMet-independent exchange reaction between [5- 3 H]-Urd-labeled substrate tRNA and protons of water at a rate that is about 1% that of the normal methylation reaction, but with identical stoichiometry. S-Adenosylhomocysteine inhibits the rate of the exchange reaction by 2-3-fold, whereas an analog having the sulfur of AdoMet replaced by nitrogen accelerates the exchange reaction 9-fold. In the presence (but not absence) of AdoMet, 5-fluorouracil-substituted tRNA (FUra-tRNA) leads to the first-order inactivation of the enzyme. This is accompanied by the formation of a stable covalent complex containing the enzyme, FUra-tRNA, and the methyl group AdoMet. A mechanism for catalysis is proposed that explains both the 5-H exchange reaction and the inhibition by FUra-tRNA: the enzyme forms a covalent Michael adduct with substrate or inhibitor tRNA by attack of a nucleophilic group of the enzyme at carbon 6 of the pyrimidine residue to be modified. As a result, an anion equivalent is generated at carbon 5 that is sufficiently reactive to be methylated by AdoMet. Preliminary experiments and precedents suggest that the nucleophilic catalyst of the enzyme is a thiol group of cysteine. The potent irreversible inhibition by FUra-tRNA suggest that a mechanism for the RNA effects of FUra may also involve irreversible inhibition of RNA-modifying enzymes

  16. Structural and catalytic characterization of mechanical mixtures of Pt/WOx-ZrO2 and Al2O3

    International Nuclear Information System (INIS)

    Contreras, J.L.; Fuentes, G.A.; Navarrete, J.; Vazquez, A.; Zeifert, B.; Salmones, J.; Nuno, L.

    2010-01-01

    The effect of the Bronsted/Lewis acid ratio on isomerization of n-heptane using Al 2 O 3 as a source of Lewis acidity and WOx/ZrO 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 2 domains, the increase of Knudsen diffusivity and the loss of Pt metallic area by strong interaction of the Pt with the WOx/ZrO 2 explain this catalytic behavior.

  17. Crystal Structure and Catalytic Mechanism of 7-Hydroxymethyl Chlorophyll a Reductase*

    Science.gov (United States)

    Wang, Xiao; Liu, Lin

    2016-01-01

    7-Hydroxymethyl chlorophyll a reductase (HCAR) catalyzes the second half-reaction in chlorophyll b to chlorophyll a conversion. HCAR is required for the degradation of light-harvesting complexes and is necessary for efficient photosynthesis by balancing the chlorophyll a/b ratio. Reduction of the hydroxymethyl group uses redox cofactors [4Fe-4S] cluster and FAD to transfer electrons and is difficult because of the strong carbon-oxygen bond. Here, we report the crystal structure of Arabidopsis HCAR at 2.7-Å resolution and reveal that two [4Fe-4S]clusters and one FAD within a very short distance form a consecutive electron pathway to the substrate pocket. In vitro kinetic analysis confirms the ferredoxin-dependent electron transport chain, thus supporting a proton-activated electron transfer mechanism. HCAR resembles a partial reconstruction of an archaeal F420-reducing [NiFe] hydrogenase, which suggests a common mode of efficient proton-coupled electron transfer through conserved cofactor arrangements. Furthermore, the trimeric form of HCAR provides a biological clue of its interaction with light-harvesting complex II. PMID:27072131

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

    Directory of Open Access Journals (Sweden)

    VERONIKA DOUBNEROVÁ

    2009-08-01

    Full Text Available The non-photosynthetic NADP-malic enzyme EC 1.1.1.40 (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.

  19. Fundamental mechanisms and reactions in non-catalytic subcritical hydrothermal processes: A review.

    Science.gov (United States)

    Yousefifar, Azadeh; Baroutian, Saeid; Farid, Mohammed M; Gapes, Daniel J; Young, Brent R

    2017-10-15

    The management and disposal of solid waste is of increasing concern across the globe. Hydrothermal processing of sludge has been suggested as a promising solution to deal with the considerable amounts of sludge produced worldwide. Such a process not only degrades organic compounds and reduces waste volume, but also provides an opportunity to recover valuable substances. Hydrothermal processing comprises two main sub-processes: wet oxidation (WO) and thermal hydrolysis (TH), in which the formation of various free radicals results in the production of different intermediates. Volatile fatty acids (VFAs), especially acetic acid, are usually the main intermediates which remain as a by-product of the process. This paper aims to review the fundamental mechanism for hydrothermal processing of sludge, and the formation of different free radicals and intermediates therein. In addition, the proposed kinetic models for the two processes (WO and TH) from the literature are reviewed and the advantages and disadvantages of each model are outlined. The effect of mass transfer as a critical component of the design and development of the processes, which has been neglected in most of these proposed models, is also reviewed, and the effect of influencing parameters on the processes' controlling step (reaction or mass transfer) is discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Structural aspects of catalytic mechanisms of endonucleases and their binding to nucleic acids

    Energy Technology Data Exchange (ETDEWEB)

    Zhukhlistova, N. E.; Balaev, V. V.; Lyashenko, A. V.; Lashkov, A. A., E-mail: alashkov83@gmail.com [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2012-05-15

    Endonucleases (EC 3.1) are enzymes of the hydrolase class that catalyze the hydrolytic cleavage of deoxyribonucleic and ribonucleic acids at any region of the polynucleotide chain. Endonucleases are widely used both in biotechnological processes and in veterinary medicine as antiviral agents. Medical applications of endonucleases in human cancer therapy hold promise. The results of X-ray diffraction studies of the spatial organization of endonucleases and their complexes and the mechanism of their action are analyzed and generalized. An analysis of the structural studies of this class of enzymes showed that the specific binding of enzymes to nucleic acids is characterized by interactions with nitrogen bases and the nucleotide backbone, whereas the nonspecific binding of enzymes is generally characterized by interactions only with the nucleic-acid backbone. It should be taken into account that the specificity can be modulated by metal ions and certain low-molecular-weight organic compounds. To test the hypotheses about specific and nonspecific nucleic-acid-binding proteins, it is necessary to perform additional studies of atomic-resolution three-dimensional structures of enzyme-nucleic-acid complexes by methods of structural biology.

  1. Mechanism of Diphtheria Toxin Catalytic Domain Delivery to the Eukaryotic Cell Cytosol and the Cellular Factors that Directly Participate in the Process

    Science.gov (United States)

    Murphy, John R.

    2011-01-01

    Research on diphtheria and anthrax toxins over the past three decades has culminated in a detailed understanding of their structure function relationships (e.g., catalytic (C), transmembrane (T), and receptor binding (R) domains), as well as the identification of their eukaryotic cell surface receptor, an understanding of the molecular events leading to the receptor-mediated internalization of the toxin into an endosomal compartment, and the pH triggered conformational changes required for pore formation in the vesicle membrane. Recently, a major research effort has been focused on the development of a detailed understanding of the molecular interactions between each of these toxins and eukaryotic cell factors that play an essential role in the efficient translocation of their respective catalytic domains through the trans-endosomal vesicle membrane pore and delivery into the cell cytosol. In this review, I shall focus on recent findings that have led to a more detailed understanding of the mechanism by which the diphtheria toxin catalytic domain is delivered to the eukaryotic cell cytosol. While much work remains, it is becoming increasingly clear that the entry process is facilitated by specific interactions with a number of cellular factors in an ordered sequential fashion. In addition, since diphtheria, anthrax lethal factor and anthrax edema factor all carry multiple coatomer I complex binding motifs and COPI complex has been shown to play an essential role in entry process, it is likely that the initial steps in catalytic domain entry of these divergent toxins follow a common mechanism. PMID:22069710

  2. Dynamics and mechanisms of catalytic processes and hot chemistry. Final report, March 1, 1972-October 31, 1984

    International Nuclear Information System (INIS)

    Spicer, L.D.

    1984-10-01

    General areas of research addressed are recoil chemistry of halogens, tritium, and sulfur, radiotracer methods for studies of chemical dynamics, thermal and photochemistry of sulfur dioxide, and photochemistry and photoassistance in catalytic systems

  3. Structure of Pioncare covariant tensor operators in quantum mechanical models

    International Nuclear Information System (INIS)

    Polyzou, W.N.; Klink, W.H.

    1988-01-01

    The structure of operators that transform covariantly in Poincare invariant quantum mechanical models is analyzed. These operators are shown to have an interaction dependence that comes from the geometry of the Poincare group. The operators can be expressed in terms of matrix elements in a complete set of eigenstates of the mass and spin operators associated with the dynamical representation of the Poincare group. The matrix elements are factored into geometrical coefficients (Clebsch--Gordan coefficients for the Poincare group) and invariant matrix elements. The geometrical coefficients are fixed by the transformation properties of the operator and the eigenvalue spectrum of the mass and spin. The invariant matrix elements, which distinguish between different operators with the same transformation properties, are given in terms of a set of invariant form factors. copyright 1988 Academic Press, Inc

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

    Science.gov (United States)

    Almonacid, Daniel E; Yera, Emmanuel R; Mitchell, John B O; Babbitt, Patricia C

    2010-03-12

    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 refine

  5. 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

    2010-03-01

    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

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

    DEFF Research Database (Denmark)

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

    2001-01-01

    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 be appl......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...

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

    OpenAIRE

    Ellman, Roger

    1999-01-01

    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...

  8. Fast Flux Test Facility sodium pump operating experience - mechanical

    International Nuclear Information System (INIS)

    Buonamici, R.

    1987-11-01

    The Heat Transport System (HTS) pumps were designed, fabricated, tested, and installed in the Fast Flux Test Facility (FFTF) Plant during the period from September 1970 through July 1977. Since completion of the installation and sodium fill in December 1978, the FFTF Plant pumps have undergone extensive testing and operation with HTS testing and reactor operation. Steady-state hydraulic and mechanical performances have been and are excellent. In all, FFTF primary and secondary pumps have operated in sodium for approximately 75,000 hours and 79,000 hours, respectively, to August 24, 1987

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

    DEFF Research Database (Denmark)

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

    2000-01-01

    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......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...

  10. 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

    2017-02-01

    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.

  11. Catalytic Mechanism of Nitrile Hydratase Proposed by Time-resolved X-ray Crystallography Using a Novel Substrate, tert-Butylisonitrile*S⃞

    Science.gov (United States)

    Hashimoto, Koichi; Suzuki, Hiroyuki; Taniguchi, Kayoko; Noguchi, Takumi; Yohda, Masafumi; Odaka, Masafumi

    2008-01-01

    Nitrile hydratases (NHases) have an unusual iron or cobalt catalytic center with two oxidized cysteine ligands, cysteine-sulfinic acid and cysteine-sulfenic acid, catalyzing the hydration of nitriles to amides. Recently, we found that the NHase of Rhodococcus erythropolis N771 exhibited an additional catalytic activity, converting tert-butylisonitrile (tBuNC) to tert-butylamine. Taking advantage of the slow reactivity of tBuNC and the photoreactivity of nitrosylated NHase, we present the first structural evidence for the catalytic mechanism of NHase with time-resolved x-ray crystallography. By monitoring the reaction with attenuated total reflectance-Fourier transform infrared spectroscopy, the product from the isonitrile carbon was identified as a CO molecule. Crystals of nitrosylated inactive NHase were soaked with tBuNC. The catalytic reaction was initiated by photo-induced denitrosylation and stopped by flash cooling. tBuNC was first trapped at the hydrophobic pocket above the iron center and then coordinated to the iron ion at 120 min. At 440 min, the electron density of tBuNC was significantly altered, and a new electron density was observed near the isonitrile carbon as well as the sulfenate oxygen of αCys114. These results demonstrate that the substrate was coordinated to the iron and then attacked by a solvent molecule activated by αCys114-SOH. PMID:18948265

  12. A conserved mechanism of autoinhibition for the AMPK kinase domain: ATP-binding site and catalytic loop refolding as a means of regulation

    International Nuclear Information System (INIS)

    Littler, Dene R.; Walker, John R.; Davis, Tara; Wybenga-Groot, Leanne E.; Finerty, Patrick J. Jr; Newman, Elena; Mackenzie, Farell; Dhe-Paganon, Sirano

    2010-01-01

    A 1.9 Å resolution crystal structure of the isolated kinase domain from the α2 subunit of human AMPK, the first from a multicellular organism, is presented. The AMP-activated protein kinase (AMPK) is a highly conserved trimeric protein complex that is responsible for energy homeostasis in eukaryotic cells. Here, a 1.9 Å resolution crystal structure of the isolated kinase domain from the α2 subunit of human AMPK, the first from a multicellular organism, is presented. This human form adopts a catalytically inactive state with distorted ATP-binding and substrate-binding sites. The ATP site is affected by changes in the base of the activation loop, which has moved into an inhibited DFG-out conformation. The substrate-binding site is disturbed by changes within the AMPKα2 catalytic loop that further distort the enzyme from a catalytically active form. Similar structural rearrangements have been observed in a yeast AMPK homologue in response to the binding of its auto-inhibitory domain; restructuring of the kinase catalytic loop is therefore a conserved feature of the AMPK protein family and is likely to represent an inhibitory mechanism that is utilized during function

  13. 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)

    2010-03-05

    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.

  14. Extended SUSY quantum mechanics, intertwining operators and coherent states

    International Nuclear Information System (INIS)

    Bagarello, F.

    2008-01-01

    We propose an extension of supersymmetric quantum mechanics which produces a family of isospectral Hamiltonians. Our procedure slightly extends the idea of intertwining operators. Several examples of the construction are given. Further, we show how to build up vector coherent states of the Gazeau-Klauder type associated to our Hamiltonians

  15. Cellular phone interference with the operation of mechanical ventilators.

    Science.gov (United States)

    Shaw, Cheryl I; Kacmarek, Robert M; Hampton, Rickey L; Riggi, Vincent; El Masry, Ashraf; Cooper, Jeffrey B; Hurford, William E

    2004-04-01

    To determine whether a cellular phone would interfere with the operation of mechanical ventilators. Laboratory study. University medical center. Fourteen mechanical ventilators. We evaluated change in operation and malfunction of the mechanical ventilators. The cellular phone (Nokia 6120i) was computer controlled, operating at 828.750 MHz analog modulation. It was operated at 16, 40, 100, 250, and 600 mW, 30 cm from the floor and 30, 15, and ventilator. Six of the 14 ventilators tested malfunctioned when a cellular phone at maximum power output was placed ventilating when the cellular phone at maximum power output was placed ventilator. One ventilator doubled the ventilatory rate and another increased the displayed tidal volume from 350 to 1033 mL. In one of the infant ventilators, displayed tidal volume increased from 21 to 100 mL. In another ventilator, the high respiratory rate alarm sounded but the rate had not changed. In a controlled laboratory setting, cellular phones placed in close proximity to some commercially available intensive care ventilators can cause malfunctions, including irrecoverable cessation of ventilation. This is most likely to occur if the cellular phone is or =3 feet from all medical devices. The current electromagnetic compatibility standards for mechanical ventilators are inadequate to prevent malfunction. Manufacturers should ensure that their products are not affected by wireless technology even when placed immediately next to the device.

  16. Developing a Mechanism for Assessment of the Mobile Operator Staff

    Directory of Open Access Journals (Sweden)

    Zhukovska Liudmyla E.

    2017-04-01

    Full Text Available The article is aimed at determining and substantiating practical recommendations on improving the assessment of staff of mobile operators based on an analysis of the existing theoretical and methodological foundations of formation and implementation of an effective mechanism for staff assessment and the suitability of their application in the competitive conditions. General tendencies in the development of mobile operators have been determined, existing approaches to assessing their staff have been explored. The article substantiates the need for cooperation and exchange of experts among mobile operators on staff assessment issues, using the assessment center technology and the use of an integrated staff assessment based on the points system, which will provide an objective assessment of each employee and will also contribute to the development of staff assessment technology for all telecommunications companies. The organizational and economic foundations for the implementation of these activities and the determination of level of their performance for mobile operators will be purpose of further researches.

  17. Versatile cable handling mechanisms for remote operator control

    Energy Technology Data Exchange (ETDEWEB)

    Collie, A.A.; White, T.S.; Christopher, M.D.; Hewer, N.D. [Portech Ltd., Portsmouth (United Kingdom)

    1996-12-31

    This paper describes a system of cable management for keeping the umbilical cables of remote operating vehicles and manipulators tidy and contained without direct intervention by operators. Two distinct types of winding mechanism have been designed. One mechanism is a fixed reel type where the cable is wound onto the reel by a rotating bail arm. The other mechanism consists of a pair of curved belts held against each other between which cable is passed. The complete system includes tension measuring and slack loop take-up devices. The whole system is controlled by a servo system in conjunction with a PC based visual graphic environment which allows a variety of mechanisms to be built up into a system able to handle up to four umbilical cables simultaneously. The control system provides additional tension sensors and cable odometers connected to the control system so that the operator has immediate perception of all the cable parameters, and by defining rules, can set up a variety of alarm situations. (Author).

  18. Versatile cable handling mechanisms for remote operator control

    International Nuclear Information System (INIS)

    Collie, A.A.; White, T.S.; Christopher, M.D.; Hewer, N.D.

    1996-01-01

    This paper describes a system of cable management for keeping the umbilical cables of remote operating vehicles and manipulators tidy and contained without direct intervention by operators. Two distinct types of winding mechanism have been designed. One mechanism is a fixed reel type where the cable is wound onto the reel by a rotating bail arm. The other mechanism consists of a pair of curved belts held against each other between which cable is passed. The complete system includes tension measuring and slack loop take-up devices. The whole system is controlled by a servo system in conjunction with a PC based visual graphic environment which allows a variety of mechanisms to be built up into a system able to handle up to four umbilical cables simultaneously. The control system provides additional tension sensors and cable odometers connected to the control system so that the operator has immediate perception of all the cable parameters, and by defining rules, can set up a variety of alarm situations. (Author)

  19. Versatile cable handling mechanisms for remote operator control

    International Nuclear Information System (INIS)

    Collie, A.A.; White, T.S.; Christopher, M.D.; Hewer, N.D.

    1996-01-01

    This paper describes a system of cable management for keeping the umbilical cables of remote operating vehicles and manipulators tidy and contained without direct intervention by operators. Two distinct types of winding mechanism have been designed. One mechanism is a fixed reel type where the cable is wound onto the reel by a rotating bail arm. The other mechanism consists of a pair of curved belts held against each other, between which cable is passed. The complete system includes tension measuring and slack loop take-up devices. The whole system is controlled by a servo system in conjunction with a PC based visual graphic environment which allows a variety of mechanisms to be built up into a system able to handle up to four umbilical cables simultaneously. The control system provides additional tension sensors and cable odometers connected to the control system so that the operator has immediate perception of all the cable parameters, and by defining rules, can set up a variety of alarm situations. (UK)

  20. Evaluation of the catalytic mechanism of AICAR transformylase by pH-dependent kinetics, mutagenesis, and quantum chemical calculations.

    Science.gov (United States)

    Shim, J H; Wall, M; Benkovic, S J; Díaz, N; Suárez, D; Merz, K M

    2001-05-23

    The catalytic mechanism of 5-aminoimidazole-4-carboxamide ribonucleotide transformylase (AICAR Tfase) is evaluated with pH dependent kinetics, site-directed mutagenesis, and quantum chemical calculations. The chemistry step, represented by the burst rates, was not pH-dependent, which is consistent with our proposed mechanism that the 4-carboxamide of AICAR assists proton shuttling. Quantum chemical calculations on a model system of 5-amino-4-carboxamide imidazole (AICA) and formamide using the B3LYP/6-31G level of theory confirmed that the 4-carboxamide participated in the proton-shuttling mechanism. The result also indicated that the amide-assisted mechanism is concerted such that the proton transfers from the 5-amino group to the formamide are simultaneous with nucleophilic attack by the 5-amino group. Because the process does not lead to a kinetically stable intermediate, the intramolecular proton transfer from the 5-amino group through the 4-carboxamide to the formamide proceeds in the same transition state. Interestingly, the calculations predicted that protonation of the N3 of the imidazole of AICA would reduce the energy barrier significantly. However, the pK(a) of the imidazole of AICAR was determined to be 3.23 +/- 0.01 by NMR titration, and AICAR is likely to bind to the enzyme with its imidazole in the free base form. An alternative pathway was suggested by modeling Lys266 to have a hydrogen-bonding interaction with the N3 of the imidazole of AICAR. Lys266 has been implicated in catalysis based on mutagenesis studies and the recent X-ray structure of AICAR Tfase. The quantum chemical calculations on a model system that contains AICA complexed with CH3NH3+ as a mimic of the Lys residue confirmed that such an interaction lowered the activation energy of the reaction and likewise implicated the 4-carboxamide. To experimentally verify this hypothesis, we prepared the K266R mutant and found that its kcat is reduced by 150-fold from that of the wild type

  1. Post-operative atrial fibrillation: a maze of mechanisms

    Science.gov (United States)

    Maesen, Bart; Nijs, Jan; Maessen, Jos; Allessie, Maurits; Schotten, Ulrich

    2012-01-01

    Post-operative atrial fibrillation (POAF) is one of the most frequent complications of cardiac surgery and an important predictor of patient morbidity as well as of prolonged hospitalization. It significantly increases costs for hospitalization. Insights into the pathophysiological factors causing POAF have been provided by both experimental and clinical investigations and show that POAF is ‘multi-factorial’. Facilitating factors in the mechanism of the arrhythmia can be classified as acute factors caused by the surgical intervention and chronic factors related to structural heart disease and ageing of the heart. Furthermore, some proarrhythmic mechanisms specifically occur in the setting of POAF. For example, inflammation and beta-adrenergic activation have been shown to play a prominent role in POAF, while these mechanisms are less important in non-surgical AF. More recently, it has been shown that atrial fibrosis and the presence of an electrophysiological substrate capable of maintaining AF also promote the arrhythmia, indicating that POAF has some proarrhythmic mechanisms in common with other forms of AF. The clinical setting of POAF offers numerous opportunities to study its mechanisms. During cardiac surgery, biopsies can be taken and detailed electrophysiological measurements can be performed. Furthermore, the specific time course of POAF, with the delayed onset and the transient character of the arrhythmia, also provides important insight into its mechanisms. This review discusses the mechanistic interaction between predisposing factors and the electrophysiological mechanisms resulting in POAF and their therapeutic implications. PMID:21821851

  2. 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.

    2011-01-01

    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

  3. Impact of selective catalytic reduction systems on the operation of coal and oil fired boilers and downstream equipment

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-07-01

    The history of the development of selective catalytic reduction (SCR) technology has clearly demonstrated that whenever the technology arrives in a new region of the world new challenges are met. This paper discusses some of these historical challenges and their particular solutions in some detail. The paper shows that the design of successful SCR systems is extremely site-specific, but that the technology continues to evolve to meet these continuously changing demands. Most recently the increased power of CFD technology has enabled SCR to meet the more stringent North American emissions criteria through optimal fluid dynamic design. 4 figs.

  4. Overcoming misconceptions in quantum mechanics with the time evolution operator

    International Nuclear Information System (INIS)

    Garcia Quijas, P C; Arevalo Aguilar, L M

    2007-01-01

    Recently, there have been many efforts to use the research techniques developed in the field of physics education research to improve the teaching and learning of quantum mechanics. In particular, part of this research is focusing on misconceptions held by students. For instance, a set of misconceptions is associated with the concept of stationary states. In this paper, we argue that a possible way to remove these is to solve the Schroedinger equation using the evolution operator method (EOM), and stress the fact that to find stationary states is only the first step in solving that equation. The EOM consists in solving the Schroedinger equation by direct integration, i.e. Ψ(x, t) = U(t)Ψ(x, 0), where U(t)=e -itH-hat/h is the time evolution operator, and Ψ(x, 0) is the initial state. We apply the evolution operator method in the case of the harmonic oscillator

  5. Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

    Science.gov (United States)

    Sauvet, A.-L.; Fouletier, J.

    The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

  6. 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

    2006-11-01

    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

  7. 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: llsh@scnu.edu.cn [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)

    2015-04-09

    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.

  8. MOPITT Mechanisms 16 Years In-Orbit Operation on TERRA

    Science.gov (United States)

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

    2016-01-01

    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

  9. A proposal for operator team behavior model and operator's thinking mechanism

    International Nuclear Information System (INIS)

    Yoshimura, Seiichi; Takano, Kenichi; Sasou, Kunihide

    1995-01-01

    Operating environment in huge systems like nuclear power plants or airplanes is changing rapidly with the advance of computer technology. It is necessary to elucidate thinking process of operators and decision-making process of an operator team in abnormal situations, in order to prevent human errors under such environment. The Central Research Institute of Electric Power Industry is promoting a research project to establish human error prevention countermeasures by modeling and simulating the thinking process of operators and decision-making process of an operator team. In the previous paper, application of multilevel flow modeling was proposed to a mental model which conducts future prediction and cause identification, and the characteristics were verified by experienced plant operators. In this paper, an operator team behavior model and a fundamental operator's thinking mechanism especially 'situation understanding' are proposed, and the proposals are evaluated by experiments using a full-scale simulator. The results reveal that some assumptions such as 'communication is done between a leader and a follower' are almost appropriate and that the situation understanding can be represented by 'probable candidates for cause, determination of a parameter which changes when an event occurs, determination of parameters which are influenced by the change of the previous parameter, determination of a principal parameter and future prediction of the principal parameter'. (author)

  10. Structural Evidence of a Major Conformational Change Triggered by Substrate Binding in DapE Enzymes: Impact on the Catalytic Mechanism.

    Science.gov (United States)

    Nocek, Boguslaw; Reidl, Cory; Starus, Anna; Heath, Tahirah; Bienvenue, David; Osipiuk, Jerzy; Jedrzejczak, Robert; Joachimiak, Andrzej; Becker, Daniel P; Holz, Richard C

    2018-02-06

    The X-ray crystal structure of the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase from Haemophilus influenzae (HiDapE) bound by the products of hydrolysis, succinic acid and l,l-DAP, was determined at 1.95 Å. Surprisingly, the structure bound to the products revealed that HiDapE undergoes a significant conformational change in which the catalytic domain rotates ∼50° and shifts ∼10.1 Å (as measured at the position of the Zn atoms) relative to the dimerization domain. This heretofore unobserved closed conformation revealed significant movements within the catalytic domain compared to that of wild-type HiDapE, which results in effectively closing off access to the dinuclear Zn(II) active site with the succinate carboxylate moiety bridging the dinculear Zn(II) cluster in a μ-1,3 fashion forming a bis(μ-carboxylato)dizinc(II) core with a Zn-Zn distance of 3.8 Å. Surprisingly, His194.B, which is located on the dimerization domain of the opposing chain ∼10.1 Å from the dinuclear Zn(II) active site, forms a hydrogen bond (2.9 Å) with the oxygen atom of succinic acid bound to Zn2, forming an oxyanion hole. As the closed structure forms upon substrate binding, the movement of His194.B by more than ∼10 Å is critical, based on site-directed mutagenesis data, for activation of the scissile carbonyl carbon of the substrate for nucleophilic attack by a hydroxide nucleophile. Employing the HiDapE product-bound structure as the starting point, a reverse engineering approach called product-based transition-state modeling provided structural models for each major catalytic step. These data provide insight into the catalytic reaction mechanism and also the future design of new, potent inhibitors of DapE enzymes.

  11. CATALYTIC COMBUSTION OF METHANE OVER Pt/γ-Al2O3 IN MICRO-COMBUSTOR WITH DETAILED CHEMICAL KINETIC MECHANISMS

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2014-11-01

    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.

  12. Hydrothermal processing of fermentation residues in a continuous multistage rig – Operational challenges for liquefaction, salt separation, and catalytic gasification

    International Nuclear Information System (INIS)

    Zöhrer, H.; De Boni, E.; Vogel, F.

    2014-01-01

    Fermentation residues are a waste stream of biomethane production containing substantial amounts of organic matter, and thus representing a primary energy source which is mostly unused. For the first time this feedstock was tested for catalytic gasification in supercritical water (T ≥ 374 °C, p ≥ 22 MPa) for methane production. The processing steps include hydrothermal liquefaction, salt separation, as well as catalytic gasification over a ruthenium catalyst in supercritical water. In continuous experiments at a feed rate of 1 kg h −1 a partial liquefaction and carbonization of some of the solids was observed. Significant amounts of heavy tars were formed. Around 50% of the feed carbon remained in the rig. Furthermore, a homogeneous coke was formed, presumably originating from condensed tars. The mineralization of sulfur and its separation in the salt separator was insufficient, because most of the sulfur was still organically bound after liquefaction. Desalination was observed at a salt separator set point temperature of 450 °C and 28 MPa; however, some of the salts could not be withdrawn as a concentrated brine. At 430 °C no salt separation took place. Higher temperatures in the salt separator were found to promote tar and coke formation, resulting in conflicting process requirements for efficient biomass liquefaction and desalination. In the salt separator effluent, solid crystals identified as struvite (magnesium ammonium phosphate) were found. This is the first report of struvite formation from a supercritical water biomass conversion process and represents an important finding for producing a fertilizer from the separated salt brine. - Highlights: • Continuous processing of fermentation residues in sub- and supercritical water. • Continuous separation of salt brines at supercritical water conditions. • Struvite crystals (magnesium ammonium phosphate) were recovered from the effluent. • Separation of sulfur from the biomass could

  13. High Resolution Crystal Structures of Streptococcus pneumoniae Nicotinamidase with Trapped Intermediates Provide Insights into Catalytic Mechanism and Inhibition by Aldehydes∥,‡

    Science.gov (United States)

    French, Jarrod B.; Cen, Yana; Sauve, Anthony A.; Ealick, Steven E.

    2010-01-01

    Nicotinamidases are salvage enzymes that convert nicotinamide to nicotinic acid. These enzymes are essential for the recycling of nicotinamide into NAD+ in most prokaryotes, most single cell and multicellular eukaryotes, but not in mammals. The significance of these enzymes for nicotinamide salvage and for NAD+ homeostasis has increased interest in nicotinamidases as possible antibiotic targets. Nicotinamidases are also regulators of intracellular nicotinamide concentrations, thereby regulating signaling of downstream NAD+ consuming enzymes, such as the NAD+-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 complexed 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 which 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 for several proposed reaction intermediates and allow for a more complete understanding of the catalytic mechanism of this enzyme. PMID:20853856

  14. High-resolution crystal structures of Streptococcus pneumoniae nicotinamidase with trapped intermediates provide insights into the catalytic mechanism and inhibition by aldehydes .

    Science.gov (United States)

    French, Jarrod B; Cen, Yana; Sauve, Anthony A; Ealick, Steven E

    2010-10-12

    Nicotinamidases are salvage enzymes that convert nicotinamide to nicotinic acid. These enzymes are essential for the recycling of nicotinamide into NAD(+) 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(+) homeostasis has stimulated interest in nicotinamidases as possible antibiotic targets. Nicotinamidases are also regulators of intracellular nicotinamide concentrations, thereby regulating signaling of downstream NAD(+)-consuming enzymes, such as the NAD(+)-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.

  15. 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)

    2010-11-11

    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.

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

    CERN Document Server

    Jorgensen, Palle E T

    1987-01-01

    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

  17. The application of Cu/SiO2 catalytic system in chemical mechanical planarization based on the stability of SiO2 sol

    International Nuclear Information System (INIS)

    Li Yan; Liu Yuling; Wang Aochen; Yang Zhixin; Sun Mingbin; Cheng Chuan; Zhang Yufeng; Zhang Nannan

    2014-01-01

    There is a lot of hydroxyl on the surface of nano SiO 2 sol used as an abrasive in the chemical mechanical planarization (CMP) process, and the chemical reaction activity of the hydroxyl is very strong due to the nano effect. In addition to providing a mechanical polishing effect, SiO 2 sol is also directly involved in the chemical reaction. The stability of SiO 2 sol was characterized through particle size distribution, zeta potential, viscosity, surface charge and other parameters in order to ensure that the chemical reaction rate in the CMP process, and the surface state of the copper film after CMP was not affected by the SiO 2 sol. Polarization curves and corrosion potential of different concentrations of SiO 2 sol showed that trace SiO 2 sol can effectively weaken the passivation film thickness. In other words, SiO 2 sol accelerated the decomposition rate of passive film. It was confirmed that the SiO 2 sol as reactant had been involved in the CMP process of copper film as reactant by the effect of trace SiO 2 sol on the removal rate of copper film in the CMP process under different conditions. In the CMP process, a small amount of SiO 2 sol can drastically alter the chemical reaction rate of the copper film, therefore, the possibility that Cu/SiO 2 as a catalytic system catalytically accelerated the chemical reaction in the CMP process was proposed. According to the van't Hoff isotherm formula and the characteristics of a catalyst which only changes the chemical reaction rate with out changing the total reaction standard Gibbs free energy, factors affecting the Cu/SiO 2 catalytic reaction were derived from the decomposition rate of Cu (OH) 2 and the pH value of the system, and then it was concluded that the CuSiO 3 as intermediates of Cu/SiO 2 catalytic reaction accelerated the chemical reaction rate in the CMP process. It was confirmed that the Cu/SiO 2 catalytic system generated the intermediate of the catalytic reaction (CuSiO 3 ) in the CMP process

  18. Piezo-Operated Shutter Mechanism Moves 1.5 cm

    Science.gov (United States)

    Glaser, Robert; Bamford, Robert

    2005-01-01

    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.

  19. Solution structure of the parvulin-type PPIase domain of Staphylococcus aureus PrsA – Implications for the catalytic mechanism of parvulins

    Directory of Open Access Journals (Sweden)

    Koskela Harri

    2009-03-01

    Full Text Available Abstract Background Staphylococcus aureus is a Gram-positive pathogenic bacterium causing many kinds of infections from mild respiratory tract infections to life-threatening states as sepsis. Recent emergence of S. aureus strains resistant to numerous antibiotics has created a need for new antimicrobial agents and novel drug targets. S. aureus PrsA is a membrane associated extra-cytoplasmic lipoprotein which contains a parvulin-type peptidyl-prolyl cis-trans isomerase domain. PrsA is known to act as an essential folding factor for secreted proteins in Gram-positive bacteria and thus it is a potential target for antimicrobial drugs against S. aureus. Results We have solved a high-resolution solution structure of the parvulin-type peptidyl-prolyl cis-trans isomerase domain of S. aureus PrsA (PrsA-PPIase. The results of substrate peptide titrations pinpoint the active site and demonstrate the substrate preference of the enzyme. With detailed NMR spectroscopic investigation of the orientation and tautomeric state of the active site histidines we are able to give further insight into the structure of the catalytic site. NMR relaxation analysis gives information on the dynamic behaviour of PrsA-PPIase. Conclusion Detailed structural description of the S. aureus PrsA-PPIase lays the foundation for structure-based design of enzyme inhibitors. The structure resembles hPin1-type parvulins both structurally and regarding substrate preference. Even though a wealth of structural data is available on parvulins, the catalytic mechanism has yet to be resolved. The structure of S. aureus PrsA-PPIase and our findings on the role of the conserved active site histidines help in designing further experiments to solve the detailed catalytic mechanism.

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

    Science.gov (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

  1. The SCOP-formalism: an Operational Approach to Quantum Mechanics

    International Nuclear Information System (INIS)

    D'Hooghe, Bart

    2010-01-01

    We present the SCOP-formalism, an operational approach to quantum mechanics. If a State-COntext-Property-System (SCOP) satisfies a specific set of 'quantum axioms,] it fits in a quantum mechanical representation in Hilbert space. We present a model in which the maximal change of state of the system due to interaction with the measurement context is controlled by a parameter N. In the case N = 2 the system reduces to a model for the spin measurements on a quantum spin-1/2 particle. In the limit N→∞ the system is classical. For the intermediate cases it is impossible to define an orthocomplementation on the set of properties. Another interesting feature is that the probability of a state transition also depends on the context which induces it. This contrasts sharply with standard quantum mechanics for which Gleason's theorem states the uniqueness of the state transition probability and independent of measurement context. We show that if a SCOP satisfies a Gleason-like condition, namely that all state transition probabilities are independent of which measurement context induces the change of state, then the lattice of properties is orthocomplemented.

  2. 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: yamamok@agr.kyushu-u.ac.jp [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)

    2013-11-01

    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.

  3. The effect of defects on the catalytic activity of single Au atom supported carbon nanotubes and reaction mechanism for CO oxidation.

    Science.gov (United States)

    Ali, Sajjad; Fu Liu, Tian; Lian, Zan; Li, Bo; Sheng Su, Dang

    2017-08-23

    The mechanism of CO oxidation by O 2 on a single Au atom supported on pristine, mono atom vacancy (m), di atom vacancy (di) and the Stone Wales defect (SW) on single walled carbon nanotube (SWCNT) surface is systematically investigated theoretically using density functional theory. We determine that single Au atoms can be trapped effectively by the defects on SWCNTs. The defects on SWCNTs can enhance both the binding strength and catalytic activity of the supported single Au atom. Fundamental aspects such as adsorption energy and charge transfer are elucidated to analyze the adsorption properties of CO and O 2 and co-adsorption of CO and O 2 molecules. It is found that CO binds stronger than O 2 on Au supported SWCNT. We clearly demonstrate that the defected SWCNT surface promotes electron transfer from the supported single Au atom to O 2 molecules. On the other hand, this effect is weaker for pristine SWCNTs. It is observed that the high density of spin-polarized states are localized in the region of the Fermi level due to the strong interactions between Au (5d orbital) and the adjacent carbon (2p orbital) atoms, which influence the catalytic performance. In addition, we elucidate both the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms of CO oxidation by O 2 . For the LH pathway, the barriers of the rate-limiting step are calculated to be 0.02 eV and 0.05 eV for Au/m-SWCNT and Au/di-SWCNT, respectively. To regenerate the active sites, an ER-like reaction occurs to form a second CO 2 molecule. The ER pathway is observed on Au/m-SWCNT, Au/SW-SWCNT and Au/SWCNT in which the Au/m-SWCNT has a smaller barrier. The comparison with a previous study (Lu et al., J. Phys. Chem. C, 2009, 113, 20156-20160.) indicates that the curvature effect of SWCNTs is important for the catalytic property of the supported single Au. Overall, Au/m-SWCNT is identified as the most active catalyst for CO oxidation compared to pristine SWCNT, SW-SWCNT and di-SWCNT. Our findings give a

  4. Catalytic treatment

    Energy Technology Data Exchange (ETDEWEB)

    Bindley, W T.R.

    1931-04-18

    An apparatus is described for the catalytic treatment of liquids, semi-liquids, and gases comprising a vessel into which the liquid, semi-liquid, or gas to be treated is introduced through a common inlet to a chamber within the vessel whence it passes to contact with a catalyst through radially arranged channels or passages to a common outlet chamber.

  5. Catalytic pyrolysis of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Vail' eva, N A; Buyanov, R A

    1979-01-01

    Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

  6. On the mechanism of sulfite activation of chloroplast thylakoid ATPase and the relation of ADP tightly bound at a catalytic site to the binding change mechanism

    International Nuclear Information System (INIS)

    Du, Z.; Boyer, P.D.

    1990-01-01

    Washed chloroplast thylakoid membranes upon exposure to [ 3 H]ADP retain in tightly bound [ 3 H]ADP on a catalytic site of the ATP synthase. The presence of sufficient endogenous or added Mg 2+ results in an enzyme with essentially no ATPase activity. Sulfite activates the ATPase, and many molecules of ATP per synthase can be hydrolyzed before most of the bound [ 3 H]ADP is released, a result interpreted as indicating that the ADP is not bound at a site participating in catalysis by the sulfite-activated enzyme. The authors present evidence that this is not the case. The Mg 2+ - and ADP-inhibited enzyme when exposed to MgATP and 20-100 mM sulfite shows a lag of about 1 min at 22 degree C and of about 15 s at 37 degree C before reaching the same steady-state rate as attained with light-activated ATPase that has not been inhibited by Mg 2+ and ADP. The lag is not eliminated if the enzyme is exposed to sulfite prior to MgATP addition, indicating that ATPase turnover is necessary for the activation. The release of most of the bound [ 3 H]ADP parallels the onset of ATPase activity, although some [ 3 H]ADP is not released even with prolonged catalytic turnover and may be on poorly active or inactive enzyme or at noncatalytic sites. The results are consistent with most of the tightly bound [ 3 H]ADP being at a catalytic site and being replaced as this Mg 2+ - and ADP-inhibited site regains equivalent participation with other catalytic sites on the activated enzyme. The sulfite activation can be explained by sulfite combination at a P i binding site of the enzyme-ADP-Mg 2+ complex to give a form more readily activated by ATP binding at an alternative site

  7. Mechanic- and hydraulic shock-absorbers - layout, construction, operation experience

    International Nuclear Information System (INIS)

    Kluge, M.

    1981-01-01

    The problem lies in the protection of the flexible supported power plant components against undesired sudden movements. Various shock absorbing systems are at disposal in this case: Mechanical and hydraulic shock absorbers, whose functioning systems are shown in figures. The operation experience showed a series of deficiencies, as demonstrated on various figures. In order to avoid them, some important recommendations are given. Requirements and layout are demonstrated according to todays' state-of-the-art. The admissible stresses, resulting from the summary of various specifications for the analytical evidence will be described. Development and construction will be explained in detail by means of pictures with cross sections of original shock absorbers. Todays' construction characteristics will be summarized. The final remark includes a request for generally valid guidelines. (orig.) [de

  8. Memory operation mechanism of fullerene-containing polymer memory

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, Anri, E-mail: anakajima@hiroshima-u.ac.jp; Fujii, Daiki [Research Institute for Nanodevice and Bio Systems, Hiroshima University, 1-4-2 Kagamiyama, Higashihiroshima, Hiroshima 739-8527 (Japan)

    2015-03-09

    The memory operation mechanism in fullerene-containing nanocomposite gate insulators was investigated while varying the kind of fullerene in a polymer gate insulator. It was cleared what kind of traps and which positions in the nanocomposite the injected electrons or holes are stored in. The reason for the difference in the easiness of programming was clarified taking the role of the charging energy of an injected electron into account. The dependence of the carrier dynamics on the kind of fullerene molecule was investigated. A nonuniform distribution of injected carriers occurred after application of a large magnitude programming voltage due to the width distribution of the polystyrene barrier between adjacent fullerene molecules. Through the investigations, we demonstrated a nanocomposite gate with fullerene molecules having excellent retention characteristics and a programming capability. This will lead to the realization of practical organic memories with fullerene-containing polymer nanocomposites.

  9. Principles of control automation of soil compacting machine operating mechanism

    Science.gov (United States)

    Anatoly Fedorovich, Tikhonov; Drozdov, Anatoly

    2018-03-01

    The relevance of the qualitative compaction of soil bases in the erection of embankment and foundations in building and structure construction is given.The quality of the compactible gravel and sandy soils provides the bearing capability and, accordingly, the strength and durability of constructed buildings.It has been established that the compaction quality depends on many external actions, such as surface roughness and soil moisture; granulometry, chemical composition and degree of elasticity of originalfilled soil for compaction.The analysis of technological processes of soil bases compaction of foreign and domestic information sources showed that the solution of such important problem as a continuous monitoring of soil compaction actual degree in the process of machine operation carry out only with the use of modern means of automation. An effective vibrodynamic method of gravel and sand material sealing for the building structure foundations for various applications was justified and suggested.The method of continuous monitoring the soil compaction by measurement of the amplitudes and frequencies of harmonic oscillations on the compactible surface was determined, which allowed to determine the basic elements of facilities of soil compacting machine monitoring system of operating, etc. mechanisms: an accelerometer, a bandpass filter, a vibro-harmonics, an on-board microcontroller. Adjustable parameters have been established to improve the soil compaction degree and the soil compacting machine performance, and the adjustable parameter dependences on the overall indexhave been experimentally determined, which is the soil compaction degree.A structural scheme of automatic control of the soil compacting machine control mechanism and theoperation algorithm has been developed.

  10. THEORETICAL CONSIDERATIONS REGARDING THE AUTOMATIC FISCAL STABILIZERS OPERATING MECHANISM

    Directory of Open Access Journals (Sweden)

    Gondor Mihaela

    2012-07-01

    Full Text Available This paper examines the role of Automatic Fiscal Stabilizers (AFS for stabilizing the cyclical fluctuations of macroeconomic output as an alternative to discretionary fiscal policy, admitting its huge potential of being an anti crisis solution. The objectives of the study are the identification of the general features of the concept of automatic fiscal stabilizers and the logical assessment of them from economic perspectives. Based on the literature in the field, this paper points out the disadvantages of fiscal discretionary policy and argue the need of using Automatic Fiscal Stabilizers in order to provide a faster decision making process, shielded from political interference, and reduced uncertainty for households and business environment. The paper conclude about the need of using fiscal policy for smoothing the economic cycle, but in a way which includes among its features transparency, responsibility and clear operating mechanisms. Based on the research results the present paper assumes that pro-cyclicality reduces de effectiveness of the Automatic Fiscal Stabilizer and as a result concludes that it is very important to avoid the pro-cyclicality in fiscal rule design. Moreover, by committing in advance to specific fiscal policy action contingent on economic developments, uncertainty about the fiscal policy framework during a recession should be reduced. Being based on logical analysis and not focused on empirical, contextualized one, the paper presents some features of AFS operating mechanism and also identifies and systematizes the factors which provide its importance and national individuality. Reaching common understanding on the Automatic Fiscal Stabilizer concept as a institutional device for smoothing the gap of the economic cycles across different countries, particularly for the European Union Member States, will facilitate efforts to coordinate fiscal policy responses during a crisis, especially in the context of the fiscal

  11. 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

    1995-12-01

    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.

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

    International Nuclear Information System (INIS)

    Salesi, Giovanni; Recami, Erasmo; Rodrigues Junior, Waldyr A.

    1995-12-01

    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

  13. Understanding the Catalytic Mechanism and the Nature of the Transition State of an Attractive Drug-Target Enzyme (Shikimate Kinase) by Quantum Mechanical/Molecular Mechanical (QM/MM) Studies.

    Science.gov (United States)

    Yao, Jianzhuang; Wang, Xia; Luo, Haixia; Gu, Pengfei

    2017-11-16

    Shikimate kinase (SK) is the fifth bacterial enzyme involved in the shikimate pathway for biosynthesis of life-indispensable components, such as aromatic amino acids. The absence of the shikimate pathway in humans makes SK an attractive target for the rational design of drugs aimed at pathogenesis bacteria, such as Mycobacterium tuberculosis and Helicobacter pylori. However, an effective inhibitor of SK (e.g., a transition-state analogue) is still not available on the market due, at least in part, to a lack of knowledge on the catalytic mechanism and the nature of the rate-limiting transition state. Herein, quantum mechanical/molecular mechanical (QM/MM) reaction coordinate, molecular dynamics (MD), and free-energy simulations have been performed to answer these questions. The results presented herein demonstrate that the phosphoryl-transfer process, which is the rate-limiting step of SK-catalyzed phosphorylation of shikimic acid (SKM), is a concerted one-step reaction proceeding through a loose transition state. The computational results agree well with those of experimental studies, specifically NMR results, X-ray crystal structure observation, and activation free-energy barrier. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Operating experience with the Harwell thermo-mechanical generators

    International Nuclear Information System (INIS)

    Cooke-Yarborough, E.H.

    1980-06-01

    The Stirling-cycle thermo-mechanical generator (TMG) provides small amounts of electrical power continuously over long periods, while requiring much less fuel than other power sources running from hydrocarbon fuel or radio-isotopes. Two of these 25-watt generators, fuelled by propane, have been used to power the UK National Buoy on two successive missions. A total of more than three years experience at sea has now been accumulated. In addition, a 60-watt version has provided the power for a major lighthouse for more than a year. An early development version of the Thermo-mechanical Generator, adapted to run from the heat of a radio-isotope source, was loaded with strontium 90 titanate in October 1974 and has run continuously in the laboratory ever since. The improvements and changes found necessary in the course of 90,000 generator-hours of running time are described, and the improvements in operational performance and reliability which have resulted are outlined. (author)

  15. Economic aspects of comprehensive mechanization of mining operations. [Poland

    Energy Technology Data Exchange (ETDEWEB)

    Zemla, F

    1978-02-01

    The development of mining equipment for longwall mining and effects of mechanization of mining operations on labor productivity and output of underground coal mines in Poland from 1950 to 1976 are discussed. Mining equipment used from 1950 to 1960 (cutters, steel or timber supports, chain conveyors, drilling and blasting), from 1960 to 1970 (cutter loaders, chain conveyors and steel supports), from 1970 to 1976 (shearer loaders, chain conveyors and powered or shield supports) is analyzed. Coal output of faces mined by mechanized equipment increased from 9.7% in 1950 to 63.1% in 1969 and to 87.6% of total coal output in 1976. The total coal output of underground coal mines increased from 99.1 Mt in 1959 to 125.0 Mt in 1969 and 179.3 Mt in 1976. Labor productivity per miner increased from 1.561 t/d in 1959 to 2.529 t/d in 1969 and to 3.433 t/d in 1976.

  16. An investigation into the applicability of the semiempirical method PM7 for modeling the catalytic mechanism in the enzyme chymotrypsin.

    Science.gov (United States)

    Stewart, James J P

    2017-05-01

    The catalytic cycle for the serine protease α-chymotrypsin was investigated in an attempt to determine the suitability of using the semiempirical method PM7 in the program MOPAC for investigating enzyme-catalyzed reactions. All six classical intermediates were modeled using standard methods, and were characterized as stable minima on the potential energy surface. Using a modified saddle point optimization method, five transition states were located and verified both by vibrational and by intrinsic reaction coordinate analysis. Some individual features, such as the hydrogen bonds in the oxyanion hole, the nature of various electrostatic interactions, and the role of Met192, were examined. This involved designing and running computational experiments to model mutations that would allow features of interest, in particular the energies involved, to be isolated. Three features within the enzyme were examined in detail: the reaction site itself, where covalent bonds were made and broken, the electrostatic effects of the buried aspartate anion, a passive but essential component of the catalytic triad, and the oxyanion hole, where hydrogen bonds help stabilize charged intermediates. With one minor exception, all phenomena investigated agreed with previously-reported descriptions. This result, along with the fact that all the techniques used were relatively straightforward, leads to the recommendation that PM7 and related methods, such as PM6-D3H4, are appropriate for modeling similar enzyme-catalyzed reactions. Graphical abstract Fifth of six transition states, showing water splitting into hydroxyl anion and a proton, to form the second tetrahedral intermediate and histidinium ion. Atoms of the water molecule involved in the hydrolysis are indicated by halos.

  17. Construction of a 3D model of nattokinase, a novel fibrinolytic enzyme from Bacillus natto. A novel nucleophilic catalytic mechanism for nattokinase.

    Science.gov (United States)

    Zheng, Zhong-liang; Zuo, Zhen-yu; Liu, Zhi-gang; Tsai, Keng-chang; Liu, Ai-fu; Zou, Guo-lin

    2005-01-01

    A three-dimensional structural model of nattokinase (NK) from Bacillus natto was constructed by homology modeling. High-resolution X-ray structures of Subtilisin BPN' (SB), Subtilisin Carlsberg (SC), Subtilisin E (SE) and Subtilisin Savinase (SS), four proteins with sequential, structural and functional homology were used as templates. Initial models of NK were built by MODELLER and analyzed by the PROCHECK programs. The best quality model was chosen for further refinement by constrained molecular dynamics simulations. The overall quality of the refined model was evaluated. The refined model NKC1 was analyzed by different protein analysis programs including PROCHECK for the evaluation of Ramachandran plot quality, PROSA for testing interaction energies and WHATIF for the calculation of packing quality. This structure was found to be satisfactory and also stable at room temperature as demonstrated by a 300ps long unconstrained molecular dynamics (MD) simulation. Further docking analysis promoted the coming of a new nucleophilic catalytic mechanism for NK, which is induced by attacking of hydroxyl rich in catalytic environment and locating of S221.

  18. On the mechanism of sulfite activation of chloroplast thylakoid ATPase and the relation of ADP tightly bound at a catalytic site to the binding change mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Du, Z.; Boyer, P.D. (Univ. of California, Los Angeles (USA))

    1990-01-16

    Washed chloroplast thylakoid membranes upon exposure to ({sup 3}H)ADP retain in tightly bound ({sup 3}H)ADP on a catalytic site of the ATP synthase. The presence of sufficient endogenous or added Mg{sup 2+} results in an enzyme with essentially no ATPase activity. Sulfite activates the ATPase, and many molecules of ATP per synthase can be hydrolyzed before most of the bound ({sup 3}H)ADP is released, a result interpreted as indicating that the ADP is not bound at a site participating in catalysis by the sulfite-activated enzyme. The authors present evidence that this is not the case. The Mg{sup 2+}- and ADP-inhibited enzyme when exposed to MgATP and 20-100 mM sulfite shows a lag of about 1 min at 22{degree}C and of about 15 s at 37{degree}C before reaching the same steady-state rate as attained with light-activated ATPase that has not been inhibited by Mg{sup 2+} and ADP. The lag is not eliminated if the enzyme is exposed to sulfite prior to MgATP addition, indicating that ATPase turnover is necessary for the activation. The release of most of the bound ({sup 3}H)ADP parallels the onset of ATPase activity, although some ({sup 3}H)ADP is not released even with prolonged catalytic turnover and may be on poorly active or inactive enzyme or at noncatalytic sites. The results are consistent with most of the tightly bound ({sup 3}H)ADP being at a catalytic site and being replaced as this Mg{sup 2+}- and ADP-inhibited site regains equivalent participation with other catalytic sites on the activated enzyme. The sulfite activation can be explained by sulfite combination at a P{sub i} binding site of the enzyme-ADP-Mg{sup 2+} complex to give a form more readily activated by ATP binding at an alternative site.

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

    Directory of Open Access Journals (Sweden)

    Bruno Bernardi

    2013-09-01

    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.

  20. Modes of mechanical ventilation for the operating room.

    Science.gov (United States)

    Ball, Lorenzo; Dameri, Maddalena; Pelosi, Paolo

    2015-09-01

    Most patients undergoing surgical procedures need to be mechanically ventilated, because of the impact of several drugs administered at induction and during maintenance of general anaesthesia on respiratory function. Optimization of intraoperative mechanical ventilation can reduce the incidence of post-operative pulmonary complications and improve the patient's outcome. Preoxygenation at induction of general anaesthesia prolongs the time window for safe intubation, reducing the risk of hypoxia and overweighs the potential risk of reabsorption atelectasis. Non-invasive positive pressure ventilation delivered through different interfaces should be considered at the induction of anaesthesia morbidly obese patients. Anaesthesia ventilators are becoming increasingly sophisticated, integrating many functions that were once exclusive to intensive care. Modern anaesthesia machines provide high performances in delivering the desired volumes and pressures accurately and precisely, including assisted ventilation modes. Therefore, the physicians should be familiar with the potential and pitfalls of the most commonly used intraoperative ventilation modes: volume-controlled, pressure-controlled, dual-controlled and assisted ventilation. Although there is no clear evidence to support the advantage of any one of these ventilation modes over the others, protective mechanical ventilation with low tidal volume and low levels of positive end-expiratory pressure (PEEP) should be considered in patients undergoing surgery. The target tidal volume should be calculated based on the predicted or ideal body weight rather than on the actual body weight. To optimize ventilation monitoring, anaesthesia machines should include end-inspiratory and end-expiratory pause as well as flow-volume loop curves. The routine administration of high PEEP levels should be avoided, as this may lead to haemodynamic impairment and fluid overload. Higher PEEP might be considered during surgery longer than 3 h

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

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    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.

  2. Formation of polyhedral ceria nanoparticles with enhanced catalytic CO oxidation activity in thermal plasma via a hydrogen mediated shape control mechanism

    International Nuclear Information System (INIS)

    Zheng Jie; Zhang Yaohua; Song Xubo; Li Xingguo

    2011-01-01

    Ceria nanoparticles with well defined facets are prepared in argon–hydrogen thermal plasma followed by controlled oxidation. With increasing hydrogen fraction in the plasma, a clear sphere-to-polyhedron shape transition is observed. The heat released during the hydrogenation of cerium, which significantly enhances the species mobility on the surface, favors the growth of well defined facets. The polyhedron ceria nanoparticles, though lower in specific surface area, exhibit superior catalytic performance for CO oxidation over the round particles, which is attributed to the higher density of the reactive {200} and {220} facets on the surface. The hydrogen mediated shape control mechanism provides new insights into the shape control of nanoparticles during thermal plasma processing.

  3. Changed membrane integration and catalytic site conformation are two mechanisms behind the increased Aβ42/Aβ40 ratio by presenilin 1 familial Alzheimer-linked mutations

    Directory of Open Access Journals (Sweden)

    Johanna Wanngren

    2014-01-01

    Full Text Available The enzyme complex γ-secretase generates amyloid β-peptide (Aβ, a 37–43-residue peptide associated with Alzheimer disease (AD. Mutations in presenilin 1 (PS1, the catalytical subunit of γ-secretase, result in familial AD (FAD. A unifying theme among FAD mutations is an alteration in the ratio Aβ species produced (the Aβ42/Aβ40 ratio, but the molecular mechanisms responsible remain elusive. In this report we have studied the impact of several different PS1 FAD mutations on the integration of selected PS1 transmembrane domains and on PS1 active site conformation, and whether any effects translate to a particular amyloid precursor protein (APP processing phenotype. Most mutations studied caused an increase in the Aβ42/Aβ40 ratio, but via different mechanisms. The mutations that caused a particular large increase in the Aβ42/Aβ40 ratio did also display an impaired APP intracellular domain (AICD formation and a lower total Aβ production. Interestingly, seven mutations close to the catalytic site caused a severely impaired integration of proximal transmembrane/hydrophobic sequences into the membrane. This structural defect did not correlate to a particular APP processing phenotype. Six selected FAD mutations, all of which exhibited different APP processing profiles and impact on PS1 transmembrane domain integration, were found to display an altered active site conformation. Combined, our data suggest that FAD mutations affect the PS1 structure and active site differently, resulting in several complex APP processing phenotypes, where the most aggressive mutations in terms of increased Aβ42/Aβ40 ratio are associated with a decrease in total γ-secretase activity.

  4. Crystalline nanotubes of {gamma}-AlOOH and {gamma}-Al{sub 2}O{sub 3}: hydrothermal synthesis, formation mechanism and catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    Lu, C L; Lv, J G; Xu, L; Guo, X F; Hou, W H [Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Hu, Y; Huang, H [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing 210009 (China)], E-mail: guoxf@nju.edu.cn, E-mail: whou@nju.edu.cn

    2009-05-27

    Crystalline nanotubes of {gamma}-AlOOH and {gamma}-Al{sub 2}O{sub 3} have been synthesized. An anionic surfactant-assisted hydrothermal process yields {gamma}-AlOOH nanotubes, and appropriate calcination treatment of the {gamma}-AlOOH nanotubes yields {gamma}-Al{sub 2}O{sub 3} nanotubes. The nanotubes were characterized by XRD, SEM, TEM, TG-DSC, FTIR and nitrogen adsorption-desorption techniques. Both the {gamma}-AlOOH and {gamma}-Al{sub 2}O{sub 3} nanotubes are crystalline, with a representative length of {approx}500 nm and diameters of 20-40 nm. The {gamma}-Al{sub 2}O{sub 3} nanotubes exhibit a very high mesoporous specific surface area (SSA) of 201.0 m{sup 2} g{sup -1} and a high mesopore volume of 0.68 cm{sup 3} g{sup -1} with an average mesopore size of 27.7 nm, as well as a high microporous SSA of 186.0 m{sup 2} g{sup -1} and a micropore volume of 0.08 cm{sup 3} g{sup -1} with an average micropore size of 0.53 nm. The formation process was discussed and a possible mechanism was proposed, in which a lamellar phase was first formed by camphorsulfonic anions and Al(III) species, and then rolled up to form the crystalline nanotubes under the hydrothermal condition. The catalytic performance of the obtained {gamma}- Al{sub 2}O{sub 3} nanotubes was tested by using the dehydration of ethanol to ethylene as a probe reaction and it was shown that the obtained {gamma}- Al{sub 2}O{sub 3} nanotubes catalyst possesses a higher catalytic activity compared with the {gamma}- Al{sub 2}O{sub 3} nanoparticles.

  5. Structures of the Mycobacterium tuberculosis GlpX protein (class II fructose-1,6-bisphosphatase): implications for the active oligomeric state, catalytic mechanism and citrate inhibition.

    Science.gov (United States)

    Wolf, Nina M; Gutka, Hiten J; Movahedzadeh, Farahnaz; Abad-Zapatero, Celerino

    2018-04-01

    The crystal structures of native class II fructose-1,6-bisphosphatase (FBPaseII) from Mycobacterium tuberculosis at 2.6 Å resolution and two active-site protein variants are presented. The variants were complexed with the reaction product fructose 6-phosphate (F6P). The Thr84Ala mutant is inactive, while the Thr84Ser mutant has a lower catalytic activity. The structures reveal the presence of a 222 tetramer, similar to those described for fructose-1,6/sedoheptulose-1,7-bisphosphatase from Synechocystis (strain 6803) as well as the equivalent enzyme from Thermosynechococcus elongatus. This homotetramer corresponds to a homologous oligomer that is present but not described in the crystal structure of FBPaseII from Escherichia coli and is probably conserved in all FBPaseIIs. The constellation of amino-acid residues in the active site of FBPaseII from M. tuberculosis (MtFBPaseII) is conserved and is analogous to that described previously for the E. coli enzyme. Moreover, the structure of the active site of the partially active (Thr84Ser) variant and the analysis of the kinetics are consistent with the previously proposed catalytic mechanism. The presence of metabolites in the crystallization medium (for example citrate and malonate) and in the corresponding crystal structures of MtFBPaseII, combined with their observed inhibitory effect, could suggest the existence of an uncharacterized inhibition of this class of enzymes besides the allosteric inhibition by adenosine monophosphate observed for the Synechocystis enzyme. The structural and functional insights derived from the structure of MtFBPaseII will provide critical information for the design of lead inhibitors, which will be used to validate this target for future chemical intervention.

  6. Measurement of quantum-mechanical operations; Die Messun Quantenmechanischer Operatoren

    Energy Technology Data Exchange (ETDEWEB)

    Wigner, E. P.

    1952-07-01

    It is shown that the validity of the conservation law for quantized values which control the interaction between the object to be measured and the measuring apparatus allows measurement of most of the operators only in extreme cases. It is noted that the conditions for measurement of operators that are unexchangeable for total charge cannot be satisfied. The same would hold for those operators that are unexchangeable for the number of heavy particles. (J.R.D.)

  7. Combustion, performance, and selective catalytic reduction of NOx for a diesel engine operated with combined tri fuel (H_2, CH_4, and conventional diesel)

    International Nuclear Information System (INIS)

    Abu-Jrai, Ahmad M.; Al-Muhtaseb, Ala'a H.; Hasan, Ahmad O.

    2017-01-01

    In this study, the effect of tri fuel (ULSD, H_2, and CH_4) operation under real exhaust gas conditions with different gaseous fuel compositions on the combustion characteristics, engine emissions, and selective catalytic reduction (SCR) after treatment was examined at low, medium, and high engine loads. Pt/Al_2O_3-SCR reactor was used and operated at different exhaust gas temperatures. Results revealed that at low load, the two gaseous fuels (H_2 and CH_4) have the same trend on combustion proccess, where both reduce the in-cylinder pressure and rate of heat release. At the high engine load there was a considerable influence appeared as an increase of the premixed combustion phase and a significant decrease of the total combustion duration. In terms of emissions, it was observed that at high engine load, fuels with high CH_4 content tend to reduce NOx formation, whereas, fuels with high H_2 content tend to reduce PM formation, moreover, combustion of tri fuel with 50:50 fuel mixture resulted in lower BSFC compared to the other ratios and hence, the best engine efficiency. The hydrocarbon-SCR catalyst has shown satisfactory performance in NOx reduction under real diesel exhaust gas in a temperature window of 180–280 °C for all engine loads. - Highlights: • Effect of tri fuel (ULSD, H_2, CH_4) on combustion and engine emissions was examined. • Fuel with high CH_4 content (H50-M50 and H25-M75) tend to reduce NOx formation. • Fuel with high H_2 content (H75-M25 and H50-M50) tend to reduce PM formation. • Increasing the percentage of H_2 in the feed gas improved the NO_x reduction. • The hydrocarbon-SCR catalyst has shown satisfactory performance in NO_x reduction.

  8. Poisoning of bubble propelled catalytic micromotors: the chemical environment matters.

    Science.gov (United States)

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

    2013-04-07

    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.

  9. IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

    Science.gov (United States)

    A groundwater treatment technology based on catalytic reductive dehalogenation has been developed to efficiently destroy chlorinated hydrocarbons in situ using a reactive well approach. The treatment process utilizes dissolved H2 as an electron donor, in...

  10. 46 CFR 113.35-13 - Mechanical engine order telegraph systems; operation.

    Science.gov (United States)

    2010-10-01

    ... 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 a...

  11. Structural and In Vivo Studies on Trehalose-6-Phosphate Synthase from Pathogenic Fungi Provide Insights into Its Catalytic Mechanism, Biological Necessity, and Potential for Novel Antifungal Drug Design

    Directory of Open Access Journals (Sweden)

    Yi Miao

    2017-07-01

    Full Text Available The disaccharide trehalose is critical to the survival of pathogenic fungi in their human host. Trehalose-6-phosphate synthase (Tps1 catalyzes the first step of trehalose biosynthesis in fungi. Here, we report the first structures of eukaryotic Tps1s in complex with substrates or substrate analogues. The overall structures of Tps1 from Candida albicans and Aspergillus fumigatus are essentially identical and reveal N- and C-terminal Rossmann fold domains that form the glucose-6-phosphate and UDP-glucose substrate binding sites, respectively. These Tps1 structures with substrates or substrate analogues reveal key residues involved in recognition and catalysis. Disruption of these key residues severely impaired Tps1 enzymatic activity. Subsequent cellular analyses also highlight the enzymatic function of Tps1 in thermotolerance, yeast-hypha transition, and biofilm development. These results suggest that Tps1 enzymatic functionality is essential for the fungal stress response and virulence. Furthermore, structures of Tps1 in complex with the nonhydrolyzable inhibitor, validoxylamine A, visualize the transition state and support an internal return-like catalytic mechanism that is generalizable to other GT-B-fold retaining glycosyltransferases. Collectively, our results depict key Tps1-substrate interactions, unveil the enzymatic mechanism of these fungal proteins, and pave the way for high-throughput inhibitor screening buttressed and guided by the current structures and those of high-affinity ligand-Tps1 complexes.

  12. Operation analysis of a Chebyshev-Pantograph leg mechanism for a single DOF biped robot

    Science.gov (United States)

    Liang, Conghui; Ceccarelli, Marco; Takeda, Yukio

    2012-12-01

    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.

  13. Features wear nodes mechanization wing aircraft operating under dynamic loads

    Directory of Open Access Journals (Sweden)

    А.М. Хімко

    2009-03-01

    Full Text Available  The conducted researches of titanic alloy ВТ-22 at dynamic loading with cycled sliding and dynamic loading in conditions of rolling with slipping. It is established that roller jamming in the carriage increases wear of rod of mechanization of a wing to twenty times. The optimum covering for strengthening wearied sites and restoration of working surfaces of wing’s mechanization rod is defined.

  14. Catalytic mechanism of Sep-tRNA:Cys-tRNA synthase: sulfur transfer is mediated by disulfide and persulfide.

    Science.gov (United States)

    Liu, Yuchen; Dos Santos, Patricia C; Zhu, Xiang; Orlando, Ron; Dean, Dennis R; Söll, Dieter; Yuan, Jing

    2012-02-17

    Sep-tRNA:Cys-tRNA synthase (SepCysS) catalyzes the sulfhydrylation of tRNA-bound O-phosphoserine (Sep) to form cysteinyl-tRNA(Cys) (Cys-tRNA(Cys)) in methanogens that lack the canonical cysteinyl-tRNA synthetase (CysRS). A crystal structure of the Archaeoglobus fulgidus SepCysS apoenzyme provides information on the binding of the pyridoxal phosphate cofactor as well as on amino acid residues that may be involved in substrate binding. However, the mechanism of sulfur transfer to form cysteine was not known. Using an in vivo Escherichia coli complementation assay, we showed that all three highly conserved Cys residues in SepCysS (Cys(64), Cys(67), and Cys(272) in the Methanocaldococcus jannaschii enzyme) are essential for the sulfhydrylation reaction in vivo. Biochemical and mass spectrometric analysis demonstrated that Cys(64) and Cys(67) form a disulfide linkage and carry a sulfane sulfur in a portion of the enzyme. These results suggest that a persulfide group (containing a sulfane sulfur) is the proximal sulfur donor for cysteine biosynthesis. The presence of Cys(272) increased the amount of sulfane sulfur in SepCysS by 3-fold, suggesting that this Cys residue facilitates the generation of the persulfide group. Based upon these findings, we propose for SepCysS a sulfur relay mechanism that recruits both disulfide and persulfide intermediates.

  15. Modification and Performance Evaluation of a Low Cost Electro-Mechanically Operated Creep Testing Machine

    OpenAIRE

    John J. MOMOH; Lanre Y. SHUAIB-BABATA; Gabriel O. ADELEGAN

    2010-01-01

    Existing mechanically operated tensile and creep testing machine was modified to a low cost, electro-mechanically operated creep testing machine capable of determining the creep properties of aluminum, lead and thermoplastic materials as a function of applied stress, time and temperature. The modification of the testing machine was necessitated by having an electro-mechanically operated creep testing machine as a demonstration model ideal for use and laboratory demonstrations, which will prov...

  16. Generalized space and linear momentum operators in quantum mechanics

    International Nuclear Information System (INIS)

    Costa, Bruno G. da; Borges, Ernesto P.

    2014-01-01

    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 ^ q , and its canonically conjugate deformed position operator x ^ 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

  17. Operator ordering in quantum mechanics and quantum gravity

    International Nuclear Information System (INIS)

    Christodoulakis, T.; Zanelli, J.

    1984-05-01

    A non-perturbative approach to the quantization of the canonical algebra of pure gravity is presented. The problem of factor ordering of operators in the constraints H-caretsub(μ)psi=0 is resolved invoking hermiticity under the invariant inner product in hyperspace - the space of all three-dimensional metrics gsub(ij)(x) - and covariance under coordinate transformations. The resulting operators H-caretsub(μ) receive corrections of order h and h 2 only, and the algebra closes up to a conformal anomaly term. It is argued that, by a convenient choice of gauge, the anomalous term can be removed. (author)

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

    Science.gov (United States)

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

    2015-04-01

    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.

  19. 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

    2015-04-01

    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.

  20. Catalytic exhaust control

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H

    1973-09-01

    Recent achievements and problems in the development of exhaust control devices in the USA are reviewed. To meet the 1976 emission standards, catalytic systems for the oxidation of carbon monoxide and hydrocarbons and for the reduction of nitrogen oxides to nitrogen and water are needed. While oxidizing catalysts using platinum, palladium, copper, vanadium, and chromium appplied on alumina or ceramic materials are more or less effective in emission control, there are no catalytic devices for the reduction of nitrogen oxides with the required useful life of 25,000 to 50,000 miles as yet available. In the case of platinum catalysts on monolithic supports, the operating temperature of 650 to 750/sup 0/C as required for the oxidation process may cause inactivation of the catalysts and fusion of the support material. The oxidation of CO and hydrocarbons is inhibited by high concentrations of CO, nitric oxide, and hydrocarbons. The use of catalytic converters requires the use of lead-free or low-lead gasoline. The nitrogen oxides conversion efficiency is considerably influenced by the oxygen-to-CO ratio of the exhaust gas, which makes limitation of this ratio necessary.

  1. Renormalizing the Kinetic Energy Operator in Elementary Quantum Mechanics

    Science.gov (United States)

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

    2009-01-01

    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…

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

    NARCIS (Netherlands)

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

    2012-01-01

    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

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

    NARCIS (Netherlands)

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

    2012-01-01

    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

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

    NARCIS (Netherlands)

    Kemerink, Martijn; Asadi, Kamal; Blom, Paul W. M.; de Leeuw, Dago M.

    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

  5. modification of sequence of unit operations in mechanized palm fruit

    African Journals Online (AJOL)

    palm fruits processing sector, and requires less .... factory mill is a fully mechanized (non-labour ... in the digested fruit are to be all just touch- ing one ... fruits with human foot to pounding with pes- ... tural Service Bulletin 148 of Food and Agri-.

  6. Second virial coefficient from the scattering operator in quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Cognola, G; Soldati, R; Zerbini, S [Libera Universita di Trento (Italy). Dept. di Matematica e Fisica

    1977-12-17

    A new expression is proposed for the second virial coefficient in quantum statistical mechanics in which there is no reference to the interaction potential, but only the S matrix appears. Then it is shown that our expression reproduces the well-known Beth-Uhlenbeck formula.

  7. 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)

    2010-04-16

    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.

  8. Metal ion coordination in the E. coli Nudix hydrolase dihydroneopterin triphosphate pyrophosphatase: New clues into catalytic mechanism.

    Directory of Open Access Journals (Sweden)

    Shannon E Hill

    Full Text Available Dihydroneopterin triphosphate pyrophosphatase (DHNTPase, a member of the Mg2+ dependent Nudix hydrolase superfamily, is the recently-discovered enzyme that functions in the second step of the pterin branch of the folate biosynthetic pathway in E. coli. DHNTPase is of interest because inhibition of enzymes in bacterial folate biosynthetic pathways is a strategy for antibiotic development. We determined crystal structures of DHNTPase with and without activating, Mg2+-mimicking metals Co2+ and Ni2+. Four metal ions, identified by anomalous scattering, and stoichiometrically confirmed in solution by isothermal titration calorimetry, are held in place by Glu56 and Glu60 within the Nudix sequence motif, Glu117, waters, and a sulfate ion, of which the latter is further stabilized by a salt bridge with Lys7. In silico docking of the DHNTP substrate reveals a binding mode in which the pterin ring moiety is nestled in a largely hydrophobic pocket, the β-phosphate activated for nucleophilic attack overlays with the crystallographic sulfate and is in line with an activated water molecule, and remaining phosphate groups are stabilized by all four identified metal ions. The structures and binding data provide new details regarding DHNTPase metal requirements, mechanism, and suggest a strategy for efficient inhibition.

  9. Sulfur mobilization in cyanobacteria: the catalytic mechanism of L-cystine C-S lyase (C-DES) from synechocystis.

    Science.gov (United States)

    Campanini, Barbara; Schiaretti, Francesca; Abbruzzetti, Stefania; Kessler, Dorothea; Mozzarelli, Andrea

    2006-12-15

    Sulfur mobilization represents one of the key steps in ubiquitous Fe-S clusters assembly and is performed by a recently characterized set of proteins encompassing cysteine desulfurases, assembly factors, and shuttle proteins. Despite the evolutionary conservation of these proteins, some degree of variability among organisms was observed, which might reflect functional specialization. L-Cyst(e)ine lyase (C-DES), a pyridoxal 5'-phosphatedependent enzyme identified in the cyanobacterium Synechocystis, was reported to use preferentially cystine over cysteine with production of cysteine persulfide, pyruvate, and ammonia. In this study, we demonstrate that C-DES sequences are present in all cyanobacterial genomes and constitute a new family of sulfur-mobilizing enzymes, distinct from cysteine desulfurases. The functional properties of C-DES from Synechocystis sp. PCC 6714 were investigated under pre-steady-state and steady-state conditions. Single wavelength and rapid scanning stopped-flow kinetic data indicate that the internal aldimine reacts with cystine forming an external aldimine that rapidly decays to a transient quinonoid species and stable tautomers of the alpha-aminoacrylate Schiff base. In the presence of cysteine, the transient formation of a dipolar species precedes the selective and stable accumulation of the enolimine tautomer of the external aldimine, with no formation of the alpha-aminoacrylate Schiff base under reducing conditions. Effective sulfur mobilization from cystine might represent a mechanism that allows adaptation of cyanobacteria to different environmental conditions and to light-dark cycles.

  10. Metal ion coordination in the E. coli Nudix hydrolase dihydroneopterin triphosphate pyrophosphatase: New clues into catalytic mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Shannon E.; Nguyen, Elaine; Ukachukwu, Chiamaka U.; Freeman, Dana M.; Quirk, Stephen; Lieberman, Raquel L.; Boggon, Titus J.

    2017-07-25

    Dihydroneopterin triphosphate pyrophosphatase (DHNTPase), a member of the Mg2+ dependent Nudix hydrolase superfamily, is the recently-discovered enzyme that functions in the second step of the pterin branch of the folate biosynthetic pathway in E. coli. DHNTPase is of interest because inhibition of enzymes in bacterial folate biosynthetic pathways is a strategy for antibiotic development. We determined crystal structures of DHNTPase with and without activating, Mg2+-mimicking metals Co2+ and Ni2+. Four metal ions, identified by anomalous scattering, and stoichiometrically confirmed in solution by isothermal titration calorimetry, are held in place by Glu56 and Glu60 within the Nudix sequence motif, Glu117, waters, and a sulfate ion, of which the latter is further stabilized by a salt bridge with Lys7. In silico docking of the DHNTP substrate reveals a binding mode in which the pterin ring moiety is nestled in a largely hydrophobic pocket, the β-phosphate activated for nucleophilic attack overlays with the crystallographic sulfate and is in line with an activated water molecule, and remaining phosphate groups are stabilized by all four identified metal ions. The structures and binding data provide new details regarding DHNTPase metal requirements, mechanism, and suggest a strategy for efficient inhibition.

  11. Structural Basis for the Catalytic Mechanism of DncV, Bacterial Homolog of Cyclic GMP-AMP Synthase.

    Science.gov (United States)

    Kato, Kazuki; Ishii, Ryohei; Hirano, Seiichi; Ishitani, Ryuichiro; Nureki, Osamu

    2015-05-05

    Cyclic dinucleotides (CDNs) play key roles as second messengers and signaling molecules in bacteria and metazoans. The newly identified dinucleotide cyclase in Vibrio cholerae (DncV) produces three different CDNs containing two 3'-5' phosphodiester bonds, and its predominant product is cyclic GMP-AMP, whereas mammalian cyclic GMP-AMP synthase (cGAS) produces only cyclic GMP-AMP containing mixed 2'-5' phosphodiester bonds. We report the crystal structures of V. cholerae and Escherichia coli DncV in complex with various nucleotides in the pre-reaction states. The high-resolution structures revealed that DncV preferably recognizes ATP and GTP as acceptor and donor nucleotides, respectively, in the first nucleotidyl transfer reaction. Considering the recently reported intermediate structures, our pre-reaction state structures provide the precise mechanism of 3'-5' linked cyclic AMP-GMP production in bacteria. A comparison with cGAS in the pre-reaction states suggests that the orientation of the acceptor nucleotide primarily determines the distinct linkage specificities between DncV and cGAS. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Electrochemical catalytic treatment of phenol wastewater

    International Nuclear Information System (INIS)

    Ma Hongzhu; Zhang Xinhai; Ma Qingliang; Wang Bo

    2009-01-01

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  13. Vapor-Driven Propulsion of Catalytic Micromotors

    Science.gov (United States)

    Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

    2015-08-01

    Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

  14. Electrochemical catalytic treatment of phenol wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Ma Hongzhu, E-mail: hzmachem@snnu.edu.cn [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Zhang Xinhai [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Ma Qingliang [Department of Applied Physics, College of Sciences, Taiyuan University of Technology, 030024 Taiyuan (China); Wang Bo [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

    2009-06-15

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  15. Progress in catalytic naphtha reforming process: A review

    International Nuclear Information System (INIS)

    Rahimpour, Mohammad Reza; Jafari, Mitra; Iranshahi, Davood

    2013-01-01

    Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane components, which is intensely demanded in our modern life. The significance of this industrial process induced researchers to investigate different aspects of catalytic naphtha reforming process intensively. Some of the investigators try to improve this process by representing more effective catalysts, while others try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The amount of these established papers is so much that may confuse some of the researchers who want to find collective information about catalytic naphtha reforming process. In the present paper, the published studies from 1949 until now are categorized into three main groups including finding suitable catalyst, revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration and mode of operation. These studies are reviewed separately, and a suitable reference is provided for those who want to have access to generalized information about catalytic naphtha reforming process. Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed as a guideline for further investigations

  16. Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; DeLaRiva, Andrew T.; Challa, Sivakumar R.

    2013-01-01

    deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental...

  17. Roles of the conserved aspartate and arginine in the catalytic mechanism of an archaeal beta-class carbonic anhydrase.

    Science.gov (United States)

    Smith, Kerry S; Ingram-Smith, Cheryl; Ferry, James G

    2002-08-01

    The roles of an aspartate and an arginine, which are completely conserved in the active sites of beta-class carbonic anhydrases, were investigated by steady-state kinetic analyses of replacement variants of the beta-class enzyme (Cab) from the archaeon Methanobacterium thermoautotrophicum. Previous kinetic analyses of wild-type Cab indicated a two-step zinc-hydroxide mechanism of catalysis in which the k(cat)/K(m) value depends only on the rate constants for the CO(2) hydration step, whereas k(cat) also depends on rate constants from the proton transfer step (K. S. Smith, N. J. Cosper, C. Stalhandske, R. A. Scott, and J. G. Ferry, J. Bacteriol. 182:6605-6613, 2000). The recently solved crystal structure of Cab shows the presence of a buffer molecule within hydrogen bonding distance of Asp-34, implying a role for this residue in the proton transport step (P. Strop, K. S. Smith, T. M. Iverson, J. G. Ferry, and D. C. Rees, J. Biol. Chem. 276:10299-10305, 2001). The k(cat)/K(m) values of Asp-34 variants were decreased relative to those of the wild type, although not to an extent which supports an essential role for this residue in the CO(2) hydration step. Parallel decreases in k(cat) and k(cat)/K(m) values for the variants precluded any conclusions regarding a role for Asp-34 in the proton transfer step; however, the k(cat) of the D34A variant was chemically rescued by replacement of 2-(N-morpholino)propanesulfonic acid buffer with imidazole at pH 7.2, supporting a role for the conserved aspartate in the proton transfer step. The crystal structure of Cab also shows Arg-36 with two hydrogen bonds to Asp-34. Arg-36 variants had both k(cat) and k(cat)/K(m) values that were decreased at least 250-fold relative to those of the wild type, establishing an essential function for this residue. Imidazole was unable to rescue the k(cat) of the R36A variant; however, partial rescue of the kinetic parameter was obtained with guanidine-HCl indicating that the guanido group of this

  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: coutinho@dim.fm.usp.br

    2009-09-15

    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. Renormalizing the kinetic energy operator in elementary quantum mechanics

    International Nuclear Information System (INIS)

    Coutinho, F A B; Amaku, M

    2009-01-01

    In this paper, we consider solutions to the three-dimensional Schroedinger equation of the form ψ(r) = u(r)/r, where u(0) ≠ 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.

  20. A Simple Catalytic Mechanism for the Direct Coupling of α-Carbonyls with Functionalized Amines: A One-Step Synthesis of Plavix

    OpenAIRE

    Evans, Ryan W.; Zbieg, Jason R.; Zhu, Shaolin; Li, Wei; MacMillan, David W. C.

    2013-01-01

    The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst...

  1. Program of assessment of mechanical and corrosion mechanical properties of reactor internals materials due to operation conditions in WWERs

    International Nuclear Information System (INIS)

    Ruscak, M.; Zamboch, M.

    1998-01-01

    Reactor internals are subject to three principle operation influences: neutron and gamma irradiation, mechanical stresses, both static and dynamic, and coolant chemistry. Several cases of damage have been reported in previous years in both boiling and pressure water reactors. They are linked with the term of irradiation assisted stress corrosion cracking as a possible damage mechanism. In WWERs, the principal material used for reactor internals is austenitic titanium stabilized stainless steel 08Kh18N10T, however high strength steels are used as well. To assess the changes of mechanical properties and to determine whether sensitivity to intergranular cracking can be increased by high neutron fluences, the experimental program has been started. The goal is to assure safe operation of the internals as well as life management for all planned operation period. The program consists of tests of material properties, both mechanical and corrosion-mechanical. Detailed neutron fluxes calculation as well as stress and deformation calculations are part of the assessment. Model of change will be proposed in order to plan inspections of the facility. In situ measurements of internals will be used to monitor exact status of structure during operation. Tensile specimens manufactured from both base metal and model weld joint have been irradiated to the total fluences of 3-20 dpa. Changes of mechanical properties are tested by the tensile test, stress corrosion cracking tests are performed in the autoclave with water loop and active loading. Operation temperature, pressure and water chemistry are chosen for the tests. (author)

  2. Statistical learning: a powerful mechanism that operates by mere exposure.

    Science.gov (United States)

    Aslin, Richard N

    2017-01-01

    How do infants learn so rapidly and with little apparent effort? In 1996, Saffran, Aslin, and Newport reported that 8-month-old human infants could learn the underlying temporal structure of a stream of speech syllables after only 2 min of passive listening. This demonstration of what was called statistical learning, involving no instruction, reinforcement, or feedback, led to dozens of confirmations of this powerful mechanism of implicit learning in a variety of modalities, domains, and species. These findings reveal that infants are not nearly as dependent on explicit forms of instruction as we might have assumed from studies of learning in which children or adults are taught facts such as math or problem solving skills. Instead, at least in some domains, infants soak up the information around them by mere exposure. Learning and development in these domains thus appear to occur automatically and with little active involvement by an instructor (parent or teacher). The details of this statistical learning mechanism are discussed, including how exposure to specific types of information can, under some circumstances, generalize to never-before-observed information, thereby enabling transfer of learning. WIREs Cogn Sci 2017, 8:e1373. doi: 10.1002/wcs.1373 For further resources related to this article, please visit the WIREs website. © 2016 Wiley Periodicals, Inc.

  3. 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.

    2007-01-01

    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

  4. Catalytic combustion of propane in a membrane reactor with separate feed of reactants—I. Operation in absence of trans-membrane pressure gradients

    NARCIS (Netherlands)

    Saracco, Guido; Veldsink, Jan Willem; Versteeg, Geert F.; Swaaij, Wim P.M. van

    1995-01-01

    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/γ-Al2O3 catalyst. The role of reactants concentration and of the feed flow rates were

  5. Catalytic combustion of propane in a membrane reactor with separate feed of reactants—II. Operation in presence of trans-membrane pressure gradients

    NARCIS (Netherlands)

    Saracco, Guido; Veldsink, Jan Willem; Versteeg, Geert F.; Swaaij, Wim P.M. van

    1995-01-01

    This is the second communication of a series dealing with an experimental and modelling study on propane catalytic combustion in a membrane reactor with separate feed of reactants. In paper I the behaviour of the reactor in the absence of trans-membrane pressure gradients was presented and

  6. Atomistic mechanisms of ReRAM cell operation and reliability

    Science.gov (United States)

    Pandey, Sumeet C.

    2018-01-01

    We present results from first-principles-based modeling that captures functionally important physical phenomena critical to cell materials selection, operation, and reliability for resistance-switching memory technologies. An atomic-scale description of retention, the low- and high-resistance states (RS), and the sources of intrinsic cell-level variability in ReRAM is discussed. Through the results obtained from density functional theory, non-equilibrium Green’s function, molecular dynamics, and kinetic Monte Carlo simulations; the role of variable-charge vacancy defects and metal impurities in determining the RS, the LRS-stability, and electron-conduction in such RS is reported. Although, the statistical electrical characteristics of the oxygen-vacancy (Ox-ReRAM) and conductive-bridging RAM (M-ReRAM) are notably different, the underlying similar electrochemical phenomena describing retention and formation/dissolution of RS are being discussed.

  7. Mechanization of drill-and-blast operations in surface mines

    Energy Technology Data Exchange (ETDEWEB)

    Rogan, B.

    1985-07-01

    Comments on recent developments in blasting techniques in modern surface mines and quarries. The tendency to use large boreholes (up to 320 mm diameter) and on site manufactured ANFO and slurry explosives is stressed. Soviet experience with ANFO and slurry explosives and with 9 types of explosive-mixing/charging vehicles is presented. One type of vehicle is used as a stable explosive mixing unit, the others (SUZN-1B, SUZN-2, SUZN-5A, SUZN-5AM, ZS-1B, MZS-1M, MAZ-509P) are used as mobile explosive mixing and loading units. Some also incorporate a borehole stemming device. Mixtures of ANFO and slurry (aquatol) explosives, explosive charging capacities (outputs 9-30 t/h) and other characteristics of mechanized explosive charging vehicles are described. Obligatory safety measures during usage are quoted. 4 refs.

  8. 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

    2008-01-01

    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.

  9. Financial Mechanism for the Implementation of Strategic and Operational Financial Decisions of Modern Enterprises

    Science.gov (United States)

    Nikeriasova, Veronika V.; Ordov, Konstantin V.; Khvostenko, Oleg A.

    2016-01-01

    In modern conditions of world depression, it is urgent for increasing the efficiency of the financial mechanism. Company's future depends on the correct choice of the financial mechanism strategy. The article deals with the issues of improving the financial mechanism of enterprises in the implementation of strategic and operational financial…

  10. Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid–base catalysis

    Science.gov (United States)

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

    2014-01-01

    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

  11. Structural and catalytic effects of an invariant purine substitution in the hammerhead ribozyme: implications for the mechanism of acid-base catalysis.

    Science.gov (United States)

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

    2014-09-01

    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

  12. Catalytic decomposition of gaseous 1,2-dichlorobenzene over CuOx/TiO₂ and CuOx/TiO₂-CNTs catalysts: Mechanism and PCDD/Fs formation.

    Science.gov (United States)

    Wang, Qiu-lin; Huang, Qun-xing; Wu, Hui-fan; Lu, Sheng-yong; Wu, Hai-long; Li, Xiao-dong; Yan, Jian-hua

    2016-02-01

    Gaseous 1,2-dichlorobenzene (1,2-DCBz) was catalytically decomposed in a fixed-bed catalytic reactor using composite copper-based titanium oxide (CuOx/TiO2) catalysts with different copper ratios. Carbon nanotubes (CNTs) were introduced to produce novel CuOx/TiO2-CNTs catalysts by the sol-gel method. The catalytic performances of CuOx/TiO2 and CuOx/TiO2-CNTs on 1,2-DCBz oxidative destruction under different temperatures (150-350 °C) were experimentally examined and the correlation between catalyst structure and catalytic activity was characterized and the role of oxygen in catalytic reaction was discussed. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generation during 1,2-DCBz catalytic oxidation by CuOx/TiO2-CNTs composite catalyst was also examined. Results indicate that the 1,2-DCBz destruction/removal efficiencies of CuOx (4 wt%)/TiO2 catalyst at 150 °C and 350 °C with a GHSV of 3400 h(-1) are 59% and 94% respectively and low-temperature (150 °C) catalytic activity of CuOx/TiO2 on 1,2-DCBz oxidation can be improved from 59 to 77% when CNTs are introduced. Furthermore, oxygen either in catalyst or from reaction atmosphere is indispensible in reaction. The former is offered to activate and oxidize the 1,2-DCBz adsorbed on catalyst, thus can be generally consumed during reaction and the oxygen content in catalyst is observed lost from 39.9 to 35.0 wt% after reacting under inert atmosphere; the latter may replenish the vacancy in catalyst created by the consumed oxygen thus extends the catalyst life and raises the destruction/removal efficiency. The introduction of CNTs also increases the Cu(2+)/Cu(+) ratio, chemisorbed oxygen concentration and surface lattice oxygen binding energy which are closely related with catalytic activity. PCDD/Fs is confirmed to be formed when 1,2-DCBz catalytically oxidized by CuOx/TiO2-CNTs composite catalyst with sufficient oxygen (21%), proper temperature (350 °C) and high concentration of 1,2-DCBz feed (120 ppm

  13. Detection of Operator Performance Breakdown as an Automation Triggering Mechanism

    Science.gov (United States)

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

    2015-01-01

    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

  14. Transient thermal-mechanical coupling behavior analysis of mechanical seals during start-up operation

    Science.gov (United States)

    Gao, B. C.; Meng, X. K.; Shen, M. X.; Peng, X. D.

    2016-05-01

    A transient thermal-mechanical coupling model for a contacting mechanical seal during start-up has been developed. It takes into consideration the coupling relationship among thermal-mechanical deformation, film thickness, temperature and heat generation. The finite element method and multi-iteration technology are applied to solve the temperature distribution and thermal-mechanical deformation as well as their evolution behavior. Results show that the seal gap transforms from negative coning to positive coning and the contact area of the mechanical seal gradually decreases during start-up. The location of the maximum temperature and maximum contact pressure move from the outer diameter to inside diameter. The heat generation and the friction torque increase sharply at first and then decrease. Meanwhile, the contact force decreases and the fluid film force and leakage rate increase.

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

    OpenAIRE

    Maher A.R. Sadiq Al-Baghdadi

    2010-01-01

    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 s...

  16. MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

  17. Essential spectra and exponential estimates of eigenfunctions of lattice operators of quantum mechanics

    International Nuclear Information System (INIS)

    Rabinovich, Vladimir S; Roch, Steffen

    2009-01-01

    This paper is devoted to estimates of the exponential decay of eigenfunctions of difference operators on the lattice Z n which are discrete analogs of the Schroedinger, Dirac and square-root Klein-Gordon operators. Our investigation of the essential spectra and the exponential decay of eigenfunctions of the discrete spectra is based on the calculus of pseudodifference operators (i.e., pseudodifferential operators on the group Z n with analytic symbols), and the limit operators method. We obtain a description of the location of the essential spectra and estimates of the eigenfunctions of the discrete spectra of the main lattice operators of quantum mechanics, namely: matrix Schroedinger operators on Z n , Dirac operators on Z 3 and square root Klein-Gordon operators on Z n .

  18. Extending the Operational Relevance of the Current Heavy Mechanized and Armor Force to 2020 and Beyond

    National Research Council Canada - National Science Library

    Boston, Gerald

    2003-01-01

    Can the U.S. Army's current heavy mechanized and armor force adapt emerging Joint Vision 2020 operational concepts, in order to remain relevant to the land power requirements of combatant commanders across...

  19. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    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.

  20. 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

    2000-01-01

    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

  1. Safety relevant failure mechanisms in the post-operational phase; Sicherheitstechnisch relevante Fehlermechanismen in der Nachbetriebsphase

    Energy Technology Data Exchange (ETDEWEB)

    Mayer, Gerhard; Stiller, Jan Christopher; Roemer, Sarah

    2017-03-15

    When the 13{sup th} amendment of the Atomic Energy Act came into force, eight Germ an nuclear power plant units had their power operating licences revoked and are now in the so-called post operation phase. Of the remaining nuclear power plants, one have by now also entered the post operation phase, with those left in operation bound for entering this phase sometime between now and the end of 2022. Therefore, failure mechanisms that are particularly relevant for post operation were to be identified and described in the frame of the present project. To do so, three major steps were taken: Firstly, recent national and international pertinent literature was evaluated to obtain indications of failure mechanisms in the post operation phase. It turned out that most of the national and international literature deals with the general procedure of the transition from power operation to decommissioning and dismantling. However, there were also some documents providing detailed indications of possible failure mechanisms in post operation. This includes e.g. the release of radioactive materials caused by the drop of containers, chemical impacts on systems important to safety in connection with decontamination work, and corrosion in connection with the storage of the core in the spent fuel pool, with the latter leading to the jamming of the fuel assemblies in the storage racks and a possible reduction of coolant circulation. In a second step, three safety analyses of pressurised water reactors prepared by the respective plant operators were evaluated to identify failure mechanisms based on systems engineering. The failure mechanisms that were found here include e.g. faults in the boric acid concentration of the reactor coolant, damage to the equipment airlock upon the unloading of Castor casks, leakages in connection with primary system decontamination, and the drop of packages holding radioactive residual materials or waste with subsequent mobilisation of radioactive aerosols

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

    International Nuclear Information System (INIS)

    Fan Hongyi; Li Chao

    2004-01-01

    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

  3. 42 CFR 433.116 - FFP for operation of mechanized claims processing and information retrieval systems.

    Science.gov (United States)

    2010-10-01

    ... and information retrieval systems. 433.116 Section 433.116 Public Health CENTERS FOR MEDICARE... 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...

  4. Mining Pribram in science and technology. Proceedings of Session R - Mechanization of mine operations

    International Nuclear Information System (INIS)

    Kolar, J.; Bernatik, O.

    1987-01-01

    The proceedings contain 30 papers of which two deal with uranium mine problems, viz.: ''Current and prospective orientation of mechanized driving of mines and underground infrastructures'' and ''The operation of rail-less mine mechanization in the Hamr area''. (J.B.)

  5. Microwave Catalytic Oxidation of Hydrocarbons in Aqueous Solutions

    National Research Council Canada - National Science Library

    Cha, Chang

    2003-01-01

    .... A sufficient amount of experimental work has been completed evaluating the performance of the microwave catalytic oxidation process and determining the effect of different operating parameters...

  6. Investigating and improving student understanding of quantum mechanical observables and their corresponding operators in Dirac notation

    Science.gov (United States)

    Marshman, Emily; Singh, Chandralekha

    2018-01-01

    In quantum mechanics, for every physical observable, there is a corresponding Hermitian operator. According to the most common interpretation of quantum mechanics, measurement of an observable collapses the quantum state into one of the possible eigenstates of the operator and the corresponding eigenvalue is measured. Since Dirac notation is an elegant notation that is commonly used in upper-level quantum mechanics, it is important that students learn to express quantum operators corresponding to observables in Dirac notation in order to apply the quantum formalism effectively in diverse situations. Here we focus on an investigation that suggests that, even though Dirac notation is used extensively, many advanced undergraduate and PhD students in physics have difficulty expressing the identity operator and other Hermitian operators corresponding to physical observables in Dirac notation. We first describe the difficulties students have with expressing the identity operator and a generic Hermitian operator corresponding to an observable in Dirac notation. We then discuss how the difficulties found via written surveys and individual interviews were used as a guide in the development of a quantum interactive learning tutorial (QuILT) to help students develop a good grasp of these concepts. The QuILT strives to help students become proficient in expressing the identity operator and a generic Hermitian operator corresponding to an observable in Dirac notation. We also discuss the effectiveness of the QuILT based on in-class evaluations.

  7. Catalytic detritiation of water

    International Nuclear Information System (INIS)

    Rogers, M.L.; Lamberger, P.H.; Ellis, R.E.; Mills, T.K.

    1977-01-01

    A pilot-scale system has been used at Mound Laboratory to investigate the catalytic detritiation of water. A hydrophobic, precious metal catalyst is used to promote the exchange of tritium between liquid water and gaseous hydrogen at 60 0 C. Two columns are used, each 7.5 m long by 2.5 cm ID and packed with catalyst. Water flow is 5-10 cm 3 /min and countercurrent hydrogen flow is 9,000-12,000 cm 3 /min. The equipment, except for the columns, is housed in an inert atmosphere glovebox and is computer controlled. The hydrogen is obtained by electrolysis of a portion of the water stream. Enriched gaseous tritium is withdrawn for further enrichment. A description of the system is included along with an outline of its operation. Recent experimental data are discussed

  8. The Linkage of Joint Operational Fires, Information Operations and the Army: Does the Army Have Effective Feedback Mechanisms that Integrate Operational Fires (Physical Destruction) and Information Operations?

    National Research Council Canada - National Science Library

    Mills, Charles

    2004-01-01

    The information revolution seems to hold a lot of promise to the U.S. economy and the U.S. military, but rigid bureaucratic hierarchies make it extremely difficult for effective integration of operational fires and information operations...

  9. Operator algebras for general one-dimensional quantum mechanical potentials with discrete spectrum

    International Nuclear Information System (INIS)

    Wuensche, Alfred

    2002-01-01

    We define general lowering and raising operators of the eigenstates for one-dimensional quantum mechanical potential problems leading to discrete energy spectra and investigate their associative algebra. The Hamilton operator is quadratic in these lowering and raising operators and corresponding representations of operators for action and angle are found. The normally ordered representation of general operators using combinatorial elements such as partitions is derived. The introduction of generalized coherent states is discussed. Linear laws for the spacing of the energy eigenvalues lead to the Heisenberg-Weyl group and general quadratic laws of level spacing to unitary irreducible representations of the Lie group SU(1, 1) that is considered in detail together with a limiting transition from this group to the Heisenberg-Weyl group. The relation of the approach to quantum deformations is discussed. In two appendices, the classical and quantum mechanical treatment of the squared tangent potential is presented as a special case of a system with quadratic level spacing

  10. Synthesis of hierarchically porous perovskite-carbon aerogel composite catalysts for the rapid degradation of fuchsin basic under microwave irradiation and an insight into probable catalytic mechanism

    Science.gov (United States)

    Wang, Yin; Wang, Jiayuan; Du, Baobao; Wang, Yun; Xiong, Yang; Yang, Yiqiong; Zhang, Xiaodong

    2018-05-01

    3D hierarchically porous perovskites LaFe0.5M0.5O3-CA (M = Mn, Cu) were synthesized by a two-step method using PMMA as template and supporting with carbon aerogel, which were characterized with SEM, TEM, XRD, XPS and FT-IR spectroscopy. The as-prepared composites were used in microwave (MW) catalytic degradation of fuchsin basic (FB) dye wastewater. Batch experiment results showed that the catalytic degradation of FB could be remarkably improved by coating with CA. And LaFe0.5Cu0.5O3-CA exhibited higher catalytic performance than LaFe0.5Mn0.5O3-CA, which had a close connection with the activity of substitution metal ion in B site of the catalysts. The FB removal fit pseudo-first-order model and the degradation rate constant increased with initial pH value and MW powder while decreases with initial FB concentration. All catalysts presented favorable recycling and stability in the repeated experiment. Radical scavenger measurements indicated that hydroxyl radicals rather than surface peroxide and hole played an important role in the catalytic process, and its quantity determined the degradation of FB. Furthermore, both Cu and Fe species were involved in the formation of active species, which were responsible to the excellent performance of the LaFe0.5Cu0.5O3-CA/MW system. Therefore, LaFe0.5Cu0.5O3-CA/MW showed to be a promising technology for the removal of organic pollutants in wastewater treatment applications.

  11. Diffusion and Bonding Mechanism of Protective γ-Al2O3 on FeCrAl Foil for Metallic Three-Way Catalytic Converter

    Directory of Open Access Journals (Sweden)

    Feriyanto Dafit

    2017-01-01

    Full Text Available High pollutant level contributed by mobile sources/land transportation that become main problems for the human health. Improving exhaust emission system by improving catalytic converter properties is one of the most effective way to produce healthy air in our environment. It is conducted by two methods i.e. ultrasonic during electroplating (UBDEL and electroplating process (EL which are not fully investigated yet as catalytic converter coating process. UBDEL is conducted using sulphamate types electrolyte solution, Frequency of 35 kHz, current of 1.28A, Voltage of 12 V, and various time of 15, 30, 45, 60 and 75 minutes. Meanwhile El method is conducted using parameters of current of 1.28A, Voltage of 12 V, stirrer speed of 60 rpm and various time of 15, 30, 45, 60 and 75 minutes. Fully γ-Al2O3 bonding to the FeCrAl substrate is shown by UBDEL 75 minutes samples proved by SEM images and Ra and Rq are 4.01 μm and 5.64 μm, respectively. Ni present on the FeCrAl substrate as other protective layer generated by Ni electroplating process that will improve thermal stability of FeCrAl at high temperature of 1000 °C. From the results, can summarized that UBDEL technique is promoted as an effective catalytic converter coating technique.

  12. 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)

    2013-03-15

    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.

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

    International Nuclear Information System (INIS)

    Feng, Yixiong; Gao, Yicong; Tan, Jianrong; Hagiwara, Ichiro

    2013-01-01

    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.

  14. A proposed new mechanism for research and development co-operation

    International Nuclear Information System (INIS)

    Dolan, T.

    2001-01-01

    Scientists in developing countries sometimes lack knowledge of recent developments, co-operation with advanced countries, and government appreciation of the importance and quality of their work. The present IAEA mechanisms like CRPs and TC projects are very helpful but do not fully meet R and D co-operation needs of these scientists. A new complementary mechanism of co-operation among the Member States is proposed that would utilize IAEA services through a suitable agreement. The IAEA could help to evaluate joint R and D proposals, to provide an example legal agreement, to monitor progress, to disseminate the results, and, in some cases, to administer joint funds. This new mechanism would be similar to ITER, but on a smaller scale, and applicable to all fields of nuclear R and D. (author)

  15. Assessment, mechanisms, prevention, and measures for quick recovery of military operation-associated fatigue

    OpenAIRE

    Zhao-shen LI; Wen HUANG

    2012-01-01

    Fatigue is a worldwide problem. Military members frequently feel fatigue in military operations, which hinders the successful completion of their tasks. In complicated international military environments, military fatigue has received great attention from the armed forces in all countries. The present paper elaborates the performances, assessment, and mechanism of fatigue in military operations. In addition, the current study discusses the prevention and rapid recovery of fatigue, aiming at p...

  16. Operational performance of the mechanized and semi-mechanized potato harvest Desempenho operacional da colheita mecanizada e semimecanizada de batata

    Directory of Open Access Journals (Sweden)

    João P. A. R. da Cunha

    2011-01-01

    Full Text Available Potato is an important crop plant throughout the world. Harvesting is a fundamental step in its production system. Maybe, it is the most complex and expensive operation. Thus, the objective of this work was to compare the cost of the mechanized and semi-mechanized harvest, the operational capacity and the production losses during the potato harvest process. The work was accomplished in a commercial farming, cultivated under pivot system, in the municipal district of Perdizes - MG, Brazil. A completely randomized design with two treatments was used: mechanized and semi-mechanized harvest. The mechanized harvest used a self-propelled harvester. In the semi-automated harvest, a digger mounted on tractor was used and the potato was manually harvested. It was concluded that the cost of mechanized harvest was 49.03% lower than the cost of semi-mechanized harvest. On average, the harvester had a work for 23 workers in manual harvest. Mechanized harvest showed losses of 2.35% of potato yield, while the semi-mechanized harvest showed losses of 6.32%.A batata é a cultura olerácea mais importante em todo o mundo. Dentre os processos que compõem seu sistema de produção, a colheita apresenta-se como etapa essencial, sendo uma das operações com maior custo agregado. O objetivo deste trabalho foi comparar a colheita mecanizada e semimecanizada da cultura da batata no que diz respeito aos custos, capacidade operacional e perdas de produção. O trabalho foi realizado em lavoura comercial, cultivada em área sob sistema de pivô central, no município de Perdizes-MG. O delineamento experimental utilizado foi o inteiramente casualizado, com dois tratamentos: colheita mecanizada e semimecanizada. A colheita mecanizada foi realizada utilizando-se de uma colhedora autopropelida. Na colheita semimecanizada, empregou-se um arrancador tratorizado seguido de catação manual. De acordo com os resultados, pôde-se concluir que o custo da colheita mecanizada foi 49

  17. The measurement problem in quantum mechanics: approximation to the phenomenon of decoherence by operational identities

    International Nuclear Information System (INIS)

    Usera, J.I.

    1996-01-01

    An approach based on bits and pieces of standard wisdom plus and operational quantum mechanical identity deduced by the author is presented here in order to convey arguments concerning the quantum theory of measurement and which betray a flavor against completive claims for quantum mechanics. Special emphasis is put on the phenomenon of decoherence. This phenomenon (which is experimentally verifiable) finds natural room within the formalism while the wave function collapse (which is not) is precluded. (Author)

  18. The likelihood of failures in the operation of the lifting mechanism electrical hook bridge crane

    Directory of Open Access Journals (Sweden)

    Ritenman I.L.

    2017-09-01

    Full Text Available Given the application of the methods of analysis of types and consequences of failures (FMEA analysis to assess the technical risk of occurrence of emergency situations during the operation of the lifting mechanism electrical hook bridge crane. The technique allows to identify the limiting elements and to determine the significance of effects in the design of the lifting mechanism, to develop measures to reduce the risk of the occurrence of an emergency.

  19. Mechanical Properties of a Unidirectional Basalt-Fiber-Reinforced Plastic Under a Loading Simulating Operation Conditions

    Science.gov (United States)

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

    2017-01-01

    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.

  20. Insight into the mechanism revealing the peroxidase mimetic catalytic activity of quaternary CuZnFeS nanocrystals: colorimetric biosensing of hydrogen peroxide and glucose

    Science.gov (United States)

    Dalui, Amit; Pradhan, Bapi; Thupakula, Umamahesh; Khan, Ali Hossain; Kumar, Gundam Sandeep; Ghosh, Tanmay; Satpati, Biswarup; Acharya, Somobrata

    2015-05-01

    Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications.Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been

  1. Enhanced catalytic activity without the use of an external light source using microwave-synthesized CuO nanopetals

    Directory of Open Access Journals (Sweden)

    Govinda Lakhotiya

    2017-05-01

    Full Text Available We report enhanced catalytic activity of CuO nanopetals synthesized by microwave-assisted wet chemical synthesis. The catalytic reaction of CuO nanopetals and H2O2 was studied with the application of external light source and also under dark conditions for the degradation of the hazardous dye methylene blue. The CuO nanopetals showed significant catalytic activity for the fast degradation of methylene blue and rhodamine B (RhB under dark conditions, without the application of an external light source. This increased catalytic activity was attributed to the co-operative role of H2O2 and the large specific surface area (≈40 m2·g−1 of the nanopetals. We propose a detail mechanism for this fast degradation. A separate study of the effect of different H2O2 concentrations for the degradation of methylene blue under dark conditions is also illustrated.

  2. Catalytic Aminohalogenation of Alkenes and Alkynes.

    Science.gov (United States)

    Chemler, Sherry R; Bovino, Michael T

    2013-06-07

    Catalytic aminohalogenation methods enable the regio- and stereoselective vicinal difunctionalization of alkynes, allenes and alkenes with amine and halogen moieties. A range of protocols and reaction mechanisms including organometallic, Lewis base, Lewis acid and Brønsted acid catalysis have been disclosed, enabling the regio- and stereoselective synthesis of halogen-functionalized acyclic amines and nitrogen heterocycles. Recent advances including aminofluorination and catalytic enantioselective aminohalogenation reactions are summarized in this review.

  3. Risk assessment of maintenance operations: the analysis of performing task and accident mechanism.

    Science.gov (United States)

    Carrillo-Castrillo, Jesús A; Rubio-Romero, Juan Carlos; Guadix, Jose; Onieva, Luis

    2015-01-01

    Maintenance operations cover a great number of occupations. Most small and medium-sized enterprises lack the appropriate information to conduct risk assessments of maintenance operations. The objective of this research is to provide a method based on the concepts of task and accident mechanisms for an initial risk assessment by taking into consideration the prevalence and severity of the maintenance accidents reported. Data were gathered from 11,190 reported accidents in maintenance operations in the manufacturing sector of Andalusia from 2003 to 2012. By using a semi-quantitative methodology, likelihood and severity were evaluated based on the actual distribution of accident mechanisms in each of the tasks. Accident mechanisms and tasks were identified by using those variables included in the European Statistics of Accidents at Work methodology. As main results, the estimated risk of the most frequent accident mechanisms identified for each of the analysed tasks is low and the only accident mechanisms with medium risk are accidents when lifting or pushing with physical stress on the musculoskeletal system in tasks involving carrying, and impacts against objects after slipping or stumbling for tasks involving movements. The prioritisation of public preventive actions for the accident mechanisms with a higher estimated risk is highly recommended.

  4. Crystal Structure of Mn2+-bound Escherichia coli L-arabinose Isomerase (ECAI) and Implications in Protein Catalytic Mechanism and Thermo-Stability

    International Nuclear Information System (INIS)

    Zhu, W.; Manjasetty, B.; Chance, M.

    2007-01-01

    The functional properties of proteins depend on their three-dimensional shapes. Protein structures can be determined by X-ray crystallography as a tool. The three-dimensional structure of the apo form of the Escherichia coli L-arabinose isomerase (ECAI) has recently been determined. ECAI is responsible for the initial stage of L-arabinose catabolism, converting arabinose into ribulose in vivo. This enzyme also plays a crucial role in catalyzing the conversion of galactose into tagatose (low calorie natural sugar) in vitro. ECAI utilizes Mn 2+ for its catalytic activity. Crystals of the ECAI + Mn 2+ complex helps to investigate the catalytic properties of the enzyme. Therefore, crystals of ECAI + Mn 2+ complex were grown using hanging drop vapor diffusion method at room temperature. Diffraction data were collected at X4C beamline, National Synchrotron Light Source, Brookhaven National Laboratory. The structure was solved by the molecular replacement technique and has been refined to Rwork of 0.23 at 2.8 (angstrom) resolution using X3A beamline computational facility. The structure was deposited to Protein Data Bank (PDB ID 2HXG). Mn 2+ ion was localized to the previously identified putative active site with octahedral coordination. Comparison of apo and holo form of ECAI structures permits the identification of structural features that are of importance to the intrinsic activity and heat stability of AI

  5. MgATP-concentration dependence of protection of yeast vacuolar V-ATPase from inactivation by 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole supports a bi-site catalytic mechanism of ATP hydrolysis

    International Nuclear Information System (INIS)

    Milgrom, Elena M.; Milgrom, Yakov M.

    2012-01-01

    Highlights: ► MgATP protects V-ATPase from inactivation by 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole. ► V-ATPase activity saturation with MgATP is not sufficient for complete protection. ► The results support a bi-site catalytic mechanism for V-ATPase. -- Abstract: Catalytic site occupancy of the yeast vacuolar V-ATPase during ATP hydrolysis in the presence of an ATP-regenerating system was probed using sensitivity of the enzyme to inhibition by 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl). The results show that, regardless of the presence or absence of the proton-motive force across the vacuolar membrane, saturation of V-ATPase activity at increasing MgATP concentrations is accompanied by only partial protection of the enzyme from inhibition by NBD-Cl. Both in the presence and absence of an uncoupler, complete protection of V-ATPase from inhibition by NBD-Cl requires MgATP concentrations that are significantly higher than those expected from the K m values for MgATP. The results are inconsistent with a tri-site model and support a bi-site model for a mechanism of ATP hydrolysis by V-ATPase.

  6. Impact of mechanized logging operations on wet and dry soils of ...

    African Journals Online (AJOL)

    Mechanization of timber harvesting operations in Tanzania involves use of machinery such as feller bunchers, skidders and tractors which are generally heavy in weight ranging from 12 to 16 tones in unloaded state. The movements of these machines induce soil compaction owing to the exerted normal pressure, vibrations ...

  7. Classical optics representation of the quantum mechanical translation operator via ABCD matrices

    International Nuclear Information System (INIS)

    Ornigotti, Marco; Aiello, Andrea

    2013-01-01

    The ABCD matrix formalism describing paraxial propagation of optical beams across linear systems is generalized to arbitrary beam trajectories. As a by-product of this study, a one-to-one correspondence between the extended ABCD matrix formalism presented here and the quantum mechanical translation operator is established. (paper)

  8. Modification and Performance Evaluation of a Low Cost Electro-Mechanically Operated Creep Testing Machine

    Directory of Open Access Journals (Sweden)

    John J. MOMOH

    2010-12-01

    Full Text Available Existing mechanically operated tensile and creep testing machine was modified to a low cost, electro-mechanically operated creep testing machine capable of determining the creep properties of aluminum, lead and thermoplastic materials as a function of applied stress, time and temperature. The modification of the testing machine was necessitated by having an electro-mechanically operated creep testing machine as a demonstration model ideal for use and laboratory demonstrations, which will provide an economical means of performing standard creep experiments. The experimental result is a more comprehensive understanding of the laboratory experience, as the technology behind the creep testing machine, the test methodology and the response of materials loaded during experiment are explored. The machine provides a low cost solution for Mechanics of Materials laboratories interested in creep testing experiment and demonstration but not capable of funding the acquisition of commercially available creep testing machines. Creep curves of strain versus time on a thermoplastic material were plotted at a stress level of 1.95MPa, 3.25MPa and 4.55MPa and temperature of 20oC, 40oC and 60oC respectively. The machine is satisfactory since it is always ready for operation at any given time.

  9. 40 CFR 280.108 - Substitution of financial assurance mechanisms by owner or operator.

    Science.gov (United States)

    2010-07-01

    ... alternate financial assurance mechanisms as specified in this subpart, provided that at all times he... 40 Protection of Environment 26 2010-07-01 2010-07-01 false Substitution of financial assurance... OWNERS AND OPERATORS OF UNDERGROUND STORAGE TANKS (UST) Financial Responsibility § 280.108 Substitution...

  10. Feeding Behavior of Aplysia: A Model System for Comparing Cellular Mechanisms of Classical and Operant Conditioning

    Science.gov (United States)

    Baxter, Douglas A.; Byrne, John H.

    2006-01-01

    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…

  11. Coupled Thermo-Mechanical and Photo-Chemical Degradation Mechanisms that determine the Reliability and Operational Lifetimes for CPV Technologies

    Energy Technology Data Exchange (ETDEWEB)

    Dauskardt, Reinhold H. [Stanford Univ., CA (United States)

    2017-04-30

    This project sought to identify and characterize the coupled intrinsic photo-chemo-mechanical degradation mechanisms that determine the reliability and operational lifetimes for CPV technologies. Over a three year period, we have completed a highly successful program which has developed quantitative metrologies and detailed physics-based degradation models, providing new insight into the fundamental reliability physics necessary for improving materials, creating accelerated testing protocols, and producing more accurate lifetime predictions. The tasks for the program were separated into two focus areas shown in the figure below. Focus Area 1, led by Reinhold Dauskardt and Warren Cai with a primary collaboration with David Miller of NREL, studied the degradation mechanisms present in encapsulant materials. Focus Area 2, led by Reinhold Dauskardt and Ryan Brock with a primary collaboration with James Ermer and Peter Hebert of Spectrolab, studied stress development and degradation within internal CPV device interfaces. Each focus area was productive, leading to several publications, including findings on the degradation of silicone encapsulant under terrestrial UV, a model for photodegradation of silicone encapsulant adhesion, quantification and process tuning of antireflective layers on CPV, and discovery of a thermal cycling degradation mechanism present in metal gridline structures.

  12. On the Structural Context and Identification of Enzyme Catalytic Residues

    Directory of Open Access Journals (Sweden)

    Yu-Tung Chien

    2013-01-01

    Full Text Available Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.

  13. Investigation of mechanical properties and operative deformation mechanism in nano-crystalline Ni–Co/SiC electrodeposits

    International Nuclear Information System (INIS)

    Lari Baghal, S.M.; Amadeh, A.; Heydarzadeh Sohi, M.

    2012-01-01

    Highlights: ► The tensile properties of Ni–Co and Ni–Co/SiC deposits were investigated. ► The SiC particles enhanced tensile strength and ductility of nano-structured composites. ► The deformation mechanism at low and high strain rates were studied. - Abstract: Ni–Co/SiC nano-composites were prepared via electrodeposition from a modified Watts bath containing SiC particles with average particle size of 50 nm, SDS as surfactant and saccharin as grain refiner in appropriate amounts. The effect of nano-particle incorporation on microstructure, mechanical properties and deformation mechanism of electrodeposits were investigated. The mechanical properties of electrodeposits were investigated by Vickers microhardness and tensile tests. The results indicated that incorporation of SiC particles into a 15 nm Ni–Co matrix had no considerable effect on its microhardness and yield strength, that is, dispersion hardening did not operate in this range of grain size. However it was observed that co-deposition of uniform distributed SiC particles can significantly improve the ultimate tensile strength and elongation to failure of the deposits. Calculation of apparent activation volume from tensile test results at different strain rates proved that incorporation of SiC nano-particles are responsible for stress-assisted activation of GB atoms mechanism that can significantly increase the plasticity. Nano-crystalline Ni–Co matrix showed a mixed mod behavior of ductile and brittle fracture whereas incorporation of SiC particles and increasing the strain rate promoted ductile fracture mode.

  14. Organization and mechanization of maintenance operations at NPPs with the WWER type reactors

    International Nuclear Information System (INIS)

    Titov, A.A.

    1983-01-01

    The structure of capital investments defining organization and mechanization of maintepance operations at NPPs with the WWER type reactors is analyzed. The trends in development of optimum decisions for organization and mechanization of repair obs at NPPs being designed taking into account the prospects of nuclear powep enginerning development, the system of NPP maintenance servicing, as well as the structure of repair-productive capacities are discussed. On the basis of the analysis of the data obtained in designing the Zaporozhskaya NPP it is shown that the capital investments for organizing and mechanization of maintenance operations at the unified NPP site with four WWER-1000 reactors reach nearly 18 roubles/kW. A conclusion is drawn that at present the design of an NPP with the WWER-1000 reactor totally meets the requirements of realization of periodic maintenance operations. It is advisable to cooperate the NPP management with that of a thermal power station from the viewpoint of using manpower, which would improve the operating conditions and labour productivity of workers engaged in repair and, consequently, reduce the capital investments and repair expenditures

  15. Assessment and validation of CT scanogram to compare per-operative and post-operative mechanical axis after navigated total knee replacement

    Science.gov (United States)

    Jain, Sunil

    2008-01-01

    Our objective was to assess and validate low-dose computed tomography (CT) scanogram as a post-operative imaging modality to measure the mechanical axis after navigated total knee replacement. A prospective study was performed to compare intra-operative and post-operative mechanical axis after navigated total knee replacements. All consecutive patients who underwent navigated total knee replacement between May and December 2006 were included. The intra-operative final axis was recorded, and post-operatively a CT scanogram of lower limbs was performed. The mechanical axis was measured and compared against the intra-operative measurement. There were 15 patients ranging in age from 57 to 80 (average 70) years. The average final intra-operative axis was 0.56° varus (4° varus to 1.5° valgus) and post-operative CT scanogram axis was 0.52° varus (3.1° varus to 1.8° valgus). The average deviation from final axes to CT scanogram axes was 0.12° valgus with a correlation coefficient of 0.9. Our study suggests that CT scanogram is an imaging modality with reasonable accuracy for measuring mechanical axis despite significantly low radiation. It also confirms a high level of correlation between intra-operative and post-operative mechanical axis after navigated total knee replacement. PMID:18696064

  16. Ageing degradation mechanisms in nuclear power plants: lessons learned from operating experience

    International Nuclear Information System (INIS)

    Bieth, M.; Zerger, B.; Duchac, A.

    2014-01-01

    This paper presents main results of a comprehensive study performed by the European Clearinghouse on Operating Experience Feedback of Nuclear Power Plants (NPP) with the support of IRSN (Institut de Surete Nucleaire et de Radioprotection) and GRS (Gesellschaft fuer Anlagen und Reaktorsicherheit mbH). Physical ageing mechanisms of Structures, Systems and Components (SSC) that eventually lead to ageing related systems and components failures at nuclear power plants were the main focus of this study. The analysis of ageing related events involved operating experience reported by NPP operators in France, Germany, USA and to the IAEA/NEA International Reporting System on operating experience for the past 20 years. A list of relevant ageing related events was populated. Each ageing related event contained in the list was analyzed and results of analysis were summarized for each ageing degradation mechanism which appeared to be the dominant contributor or direct cause. This paper provides insights into ageing related operating experience as well as recommendations to deal with the physical ageing of nuclear power plant SSC important to safety. (authors)

  17. Estimated Mortality of Selected Migratory Bird Species from Mowing and Other Mechanical Operations in Canadian Agriculture

    Directory of Open Access Journals (Sweden)

    Joerg Tews

    2013-12-01

    Full Text Available Mechanical operations such as mowing, tilling, seeding, and harvesting are well-known sources of direct avian mortality in agricultural fields. However, there are currently no mortality rate estimates available for any species group or larger jurisdiction. Even reviews of sources of mortality in birds have failed to address mechanical disturbance in farm fields. To overcome this information gap we provide estimates of total mortality rates by mechanical operations for five selected species across Canada. In our step-by-step modeling approach we (i quantified the amount of various types of agricultural land in each Bird Conservation Region (BCR in Canada, (ii estimated population densities by region and agricultural habitat type for each selected species, (iii estimated the average timing of mechanical agricultural activities, egg laying, and fledging, (iv and used these values and additional demographical parameters to derive estimates of total mortality by species within each BCR. Based on our calculations the total annual estimated incidental take of young ranged from ~138,000 for Horned Lark (Eremophila alpestris to as much as ~941,000 for Savannah Sparrow (Passerculus sandwichensis. Net losses to the fall flight of birds, i.e., those birds that would have fledged successfully in the absence of mechanical disturbance, were, for example ~321,000 for Bobolink (Dolichonyx oryzivorus and ~483,000 for Savannah Sparrow. Although our estimates are subject to an unknown degree of uncertainty, this assessment is a very important first step because it provides a broad estimate of incidental take for a set of species that may be particularly vulnerable to mechanical operations and a starting point for future refinements of model parameters if and when they become available.

  18. Origami-based tunable truss structures for non-volatile mechanical memory operation.

    Science.gov (United States)

    Yasuda, Hiromi; Tachi, Tomohiro; Lee, Mia; Yang, Jinkyu

    2017-10-17

    Origami has recently received significant interest from the scientific community as a method for designing building blocks to construct metamaterials. However, the primary focus has been placed on their kinematic applications by leveraging the compactness and auxeticity of planar origami platforms. Here, we present volumetric origami cells-specifically triangulated cylindrical origami (TCO)-with tunable stability and stiffness, and demonstrate their feasibility as non-volatile mechanical memory storage devices. We show that a pair of TCO cells can develop a double-well potential to store bit information. What makes this origami-based approach more appealing is the realization of two-bit mechanical memory, in which two pairs of TCO cells are interconnected and one pair acts as a control for the other pair. By assembling TCO-based truss structures, we experimentally verify the tunable nature of the TCO units and demonstrate the operation of purely mechanical one- and two-bit memory storage prototypes.Origami is a popular method to design building blocks for mechanical metamaterials. Here, the authors assemble a volumetric origami-based structure, predict its axial and rotational movements during folding, and demonstrate the operation of mechanical one- and two-bit memory storage.

  19. The origin of the algebra of quantum operators in the stochastic formulation of quantum mechanics

    International Nuclear Information System (INIS)

    Davidson, M.

    1979-01-01

    The origin of the algebra of the non-commuting operators of quantum mechanics is explained in the general Fenyes-Nelson stochastic models in which the diffusion constant is a free parameter. This is achieved by continuing the diffusion constant to imaginary values, a continuation which destroys the physical interpretation, but does not affect experimental predictions. This continuation leads to great mathematical simplification in the stochastic theory, and to an understanding of the entire mathematical formalism of quantum mechanics. It is more than a formal construction because the diffusion parameter is not an observable in these theories. (Auth.)

  20. Operating a pneumatic-mechanical flotation machine for coal-slurry flotation

    Energy Technology Data Exchange (ETDEWEB)

    Shmaenok, N M; Bedran, N G; Konstantinov, V K; Kochetkov, Yu I; Sysoev, V S

    1976-01-01

    The FPM-GMO-1.6 pneumatic-mechanical flotation machine is easy to operate and regulate and maintains a high throughput at a low energy consumption. The flotation process is stable, the quality of the concentrate and tailings satisfactory, and the selectivity of separation high. The machine cannot handle coal slurries at higher throughputs because the rate of froth removal is too low across the entire flotation front. Experience on the pneumatic-mechanical flotation machine at the ''Kolosnikovskaya'' Central Washery indicates that a similar machine should be developed for a throughput of 1000 m/sup 3//hr.

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

    Science.gov (United States)

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-06-01

    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. A study on naphtha catalytic reforming reactor simulation and analysis

    OpenAIRE

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-01-01

    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 uni...

  3. Combination study of operation characteristics and heat transfer mechanism for pulsating heat pipe

    International Nuclear Information System (INIS)

    Cui, Xiaoyu; Zhu, Yue; Li, Zhihua; Shun, Shende

    2014-01-01

    Pulsating heat pipe (PHP) is becoming a promising heat transfer device for the application like electronics cooling. However, due to its complicated operation mechanism, the heat transfer properties of the PHP still have not been fully understood. This study experimentally investigated on a closed-loop PHP charged with four types of working fluids, deionized water, methanol, ethanol and acetone. Combined with the visualization experimental results from the open literature, the operation characteristics and the corresponding heat transfer mechanisms for different heat inputs (5 W up to 100 W) and different filling ratios (20% up to 95%) have been presented and elaborated. The results show that heat-transfer mechanism changed with the transition of operation patterns; before valid oscillation started, the thermal resistance was not like that described in the open literature where it decreased almost linearly, but would rather slowdown descending or even change into rise first before further decreasing (i.e. an inflection point existed); when the heat input further increased to certain level, e.g. 65 W or above, there presented a limit of heat-transfer performance which was independent of the types of working fluids and the filling ratios, but may be related to the structure, the material, the size and the inclination of the PHP. - Highlights: •The thermal mechanisms altered accordingly with the operation features in the PHP. •Unlike conventional heat pipes, continuous temperature soaring would not happen in the PHP. •Before the oscillation start-up, there existed a heat-transfer limit for the relatively stagnated flow in the PHP. •A limit of thermal performance existed in the PHP at relatively high heat inputs

  4. SHORT COMMUNICATION CATALYTIC KINETIC ...

    African Journals Online (AJOL)

    IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...

  5. Catalytic distillation process

    Science.gov (United States)

    Smith, L.A. Jr.

    1982-06-22

    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.

  6. Application Value of Slider-Crank Mechanism in Pick-and-Place Operation of Delta Robot

    Directory of Open Access Journals (Sweden)

    Zhe QIN

    2018-01-01

    Full Text Available By absorbing the advantages of the rotary-driven Delta robot and linear-driven Delta robot, a Delta robot for pick-and-place operation that forms a crank-slider at the drive joint is designed.To take the most common gate shaped curve in Cartesian space as the motion trail of robotic pick-and-place operation, according to the kinematics inverse solution theory of Delta robot, this thesis mainly solves the output angular velocity of robot-driven joint. Establishing the static transfer mathematical model and solving the forced condition of driving joint. The simulation analysis show that after the upper slider-crank mechanism is connected to the driving joint, the angular velocity of the driving joint changes suddenly, which caused a rigid impact on the robot in the picking and releasing operation, though the force of the driving joint can be made smaller.

  7. Catalytic distillation structure

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-04-17

    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.

  8. Mechanization of operations in underground workings in coal mines and research project trends. [Poland

    Energy Technology Data Exchange (ETDEWEB)

    Reich, K; Skoczynski, W; Sikora, W

    1985-01-01

    Structure of black coal reserves of Poland, imported and Polish made equipment for underground mining, prospects for mechanization of selected operations in underground mines and research programs of the KOMAG Center for Mechanization of Mining are evaluated. Prospects for longwall mining with caving or stowing in thick coal seams (slice mining), thin (0.8 to 1.2 m), level or inclined coal seams and steep seams are analyzed. The following equipment for mechanization of underground mining is evaluated: integrated face systems, shearer loaders, chain conveyors, belt conveyors, coal plows, equipment for mine drivage, hoists, drive systems for mining equipment. The following research programs of the KOMAG Center are reviewed: modernization of face systems for coal seams with uncomplicated mining conditions, development of equipment for thin seam mining, development of types of mining equipment for coal seams from 1.5 to 3.0 m thick with dip angles to 25 degrees, modernization of equipment for thick seam mining, increasing efficiency of mine drivage (new types of heading machines, materials handling equipment for mine drivage), mechanization of auxiliary operations in underground coal mines, improving quality of mining equipment, development of equipment for coal preparation, increasing occupational safety in underground mining.

  9. Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

    Science.gov (United States)

    Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

    2014-12-21

    Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

  10. 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

    2016-11-01

    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.

  11. Study of the neuroendocrine and immunologic mechanism of fatigue caused by military operations

    Directory of Open Access Journals (Sweden)

    Xin LI

    2012-01-01

    Full Text Available Objective  To observe the regularity of the changes in neuroendocrine-immune system caused by fatigue due to military operations, and explore the mechanism by which fatigue occurs in military operations. Methods  The subjects were 240 soldiers belonging to a field artillery force. The medical history and physical examination were taken before military operations, and fatigue assessment scale was accomplished as well. The following variables were measured in all the subjects: pituitary-adrenal [adrenocorticotropic hormone (ACTH, cortical hormone (B, 24-h urinary free cortisol (UFC], pituitary-gonadal [luteinizing hormone (LH, testosterone (T, estradiol (E2], pituitary-thyroid functions [serum thyroid stimulating hormone (TSH, tetraiodothyronine (TT4, triiodothyronine (TT3, free thyroxine (FT4, and free triiodothyronine (FT3], and cellular immune parameters (CD3+, CD4+, CD8+, CD4+/CD8+, B, NK. After 7 d of large-scale and high-intensity field exercises, the above variables were again measured in all the subjects. Results  After high-intensity military operations, the unpleasant feelings were significantly increased, and the compulsive and psychotic scores significantly decreased in the soldiers. In addition, the pituitary-adrenal and pituitary-gonadal hormone levels also decreased (all PPPConclusion  The depressed psychological tolerance in soldiers is the psychological factor of fatigue after a high-intensity military operation. The hypocorticoidism and inhibition of hypothalamic-pituitary-gonadal axis are the pathophysiological basis of military operation fatigue. Suppression of immune function is an important reason for an increase of susceptibility to disease after high-intensity military operations.

  12. The Operation Mechanisms of External Quality Assurance Frameworks of Foreign Higher Education and Implications for Graduate Education

    Science.gov (United States)

    Lin, Mengquan; Chang, Kai; Gong, Le

    2016-01-01

    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…

  13. 41 CFR 102-85.175 - Are the standard level services for cleaning, mechanical operation, and maintenance identified in...

    Science.gov (United States)

    2010-07-01

    ... services for cleaning, mechanical operation, and maintenance identified in an OA? 102-85.175 Section 102-85... of Service § 102-85.175 Are the standard level services for cleaning, mechanical operation, and maintenance identified in an OA? Unless specified otherwise in the OA, standard level services for cleaning...

  14. Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation.

    Science.gov (United States)

    Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming

    2016-09-01

    A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.

  15. Catalytic cracking models developed for predictive control purposes

    Directory of Open Access Journals (Sweden)

    Dag Ljungqvist

    1993-04-01

    Full Text Available The paper deals with state-space modeling issues in the context of model-predictive control, with application to catalytic cracking. Emphasis is placed on model establishment, verification and online adjustment. Both the Fluid Catalytic Cracking (FCC and the Residual Catalytic Cracking (RCC units are discussed. Catalytic cracking units involve complex interactive processes which are difficult to operate and control in an economically optimal way. The strong nonlinearities of the FCC process mean that the control calculation should be based on a nonlinear model with the relevant constraints included. However, the model can be simple compared to the complexity of the catalytic cracking plant. Model validity is ensured by a robust online model adjustment strategy. Model-predictive control schemes based on linear convolution models have been successfully applied to the supervisory dynamic control of catalytic cracking units, and the control can be further improved by the SSPC scheme.

  16. Mechanical stress analysis for a fuel rod under normal operating conditions

    International Nuclear Information System (INIS)

    Pino, Eddy S.; Giovedi, Claudia; Serra, Andre da Silva; Abe, Alfredo Y.

    2013-01-01

    Nuclear reactor fuel elements consist mainly in a system of a nuclear fuel encapsulated by a cladding material subject to high fluxes of energetic neutrons, high operating temperatures, pressure systems, thermal gradients, heat fluxes and with chemical compatibility with the reactor coolant. The design of a nuclear reactor requires, among a set of activities, the evaluation of the structural integrity of the fuel rod submitted to different loads acting on the fuel rod and the specific properties (dimensions and mechanical and thermal properties) of the cladding material and coolant, including thermal and pressure gradients produced inside the rod due to the fuel burnup. In this work were evaluated the structural mechanical stresses of a fuel rod using stainless steel as cladding material and UO 2 with a low degree of enrichment as fuel pellet on a PWR (pressurized water reactor) under normal operating conditions. In this sense, tangential, radial and axial stress on internal and external cladding surfaces considering the orientations of 0 deg, 90 deg and 180 deg were considered. The obtained values were compared with the limit values for stress to the studied material. From the obtained results, it was possible to conclude that, under the expected normal reactor operation conditions, the integrity of the fuel rod can be maintained. (author)

  17. synthesis, characterization, electrical and catalytic studies of some

    African Journals Online (AJOL)

    B. S. Chandravanshi

    catalytic activity of the VO(IV) and Mn(III) complexes have been tested in the epoxidation reaction of styrene ... Vanadyl sulfate pentahydrate, chromium chloride hexahydrate, anhydrous ferric ..... The catalytic oxidation of styrene gives the products styrene oxide, benzaldehyde, benzoic acid, ... bond via a radical mechanism.

  18. Catalytic nanoporous membranes

    Science.gov (United States)

    Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

    2013-08-27

    A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

  19. The value of the intra-operative clinical mechanical axis measurement in open-wedge valgus high tibial osteotomies

    NARCIS (Netherlands)

    van de Pol, G.J.; Verdonschot, Nicolaas Jacobus Joseph; van Kampen, A.

    2012-01-01

    Introduction: In high tibial osteotomies (HTO) the correction needs to be precise and intra-operative assessment is essential. The purpose of this study was to evaluate the use of the intra-operative clinical mechanical axis measurement and compare it to the post-operative weight bearing situation

  20. The Permanent Magnet Operating Mechanism of Double Coil Parallel Driven at a High Speed

    Directory of Open Access Journals (Sweden)

    WEI Xau-Lao

    2017-02-01

    Full Text Available Abstract:Operating mechanism is the main part of breaker,and the quality of breaker will directly influence the safe operation of power system. Because of the continuous improvement requirements of switch,in order to mak this actuator faster and more powerful closing,this paper proposes a double coil parallel driven permanent magnet actuator at a high speed. This paper expounds the working principle of single and double coil parallel driven permanent magnet actuator. It uses Ansoft building model and contrasts test results. In prance we designed and produced the single and double coil parallel driven permanent magnet actuator for experimental study. The simulation and experiment results show that double coil parallel driven permanent magnet actuator,compared with single coil parallel driven permanent magnet actuator,has a better and faster action performance. Thus,the double coil parallel driven permanent magnet actuator achieves a kind of optimization.

  1. 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

    2015-04-01

    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.

  2. 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)

    2011-01-01

    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.

  3. Mechanism of single-frequency operation of the hybrid-CO2 laser

    International Nuclear Information System (INIS)

    Gondhalekar, A.; Heckenberg, N.R.; Holzhauer, E.

    1975-01-01

    The mechanism of a new method of obtaining high-power single-frequency pulses from a TEA-CO 2 laser is discussed. Measurements of the shape and monochromaticity of pulses from the hybrid laser which has both a TEA and a low-pressure gain section inside one resonator are presented. The mechanism of single-frequency operation of the hybrid laser is discussed with reference to numerical solutions of simplified rate equations. The low-pressure section provides gain only over a narrow range of frequencies so that a mode lying in that band-width builds up faster than neighboring modes to give a single-frequency pulse resembling in overall shape the normal TEA laser pulse. If the system is already lasing when the TEA discharge begins, the single-mode radiation already present rapidly grows to give a single-frequency pulse lacking a gain-switched peak. (U.S.)

  4. An overview of current research on EU ETS: Evidence from its operating mechanism and economic effect

    International Nuclear Information System (INIS)

    Zhang, Yue-Jun; Wei, Yi-Ming

    2010-01-01

    The European Union Emissions Trading Scheme (EU ETS) is supposed to be an important mechanism for addressing climate change. Up to now, the theoretical foundation of EU ETS has been widely acknowledged, but empirical research on its current situation has only been published recently or is forthcoming. Therefore, this paper is aimed to summarize the main arguments of empirical studies on the EU ETS, in terms of two aspects, i.e., the operating mechanism and economic effect of the EU ETS, which are two crucial topics and have been attached much attention. Based on the shortcomings of current research and future requirements of the EU ETS evolution, finally, we also present some further directions of the EU ETS research. Overall, the research overview here may be helpful to recognize the features of the EU ETS and its effect on others. (author)

  5. Requirements on the mechanical design of reactor systems operating at elevated temperature

    International Nuclear Information System (INIS)

    Schulz, H.; Glahn, M.

    1979-01-01

    The paper presents the contemporary status of the requirements on the mechanical design and analysis developed during the licensing procedure of reactor systems operating at elevated temperature. General requirements for the design at elevated temperature are reviewed. The main proposal is to point out some limit strain criteria which are not included in present design guidelines and codes. The developed strain criteria are used to limit the component deformations in case of power excursions like the Bethe-Tait accident. It is also applicable for loads arising from other faulted conditions. (orig.)

  6. Parameterization of mechanical process operations taking into consideration a coefficient of variation and tool life

    Directory of Open Access Journals (Sweden)

    A. S. Sgibnev

    2014-01-01

    Full Text Available This article describes the results of studies on methods for improving the reliability of mechanical process operations of hard-to-machine materials. In serial production hard-to-machine materials processing should be characterized by high reliability, in particular, low dispersion tool life.The aim is to analyze the reliability of a part of the technological system, i.e. the tool for mechanical processing of hard-to-machine materials.The paper analyzes the effect of various input parameters of the technological system (processed material, tool material, technological environment, operating parameters (processing modes on the reliability of the technological system. A feature of this work is to obtain quantitative characteristics of reliability for processing just the hard-to-machine materials. It is an important problem-solving because of the high cost of both the materials and the tool.For various tool, processed materials, and process operation conditions the experiments have been conducted, and, when machining, the tool life has been recorded, thus allowing to obtain the coefficient of variation for high production run of tool. Comparison of coefficients of variation resulted in offering the tool material, process environment, and operation conditions to improve the reliability of the technological system for the specific brands of corrosion resistant steels and alloys and tungsten.It is shown that the tool material and technological environment have the biggest influence on the tool life period T and its coefficient of variation varT. It is noted that materials with a complicated composition have the higher life volatility as compared with the resistance simple alloys. It is shown that an increasing cutting speed is reduced after a certain value of the coefficient of variation due to entrainment outgrowth formed on the cutting edge of the tool.The results obtained allow machining production engineers at the enterprises of serial

  7. The optimization, kinetics and mechanism of m-cresol degradation via catalytic wet peroxide oxidation with sludge-derived carbon catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yamin [Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Wei, Huangzhao; Zhao, Ying [Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Sun, Wenjing [Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Sun, Chenglin, E-mail: clsun@dicp.ac.cn [Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2017-03-15

    Highlights: • The sludge derived carbon modified with 0 °C acid was used as catalyst in CWPO. • RSM was used to optimize CWPO reaction conditions of m-cresol for the first time. • The kinetic model was disclosed to be correlated with residue target concentration. • The proposed degradation pathways of m-cresol were well proven by DFT method. - Abstract: The sludge-derived carbon catalyst modified with 0 °C HNO{sub 3} solution was tested in catalytic wet peroxide oxidation of m-cresol (100 mg L{sup −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, C{sub 0,H2O2(30%)} = 1.20 g L{sup −1} (lower than the stoichiometric amount of 1.80 g L{sup −1}) and C{sub cat} = 0.80 g L{sup −1}, with 96% of m-cresol and 47% of TOC converted after 16 min and 120 min of reaction, respectively, and ξ (mg TOC/g H{sub 2}O{sub 2} fed) = 83.6 mg/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 H{sub 2}O{sub 2} exactly provide convincing proof of three-dimensional response surfaces analysis by RSM, which showed the influence of the interaction between organics and H{sub 2}O{sub 2} on effective H{sub 2}O{sub 2} 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.

  8. LORETA Neurofeedback in the Precuneus: Operant Conditioning in Basic Mechanisms of Self-Regulation.

    Science.gov (United States)

    Cannon, Rex L; Baldwin, Debora R; Diloreto, Dominic J; Phillips, Sherman T; Shaw, Tiffany L; Levy, Jacob J

    2014-10-01

    Low-resolution brain electomagnetic tomography (LORETA) neurofeedback provides a mechanism to influence the electrical activity of the brain in intracranial space. The aim of this study was to determine the effects of LORETA neurofeedback (LNFB) in the precuneus as a mechanism for improving self-regulation in controls and a heterogeneous diagnostic group (DX). Thirteen participants completed between 10 and 20 sessions of LNFB training in a 3-voxel cluster in the left precuneus. The participants included 5 nonclinical university students, and 8 adults with heterogeneous psychiatric diagnoses. We assessed the effects of LNFB with neurophysiological measures as well as pre- and post-Personality Assessment Inventory (PAI) subscales and selected subtests from the Delis-Kaplan Executive Function System (DKEFS). There was a significant total relative power increase at the precuneus for baseline contrasts for the control group. The DX group did not reach significant levels. All participants showed improvements in executive functions and tended to report significantly less psychopathology. The basic neural mechanisms of self-regulation are poorly understood. The data obtained in this study demonstrate that LNFB in a heterogeneous population enhances executive functions while concordantly decreasing endorsement of psychological symptoms. The alpha frequency in the brain may represent integrative functioning relative to operant efficiency and self-regulatory mechanisms. © EEG and Clinical Neuroscience Society (ECNS) 2014.

  9. Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts.

    Science.gov (United States)

    Taylor, Martin J; Jiang, Li; Reichert, Joachim; Papageorgiou, Anthoula C; Beaumont, Simon K; Wilson, Karen; Lee, Adam F; Barth, Johannes V; Kyriakou, Georgios

    2017-04-20

    Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.

  10. Effect of annealing temperature on the structure and coke-resistance of nickel–iron bimetallic catalytic layer for in situ methane steam reforming in SOFC operation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xuehua; Zhang, Hanqing; Zhao, DanDan; Tang, Dian; Zhang, Teng, E-mail: teng_zhang@fzu.edu.cn

    2014-11-15

    Highlights: • An intermediate FeNi{sub 3} phase forms in all N{sub i0.75}Fe{sub 0.25} catalysts in present work. • The catalyst annealed at 705 °C has smallest calculated surface energy. • The catalyst annealed at 705 °C also exhibits the best coke resistance in methane. • The cell with catalyst layer annealed at 705 °C has the best stability in methane. - Abstract: In this paper, the effect on coke formation of adding a Ni{sub 0.75}Fe{sub 0.25} catalyst layer to the anode side of a fuel cell running on methane is investigated. The formation of an intermediate FeNi{sub 3} phase can be observed in catalysts annealed at different temperatures. The catalyst annealed at 705 °C has the smallest calculated surface energy and grain size among all catalysts annealed at different temperatures. In addition, the O{sub 2}-TPO profiles and Raman spectra of spent anode material reveal that the catalyst annealed at 705 °C has the best coke resistance among all catalysts. Moreover, the cell with catalyst layer annealed at 705 °C, under a current density of 600 mA cm{sup −2} at 650 °C, experiences a decrease of 10% after operating in methane for 260 min, which is much more stable than that without catalyst layer (a decrease of 50%)

  11. 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

    2011-10-01

    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.

  12. Steam reformer with catalytic combustor

    Science.gov (United States)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  13. Optimum ratio of main mechanized operations for direct-flow fertilizers introduction

    Directory of Open Access Journals (Sweden)

    V. P. Uvarov

    2016-01-01

    Full Text Available Use of transport and technological means is carried out according to the direct-flow scheme and includes stage-by-stage performance as the main standard-setting operations (fertilizers transportation, movement and their distribution across a field, and auxiliary (return from a field and loading of fertilizers. The method of comparison of main types of operations at fertilizers application is given. An estimation criterion is a ratio of cargo movements on a road and across a field, proportionality coefficient between movement of freight and a fertilizers distribution area across the field. These indicators depend on transportation distances and doses of fertilizers application, and also on technology factor that is freight moving frequency across the field. The last characteristic is taken as the optimized parameter. An extremum of this indicator was searched due to a classical method. Optimum values of estimated indicators with the accounting of a variation of a ratio of load capacity and operating width of technical means are received. Concrete combinations of transportation distances and doses of fertilizers application are specified. The authors defined conditions of effective use of tractor and perspective automobile transport and technological means. They recommended to use the automeans allowing to change operating width. Realization of the stated methodological approach will make it possible to select an optimum ratio of the mechanized operations at direct-flow fertilizers application, to exclude additional cargo movements across the field, to cut fuel consumption, to increase productivity. Productivity of transport and technological means increases by 2.0; 1.3 and 1.15 times respectively to length of furrow 3; 9 and 27 km at fertilizers application by a dose of 0.06 kg per sq.m.

  14. Multidimensional Generalized Functions in Aeroacoustics and Fluid Mechanics. Part 1; Basic Concepts and Operations

    Science.gov (United States)

    Farassat, Fereidoun; Myers, Michael K.

    2011-01-01

    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.

  15. The evolution of catalytic function

    Science.gov (United States)

    Maurel, Marie-Christine; Ricard, Jacques

    2006-03-01

    It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells. Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”. In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution. We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.

  16. Structure, computational and biochemical analysis of PcCel45A endoglucanase from Phanerochaete chrysosporium and catalytic mechanisms of GH45 subfamily C members

    DEFF Research Database (Denmark)

    Godoy, Andre S.; Pereira, Caroline S.; Ramia, Marina Paglione

    2018-01-01

    The glycoside hydrolase family 45 (GH45) of carbohydrate modifying enzymes is mostly comprised of ß-1,4-endoglucanases. Significant diversity between the GH45 members has prompted the division of this family into three subfamilies: A, B and C, which may differ in terms of the mechanism, general a...

  17. Approach to Operational Experimental Estimation of Static Stresses of Elements of Mechanical Structures

    Science.gov (United States)

    Sedov, A. V.; Kalinchuk, V. V.; Bocharova, O. V.

    2018-01-01

    The evaluation of static stresses and strength of units and components is a crucial task for increasing reliability in the operation of vehicles and equipment, to prevent emergencies, especially in structures made of metal and composite materials. At the stage of creation and commissioning of structures to control the quality of manufacturing of individual elements and components, diagnostic control methods are widely used. They are acoustic, ultrasonic, X-ray, radiation methods and others. The using of these methods to control the residual life and the degree of static stresses of units and parts during operation is fraught with great difficulties both in methodology and in instrumentation. In this paper, the authors propose an effective approach of operative control of the degree of static stresses of units and parts of mechanical structures which are in working condition, based on recording the changing in the surface wave properties of a system consisting of a sensor and a controlled environment (unit, part). The proposed approach of low-frequency diagnostics of static stresses presupposes a new adaptive-spectral analysis of a surface wave created by external action (impact). It is possible to estimate implicit stresses of structures in the experiment due to this approach.

  18. Control rod driving mechanism of reactor, control device and operation method therefor

    International Nuclear Information System (INIS)

    Ariyoshi, Masahiko; Matsumoto, Fujio; Matsumoto, Koji; Kinugasa, Kunihiko; Nara, Yoshihiko; Otama, Kiyomaro; Mikami, Takao

    1998-01-01

    The present invention provides a device for and a method of directly driving control rods of an FBR type reactor linearly by a cylinder type linear motor while having a driving shaft as an electric conductor. Namely, a linear induction motor drives a driving shaft connected with a control rod and vertically moving the control rod by electromagnetic force as an electric conductor. The position of the control rod is detected by a position detector. The driving shaft is hung by a wire by way of an electromagnet which is attachably/detachably held. With such a constitution, the driving shaft connected with the control rod can be vertically moved linearly, stopped or kept. Since they can be driven smoothly at a wide range speed, the responsibility and reliability of the reactor operation can be improved. In addition, since responsibility of the control rod operation is high, scram can be conducted by the linear motor. Since the driving mechanism can be simplified, maintenance and inspection operation can be mitigated. (I.S.)

  19. Analytical Kinematics and Coupled Vibrations Analysis of Mechanical System Operated by Solar Array Drive Assembly

    Science.gov (United States)

    Sattar, M.; Wei, C.; Jalali, A.; Sattar, R.

    2017-07-01

    To address the impact of solar array (SA) anomalies and vibrations on performance of precision space-based operations, it is important to complete its accurate jitter analysis. This work provides mathematical modelling scheme to approximate kinematics and coupled micro disturbance dynamics of rigid load supported and operated by solar array drive assembly (SADA). SADA employed in analysis provides a step wave excitation torque to activate the system. Analytical investigations into kinematics is accomplished by using generalized linear and Euler angle coordinates, applying multi-body dynamics concepts and transformations principles. Theoretical model is extended, to develop equations of motion (EoM), through energy method (Lagrange equation). The main emphasis is to research coupled frequency response by determining energies dissipated and observing dynamic behaviour of internal vibratory systems of SADA. The disturbance model captures discrete active harmonics of SADA, natural modes and vibration amplifications caused by interactions between active harmonics and structural modes of mechanical assembly. The proposed methodology can help to predict true micro disturbance nature of SADA operating rigid load. Moreover, performance outputs may be compared against actual mission requirements to assess precise spacecraft controller design to meet next space generation stringent accuracy goals.

  20. Model for Sucker-Rod Pumping Unit Operating Modes Analysis Based on SimMechanics Library

    Science.gov (United States)

    Zyuzev, A. M.; Bubnov, M. V.

    2018-01-01

    The article provides basic information about the process of a sucker-rod pumping unit (SRPU) model developing by means of SimMechanics library in the MATLAB Simulink environment. The model is designed for the development of a pump productivity optimal management algorithms, sensorless diagnostics of the plunger pump and pumpjack, acquisition of the dynamometer card and determination of a dynamic fluid level in the well, normalization of the faulty unit operation before troubleshooting is performed by staff as well as equilibrium ratio determining by energy indicators and outputting of manual balancing recommendations to achieve optimal power consumption efficiency. Particular attention is given to the application of various blocks from SimMechanics library to take into account the pumpjack construction principal characteristic and to obtain an adequate model. The article explains in depth the developed tools features for collecting and analysis of simulated mechanism data. The conclusions were drawn about practical implementation possibility of the SRPU modelling results and areas for further development of investigation.

  1. Catalytic Transformation of Ethylbenzene over Y-Zeolite-based Catalysts

    KAUST Repository

    Al-Khattaf, Sulaiman

    2008-01-01

    Catalytic transformation of ethylbenzene (EB) has been investigated over ultrastable Y (USY)-zeolite-based catalysts in a novel riser simulator at different operating conditions. The effect of reaction conditions on EB conversion is reported

  2. Catalytic Conversion of Biofuels

    DEFF Research Database (Denmark)

    Jørgensen, Betina

    This thesis describes the catalytic conversion of bioethanol into higher value chemicals. The motivation has been the unavoidable coming depletion of the fossil resources. The thesis is focused on two ways of utilising ethanol; the steam reforming of ethanol to form hydrogen and the partial oxida...

  3. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

  4. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  5. Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

    and the oxidative coupling of methane. These two reactions have tremendous technological significance for practical application in industry. An understanding of the fundamental aspects and reaction mechanisms of the catalytic reactions reviewed in this study would

  6. Quantum-mechanical analysis of amino acid residues function in the proton transport during F0F1-ATP synthase catalytic cycle

    Science.gov (United States)

    Ivontsin, L. A.; Mashkovtseva, E. V.; Nartsissov, Ya R.

    2017-11-01

    Implications of quantum-mechanical approach to the description of proton transport in biological systems are a tempting subject for an overlapping of fundamental physics and biology. The model of proton transport through the integrated membrane enzyme FoF1-ATP synthase responsible for ATP synthesis was developed. The estimation of the mathematical expectation of the proton transfer time through the half-channel was performed. Observed set of proton pathways through the inlet half-channel showed the nanosecond timescale highly dependable of some amino acid residues. There were proposed two types of crucial amino acids: critically localized (His245) and being a part of energy conserving system (Asp119).

  7. Selecting and calculating joint operation of oil and petroleum gas collection systems, and mechanized production methods

    Energy Technology Data Exchange (ETDEWEB)

    Guseva, L S; D' yachuk, A I; Davydova, L V; Maslov, V P; Salyautdinova, R M; Suslov, V M

    1979-01-01

    The possibility is examined of formalizing the indicated procedure in the process of performing step by step calculations. At the first step, considering limitations imposed by the dominating parameters, preliminary selection is performed of the acceptable combination of the type of collection system and methods of mechanized production for the development conditions examined. The second step provides for physical simulation at a well of an experimental section of time-variable conditions of field development. The values of the technological indices thus defined are then considered to be reliable information for technico-economic calculations. Parallel research is done on the technological features of operation of the collection systems chosen and their individual elements (pipeline system, separation units, etc.), which the experimental section is fitted with beforehand. Material is given which illustrates in detail the basic assumptions of the technique proposed and the calculation procedure.

  8. Optimum Design of a Coil Spring for Improving the Performance of a Spring -Operated Mechanism

    International Nuclear Information System (INIS)

    Lee, Dae Woo; Sohn, Jeong Hyun; Yoo, Wan Suk

    2016-01-01

    In this study, a release test bed is designed to evaluate the dynamic behaviors of a coil spring. From the release tests, the dynamic behaviors of a coil spring are analyzed. A lumped parameter spring model was established for numerical simulation of a spring. The design variables of a coil spring are optimized by using the design of experiments approach. Two-level factorial designs are used for the design optimization, and the primary effects of the design variables are analyzed. Based on the results of the interaction analysis and design sensitivity analysis, the level of the design variables is rearranged. Finally, the mixed-level factorial design is used for the optimum design process. According to the optimum design of the opening spring, the dynamic performance of the spring-operated mechanism increases by 2.90

  9. Thermal and mechanical properties of aluminized fabrics for use in ferrous metal handling operations.

    Science.gov (United States)

    Wren, J E; Scott, W D; Bates, C E

    1977-11-01

    Protective garments are normally worn in molten handling operations to provide some protection against molten metal splashes. These garments are also intended to provide protection against radiant heat, and they should be as heat resistant and comfortable as possible. Asbestos-based fabrics have been employed for many years, but recently some concern has been expressed over possible asbestos exposure. This program was undertaken to explore the ability of several types of fabrics to resist heat transfer during molten metal impact. A molten metal splash test, along with standard methods for determining tensile strength, flame resistance, and abrasion-flexing resistance were used to evaluate several classes of protective fabrics. The results indicate that there are materials available that offer equal or better mechanical properties and thermal protection compared to aluminized asbestos.

  10. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    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.

  11. Stepwise dissection and visualization of the catalytic mechanism of haloalkane dehalogenase LinB using molecular dynamics simulations and computer graphics.

    Science.gov (United States)

    Negri, Ana; Marco, Esther; Damborsky, Jiri; Gago, Federico

    2007-10-01

    The different steps of the dehalogenation reaction carried out by LinB on three different substrates have been characterized using a combination of quantum mechanical calculations and molecular dynamics simulations. This has allowed us to obtain information in atomic detail about each step of the reaction mechanism, that is, substrate entrance and achievement of the near-attack conformation, transition state stabilization within the active site, halide stabilization, water molecule activation and subsequent hydrolytic attack on the ester intermediate with formation of alcohol, and finally product release. Importantly, no bias or external forces were applied during the whole procedure so that both intermediates and products were completely free to sample configuration space in order to adapt to the plasticity of the active site and/or search for an exit. Differences in substrate reactivity were found to be correlated with the ease of adopting the near-attack conformation and two different exit pathways were found for product release that do not interfere with substrate entrance. Additional support for the different entry and exit pathways was independently obtained from an examination of the enzyme's normal modes.

  12. Experience feedback of operational events of the control rod assembly and its drive mechanism in nuclear power plants

    International Nuclear Information System (INIS)

    Zhou Hong; Xiao Zhi; Tao Shusheng; Zheng Lixin; Chen Zhaolin

    2013-01-01

    Seventeen operational events of the control rod assembly and its drive mechanism are collected from 1992 to 2012 important nuclear operational events and feedback in referred nuclear power plants. After investigated and classified, several important issues, such as the impact of control rod swell and fuel assembly distortion, control rod drive mechanism leakage, and the control system reliability of control rod, are emphatically analyzed. Some suggestions of experience feedback are proposed. (authors)

  13. Degradation Mechanism in a Direct Carbon Fuel Cell Operated with Demineralised Brown Coal

    International Nuclear Information System (INIS)

    Rady, Adam C.; Giddey, Sarbjit; Kulkarni, Aniruddha; Badwal, Sukhvinder P.S.; Bhattacharya, Sankar

    2014-01-01

    Graphical abstract: - Highlights: • Degradation mechanism studied for demineralised coal in a direct carbon fuel cell. • Diffusion limited processes dominate the electrode polarisation losses in pure N 2 . • Major fuel cell performance loss occurred due to loss of carbon/anode contacts. • The anode retained its phase structure with minor other phases formed in operation. - Abstract: The performance of a demineralised and devolatilised coal from the Morwell mine in the Latrobe Valley, Victoria, has been investigated in a direct carbon fuel cell (DCFC) operated at 850 °C. The focus of the investigation has been on understanding degradation issues as a function of time involving a sequence of electrochemical impedance spectroscopy and voltage-current characteristic. Diffusion limited processes dominate the electrode polarisation losses in pure N 2 atmosphere, however, these decrease substantially in the presence of CO 2 as the anode chamber purge gas, due to in situ generation of fuel species by the reaction of CO 2 with carbon. Post-mortem analysis of anode by SEM and XRD revealed only a minor degradation due to its reduction, particle agglomeration as well as the formation of small quantity of new phases. However, major fuel cell performance degradation (increase of ohmic resistive and electrode polarisation losses) occurred due to loss of carbon/anode contacts and a reduction in the electron-conducting pathways as the fuel was consumed. The investigations revealed that the demineralised coal char can be used as a viable fuel for DCFC, however, further developments on anode materials and fuel feed mechanism would be required to achieve long-term sustained performance

  14. Detection mechanism and characteristics of ZnO-based N2O sensors operating with photons

    Science.gov (United States)

    Jeong, T. S.; Yu, J. H.; Mo, H. S.; Kim, T. S.; Youn, C. J.; Hong, K. J.

    2013-11-01

    N2O sensors made with ZnO-based ZnCdO films were grown on Pyrex substrates by using the RF co-sputtering method. The structure of the N2O sensor was electrode/sensor/glass/illuminant. The mechanism of the photo-assisted oxidation and reduction process on the surface of the N2O sensors was investigated using light from a UV lamp and violet light emitting diode (LED). For photon exposure wavelengths of 365 and 405 nm, the sensitivity of the ZnO-based ZnCdO sensors was measured. From these measurements, the values of the sensitivity of the sensors with x = 0, 0.01, and 0.05 were found to be S = 1.44, 1.39, and 1.33 under LED light with a wavelength of 405 nm, respectively. These sensitivities were compared to those of SnO2 and WO3 materials measured at operating temperatures of 300-600 °C. Also, under exposure with UV light, the response times were observed to be 130 to 270 sec. These response times were slightly slower than that for the traditional method of thermal heating. However, they indicate that the described photon exposure method for N2O detection can replace the conventional heating mode. Consequently, we demonstrated that portable N2O sensors for room-temperature operation could be fabricated without thermal heating.

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

    Directory of Open Access Journals (Sweden)

    Hyun-Woo Kim

    2015-06-01

    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.

  16. Understanding Physiological and Degenerative Natural Vision Mechanisms to Define Contrast and Contour Operators

    Science.gov (United States)

    Demongeot, Jacques; Fouquet, Yannick; Tayyab, Muhammad; Vuillerme, Nicolas

    2009-01-01

    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. PMID:19547712

  17. 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.

  18. Determination of the Structure and Catalytic Mechanism of Sorghum bicolor Caffeic Acid O-Methyltransferase and the Structural Impact of Three brown midrib12 Mutations1[W

    Science.gov (United States)

    Green, Abigail R.; Lewis, Kevin M.; Barr, John T.; Jones, Jeffrey P.; Lu, Fachuang; Ralph, John; Vermerris, Wilfred; Sattler, Scott E.; Kang, ChulHee

    2014-01-01

    Using S-adenosyl-methionine as the methyl donor, caffeic acid O-methyltransferase from sorghum (Sorghum bicolor; SbCOMT) methylates the 5-hydroxyl group of its preferred substrate, 5-hydroxyconiferaldehyde. In order to determine the mechanism of SbCOMT and understand the observed reduction in the lignin syringyl-to-guaiacyl ratio of three brown midrib12 mutants that carry COMT gene missense mutations, we determined the apo-form and S-adenosyl-methionine binary complex SbCOMT crystal structures and established the ternary complex structure with 5-hydroxyconiferaldehyde by molecular modeling. These structures revealed many features shared with monocot ryegrass (Lolium perenne) and dicot alfalfa (Medicago sativa) COMTs. SbCOMT steady-state kinetic and calorimetric data suggest a random bi-bi mechanism. Based on our structural, kinetic, and thermodynamic results, we propose that the observed reactivity hierarchy among 4,5-dihydroxy-3-methoxycinnamyl (and 3,4-dihydroxycinnamyl) aldehyde, alcohol, and acid substrates arises from the ability of the aldehyde to stabilize the anionic intermediate that results from deprotonation of the 5-hydroxyl group by histidine-267. Additionally, despite the presence of other phenylpropanoid substrates in vivo, sinapaldehyde is the preferential product, as demonstrated by its low Km for 5-hydroxyconiferaldehyde. Unlike its acid and alcohol substrates, the aldehydes exhibit product inhibition, and we propose that this is due to nonproductive binding of the S-cis-form of the aldehydes inhibiting productive binding of the S-trans-form. The S-cis-aldehydes most likely act only as inhibitors, because the high rotational energy barrier around the 2-propenyl bond prevents S-trans-conversion, unlike alcohol substrates, whose low 2-propenyl bond rotational energy barrier enables rapid S-cis/S-trans-interconversion. PMID:24948836

  19. Determination of the Structure and Catalytic Mechanism of Sorghum bicolor Caffeic Acid O-Methyltransferase and the Structural Impact of Three brown midrib12 Mutations.

    Science.gov (United States)

    Green, Abigail R; Lewis, Kevin M; Barr, John T; Jones, Jeffrey P; Lu, Fachuang; Ralph, John; Vermerris, Wilfred; Sattler, Scott E; Kang, ChulHee

    2014-08-01

    Using S-adenosyl-methionine as the methyl donor, caffeic acid O-methyltransferase from sorghum (Sorghum bicolor; SbCOMT) methylates the 5-hydroxyl group of its preferred substrate, 5-hydroxyconiferaldehyde. In order to determine the mechanism of SbCOMT and understand the observed reduction in the lignin syringyl-to-guaiacyl ratio of three brown midrib12 mutants that carry COMT gene missense mutations, we determined the apo-form and S-adenosyl-methionine binary complex SbCOMT crystal structures and established the ternary complex structure with 5-hydroxyconiferaldehyde by molecular modeling. These structures revealed many features shared with monocot ryegrass (Lolium perenne) and dicot alfalfa (Medicago sativa) COMTs. SbCOMT steady-state kinetic and calorimetric data suggest a random bi-bi mechanism. Based on our structural, kinetic, and thermodynamic results, we propose that the observed reactivity hierarchy among 4,5-dihydroxy-3-methoxycinnamyl (and 3,4-dihydroxycinnamyl) aldehyde, alcohol, and acid substrates arises from the ability of the aldehyde to stabilize the anionic intermediate that results from deprotonation of the 5-hydroxyl group by histidine-267. Additionally, despite the presence of other phenylpropanoid substrates in vivo, sinapaldehyde is the preferential product, as demonstrated by its low K m for 5-hydroxyconiferaldehyde. Unlike its acid and alcohol substrates, the aldehydes exhibit product inhibition, and we propose that this is due to nonproductive binding of the S-cis-form of the aldehydes inhibiting productive binding of the S-trans-form. The S-cis-aldehydes most likely act only as inhibitors, because the high rotational energy barrier around the 2-propenyl bond prevents S-trans-conversion, unlike alcohol substrates, whose low 2-propenyl bond rotational energy barrier enables rapid S-cis/S-trans-interconversion. © 2014 American Society of Plant Biologists. All Rights Reserved.

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

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2010-01-01

    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: 1.2.1.1 The materials handled or processed constitute a significant radiation hazard to man or to the environment. 1.2.1.2 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. 1.2.1.3 The ...

  1. Policies for the design and operation of the clean development mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Hourcade, J.Ch. [Centre International de Recherche sur l' Environnement et le Developpement (CIRED-CNRS/EHESS), 94 - Nogent sur Marne (France); Toman, M. [Resources for the Future (RFF), Washington D.C. (United States)

    2003-07-01

    On September 24-25 1999, CIRED and RFF held a workshop at CIRED to explore a number of key policy issues surrounding the design and operation of the Clean Development Mechanism (CDM). This mechanism, created as part of the 1997 Kyoto Protocol to the United Nations Framework Convention on Climate Change (FCCC), has been the subject of much ongoing negotiation and debate. The multinational participants assembled not to seek consensus but to promote better understanding of commonalties and differences in views in a non politicized setting, as well as to see what new ideas and understandings might emerge from the discussions. The meetings were informal and ''off the record'' to promote frank exchange. This document is a summary of the discussions as seen through the eyes of the two co-organizers. We have tried to reflect as well as possible the range and diversity of the thoughts expressed at the meeting, and we have circulated this summary to other participants for their comments. But we alone are responsible for its content. (author)

  2. Nonlinear operators and nonlinear transformations studied via the differential form of the completeness relation in quantum mechanics

    International Nuclear Information System (INIS)

    Fan Hongyi; Yu Shenxi

    1994-01-01

    We show that the differential form of the fundamental completeness relation in quantum mechanics and the technique of differentiation within an ordered product (DWOP) of operators provide a new approach for calculating normal product expansions of some nonlinear operators and study some nonlinear transformations. Their usefulness in perturbative calculations is pointed out. (orig.)

  3. Concentric catalytic combustor

    Science.gov (United States)

    Bruck, Gerald J [Oviedo, FL; Laster, Walter R [Oviedo, FL

    2009-03-24

    A catalytic combustor (28) includes a tubular pressure boundary element (90) having a longitudinal flow axis (e.g., 56) separating a first portion (94) of a first fluid flow (e.g., 24) from a second portion (95) of the first fluid flow. The pressure boundary element includes a wall (96) having a plurality of separate longitudinally oriented flow paths (98) annularly disposed within the wall and conducting respective portions (100, 101) of a second fluid flow (e.g., 26) therethrough. A catalytic material (32) is disposed on a surface (e.g., 102, 103) of the pressure boundary element exposed to at least one of the first and second portions of the first fluid flow.

  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

    2015-09-01

    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. Fe(Ⅲ) ions enhanced catalytic properties of (BiO)2CO3 nanowires and mechanism study for complete degradation of xanthate.

    Science.gov (United States)

    Guo, Yujiao; Cui, Kuixin; Hu, Mingyi; Jin, Shengming

    2017-08-01

    The wire-like Fe 3+ -doped (BiO) 2 CO 3 photocatalyst was synthesized by a hydrothermal method. The photocatalytic property of Fe 3+ -doped (BiO) 2 CO 3 nanowires was evaluated through degradation of sodium isopropyl xanthate under UV-visible light irradiation. The as-prepared Fe 3+ -doped (BiO) 2 CO 3 nanowires were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) in detail. The results of XRD showed that the crystallinity of (BiO) 2 CO 3 nanowires decreased when Fe 3+ ions were introduced into the solution system. XPS results illustrated that xanthate could be absorbed on the surface of Fe 3+ -doped (BiO) 2 CO 3 nanowires to produce BiS bond at the beginning of the reaction, which could broaden the visible light absorption. FTIR spectra confirmed the formation of SO 4 2- after photocatalytic decomposition of xanthate solution. The Fe 3+ -doped (BiO) 2 CO 3 nanowires showed an enhanced photocatalytic activity for decomposition of xanthate due to the narrower band gap and larger BET surface area, comparing with pure (BiO) 2 CO 3 nanowires. By the results of UV-vis spectra of the solution and FTIR spectra of recycled Fe 3+ -doped (BiO) 2 CO 3 , the xanthate was oxidized completely into CO 2 and SO 4 2- . The photocatalytic degradation process of xanthate followed a pseudo-second-order kinetics model. The mechanism of enhanced photocatalytic activity was proposed as well. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Characterization of ultrathin insulators in CMOS technology: Wearout and failure mechanisms due to processing and operation

    Science.gov (United States)

    Okandan, Murat

    In the CMOS technology the gate dielectric is the most critical layer, as its condition directly dictates the ultimate performance of the devices. In this thesis, the wear-out and failure mechanisms in ultra-thin (around 50A and lower) oxides are investigated. A new degradation phenomenon, quasi-breakdown (or soft-breakdown), and the annealing and stressing behavior of devices after quasi-breakdown are considered in detail. Devices that are in quasi-breakdown continue to operate as switches, but the gate leakage current is two orders of magnitude higher than the leakage in healthy devices and the stressing/annealing behavior of the devices are completely altered. This phenomenon is of utmost interest, since the reduction in SiO2 dielectric thickness has reached its physical limits, and the quasi-breakdown behavior is seen to dominate as a failure mode in this regime. The quasi-breakdown condition can be brought on by stresses during operation or processing. To further study this evolution through stresses and anneals, cyclic current-voltage (I-V) measurement has been further developed and utilized in this thesis. Cyclic IV is a simple and fast, two terminal measurement technique that looks at the transient current flowing in an MOS system during voltage sweeps from accumulation to inversion and back. During these sweeps, carrier trapping/detrapping, generation and recombination are observed. An experimental setup using a fast electrometer and analog to digital conversion (A/D) card and the software for control of the setup and data analysis were also developed to gain further insight into the detailed physics involved. Overall, the crucial aspects of wear-out and quasi-breakdown of ultrathin dielectrics, along with the methods for analyzing this evolution are presented in this thesis.

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

    Directory of Open Access Journals (Sweden)

    G. L. Siscoe

    2009-08-01

    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

  8. Quantum Hamilton mechanics: Hamilton equations of quantum motion, origin of quantum operators, and proof of quantization axiom

    International Nuclear Information System (INIS)

    Yang, C.-D.

    2006-01-01

    This paper gives a thorough investigation on formulating and solving quantum problems by extended analytical mechanics that extends canonical variables to complex domain. With this complex extension, we show that quantum mechanics becomes a part of analytical mechanics and hence can be treated integrally with classical mechanics. Complex canonical variables are governed by Hamilton equations of motion, which can be derived naturally from Schroedinger equation. Using complex canonical variables, a formal proof of the quantization axiom p → p = -ih∇, which is the kernel in constructing quantum-mechanical systems, becomes a one-line corollary of Hamilton mechanics. The derivation of quantum operators from Hamilton mechanics is coordinate independent and thus allows us to derive quantum operators directly under any coordinate system without transforming back to Cartesian coordinates. Besides deriving quantum operators, we also show that the various prominent quantum effects, such as quantization, tunneling, atomic shell structure, Aharonov-Bohm effect, and spin, all have the root in Hamilton mechanics and can be described entirely by Hamilton equations of motion

  9. Advanced operational strategy for the IRIS reactor: Load follow through mechanical shim (MSHIM)

    International Nuclear Information System (INIS)

    Franceschini, Fausto; Petrovic, Bojan

    2008-01-01

    The renaissance of nuclear power brings more attention to advanced reactor designs and their improved performance and flexibility, including their enhanced load follow capability. Reactor control strategy used to perform transients including power changes has impact on the overall control system design. In particular, as the power change is performed within a load follow maneuver, several modifications occur in the core from a neutronic view point: the fuel and moderator temperature change, the xenon concentration and distribution are modified, the power distribution skewed axially, etc. These changes need to be adequately counterbalanced to keep both the core critical and the power distribution acceptable. The traditional approach in PWRs is to compensate for the reactivity change due to the power variation by adjusting the soluble boron concentration and moving a limited number of control rod banks. However, advanced reactors may adopt a different strategy for a variety of reasons. For example, water-cooled reactors that do not use soluble boron in coolant obviously cannot use its adjustment for this purpose. Moreover, Integral Primary System Reactors (IPSRs) using soluble boron, due to their integral design, have a large inventory of primary coolant. Therefore dilution/boration strategy, while in principle an option, becomes expensive for short time changes and leads to large volume of liquid effluent, in particular toward the end of cycle. Therefore, a capability to perform load follow without changing soluble boron concentration is very desirable for a range of reactor designs. International Reactor Innovative and Secure (IRIS) is an advanced medium-size IPSR that has been selected as the reference reactor for the purpose of this study. A capability to perform load follow maneuvers without changing soluble boron concentration has been examined and demonstrated through implementation of the Westinghouse Mechanical Shim (MSHIM) control strategy. A control bank

  10. Research on electricity market operation mechanism and its benefit of demand side participation

    Science.gov (United States)

    Han, Shuai; Yan, Xu; Qin, Li-juan; Lin, Xi-qiao; Zeng, Bo

    2017-08-01

    Demand response plays an important role in maintaining the economic stability of the system, and has the characteristics of high efficiency, low cost, fast response, good environmental benefits and so on. Demand side resource is an important part of electricity market. The research of demand side resources in our country is still in the initial stage, but the opening of the electricity sales side provides a broad prospect for the development of electricity market. This paper summarizes the main types of demand side resources in our country, analyzes the economic principle of demand response from the micro perspective, puts forward some suggestions on the operation mechanism of China’s demand side resources participating in the electricity market under the condition of electricity sales side opening, analyzes the current situation of pricing in the electricity wholesale market and sets up the pricing strategy of the centralized wholesale market with the demand side power supply participating in quotation, which makes the social and economic benefits reach the maximum.

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

    CERN Document Server

    Isozumi, Y; Kishimoto, S

    2002-01-01

    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...

  12. Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism.

    Science.gov (United States)

    Sun, Chencheng; Xiong, Bowen; Pan, Yang; Cui, Hao

    2017-02-01

    Polyaniline (PANI) prepared by chemical oxidation was studied for adsorption removal of tannic acid (TA) from aqueous solution. Batch adsorption studies were carried out under different adsorbent dosages, pH, ionic strength, initial TA concentration and coexisting anions. Solution pH had an important impact on TA adsorption onto PANI with optimal removal in the pH range of 8-11. TA adsorption on PANI at three ionic strength levels (0.02, 0.2 and 2molL -1 NaCl) could be well described by Langmuir model (monolayer adsorption process) and the maximum adsorption capacity was 230, 223 and 1023mgg -1 , respectively. Kinetic data showed that TA adsorption on PANI fitted well with pseudo-second-order model (controlled by chemical process). Among the coexisting anions tested, PO 4 3- significantly inhibited TA adsorption due to the enhancement of repulsive interaction. Continuous flow adsorption studies indicated good flexibility and adaptability of the PANI adsorbent under different flow rates and influent TA concentrations. The mechanism controlling TA adsorption onto PANI under different operating conditions was analyzed with the combination of electrostatic interactions, hydrogen bonding, π-π interactions and Van der Waals interactions. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. 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

    2015-06-01

    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.

  14. Building a Mechanism for the Function of an Innovation-Oriented Machine-Building Enterprise in Operating the Development

    Directory of Open Access Journals (Sweden)

    Boiarynova Кateryna О.

    2017-07-01

    Full Text Available The article is aimed at developing and substantiating a mechanism for the function of an innovation-oriented machine-building enterprise in operating the development in order to increase effectuality in the space of ecosystem of operation and to satisfy the economic interests of development. The article proposes a mechanism for the function of an innovation-oriented machine-building enterprise in operating the development, its structure and building based on a business model; operating the development through responsibility centers; functional transformation of economic interest of actors in the ecosystem of function into the economic interest of enterprise; use of economic-institutional regulators and management technologies. Implementation of the mechanism would ensure the value of enterprise, the ability to manage development with the prolonged satisfaction of the joint economic interest, the ability to operate the economic interest of actors in the ecosystem, and maintenance the development mode in the operating process. Prospect for further research will be development of technologies for implementation of the proposed mechanism in the machine-building enterprises.

  15. Performance Analysis of a Burst Transmission Mechanism Using Microsleep Operation for Green IEEE 802.11 WLANs

    Directory of Open Access Journals (Sweden)

    Raul Palacios-Trujillo

    2017-07-01

    Full Text Available This paper evaluates the performance of a burst transmission mechanism using microsleep operation to support high energy efficiency in IEEE 802.11 Wireless Local Area Networks (WLANs. This mechanism is an implementation of the IEEE 802.11ac Transmission Opportunity Power Save Mode (TXOP PSM. A device using the TXOP PSM-based mechanism can switch to a low-power sleep state for the time that another device transmits a burst of data frames to a third one. This operation is called microsleep and its feasibility strongly depends on the time and energy consumption that a device incurs in the transitions from and to the sleep state. This paper accounts for the impact of these transitions in the derivation of an analytical model to calculate the energy efficiency of the TXOP PSM-based mechanism under network saturation. Results obtained show that the impact of the transition requirements on the feasibility of microsleep operation can be significant depending on the selected system parameters, although it can be reduced by using burst transmissions. When microsleep operation is feasible, the TXOP PSM-based mechanism can improve the energy efficiency of other legacy mechanisms by up to 424% under high traffic loads.

  16. Catalytic hydrogen recombination for nuclear containments

    International Nuclear Information System (INIS)

    Koroll, G.W.; Lau, D.W.P.; Dewit, W.A.; Graham, W.R.C.

    1994-01-01

    Catalytic recombiners appear to be a credible option for hydrogen mitigation in nuclear containments. The passive operation, versatility and ease of back fitting are appealing for existing stations and new designs. Recently, a generation of wet-proofed catalyst materials have been developed at AECL which are highly specific to H 2 -O 2 , are active at ambient temperatures and are being evaluated for containment applications. Two types of catalytic recombiners were evaluated for hydrogen removal in containments based on the AECL catalyst. The first is a catalytic combustor for application in existing air streams such as provided by fans or ventilation systems. The second is an autocatalytic recombiner which uses the enthalpy of reaction to produce natural convective flow over the catalyst elements. Intermediate-scale results obtained in 6 m 3 and 10 m 3 spherical and cylindrical vessels are given to demonstrate self-starting limits, operating limits, removal capacity, scaling parameters, flow resistance, mixing behaviour in the vicinity of an operating recombiner and sensitivity to poisoning, fouling and radiation. (author). 13 refs., 10 figs

  17. Catalytic biomass pyrolysis process

    Science.gov (United States)

    Dayton, David C.; Gupta, Raghubir P.; Turk, Brian S.; Kataria, Atish; Shen, Jian-Ping

    2018-04-17

    Described herein are processes for converting a biomass starting material (such as lignocellulosic materials) into a low oxygen containing, stable liquid intermediate that can be refined to make liquid hydrocarbon fuels. More specifically, the process can be a catalytic biomass pyrolysis process wherein an oxygen removing catalyst is employed in the reactor while the biomass is subjected to pyrolysis conditions. The stream exiting the pyrolysis reactor comprises bio-oil having a low oxygen content, and such stream may be subjected to further steps, such as separation and/or condensation to isolate the bio-oil.

  18. Catalytic reforming methods

    Science.gov (United States)

    Tadd, Andrew R; Schwank, Johannes

    2013-05-14

    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  19. On the definition of the time evolution operator for time-independent Hamiltonians in non-relativistic quantum mechanics

    Science.gov (United States)

    Amaku, Marcos; Coutinho, Francisco A. B.; Masafumi Toyama, F.

    2017-09-01

    The usual definition of the time evolution operator e-i H t /ℏ=∑n=0∞1/n ! (-i/ℏHt ) n , where H is the Hamiltonian of the system, as given in almost every book on quantum mechanics, causes problems in some situations. The operators that appear in quantum mechanics are either bounded or unbounded. Unbounded operators are not defined for all the vectors (wave functions) of the Hilbert space of the system; when applied to some states, they give a non-normalizable state. Therefore, if H is an unbounded operator, the definition in terms of the power series expansion does not make sense because it may diverge or result in a non-normalizable wave function. In this article, we explain why this is so and suggest, as an alternative, another definition used by mathematicians.

  20. 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

    2014-04-02

    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.

  1. SPECIFIC DEGRADATION STRUCTURE FEATURES AND MECHANICAL PROPERTIES OF FURNACE AND HEAT POWER EQUIPMENT ELEMENTS AFTER LONG-TERM OPERATION

    Directory of Open Access Journals (Sweden)

    F. I. Panteleenko

    2012-01-01

    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.

  2. Effect of radioactive radiation on catalytic properties of solid materials

    Energy Technology Data Exchange (ETDEWEB)

    Sokol' skii, D V; Kuzembaev, K K; Kel' man, I V [AN Kazakhskoj SSR, Alma-Ata. Inst. Organicheskogo Kataliza i Ehlektrokhimii

    1977-05-01

    General survey is made of the problem of radiation modification of the action of solid catalysts with respect to the various types of heterogeneous catalytic reactions. Consideration is given to the key mechanisms responsible for radiation damage in the interaction of high-energy radiation with a solid body. The effect of ionizing radiation on the adsorption capacity and catalytic activity of solid bodies is discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Preuss, S.

    2007-11-15

    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.)

  4. The likelihood of failures in the operation of the mechanism of movement of a cargo truck electrical hook bridge crane

    Directory of Open Access Journals (Sweden)

    Ritenman I.L.

    2018-03-01

    Full Text Available Given the application of the methods of analysis of types and consequences of failures (FMEA analysis to assess the technical risk of occurrence of emergency situations during the operation of the lifting mechanism electrical hook bridge crane. The technique allows to identify the limiting elements and to determine the significance of effects in the design of the lifting mechanism, to develop measures to reduce the risk of the occurrence of an emergency.

  5. The likelihood of failures in the operation of the mechanism of movement of a cargo truck electrical hook bridge crane

    Directory of Open Access Journals (Sweden)

    Ritenman I.L.

    2017-12-01

    Full Text Available Given the application of the methods of analysis of types and consequences of failures (FMEA analysis to assess the technical risk of occurrence of emergency situations during the operation of the lifting mechanism electrical hook bridge crane. The technique allows to identify the limiting elements and to determine the significance of effects in the design of the lifting mechanism, to develop measures to reduce the risk of the occurrence of an emergency.

  6. Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

    Science.gov (United States)

    Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

    2010-02-05

    Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

  7. Catalytic pleat filter bags for combined particulate separation and nitrogen oxides removal from flue gas streams

    International Nuclear Information System (INIS)

    Park, Young Ok; Choi, Ho Kyung

    2010-01-01

    The development of a high temperature catalytically active pleated filter bag with hybrid filter equipment for the combined removal of particles and nitrogen oxides from flue gas streams is presented. A special catalyst load in stainless steel mesh cartridge with a high temperature pleated filter bag followed by optimized catalytic activation was developed to reach the required nitrogen oxides levels and to maintain the higher collection efficiencies. The catalytic properties of the developed high temperature filter bags with hybrid filter equipment were studied and demonstrated in a pilot scale test rig and a demonstration plant using commercial scale of high temperature catalytic pleated filter bags. The performance of the catalytic pleated filter bags were tested under different operating conditions, such as filtration velocity and operating temperature. Moreover, the cleaning efficiency and residual pressure drop of the catalyst loaded cartridges in pleated filter bags were tested. As result of theses studies, the optimum operating conditions for the catalytic pleated filter bags are determined. (author)

  8. Performance simulations of catalytic converters during the Federal Test Procedure

    Energy Technology Data Exchange (ETDEWEB)

    Shen, H.; Shamim, T.; Sengupta, S.; Son, S.; Adamczyk, A.A.

    1999-07-01

    A numerical study is carried out to predict the tailpipe emissions and emission conversion efficiencies of unburned hydrocarbon, nitrogen oxide and carbon monoxide flowing through a catalytic converter during the Federal Test Procedure (FTP). The model considers the effect of heat transfer in the catalytic converter, coupled with catalyst chemical kinetics, including an oxygen storage mechanism. The resulting governing equations based on the conservation of mass and energy are solved by a tridiagonal matrix algorithm (TDMA) with a successive line under relaxation method. The numerical scheme for this non-linear problem is found to have good convergence efficiency. The simulation for the complete FTP cycle is accomplished in less than fifteen minutes on a desktop personal computer. A 13-step reaction mechanism plus a nine-step O{sub 2} storage mechanism is used to simulate the chemical kinetics. The energy equations include the heat loss due to conduction and convection plus the energy liberated by chemical reactions. The effect of radiation is assumed to be negligible and is not considered. The results of the numerical model for both the instantaneous and accumulated emissions are found to be in good agreement with experimental measurements. The conversion efficiencies of HC, CO and NO as predicted by the model are found to be within 5% of those dynamic measurements, and calculated results of accumulated HC, CO and NO{sub x} are in fair agreement with experimental measurements. The transient measurements are also used to check the robustness of the numerical model. The model is found to be robust and hence can simulate various operating conditions of engine output to the converter.

  9. Low and medium heating value coal gas catalytic combustor characterization

    Science.gov (United States)

    Schwab, J. A.

    1982-01-01

    Catalytic combustion with both low and medium heating value coal gases obtained from an operating gasifier was demonstrated. A practical operating range for efficient operation was determined, and also to identify potential problem areas were identified for consideration during stationary gas turbine engine design. The test rig consists of fuel injectors, a fuel-air premixing section, a catalytic reactor with thermocouple instrumentation and a single point, water cooled sample probe. The test rig included inlet and outlet transition pieces and was designed for installation into an existing test loop.

  10. Structural and In Vivo Studies on Trehalose-6-Phosphate Synthase from Pathogenic Fungi Provide Insights into Its Catalytic Mechanism, Biological Necessity, and Potential for Novel Antifungal Drug Design

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Yi; Tenor, Jennifer L.; Toffaletti, Dena L.; Maskarinec, Stacey A.; Liu, Jiuyu; Lee, Richard E.; Perfect, John R.; Brennan, Richard G.; Hendrickson, Wayne A.

    2017-07-25

    ABSTRACT

    The disaccharide trehalose is critical to the survival of pathogenic fungi in their human host. Trehalose-6-phosphate synthase (Tps1) catalyzes the first step of trehalose biosynthesis in fungi. Here, we report the first structures of eukaryotic Tps1s in complex with substrates or substrate analogues. The overall structures of Tps1 fromCandida albicansandAspergillus fumigatusare essentially identical and reveal N- and C-terminal Rossmann fold domains that form the glucose-6-phosphate and UDP-glucose substrate binding sites, respectively. These Tps1 structures with substrates or substrate analogues reveal key residues involved in recognition and catalysis. Disruption of these key residues severely impaired Tps1 enzymatic activity. Subsequent cellular analyses also highlight the enzymatic function of Tps1 in thermotolerance, yeast-hypha transition, and biofilm development. These results suggest that Tps1 enzymatic functionality is essential for the fungal stress response and virulence. Furthermore, structures of Tps1 in complex with the nonhydrolyzable inhibitor, validoxylamine A, visualize the transition state and support an internal return-like catalytic mechanism that is generalizable to other GT-B-fold retaining glycosyltransferases. Collectively, our results depict key Tps1-substrate interactions, unveil the enzymatic mechanism of these fungal proteins, and pave the way for high-throughput inhibitor screening buttressed and guided by the current structures and those of high-affinity ligand-Tps1 complexes.

    IMPORTANCEInvasive fungal diseases have emerged as major threats, resulting in more than 1.5 million deaths annually worldwide. This epidemic has been further complicated by increasing resistance to all major classes of antifungal drugs in the clinic. Trehalose biosynthesis is essential for the fungal stress response and virulence. Critically, this biosynthetic pathway is absent in

  11. The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study

    DEFF Research Database (Denmark)

    Fristrup, Peter; Kreis, Michael; Palmelund, Anders

    2008-01-01

    that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)-H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement...

  12. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    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 ...

  13. Substantial-Motivational Mechanism for Substantiation of Tolling Operations in Conditions of the European Integration

    OpenAIRE

    Melnyk Olga G; Kots Iryna I.

    2016-01-01

    The article is concerned with conceptualization of substance, distinguishing characteristics and motives of the implementation of tolling operations in conditions of the European integration. The study, based on the systematization and analysis of existing scientific approaches to definition of essence of tolling and tolling operations, has disclosed the dominating poli-positionality and ambiguity in this area. Economical autonomy of tolling operations has been determined, t...

  14. Buckling resistance calculation of Guide Thimbles for the mechanical design of fuel assembly type PWR under normal reactor operating conditions

    International Nuclear Information System (INIS)

    Cruz, C.B.L.

    1990-01-01

    The calculations demonstrate the fulfillment of one of the mechanical design criteria for the Fuel Assembly Structure under normal reactor operating conditions. The calculations of stresses in the Guide Thimbles are performed with the aid of the program ANSYS. This paper contains program parameters and modelling of a typical Fuel Assembly for a Reactor similar to ANGRA II. (author)

  15. Non-thermal plasmas for non-catalytic and catalytic VOC abatement

    International Nuclear Information System (INIS)

    Vandenbroucke, Arne M.; Morent, Rino; De Geyter, Nathalie; Leys, Christophe

    2011-01-01

    Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

  16. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    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.

  17. A charged particle interacting with a stationary magnetic monopole: quantum mechanics based on the kinetic momentum operators

    International Nuclear Information System (INIS)

    Raković, Milun J

    2011-01-01

    The standard quantum mechanical description of the motion of a charged particle in the field of a stationary magnetic monopole is notorious for the presence of unnatural singularities in the Hamiltonian operator originating in the vector potential A(r) used to describe the magnetic field of the monopole. In this paper, an elementary quantum mechanical formulation of the problem which involves only the physically observable field B(r) is presented. This is achieved by treating as a fundamental observable of the charged particle its kinetic momentum instead of the linear momentum p. An irreducible representation of the fundamental commutation relations involving the operators r-hat. It is shown that the existence of an irreducible representation requires that Dirac’s charge quantization condition is satisfied. Also, it is demonstrated that, from the quantum mechanical perspective, the singularities (appearing when the vector potential is introduced) are in fact properties of coordinate representations of the fundamental commutation relations. (paper)

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

    Directory of Open Access Journals (Sweden)

    B. Thamaraikannan

    2014-01-01

    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.

  19. COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER; FINAL

    International Nuclear Information System (INIS)

    Phillip E. Savage

    1999-01-01

    phenoxy radicals, which then react in the fluid phase by the same mechanism operative for non-catalytic SCWO of phenol. The rates of phenol disappearance and CO(sub 2) formation are sensitive to the phenol and O(sub 2) concentrations, but independent of the water density. Power-law rate expressions were developed to correlate the catalytic kinetics. The catalytic kinetics were also consistent with a Langmuir-Hinshelwood rate law derived from a dual-site mechanism comprising the following steps: reversible adsorption of phenol on one type of catalytic site, reversible dissociative adsorption of oxygen on a different type of site, and irreversible, rate-determining surface reaction between adsorbed phenol and adsorbed oxygen

  20. Mechanical performance of hemp fiber polypropylene composites at different operating temperatures

    Science.gov (United States)

    Mehdi Tajvidi; Nazanin Motie; Ghonche Rassam; Robert H. Falk; Colin Felton

    2010-01-01

    In order to quantify the effect of temperature on the mechanical properties of hemp fiber polypropylene composites, formulations containing 25% and 40% (by weight) hemp fiber were produced and tested at three representative temperatures of 256, 296, and 336 K. Flexural, tensile, and impact tests, as well as dynamic mechanical analysis, were performed and the reduction...

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

    Directory of Open Access Journals (Sweden)

    Božek Pavol

    2014-08-01

    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.

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

    Science.gov (United States)

    Božek, Pavol; Turygin, Yuri

    2014-08-01

    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. Catalytic hydrotreatment of refinery waste

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The object of the project is to produce liquid hydrocarbons by the catalytic hydroprocessing of solid refinery wastes (hard pitches) in order to improve the profitability of deep conversion processes and reduce the excess production of heavy fuels. The project was mostly carried out on the ASVAHL demonstration platform site, at Solaize, and hard pitches were produced primarily by deasphalting of atmospheric or vacuum distillation residues. The project includes two experimental phases and an economic evaluation study phase. In phase 1, two granular catalysts were used to transform pitch into standard low sulphur fuel oil: a continuously moving bed, with demetallation and conversion catalyst; a fixed bed, with hydrorefining catalyst. In phase 2 of the project, it was proven that a hydrotreatment process using a finely dispersed catalyst in the feedstock, can, under realistic operating conditions, transform with goods yields hard pitch into distillates that can be refined through standard methods. In phase 3 of the project, it was shown that the economics of such processes are tightly linked to the price differential between white and black oil products, which is expected to increase in the future. Furthermore, the evolution of environmental constraints will impel the use of such methods, thus avoiding the coproduction of polluting solid residues.

  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: pengxb@ipp.ac.cn [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)

    2016-04-15

    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. Thermo-mechanical analysis of a user filter assembly for undulator/wiggler operations at the Advanced Photon Source

    International Nuclear Information System (INIS)

    Nian, H.L.T.; Kuzay, T.M.; Collins, J.; Shu, D.; Benson, C.; Dejus, R.

    1996-01-01

    This paper reports a thermo-mechanical study of a beamline filter (user filter) for undulator/wiggler operations. It is deployed in conjunction with the current commissioning window assembly on the APS insertion device (ID) front ends. The beamline filter at the Advanced Photon Source (APS) will eventually be used in windowless operations also. Hence survival and reasonable life expectancy of the filters under intense insertion device (ID) heat flu are crucial to the beamline operations. To accommodate various user requirements, the filter is configured to be a multi-choice type and smart to allow only those filter combinations that will be safe to operate with a given ring current and beamline insertion device gap. However, this paper addresses only the thermo-mechanical analysis of individual filter integrity and safety in all combinations possible. The current filter design is configured to have four filter frames in a cascade with each frame holding five filters. This allows a potential 625 total filter combinations. Thermal analysis for all of these combinations becomes a mammoth task considering the desired choices for filter materials (pyrolitic graphite and metallic filters), filter thicknesses, undulator gaps, and the beam currents. The paper addresses how this difficult task has been reduced to a reasonable effort and computational level. Results from thermo-mechanical analyses of the filter combinations are presented both in tabular and graphical format

  6. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis

    International Nuclear Information System (INIS)

    Greenwood, Alexander I.; Rogals, Monique J.; De, Soumya; Lu, Kun Ping; Kovrigin, Evgenii L.; Nicholson, Linda K.

    2011-01-01

    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 cat cis and apparent Michaelis constants, K M 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 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 k cat cis , k cat trans , K D cis , and K D trans 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.

  7. Model-based analysis of the effect of different operating conditions on fouling mechanisms in a membrane bioreactor.

    Science.gov (United States)

    Sabia, Gianpaolo; Ferraris, Marco; Spagni, Alessandro

    2016-01-01

    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.

  8. Detection circuit of solenoid valve operation and control rod drive mechanism utilizing the circuit

    International Nuclear Information System (INIS)

    Ono, Takehiko.

    1976-01-01

    Object: To detect the operation of a plunger and detect opening and closing operations of a solenoid valve driving device due to change in impedance of a coil for driving the solenoid valve to judge normality and abnormality of the solenoid valve, thereby increasing reliance and safety of drive and control apparatus of control rods. Structure: An arrangement comprises a drive and operation detector section wherein the operation of a solenoid driving device for controlling power supply to a coil for driving the solenoid valve to control opening and closing of the solenoid valve, and a plunger operation detector section for detecting change in impedance of the drive coil to detect that the plunger of the solenoid valve is either in the opening direction or closing direction, whereby a predetermined low voltage such as not to activate the solenoid valve even when the solenoid valve is open or closed is applied to detect a current flowing into the coil at that time, thus detecting an operating state of the plunger. (Yoshino, Y.)

  9. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    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

  10. Effectiveness and efficiency of the two trolley system as an infection control mechanism in the operating theatre.

    Science.gov (United States)

    Tuisawana, Viliame

    2009-11-01

    A good infection control manager understands the need to prevent a complete cycle of infection. The Infection Control Working Group Manual of Fiji, emphasised that the Cycle of Infection is the series of stage in which infection is spread. Operating theatres have infection control protocols. Most equipments and instruments used in operating theatre circulate within the theatre. The theatre trolleys are a main component in managing an operating theatre but the least recognised. This paper reviews the effectiveness and efficiency of the current two-trolley system as an infection control mechanism in theatre. The paper will discuss infection control using the current trolley system in relation to the layout of Labasa Hospital operating theatre, human resource, equipment standard and random swab results. The following are random swab results of theatre equipments taken by the Infection Control Nurse from 2006 to 2008. The Labasa Hospital Infection Committee have discouraged random swab sample from mid 2008 based on new guidelines on infection control. The two trolley system, in which an allocated outside trolley transports patients from the ward to a semi-sterile area in theatre. The inside trolley which transports the patient to the operating table. The two trolley system means more trolleys, extra staffs for lifting, additional handling of very sick patients, congestion and delay in taking patients to operating table in theatres should be considered. The one-trolley system in theatre greatly reduces the chances of manually lifting patients, thus reducing the risk of patient injury from fall and risk of back injuries to nurses. There are other evident based practices which can compliment the one trolley system for an effective infection control mechanism in theatres. The Fiji Infection Control Manual (2002) emphases the importance of regularly cleaning the environment and equipments in theatre but there is never a mention about using a two trolley system as an

  11. Uranium mine venting during operation of self-propelled Diesel engine mechanisms

    International Nuclear Information System (INIS)

    Hemer, M.

    1983-01-01

    A draft directive has been issued for the ventilation of uranium mines which takes into consideration the concentration of radon daughter products, radon volume activity as well as the concentration of harmful wastes emitted by the Diesel engines of mining mechanisms. The mathematical relations are given for the calculation of the required amount of pure mine winds. Also listed are the technical requirements for ventilation, dust emission and the control and maintenance of mining mechanisms. (M.D.)

  12. A review of the Z2-FET 1T-DRAM memory: Operation mechanisms and key parameters

    Science.gov (United States)

    Cristoloveanu, S.; Lee, K. H.; Parihar, M. S.; El Dirani, H.; Lacord, J.; Martinie, S.; Le Royer, C.; Barbe, J.-Ch.; Mescot, X.; Fonteneau, P.; Galy, Ph.; Gamiz, F.; Navarro, C.; Cheng, B.; Duan, M.; Adamu-Lema, F.; Asenov, A.; Taur, Y.; Xu, Y.; Kim, Y.-T.; Wan, J.; Bawedin, M.

    2018-05-01

    The band-modulation and sharp-switching mechanisms in Z2-FET device operated as a capacitorless 1T-DRAM memory are reviewed. The main parameters that govern the memory performance are discussed based on detailed experiments and simulations. This 1T-DRAM memory does not suffer from super-coupling effect and can be integrated in sub-10 nm thick SOI films. It offers low leakage current, high current margin, long retention, low operating voltage especially for programming, and high speed. The Z2-FET is suitable for embedded memory applications.

  13. 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)

    2015-06-30

    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.

  14. Catalytic applications of bio-inspired nanomaterials

    Science.gov (United States)

    Pacardo, Dennis Kien Balaong

    The biomimetic synthesis of Pd nanoparticles was presented using the Pd4 peptide, TSNAVHPTLRHL, isolated from combinatorial phage display library. Using this approach, nearly monodisperse and spherical Pd nanoparticles were generated with an average diameter of 1.9 +/- 0.4 nm. The peptide-based nanocatalyst were employed in the Stille coupling reaction under energy-efficient and environmentally friendly reaction conditions of aqueous solvent, room temperature and very low catalyst loading. To this end, the Pd nanocatalyst generated high turnover frequency (TOF) value and quantitative yields using ≥ 0.005 mol% Pd as well as catalytic activities with different aryl halides containing electron-withdrawing and electron-donating groups. The Pd4-capped Pd nanoparticles followed the atom-leaching mechanism and were found to be selective with respect to substrate identity. On the other hand, the naturally-occurring R5 peptide (SSKKSGSYSGSKGSKRRIL) was employed in the synthesis of biotemplated Pd nanomaterials which showed morphological changes as a function of Pd:peptide ratio. TOF analysis for hydrogenation of olefinic alcohols showed similar catalytic activity regardless of nanomorphology. Determination of catalytic properties of these bio-inspired nanomaterials are important as they serve as model system for alternative green catalyst with applications in industrially important transformations.

  15. 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)

    2013-11-01

    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.)

  16. Some applicationS of non-Hermitian operators in quantum mechanics and quantum field theory

    International Nuclear Information System (INIS)

    Recami, E.; Rodrigues, W.A. Jr.; Smrz, P.

    1983-01-01

    Due to the possibility of rephrasing it in terms of Lie-admissible algebras, some work done in the past in collaboration with A., Agodi, M., Baldo and V.S., Olkhovsky is here reported. Such work led to the introduction of non-Hermitian operators in (classical and relativistic) quantum theory. In particular: (i) the association of unstable states (decaying 'Resonances') with the eigenvectors of non-Hermitian hamiltonians; (ii) the problem of the four position operators for relativistic spin-zero particles are dealth with

  17. An Analysis of Modern Japanese Think Tank Prototype——SMR Investigation Organization and Its Operation Mechanism

    Directory of Open Access Journals (Sweden)

    Huang Wenyue

    2017-12-01

    Full Text Available [Purpose/significance] Through an analysis of SMR investigatory apparatus business and its operation mechanism, this paper discusses the development model of the investigation organ, the South Manchuria Railway think tank, and reveals the militarism influence on the early Japanese think tank development. [Method/process] This paper combed the SMR’s important survey agencies development pattern by the case study and literature survey and also discussed the key mechanism of operation system and organization characteristics. The evaluation of reports directed by the SMR provided references. [Result/conclusion] The SMR, as a colonial and aggressive policy tool, its surveys were done for the government and military authorities. With independent sources of information, the use of network intelligence structure and the combination of resident literature collection with field investigation, the collection of professional analysis personnel, the SMR investigation organization completes the decision-making through the scientific method and has reference value.

  18. 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)

    2016-07-01

    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.

  19. 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)

    2016-03-15

    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.

  20. Increasing nuclear safety and operational reliability by upgrading the charging pump mechanical sealing system

    International Nuclear Information System (INIS)

    Loenhout, Gerard van; Nilsson, Peter; Jehander, Magnus

    2016-01-01

    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.

  1. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    126, No. 2, March 2014, pp. 341–351. c Indian Academy of Sciences. ... enhancement was realized by catalyst design, appropriate choice of reactor, better injection and .... Gas–liquid and liquid–solid transport processes in catalytic reactors.5.

  2. Estimation of Lifetime Duration for a Lever Pin of Runner Blade Operating Mechanism using a Graphic – analytic Method

    Directory of Open Access Journals (Sweden)

    Ana-Maria Budai

    2015-09-01

    Full Text Available In this paper are presented a graphic - analytic method that can be used to estimate the fatigue lifetime duration for an operating mechanism lever pin to a Kaplan turbine. The presented calculus algorithm is adapted from the one used by Fuji Electric to made strength calculus in order to refurbish a Romanian hydropower plant, equipped with a Kaplan turbine. The graphic part includes a 3D fatigue diagram for rotating bending stress designed by Fuji Electric specialists.

  3. Dust captures effectiveness of scrubber systems on mechanical miners operating in larger roadways.

    CSIR Research Space (South Africa)

    Hole, BJ

    1998-03-01

    Full Text Available The project was directed towards bord and pillar working by mechanised miners operating in larger section roadways, where the problem of scrubber capture tends to be greatest owing to the limited size of the zone of influence around exhaust...

  4. Concentrating solar power plant investment and operation decisions under different price and support mechanisms

    International Nuclear Information System (INIS)

    Kost, Christoph; Flath, Christoph M.; Möst, Dominik

    2013-01-01

    The dispatch opportunities provided by storage-enhanced Concentrating Solar Power (CSP) plants have direct implications on the investment decisions as not only nameplate capacity but also the storage capacity and the solar multiple play a crucial role for the viability of the plant investment. By integrating additional technical aspects and operation strategies, this paper extends the optimization model proposed by Madaeni et al., How Thermal Energy Storage Enhances the Economic Viability of Concentrating Solar Power. Using a mixed integer maximization approach the paper yields both the optimal layout decision and the operation of CSP plants. Subsequently, the economic value of CSP storage is analyzed via energy modeling of a Spanish plant location under the respective wholesale market prices as well as the local feed-in tariff. The analysis shows that investment incentives for CSP plants with storage need to appropriately account for the interdependency between the price incentives and the plant operating strategy. As the resulting revenue characteristics influence the optimal size of solar field and storage differing operating strategies also give rise to differing optimal plant layouts. Most noteworthy, the current Spanish support scheme offers only limited incentives for larger thermal storage capacity. - Highlights: • Dispatch opportunities of CSP have direct implications on both investment and operational decisions. • Valuation approach with a single mixed integer maximization problem. • Profitability of CSP plants under the premium feed-in tariff in Spain was assessed. • Layout decision and storage size are influenced by remuneration scheme. • Discuss alternative remuneration schemes for “dispatchable” RE technologies

  5. Extending a real-time operating system with a mechanism for criticality-level changes

    NARCIS (Netherlands)

    Gupta, T.

    2015-01-01

    Systems robustness, cost reduction and certification play an important role in the automotive domain. If there is a fault, e.g. task overshooting its allocated execution time, sufficient mechanisms should be available to safeguard the system against those. Applications of different criticalities

  6. USE OF THE THERMOVISION TO INCREASE SAFETY IN OPERATING OF THE MECHANICAL SYSTEMS

    Directory of Open Access Journals (Sweden)

    Marin NEACSA

    2013-05-01

    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

  7. IMPLEMENTATION OF MULTIAGENT REINFORCEMENT LEARNING MECHANISM FOR OPTIMAL ISLANDING OPERATION OF DISTRIBUTION NETWORK

    DEFF Research Database (Denmark)

    Saleem, Arshad; Lind, Morten

    2008-01-01

    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...

  8. Mechanical testing - designers need: a view at component design and operations stages

    International Nuclear Information System (INIS)

    Shrivastava, S.K.

    2007-01-01

    Mechanical design of any component requires knowledge of values of various material properties which designer(s) make(s) use in designing the component. In design of nuclear power plant components, it assumes even greater importance in view of degree of precision and accuracy with which the values of various properties are required. This is in turn demands, high accuracy in testing machines and measuring methods. In this paper, attempt has been made to bring out that even from conventional tension test, how designer today looks for availability of engineering stress-strain diagram preferably through digitally acquired data points during the test from which he can derive values of Ramberg-Osgood parameters for use in fracture mechanics based analysis. Attempt has been also made to provide account of some of important fracture mechanics related tests which have been evolved in last two decades and designers need for evolution of simple test techniques to measure many more fracture mechanics related parameters as well as cater to constraints such as shape and size of material available from the components. Nuclear power plant has been primarily kept in view and ASME. Section III NB, ASME Section XI and relevant ASTM Standards have been taken as standard references. Further pressure retaining materials of pressure vessels/Reactor Pressure Vessels have been kept in view. (author)

  9. Plasma-catalytic reforming of liquid hydrocarbons

    International Nuclear Information System (INIS)

    Nedybaliuk, O.A.; Chernyak, V.Ya; Kolgan, V.V.; Iukhymenko, V.V.; Solomenko, O.V.; Fedirchyk, I.I.; Martysh, E.V.; Demchina, V.P.; Klochok, N.V.; Dragnev, S.V.

    2015-01-01

    The series of experiments studying the plasma-catalytic reforming of liquid hydrocarbons was carried out. The dynamic plasma-liquid system based on a low-power rotating gliding arc with solid electrodes was used for the investigation of liquid hydrocarbons reforming process. Conversion was done via partial oxidation. A part of oxidant flow was activated by the discharge. Synthesis-gas composition was analysed by means of mass-spectrometry and gas-chromatography. A standard boiler, which operates on natural gas and LPG, was used for the burning of synthesis-gas

  10. The mechanism of specific capacitance improvement of supercapacitors based on MnO{sub 2} at an elevated operating temperature

    Energy Technology Data Exchange (ETDEWEB)

    Xu Juliang; Li Zhao; Han Dong; Deng Bo; Li Jin; Jiang Yiming, E-mail: corrosion@fudan.edu.cn

    2012-07-01

    Amorphous nanostructured MnO{sub 2} film was anodically deposited onto economical duplex stainless steel substrate. The obtained MnO{sub 2} film was characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy for microstructural, morphological, and compositional studies. The capacitive behavior was systematically investigated by cyclic voltammetry, charge-discharge cycling and electrochemical impedance spectroscopy (EIS) in 1 M Na{sub 2}SO{sub 4} electrolyte at different operating temperatures ranging from 20 to 60 Degree-Sign C. The specific capacitance (SC) was improved with an increase of operating temperature, and the highest SC of 398 F/g was achieved at a scan rate of 10 mV/s and operating temperature of 60 Degree-Sign C. The mechanism of SC improvement at elevated operating temperature was investigated using EIS. With an increase of operating temperature, the conductivity of electrolyte was improved, and the charge-transfer resistance (R{sub ct}) was decreased. The temperature dependence of 1/R{sub ct} follows an Arrhenius equation. The MnO{sub 2} film was electrochemically activated at 60 Degree-Sign C due to the formation of Na{sub y}MnO{sub 2} after discharging. - Highlights: Black-Right-Pointing-Pointer MnO{sub 2} was anodically deposited onto duplex stainless steel substrate. Black-Right-Pointing-Pointer The effect of operating temperature on the performance of MnO{sub 2} was studied. Black-Right-Pointing-Pointer The mechanism of specific capacitance improvement was investigated.

  11. 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

    2016-01-01

    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.

  12. Catalytic partial oxidation of pyrolysis oils

    Science.gov (United States)

    Rennard, David Carl

    2009-12-01

    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

  13. 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)

    2004-07-01

    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)

  14. PARAMETER DETERMINATION FOR ADDITIONAL OPERATING FORCE MECHANISM IN DEVICE FOR PNEUMO-CENTRIFUGAL MACHINING OF BALL-SHAPED WORKPIECES

    Directory of Open Access Journals (Sweden)

    A. A. Sukhotsky

    2014-01-01

    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

  15. A Novel Operant-based Behavioral Assay of Mechanical Allodynia in the Orofacial Region of Rats

    Science.gov (United States)

    Rohrs, Eric L.; Kloefkorn, Heidi E.; Lakes, Emily H.; Jacobs, Brittany Y.; Neubert, John K.; Caudle, Robert M.; Allen, Kyle D.

    2015-01-01

    Background Detecting behaviors related to orofacial pain in rodent models often relies on subjective investigator grades or methods that place the animal in a stressful environment. In this study, an operant-based behavioral assay is presented for the assessment of orofacial tactile sensitivity in the rat. New Methods In the testing chamber, rats are provided access to a sweetened condensed milk bottle; however, a 360° array of stainless steel wire loops impedes access. To receive the reward, an animal must engage the wires across the orofacial region. Contact with the bottle triggers a motor, requiring the animal to accept increasing pressure on the face during the test. To evaluate this approach, tolerated bottle distance was measured for 10 hairless Sprague-Dawley rats at baseline and 30 minutes after application of capsaicin cream (0.1%) to the face. The experiment was repeated to evaluate the ability of morphine to reverse this effect. Results The application of capsaicin cream reduced tolerated bottle distance measures relative to baseline (porofacial sensitivity is presented using an operant system. Conclusions This operant device allows for consistent measurement of heightened tactile sensitivity in the orofacial regions of the rat. PMID:25823368

  16. Operating Mechanisms of Mesoscopic Perovskite Solar Cells through Impedance Spectroscopy and J-V Modeling.

    Science.gov (United States)

    Zarazúa, Isaac; Sidhik, Siraj; Lopéz-Luke, Tzarara; Esparza, Diego; De la Rosa, Elder; Reyes-Gomez, Juan; Mora-Seró, Iván; Garcia-Belmonte, Germà

    2017-12-21

    The performance of perovskite solar cell (PSC) is highly sensitive to deposition conditions, the substrate, humidity, and the efficiency of solvent extraction. However, the physical mechanism involved in the observed changes of efficiency with different deposition conditions has not been elucidated yet. In this work, PSCs were fabricated by the antisolvent deposition (AD) and recently proposed air-extraction antisolvent (AAD) process. Impedance analysis and J-V curve fitting were used to analyze the photogeneration, charge transportation, recombination, and leakage properties of PSCs. It can be elucidated that the improvement in morphology of perovskite film promoted by AAD method leads to increase in light absorption, reduction in recombination sites, and interstitial defects, thus enhancing the short-circuit current density, open-circuit voltage, and fill factor. This study will open up doors for further improvement of device and help in understanding its physical mechanism and its relation to the deposition methods.

  17. Heterogeneous-catalytic redox reactions in nitrate - formate systems

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

    2000-01-01

    It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

  18. 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)

    2006-05-15

    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.

  19. Modeling operation of mechanism of holistic management of technological processes at enterprise

    Science.gov (United States)

    Igorevich Shanin, Igor; Aleksandrovna Boris, Olga

    2018-03-01

    Enterprises applying modeling and technological process management approaches represent a sector of a new innovative economic system. First of all, they are innovators using innovative proposals and various resources to solve practical problems. Their work leads to balanced positive technological changes. In other words, they constitute industrial entrepreneurship with innovative goals and vice versa - innovative entrepreneurship with industrial objectives. It should be noted that the mechanism of holistic management of technological processes at the enterprise combines a traditional industrial organization of production, an innovative and technological enterprise. The enterprise borrows industrial targets from the latter one, an innovative component - from innovative activity and entrepreneurial approaches to holistic management - from a commercial firm.

  20. Access Control Mechanism for Blog Posts with Fine-Grained Ability Using Simple Operations

    Institute of Scientific and Technical Information of China (English)

    Yi-Hui Chen; Chi-Shiang Chan; Yuan-Yu Tsai

    2017-01-01

    Access control enables the owners to assign different users different permissions to see different views. The current blog system does not support fine-grained authorization. That is, the bloggers disallow to just assign partial contents of the blog posts (i.e., a paragraph or several paragraphs) to readers. The management cost is no doubt to be significantly increased while handling the authorizations on the huge amount of blog articles. In this paper, we propose a scheme for supporting a fine-grained access control mechanism on blog articles. The advantage is that bloggers are able to authorize partial contents of blog posts to different users or groups of users.

  1. Glutamatergic mechanisms for speed control and network operation in the rodent locomotor CPG

    DEFF Research Database (Denmark)

    Talpalar, Adolfo E.; Kiehn, Ole

    2010-01-01

    in mammals have produced conflicting results regarding the necessity and role of the different ionotropic glutamate receptors (GluRs) in the CPG function. Here, we use electrophysiological and pharmacological techniques in the in vitro neonatal mouse lumbar spinal cord to investigate the role of a broad...... mechanisms acting at various network levels. AMPA and kainate receptors are necessary for generating the highest locomotor frequencies. For coordination, NMDARs are more important than non-NMDARs for conveying the rhythmic signal from the network to the motor neurons during long-lasting and steady locomotor...

  2. QUALITY MANAGEMENT OPERATION MECHANISMS FOR THE PROTECTION OF INFORMATION IN THE INFO-COMMUNICATION SYSTEMS

    Directory of Open Access Journals (Sweden)

    S. V. Belokurov

    2015-01-01

    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.

  3. Reconstitution of a eukaryotic replisome reveals suppression mechanisms that define leading/lagging strand operation

    Science.gov (United States)

    Georgescu, Roxana E; Schauer, Grant D; Yao, Nina Y; Langston, Lance D; Yurieva, Olga; Zhang, Dan; Finkelstein, Jeff; O'Donnell, Mike E

    2015-01-01

    We have reconstituted a eukaryotic leading/lagging strand replisome comprising 31 distinct polypeptides. This study identifies a process unprecedented in bacterial replisomes. While bacteria and phage simply recruit polymerases to the fork, we find that suppression mechanisms are used to position the distinct eukaryotic polymerases on their respective strands. Hence, Pol ε is active with CMG on the leading strand, but it is unable to function on the lagging strand, even when Pol δ is not present. Conversely, Pol δ-PCNA is the only enzyme capable of extending Okazaki fragments in the presence of Pols ε and α. We have shown earlier that Pol δ-PCNA is suppressed on the leading strand with CMG (Georgescu et al., 2014). We propose that CMG, the 11-subunit helicase, is responsible for one or both of these suppression mechanisms that spatially control polymerase occupancy at the fork. DOI: http://dx.doi.org/10.7554/eLife.04988.001 PMID:25871847

  4. Surface studies of thermionic cathodes and the mechanism of operation of an impregnated tungsten cathode

    International Nuclear Information System (INIS)

    Forman, R.

    1976-09-01

    The surface properties of conventional impregnated cathodes were investigated by the use of Auger spectroscopy and work function measurements, and these were compared with a synthesized barium- or barium oxide coated tungsten surface. The barium- and barium oxide coated surfaces were prepared by evaporating barium onto a tungsten surface that can be heated to elevated temperatures. Multilayer or monolayer coverages can be investigated using this technique. The results of this study show that the surface of an impregnated tungsten cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on partially oxidized tungsten, using the criteria of identical Auger patterns and work functions. Desorption measurements of barium from a tungsten surface were also made. These results in conjunction with Auger and work function data were interpreted to show that throughout most of its life an impregnated cathode operating in the range of 1100 C has a partial monolayer rather than a monolayer of barium on its surface

  5. The design, fabrication and operation of the mechanical systems for the Neutral Beam Engineering Test Facility

    International Nuclear Information System (INIS)

    Patterson, J.A.; Fong, M.; Koehler, G.W.; Low, W.; Purgalis, P.; Wells, R.P.

    1983-01-01

    The Neutral Beam Engineering Test Facility (NBETF) at the Lawrence Berkeley Laboratory (LBL) is a National Test Facility used to develop long pulse Neutral Beam Sources. The Facility will test sources up to 120 keV, 50 A, with 30 s beam-on times with a 10% duty factor. For this application, an actively cooled beam dump is required and one has been constructed capable of dissipating a wide range of power density profiles. The flexibility of the design is achieved by utilizing a standard modular panel design which is incorporated into a moveable support structure comprised of eight separately controllable manipulator assemblies. The thermal hydraulic design of the panels permits the dissipation of 2 kW/cm 2 anywhere on the panel surface. The cooling water requirements of the actively cooled dump system are provided by the closed loop Primary High Pressure Cooling Water System. To minimize the operating costs of continuously running this high power system, a variable speed hydraulic drive is used for the main pump. During beam pulses, the pump rotates at high speed, then cycles to low speed upon completion of the beam shot. A unique neutralizer design has been installed into the NBETF beamline. This is a gun-drilled moveable brazed assembly which provides continuous armoring of the beamline near the source. The unit penetrates the source mounting valve during operation and retracts to permit the valve to close as needed. The beamline also has an inertially cooled duct calorimeter assembly. This assembly is a moveable hinged matrix of copper plates that can be used as a beam stop up to pulse lengths of 50 ms. The beamline is also equipped with many beam scraper plates of differing detail design and dissipation capabilities

  6. Novel sensing approach for LPG leakage detection: Part I: Operating Mechanism and Preliminary Results

    KAUST Repository

    Mukhopadhyay, Subhas

    2015-10-30

    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.

  7. Novel sensing approach for LPG leakage detection: Part I: Operating Mechanism and Preliminary Results

    KAUST Repository

    Mukhopadhyay, Subhas; Nag, Anindya; Zia, Asif; Li, Xie; Kosel, Jü rgen

    2015-01-01

    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.

  8. Correlations between operating conditions, microstructure and mechanical properties of twin wire arc sprayed steel coatings

    International Nuclear Information System (INIS)

    Jandin, G.; Liao, H.; Feng, Z.Q.; Coddet, C.

    2003-01-01

    An experimental design matrix was set up in which carbon steel coatings were deposited with a twin wire arc spray gun (TAFA 9000 TM ), using either compressed air or nitrogen as spraying gas. The coating's mechanical properties were studied. Some correlations were made between these properties, spraying conditions and the microstructure of the deposits. Young's modulus was estimated by the single beam method using finite element modeling. Results show that direct relationships do exist between spray conditions, oxide content in the coating and microhardness. Young's modulus of the coatings depends on the lamella thickness and the oxide content. When increasing the compressed air flow rate, Young's modulus increases at first because smaller particles and finer lamellae were made and it decreases later because of a higher oxide content. The increase of nitrogen flow rate lowers the oxide content and increases Young's modulus

  9. An electron counting mechanism for the open counter operated in air

    International Nuclear Information System (INIS)

    Noguchi, T.; Nagashima, S.; Uda, M.

    1994-01-01

    An electron counting mechanism for an open or air filled counter has been explicitly explained for the first time. Electrons emitted from a solid surface or formed in air by radiations are transported to the neighborhood of the anode in the counter in the form of O 2 - ions, and are detached from the ions and multiplied in the proximity to the anode through electronic avalanche process. The estimation of the number of the emitted electrons from observed count rates has successively been performed by expressing the dead time as the sum of time intervals necessary for quenching using an external circuit and for drifting of the O 2 - ions, and also by taking into account the reduction in the number of electrons during transportation, which is due to scattering of the O 2 - ions in air. (orig.)

  10. Degradation of mechanical properties of CrMo creep resistant steel operating under conditions of creep

    Directory of Open Access Journals (Sweden)

    J. Michel

    2012-01-01

    Full Text Available Mechanical properties of a steam tube made of CrMo creep resistant steel are analysed in this contribution after up to 2,6•105 hours service life in creep conditions at temperature 530 °C and calculated stress level in the tube wall 46,5 MPa. During service life there were in the steel gradual micro structure changes, fi rst pearlite spheroidization, precipitation, coaugulation and precipitate coarsening. Nevertheless the strength and deformation properties of the steel (Re, Rm, A5, Z, and the resistance to brittle fracture and the creep strength limit, were near to unchanged after 2,1•105 hours in service. The steam tube is now in service more than 2,6•105 h.

  11. World Health Organization's Innovative Direct Disbursement Mechanism for Payment of Grassroots Immunization Personnel and Operations in Nigeria: 2004–2015

    Science.gov (United States)

    Yehualashet, Yared G.; Wadda, Alieu; Agblewonu, Koffi B.; Zhema, Theophilus; Ibrahim, Al-asi A.; Corr, Alhagie; Linkins, Jennifer; Mkanda, Pascal; Vaz, Rui G.; Nsubuga, Peter; Ashogbon, Daniel

    2016-01-01

    Background. Following the 1988 World Health Assembly resolution to eradicate polio, the government of Nigeria, with support from partners, has been implementing several rounds of supplementary immunization activities (SIAs) each year. In addition to the technical requirements, the success of the polio eradication initiative depends on timely provision of adequate financial resources. Disbursement of funds for SIAs and payment of allowances to numerous vaccination personnel at the grassroots level are enormous operational challenges in a country the size of Nigeria. Upon donors' request for a transparent and effective payment mechanism, the World Health Organization (WHO), in consultation with national counterparts, created the innovative direct disbursement mechanism (DDM) in 2004. The objective of the DDM was to timely deploy operational funds at the field level and directly pay vaccination personnel allowances at the grassroots level. Methods. A detailed operational guideline for funds disbursement was developed in close consultation with central and field stakeholders. Multiyear financial resource requirements and operational budgets for every campaign were produced by an interagency-coordinated finance subcommittee. The WHO engaged a bank and an accounting firm as DDM partners to support disbursement of and accounting for the SIA funds, respectively. The 37 WHO field offices were equipped with electronic financial systems to support the DDM process, and temporary payment sites were set up to facilitate payment to vaccination personnel at the grassroots level. Coordination meetings among DDM partners were held regularly to reconcile financial records and address operational challenges. Results. Between 2004 and 2014, DDM supported 99 polio and nonpolio vaccination campaigns, disbursing more than $370 million to about 16 million beneficiaries across 280 temporary payment sites. To mitigate security risks and reduce operational costs, the WHO and DDM

  12. World Health Organization's Innovative Direct Disbursement Mechanism for Payment of Grassroots Immunization Personnel and Operations in Nigeria: 2004-2015.

    Science.gov (United States)

    Yehualashet, Yared G; Wadda, Alieu; Agblewonu, Koffi B; Zhema, Theophilus; Ibrahim, Al-Asi A; Corr, Alhagie; Linkins, Jennifer; Mkanda, Pascal; Vaz, Rui G; Nsubuga, Peter; Ashogbon, Daniel

    2016-05-01

    Following the 1988 World Health Assembly resolution to eradicate polio, the government of Nigeria, with support from partners, has been implementing several rounds of supplementary immunization activities (SIAs) each year. In addition to the technical requirements, the success of the polio eradication initiative depends on timely provision of adequate financial resources. Disbursement of funds for SIAs and payment of allowances to numerous vaccination personnel at the grassroots level are enormous operational challenges in a country the size of Nigeria. Upon donors' request for a transparent and effective payment mechanism, the World Health Organization (WHO), in consultation with national counterparts, created the innovative direct disbursement mechanism (DDM) in 2004. The objective of the DDM was to timely deploy operational funds at the field level and directly pay vaccination personnel allowances at the grassroots level. A detailed operational guideline for funds disbursement was developed in close consultation with central and field stakeholders. Multiyear financial resource requirements and operational budgets for every campaign were produced by an interagency-coordinated finance subcommittee. The WHO engaged a bank and an accounting firm as DDM partners to support disbursement of and accounting for the SIA funds, respectively. The 37 WHO field offices were equipped with electronic financial systems to support the DDM process, and temporary payment sites were set up to facilitate payment to vaccination personnel at the grassroots level. Coordination meetings among DDM partners were held regularly to reconcile financial records and address operational challenges. Between 2004 and 2014, DDM supported 99 polio and nonpolio vaccination campaigns, disbursing more than $370 million to about 16 million beneficiaries across 280 temporary payment sites. To mitigate security risks and reduce operational costs, the WHO and DDM partners introduced mobile payment to

  13. Catalytic bioreactors and methods of using same

    Science.gov (United States)

    Worden, Robert Mark; Liu, Yangmu Chloe

    2017-07-25

    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  14. Passive hybrid force-position control for tele-operation based on real-time simulation of a virtual mechanism

    International Nuclear Information System (INIS)

    Joly, L.; Andriot, C.

    1995-01-01

    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

  15. Design and development of improved ballscrew and control circuit for reactivity mechanisms of 220 MWe PHWR operating stations

    International Nuclear Information System (INIS)

    Jain, A.K.; Rama Mohan, N.; Mathew, Jimmy; Mathur, M.K.; Roy, S.; Ingle, V.J.; Ghoshal, B.; Ashok Kumar, B.; Patil, D.C.; Dwivedi, K.P.; Bhambra, H.S.

    2006-01-01

    There has been persistent failure of Ballscrews used for Reactivity Mechanism in standardised 220 MWe PHWR units. The detailed review of failures indicated that on one hand the number of demands for operation of Absorber Rod and Regulating Rod had increased due to use of digital circuit in the drive control system as compared analog circuits used earlier. On the other hand, the existing design of ballscrew had some inherent weaknesses to withstand the loads generated during starting and stopping of the regulating rods. To solve these problems two-pronged approach was adopted. The control problem was traced to overshooting of the servomotor of Absorber Rod and Regulating Rod to the full speed at the time of starting and thereafter, settling to the required speed. This sudden overshooting produces a jerk in the drive mechanism. A modified circuit has been evolved to solve this problem. Also, Changing the dead band and gain of control circuits have reduced the number of rod movements. A 'new design' of Ballscrew assembly was finalised by NPCIL with a view to withstand the severe loads generated during starting and stopping of the regulating rods and to achieve enhanced service life under water-lubrication condition. Based on this design, prototype assemblies were successfully manufactured by two Indian manufacturers. The design was cleared for manufacturing of the bulk production of Ballscrew assemblies after evaluation of its performance during rigorous 'Acceptance Testing'. Two ballscrews of new design were installed in the KGS-1 reactor and are operating since July 2005. This paper covers operational feedback including ballscrew failures in various units, Design/Development of Modified Reactivity Mechanism Ballscrews and Control Circuit based on analysis of underlying causes of failures and feedback on performance of new design. (author)

  16. Tower Shielding Reactor II design and operation report. Vol. 3. Assembling and testing of the control mechanism assembly

    International Nuclear Information System (INIS)

    Ward, D.R.; Holland, L.B.

    1979-09-01

    The mechanisms that are operated to control the reactivity of the Tower Shielding Reactor II(TSR-II) are mounted on a Control Mechanism Housing (CMH) that is centered inside the reactor core. The information required to procure, fabricate, inspect, and assemble a CMH is contained in the ORNL engineering drawings listed in the appropriate sections. The components are fabricated and inspected from these drawings in accordance with a Quality Assurance Plan and a Manufacturing Plan. The material in this report describes the acceptance and performance tests of CMH subassemblies used ty the Tower Shielding Facility (TSF) staff but it can also be used by personnel fabricating the components. This information which was developed and used before the advent of the formalized QA Program and Manufacturing Plans evolved during the fabrication and testing of the first five CMHs

  17. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

    2007-01-01

    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....

  18. Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations.

    Science.gov (United States)

    Mehta, Meera; Holthausen, Michael H; Mallov, Ian; Pérez, Manuel; Qu, Zheng-Wang; Grimme, Stefan; Stephan, Douglas W

    2015-07-06

    Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Phosphorus doped TiO2 as oxygen sensor with low operating temperature and sensing mechanism

    International Nuclear Information System (INIS)

    Han, Zhizhong; Wang, Jiejie; Liao, Lan; Pan, Haibo; Shen, Shuifa; Chen, Jianzhong

    2013-01-01

    Nano-scale TiO 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 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 2 , further phosphorus can connect with Ti 4+ through the bond of Ti-O-P. The positive shifts of XPS peaks indicate that electron depleted layer of P-doped TiO 2 is narrowed compared with that of pure TiO 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 2 is improved, and the 5 mol% P-doped sample has the optimal oxygen sensing properties.

  20. Design, fabrication and operation of the mechanical systems for the Neutral Beam Engineering Test Facility

    International Nuclear Information System (INIS)

    Paterson, J.A.; Biagi, L.A.; Fong, M.; Koehler, G.W.; Low, W.; Purgalis, P.; Wells, R.P.

    1983-12-01

    The Neutral Beam Engineering Test Facility (NBETF) at Lawrence Berkeley Laboratory (LBL) is a National Test Facility used to develop long pulse Neutral Beam Sources. The Facility will test sources up to 120 keV, 50 A, with 30 s beam-on times with a 10% duty factor. For this application, an actively cooled beam dump is required and one has been constructed capable of dissipating a wide range of power density profiles. The flexibility of the design is achieved by utilizing a standard modular panel design which is incorporated into a moveable support structure comprised of eight separately controllable manipulator assemblies. A unique neutralizer design has been installed into the NBETF beamline. This is a gun-drilled moveable brazed assembly which provides continuous armoring of the beamline near the source. The unit penetrates the source mounting valve during operation and retracts to permit the valve to close as needed. The beamline is also equpped with many beam scraper plates of differing detail design and dissipation capabilities

  1. Theoretical comparison, equivalent transformation, and conjunction operations of electromagnetic induction generator and triboelectric nanogenerator for harvesting mechanical energy.

    Science.gov (United States)

    Zhang, Chi; Tang, Wei; Han, Changbao; Fan, Fengru; Wang, Zhong Lin

    2014-06-11

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (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.

  3. Evolutionary pattern, operation mechanism and policy orientation of low carbon economy development

    Directory of Open Access Journals (Sweden)

    X. Dou

    2016-10-01

    Full Text Available The essence of low carbon economy development is a continuous evolution and innovation process of socio-economic system from traditional high carbon economy to new sustainable green low carbon economy to achieve a sustainable dynamic balance and benign interactive development of various elements between society, economy and natural ecosystem. At the current stage, China’s socio-economy is showing the feature of "three high" (high energy consumption, high emissions and high pollution. In this case, quickly to promote the development of green low carbon economy is necessary and urgent. This research indicates that, low carbon economy development is achieved by micro-economic agents such as households, businesses and social intermediary organizations through Government’s guidance and the role of market mechanism. In low carbon economy development, the state (government is a leader and markets are core, while economic agents (e.g., households, businesses and social intermediary organizations are basis. For this reason, it is necessary to build an effective cleaner development and incentive-compatible policy system oriented to end-users.

  4. Conduction mechanism in operating a LiMn{sub 2}O{sub 4} cathode

    Energy Technology Data Exchange (ETDEWEB)

    Marzec, J.; Swierczek, K.; Molenda, J. [Faculty of Materials Science and Ceramics, Stanislaw Staszic University of Mining and Metallurgy, Al. Mickiewicza 30, 30-059 Cracow (Poland); Przewoznik, J. [Faculty of Physics and Nuclear Techniques, Stanislaw Staszic University of Mining and Metallurgy, Al. Mickiewicza 30, 30-059 Cracow (Poland); Simon, D.R.; Kelder, E.M.; Schoonman, J. [Delft Interfaculty Research Center: Sustainable Energy, Delft University of Technology, Julianalaan 136, 2628 DL Delft (Netherlands)

    2002-02-02

    Two series of the Li{sub x}Mn{sub 2}O{sub 4} spinel samples were studied at low temperatures (200-300 K) on electrical, thermal (DSC) and structural (X-ray diffraction (XRD)) properties for different lithium contents. Results obtained for deintercalated spinel samples with x=1 revealed the existence of a broad (100 K) phase transition that can be attributed to the molecular polaron condensation, leading to the orthorhombic distortion of the initial cubic form. The differential scanning calorimetry (DSC) measurement results enable us to regard the phase transition as a form of order-disorder one. Corresponding thermoelectric power (TEP) and electrical conductivity measurements fall within such description, moreover, indicating clear inconsistency between the measured regular DC conductivity of the spinel sample and that observed for the cathode in the working lithium cell. This discrepancy points to an alternative charge transport mechanism existing in the manganese spinel cathode, and it seems to be essential for the lithium cell performance.

  5. 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

    2011-12-01

    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.

  6. 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)

    2011-01-01

    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.

  7. Catalytic dehydration of ethanol using transition metal oxide catalysts.

    Science.gov (United States)

    Zaki, T

    2005-04-15

    The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe(2)O(3), Mn(2)O(3), and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorption-desorption at -196 degrees C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200-500 degrees C using a catalytic flow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents.

  8. Hydrogen production via catalytic processing of renewable feedstocks

    International Nuclear Information System (INIS)

    Nazim Muradov; Franklyn Smith; Ali T-Raissi

    2006-01-01

    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 4 -CO 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 4 -CO 2 feedstock, and (4) fabricate and test a bench-scale hydrogen production unit. Experimental data obtained from catalytic reformation of the CH 4 -CO 2 and CH 4 -CO 2 -O 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)

  9. Electro-catalytic degradation of sulfisoxazole by using graphene anode.

    Science.gov (United States)

    Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng

    2016-05-01

    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. Copyright © 2015. Published by Elsevier B.V.

  10. Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

    Energy Technology Data Exchange (ETDEWEB)

    Eteman, Shahrokh

    2013-06-30

    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.

  11. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.

    1983-04-01

    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author) [pt

  12. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    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...... and quantum state merging, and leads to a resource theory of decoupling....

  13. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    were characterized by infrared, electronic, electron paramagnetic resonance ... The catalytic oxidation property of ruthenium(III) complexes were also ... cies at room temperature. ..... aldehyde part of Schiff base ligands, catalytic activ- ity of new ...

  14. Mechanics

    CERN Document Server

    Hartog, J P Den

    1961-01-01

    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

  15. Study of catalytic phenomena in radiation chemistry

    International Nuclear Information System (INIS)

    Dran, J.C.

    1965-01-01

    Two phenomena have been studied: the action of γ rays from radio-cobalt on the adsorption and catalytic properties of ZnO and NiO in. relationship with the heterogeneous oxidation of CO, and the homogeneous catalysis by OsO 4 of the oxidation of various aqueous phase solutes by the same radiation. The prior irradiation of ZnO and of NiO does not modify their catalytic activity but generally increases the adsorption energy of -the gases CO and O 2 . The influence of the radiations appears to be connected with the presence of traces of water on ZnO and of an excess of oxygen on NiO. Osmium tetroxide which is not degraded by irradiation in acid solution, accelerates the radiolytic oxidation of certain compounds (Te IV , Pt 11 , As 111 ) in the presence of oxygen, as a result of its sensitizing effect on the oxidation by H 2 O 2 . In the case of phosphites on the other hand, OsO 4 has a protecting action under certain conditions of acidity and may suppress entirely the chain reaction which characterizes the oxidation of this solute byγ rays. A general mechanism is proposed for these phenomena. The rate constant for the OsO 4 + HO 2 reaction is calculated to be 5.7 x 10 5 l.mol -1 . sec -1 . (author) [fr

  16. Catalytic hydroprocessing of heavy oil feedstocks

    International Nuclear Information System (INIS)

    Okunev, A G; Parkhomchuk, E V; Lysikov, A I; Parunin, P D; Semeikina, V S; Parmon, V N

    2015-01-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references

  17. Catalytic hydroprocessing of heavy oil feedstocks

    Science.gov (United States)

    Okunev, A. G.; Parkhomchuk, E. V.; Lysikov, A. I.; Parunin, P. D.; Semeikina, V. S.; Parmon, V. N.

    2015-09-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references.

  18. Analysis on the Load Carrying Mechanism Integrated as Heterogeneous Co-operative Manipulator in a Walking Wheelchair

    Science.gov (United States)

    Rajay Vedaraj, I. S.; Jain, Ritika; Rao, B. V. A.

    2014-07-01

    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

  19. Analysis on the Load Carrying Mechanism Integrated as Heterogeneous Co-operative Manipulator in a Walking Wheelchair

    International Nuclear Information System (INIS)

    Vedaraj, I S Rajay; Jain, Ritika; Rao, B V A

    2014-01-01

    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

  20. Solar reforming of methane in a direct absorption catalytic reactor on a parabolic dish. 2: Modeling and analysis

    Science.gov (United States)

    Skocypec, Russell D.; Hogan, Roy E., Jr.; Muir, James F.

    1991-01-01

    The catalytically enhanced solar absorption receiver (CAESAR) experiment was conducted to determine the thermal, chemical, and mechanical performance of a commercial-scale, dish-mounted, direct catalytic absorption receiver (DCAR) reactor over a range of steady state and transient (cloud) operating conditions. The focus of the experiment is on global performance such as receiver efficiencies and overall methane conversion; it was not intended to provide data for code validation. A numerical model was previously developed to provide guidance in the design of the absorber. The one-dimensional, planar and steady-state model incorporates, the following energy transfer mechanisms: solar and infrared radiation, heterogeneous chemical reaction, conduction in the solid phase, and convection between the fluid and solid phases. A number of upgrades to the model and improved property values are presented here. Model predictions are shown to bound the experimental axial thermocouple data when experimental uncertainties are included. Global predictions are made using a technique in which the incident solar flux distribution is subdivided into flux contour bands. Model predictions for each band are then spatially integrated to provide global predictions such as reactor efficiencies and methane conversions. Global predictions are shown to compare well with experimental data. Reactor predictions for anticipated operating conditions suggest a further decrease in optical density at the front of the absorber inner disk may be beneficial. The need to conduct code-validation experiments is identified as being essential in improving the confidence in the capability to predict large-scale reactor operation.

  1. Catalytic hydrodeoxygenation of dibenzofuran

    Energy Technology Data Exchange (ETDEWEB)

    La Vopa, V.; Satterfield, C.N.

    The hydrodeoxygenation of dibenzofuran (DBF) on a sulfided NiMo/Al/sub 2/O/sub 3/ catalyst was studied at 350-390 C and 7.0 MPa. The major products isolated were single-ring hydrocarbons, cyclohexane predominating; the remainder were double-ring hydrocarbons, cyclohexylbenzene predominating. No oxygen-containing species other than water were isolated in any significant amount. The initial reactions in the hydrodeoxygenation of DBF are rate-limiting. The non-sulfided (oxide) catalyst is much less active, and double-ring products predominate over single-ring products. From studies of possible intermediates it appears that on a sulfided catalyst two pathways operate in parallel for the hydrodeoxygenation of dibenzofuran: (1) hydrogenation of DBF to hexahydro DBF, which reacts via 2-cyclohexylphenol to form signle-ring hydrocarbons; (2) direct hydrogenolysis via 2-phenylphenol, without prior ring hydrogenation, to form biphenyl and cyclohexylbenzene (a minor route). On this catalyst the overall reaction is first order with respect to hydrogen and to DBF and exhibits an apparent activation energy of 67 kJ/mol. 26 refs., 16 figs., 3 tabs.

  2. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents.

    Science.gov (United States)

    Lushchekina, Sofya V; Schopfer, Lawrence M; Grigorenko, Bella L; Nemukhin, Alexander V; Varfolomeev, Sergei D; Lockridge, Oksana; Masson, Patrick

    2018-01-01

    Organophosphorus agents (OPs) are irreversible inhibitors of acetylcholinesterase (AChE). OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants ( k cat / K m > 10 6 M -1 min -1 ) are required, so that low enzyme doses can be administered. Cholinesterases (ChE) are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase) activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that introducing

  3. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents

    Directory of Open Access Journals (Sweden)

    Sofya V. Lushchekina

    2018-03-01

    Full Text Available Organophosphorus agents (OPs are irreversible inhibitors of acetylcholinesterase (AChE. OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants (kcat/Km > 106 M−1min−1 are required, so that low enzyme doses can be administered. Cholinesterases (ChE are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that

  4. Biofiltration of volatile pollutants: Engineering mechanisms for improved design, long-term operation, prediction, and implementation. 1997 annual progress report

    International Nuclear Information System (INIS)

    Barton, J.W.; Davison, B.H.; Klasson, K.T.

    1997-01-01

    'Biofiltration systems can be used to treat volatile organic compounds (VOCs); however, the systems are poorly understood and are currently operated as black boxes. Common operational problems associated with biofilters include fouling, deactivation, and overgrowth, all of which make biofilters ineffective for continuous, long-term use. The objective of this investigation is to develop generic methods for long-term stable operation, in particular by using selective limitation of supplemental nutrients while maintaining high activity and the ability to regenerate biofilter activity. As part of this effort, the authors will provide a deeper fundamental understanding of the important biological and transport mechanisms in biodestruction of sparingly soluble VOCs and will extend this engineering approach and developed mathematical models to two additional systems of high-priority environmental management (EM) relevance-direct degradation and cometabolic degradation of priority pollutants such as BTEX (benzene, toluene, ethylbenzene, and xylene) and TCE (trichioroethylene), respectively. Preliminary results indicate that the author can control overgrowth of the biofilm while sustaining high degradation rates and develop basic predictive models that elucidate mass transfer and kinetic limitations in this system for alkanes. The alkanes are degraded into CO, and waterwith minimal biomass (due to the methodology proposed). This system will be used to test and model additional supplemental nutrient feeding strategies as well as methods to increase the fundamental driving forces by modification of the system. Models will be extended to non-steady-state, long-term operation. The author will examine the nature of the mixed microbial community in the VOC-degrading biofilm and test for new degradative activities. He will use cosolvents with surfactant properties to enhance hydrocarbon solubility in the biofilm and evaluate their impact on mass transfer and reaction rate in an

  5. Catalytic process for tritium exchange reaction

    International Nuclear Information System (INIS)

    Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

    2001-01-01

    The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

  6. Material characterisation and preliminary mechanical design for the HL-LHC shielded beam screens operating at cryogenic temperatures

    International Nuclear Information System (INIS)

    Garion, C; Dufay-Chanat, L; Koettig, T; Machiocha, W; Morrone, M

    2015-01-01

    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. (paper)

  7. 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

    2015-05-26

    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.

  8. 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

    2015-01-01

    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...

  9. Material characterisation and preliminary mechanical design for the HL-LHC shielded beam screens operating at cryogenic temperatures.

    Science.gov (United States)

    Garion, C.; Dufay-Chanat, L.; Koettig, T.; Machiocha, W.; Morrone, M.

    2015-12-01

    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.

  10. Oscillatory behaviour of catalytic properties, structure and temperature during the catalytic partial oxidation of methane on Pd/Al2O3

    DEFF Research Database (Denmark)

    Kimmerle, B.; Baiker, A.; Grunwaldt, Jan-Dierk

    2010-01-01

    Pd/Al2O3 catalysts showed an oscillatory behaviour during the catalytic partial oxidation (CPO) of methane, which was investigated simultaneously by IR-thermography, X-ray absorption spectroscopy, and online mass-spectrometry to correlate the temperature, state of the catalyst and catalytic...... to self-reduction leading to extinction of the process. The latter was the key driver for the oscillations and thus gave additional insight into the mechanism of partial methane oxidation....

  11. Smoke emissions from a catalytic wood stove

    International Nuclear Information System (INIS)

    Cowburn, D.A.; Stephens, N.P.J.

    1994-01-01

    The work reported here was concerned with testing a catalytic wood burning stove (roomheater) following the most applicable UK procedures. The identical stove has also been tested in several other nations to their individual procedures. The results will be submitted to the International Energy Agency (IEA) such that appropriate comparisons can be made. The results comprised: burning rate; an indicative appliance efficiency; heat output; carbon dioxide emissions; carbon monoxide emissions; and smoke emissions. These results were determined with the appliance at three nominal burning rates (high, medium and low). Comparing the results with those obtained in other countries indicates good agreement except when the appliance was operated at low burning rates, under which conditions the UK results indicate significantly worse smoke emissions than those measured by other researchers. (author)

  12. LOGIC WITH EXCEPTION ON THE ALGEBRA OF FOURIER-DUAL OPERATIONS: NEURAL NET MECHANISM OF COGNITIVE DISSONANCE REDUCING

    Directory of Open Access Journals (Sweden)

    A. V. Pavlov

    2014-01-01

    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

  13. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson

    2013-01-01

    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

  14. Catalytic processes for cleaner fuels

    International Nuclear Information System (INIS)

    Catani, R.; Marchionna, M.; Rossini, S.

    1999-01-01

    More stringent limitations on vehicle emissions require different measurement: fuel reformulation is one of the most important and is calling for a noticeable impact on refinery assets. Composition rangers of the future fuels have been defined on a time scale. In this scenario the evolution of catalytic technologies becomes a fundamental tool for allowing refinery to reach the fixed-by-law targets. In this paper, the refinery process options to meet each specific requirements of reformulated fuels are surveyed [it

  15. Physical chemistry of catalytic reduction of nitroarenes using various nanocatalytic systems: past, present, and future

    International Nuclear Information System (INIS)

    Begum, Robina; Rehan, Rida; Farooqi, Zahoor H.; Butt, Zonarah; Ashraf, Sania

    2016-01-01

    The catalytic reduction of nitroarenes under various catalytic systems has been widely reported in the flood of publications during last twenty years. This reaction has become a benchmark for testing catalytic activity of inorganic nanoparticles stabilized in various systems. This tutorial review presents design and classification of inorganic nanocatalysts along with their stabilizing agents used for catalytic reduction of nitroarenes. The techniques used for characterization of catalysts have been highlighted in this review. The mechanism of catalytic reduction has been described in a tutorial way. Factors affecting the rate of reduction of nitroarenes in the presence of metal nanoparticles stabilized in polyelectrolyte brushes, polyionic liquids, micelles, dendrimers, and microgels have been discussed for further development in this area.Graphical abstract

  16. Physical chemistry of catalytic reduction of nitroarenes using various nanocatalytic systems: past, present, and future

    Energy Technology Data Exchange (ETDEWEB)

    Begum, Robina [University of the Punjab, Centre for Undergraduate Studies (Pakistan); Rehan, Rida; Farooqi, Zahoor H., E-mail: zhfarooqi@gmail.com; Butt, Zonarah; Ashraf, Sania [University of the Punjab, Institute of Chemistry (Pakistan)

    2016-08-15

    The catalytic reduction of nitroarenes under various catalytic systems has been widely reported in the flood of publications during last twenty years. This reaction has become a benchmark for testing catalytic activity of inorganic nanoparticles stabilized in various systems. This tutorial review presents design and classification of inorganic nanocatalysts along with their stabilizing agents used for catalytic reduction of nitroarenes. The techniques used for characterization of catalysts have been highlighted in this review. The mechanism of catalytic reduction has been described in a tutorial way. Factors affecting the rate of reduction of nitroarenes in the presence of metal nanoparticles stabilized in polyelectrolyte brushes, polyionic liquids, micelles, dendrimers, and microgels have been discussed for further development in this area.Graphical abstract.

  17. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  18. Catalytic combustion in gas stoves - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

    2003-06-01

    . To overcome the latter, improved aeration of the system is needed, e.g. modification of nozzle-size and/or flame port plate. The effects of installing a retro-fit catalytic design onto the burner in the gas oven were also examined. Similar to the burners of the cooking plates, the emitted NO{sub x} was greatly reduced, i.e. up to 90 %. Other on-going projects using similar catalyst concepts as in this study have shown that the life-time of the catalyst, i.e. the mechanical stability and the catalytic activity, is extremely good (> 1000 h). To examine if this durability of the catalyst is limited in this specific application by deactivation caused by possible food spillage, a number of commonly used food ingredients were painted onto the catalysts and the activity of the catalyst prior to and after the 'deactivation' was investigated. The results show that no ingredients of organic type (fat, milk, egg, sugar) have any significant impact on the catalytic activity. Salt however was seen to block active reaction sites of the catalyst, but the tests showed that the catalyst could in this case be easily re-activated by simply washing it in water. The design modifications are very modest and the amount of catalyst is small, costing about 6-10 SEK (0.80-1.2 USD) per cooking plate.

  19. Heart rate variability at limiting stationarity: evidence of neuro-cardiac control mechanisms operating at ultra-low frequencies

    International Nuclear Information System (INIS)

    Fisher, A C; Groves, D; Eleuteri, A; Mesum, P; Patterson, D; Taggart, P

    2014-01-01

    This study considers the linkage of exogenously stimulated emotional stress with the neurogenic regulation of heart rate operating at very low frequencies. The objectives were three-fold: to consider the present evidence that such a linkage exists as a primary phenomenon; to compare the potential of a frequency-domain method and a time-domain method in revealing this phenomenon by characterizing heart rate variability (HRV) at frequencies of [0.0005…0.4] Hz and to design, implement and report a physiological experiment in which alternating periods of exposure to bland and high valence visual stimuli might reveal this phenomenon. A methodical challenge was to optimize the length of exposure to the stimulus such that subjects did not have time to habituate to stimuli, whilst acquiring sufficient data (heart beats) such that the ultra-low frequency (ULF) components of HRV could be described. With exposure times set to approximately 5 min, during which time the strength of the stimulus and the corresponding evoked response were considered stationary, the lowest HRV frequency component that could be characterized was 0.003 Hz. In trials with parametrically defined test data, the time-domain method based on the Ornstein–Uhlenbeck Gaussian process (OU-GP) was shown to be better than the frequency-domain method in describing the ULF components of the HRV. In an experimental cohort of 16 subjects, analysis using the OU-GP revealed evidence of cardiac regulatory mechanisms influenced by emotional valence operating in the bandwidth (ULF*) [0.002…0.01] Hz. (paper)

  20. Upgrading the lubricity of bio-oil via homogeneous catalytic esterification under vacuum distillation conditions

    International Nuclear Information System (INIS)

    Xu, Yufu; Zheng, Xiaojing; Peng, Yubin; Li, Bao; Hu, Xianguo; Yin, Yanguo

    2015-01-01

    In order to accelerate the application of bio-oil in the internal combustion engines, homogeneous catalytic esterification technology under vacuum distillation conditions was used to upgrade the crude bio-oil. The lubricities of the crude bio-oil (BO) and refined bio-oil with homogeneous catalytic esterification (RBO hce ) or refined bio-oil without catalyst but with distillation operation (RBO wc ) were evaluated by a high frequency reciprocating test rig according to the ASTM D 6079 standard. The basic physiochemical properties and components of the bio-oils were analyzed. The surface morphology, contents and chemical valence of active elements on the worn surfaces were investigated by scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy, respectively. The results show that RBO hce has better lubricities than those of BO, but RBO wc has worse lubricities than those of BO. The tribological mechanisms of the bio-oils are attributed to the combined actions of lubricating films and factors that will break the film. Compared with BO, plenty of phenols in RBO wc results in corrosion of the substrate and destroys the integrity of the lubricating films, which is responsible for its corrosive wear. However, more esters and alkanes in RBO hce contribute to forming a complete boundary lubricating film on the rubbed surfaces which result in its excellent antifriction and antiwear properties. - Highlights: • Refined bio-oil was prepared through homogeneous catalytic esterification technology. • Properties of the bio-oils before and after refining were assessed by HFRR. • Refined bio-oil showed better lubricities than crude bio-oil. • More esters and alkanes in refined bio-oil contributed to forming superior boundary lubrication

  1. Mechanics

    CERN Document Server

    Chester, W

    1979-01-01

    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...

  2. 40 CFR 63.1565 - What are my requirements for organic HAP emissions from catalytic cracking units?

    Science.gov (United States)

    2010-07-01

    ... HAP emissions from catalytic cracking units? 63.1565 Section 63.1565 Protection of Environment... are my requirements for organic HAP emissions from catalytic cracking units? (a) What emission... according to the procedures in the plan. (4) The emission limitations and operating limits for organic HAP...

  3. 40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true What are my requirements for metal HAP... requirements for metal HAP emissions from catalytic cracking units? (a) What emission limitations and work... and operating limits for metal HAP emissions from catalytic cracking units required in paragraphs (a...

  4. Oxyfuel combustion using a catalytic ceramic membrane reactor

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Xiaoyao; Li, K. [Department of Chemical Engineering, Imperial College London, University of London, South Kensington, London SW7 2AZ (United Kingdom); Thursfield, A.; Metcalfe, I.S. [School of Chemical Engineering and Advanced Materials, Newcastle University, Newcastle upon Tyne, NE1 7RU (United Kingdom)

    2008-02-29

    Membrane catalytic combustion (MCC) is an environmentally friendly technique for heat and power generation from methane. This work demonstrates the performances of a MCC perovskite hollow fibre membrane reactor for the catalytic combustion of methane. The ionic-electronic La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-{alpha}} (LSCF6428) mixed conductor, in the form of an oxygen-permeable hollow fibre membrane, has been prepared successfully by means of a phase-inversion spinning/sintering technique. For this process polyethersulfone (PESf) was used as a binder, N-methyl-2-pyrrollidone (NMP) as solvent and polyvinylpyrrolidone (PVP, K16-18) as an additive. With the prepared LSCF6428 hollow fibre membranes packed with catalyst, hollow fibre membrane reactors (HFMRs) have been assembled to perform the catalytic combustion of methane. A simple mathematical model that combines the local oxygen permeation rate with approximate catalytic reaction kinetics has been developed and can be used to predict the performance of the HFMRs for methane combustion. The effects of operating temperature and methane and air feed flow rates on the performance of the HFMR have been investigated both experimentally and theoretically. Both the methane conversion and oxygen permeation rate can be improved by means of coating platinum on the air side of the hollow fibre membranes. (author)

  5. Catalytic hot gas cleaning of gasification gas

    Energy Technology Data Exchange (ETDEWEB)

    Simell, P. [VTT Energy, Espoo (Finland). Energy Production Technologies

    1997-12-31

    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

  6. IN SITU INFRARED STUDY OF CATALYTIC DECOMPOSITION OF NITRIC OXIDE (NO); FINAL

    International Nuclear Information System (INIS)

    Unknown

    1999-01-01

    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

  7. Inverse operator theory method mathematics-mechanization for the solutions of nonlinear equations and some typical applications in nonlinear physics

    International Nuclear Information System (INIS)

    Fang Jinqing; Yao Weiguang

    1992-12-01

    Inverse operator theory method (IOTM) has developed rapidly in the last few years. It is an effective and useful procedure for quantitative solution of nonlinear or stochastic continuous dynamical systems. Solutions are obtained in series form for deterministic equations, and in the case of stochastic equation it gives statistic measures of the solution process. A very important advantage of the IOTM is to eliminate a number of restrictive and assumption on the nature of stochastic processes. Therefore, it provides more realistic solutions. The IOTM and its mathematics-mechanization (MM) are briefly introduced. They are used successfully to study the chaotic behaviors of the nonlinear dynamical systems for the first time in the world. As typical examples, the Lorentz equation, generalized Duffing equation, two coupled generalized Duffing equations are investigated by the use of the IOTM and the MM. The results are in good agreement with ones by the Runge-Kutta method (RKM). It has higher accuracy and faster convergence. So the IOTM realized by the MM is of potential application valuable in nonlinear science

  8. Fractional corresponding operator in quantum mechanics and applications: A uniform fractional Schrödinger equation in form and fractional quantization methods

    International Nuclear Information System (INIS)

    Zhang, Xiao; Wei, Chaozhen; Liu, Yingming; Luo, Maokang

    2014-01-01

    In this paper we use Dirac function to construct a fractional operator called fractional corresponding operator, which is the general form of momentum corresponding operator. Then we give a judging theorem for this operator and with this judging theorem we prove that R–L, G–L, Caputo, Riesz fractional derivative operator and fractional derivative operator based on generalized functions, which are the most popular ones, coincide with the fractional corresponding operator. As a typical application, we use the fractional corresponding operator to construct a new fractional quantization scheme and then derive a uniform fractional Schrödinger equation in form. Additionally, we find that the five forms of fractional Schrödinger equation belong to the particular cases. As another main result of this paper, we use fractional corresponding operator to generalize fractional quantization scheme by using Lévy path integral and use it to derive the corresponding general form of fractional Schrödinger equation, which consequently proves that these two quantization schemes are equivalent. Meanwhile, relations between the theory in fractional quantum mechanics and that in classic quantum mechanics are also discussed. As a physical example, we consider a particle in an infinite potential well. We give its wave functions and energy spectrums in two ways and find that both results are the same

  9. Catalytic activity of metal borides in the reaction of decomposition

    International Nuclear Information System (INIS)

    Labodi, I.; Korablev, L.I.; Tavadyan, L.A.; Blyumberg, Eh.A.

    1982-01-01

    Catalytic effect of CoB, MoB 2 , ZrB 2 and NbB 2 , prepared by the method of self-propagating high-temperature synthesis, on decomposition of tertiary butyl hydroperoxide has been studied. A technigue of determination of action mechanism of heterogeneous catalysts in liquid-phase process is suggested. It is established that CoB in contrast to other metal borides catalyzes only hydroperoxide decomposition into radicals

  10. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    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

  11. Catalytic Organometallic Reactions of Ammonia

    Science.gov (United States)

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  12. Catalytic cracking of hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    1940-09-12

    A process is described for the vapor phase catalytic cracking of hydrocarbon oils boiling substantially in the gas oil range. The reaction takes place in the presence of a solid catalyst between 700 to 900/sup 0/F under pressure between atmospheric and 400 psi. A gas containing between 20 and 90 mol % of free hydrogen is used. The reaction is allowed to proceed until consumption of the free begins. The reaction is discontinued at that point and the catalyst is regenerated for further use.

  13. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    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.

  14. High-Temperature Compatible Nickel Silicide Thermometer And Heater For Catalytic Chemical Microreactors

    DEFF Research Database (Denmark)

    Jensen, Søren; Quaade, U.J.; Hansen, Ole

    2005-01-01

    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...

  15. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  16. Petrochemical promoters in catalytic cracking

    International Nuclear Information System (INIS)

    Gomez, Maria; Vargas, Clemencia; Lizcano, Javier

    2010-01-01

    This study is based on the current scheme followed by a refinery with available Catalytic Cracking capacity to process new feedstocks such as Straight Run Naphtha and Naphthas from FCC. These feedstocks are of petrochemical interest to produce Ethane, Ethylene, Propylene, i-Butane, Toluene and Xylene. To evaluate the potential of these new streams versus the Cracking-charged Residues, it was performed a detailed chemical analysis on the structural groups in carbons [C1-C12] at the reactor product obtained in pilot plant. A catalyst with and without Propylene Promoter Additive was used. This study analyzes the differences in the chemical composition of the feedstocks, relating them to the yield of each petrochemical product. Straight Run Naphthas with a high content of Naphthenes, and Paraffines n[C5-C12] and i[C7-C12] are selective to the production of i-Butane and Propane, while Naphthas from FCC with a high content of n[C5-C12]Olefins, i-Olefins, and Aromatics are more selective to Propylene, Toluene, and Xylene. Concerning Catalytic Cracking of Naphthas, the Additive has similar selectivity for all the petrochemical products, their yields increase by about one point with 4%wt of Additive, while in cracking of Residues, the Additive increases in three points Propylene yield, corresponding to a selectivity of 50% (?C3= / ?LPG).

  17. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

    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. Catalytic converters in the fireplace

    International Nuclear Information System (INIS)

    Kouki, J.

    1995-01-01

    In addition to selecting the appropriate means of heating and using dry fuel, the amount of harmful emissions contained by flue gases produced by fireplaces can be reduced by technical means. One such option is to use an oxidising catalytic converter. Tests at TTS Institute's Heating Studies Experimental Station have focused on two such converters (dense and coarse) mounted in light-weight iron heating stoves. The ability of the dense catalytic converter to oxidise carbon monoxide gases proved to be good. The concentration of carbon monoxide in the flue gases was reduced by as much as 90 %. Measurements conducted by VTT (Technical Research Centre of Finland) showed that the conversion of other gases, e.g. of methane, was good. The exhaust resistance caused by the dense converter was so great as to necessitate the mounting of a fluegas evacuation fan in the chimney for the purpose of creating sufficient draught. When relying on natural draught, the dense converter requires a chimney of at least 7 metres and a by-pass connection while the fire is being lit. In addition, the converter will have to be constructed to be less dense and this will mean that it's capability to oxidise non-combusted gases will be reduced. The coarse converter did not impair the draught but it's oxidising property was insufficient. With the tests over, the converter was not observed to have become blocked up by impurities

  19. Co-operatives as a development mechanism to support job creation and sustainable waste management in South Africa

    CSIR Research Space (South Africa)

    Godfrey, Linda K

    2017-06-01

    Full Text Available relating to infrastructure, operations, and capability. They still operate largely on the fringe of municipal solid waste management, and have not been integrated effectively into such formal collection systems, making it difficult for them to access...

  20. Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins

    Science.gov (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