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Sample records for catalytic mechanism operating

  1. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones

    2011-03-31

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

  2. 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.)

  3. 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.

  4. 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

  5. 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.

  6. Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation

    Science.gov (United States)

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

    2016-05-01

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

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

    Directory of Open Access Journals (Sweden)

    Ruihan Zhang

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G

    2005-11-30

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

  12. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-03-01

    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  13. 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

    ... Emissions From Catalytic Reforming Units 16 Table 16 to Subpart UUU of Part 63 Protection of Environment... Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63... Catalytic Reforming Units As stated in § 63.1566(a)(2), you shall meet each operating limit in the following...

  14. 40 CFR Table 2 to Subpart Uuu of... - Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

    Science.gov (United States)

    2010-07-01

    ... Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63... Emissions From Catalytic Cracking Units 2 Table 2 to Subpart UUU of Part 63 Protection of Environment... Catalytic Cracking Units As stated in § 63.1564(a)(2), you shall meet each operating limit in the following...

  15. 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

    ... Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63... Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment... Catalytic Cracking Units As stated in § 63.1565(a)(2), you shall meet each operating limit in the following...

  16. 40 CFR Table 28 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Inorganic HAP Emissions From Catalytic Reforming...

    Science.gov (United States)

    2010-07-01

    ... Limits for Inorganic HAP Emissions From Catalytic Reforming Units 28 Table 28 to Subpart UUU of Part 63... Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and... Compliance With Operating Limits for Inorganic HAP Emissions From Catalytic Reforming Units As stated in § 63...

  17. 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...

  18. 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

  19. Linear operators for quantum mechanics

    CERN Document Server

    Jordan, Thomas F

    1969-01-01

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

  20. Quantum mechanics with difference operators

    International Nuclear Information System (INIS)

    Dobrev, V.K.; Doebner, H.-D.; Twarock, R.

    2002-07-01

    A formulation of quantum mechanics with additive and multiplicative (q-) difference operators instead of differential operators is studied from first principles. Borel-quantisation on smooth configuration spaces is used as guiding quantisation method. After a short discussion this method is translated step-by-step to a framework based on difference operators. To restrict the resulting plethora of possible quantisations additional assumptions motivated by simplicity and plausibility are required. Multiplicative difference operators and the corresponding q-Borel kinematics are given on the circle and its N-point discretisation; the connection to q-deformations of the Witt algebra is discussed. For a 'natural' choice of the q-kinematics a corresponding q-difference evolution equation is obtained. This study shows general difficulties for a generalisation of a physical theory from a known one to a 'new' framework. (author)

  1. Theoretical study of the catalytic desulfurization mechanism of ...

    African Journals Online (AJOL)

    The desulfurization process of compounds implicates two steps. The first step is the adsorption process on the catalytic site and the second, the breaking of the carbon-heteroatom bond leading to the heteroatom elimination. The adsorption process of thiiren have been studied and published in previous works. The results ...

  2. 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

  3. 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

  4. Mechanism of Transition-Metal Nanoparticle Catalytic Graphene Cutting.

    Science.gov (United States)

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

    2014-04-03

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

  5. 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.

  6. Catalytic ozonation of sulfamethoxazole by composite iron-manganese silicate oxide: cooperation mechanism between adsorption and catalytic reaction.

    Science.gov (United States)

    Gao, Guoying; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Chu, Wei

    2016-11-01

    A systematic investigation of the cooperation mechanism between adsorption and catalytic reaction during the catalytic ozonation of sulfamethoxazole (SMX) by composite iron-manganese silicate oxide (FMSO) was carried out in this work. Results showed that the total organic carbon (TOC) removal increased significantly from 27 % (sole-ozonation) to 79.8 % (FMSO catalytic ozonation). The presence of FMSO in the ozonation process effectively enhanced the ozone utilization efficiency and accelerated the transformation of ozone into hydroxyl radicals. The latter result was verified by the indirect method, using NaHSO 3 as the reductor, and the direct electron spin resonance (ESR) determination technology. The adsorption of SMX on FMSO was minimal (1.8 %). However, ozone rapidly converted SMX into various intermediates, which was exhibited by the much higher adsorption affinity on the surface of FMSO than that of SMX. The accumulation of various intermediates on the FMSO surface also increased their contact probability with the ·OH radicals generated by the ozone decomposition. The continuous interaction of intermediates with ·OH radicals could further promote the benign cycling of the release of adsorption sites and the succeeding adsorption/decomposition of ozone and intermediates on FMSO. This could be another reason for the higher and faster TOC removal rate.

  7. 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

  8. 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

  9. 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.

  10. 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.

    2017-01-01

    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. PMID:28660882

  11. Quantum mechanics/molecular mechanics study of the catalytic cycle of water splitting in photosystem II.

    Science.gov (United States)

    Sproviero, Eduardo M; Gascón, José A; McEvoy, James P; Brudvig, Gary W; Batista, Victor S

    2008-03-19

    This paper investigates the mechanism of water splitting in photosystem II (PSII) as described by chemically sensible models of the oxygen-evolving complex (OEC) in the S0-S4 states. The reaction is the paradigm for engineering direct solar fuel production systems since it is driven by solar light and the catalyst involves inexpensive and abundant metals (calcium and manganese). Molecular models of the OEC Mn3CaO4Mn catalytic cluster are constructed by explicitly considering the perturbational influence of the surrounding protein environment according to state-of-the-art quantum mechanics/molecular mechanics (QM/MM) hybrid methods, in conjunction with the X-ray diffraction (XRD) structure of PSII from the cyanobacterium Thermosynechococcus elongatus. The resulting models are validated through direct comparisons with high-resolution extended X-ray absorption fine structure spectroscopic data. Structures of the S3, S4, and S0 states include an additional mu-oxo bridge between Mn(3) and Mn(4), not present in XRD structures, found to be essential for the deprotonation of substrate water molecules. The structures of reaction intermediates suggest a detailed mechanism of dioxygen evolution based on changes in oxidization and protonation states and structural rearrangements of the oxomanganese cluster and surrounding water molecules. The catalytic reaction is consistent with substrate water molecules coordinated as terminal ligands to Mn(4) and calcium and requires the formation of an oxyl radical by deprotonation of the substrate water molecule ligated to Mn(4) and the accumulation of four oxidizing equivalents. The oxyl radical is susceptible to nucleophilic attack by a substrate water molecule initially coordinated to calcium and activated by two basic species, including CP43-R357 and the mu-oxo bridge between Mn(3) and Mn(4). The reaction is concerted with water ligand exchange, swapping the activated water by a water molecule in the second coordination shell of

  12. 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)

  13. 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.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

    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 β-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.

  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

    ... Limits for Organic HAP Emissions From Catalytic Reforming Units 21 Table 21 to Subpart UUU of Part 63... Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and... Compliance With Operating Limits for Organic HAP Emissions From Catalytic Reforming Units As stated in § 63...

  16. 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

    ... Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and... 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...

  17. 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

    ... Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and... 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...

  18. 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

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

    DEFF Research Database (Denmark)

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

    1992-01-01

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

  20. 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.

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

    Directory of Open Access Journals (Sweden)

    Xiangqian Kong

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

  2. 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.

  3. Catalytic coupling reaction mechanism of 4-nitrobenzenethiol on silver clusters: a density functional theoretical study.

    Science.gov (United States)

    Chen, Xiao; Wei, Wei; Li, Laicai; Liu, Liuxie; Pan, Rui; Tian, Anmin

    2017-10-23

    The catalytic coupling reaction mechanism of the transformation from 4-nitrobenzenethiol (4-NBT) to 4,4'-dimercaptoazobenzene (4,4'-DMAB) on a silver cluster was studied by density functional theory. Reactants, intermediates, transition states and products were optimized with the B3LYP method using the 6-311 + G(d,p) basis set (Ag using the pseudo potential basis set of LanL2DZ). Transition states and intermediates were confirmed by the corresponding vibration analysis and intrinsic reaction coordinates (IRC). Consistent with literature reports, the key point of the transformation from 4-NBT absorbed on the surface of Ag 5 clusters to 4,4'-DMAB is the elimination of two O atoms on the amino group. Meanwhile, the catalytic coupling reaction of 4-nitrobenzenethiol on a silver cluster is easy to carry out under irradiation. The possibility of "inter system channeling" (ISC) between different potential energy surfaces in the coupling reaction of 4-NBT is further discussed. The irradiation has an auxiliary catalytic effect on the coupling reaction. Our research results can explain the observed experimental phenomena. Graphical abstract Catalytic coupling reaction mechanism of the transformation from 4-nitrothiophenol (4-NBT) to 4,4'-dimercaptoazobenzene (4,4'-DMAB) on silver clusters studied by density functional theory.

  4. 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

  5. X-ray, neutron and NMR studies of the catalytic mechanism of aspartic proteinases.

    Science.gov (United States)

    Coates, Leighton; Erskine, Peter T; Mall, Sanjay; Gill, Raj; Wood, Steve P; Myles, Dean A A; Cooper, Jonathan B

    2006-09-01

    Current proposals for the catalytic mechanism of aspartic proteinases are largely based on X-ray structures of bound oligopeptide inhibitors possessing non-hydrolysable analogues of the scissile peptide bond. Until recent years, the positions of protons on the catalytic aspartates and the ligand in these complexes had not been determined with certainty due to the inadequate resolution of these analyses. There has been much interest in locating the catalytic protons at the active site of aspartic proteinases since this has major implications for detailed understanding of the mechanism of action and the design of improved transition state mimics for therapeutic applications. In this review we discuss the results of studies which have shed light on the locations of protons at the catalytic centre. The first direct determination of the proton positions stemmed from neutron diffraction data collected from crystals of the fungal aspartic proteinase endothiapepsin bound to a transition state analogue (H261). The neutron structure of the complex at a resolution of 2.1 A provided evidence that Asp 215 is protonated and that Asp 32 is the negatively charged residue in the transition state complex. Atomic resolution X-ray studies of inhibitor complexes have corroborated this finding. A similar study of the native enzyme established that it, unexpectedly, has a dipeptide bound at the catalytic site which is consistent with classical reports of inhibition by short peptides and the ability of pepsins to catalyse transpeptidation reactions. Studies by NMR have confirmed the findings of low-barrier and single-well hydrogen bonds in the complexes with transition state analogues.

  6. Theoretical modeling study for the phosphonylation mechanisms of the catalytic triad of acetylcholinesterase by sarin.

    Science.gov (United States)

    Wang, Jing; Gu, Jiande; Leszczynski, Jerzy

    2008-03-20

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

  7. Catalytic mechanism of hydrogenase from Azotobacter vinelandii. Final technical report, August 1, 1994--July 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Arp, D.J.

    1997-10-01

    This project is focused on investigations of the catalytic mechanism of the hydrogenase found in the aerobic, N{sub 2}-fixing microorganism Azotobacter vinelandii. This report summarizes the progress during the first two years of the current project and include the anticipated course of the research for the remaining year of the current project. Because the current proposal represents a change in direction, the authors also include a brief progress report of prior DOE-sponsored research dealing with hydrogenases.

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

    OpenAIRE

    Dubinko, Volodymyr; Laptev, Denis; Irwin, Klee

    2016-01-01

    Quasicrystals (QCs) are a novel form of matter, which are neither crystalline nor amorphous. Among many surprising properties of QCs is their high catalytic activity. We propose a mechanism explaining this peculiarity based on unusual dynamics of atoms at special sites in QCs, namely, localized anharmonic vibrations (LAVs) and phasons. In the former case, one deals with a large amplitude (~ fractions of an angstrom) time-periodic oscillations of a small group of atoms around their stable posi...

  9. 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

  10. 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

  11. Probing the Catalytic Mechanism of Vibrio harveyi GH20 β-N-Acetylglucosaminidase by Chemical Rescue.

    Directory of Open Access Journals (Sweden)

    Piyanat Meekrathok

    Full Text Available Vibrio harveyi GH20 β-N-acetylglucosaminidase (VhGlcNAcase is a chitinolytic enzyme responsible for the successive degradation of chitin fragments to GlcNAc monomers, activating the onset of the chitin catabolic cascade in marine Vibrios.Two invariant acidic pairs (Asp303-Asp304 and Asp437-Glu438 of VhGlcNAcase were mutated using a site-directed mutagenesis strategy. The effects of these mutations were examined and the catalytic roles of these active-site residues were elucidated using a chemical rescue approach. Enhancement of the enzymic activity of the VhGlcNAcase mutants was evaluated by a colorimetric assay using pNP-GlcNAc as substrate.Substitution of Asp303, Asp304, Asp437 or Glu438 with Ala/Asn/Gln produced a dramatic loss of the GlcNAcase activity. However, the activity of the inactive D437A mutant was recovered in the presence of sodium formate. Our kinetic data suggest that formate ion plays a nucleophilic role by mimicking the β-COO-side chain of Asp437, thereby stabilizing the reaction intermediate during both the glycosylation and the deglycosylation steps.Chemical rescue of the inactive D437A mutant of VhGlcNAcase by an added nucleophile helped to identify Asp437 as the catalytic nucleophile/base, and hence its acidic partner Glu438 as the catalytic proton donor/acceptor.Identification of the catalytic nucleophile of VhGlcNAcases supports the proposal of a substrate-assisted mechanism of GH20 GlcNAcases, requiring the catalytic pair Asp437-Glu438 for catalysis. The results suggest the mechanistic basis of the participation of β-N-acetylglucosaminidase in the chitin catabolic pathway of marine Vibrios.

  12. 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.

  13. 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)

  14. Mechanism of Catalytic Microtubule Depolymerization via KIF2-Tubulin Transitional Conformation

    Directory of Open Access Journals (Sweden)

    Tadayuki Ogawa

    2017-09-01

    Full Text Available Microtubules (MTs are dynamic structures that are fundamental for cell morphogenesis and motility. MT-associated motors work efficiently to perform their functions. Unlike other motile kinesins, KIF2 catalytically depolymerizes MTs from the peeled protofilament end during ATP hydrolysis. However, the detailed mechanism by which KIF2 drives processive MT depolymerization remains unknown. To elucidate the catalytic mechanism, the transitional KIF2-tubulin complex during MT depolymerization was analyzed through multiple methods, including atomic force microscopy, size-exclusion chromatography, multi-angle light scattering, small-angle X-ray scattering, analytical ultracentrifugation, and mass spectrometry. The analyses outlined the conformation in which one KIF2core domain binds tightly to two tubulin dimers in the middle pre-hydrolysis state during ATP hydrolysis, a process critical for catalytic MT depolymerization. The X-ray crystallographic structure of the KIF2core domain displays the activated conformation that sustains the large KIF2-tubulin 1:2 complex.

  15. New insights into the active site structure and catalytic mechanism of tyrosinase and its related proteins.

    Science.gov (United States)

    Olivares, Concepcion; Solano, Francisco

    2009-12-01

    Tyrosinases are widely distributed in nature. They are copper-containing oxidases belonging to the type 3 copper protein family, together with catechol oxidases and haemocyanins. Tyrosinases are essential enzymes in melanin biosynthesis and therefore responsible for pigmentation of skin and hair in mammals, where two more enzymes, the tyrosinase-related proteins (Tyrps), participate in the pathway. The structure and catalytic mechanism of mammalian tyrosinases have been extensively studied but they are not completely understood because of the lack of information on the tertiary structure. The availability of crystallographic data of one plant catechol oxidase and one bacterial tyrosinase has improved the model of the three-dimensional structure of the active site of the enzyme. Furthermore, sequence comparison of tyrosinase and the Tyrps reveals that the three orthologue proteins share many key structural features, because of their common origin from an ancestral gene, although the specific residues responsible for their different catalytic capabilities have not been identified yet. This review summarizes our current knowledge of tyrosinase and Tyrps structure and function and describes the catalytic mechanism of tyrosinase and Dct/Tyrp2, which are better characterized.

  16. A Review of the Catalytic Mechanism of Human Manganese Superoxide Dismutase

    Directory of Open Access Journals (Sweden)

    Jahaun Azadmanesh

    2018-01-01

    Full Text Available Superoxide dismutases (SODs are necessary antioxidant enzymes that protect cells from reactive oxygen species (ROS. Decreased levels of SODs or mutations that affect their catalytic activity have serious phenotypic consequences. SODs perform their bio-protective role by converting superoxide into oxygen and hydrogen peroxide by cyclic oxidation and reduction reactions with the active site metal. Mutations of SODs can cause cancer of the lung, colon, and lymphatic system, as well as neurodegenerative diseases such as Parkinson’s disease and amyotrophic lateral sclerosis. While SODs have proven to be of significant biological importance since their discovery in 1968, the mechanistic nature of their catalytic function remains elusive. Extensive investigations with a multitude of approaches have tried to unveil the catalytic workings of SODs, but experimental limitations have impeded direct observations of the mechanism. Here, we focus on human MnSOD, the most significant enzyme in protecting against ROS in the human body. Human MnSOD resides in the mitochondrial matrix, the location of up to 90% of cellular ROS generation. We review the current knowledge of the MnSOD enzymatic mechanism and ongoing studies into solving the remaining mysteries.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-03-24

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

  18. 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. 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)

  1. DFT study of the 1-octene metathesis reaction mechanism with WCl6/C catalytic system.

    Science.gov (United States)

    Yüksel, Dilek; Düz, Bülent; Sevin, Fatma

    2008-05-22

    A catalytic system consisting of tungsten carbene generated from WCl(6) and an atomic carbon is investigated theoretically for the metathesis of 1-octene at B3LYP/extended LANL2DZ level of DFT. The ground-state geometries and charge distributions of the structures belonging to the reaction mechanism are located. Energetics for the complete set of reactions, involving the formation of the tungsten carbene precatalyst, Cl(4)WCCl(2), the formation of tungsten methylidene and tungsten heptylidene with this precatalyst, and finally productive and degenerative metathesis steps with these alkylidene species are calculated in terms of total electronic energy and thermal energies. The free-energy (ΔG(298)) surfaces of the structures involved in the related reactions are constructed. In addition, solvent effects on the single point energies of the structures are investigated for two different solvents, namely, cyclohexane and chloroform. The results indicate that the formation of the catalytically active heptylidene is energetically favored in comparison to the formation of methylidene, while the degenerative and productive metathesis steps are competitive. In the catalytic cycle, the formation of ethylene is exothermic, while the formation of 7-tetradecene is endothermic. As expected, solvent effects on the metathesis reactions are minor and solvation does not cause any change in the directions of the overall metathesis reactions.

  2. 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

  3. (Catalytic mechanism of hydrogenase from aerobic N sub 2 -fixing microorganisms)

    Energy Technology Data Exchange (ETDEWEB)

    Arp, D.J.

    1990-01-01

    Hydrogenases are enzymes which catalyze reactions involving dihydrogen. They serve integral roles in a number of microbial metabolic pathways. Our research is focussed on investigations of the catalytic mechanism of the hydrogenases found in aerobic, N{sub 2}-fixing microorganisms such as Azotobacter vinelandii and the agronomically important Bradyrhizobium japonicum as well as microorganisms with similar hydrogenases. The hydrogenases isolated from these microorganisms are Ni- and Fe-containing heterodimers. Our work has focussed on three areas during the last grant period. In all cases, a central theme has been the role of inhibitors in the characteristics under investigation. In addition, a number of collaborative efforts have yielded interesting results. In metalloenzymes such as hydrogenase, inhibitors often influence the activity of the enzyme through ligand interactions with redox centers, often metals, within the enzyme. Therefore, investigations of the ability of various compounds to inhibit an enzyme's activity, as well as the mechanism of inhibition, can provide insight into the catalytic mechanism of the enzyme as well as the role of various redox centers in catalysis. We have investigated in detail four inhibitors of A. vinelandii and the results are summarized here. The influence of these inhibitors on the spectral properties of the enzyme are summarized. Electron paramagnetic resonance and ultraviolet spectra investigations are discussed. 9 figs.

  4. On the catalytic mechanism and stereospecificity of Escherichia coli L-threonine aldolase.

    Science.gov (United States)

    di Salvo, Martino L; Remesh, Soumya G; Vivoli, Mirella; Ghatge, Mohini S; Paiardini, Alessandro; D'Aguanno, Simona; Safo, Martin K; Contestabile, Roberto

    2014-01-01

    L-threonine aldolases (L-TAs) represent a family of homologous pyridoxal 5'-phosphate-dependent enzymes found in bacteria and fungi, and catalyse the reversible cleavage of several L-3-hydroxy-α-amino acids. L-TAs have great biotechnological potential, as they catalyse the formation of carbon-carbon bonds, and therefore may be exploited for the bioorganic synthesis of L-3-hydroxyamino acids that are biologically active or constitute building blocks for pharmaceutical molecules. Many L-TAs, showing different stereospecificity towards the Cβ configuration, have been isolated. Because of their potential to carry out diastereoselective syntheses, L-TAs have been subjected to structural, functional and mechanistic studies. Nevertheless, their catalytic mechanism and the structural bases of their stereospecificity have not been elucidated. In this study, we have determined the crystal structure of low-specificity L-TA from Escherichia coli at 2.2-Å resolution, in the unliganded form and cocrystallized with L-serine and L-threonine. Furthermore, several active site mutants have been functionally characterized in order to elucidate the reaction mechanism and the molecular bases of stereospecificity. No active site catalytic residue was revealed, and a structural water molecule was assumed to act as the catalytic base in the retro-aldol cleavage reaction. Interestingly, the very large active site opening of E. coli L-TA suggests that much larger molecules than L-threonine isomers may be easily accommodated, and L-TAs may actually have diverse physiological functions in different organisms. Substrate recognition and reaction specificity seem to be guided by the overall microenvironment that surrounds the substrate at the enzyme active site, rather than by one ore more specific residues. © 2013 FEBS.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-01-01

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

  6. A Common Catalytic Mechanism for Proteins of the HutI Family

    Energy Technology Data Exchange (ETDEWEB)

    Tyagi,R.; Eswaramoorthy, S.; Burley, S.; Raushel, F.; Swaminathan, S.

    2008-01-01

    Imidazolonepropionase (HutI) (imidazolone-5-propanote hydrolase, EC 3.5.2.7) is a member of the amidohydrolase superfamily and catalyzes the conversion of imidazolone-5-propanoate to N-formimino-l-glutamate in the histidine degradation pathway. We have determined the three-dimensional crystal structures of HutI from Agrobacterium tumefaciens (At-HutI) and an environmental sample from the Sargasso Sea Ocean Going Survey (Es-HutI) bound to the product [N-formimino-l-glutamate (NIG)] and an inhibitor [3-(2, 5-dioxoimidazolidin-4-yl)propionic acid (DIP)], respectively. In both structures, the active site is contained within each monomer, and its organization displays the landmark feature of the amidohydrolase superfamily, showing a metal ligand (iron), four histidines, and one aspartic acid. A catalytic mechanism involving His265 is proposed on the basis of the inhibitor-bound structure. This mechanism is applicable to all HutI forms.

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

    NARCIS (Netherlands)

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

    2002-01-01

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

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

    NARCIS (Netherlands)

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

    2002-01-01

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

  9. 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.

  10. Active site structure and catalytic mechanism of phosphodiesterase for degradation of intracellular second messengers

    Science.gov (United States)

    Zhan, Chang-Guo

    2002-03-01

    Phosphodiesterases are clinical targets for a variety of biological disorders, because this superfamily of enzymes regulate intracellular concentration of cyclic nucleotides that serve as the second messengers playing a critical role in a variety of physiological processes. Understanding structure and mechanism of a phosphodiesterase will provide a solid basis for rational design of the more efficient therapeutics. Although a three-dimensional X-ray crystal structure of the catalytic domain of human phosphodiesterase 4B2B was recently reported, it was uncertain whether a critical bridging ligand in the active site is a water molecule or a hydroxide ion. The identity of this bridging ligand has been determined by performing first-principles quantum chemical calculations on models of the active site. All the results obtained indicate that this critical bridging ligand in the active site of the reported X-ray crystal structure is a hydroxide ion, rather than a water molecule, expected to serve as the nucleophile to initialize the catalytic degradation of the intracellular second messengers.

  11. Carbohydrate synthesis by disaccharide phosphorylases: reactions, catalytic mechanisms and application in the glycosciences.

    Science.gov (United States)

    Luley-Goedl, Christiane; Nidetzky, Bernd

    2010-12-01

    Disaccharide phosphorylases are glycosyltransferases (EC 2.4.1.α) of specialized carbohydrate metabolism in microorganisms. They catalyze glycosyl transfer to phosphate using a disaccharide as donor substrate. Phosphorylases for the conversion of naturally abundant disaccharides including sucrose, maltose, α,α-trehalose, cellobiose, chitobiose, and laminaribiose have been described. Structurally, these disaccharide phosphorylases are often closely related to glycoside hydrolases and transglycosidases. Mechanistically, they are categorized according the stereochemical course of the reaction catalyzed, whereby the anomeric configuration of the disaccharide donor substrate may be retained or inverted in the sugar 1-phosphate product. Glycosyl transfer with inversion is thought to occur through a single displacement-like catalytic mechanism, exemplified by the reaction coordinate of cellobiose/chitobiose phosphorylase. Reaction via configurational retention takes place through the double displacement-like mechanism employed by sucrose phosphorylase. Retaining α,α-trehalose phosphorylase (from fungi) utilizes a different catalytic strategy, perhaps best described by a direct displacement mechanism, to achieve stereochemical control in an overall retentive transformation. Disaccharide phosphorylases have recently attracted renewed interest as catalysts for synthesis of glycosides to be applied as food additives and cosmetic ingredients. Relevant examples are lacto-N-biose and glucosylglycerol whose enzymatic production was achieved on multikilogram scale. Protein engineering of phosphorylases is currently pursued in different laboratories with the aim of broadening the donor and acceptor substrate specificities of naturally existing enzyme forms, to eventually generate a toolbox of new catalysts for glycoside synthesis. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 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.

  13. 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.

  14. Modeling the detailed kinetics of mitochondrial cytochrome c oxidase: Catalytic mechanism and nitric oxide inhibition.

    Science.gov (United States)

    Pannala, Venkat R; Camara, Amadou K S; Dash, Ranjan K

    2016-11-01

    Cytochrome c oxidase (CcO) catalyzes the exothermic reduction of O 2 to H 2 O by using electrons from cytochrome c, and hence plays a crucial role in ATP production. Although details on the enzyme structure and redox centers involved in O 2 reduction have been known, there still remains a considerable ambiguity on its mechanism of action, e.g., the number of sequential electrons donated to O 2 in each catalytic step, the sites of protonation and proton pumping, and nitric oxide (NO) inhibition mechanism. In this work, we developed a thermodynamically constrained mechanistic mathematical model for the catalytic action of CcO based on available kinetic data. The model considers a minimal number of redox centers on CcO and couples electron transfer and proton pumping driven by proton motive force (PMF), and accounts for the inhibitory effects of NO on the reaction kinetics. The model is able to fit well all the available kinetic data under diverse experimental conditions with a physiologically realistic unique parameter set. The model predictions show that: 1) the apparent K m of O 2 varies considerably and increases from fully reduced to fully oxidized cytochrome c depending on pH and the energy state of mitochondria, and 2) the intermediate enzyme states depend on pH and cytochrome c redox fraction and play a central role in coupling mitochondrial respiration to PMF. The developed CcO model can easily be integrated into existing mitochondrial bioenergetics models to understand the role of the enzyme in controlling oxidative phosphorylation in normal and disease conditions. Copyright © 2016 the American Physiological Society.

  15. 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

    phosphatidylcholine, in phospholipase C. This catalytically essential water molecule, after being activated by an acidic residue (Asp55), performs the nucleophilic attack on the phosphorus atom in the substrate, leading to a trigonal bipyramidal pentacoordinated intermediate (and structurally similar transition state...... 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...... the complex and a water molecule. The nucleophilic water molecule is positioned at a distance (3.8 A) from the phosphorus atom in the substrate, which is in good agreement with experimentally observed distances. Finally, the stability of the complex between phospholipase C, the substrate, and the nucleophilic...

  16. Operating envelope of a short contact time fuel reformer for propane catalytic partial oxidation

    Science.gov (United States)

    Waller, Michael G.; Walluk, Mark R.; Trabold, Thomas A.

    2015-01-01

    Fuel cell technology has yet to realize widespread deployment, in part because of the hydrogen fuel infrastructure required for proton exchange membrane systems. One option to overcome this barrier is to produce hydrogen by reforming propane, which has existing widespread infrastructure, is widely used by the general public, easily transported, and has a high energy density. The present work combines thermodynamic modeling of propane catalytic partial oxidation (cPOx) and experimental performance of a Precision Combustion Inc. (PCI) Microlith® reactor with real-time soot measurement. Much of the reforming research using Microlith-based reactors has focused on fuels such as natural gas, JP-8, diesel, and gasoline, but little research on propane reforming with Microlith-based catalysts can be found in literature. The aim of this study was to determine the optimal operating parameters for the reformer that maximizes efficiency and minimizes solid carbon formation. The primary parameters evaluated were reformate composition, carbon concentration in the effluent, and reforming efficiency as a function of catalyst temperature and O2/C ratio. Including the lower heating values for product hydrogen and carbon monoxide, efficiency of 84% was achieved at an O2/C ratio of 0.53 and a catalyst temperature of 940 °C, resulting in near equilibrium performance. Significant solid carbon formation was observed at much lower catalyst temperatures, and carbon concentration in the effluent was determined to have a negative linear relationship at T reactor displayed good stability during more than 80 experiments with temperature cycling from 360 to 1050 °C.

  17. QM/MM study of catalytic mechanism of Xylanase Cex from Cellulomonas fimi.

    Science.gov (United States)

    Liu, Jingli; Zhang, Chunchun; Xu, Dingguo

    2012-07-01

    Xylanase Cex from Cellulomonas fimi is a bifunctional enzyme that catalyzes the degradation of both cellulose and xylan. As a result, it might find valuable applications in production of biofuels. In this work, we presented a detailed theoretical investigation of hydrolysis of the xylopentaose molecule catalyzed by Cex, using a hybrid quantum mechanical and molecular mechanical approach. Our results support the experimental observation that the hydrolysis proceeds via the net retention mechanism. More interestingly, our simulations indicate that the xylose unit at -1 binding site should take a boat (B₂,₅) conformation as a possible reactive conformer, while the oxo-carbenium ion-like transition states take the combination of B₂,₅/⁰S₂ for glycosylation, and ⁰S₂/⁰,³B for deglycosylation. Our molecular dynamics simulations of mutants further suggest that two catalytic residues (E127 and E233) play the vital role in this ring distortion. Indeed, this conformational change is necessary to facilitate the first step of nucleophilic attack by E233 at the anomeric carbon center. Copyright © 2012 Elsevier Inc. All rights reserved.

  18. 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.

  19. 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

  20. 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.

  1. Structures and kinetics for plant nucleoside triphosphate diphosphohydrolases support a domain motion catalytic mechanism.

    Science.gov (United States)

    Summers, Emma L; Cumming, Mathew H; Oulavallickal, Tifany; Roberts, Nicholas J; Arcus, Vickery L

    2017-08-01

    Extracellular nucleoside triphosphate diphosphohydrolases (NTPDases) are enzymes that hydrolyze extracellular nucleotides to the respective monophosphate nucleotides. In the past 20 years, NTPDases belonging to mammalian, parasitic and prokaryotic domains of life have been discovered, cloned and characterized. We reveal the first structures of NTPDases from the legume plant species Trifolium repens (7WC) and Vigna unguiculata subsp. cylindrica (DbLNP). Four crystal structures of 7WC and DbLNP were determined at resolutions between 1.9 and 2.6 Å. For 7WC, structures were determined for an -apo form (1.89 Å) and with the product AMP (2.15 Å) and adenine and phosphate (1.76 Å) bound. For DbLNP, a structure was solved with phosphate and manganese bound (2.60 Å). Thorough kinetic data and analysis is presented. The structure of 7WC and DbLNP reveals that these NTPDases can adopt two conformations depending on the molecule and co-factor bound in the active site. A central hinge region creates a "butterfly-like" motion of the domains that reduces the width of the inter-domain active site cleft upon molecule binding. This phenomenon has been previously described in Rattus norvegicus and Legionella pneumophila NTPDaseI and Toxoplasma gondii NTPDaseIII suggesting a common catalytic mechanism across the domains of life. © 2017 The Protein Society.

  2. 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.

  3. 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.

  4. 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.

  5. 40 CFR Table 23 to Subpart Uuu of... - Operating Limits for Inorganic HAP Emission Limitations for Catalytic Reforming Units

    Science.gov (United States)

    2010-07-01

    ... Emission Limitations for Catalytic Reforming Units 23 Table 23 to Subpart UUU of Part 63 Protection of... Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery... Emission Limitations for Catalytic Reforming Units As stated in § 63.1567(a)(2), you shall meet each...

  6. 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.

  7. Solid-oxide fuel cell operated on in situ catalytic decomposition products of liquid hydrazine

    Science.gov (United States)

    Gu, Hongxia; Ran, Ran; Zhou, Wei; Shao, Zongping; Jin, Wanqin; Xu, Nanping; Ahn, Jeongmin

    Hydrazine was examined as a fuel for a solid-oxide fuel cell (SOFC) that employed a typical nickel-based anode. An in situ catalytic decomposition of hydrazine at liquid state under room temperature and ambient pressure before introducing to the fuel cell was developed by applying a Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ (BSCF) oxide catalyst. Catalytic testing demonstrated that liquid N 2H 4 can be decomposed to gaseous NH 3 and H 2 at a favorable rate and at a temperature as low as 20 °C and H 2 selectivity reaching values as high as 10% at 60 °C. Comparable fuel cell performance was observed using either the in situ decomposition products of hydrazine or pure hydrogen as fuel. A peak power density of ∼850 mW cm -2 at 900 °C was obtained with a typical fuel cell composed of scandia-stabilized zirconia and La 0.8Sr 0.2MnO 3 cathode. The high energy and power density, easy storage and simplicity in fuel delivery make it highly attractive for portable applications.

  8. 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

  9. 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

  10. Analysis of costs and returns of mechanized fishing boat operations ...

    African Journals Online (AJOL)

    Analysis of costs and returns of mechanized fishing boat operations in India. KS Bose, PV Sarma. Abstract. This article makes an attempt to analyze the cost and returns of Mechanized Fishing Boat Operators (MFBO's) and the determinants of the selected MFBOs. The study is based on a sample of 180 MFBOs operating ...

  11. Characterization and mechanism insight of accelerated catalytic promiscuity of Sulfolobus tokodaii (ST0779) peptidase for aldol addition reaction.

    Science.gov (United States)

    Li, Rong; Perez, Bianca; Jian, Hui; Jensen, Mads Mørk; Gao, Renjun; Dong, Mingdong; Glasius, Marianne; Guo, Zheng

    2015-11-01

    A novel peptidase from thermophilic archaea Sulfolobus tokodaii (ST0779) is examined for its catalytic promiscuity of aldol addition, which shows comparable activity as porcine pancreatic lipase (PPL, one of the best enzymes identified for biocatalytic aldol addition) at 30 °C but much accelerated activity at elevated temperature. The molecular catalytic efficiency kcat/Km (M(-1) s(-1)) of this thermostable enzyme at 55 °C adds up to 140 times higher than that of PPL at its optimum temperature 37 °C. The fluorescence quenching analysis depicts that the binding constants of PPL are significantly higher than those of ST0779, and their numbers of binding sites show opposite temperature dependency. Thermodynamic parameters estimated by fluorescence quenching analysis unveil distinctly different substrate-binding modes between PPL and ST0779: the governing binding interaction between PPL and substrates is hydrophobic force, while the dominating substrate-binding forces for ST0779 are van der Waals and H-bonds interactions. A reasonable mechanism for ST0779-catalyzed aldol reaction is proposed based on kinetic study, spectroscopic analysis, and molecular stereostructure simulation. This work represents a successful example to identify a new enzyme for catalytic promiscuity, which demonstrates a huge potential to discover and exploit novel biocatalyst from thermophile microorganism sources.

  12. Enhancement mechanism of heterogeneous catalytic ozonation by cordierite-supported copper for the degradation of nitrobenzene in aqueous solution.

    Science.gov (United States)

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

    2009-03-15

    The use of cordierite or Cu-cordierite for heterogeneous catalytic ozonation enhances significantly the degradation efficiency and the TOC removal of nitrobenzene in aqueous solution relative to ozonation alone, owing to the synergistic effect between ozone and the catalysts, and the modification process with Cu can increase the catalytic activity of cordierite forthe ozonation of nitrobenzene. The adsorption of nitrobenzene is too small to make a significant contribution to the degradation of nitrobenzene in either of the processes of catalytic ozonation. The initiation of hydroxyl radical (*OH) improves as the amount of Cu-cordierite catalyst is increased, meaning that the degradation of nitrobenzene is mainly attributed to *OH oxidation. The modification by loading Cu increases the density of surface hydroxyl groups and the pH at the point of zero charge (pH(PZC)) of raw cordierite. The investigation of the enhancement mechanism confirms that the modification by loading Cu causes changes of density of surface hydroxyl groups, pH(PZC), and /pH - pH(PZC)/, resulting in the acceleration initiation of *OH which can promote the degradation of nitrobenzene. The result shows that the optimal critical loading percentage of Cu is 3% under the present experimental conditions.

  13. New Ulvan-Degrading Polysaccharide Lyase Family: Structure and Catalytic Mechanism Suggests Convergent Evolution of Active Site Architecture.

    Science.gov (United States)

    Ulaganathan, ThirumalaiSelvi; Boniecki, Michal T; Foran, Elizabeth; Buravenkov, Vitaliy; Mizrachi, Naama; Banin, Ehud; Helbert, William; Cygler, Miroslaw

    2017-05-19

    Ulvan is a complex sulfated polysaccharide biosynthesized by green seaweed and contains predominantly rhamnose, xylose, and uronic acid sugars. Ulvan-degrading enzymes have only recently been identified and added to the CAZy ( www.cazy.org ) database as family PL24, but neither their structure nor catalytic mechanism(s) are yet known. Several homologous, new ulvan lyases, have been discovered in Pseudoalteromonas sp. strain PLSV, Alteromonas LOR, and Nonlabens ulvanivorans, defining a new family PL25, with the lyase encoded by the gene PLSV_3936 being one of them. This enzyme cleaves the glycosidic bond between 3-sulfated rhamnose (R3S) and glucuronic acid (GlcA) or iduronic acid (IdoA) via a β-elimination mechanism. We report the crystal structure of PLSV_3936 and its complex with a tetrasaccharide substrate. PLSV_3936 folds into a seven-bladed β-propeller, with each blade consisting of four antiparallel β-strands. Sequence conservation analysis identified a highly conserved region lining at one end of a deep crevice on the protein surface. The putative active site was identified by mutagenesis and activity measurements. Crystal structure of the enzyme with a bound tetrasaccharide substrate confirmed the identity of base and acid residues and allowed determination of the catalytic mechanism and also the identification of residues neutralizing the uronic acid carboxylic group. The PLSV_3936 structure provides an example of a convergent evolution among polysaccharide lyases toward a common active site architecture embedded in distinct folds.

  14. 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...... to dissociation. Our analysis of the dissociation process suggests that it is not possible to define, in some well specified way, a precursor state at typical temperatures in the technical ammonia synthesis. The kinetic scheme for the complete ammonia synthesis without the precursor state can still account...... for the observed conversion to ammonia. We have constructed an empirical potential energy surface for N-2/Fe(111) which has barriers to dissociation even larger than for the previously studied N-2/Re system. It is shown that the presence of barriers is consistent with the observation that the activation energy...

  15. 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.

  16. Catalytic Mechanism of Salicylate Dioxygenase: QM/MM Simulations Reveal the Origin of Unexpected Regioselectivity of the Ring Cleavage.

    Science.gov (United States)

    Roy, Subhendu; Kästner, Johannes

    2017-07-03

    Salicylate 1,2-dioxygenase (SDO) was the first enzyme discovered, in the family of iron dioxygenases, to catalyze the ring cleavage of a monohydroxylated aromatic compound, salicylate, without a proton donor. Salicylate is not electron-rich like the familiar dihydroxy or aromatic substrates with an electron-donating group that are utilized in the well-known dioxygenases. SDO carries out the intramolecular C-C bond cleavage in salicylate bearing the OH and COOH groups with high regioselectivity in comparison with the extradiol and intradiol dioxygenases. The catalytic cleavage of a nonactivated substrate like salicylate that lacks an electron-donating group, also in the absence of a proton source, raises many puzzling questions about the oxy intermediates in the reaction pathway of dioxygenase enzymes in general. To answer these fundamental queries, we have investigated the full catalytic mechanism of SDO by a combination of quantum mechanics and molecular mechanics (QM/MM) calculations. Herein, our QM/MM study has several unexpected and interesting implications for the mechanistic pathway of SDO in comparison to the experimental observations. Importantly, it unravels the basis for the unexpected "intra"-cleavage regioselectivity in SDO. Ostensibly a similar alkylperoxo intermediate is formed in SDO much like in the extradiol and intradiol dioxygenases. In stark contrast to the two diol enzymes, the O-O bond breaking leads to an unprotonated gem-hydroxy carboxylate intermediate, a paradigm analogue of the elusive gem diol intermediate. This unprotonated gem-hydroxy carboxylate intermediate exclusively dictates the C-C cleavage regiospecificity in SDO, which is unprecedented in the family of dioxygenases. It forms a seven-membered lactone species, which eventually forms the ring-cleavage final product by incorporation of two oxygen atoms in the salicylate. Thus, our computational study unravels a detailed reaction pathway of the oxidative cleavage of salicylate

  17. 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 ...

  18. MECHANIZATION OF FARM OPERATIONS IN 1965.

    Science.gov (United States)

    SANDERS, GROVER H.

    INCREASED MECHANIZATION, MORE EXTENSIVE USE OF CHEMICALS, AND OTHER TECHNOLOGICAL DEVELOPMENTS HAVE REDUCED FARM-LABOR NEEDS AND INCREASED AGRICULTURAL PRODUCTION. COTTON, SUGAR BEETS, POTATOES, AND VEGETABLES FOR PROCESSING ARE SOME OF THE CROPS REQUIRING FEWER MAN-HOURS DUE TO NEW OR IMPROVED TECHNOLOGY. CONTINUOUS EFFORT HAS BEEN MADE TO DESIGN…

  19. Structure and Molecular Dynamics Simulations of Protein Tyrosine Phosphatase Non-Receptor 12 Provide Insights into the Catalytic Mechanism of the Enzyme

    Directory of Open Access Journals (Sweden)

    Hui Dong

    2017-12-01

    Full Text Available Protein tyrosine phosphatase non-receptor 12 (PTPN12 is an important protein tyrosine phosphatase involved in regulating cell adhesion and migration as well as tumorigenesis. Here, we solved a crystal structure of the native PTPN12 catalytic domain with the catalytic cysteine (residue 231 in dual conformation (phosphorylated and unphosphorylated. Combined with molecular dynamics simulation data, we concluded that those two conformations represent different states of the protein which are realized during the dephosphorylation reaction. Together with docking and mutagenesis data, our results provide a molecular basis for understanding the catalytic mechanism of PTPN12 and its role in tumorigenesis.

  20. 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.

  1. 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)

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

    Directory of Open Access Journals (Sweden)

    Chaikuad Apirat

    2012-06-01

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

  3. Newton-Wigner position operator and the corresponding spin operator in relativistic quantum mechanics

    Science.gov (United States)

    Choi, Taeseung

    2015-03-01

    A relativistic spin operator is the difference between the total and the orbital angular momentum. As the unique position operator for a localized state, the remarkable Newton-Wigner position operator, which has all the desirable commutation relations of a position operator, can give a proper spin operator. Historically, the three important spin operators proposed by Bogolubov et al., Pryce, and Foldy-Woutheysen, respectively were investigated to manifest a spin operator corresponding to the Newton-Wigner position operator. We clarify a unique spin operator in relativistic quantum mechanics, which can be described by using the Dirac Hamiltonian.

  4. 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)

  5. 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.

  6. Structure-function analyses of a PL24 family ulvan lyase reveal key features and suggest its catalytic mechanism.

    Science.gov (United States)

    Ulaganathan, ThirumalaiSelvi; Helbert, William; Kopel, Moran; Banin, Ehud; Cygler, Miroslaw

    2018-01-30

    Ulvan is a major cell wall component of green algae of the genus Ulva and some marine bacteria encode enzymes that can degrade this polysaccharide. The first ulvan degrading lyases have been recently characterized and several putative ulvan lyases have been recombinantly expressed, confirmed as ulvan lyases and partially characterized. Two families of ulvan degrading lyases, PL24 and PL25, have recently been established. The PL24 lyase LOR_107 from the bacterial Alteromonadales sp. strain LOR degrades ulvan endolytically, cleaving the bond at the C4 of a glucuronic acid. However, the mechanism and LOR_107 structural features involved are unknown. We present here the crystal structure of LOR_107, representing the first PL24 family structure. We found that LOR_107 adopts a seven-bladed β-propeller fold with a deep canyon on one side of the protein. Comparative sequence analysis revealed a cluster of conserved residues within this canyon, and site-directed mutagenesis disclosed several residues essential for catalysis. We also found that LOR_107 uses the His/Tyr catalytic mechanism, common to several PL families. We captured a tetrasaccharide substrate in the structures of two inactive mutants, which indicated a two-step binding event, with the first substrate interaction near the top of the canyon coordinated by Arg-320, followed by sliding of the substrate into the canyon toward the active-site residues. Surprisingly, the LOR_107 structure was very similar to that of PL25 family PLSV_3936, despite only ~14% sequence identity between the two enzymes. On the basis of our structural and mutational analyses, we propose a catalytic mechanism for LOR_107 that differs from the typical His/Tyr mechanism. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

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

    African Journals Online (AJOL)

    MODIFICATION OF SEQUENCE OF UNIT. OPERATIONS IN MECHANIZED PALM FRUIT. PROCESSING. B.N. Nwankwojikea, A.O. Odukweb, J.C. Agunwambac a. Department of Mechanical Engineering, Michael Okpara University of Agriculture,. Umudike, Abia State, Nigeria. b. Department of Mechanical Engineering, ...

  8. Theoretical study of catalytic mechanism for single-site water oxidation process.

    Science.gov (United States)

    Lin, Xiangsong; Hu, Xiangqian; Concepcion, Javier J; Chen, Zuofeng; Liu, Shubin; Meyer, Thomas J; Yang, Weitao

    2012-09-25

    Water oxidation is a linchpin in solar fuels formation, and catalysis by single-site ruthenium complexes has generated significant interest in this area. Combining several theoretical tools, we have studied the entire catalytic cycle of water oxidation for a single-site catalyst starting with [Ru(II)(tpy)(bpm)(OH(2))](2+) (i.e., [Ru(II)-OH(2)](2+); tpy is 2,2':6',2''-terpyridine and bpm is 2,2'-bypyrimidine) as a representative example of a new class of single-site catalysts. The redox potentials and pK(a) calculations for the first two proton-coupled electron transfers (PCETs) from [Ru(II)-OH(2)](2+) to [Ru(IV) = O](2+) and the following electron-transfer process to [Ru(V) = O](3+) suggest that these processes can proceed readily in acidic or weakly basic conditions. The subsequent water splitting process involves two water molecules, [Ru(V) = O](3+) to generate [Ru(III)-OOH](2+), and H(3)O(+) with a low activation barrier (~10 kcal/mol). After the key O-O bond forming step in the single-site Ru catalysis, another PECT process oxidizes [Ru(III)-OOH](2+) to [Ru(IV)-OO](2+) when the pH is lower than 3.7. Two possible forms of [Ru(IV)-OO](2+), open and closed, can exist and interconvert with a low activation barrier (catalytic cycle. This understanding is helpful in the design of new catalysts for water oxidation.

  9. 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

  10. Anatomy of an energy-coupling mechanism--the interlocking catalytic cycles of the ATP sulfurylase-GTPase system.

    Science.gov (United States)

    Sun, Meihao; Leyh, Thomas S

    2005-10-25

    ATP sulfurylase, from Escherichia coli K-12, conformationally couples the rates and chemical potentials of the two reactions that it catalyzes, GTP hydrolysis and activated sulfate synthesis. The enzyme is rare among such coupling systems in that it links the potentials of small-molecule chemistries to one another, rather than to vectorial motion. The pre-steady-state stages of the catalytic cycle of ATP sulfurylase were studied using tools capable of distinguishing between enzyme-bound and solution-phase product for each of the four products of the enzyme. The study reveals that the two chemistries are linked at multiple points in the reaction coordinate. Linking begins with an isomerization prior to chemistry that initiates an ordered cleavage of the beta,gamma and alpha,beta bonds of GTP and ATP, respectively; the rates of these three sequential events increase successively, causing them to appear simultaneous. Linking is again seen in the late stages of the catalytic cycle: product release is ordered with P(i) departing prior to either GDP or PP(i). Release rate constants are determined for each product and used to construct a quantitative model of the mechanism that accurately predicts the behavior of this complex system.

  11. 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.)

  12. Sup(*)-algebras of unbounded operators in statistical mechanics

    International Nuclear Information System (INIS)

    Moore, S.M.

    1978-01-01

    A formulation of statistical mechanics is proposed which employs algebraic methods and unbounded operators. A tentative axiom system is developed which includes the KMS condition as the definition of equilibrium state. (author)

  13. Different Mechanisms of Catalytic Complex Formation in Two L-Tryptophan Processing Dioxygenases

    Directory of Open Access Journals (Sweden)

    Karin Nienhaus

    2018-01-01

    Full Text Available The human heme enzymes tryptophan 2,3-dioxygenase (hTDO and indoleamine 2,3 dioxygenase (hIDO catalyze the initial step in L-tryptophan (L-Trp catabolism, the insertion of dioxygen into L-Trp. Overexpression of these enzymes causes depletion of L-Trp and accumulation of metabolic products, and thereby contributes to tumor immune tolerance and immune dysregulation in a variety of disease pathologies. Understanding the assembly of the catalytically active, ternary enzyme-substrate-ligand complexes is not yet fully resolved, but an essential prerequisite for designing efficient and selective de novo inhibitors. Evidence is mounting that the ternary complex forms by sequential binding of ligand and substrate in a specific order. In hTDO, the apolar L-Trp binds first, decreasing active-site solvation and, as a result, reducing non-productive oxidation of the heme iron by the dioxygen ligand, which may leave the substrate bound to a ferric heme iron. In hIDO, by contrast, dioxygen must first coordinate to the heme iron because a bound substrate would occlude ligand access to the heme iron, so the ternary complex can no longer form. Consequently, faster association of L-Trp at high concentrations results in substrate inhibition. Here, we summarize our present knowledge of ternary complex formation in hTDO and hIDO and relate these findings to structural peculiarities of their active sites.

  14. Structural and biochemical characterization of MCAT from photosynthetic microorganism Synechocystis sp. PCC 6803 reveal its stepwise catalytic mechanism.

    Science.gov (United States)

    Liu, Yinghui; Feng, Yanbin; Wang, Yayue; Li, Xia; Cao, Xupeng; Xue, Song

    2015-02-13

    Malonyl-coenzyme A: acyl-carrier protein transacylase (MCAT) catalyzes the transfer of malonyl group from malonyl-CoA to the holo-acyl carrier protein (Holo-ACP), yielding malonyl-ACP. The overall reaction has been extensively studied in heterotrophic microorganisms, while its mechanism in photosynthetic autotrophs as well as the stepwise reaction information remains unclear. Here the 2.42 Å crystal structure of MCAT from photosynthetic microorganism Synechocystis sp. PCC 6803 is presented. It demonstrates that Arg113, Ser88 and His188 constitute catalytic triad. The second step involved ACP-MCAT-malonyl intermediate is speed-limited instead of the malonyl-CoA-MCAT intermediate in the first step. Therefore His87, Arg113 and Ser88 render different contributions for the two intermediates. Additionally, S88T mutant initializes the reaction by H87 deprotonating S88T which is different from the wild type. Copyright © 2015 Elsevier Inc. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Julie A Tucker

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

  16. 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 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

  17. Projection operator techniques in Lagrangian mechanics: symmetrically coupled oscillators

    OpenAIRE

    J. N. Boyd; P. N. Raychowdhury

    1980-01-01

    We apply projection operator techniques to the computation of the natural frequencies of oscillation for three symmetrically coupled mechanical systems. In each case, the rotation subgroup of the full symmetry group is used to determine the projection operators with the result that the Lagrangian must be expressed in terms of complex-valued coordinates. In the coordinate system obtained from the action of the projection operators upon the original coordinates, the Lagrangian yields equations ...

  18. Catalytic degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nano-Fe2O3activated peroxymonosulfate: Influential factors and mechanism determination.

    Science.gov (United States)

    Jaafarzadeh, Nematollah; Ghanbari, Farshid; Ahmadi, Mehdi

    2017-02-01

    2,4-Dichlorophenoxyacetic acid (2,4-D) is one of the most applicable herbicides in the world. Therefore, its residue in aquatic environment threatens the human health and ecosystems. In this study, Fe 2 O 3 (hematite) nanoparticles (HNPs) were synthesized, and the characteristics of the obtained HNPs were determined using X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) technique, and particle size analyzer (PSA). The catalytic activity of HNPs was evaluated for the activation of peroxymonosulfate (PMS) for the degradation of 2,4-D. The effects of the operating parameters were studied for the PMS/HNPs system. The results showed that the acidic condition provided higher efficiency, while overdosing of PMS had a scavenging effect. The PMS/HNPs showed high efficiency in comparison with the homogeneous forms of iron (Fe 2+ and Fe 3+ ). Reusability of HNPs was studied in five consequent usages. The presence of the anions (chloride, nitrate, and hydrogen phosphate) reduced the 2,4-D degradation. Moreover, the catalytic activity of HNPs was also investigated in the presence of other oxidants. UV irradiation increased the function of PMS/HNPs and its mechanism was described. The order of 2,4-D removal for the oxidants was PMS > persulfate > H 2 O 2  > percarbonate. A total of 29.7% of 2,4-D chlorine content was released during the destruction of 2,4-D. The quenching study showed that sulfate radical was the major agent in the degradation of 2,4-D. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Structures of intermediates along the catalytic cycle of terminal deoxynucleotidyltransferase: dynamical aspects of the two-metal ion mechanism.

    Science.gov (United States)

    Gouge, Jérôme; Rosario, Sandrine; Romain, Félix; Beguin, Pierre; Delarue, Marc

    2013-11-15

    Terminal deoxynucleotidyltransferase (Tdt) is a non-templated eukaryotic DNA polymerase of the polX family that is responsible for the random addition of nucleotides at the V(D)J junctions of immunoglobulins and T-cell receptors. Here we describe a series of high-resolution X-ray structures that mimic the pre-catalytic state, the post-catalytic state and a competent state that can be transformed into the two other ones in crystallo via the addition of dAMPcPP and Zn(2+), respectively. We examined the effect of Mn(2+), Co(2+) and Zn(2+) because they all have a marked influence on the kinetics of the reaction. We demonstrate a dynamic role of divalent transition metal ions bound to site A: (i) Zn(2+) (or Co(2+)) in Metal A site changes coordination from octahedral to tetrahedral after the chemical step, which explains the known higher affinity of Tdt for the primer strand when these ions are present, and (ii) metal A has to leave to allow the translocation of the primer strand and to clear the active site, a typical feature for a ratchet-like mechanism. Except for Zn(2+), the sugar puckering of the primer strand 3' terminus changes from C2'-endo to C3'-endo during catalysis. In addition, our data are compatible with a scheme where metal A is the last component that binds to the active site to complete its productive assembly, as already inferred in human pol beta. The new structures have potential implications for modeling pol mu, a closely related polX implicated in the repair of DNA double-strand breaks, in a complex with a DNA synapsis. © 2013.

  20. New Insight into the Catalytic Mechanism of Bacterial MraY from Enzyme Kinetics and Docking Studies*

    Science.gov (United States)

    Liu, Yao; Rodrigues, João P. G. L. M.; Bonvin, Alexandre M. J. J.; Zaal, Esther A.; Berkers, Celia R.; Heger, Michal; Gawarecka, Katarzyna; Swiezewska, Ewa; Breukink, Eefjan; Egmond, Maarten R.

    2016-01-01

    Phospho-MurNAc-pentapeptide translocase (MraY) catalyzes the synthesis of Lipid I, a bacterial peptidoglycan precursor. As such, MraY is essential for bacterial survival and therefore is an ideal target for developing novel antibiotics. However, the understanding of its catalytic mechanism, despite the recently determined crystal structure, remains limited. In the present study, the kinetic properties of Bacillus subtilis MraY (BsMraY) were investigated by fluorescence enhancement using dansylated UDP-MurNAc-pentapeptide and heptaprenyl phosphate (C35-P, short-chain homolog of undecaprenyl phosphate, the endogenous substrate of MraY) as second substrate. Varying the concentrations of both of these substrates and fitting the kinetics data to two-substrate models showed that the concomitant binding of both UDP-MurNAc-pentapeptide-DNS and C35-P to the enzyme is required before the release of the two products, Lipid I and UMP. We built a model of BsMraY and performed docking studies with the substrate C35-P to further deepen our understanding of how MraY accommodates this lipid substrate. Based on these modeling studies, a novel catalytic role was put forward for a fully conserved histidine residue in MraY (His-289 in BsMraY), which has been experimentally confirmed to be essential for MraY activity. Using the current model of BsMraY, we propose that a small conformational change is necessary to relocate the His-289 residue, such that the translocase reaction can proceed via a nucleophilic attack of the phosphate moiety of C35-P on bound UDP-MurNAc-pentapeptide. PMID:27226570

  1. 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)

  2. 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...

  3. 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...

  4. Counter operation in nonlinear micro-electro-mechanical resonators

    International Nuclear Information System (INIS)

    Yao, Atsushi; Hikihara, Takashi

    2013-01-01

    This Letter discusses a logical operation of multi-memories that consist of coupled nonlinear micro-electro-mechanical systems (MEMS) resonators. A MEMS resonator shows two coexisting stable states when nonlinear responses appear. Previous studies addressed that a micro- or nano-electrical-mechanical resonator can be utilized as a mechanical 1-bit memory or mechanical logic gates. The next phase is the development of logic system with coupled multi-resonators. From the viewpoint of application of nonlinear dynamics in coupled MEMS resonators, we show the first experimental success of the controlling nonlinear behavior as a 2-bit binary counter.

  5. The mechanism for catalytic hydrosilylation by bis(imino)pyridine iron olefin complexes supported by broken symmetry density functional theory.

    Science.gov (United States)

    Lam, Yan Choi; Nielsen, Robert J; Goddard, William A; Dash, Aswini K

    2017-09-26

    Density functional theory (DFT, B3LYP-D3 with implicit solvation in toluene) was used to investigate the mechanisms of olefin hydrosilylation catalyzed by PDI(Fe) (bis(imino)pyridine iron) complexes, where PDI = 2,6-(ArN[double bond, length as m-dash]CMe) 2 (C 5 H 3 N) with Ar = 2,6-R 2 -C 6 H 3 . We find that the rate-determining step for hydrosilylation is hydride migration from Et 3 SiH onto the Fe-bound olefin to form (PDI)Fe(alkyl)(SiEt 3 ). This differs from the mechanism for the Pt Karstedt catalyst in that there is no prior Si-H oxidative addition onto the Fe center. (PDI)Fe(alkyl)(SiEt 3 ) then undergoes C-Si reductive elimination to form (PDI)Fe, which coordinates an olefin ligand to regenerate the resting state (PDI)Fe(olefin). In agreement with experimental observations, we found that anti-Markovnikov hydride migration has a 5.1 kcal mol -1 lower activation enthalpy than Markovnikov migration. This system has an unusual anti-ferromagnetic coupling between high spin electrons on the Fe center and the unpaired spin in the pi system of the non-innocent redox-active PDI ligand. To describe this with DFT, we used the "broken-symmetry" approach to establish the ground electronic and spin state of intermediates and transition states over the proposed catalytic cycles.

  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. Control and shutdown mechanism operating experience of TAPS

    International Nuclear Information System (INIS)

    Bhasin, B.K.; Upadhyaya, T.C.

    1997-01-01

    Tarapur Atomic Power Station is one of the oldest operating GE, BWR units in the world. There are two independent types of reactivity control mechanisms to shutdown the reactor, namely fast acting CRD system and the slow acting liquid poison system in the event of any abnormal situations. The fast acting CRD system is also capable of maneuvering the reactor power. An effort is made here to highlight the features of these control mechanisms. This paper also describes valuable operating experiences and challenges faced in maintaining its availability and reliability. (author)

  8. 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...

  9. Structural insights into the catalytic mechanism of Trypanosoma cruzi trans-sialidase.

    Science.gov (United States)

    Amaya, María Fernanda; Watts, Andrew G; Damager, Iben; Wehenkel, Annemarie; Nguyen, Tong; Buschiazzo, Alejandro; Paris, Gastón; Frasch, A Carlos; Withers, Stephen G; Alzari, Pedro M

    2004-05-01

    Sialidases are a superfamily of sialic-acid-releasing enzymes that are of significant interest due to their implication as virulence factors in the pathogenesis of a number of diseases. However, extensive studies of viral and microbial sialidases have failed to provide a comprehensive picture of their mechanistic properties, in part because the structures of competent enzyme-substrate complexes and reaction intermediates have never been described. Here we report these structures for the Trypanosoma cruzi trans-sialidase (TcTS), showing that catalysis by sialidases occurs via a similar mechanism to that of other retaining glycosidases, but with some intriguing differences that may have evolved in response to the substrate structure.

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

    OpenAIRE

    VERONIKA DOUBNEROVÁ; LUCIE POTŮČKOVÁ; KAREL MÜLLER; HELENA RYŠLAVÁ

    2009-01-01

    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. Interm...

  11. 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+.

  12. Projection operator techniques in Lagrangian mechanics: symmetrically coupled oscillators

    Directory of Open Access Journals (Sweden)

    J. N. Boyd

    1980-01-01

    Full Text Available We apply projection operator techniques to the computation of the natural frequencies of oscillation for three symmetrically coupled mechanical systems. In each case, the rotation subgroup of the full symmetry group is used to determine the projection operators with the result that the Lagrangian must be expressed in terms of complex-valued coordinates. In the coordinate system obtained from the action of the projection operators upon the original coordinates, the Lagrangian yields equations of motion which are separated to the maximum extent made possible by symmetry considerations.

  13. 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...

  14. Catalytic growth of metallic tungsten whiskers based on the vapor-solid-solid mechanism

    International Nuclear Information System (INIS)

    Wang, S L; He, Y H; Huang, B Y; Zou, J; Wang, Y; Huang, H; Liu, C T; Liaw, P K

    2008-01-01

    Metallic W whiskers with tip diameters of 50-250 nm and lengths of 2-4 μm have been successfully synthesized in large quantities using Co-Ni alloyed catalysts. The relatively low growth temperature of 850 deg. C and the large catalyst size (over 100 nm) suggest that the growth of the W whiskers must be governed by the vapor-solid-solid mechanism. Our results show that the vapor-solid-solid model is suitable not only for the growth of nano-scaled whiskers with diameters below 100 nm, but also for submicro-scaled whiskers with diameters well above 100 nm. This technique has great potential to synthesize well controlled metallic whiskers

  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. 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.

  17. Operating Systems-Functions, Protection and Security Mechanisms

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 7; Issue 4. Operating Systems - Functions, Protection and Security Mechanisms. M Suresh Babu. General Article Volume 7 Issue 4 April 2002 pp 60-66. Fulltext. Click here to view fulltext PDF. Permanent link:

  18. 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.

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

    African Journals Online (AJOL)

    the observation of the traditional system prac- ticed in West Africa where the fruit and its processing technologies originated. For this reason it makes economic sense to reexam- ine and compare thoroughly, all activities in- volved in each unit operation of both the tra- ditional and mechanized palm fruit processing methods ...

  20. 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

  1. 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.

  2. 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.

  3. Mechanisms of microregulation of private hospitals by health plan operators.

    Science.gov (United States)

    Ugá, Maria Alicia Domínguez; Vasconcellos, Miguel Murat; Lima, Sheyla Maria Lemos; Portela, Margareth Crisóstomo; Gerschman, Silvia

    2009-10-01

    To analyze the mechanisms employed by health plan operators for microregulation of clinical management and health care qualification within care-providing hospitals. A nation-wide cross-sectional study was carried out. The universe consisted of hospitals which provided care to health plan operators in 2006. A sample of 83 units was selected, stratified by Brazilian macroregion and type of hospital. Data were obtained by means of a questionnaire administered to hospital managers. Microregulation of hospitals by health plan operators was minimal or almost absent in terms of health care qualification. Operator activity focused predominantly on intense control of the amount of services used by patients. Hospitals providing services to health plan operators did not constitute health micro-systems parallel or supplementary to the Sistema Unico de Saúde (SUS - Brazilian National Health System). The private care-providing hospitals were predominantly associated with SUS. However, these did not belong to a private care-provider network, even though their service usage was subject to strong regulation by health plan operators. Operator intervention in the form of system management was incipient or virtually absent. Roughly one-half of investigated hospitals reported adopting clinical directives, whereas only 25.4% reported managing pathology and 30.5% reported managing cases. Contractual relationships between hospitals and health plan operators are merely commercial contracts with little if any incorporation of aspects related to the quality of care, being generally limited to aspects such as establishment of prices, timeframes, and payment procedures.

  4. 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

  5. Control of ionizable residues in the catalytic mechanism of tryptophan synthase from Salmonella typhimurium.

    Science.gov (United States)

    Raboni, Samanta; Mozzarelli, Andrea; Cook, Paul F

    2007-11-13

    The tryptophan synthase alpha2beta2 complex catalyzes the last two steps in the biosynthesis of l-tryptophan in bacteria, plants, and fungi, the conversion of indole-3-glycerol phosphate and l-serine to l-tryptophan, glyceraldehyde 3-phosphate, and water. The beta-subunit binds pyridoxal 5'-phosphate and catalyzes the beta-replacement reaction with serine and indole. Structural, spectral, and kinetic studies indicate that different monovalent cations stabilize the alternative enzyme conformations and equilibrium distribution of the internal, external, and alpha-aminoacrylate Schiff base. To improve our understanding of the role of monovalent cations, the pH dependence of steady-state and pre-steady-state kinetic parameters and primary kinetic deuterium isotope effects were measured in the presence of l-serine and [alpha-2H]-l-serine in the absence and presence of Na+, K+, and Cs+. For the interpretation of the data obtained in this study, it was necessary to re-interpret a number of results published previously. Overall, data suggest that the enzyme exists in two conformers that equilibrate slowly either in the absence of substrates and monovalent cations or in the presence of K+ or Cs+, whereas they equilibrate faster in the presence of Na+. The rate of interconversion of the conformers increases as a group on the enzyme with a pKa of approximately 8 becomes deprotonated. The pH dependence of deuterium isotope effects is suggestive of a mechanism in which a pH-dependent conformational change that closes the active site precedes the chemical steps, likely a result of formation of one or more salt bridges. As the pH increases, the reaction becomes more committed to proceed to products, which causes the deuterium isotope effect to decrease to a value of unity at high pH. The closure of the site is modulated by the different monovalent cations and is fastest in the presence of Na+, which exhibits the maximum isotope effect of 5.7 (likely the intrinsic effect) on V

  6. 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)

  7. 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).

  8. 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)

  9. 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

  10. 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

  11. 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.

  12. 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...... to be applied to the structure or force signals to be measured. All the parameter estimation is based upon the response signals, thereby minimising the work of preparation for the test. This test case is a controlled lab set-up enabling different parameter estimation methods techniques to be used and compared...

  13. 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)

  14. 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

  15. Catalytic Mechanism of Cruzain from Trypanosoma cruzi As Determined from Solvent Kinetic Isotope Effects of Steady-State and Pre-Steady-State Kinetics.

    Science.gov (United States)

    Zhai, Xiang; Meek, Thomas D

    2018-02-02

    Cruzain, an important drug target for Chagas disease, is a member of clan CA of the cysteine proteases. Understanding the catalytic mechanism of cruzain is vital to the design of new inhibitors. To this end, we have determined pH-rate profiles for substrates and affinity agents and solvent kinetic isotope effects in pre-steady-state and steady-state modes using three substrates: Cbz-Phe-Arg-AMC, Cbz-Arg-Arg-AMC, and Cbz-Arg-Ala-AMC. The pH-rate profile of k cat /K m for Cbz-Arg-Arg-AMC indicated pK 1 = 6.6 (unprotonated) and pK 2 ∼ 9.6 (protonated) groups were required for catalysis. The temperature dependence of the pK = 6.2-6.6 group exhibited a ΔH ion value of 8.4 kcal/mol, typical of histidine. The pH-rate profile of inactivation by iodoacetamide confirmed that the catalytic cysteine possesses a pK a of 9.8. Normal solvent kinetic isotope effects were observed for both D 2 O k cat (1.6-2.1) and D 2 O k cat /K m (1.1-1.4) for all three substrates. Pre-steady-state kinetics revealed exponential bursts of AMC production for Cbz-Phe-Arg-AMC and Cbz-Arg-Arg-AMC, but not for Cbz-Arg-Ala-AMC. The overall solvent isotope effect on k cat can be attributed to the solvent isotope effect on the deacylation step. Our results suggest that cruzain is unique among papain-like cysteine proteases in that the catalytic cysteine and histidine have neutral charges in the free enzyme. The generation of the active thiolate of the catalytic cysteine is likely preceded (and possibly triggered) by a ligand-induced conformational change, which could bring the catalytic dyad into the proximity to effect proton transfer.

  16. Isometric operators, isospectral Hamiltonians, and supersymmetric quantum mechanics

    International Nuclear Information System (INIS)

    Pursey, D.L.

    1986-01-01

    Isometric operators are used to provide a unified theory of the three established procedures for generating one-parameter families of isospectral Hamiltonians. All members of the same family of isospectral Hamiltonians are unitarily equivalent, and the unitary transformations between them form a group isomorphic with the additive group of real numbers. The theory is generalized by including the parameter identifying a member of an isospectral family as a new variable. The unitary transformations within a family correspond to translations in the parameter space. The generator of infinitesimal translations represents a conserved quantity in the extended theory. Isometric operators are then applied to the development of models of supersymmetric quantum mechanics. In addition to the standard models based on the Darboux procedure, I show how to construct models based on the Abraham-Moses and Pursey procedures. The formalism shows that the Nieto ambiguity present in all models of supersymmetric quantum mechanics can be interpreted as a renormalization of the ground state of the supersymmetric system. This allows a generalization of supersymmetric quantum mechanics analogous to that developed for systems of isospectral Hamiltonians

  17. Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

    Science.gov (United States)

    Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

    2017-10-01

    Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

  18. 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

  19. 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

  20. Quantum mechanics 1. Path-integral formulation and operator formalism

    International Nuclear Information System (INIS)

    Reinhardt, Hugo

    2012-01-01

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

  1. On the catalytic mechanism of polysaccharide lyases: evidence of His and Tyr involvement in heparin lysis by heparinase I and the role of Ca2+.

    Science.gov (United States)

    Córdula, Carolina R; Lima, Marcelo A; Shinjo, Samuel K; Gesteira, Tarsis F; Pol-Fachin, Laércio; Coulson-Thomas, Vivien J; Verli, Hugo; Yates, Edwin A; Rudd, Timothy R; Pinhal, Maria A S; Toma, Leny; Dietrich, Carl P; Nader, Helena B; Tersariol, Ivarne L S

    2014-01-01

    The structurally diverse polysaccharide lyase enzymes are distributed from plants to animals but share common catalytic mechanisms. One, heparinase I (F. heparinum), is employed in the production of the major anticoagulant drug, low molecular weight heparin, and is a mainstay of cell surface proteoglycan analysis. We demonstrate that heparinase I specificity and efficiency depend on the cationic form of the substrate. Ca(2+)-heparin, in which α-L-iduronate-2-O-sulfate residues adopt (1)C4 conformation preferentially, is a substrate, while Na(+)-heparin is an inhibitor. His and Tyr residues are identified in the catalytic step and a model based on molecular dynamics and docking is proposed, in which deprotonated His203 initiates β-elimination by abstracting the C5 proton of the α-L-iduonate-2-O-sulfate residue in the substrate, and protonated Tyr357 provides the donor to the hexosamine leaving group.

  2. Mechanisms of renewal after the extinction of discriminated operant behavior.

    Science.gov (United States)

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

    2014-07-01

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

  3. 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

  4. 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

  5. Influence of monomer concentration during polymerization on performance and catalytic mechanism of resultant poly(3,4-ethylenedioxythiophene) counter electrodes for dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Han, Ruobing; Lu, Shan; Wang, Yanjie; Zhang, Xuehua; Wu, Qiang; He, Tao

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: •EDOT concentration has great impact on the properties of as-prepared PEDOT CEs. •PEDOT CE polymerized with low EDOT concentration shows better conductivity. •PEDOT polymerized with high EDOT concentration has more catalytic reaction centers. •Undoped EDOT units in PEDOT are key catalytic centers for I − /I 3 − redox reaction. •PEDOT CEs based DSSCs exhibit comparable power conversion efficiency to Pt CE. -- Abstract: Poly(3,4-ethylenedioxythiophene) (PEDOT) films doped by perchlorate ions (ClO 4 − ) have been prepared via electropolymerization with different EDOT monomer concentration and used as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). The effect of EDOT monomer concentration on the properties of obtained PEDOT CEs has been thoroughly investigated. The sponge like porous microstructure of the PEDOT films breaks gradually with the increase of EDOT concentration. Meanwhile, the conductivity of the PEDOT CEs decreases gradually due to the decreased ClO 4 − doping level. The catalytic mechanism is mainly comprised of the formation of weakly bonded iodine species on the undoped EDOT units, and formation and reduction of the intermediates. The undoped EDOT units in the PEDOT chain are the key catalytic reaction centers for I − /I 3 − redox reaction. The catalytic activity of the PEDOT CEs for I − /I 3 − redox reaction increases with the increase of EDOT concentration by virtue of the increased catalytic reaction centers in the PEDOT chain (i.e., increased undoped EDOT units due to the decreased ClO 4 − doping level). DSSC based on PEDOT CE polymerized with 0.05 M of EDOT and 0.1 M of LiClO 4 shows good photovoltaic performance, with a power conversion efficiency of 7.42%. This result is comparable to the Pt CE based-solar cell (7.41%), suggesting that PEDOT CEs may substitute the expensive Pt CEs in the DSSCs

  6. The operating performance and products distribution of the catalytic oxidation of methyl-isobutyl-ketone over a Pt/gamma-Al2O3 catalyst.

    Science.gov (United States)

    Tseng, Ting-Ke; Chu, Hsin; Ko, Tzu-Hsing; Chung, Lung-Kai

    2005-06-30

    Catalytic oxidation is one of the cost-effective technologies to solve the troublesome volatile organic compounds. This study treated methyl-isobutyl-ketone (MIBK) by a commercial catalyst, Pt/gamma-Al(2)O(3), in a fixed-bed reactor. The effects of operating factors, such as operating temperature, MIBK concentration, space velocity, and O(2) concentration, on the performance of the catalyst were investigated. The products and reactants distributions from the oxidation of MIBK over Pt/gamma-Al(2)O(3) were observed. The results show that the products containing carbon atoms are CO, CO(2), and C(3)H(6)O. Two catalyst life-tests were also carried out to characterize the deactivation effect of MIBK. The result shows that the deactivation effect may be due to the coke on the catalyst surface at 423 K. From the statistical analysis, the operating temperature is the most effective factor on the conversion of MIBK. The catalysts were also characterized by surface area analysis and elemental analysis before and after the test. The results show that the catalytic deactivation may be due to carbon coating. At low temperature (423 K), the phenomenon of carbon coating was more obvious than that at high temperature (573 K). The product distributions from the oxidation of MIBK over Pt/gamma-Al(2)O(3) were analyzed by GC. The results indicate that the C(3)H(6)O is formed from the beginning, presenting a peak at 423 K, 6.54 ppm. The CO concentration also peaked at the same temperature, 6.84 ppm.

  7. 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.

  8. 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.

  9. The Conservation of Structure and Mechanism of Catalytic Action in a Family of Thiamin Pyrophosphate (TPP)-dependent Enzymes

    Science.gov (United States)

    Dominiak, P.; Ciszak, Ewa

    2004-01-01

    Thiamin pyrophosphate (TPP)-dependent enzymes are a divergent family of TPP and metal ion binding proteins that perform a wide range of functions with the common decarboxylation steps of a -(O=)C-C(OH)- fragment of alpha-ketoacids and alpha- hydroxyaldehydes. To determine how structure and catalytic action are conserved in the context of large sequence differences existing within this family of enzymes, we have carried out an analysis of TPP-dependent enzymes of known structures. The common structure of TPP-dependent enzymes is formed at the interface of four alpha/beta domains from at least two subunits, which provide for two metal and TPP-binding sites. Residues around these catalytic sites are conserved for functional purpose, while those further away from TPP are conserved for structural reasons. Together they provide a network of contacts required for flip-flop catalytic action within TPP-dependent enzymes. Thus our analysis defines a TPP-action motif that is proposed for annotating TPP-dependent enzymes for advancing functional proteomics.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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)

  17. Low-temperature catalytic oxidation of aldehyde mixtures using wood fly ash: kinetics, mechanism, and effect of ozone.

    Science.gov (United States)

    Kolar, Praveen; Kastner, James R

    2010-02-01

    Poultry rendering emissions contain volatile organic compounds (VOCs) that are nuisance, odorous, and smog and particulate matter precursors. Present treatment options, such as wet scrubbers, do not eliminate a significant fraction of the VOCs emitted including, 2-methylbutanal (2-MB), 3-methylbutanal, and hexanal. This research investigated the low-temperature (25-160 degrees C) catalytic oxidation of 2-MB and hexanal vapors in a differential, plug flow reactor using wood fly ash (WFA) as a catalyst and oxygen and ozone as oxidants. The oxidation rates of 2-MB and hexanal ranged between 3.0 and 3.5 x 10(-9)mol g(-1)s(-1) at 25 degrees C and the activation energies were 2.2 and 1.9 kcal mol(-1), respectively. The catalytic activity of WFA was comparable to other commercially available metal and metal oxide catalysts. We theorize that WFA catalyzed a free radical reaction in which 2-butanone and CO(2) were formed as end products of 2-MB oxidation, while CO(2), pentanal, and butanal were formed as end products of hexanal oxidation. When tested as a binary mixture at 25 and 160 degrees C, no inhibition was observed. Additionally, when ozone was tested as an oxidant at 160 degrees C, 100% removal was achieved within a 2-s reaction time. These results may be used to design catalytic oxidation processes for VOC removal at poultry rendering facilities and potentially replace energy and water intensive air pollution treatment technologies currently in use. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  18. Fenton-like degradation of sulfamethazine using Fe3O4/Mn3O4nanocomposite catalyst: kinetics and catalytic mechanism.

    Science.gov (United States)

    Wan, Zhong; Wang, Jianlong

    2017-01-01

    The kinetics and catalytic mechanism of sulfamethazine (SMT) degradation using Fe 3 O 4 /Mn 3 O 4 nanocomposite as catalysts in heterogeneous Fenton-like process were investigated. The degradation process of SMT conformed to first-order kinetic model. The apparent activation energy (E a ) of the process was calculated to be 40.5 kJ/mol. The reusability and stability of the catalysts were evaluated based on the results of the successive batch experiments. The intermediates were identified and quantified by ion chromatography (IC), high-performance liquid chromatography (HPLC), and gas chromatography-mass spectrometry (GC-MS). The results suggested that the bonds of S-C, N-C, and S-N were broken mainly by ·OH attack to form the organic compounds, which were gradually decomposed into small-molecule organic acids, such as oxalic acid, propionic acid, and formic acid. The possible catalytic mechanism for SMT degradation was tentatively proposed.

  19. Oxygen exchange between acetate and the catalytic glutamate residue in glutaconate CoA-transferase from Acidaminococcus fermentans. Implications for the mechanism of CoA-ester hydrolysis.

    Science.gov (United States)

    Selmer, T; Buckel, W

    1999-07-23

    The exchange of oxygen atoms between acetate, glutaryl-CoA, and the catalytic glutamate residue in glutaconate CoA-transferase from Acidaminococcus fermentans was analyzed using [(18)O(2)]acetate together with matrix-assisted laser desorption/ionization time of flight mass spectrometry of an appropriate undecapeptide. The exchange reaction was shown to be site-specific, reversible, and required both glutaryl-CoA and [(18)O(2)]acetate. The observed exchange is in agreement with the formation of a mixed anhydride intermediate between the enzyme and acetate. In contrast, with a mutant enzyme, which was converted to a thiol ester hydrolyase by replacement of the catalytic glutamate residue by aspartate, no (18)O uptake from H(2)(18)O into the carboxylate was detectable. This result is in accord with a mechanism in which the carboxylate of aspartate acts as a general base in activating a water molecule for hydrolysis of the thiol ester intermediate. This mechanism is further supported by the finding of a significant hydrolyase activity of the wild-type enzyme using acetyl-CoA as substrate, whereas glutaryl-CoA is not hydrolyzed. The small acetate molecule in the substrate binding pocket may activate a water molecule for hydrolysis of the nearby enzyme-CoA thiol ester.

  20. 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.

  1. Mechanical optimization of superconducting cavities in continuous wave operation

    Directory of Open Access Journals (Sweden)

    Sam Posen

    2012-02-01

    Full Text Available Several planned accelerator facilities call for hundreds of elliptical cavities operating cw with low effective beam loading, and therefore require cavities that have been mechanically optimized to operate at high Q_{L} by minimizing df/dp, the sensitivity to microphonics detuning from fluctuations in helium pressure. Without such an optimization, the facilities would suffer either power costs driven up by millions of dollars or an extremely high per-cavity trip rate. ANSYS simulations used to predict df/dp are presented as well as a model that illustrates factors that contribute to this parameter in elliptical cavities. For the Cornell Energy Recovery Linac (ERL main linac cavity, df/dp is found to range from 2.5 to 17.4  Hz/mbar, depending on the radius of the stiffening rings, with minimal df/dp for very small or very large radii. For the Cornell ERL injector cavity, simulations predict a df/dp of 124  Hz/mbar, which fits well within the range of measurements performed with the injector cryomodule. Several methods for reducing df/dp are proposed, including decreasing the diameter of the tuner bellows and increasing the stiffness of the enddishes and the tuner. Using measurements from a Tesla Test Facility cavity as the baseline, if both of these measures were implemented and the stiffening rings were optimized, simulations indicate that df/dp would be reduced from ∼30  Hz/mbar to just 2.9  Hz/mbar, and the power required to maintain the accelerating field would be reduced by an order of magnitude. Finally, other consequences of optimizing the stiffening ring radius are investigated. It is found that stiffening rings larger than 70% of the iris-equator distance make the cavity impossible to tune. Small rings, on the other hand, leave the cavity susceptible to plastic deformation during handling and have lower frequency mechanical resonances, which is undesirable for active compensation of microphonics. Additional simulations

  2. The catalytic mechanism of NADH-dependent reduction of 9,10-phenanthrenequinone by Candida tenuis xylose reductase reveals plasticity in an aldo-keto reductase active site.

    Science.gov (United States)

    Pival, Simone L; Klimacek, Mario; Nidetzky, Bernd

    2009-06-12

    Despite their widely varying physiological functions in carbonyl metabolism, AKR2B5 (Candida tenuis xylose reductase) and many related enzymes of the aldo-keto reductase protein superfamily utilise PQ (9,10-phenanthrenequinone) as a common in vitro substrate for NAD(P)H-dependent reduction. The catalytic roles of the conserved active-site residues (Tyr51, Lys80 and His113) of AKR2B5 in the conversion of the reactive alpha-dicarbonyl moiety of PQ are not well understood. Using wild-type and mutated (Tyr51, Lys80 and His113 individually replaced by alanine) forms of AKR2B5, we have conducted steady-state and transient kinetic studies of the effects of varied pH and deuterium isotopic substitutions in coenzyme and solvent on the enzymatic rates of PQ reduction. Each mutation caused a 10(3)-10(4)-fold decrease in the rate constant for hydride transfer from NADH to PQ, whose value in the wild-type enzyme was determined as approximately 8 x 10(2) s(-1). The data presented support an enzymic mechanism in which a catalytic proton bridge from the protonated side chain of Lys80 (pK=8.6+/-0.1) to the carbonyl group adjacent to the hydride acceptor carbonyl facilitates the chemical reaction step. His113 contributes to positioning of the PQ substrate for catalysis. Contrasting its role as catalytic general acid for conversion of the physiological substrate xylose, Tyr51 controls release of the hydroquinone product. The proposed chemistry of AKR2B5 action involves delivery of both hydrogens required for reduction of the alpha-dicarbonyl substrate to the carbonyl group undergoing (stereoselective) transformation. Hydride transfer from NADH probably precedes the transfer of a proton from Tyr51 whose pK of 7.3+/-0.3 in the NAD+-bound enzyme appears suitable for protonation of a hydroquinone anion (pK=8.8). These results show that the mechanism of AKR2B5 is unusually plastic in the exploitation of the active-site residues, for the catalytic assistance provided to carbonyl group

  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. 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

  5. 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

  6. Structural and Mechanistic Analysis of a Novel Class of Shikimate Dehydrogenases: Evidence for a Conserved Catalytic Mechanism in the Shikimate Dehydrogenase Family

    Energy Technology Data Exchange (ETDEWEB)

    Peek, James; Lee, John; Hu, Shi; Senisterra, Guillermo; Christendat, Dinesh (Toronto)

    2011-10-27

    Shikimate dehydrogenase (SDH) catalyzes the reversible NADPH-dependent reduction of 3-dehydroshikimate to shikimate. This reaction represents the fourth step of the shikimate pathway, the essential route for the biosynthesis of the aromatic amino acids in plants, fungi, bacteria, and apicomplexan parasites. The absence of this pathway in animals makes it an attractive target for herbicides and antimicrobials. At least four functionally distinct enzyme classes, AroE, YdiB, SDH-like (SdhL), and AroE-like1 (Ael1), utilize shikimate as a substrate in vitro and form the SDH family. Crystal structures have been determined for AroE, YdiB, and SdhL. In this study, we have determined the first representative crystal structure of an Ael1 enzyme. We demonstrate that Ael1 shares a similar overall structure with the other members of the SDH family. This high level of structural conservation extends to the active sites of the enzymes. In particular, an ionizable active site lysine and aspartate are present in all SDH homologues. Two distinct biochemical roles have been reported for this Lys-Asp pair: as binding residues in YdiB and as a catalytic dyad in AroE and SdhL. Here, we establish that the residues function as a catalytic dyad in Ael1 and, interestingly, in at least one YdiB homologue. The conservation of three-dimensional fold, active site architecture, and catalytic mechanism among members of the SDH family will facilitate the design of drugs targeting the shikimate pathway.

  7. 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.

  8. Kinetic Analysis of Autotaxin Reveals Substrate-specific Catalytic Pathways and a Mechanism for Lysophosphatidic Acid Distribution*

    Science.gov (United States)

    Saunders, Lauren P.; Cao, Wenxiang; Chang, William C.; Albright, Ronald A.; Braddock, Demetrios T.; De La Cruz, Enrique M.

    2011-01-01

    Autotaxin (ATX) is a secreted lysophospholipase D that hydrolyzes lysophosphatidylcholine (LPC) into lysophosphatidic acid (LPA), initiating signaling cascades leading to cancer metastasis, wound healing, and angiogenesis. Knowledge of the pathway and kinetics of LPA synthesis by ATX is critical for developing quantitative physiological models of LPA signaling. We measured the individual rate constants and pathway of the LPA synthase cycle of ATX using the fluorescent lipid substrates FS-3 and 12-(N-methyl-N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl))-LPC. FS-3 binds rapidly (k1 ≥500 μm−1 s−1) and is hydrolyzed slowly (k2 = 0.024 s−1). Release of the first hydrolysis product is random and rapid (≥1 s−1), whereas release of the second is slow and rate-limiting (0.005–0.007 s−1). Substrate binding and hydrolysis are slow and rate-limiting with LPC. Product release is sequential with choline preceding LPA. The catalytic pathway and kinetics depend strongly on the substrate, suggesting that ATX kinetics could vary for the various in vivo substrates. Slow catalysis with LPC reveals the potential for LPA signaling to spread to cells distal to the site of LPC substrate binding by ATX. An ATX mutant in which catalytic threonine at position 210 is replaced with alanine binds substrate weakly, favoring a role for Thr-210 in binding as well as catalysis. FTY720P, the bioactive form of a drug currently used to treat multiple sclerosis, inhibits ATX in an uncompetitive manner and slows the hydrolysis reaction, suggesting that ATX inhibition plays a significant role in lymphocyte immobilization in FTY720P-based therapeutics. PMID:21719699

  9. Structural and mutational analyses of the Leptospira interrogans virulence-related heme oxygenase provide insights into its catalytic mechanism.

    Directory of Open Access Journals (Sweden)

    Anabel Soldano

    Full Text Available Heme oxygenase from Leptospira interrogans is an important virulence factor. During catalysis, redox equivalents are provided to this enzyme by the plastidic-type ferredoxin-NADP+ reductase also found in L. interrogans. This process may have evolved to aid this bacterial pathogen to obtain heme-iron from their host and enable successful colonization. Herein we report the crystal structure of the heme oxygenase-heme complex at 1.73 Å resolution. The structure reveals several distinctive features related to its function. A hydrogen bonded network of structural water molecules that extends from the catalytic site to the protein surface was cleared observed. A depression on the surface appears to be the H+ network entrance from the aqueous environment to the catalytic site for O2 activation, a key step in the heme oxygenase reaction. We have performed a mutational analysis of the F157, located at the above-mentioned depression. The mutant enzymes were unable to carry out the complete degradation of heme to biliverdin since the reaction was arrested at the verdoheme stage. We also observed that the stability of the oxyferrous complex, the efficiency of heme hydroxylation and the subsequent conversion to verdoheme was adversely affected. These findings underscore a long-range communication between the outer fringes of the hydrogen-bonded network of structural waters and the heme active site during catalysis. Finally, by analyzing the crystal structures of ferredoxin-NADP+ reductase and heme oxygenase, we propose a model for the productive association of these proteins.

  10. Spectral properties of certain composition operators arising in statistical mechanics

    International Nuclear Information System (INIS)

    Mayer, D.H.

    1979-01-01

    By applying the theory of linear positive operators in a Banach space we derive spectral properties of certain composition operators in the Banach space A infinitely (Omega) of holomorphic functions over some domain Omega contains Csup(n). Examples of such operators are provided by the so called generalized transfer matrices of classical one-dimensional lattice systems. (orig.)

  11. 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.

  12. Catalytic devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Zhang, Xiang

    2018-01-23

    This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

  13. Cobalt-Catalyzed [2π + 2π] Cycloadditions of Alkenes: Scope, Mechanism, and Elucidation of Electronic Structure of Catalytic Intermediates

    Science.gov (United States)

    2015-01-01

    Aryl-substituted bis(imino)pyridine cobalt dinitrogen compounds, (RPDI)CoN2, are effective precatalysts for the intramolecular [2π + 2π] cycloaddition of α,ω-dienes to yield the corresponding bicyclo[3.2.0]heptane derivatives. The reactions proceed under mild thermal conditions with unactivated alkenes, tolerating both amine and ether functional groups. The overall second order rate law for the reaction, first order with respect to both the cobalt precatalyst and the substrate, in combination with electron paramagnetic resonance (EPR) spectroscopic studies established the catalyst resting state as dependent on the identity of the precatalyst and diene substrate. Planar S =1/2 κ3-bis(imino)pyridine cobalt alkene and tetrahedral κ2-bis(imino)pyridine cobalt diene complexes were observed by EPR spectroscopy and in the latter case structurally characterized. The hemilabile chelate facilitates conversion of a principally ligand-based singly occupied molecular orbital (SOMO) in the cobalt dinitrogen and alkene compounds to a metal-based SOMO in the diene intermediates, promoting C–C bond-forming oxidative cyclization. Structure–activity relationships on bis(imino)pyridine substitution were also established with 2,4,6-tricyclopentyl-substituted aryl groups, resulting in optimized catalytic [2π + 2π] cycloaddition. The cyclopentyl groups provide a sufficiently open metal coordination sphere that encourages substrate coordination while remaining large enough to promote a challenging, turnover-limiting C(sp3)–C(sp3) reductive elimination. PMID:26030841

  14. 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.

  15. 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.

  16. 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...

  17. 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.

  18. An operating system for multicore and clouds: Mechanisms and implementation

    OpenAIRE

    Wentzlaff, David M.; Gruenwald, Charles; Beckmann, Nathan Zachary; Modzelewski, Kevin; Belay, Adam M.; Youseff, Lamia; Miller, Jason E.; Agarwal, Anant

    2010-01-01

    Cloud computers and multicore processors are two emerging classes of computational hardware that have the potential to provide unprecedented compute capacity to the average user. In order for the user to effectively harness all of this computational power, operating systems (OSes) for these new hardware platforms are needed. Existing multicore operating systems do not scale to large numbers of cores, and do not support clouds. Consequently, current day cloud systems push ...

  19. Quantum mechanical operator realization of the Stirling numbers theory studied by virtue of the operator Hermite polynomials method

    International Nuclear Information System (INIS)

    Fan Hong-Yi; Lou Sen-Yue

    2015-01-01

    Based on the operator Hermite polynomials method (OHPM), we study Stirling numbers in the context of quantum mechanics, i.e., we present operator realization of generating function formulas of Stirling numbers with some applications. As a by-product, we derive a summation formula involving both Stirling number and Hermite polynomials. (paper)

  20. 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...

  1. 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.

  2. Generalized space and linear momentum operators in quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-15

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

  3. 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.

  4. 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…

  5. Arcsecond grating drive mechanism for operation at 4 K

    Science.gov (United States)

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

    1991-12-01

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

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Spencer Operator and Applications: From Continuum Mechanics to Mathematical physics

    OpenAIRE

    Pommaret, Jean-François

    2011-01-01

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

  12. 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.

  13. 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.

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

    Directory of Open Access Journals (Sweden)

    Tomáš Trnka

    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.

  15. 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.

  16. Research on the operational reliability system control methodology and its application for aerospace mechanism

    OpenAIRE

    Xin Gao; Haoxin Wu; Mingtao Du; Gang Chen; Hanxu Sun; Qingxuan Jia; Yifan Wang

    2016-01-01

    According to the characteristics of space missions and space environment, to slow performance deterioration and possible reliability attenuation for aerospace mechanisms, an operational reliability system control methodology is proposed in this article. A space manipulator – a kind of typical complicated aerospace mechanism – is chosen as the research object. First, considering relevant materials and structure mechanism of joint and link parts, the influence factors of operational reliability...

  17. 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…

  18. Molecular basis of arabinobio-hydrolase activity in phytopathogenic fungi: crystal structure and catalytic mechanism of Fusarium graminearum GH93 exo-alpha-L-arabinanase.

    Science.gov (United States)

    Carapito, Raphaël; Imberty, Anne; Jeltsch, Jean-Marc; Byrns, Simon C; Tam, Pui-Hang; Lowary, Todd L; Varrot, Annabelle; Phalip, Vincent

    2009-05-01

    The phytopathogenic fungus Fusarium graminearum secretes a very diverse pool of glycoside hydrolases (GHs) aimed at degrading plant cell walls. alpha-l-Arabinanases are essential GHs participating in the complete hydrolysis of hemicellulose, a natural resource for various industrial processes, such as bioethanol or pharmaceuticals production. Arb93A, the exo-1,5-alpha-l-arabinanase of F. graminearum encoded by the gene fg03054.1, belongs to the GH93 family, for which no structural data exists. The enzyme is highly active (1065 units/mg) and displays a strict substrate specificity for linear alpha-1,5-l-arabinan. Biochemical assays and NMR experiments demonstrated that the enzyme releases alpha-1,5-l-arabinobiose from the nonreducing end of the polysaccharide. We determined the crystal structure of the native enzyme and its complex with alpha-1,5-l-arabinobiose, a degradation product of alpha-Me-1,5-l-arabinotetraose, at 1.85 and 2.05A resolution, respectively. Arb93A is a monomeric enzyme, which presents the six-bladed beta-propeller fold characteristic of sialidases of clan GHE. The configuration of the bound arabinobiose is consistent with the retaining mechanism proposed for the GH93 family. Catalytic residues were proposed from the structural analysis, and site-directed mutagenesis was used to validate their role. They are significantly different from those observed for GHE sialidases.

  19. Mechanism of Catalytic Water Oxidation by the Ruthenium Blue Dimer Catalyst: Comparative Study in D2O versus H2O

    Directory of Open Access Journals (Sweden)

    Yulia Pushkar

    2013-01-01

    Full Text Available Water oxidation is critically important for the development of energy solutions based on the concept of artificial photosynthesis. In order to gain deeper insight into the mechanism of water oxidation, the catalytic cycle for the first designed water oxidation catalyst, cis,cis-[(bpy2(H2ORuIIIORuIII(OH2(bpy2]4+ (bpy is 2,2-bipyridine known as the blue dimer (BD, is monitored in D2O by combined application of stopped flow UV-Vis, electron paramagnetic resonance (EPR and resonance Raman spectroscopy on freeze quenched samples. The results of these studies show that the rate of formation of BD[4,5] by Ce(IV oxidation of BD[3,4] (numbers in square bracket denote oxidation states of the ruthenium (Ru centers in 0.1 M HNO3, as well as further oxidation of BD[4,5] are slower in D2O by 2.1–2.5. Ce(IV oxidation of BD[4,5] and reaction with H2O result in formation of an intermediate, BD[3,4]′, which builds up in reaction mixtures on the minute time scale. Combined results under the conditions of these experiments at pH 1 indicate that oxidation of BD[3,4]′ is a rate limiting step in water oxidation with the BD catalyst.

  20. 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.

  1. 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.

  2. 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.

  3. Mechanical Properties of Gas Shale During Drilling Operations

    Science.gov (United States)

    Yan, Chuanliang; Deng, Jingen; Cheng, Yuanfang; Li, Menglai; Feng, Yongcun; Li, Xiaorong

    2017-07-01

    The mechanical properties of gas shale significantly affect the designs of drilling, completion, and hydraulic fracturing treatments. In this paper, the microstructure characteristics of gas shale from southern China containing up to 45.1% clay were analyzed using a scanning electron microscope. The gas shale samples feature strongly anisotropic characteristics and well-developed bedding planes. Their strength is controlled by the strength of both the matrix and the bedding planes. Conventional triaxial tests and direct shear tests are further used to study the chemical effects of drilling fluids on the strength of shale matrix and bedding planes, respectively. The results show that the drilling fluid has a much larger impact on the strength of the bedding plane than that of the shale matrix. The impact of water-based mud (WBM) is much larger compared with oil-based mud. Furthermore, the borehole collapse pressure of shale gas wells considering the effects of drilling fluids are analyzed. The results show that the collapse pressure increases gradually with the increase of drilling time, especially for WBM.

  4. 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.

  5. Hybrid lean premixing catalytic combustion system for gas turbines

    Science.gov (United States)

    Critchley, Ian L.

    2003-12-09

    A system and method of combusting a hydrocarbon fuel is disclosed. The system combines the accuracy and controllability of an air staging system with the ultra-low emissions achieved by catalytic combustion systems without the need for a pre-heater. The result is a system and method that is mechanically simple and offers ultra-low emissions over a wide range of power levels, fuel properties and ambient operating conditions.

  6. CNT Arrays Grown upon Catalytic Nickel Particles as Applied in the Nanoelectronic Devices: Ab Initio Simulation of Growth Mechanism

    Science.gov (United States)

    Zhukovskii, Yu. F.; Kotomin, E. A.; Piskunov, S.; Bellucci, S.

    Carbon nanotubes, due to their exceptional and unique properties, have aroused a lot of research interest making them promising candidates as interconnects for future high-speed nanoelectronics. To predict a growth mechanism for carbon nanotubes (CNTs) upon a metal particle as synthesized in the porous membrane block then incorporated in the nanoelectronic device, we have performed a series of large-scale DFT-LCAO calculations using the CRYSTAL-06 code. Carbon adatoms can appear upon the densely-packed Ni(111) catalyst surface due to dissociation of hydrocarbon molecules (e.g., CH4) when applying the CVD method for the nanotube growth. We have started with adsorption properties of carbon atoms. Then, we have simulated the regular C/Ni(111) interface, where adatoms initially form a monolayer which can be disintegrated to nanoflakes gradually transforming into CNT embryos (in the form of semi-fullerenes) and, finally, into the capped CNTs (d C-C ≈ 1.42 Å) with either armchair or zigzag chirality. Periodicity of this system results in models of infinite arrays (bundles) of single-walled (SW) CNTs with a diameter 8.0-8.2 Å and the inter-tube distance 4.2-4.6 Å (depending on chirality). Analyzing the results of calculations on the CNT/Ni interconnect, we have observed a considerable transfer of the electronic charge from the metallic catalyst towards the nanotube (up to ˜1.4 e per contacting C atom) accompanying by substantial redistribution of the electronic density, especially in the case of nanostructured Ni(111) containing nickel nanoclusters. The nanostructured morphology of metal substrate has been found to be the most effective for the growth of CNT bundles.

  7. 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

  8. 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

  9. 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.; van Sint Annaland, 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

  10. Evidence for an induced conformational change in the catalytic mechanism of homoisocitrate dehydrogenase for Saccharomyces cerevisiae: Characterization of the D271N mutant enzyme.

    Science.gov (United States)

    Hsu, Chaonan; West, Ann H; Cook, Paul F

    2015-10-15

    Homoisocitrate dehydrogenase (HIcDH) catalyzes the NAD(+)-dependent oxidative decarboxylation of HIc to α-ketoadipate, the fourth step in the α-aminoadipate pathway responsible for the de novo synthesis of l-lysine in fungi. A mechanism has been proposed for the enzyme that makes use of a Lys-Tyr pair as acid-base catalysts, with Lys acting as a base to accept a proton from the α-hydroxyl of homoisocitrate, and Tyr acting as an acid to protonate the C3 of the enol of α-ketoadipate in the enolization reaction. Three conserved aspartate residues, D243, D267 and D271, coordinate Mg(2+), which is also coordinated to the α-carboxylate and α-hydroxyl of homoisocitrate. On the basis of kinetic isotope effects, it was proposed that a conformational change to close the active site and organize the active site for catalysis contributed to rate limitation of the overall reaction of the Saccharomyces cerevisiae HIcDH (Lin, Y., Volkman, J., Nicholas, K. M., Yamamoto, T., Eguchi, T., Nimmo, S. L., West, A. H., and Cook, P. F. (2008) Biochemistry47, 4169-4180.). In order to test this hypothesis, site-directed mutagenesis was used to change D271, a metal ion ligand and binding determinant for MgHIc, to N. The mutant enzyme was characterized using initial rate studies. A decrease of 520-fold was observed in V and V/KMgHIc, suggesting the same step(s) limit the reaction at limiting and saturating MgHIc concentrations. Solvent kinetic deuterium isotope effects (SKIE) and viscosity effects are consistent with a rate-limiting pre-catalytic conformational change at saturating reactant concentrations. In addition, at limiting MgHIc, an inverse (SKIE) of 0.7 coupled to a significant normal effect of viscosogen (2.1) indicates equilibrium binding of MgHIc prior to the rate-limiting conformational change. The maximum rate exhibits a small partial change at high pH suggesting a pH-dependent conformational change, while V/KMgHIc exhibits the same partial change observed in V, and a

  11. 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...

  12. 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...

  13. 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.

  14. MIO Cortex: Memory Mechanisms for Operator-Expert Networked Decision Support

    Science.gov (United States)

    2013-06-01

    knowledge in such networked DSS: – social or organizational memory as exemplified by reach back to subject matter experts – software encoded knowledge...MIO Cortex: Memory Mechanisms for Operator-Expert Networked Decision Support Dr. Alex Bordetsky, Professor Steven Mullins, PhD student 19 Jun...DATE JUN 2013 2. REPORT TYPE 3. DATES COVERED 00-00-2013 to 00-00-2013 4. TITLE AND SUBTITLE MIO Cortex: Memory Mechanisms for Operator-Expert

  15. Research on the operational reliability system control methodology and its application for aerospace mechanism

    Directory of Open Access Journals (Sweden)

    Xin Gao

    2016-11-01

    Full Text Available According to the characteristics of space missions and space environment, to slow performance deterioration and possible reliability attenuation for aerospace mechanisms, an operational reliability system control methodology is proposed in this article. A space manipulator – a kind of typical complicated aerospace mechanism – is chosen as the research object. First, considering relevant materials and structure mechanism of joint and link parts, the influence factors of operational reliability for space manipulator are divided. Then, by introducing the responding layer factors, a mapping relationship between the influence factors of operational reliability and control variables is analysed. On this basis, a new method to build a hierarchical control system of operational reliability for the aerospace mechanisms is proposed. In this method, the mechanism how the influence factors of operational reliability are introduced into the control system is defined, and an operational reliability system control model is built, which is made up of task planning, path planning, and motion control. Finally, the proposed methodology is further explained with the operational stability of a space manipulator as an example. After analysing the mapping relationship among the influence factors of operational reliability, the factors of responding layer and control variables, a multi-objective optimization method based on Nondominated Sorting Genetic Algorithm II (NSGA-II is proposed to ensure the operation stability for a space manipulator. These optimization objectives are introduced into the optimized control model at path planning level as constraints. According to these constraints, the optimized control system can be adjusted to improve the operation stability of the manipulator, and the operational reliability is also improved during this process correspondingly. Simulation results prove the effectiveness of the proposed method.

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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.)

  2. 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...

  3. 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...

  4. 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.

  5. 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

  6. 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...

  7. 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)

  8. 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

  9. Diesel engine catalytic combustor system. [aircraft engines

    Science.gov (United States)

    Ream, L. W. (Inventor)

    1984-01-01

    A low compression turbocharged diesel engine is provided in which the turbocharger can be operated independently of the engine to power auxiliary equipment. Fuel and air are burned in a catalytic combustor to drive the turbine wheel of turbine section which is initially caused to rotate by starter motor. By opening a flapper value, compressed air from the blower section is directed to catalytic combustor when it is heated and expanded, serving to drive the turbine wheel and also to heat the catalytic element. To start, engine valve is closed, combustion is terminated in catalytic combustor, and the valve is then opened to utilize air from the blower for the air driven motor. When the engine starts, the constituents in its exhaust gas react in the catalytic element and the heat generated provides additional energy for the turbine section.

  10. Catalytic oxidation of volatile organic compounds (VOCs) - A review

    Science.gov (United States)

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

    2016-09-01

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

  11. 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)

  12. 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.

  13. 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

  14. Catalytic interface erosion

    International Nuclear Information System (INIS)

    Meng, H.; Cohen, E.G.D.

    1995-01-01

    We study interface erosion processes: catalytic erosions. We present two cases. (1) The erosion of a completely occupied lattice by one single moving particle starting from somewhere inside the lattice, considering deterministic as well as probabilistic erosion rules. In the latter case, the eroded regions appear to have interfaces with continuously tunable fractal dimensions. (2) The kinetic roughening of an initially flat surface, where ballistic or diffusion-limited particles, which remain intact themselves, erode the surface coming from the outside, using the same erosion rules as in (1). Many features resembling realistic interfaces, for example, islands and inlets, are generated. The dependence of the surface width on the system size is due to both the erosion mechanism and the way particles move before reaching the surface

  15. Structural and molecular basis for the novel catalytic mechanism and evolution of DddP, an abundant peptidase-like bacterial Dimethylsulfoniopropionate lyase: a new enzyme from an old fold.

    Science.gov (United States)

    Wang, Peng; Chen, Xiu-Lan; Li, Chun-Yang; Gao, Xiang; Zhu, De-yu; Xie, Bin-Bin; Qin, Qi-Long; Zhang, Xi-Ying; Su, Hai-Nan; Zhou, Bai-Cheng; Xun, Lu-ying; Zhang, Yu-Zhong

    2015-10-01

    The microbial cleavage of dimethylsulfoniopropionate (DMSP) generates volatile dimethyl sulfide (DMS) and is an important step in global sulfur and carbon cycles. DddP is a DMSP lyase in marine bacteria, and the deduced dddP gene product is abundant in marine metagenomic data sets. However, DddP belongs to the M24 peptidase family according to sequence alignment. Peptidases hydrolyze C-N bonds, but DddP is deduced to cleave C-S bonds. Mechanisms responsible for this striking functional shift are currently unknown. We determined the structures of DMSP lyase RlDddP (the DddP from Ruegeria lacuscaerulensis ITI_1157) bound to inhibitory 2-(N-morpholino) ethanesulfonic acid or PO4 (3-) and of two mutants of RlDddP bound to acrylate. Based on structural, mutational and biochemical analyses, we characterized a new ion-shift catalytic mechanism of RlDddP for DMSP cleavage. Furthermore, we suggested the structural mechanism leading to the loss of peptidase activity and the subsequent development of DMSP lyase activity in DddP. This study sheds light on the catalytic mechanism and the divergent evolution of DddP, leading to a better understanding of marine bacterial DMSP catabolism and global DMS production. © 2015 The Authors. Molecular Microbiology published by John Wiley & Sons Ltd.

  16. 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.

  17. Molecular mechanisms of isocitrate dehydrogenase 1 (IDH1) mutations identified in tumors: The role of size and hydrophobicity at residue 132 on catalytic efficiency.

    Science.gov (United States)

    Avellaneda Matteo, Diego; Grunseth, Adam J; Gonzalez, Eric R; Anselmo, Stacy L; Kennedy, Madison A; Moman, Precious; Scott, David A; Hoang, An; Sohl, Christal D

    2017-05-12

    Isocitrate dehydrogenase 1 (IDH1) catalyzes the reversible NADP + -dependent conversion of isocitrate (ICT) to α-ketoglutarate (αKG) in the cytosol and peroxisomes. Mutations in IDH1 have been implicated in >80% of lower grade gliomas and secondary glioblastomas and primarily affect residue 132, which helps coordinate substrate binding. However, other mutations found in the active site have also been identified in tumors. IDH1 mutations typically result in a loss of catalytic activity, but many also can catalyze a new reaction, the NADPH-dependent reduction of αKG to d-2-hydroxyglutarate (D2HG). D2HG is a proposed oncometabolite that can competitively inhibit αKG-dependent enzymes. Some kinetic parameters have been reported for several IDH1 mutations, and there is evidence that mutant IDH1 enzymes vary widely in their ability to produce D2HG. We report that most IDH1 mutations identified in tumors are severely deficient in catalyzing the normal oxidation reaction, but that D2HG production efficiency varies among mutant enzymes up to ∼640-fold. Common IDH1 mutations have moderate catalytic efficiencies for D2HG production, whereas rarer mutations exhibit either very low or very high efficiencies. We then designed a series of experimental IDH1 mutants to understand the features that support D2HG production. We show that this new catalytic activity observed in tumors is supported by mutations at residue 132 that have a smaller van der Waals volume and are more hydrophobic. We report that one mutation can support both the normal and neomorphic reactions. These studies illuminate catalytic features of mutations found in the majority of patients with lower grade gliomas. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. 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.

  19. 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 ...

  20. 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...

  1. 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.

  2. 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…

  3. 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)

  4. Investigation of the catalytic mechanism of the hotdog-fold enzyme superfamily Pseudomonas sp. strain CBS3 4-hydroxybenzoyl-CoA thioesterase.

    Science.gov (United States)

    Zhuang, Zhihao; Latham, John; Song, Feng; Zhang, Wenhai; Trujillo, Michael; Dunaway-Mariano, Debra

    2012-01-24

    The 4-hydroxybenzoyl-CoA (4-HB-CoA) thioesterase from Pseudomonas sp. strain CBS3 catalyzes the final step of the 4-chlorobenzoate degradation pathway, which is the hydrolysis of 4-HB-CoA to coenzyme A (CoA) and 4-hydroxybenzoate (4-HB). In previous work, X-ray structural analysis of the substrate-bound thioesterase provided evidence of the role of an active site Asp17 in nucleophilic catalysis [Thoden, J. B., Holden, H. M., Zhuang, Z., and Dunaway-Mariano, D. (2002) X-ray crystallographic analyses of inhibitor and substrate complexes of wild-type and mutant 4-hydroxybenzoyl-CoA thioesterase. J. Biol. Chem. 277, 27468-27476]. In the study presented here, kinetic techniques were used to test the catalytic mechanism that was suggested by the X-ray structural data. The time course for the multiple-turnover reaction of 50 μM [(14)C]-4-HB-CoA catalyzed by 10 μM thioesterase supported a two-step pathway in which the second step is rate-limiting. Steady-state product inhibition studies revealed that binding of CoA (K(is) = 250 ± 70 μM; K(ii) = 900 ± 300 μM) and 4-HB (K(is) = 1.2 ± 0.2 mM) is weak, suggesting that product release is not rate-limiting. A substantial D(2)O solvent kinetic isotope effect (3.8) on the steady-state k(cat) value (18 s(-1)) provided evidence that a chemical step involving proton transfer is the rate-limiting step. Taken together, the kinetic results support a two-chemical pathway. The microscopic rate constants governing the formation and consumption of the putative aspartyl 17-(4-hydroxybenzoyl)anhydride intermediate were determined by simulation-based fitting of a kinetic model to time courses for the substrate binding reaction (5.0 μM 4-HB-CoA and 0.54 μM thioesterase), single-turnover reaction (5 μM [(14)C]-4-HB-CoA catalyzed by 50 μM thioesterase), steady-state reaction (5.2 μM 4-HB-CoA catalyzed by 0.003 μM thioesterase), and transient-state multiple-turnover reaction (50 μM [(14)C]-4-HB-CoA catalyzed by 10 μM thioesterase

  5. 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.

  6. Research on determination of operating posture of a complicated opto-mechanical structure

    Science.gov (United States)

    Su, Ruifeng; Zhu, Mingzhi; Chen, Xiaojuan; Wu, Wenkai; Huang, Zhan; Wang, Baoxu

    2016-10-01

    Operating posture of complicated opto-mechanical structures critically matter gravity-induced distortion of the structure, and further affect optical performance. With the aim to solve this problem, determination of operating postures of a supporting system of a KDP crystal is studied. A concept of key stiffness component is firstly proposed in this paper, as far as the authors are concerned, taking advantage of which gravity-induced distortion of the supporting system is analyzed, as well as the rotation of the KDP crystal that is cased by the distortion of the supporting system. Furthermore, effects of operating postures of the supporting system on the distortion of the supporting system and the rotation of the KDP crystal are investigated. It is demonstrated that key stiffness component is of great insignificance to distortion of the supporting system, and it could function as a guidance in determination of operating posture of the supporting system.

  7. 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

  8. 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.

  9. 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

  10. Catalytic Oligopeptide Synthesis.

    Science.gov (United States)

    Liu, Zijian; Noda, Hidetoshi; Shibasaki, Masakatsu; Kumagai, Naoya

    2018-02-02

    Waste-free catalytic assembly of α-amino acids is fueled by a multiboron catalyst that features a characteristic B 3 NO 2 heterocycle, providing a versatile catalytic protocol wherein functionalized natural α-amino acid units are accommodated and commonly used protecting groups are tolerated. The facile dehydrative conditions eliminate the use of engineered peptide coupling reagents, exemplifying a greener catalytic alternative for peptide coupling. The catalysis is sufficiently robust to enable pentapeptide synthesis, constructing all four amide bond linkages in a catalytic fashion.

  11. 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)

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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

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

    Directory of Open Access Journals (Sweden)

    S. Woods

    2014-01-01

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

  18. 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.

  19. 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.

  20. Structure-function relationships in human glutathione-dependent formaldehyde dehydrogenase. Role of Glu-67 and Arg-368 in the catalytic mechanism.

    Science.gov (United States)

    Sanghani, Paresh C; Davis, Wilhelmina I; Zhai, LanMin; Robinson, Howard

    2006-04-18

    The active-site zinc in human glutathione-dependent formaldehyde dehydrogenase (FDH) undergoes coenzyme-induced displacement and transient coordination to a highly conserved glutamate residue (Glu-67) during the catalytic cycle. The role of this transient coordination of the active-site zinc to Glu-67 in the FDH catalytic cycle and the associated coenzyme interactions were investigated by studying enzymes in which Glu-67 and Arg-368 were substituted with Leu. Structures of FDH.adenosine 5'-diphosphate ribose (ADP-ribose) and E67L.NAD(H) binary complexes were determined. Steady-state kinetics, isotope effects, and presteady-state analysis of the E67L enzyme show that Glu-67 is critical for capturing the substrates for catalysis. The catalytic efficiency (V/K(m)) of the E67L enzyme in reactions involving S-nitrosoglutathione (GSNO), S-hydroxymethylglutathione (HMGSH) and 12-hydroxydodecanoic acid (12-HDDA) were 25 000-, 3000-, and 180-fold lower, respectively, than for the wild-type enzyme. The large decrease in the efficiency of capturing GSNO and HMGSH by the E67L enzyme results mainly because of the impaired binding of these substrates to the mutant enzyme. In the case of 12-HDDA, a decrease in the rate of hydride transfer is the major factor responsible for the reduction in the efficiency of its capture for catalysis by the E67L enzyme. Binding of the coenzyme is not affected by the Glu-67 substitution. A partial displacement of the active-site zinc in the FDH.ADP-ribose binary complex indicates that the disruption of the interaction between Glu-67 and Arg-368 is involved in the displacement of active-site zinc. Kinetic studies with the R368L enzyme show that the predominant role of Arg-368 is in the binding of the coenzyme. An isomerization of the ternary complex before hydride transfer is detected in the kinetic pathway of HMGSH. Steps involved in the binding of the coenzyme to the FDH active site are also discerned from the unique conformation of the coenzyme

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

    Science.gov (United States)

    Chien, Yu-Tung; Huang, Shao-Wei

    2013-01-01

    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. PMID:23484160

  2. 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.

  3. 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…

  4. 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...

  5. Flight Performance Handbook for Orbital Operations: Orbital Mechanics and Astrodynamics Formulae, Theorems, Techniques, and Applications

    Science.gov (United States)

    Ambrosio, Alphonso; Blitzer, Leon; Conte, S.D.; Cooper, Donald H.; Dergarabedian, P.; Dethlefsen, D.G.; Lunn, Richard L.; Ireland, Richard O.; Jensen, Arnold A.; Kang, Garfield; hide

    1961-01-01

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

  6. 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.

  7. 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...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-01-01

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

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

    CERN Document Server

    Jackson, John David

    1962-01-01

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

  10. 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)

  11. 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.

  12. 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.

  13. Catalytic Functions of Standards

    NARCIS (Netherlands)

    K. Blind (Knut)

    2009-01-01

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

  14. 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.

  15. High-effective approach from amino acid esters to chiral amino alcohols over Cu/ZnO/Al2O3 catalyst and its catalytic reaction mechanism

    Science.gov (United States)

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

    2016-01-01

    Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface. PMID:27619990

  16. DRIFT studies on promotion mechanism of H3PW12O40 in selective catalytic reduction of NO with NH3.

    Science.gov (United States)

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

    2016-01-01

    Heteropoly acids (HPAs) have been effectively utilized in selective catalytic reduction (SCR) of NO to improve the NH3 absorption capacity and alkaline/alkali metal resistance for SCR catalysts. However, despite the promise on super-acidities, their other properties that would work on SCR process are still lack of exploration. In this study, a 12-tungstaphosphoric acid (H3PW12O40, HPW) was selected to modify a well-reported CeO2 catalyst. The resulted CeO2/HPW catalyst was subsequently utilized for SCR of NO with excess NH3, which revealed a significantly promoted performance in SCR reaction. DRIFT analyses showed that the unique NO2 absorption capacity of HPW could prevent the NO2 being further oxidized into nitrate species and the abundant Brønsted acid sites could effectively retain the NH3, avoiding them being over-oxidized at evaluated temperatures. The presence of NO2 was demonstrated able to induce a so called "fast SCR" reaction over the CeO2/HPW catalyst, which effectively facilitated the SCR reaction. Furthermore, we have also constructed a CeO2@HPW catalyst, which showed an enhanced SO2 poisoning resistance in SCR reaction. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. 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.

  18. 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.

  19. 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)

    2017-01-01

    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. PMID:29225721

  20. 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.

  1. 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.

  2. 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.)

  3. [Operational mechanism modification of bone mechanostat in an animal model of nutritional stress: effect of propranolol].

    Science.gov (United States)

    Pintos, Patricia Mabel; Lezón, Christian Esteban; Bozzini, Clarisa; Friedman, Silvia María; Boyer, Patricia Mónica

    2013-01-01

    Propranolol (P) treatment exerts a preventive effect against the detrimental consequences to bone status in mildly chronically food-restricted growing rats (NGR) by an increment in cortical bone and by improving its spatial distribution. To study the effect of beta-blocker on operational mechanism of bone mechanostat in an animal model of nutritional stress. Weanling male Wistar rats were randomly assigned to four groups: control (C), C + P (CP), NGR and NGR + P (NGRP). C and CP rats were fed freely with the standard diet. NGR and NGRP rats received, for 4 weeks, 80% of the amount of food consumed by C and CP respectively, the previous day, corrected by body weight. Propranolol (7 mg/kg/day) was injected ip 5 days per week, for four weeks in CP and NGRP rats. C and NGR received saline injections at an identical dosage regimen. Body weight and length were determined during the experimental period. Dietary intake was registered daily. Animals were sacrificed after 4 weeks of food restriction. Immediately, cuadriceps, femur and tibiae from each animal were dissected and weighed, and histomorphometric and mechanical studies were performed. Serum a-CTX, osteocalcin, intact PTH, calcium and phosphorous were determined. Body protein (% prot) was measured in all groups. Food restriction induced detrimental effects on body and femoral growth, load-bearing capacity (Wf), % prot and cuadriceps weight in NGR us. C (p 0.05). However, Wf NGRP vs. NGR was significantly higher (p 0.05). Serum osteocalcin, intact PTH, calcium and phospho- rous showed no significant difference between groups (p > 0.05). These results suggest that modeling increase in bone mass and strength in NGRP rats could be due to an anticatabolic interaction of the beta-blocker propranolol on operational mechanism of bone mechanostat in an animal model of nutritional stress.

  4. 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.

  5. 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.

  6. Enhancement of operating flux in a membrane bio-reactor coupled with a mechanical sieve unit.

    Science.gov (United States)

    Park, Seongjun; Yeon, Kyung-Min; Moon, Seheum; Kim, Jong-Oh

    2018-01-01

    Filtration flux is one of the key factors in regulating the performance of membrane bio-reactors (MBRs) for wastewater treatment. In this study, we explore the effectiveness of a mechanical sieve unit for effective flux enhancement through retardation of the fouling effect in a modified MBR system (SiMBR). In brief, the coarse sieve unit having 100 μm and 50 μm permits small size microorganism flocs to adjust the biomass concentration from the suspended basin to the membrane basin. As a result, the reduced biofouling effect due to the lowered biomass concentration from 7800 mg/L to 2400 mg/L, enables higher flux through the membrane. Biomass rejection rate of the sieve is identified to be the crucial design parameter for the flux enhancement through the incorporation of numerical simulations and operating critical-flux measurement in a batch reactor. Then, the sieve unit is prepared for 10 L lab-scale continuous SiMBR based on the correlation between sieve pore size and biomass rejection characteristics. During continuous operation of lab-scale SiMBR, biomass concentration is maintained with a higher biomass concentration in the aerobic basin (7400 mg/L) than that in the membrane basin (2400 mg/L). In addition, the SiMBR operations are conducted using three different commercial hollow fiber membranes to compare the permeability to that of conventional MBR operations. For all cases, the modified MBR having a sieve unit clearly results in enhanced permeability. These results successfully validate that SiMBR can effectively improve flux through direct reduction of biomass concentration. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. 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.

    Science.gov (United States)

    Omotayo, T I; Akinyemi, G S; Omololu, P A; Ajayi, B O; Akindahunsi, A A; Rocha, J B T; Kade, I J

    2015-01-01

    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 Fe(2+)-mediated in vitro oxidative stress model. The results show that Fe(2+) 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 Fe(2+) 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 Fe(2+) may involve complex multi-component mechanisms which may partly involve an initial oxidation of the critical thiols of the enzyme directly mediated by Fe(2+) 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. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    T.I. Omotayo

    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.

  9. 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.

  10. Numerical and experimental investigation on the performance of lean burn catalytic combustion for gas turbine application

    Science.gov (United States)

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

    2015-04-01

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

  11. 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

  12. Mechanical coolers operating below 4.5 K for space application

    International Nuclear Information System (INIS)

    Narasaki, Katsuhiro; Tsunematsu, Shouji; Kanao, Kenichi; Murakami, Hiroshi; Nakagawa, Takao; Mitsuda, Kazuhisa; Inatani, Junji; Sugita, Hiroyuki; Murakami, Masahide

    2006-01-01

    This paper reports the 4 K- and 1 K-class mechanical coolers developed for space use. The 4 K-class cooler has been developed for Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES), which is to be operated onboard the International Space Station (ISS). The cooling capacity is 20 mW at 4.5 K, with the total input power of approximately 120 W. The 1 K-class cooler has been developed for cooling far-infrared detectors to 1.7 K in the Space Infrared Telescope for Cosmology and Astrophysics (SPICA). The cooling capacity is 10 mW at 1.7 K and the total input power to the cooler is about 180 W. A future possible cryogen-free cooling system for temperature below 0.1 K is also presented, which uses these coolers as a pre-cooler

  13. Plant Protochlorophyllide Oxidoreductases A and B: CATALYTIC EFFICIENCY AND INITIAL REACTION STEPS.

    Science.gov (United States)

    Garrone, Alessio; Archipowa, Nataliya; Zipfel, Peter F; Hermann, Gudrun; Dietzek, Benjamin

    2015-11-20

    The enzyme protochlorophyllide oxidoreductase (POR, EC 1.3.1.33) has a key role in plant development. It catalyzes one of the later steps in chlorophyll synthesis, the light-induced reduction of protochlorophyllide (PChlide) into chlorophyllide (Chlide) in the presence of NADPH. Two isozymes of plant POR, POR A and POR B from barley, which differ in their function during plant life, are compared with respect to their substrate binding affinity, catalytic efficiency, and catalytic mechanism. POR B as compared with POR A shows an 5-fold higher binding affinity for PChlide and an about 6-fold higher catalytic efficiency measured as kcat/Km. Based on the reaction intermediates, which can be trapped at low temperatures the same reaction mechanism operates in both POR A and POR B. In contrast to results reported for POR enzymes from cyanobacteria, the initial light-driven step, which occurs at temperatures below 180 K already involves the full chemistry of the photoreduction and yields the reaction product, Chlide, in an enzyme-bound form. The subsequent dark reactions, which include cofactor (NADP(+)) release and cofactor (NADPH) rebinding, show different temperature dependences for POR A and POR B and suggest a higher conformational flexibility of POR B in the surrounding active center. Both the higher substrate binding affinity and well adapted enzyme dynamics are held responsible for the increased catalytic activity of POR B as compared with POR A. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-11-01

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

  15. 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.

  16. 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.

  17. 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.

  18. 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 ...

  19. 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)

  20. 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.

  1. 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...

  2. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    W. R. Laster; E. Anoshkina

    2008-01-31

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

  3. Catalytic Combustor for Fuel-Flexible Turbine

    Energy Technology Data Exchange (ETDEWEB)

    Laster, W. R.; Anoshkina, E.

    2008-01-31

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

  4. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

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    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 ...

  5. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(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 titanium is

  6. A computational study of detoxification of lewisite warfare agents by British anti-lewisite: catalytic effects of water and ammonia on reaction mechanism and kinetics.

    Science.gov (United States)

    Sahu, Chandan; Pakhira, Srimanta; Sen, Kaushik; Das, Abhijit K

    2013-04-25

    trans-2-Chlorovinyldichloroarsine (lewisite, L agent, Lew-I) acts as a blistering agents. British anti-lewisite (BAL, 2,3-dimercaptopropanol) has long been used as an L-agent antidote. The main reaction channels for the detoxification proceed via breaking of As-Cl bonds and formation of As-S bonds, producing stable, nontoxic ring product [(2-methyl-1,3,2-dithiarsolan-4-yl)methanol]. M06-2X/GENECP calculations have been carried out to establish the enhanced rate of detoxification mechanism in the presence of NH3 and H2O catalysts in both gas and solvent phases, which has been modeled by use of the polarized continuum model (PCM). In addition, natural bond orbital (NBO) and atoms in molecules (AIM) analysis have been performed to characterize the intermolecular hydrogen bonding in the transition states. Transition-state theory (TST) calculation establishes that the rates of NH3-catalyzed (2.88 × 10(-11) s(-1)) and H2O-catalyzed (2.42 × 10(-11) s(-1)) reactions are reasonably faster than the uncatalyzed detoxification (5.44 × 10(-13) s(-1)). The results obtained by these techniques give new insight into the mechanism of the detoxification process, identification and thermodynamic characterization of the relevant stationary species, the proposal of alternative paths on modeled potential energy surfaces for uncatalyzed reaction, and the rationalization of the mechanistic role played by catalysts and solvents.

  7. 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.

  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. Active Component Migration and Catalytic Properties of Nitrogen Modified Composite Catalytic Materials

    Directory of Open Access Journals (Sweden)

    Miaomiao Li

    2018-03-01

    Full Text Available During the catalytic combustion reaction of methane, the migration of the active species on surface facilitates the catalytic reaction, and the element doping can improve the redox performance of the catalyst. Nitrogen-modified perovskite type composite catalysts were prepared by hydrothermal method and then characterized by X-ray diffractometer (XRD, scanning electron microscopy (SEM, Brunauer-Emmett-Teller (BET, temperature-programmed reductions (TPR, and X-ray photoelectron spectra (XPS. The results revealed that nitrogen sources (urea, biuret, melamine, carbohydrazide, and semicarbazide hydrochloride and nitrogen source addition changed the catalytic performance in physical and chemical properties, the migration of reactive species and the catalytic performance. When the addition amount of semicarbazide hydrochloride was three times that of LaCoO3, the composite catalysts had high Co3+/Co2+ (1.39 and Oads/Olat (15.18 and showed the best catalytic performance: the temperatures that are required for achieving methane conversion of 50% and 90% were 277 and 360 °C, which are more effective than noble metal oxides. Moreover, the in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS were applied to elucidate the efficient for CH4 removal and also can further explain the surface reaction mechanism of the composite catalyst during the methane catalytic combustion.

  10. Structural determinants of APOBEC3B non-catalytic domain for molecular assembly and catalytic regulation

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Xiao; Yang, Hanjing; Arutiunian, Vagan; Fang, Yao; Besse, Guillaume; Morimoto, Cherie; Zirkle, Brett; Chen, Xiaojiang S. (USC)

    2017-05-30

    The catalytic activity of human cytidine deaminase APOBEC3B (A3B) has been correlated with kataegic mutational patterns within multiple cancer types. The molecular basis of how the N-terminal non-catalytic CD1 regulates the catalytic activity and consequently, biological function of A3B remains relatively unknown. Here, we report the crystal structure of a soluble human A3B-CD1 variant and delineate several structural elements of CD1 involved in molecular assembly, nucleic acid interactions and catalytic regulation of A3B. We show that (i) A3B expressed in human cells exists in hypoactive high-molecular-weight (HMW) complexes, which can be activated without apparent dissociation into low-molecular-weight (LMW) species after RNase A treatment. (ii) Multiple surface hydrophobic residues of CD1 mediate the HMW complex assembly and affect the catalytic activity, including one tryptophan residue W127 that likely acts through regulating nucleic acid binding. (iii) One of the highly positively charged surfaces on CD1 is involved in RNA-dependent attenuation of A3B catalysis. (iv) Surface hydrophobic residues of CD1 are involved in heterogeneous nuclear ribonucleoproteins (hnRNPs) binding to A3B. The structural and biochemical insights described here suggest that unique structural features on CD1 regulate the molecular assembly and catalytic activity of A3B through distinct mechanisms.

  11. 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.

  12. IDENTIFICATION OF CATALYTIC METAL ION LIGANDS IN RIBOZYMES

    Science.gov (United States)

    Frederiksen, John K.; Piccirilli, Joseph A.

    2012-01-01

    Site-bound metal ions participate in the catalytic mechanisms of many ribozymes. Understanding these mechanisms therefore requires knowledge of the specific ligands on both substrate and ribozyme that coordinate these catalytic metal ions. A number of different structural and biochemical strategies have been developed and refined for identifying metal ion binding sites within ribozymes, and for assessing the catalytic contributions of the metal ions bound at those sites. We review these approaches and provide examples of their application, focusing in particular on metal ion rescue experiments and their roles in the construction of the transition state models for the Tetrahymena group I and RNase P ribozymes. PMID:19651216

  13. 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.

  14. 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.

  15. 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...

  16. Analysis of the Mechanism Hindering Sustainable Forestry Operations: A Case Study of Japanese Forest Management

    Directory of Open Access Journals (Sweden)

    Yukari Fuchigami

    2016-08-01

    Full Text Available We investigated local forest management practices in Osaka, Japan aiming to clarify mechanisms that hinder long-term, sustainable forestry operation by carrying out forest surveys and interview surveys. Because mountain districts in Japan now face declining and aging populations, forestry work has shifted to forest owners’ associations, with efficient forest management being required on an ad hoc basis as a result of the subsidy system. We found that the forest management plan for the study site utilized only one-seventh of the economic value of the forest, mainly due to the local forestry structure and an inefficient subsidy system that requires efficiency. The income yielded by timber undergoing such forest management and distribution processes is too low to permit forest owners to carry out sufficient forest cultivation. To effectively utilize the wood, a subsidy system that takes a long-term view and a timber market that puts an appropriate price on wood are needed. We argue that it is important to bolster the management position of the Japanese Forest Owners’ Associations for design an institutional scheme that enables to practice forestry management from a long-term perspective.

  17. Human motion segmentation and recognition using machine vision for mechanical assembly operation.

    Science.gov (United States)

    Jiang, Qiannan; Liu, Mingzhou; Wang, Xiaoqiao; Ge, Maogen; Lin, Ling

    2016-01-01

    The observation, decomposition and record of motion are usually accomplished through artificial means during the process of motion analysis. This method not only has a heavy workload, its efficiency is also very low. To solve this problem, this paper proposes a novel method to segment and recognize continuous human motion automatically based on machine vision for mechanical assembly operation. First, the content-based dynamic key frame extraction technology was utilized to extract key frames from video stream, and then automatic segmentation of action was implemented. Further, the SIFT feature points of the region of interest (ROIs) were extracted, on the basis of which the characteristic vector of the key frame was derived. The feature vector can be used not only to represent the characteristic of motion, but also to describe the connection between motion and environment. Finally, the classifier is constructed based on support vector machine (SVM) to classify feature vectors, and the type of therblig is identified according to the classification results. Our approach enables robust therblig recognition in challenging situations (such as changing of light intensity, dynamic backgrounds) and allows automatic segmentation of motion sequences. Experimental results demonstrate that our approach achieves recognition rates of 96.00 % on sample video which captured on the assembly line.

  18. Mechanical Conflict System: A Novel Operant Method for the Assessment of Nociceptive Behavior.

    Directory of Open Access Journals (Sweden)

    Steven E Harte

    Full Text Available A new operant test for preclinical pain research, termed the Mechanical Conflict System (MCS, is presented. Rats were given a choice either to remain in a brightly lit compartment or to escape to a dark compartment by crossing an array of height-adjustable nociceptive probes. Latency to escape the light compartment was evaluated with varying probe heights (0, .5, 1, 2, 3, and 4 mm above compartment floor in rats with neuropathic pain induced by constriction nerve injury (CCI and in naive control rats. Escape responses in CCI rats were assessed following intraperitoneal administration of pregabalin (10 and 30 mg/kg, morphine (2.5 and 5 mg/kg, and the tachykinin NK1 receptor antagonist, RP 67580 (1 and 10 mg/kg. Results indicate that escape latency increased as a function of probe height in both naive and CCI rats. Pregabalin (10 and 30 mg/kg and morphine (5 mg/kg, but not RP 67580, decreased latency to escape in CCI rats suggesting an antinociceptive effect. In contrast, morphine (10 mg/kg but not pregabalin (30 mg/kg increased escape latency in naive rats suggesting a possible anxiolytic action of morphine in response to light-induced fear. No order effects following multiple test sessions were observed. We conclude that the MCS is a valid method to assess behavioral signs of affective pain in rodents.

  19. 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.

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

    Directory of Open Access Journals (Sweden)

    Ezequiel de Oliveira

    2007-06-01

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

  1. 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.

  2. Catalytic thermal barrier coatings

    Science.gov (United States)

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

    2009-06-02

    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  3. 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.

  4. Effect of nitrogen-containing impurities on the activity of perovskitic catalysts for the catalytic combustion of methane.

    Science.gov (United States)

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

    2012-11-05

    LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.

  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. 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.

  7. 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.)

  8. Effect of operating frequency and phase angle on performance of Alpha Stirling cryocooler driven by a novel compact mechanism

    International Nuclear Information System (INIS)

    Sant, K D; Bapat, S L

    2015-01-01

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

  9. Neural Operant Conditioning as a Core Mechanism of Brain-Machine Interface Control

    OpenAIRE

    Yoshio Sakurai; Kichan Song

    2016-01-01

    The process of changing the neuronal activity of the brain to acquire rewards in a broad sense is essential for utilizing brain-machine interfaces (BMIs), which is essentially operant conditioning of neuronal activity. Currently, this is also known as neural biofeedback, and it is often referred to as neurofeedback when human brain activity is targeted. In this review, we first illustrate biofeedback and operant conditioning, which are methodological background elements in neural operant cond...

  10. 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...

  11. Operational Determination of Physical and Mechanical Properties of Cast Samples of High-Strength Iron by Means of a Magnetic-Mechanical Method

    Science.gov (United States)

    Slyusarev, Yu. K.; Braga, A. V.; Slyusarev, I. Yu.

    2017-09-01

    The effect of the chemical composition of high-strength cast iron VCh35 on the content, shape and diameter of graphite inclusions and on the presence of structurally-free cementite and defects is studied. A relationship is determined between the structure and metallurgical defects and characteristics of the mechanical and magnetic rigidity of cast samples. Relationships are established in a group of factors and property characteristics: chemical composition - microstructure - mechanical rigidity - magnetic stiffness. The basis of a method is established making it possible to perform operative non-destructive monitoring of the melt quality preparation for high-strength iron casting.

  12. 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

  13. Lessons Learned From the Development, Operation, and Review of Mechanical Systems on the Space Shuttle, International Space Station, and Payloads

    Science.gov (United States)

    Dinsel, Alison; Jermstad, Wayne; Robertson, Brandan

    2006-01-01

    The Mechanical Design and Analysis Branch at the Johnson Space Center (JSC) is responsible for the technical oversight of over 30 mechanical systems flying on the Space Shuttle Orbiter and the International Space Station (ISS). The branch also has the responsibility for reviewing all mechanical systems on all Space Shuttle and International Space Station payloads, as part of the payload safety review process, through the Mechanical Systems Working Group (MSWG). These responsibilities give the branch unique insight into a large number of mechanical systems, and problems encountered during their design, testing, and operation. This paper contains narrative descriptions of lessons learned from some of the major problems worked on by the branch during the last two years. The problems are grouped into common categories and lessons learned are stated.

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

    Directory of Open Access Journals (Sweden)

    Melnyk Olga G

    2016-02-01

    Full Text Available 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, their difference from the operations with customerfurnished raw materials has been allocated, substance and characteristics of tolling operations has been conceptually grounded, motives of their implementation for both the customer and the provider has been systematized. It is proved that implementation of tolling operations will address the pivotal financial, production and staffing problems of domestic enterprises and ensure their progressive development in conditions of the European integration. Prospect of further research is developing a conceptual framework for management of tolling operations, which will provide targeted exposure of management system on the controlled system, which is directly involved in the implementation of tolling operations, with a view to enhancing the efficiency of tolling process

  15. 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)

  16. Neural Operant Conditioning as a Core Mechanism of Brain-Machine Interface Control

    Directory of Open Access Journals (Sweden)

    Yoshio Sakurai

    2016-08-01

    Full Text Available The process of changing the neuronal activity of the brain to acquire rewards in a broad sense is essential for utilizing brain-machine interfaces (BMIs, which is essentially operant conditioning of neuronal activity. Currently, this is also known as neural biofeedback, and it is often referred to as neurofeedback when human brain activity is targeted. In this review, we first illustrate biofeedback and operant conditioning, which are methodological background elements in neural operant conditioning. Then, we introduce research models of neural operant conditioning in animal experiments and demonstrate that it is possible to change the firing frequency and synchronous firing of local neuronal populations in a short time period. We also debate the possibility of the application of neural operant conditioning and its contribution to BMIs.

  17. 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.

  18. The antitumor mechanism of di-2-pyridylketone 2-pyridine carboxylic acid hydrazone and its copper complex in ROS generation and topoisomerase inhibition, and hydrazone involvement in oxygen-catalytic iron mobilization.

    Science.gov (United States)

    Huang, Tengfei; Li, Cuiping; Sun, Xingzhi; Zhu, Zhenfu; Fu, Yun; Liu, Youxun; Yuan, Yanbin; Li, Shaoshan; Li, Changzheng

    2015-11-01

    Iron depletion and stimulation of iron-dependent free radical damage is a rapidly developing field for chelation therapy, but the iron mobilization from ferritin by chelators has received less attention. In this study, the di-2-pyridylketone 2-pyridine carboxylic acid hydrazone (DPPCAH) and its copper complex was prepared and characterized by NMR and MS spectra. The proliferation inhibition assay showed that both DPPCAH and its copper complex exhibited selectively proliferation inhibition for HepG2 (IC50, 4.6 ± 0.2 µM for DPPACH and 1.3 ± 0.2 µM for its copper complex), but less inhibition for HCT-116 cell line (IC50, >100 µM for DPPACH and 7.8 ± 0.4 µM for its copper complex). The mechanistic studies revealed that DPPACH could remove iron from ferritin in a oxygen-catalytic manner, and contributed to redox activity of labile iron pool (LIP), that is less reported for the chelators that possess significant biological activity. The reactive oxygen species (ROS) generation and DNA cleavage assay in vitro and in vivo showed that both DPPACH-Fe(II) and DPPACH-Cu were redox-active species, indicating that ROS may mediate their antitumor activity. Further study revealed that both DPPACH and its copper complex displayed certain degree of inhibition of type II topoisomerase (Top) which contributed to their antitumor activity. Thus, the mechanism that iron mobilization by DPPACH from ferritin contributed to LIP was proposed, and both DPPACH and its copper complex were involved in ROS generation and Top II inhibition for their antitumor activities.

  19. 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.

  20. 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.

  1. 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.

  2. 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...

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

    International Nuclear Information System (INIS)

    Li, W.X.; Song, Y.T.; Ye, M.Y.; Peng, X.B.; Wu, S.T.; Qian, X.Y.; Zhu, C.C.

    2016-01-01

    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.

  4. 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)

  5. Operationalizing the Interagency Coordination Mechanisms between State and Department of Defense for Stabilization and Reconstruction Operations

    Science.gov (United States)

    2006-06-16

    on the civil environment; monitor operations to minimize the negative impacts of both sides, to identify requirements for follow-on CA operations...PDAS Marcia Wong 58 Early Warning and Prevention (EWP) Director: Dou Planning ( PLN ) Director: Barbara Stephenson Best...strength of the model; the four tools are the CRSG assessment, the planning framework, the essential task matrix , and the metrics developed. The format

  6. 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.

  7. 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

  8. 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

  9. A generic basis for some simple light-operated mechanical molecular machines.

    Science.gov (United States)

    Pérez, Emilio M; Dryden, David T F; Leigh, David A; Teobaldi, Gilberto; Zerbetto, Francesco

    2004-10-06

    A novel type of mechanical switch is described in which light-induced translation of a macrocycle in a [2]rotaxane quenches anthracene fluorescence. Features of the system include the remarkable 200:1 difference in fluorescence intensity between the two positional states of the molecule ( approximately 85:1 between one isomer and the photostationary state). In principle the same concept could be used for mechanically switching virtually any property that can be influenced by functional group proximity effects.

  10. Catalytic Antibodies: Concept and Promise

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Catalytic Antibodies: Concept and Promise. Desirazu N Rao Bharath Wootla. General Article Volume 12 Issue ... Keywords. Catalytic antibodies; abzymes; hybridome technology; Diels– Alder reaction; Michaelis– Menten kinetics; Factor VIII.

  11. 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.

  12. Catalytic wet oxidation of black liquor

    OpenAIRE

    Viader Riera, Gerard

    2012-01-01

    The major aspects of wet air oxidation and catalytic wet air oxidation have been reviewed in this work paying special attention to the reaction mechanisms, kinetics and the industrial process. In the experimental section a set of heterogeneous catalysts have been tested in the wet oxidation of non-wood black liquor. The oxidation runs were performed batchwise in a laboratory-scale mechanically stirred slurry reactor for 1 h at a temperature of 170°C and total pressure of 12 bar. Pure oxygen w...

  13. Tolerance to anatoxin-a and nicotine on operant behavior: A search for mechanisms.

    Science.gov (United States)

    Anatoxin-a is a cyanobacterial toxin of concern to EPA as it can contaminate water supplies and poison a wide variety of species by stimulating nicotinic receptors. Research has shown tolerance to the effects of (+)anatoxin-a and nicotine on operant behavior with weekly administr...

  14. The mechanism of light emission from a scanning tunnelling microscope operating in air.

    Science.gov (United States)

    Rogez, B; Cao, S; Dujardin, G; Comtet, G; Moal, E Le; Mayne, A; Boer-Duchemin, E

    2016-11-18

    The scanning tunnelling microscope (STM) may be used as a low-energy, electrical nanosource of surface plasmon polaritons and light. In this article, we demonstrate that the optimum mode of operation of the STM for maximum photon emission is completely different in air than in vacuum. To this end, we investigate the emission of photons, the variation in the relative tip-sample distance and the measured current as a function of time for an STM operating in air. Contrary to the case of an STM operating in vacuum, the measured current between the tip and sample for an STM in air is very unstable (rapidly fluctuating in time) when the applied voltage between the tip and sample is in the ∼1.5-3 V range (i.e., in the energy range of visible photons). The photon emission occurs in short (50 μs) bursts when the STM tip is closest to the sample. The current instabilities are shown to be a key ingredient for producing intense light emission from an STM operating in air (photon emission rate several orders of magnitude higher than for stable current). These results are explained in terms of the interplay between the tunnel current and the electrochemical current in the ubiquitous thin water layer that exists when working in air.

  15. Proton migration mechanism for operational instabilities in organic field-effect transistors

    NARCIS (Netherlands)

    Sharma, A.; Mathijssen, S.G.J.; Smits, E.C.P.; Kemerink, M.; Leeuw, D.M. de; Bobbert, P.A.

    2010-01-01

    Organic field-effect transistors exhibit operational instabilities involving a shift of the threshold gate voltage when a gate bias is applied. For a constant gate bias the threshold voltage shifts toward the applied gate bias voltage, an effect known as the bias-stress effect. Here, we report on a

  16. 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...

  17. 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.

  18. 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

  19. 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.

  20. Highly sensitive methane catalytic combustion micro-sensor based on mesoporous structure and nano-catalyst.

    Science.gov (United States)

    Su, Jiacan; Cao, Liehu; Li, Liang; Wei, Jie; Li, Gengnan; Yuan, Yinyin

    2013-10-21

    In order to get a methane catalytic combustion micro-sensor, two different catalytic systems used in traditional methane catalytic combustion sensors were fabricated into a mesoporous structure and their catalytic activities were investigated. In comparison, the Rh2O3-Al2O3 system can form more a uniform mesoporous structure and has a much higher specific surface area. Even more importantly, it has relatively higher catalytic activity and stability for the methane catalytic combustion reaction. After being coated on a microelectro-mechanical system (MEMS) micro-heater, a catalytic combustion type methane micro-sensor was fabricated. The meso-structured Rh2O3-Al2O3 hybrid based MEMS sensor demonstrated a short T90 response time, relatively high signal output, high enough signal/noise ratio for practical detecting and strong anti-poison properties.

  1. 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

  2. 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)

  3. First year in operating a mechanical detrasher system at a sugarcane factory in Louisiana

    Science.gov (United States)

    Over the past 2 years, a new prototype mechanical detrasher system was built at a Louisiana sugarcane factory by American Biocarbon LLC. It was built to remove sugarcane trash (top stalks and leaves) before processing, and for the manufacture and sale of value-added-products from the removed trash,...

  4. Two-Swim Operators in the Modified Bacterial Foraging Algorithm for the Optimal Synthesis of Four-Bar Mechanisms

    Science.gov (United States)

    Hernández-Ocaña, Betania; Pozos-Parra, Ma. Del Pilar; Mezura-Montes, Efrén; Portilla-Flores, Edgar Alfredo; Vega-Alvarado, Eduardo; Calva-Yáñez, Maria Bárbara

    2016-01-01

    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. PMID:27057156

  5. 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.

  6. Newton Leibniz integration for ket-bra operators in quantum mechanics (V)—Deriving normally ordered bivariate-normal-distribution form of density operators and developing their phase space formalism

    Science.gov (United States)

    Fan, Hong-yi

    2008-06-01

    We show that Newton-Leibniz integration over Dirac's ket-bra projection operators with continuum variables, which can be performed by the technique of integration within ordered product (IWOP) of operators [Hong-yi Fan, Hai-liang Lu, Yue Fan, Ann. Phys. 321 (2006) 480], can directly recast density operators and generalized Wigner operators into normally ordered bivariate-normal-distribution form, which has resemblance in statistics. In this way the phase space formalism of quantum mechanics can be developed. The Husimi operator, entangled Husimi operator and entangled Wigner operator for entangled particles with different masses are naturally introduced by virtue of the IWOP technique, and their physical meanings are explained.

  7. JOYO MK-III heat transport system renovation operation. Primary heat transport mechanical system (IHXs (intermediate heat exchangers))

    International Nuclear Information System (INIS)

    Ohshima, Jun; Ashida, Takashi; Isozaki, Kazunori; Sumino, Kouzou; Yamaguchi, Akira; Sakaba, Hideo; Tomita, Naoki; Ozawa, Kenji

    2004-04-01

    The MK-III project to improve the irradiation capability of the experimental fast reactor JOYO have been carried out since 1987. The increase of fast neutron flux and the enlargement of irradiation field increase the reactor thermal power from 100 MWt to 140 MWt. To accommodate the increased thermal power, the IHXs and the IHX connecting piping were replaced. The IHXs were replaced with securing cooling system boundary in high dose rate surroundings and very limited operation space of the radiation controlled area in the containment vessel. Primary sodium contains radioactive 22 Na, 24 Na and radioactive CPs such as 60 Co and 54 Mn, and this sodium adhered to the inner surface of IHXs and pipe. Therefore, the renovation procedure and method were carefully examined based on the JOYO operation and maintenance experiences and research and development results on the sodium handling technique. The major results obtained in the primary heat transport mechanical system (IHXs) renovation operation were shown as follows; (1) The mock up tests to optimize the operating methods, to check the operability and for workers training were useful for reduction of radiation exposure by shortening the operation time in high dose rate surrounding. (2) The effectiveness of seal bag for prevention of impurity ingress to the sodium system and contamination during sodium boundary opening (cutting pipes, sodium removal and welding pipes) was confirmed. (3) The pipes were cut without foreign object such as cutting piece and tool ingress by careful examination of cutting procedure and methods such as bite, roller cutter. (4) The temporary closing equipment such as seal cap and seal plug were effectively worked to seal the cooling system boundary between cutting and welding pipes. (5) Sodium adhered on the inner surfaces of pipe was effectively and safely removed by a mechanical scraper or drill and a cloth moistened by a mixture of alcohol and water. (6) Control of low gas pressure difference

  8. Structural and mechanical degradation of 09Mn2Si pipe steel after long-term operation

    Science.gov (United States)

    Panin, S. V.; Marushchak, P. O.; Vlasov, I. V.; Eremin, A. V.; Byakov, A. V.; Syromyatnikova, A. S.; Stankevich, R.

    2017-12-01

    A comprehensive study of the structure and impact toughness of 09Mn2Si steel used in the construction of the main gas pipeline "Mastakh-Berge-Yakutsk" (taken from the linear part with the outer diameter of 530 mm and the wall thickness of 7 mm) after 37 years of operation was carried out. A comparative analysis of results obtained for the emergency stock steel was conducted. It was shown that long-term operation does not give rise to a substantial redistribution of cementite. Deformation aging is slightly expressed and is manifested through precipitation of finely dispersed carbides in the grain bulk. The revealed structure degradation almost does not make sense under hardness measurement. The most pronounced manifestation of structure changes is related to decreasing impact toughness of 09Mn2Si steel which reaches ˜2 times under negative temperatures.

  9. 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

  10. Effects of Operating Temperatures and Accelerated Environmental Ageing on the Mechanical Properties of a Glass-Vinylester Composite

    Science.gov (United States)

    Klasztorny, M.; Nycz, D. B.; Romanowski, R. K.; Gotowicki, P.; Kiczko, A.; Rudnik, D.

    2017-07-01

    Experimental identification of the mechanical properties of a selected glass-vinylester structural composite is developed, performed, and analysed taking into account accelerated environmental ageing and three operating temperatures (-20, 20, and 55°C) corresponding to the operating temperature range for composite footbridges in the Central Europe. The main constituents of the composite fabricated using infusion technology are a bidirectional balanced stitched E-glass fabric and a flame retardant, vinylester resin. After homogenization, the composite reinforced with one fabric forms a single lamina and is modeled as a linear elastic-brittle orthotropic material. Full sets of material constants were identified for the initial and aged composites at the selected operating temperatures. The accelerated environmental ageing of the composite was performed on 4-layer symmetric laminate platelets protected with a 300-mm-thick gelcoat layer, using an ageing chamber and a relevant ageing programme. A comparative analysis was carried out in order to determine the effects of operating temperature and accelerated environmental ageing on the material constants of the GFRP composite. It is found that the composite tested can be modeled as a linear elastic-brittle orthotropic material to the level of 20% of its strength in each strength test. The impact of the accelerated environmental ageing and operating temperature in the range from -20 to 55°C on the elastic/strength/ultimate strain constants of the selected E-glass/vinylester composite can be significant and different for individual constants.

  11. Modeling and analysis of hydraulic dashpot for impact free operation in a shut-off rod drive mechanism

    Directory of Open Access Journals (Sweden)

    Narendra K. Singh

    2016-09-01

    Full Text Available Rotary hydraulic dashpot used for shut-off rod drive mechanism application of a nuclear reactor has been studied in this paper for impact free operation. The rotary hydraulic dashpot has been modeled as a system with 1 degree of freedom (DOF and the simulation results are experimentally validated. The dashpot is modeled as a hinge joint with moving and fixed vanes as rigid bodies. Shut-off rods are used to shut-down a nuclear reactor and hydraulic dashpot absorbs the energy of freely falling shut-off rod at the end of rod travel. With the increase in the environmental temperature the dashpot becomes underdamped at a point because of reduction in the viscosity of oil and results into impact on mechanism components. Hydraulic dashpot designs are finalized with an optimum combination of dashpot clearances and oil viscosity to meet the drop time criterion and impact free operation at room temperature as well as at elevated temperature. Also with the change in mechanical loads the dashpot becomes underdamped. So the study is further extended to see the effects of various parameters such as moment of inertia, constraint angle and applied moment on the dashpot. Study is focused on obtaining dashpot responses in terms of relative rotation, relative angular velocity and relative angular acceleration at various environmental temperatures. Finite element commercial code COMSOL Multiphysics 5.1 has been used for numerical simulations. Equations for both rigid body dynamics and heat transfer in solids are solved simultaneously. Thus, energy absorbed and local temperature rise in the dashpot operation is also obtained. Both simulation and experimental results at wide range of environmental temperature are presented and compared in this paper. This study forms a good tool to design a hydraulic dashpot, which gives impact free operation in a shut-off rod free fall.

  12. Editing mechanism of aminoacyl-tRNA synthetases operates by a hybrid ribozyme/protein catalyst.

    Science.gov (United States)

    Hagiwara, Yohsuke; Field, Martin J; Nureki, Osamu; Tateno, Masaru

    2010-03-03

    Aminoacyl-tRNA synthetases (aaRSs) are critical for the translational process, catalyzing the attachment of specific amino acids to their cognate tRNAs. To ensure formation of the correct aminoacyl-tRNA, and thereby enhance the reliability of translation, several aaRSs have an editing capability that hinders formation of misaminoacylated tRNAs. We investigated theoretically the mechanism of the editing reaction for a class I enzyme, leucyl-tRNA synthetase (LeuRS), complexed with a misaminoacylated tRNA(Leu), employing ab initio hybrid quantum mechanical/molecular mechanical potentials in conjunction with molecular dynamics simulations. It is shown that the water molecule that acts as the nucleophile in the editing reaction is activated by a 3'-hydroxyl group at the 3'-end of tRNA(Leu) and that the O2' atom of the leaving group of the substrate is capped by one of the water's hydrogen atoms. Thus, it is shown that editing is a self-cleavage reaction of the tRNA and so it is the tRNA, and not the protein, that drives the reaction. The protein does, however, have an important stabilizing effect on some high-energy intermediates along the reaction path, which is more efficient than the ribozyme would be alone. This indicates that editing is achieved by a novel "hybrid ribozyme/protein catalyst". Analysis of existing experimental data and additional modeling shows that this ribozymal mechanism appears to be widespread, occurring in the ribosome as well as in other aaRSs. It also suggests transitional forms that could have played an important role in the RNA world hypothesis for the origin of life.

  13. A Study on the Operation Mechanism of Ongnu, the Astronomical Clock in Sejong Era

    Directory of Open Access Journals (Sweden)

    Sang Hyuk Kim

    2011-03-01

    Full Text Available Ongnu (Jade Clepsydra; also called Heumgyeonggaknu is a water clock was made by Jang Yeong-sil in 1438. It is not only an automatic water clock that makes the sound at every hour on the hour by striking bell, drum and gong, but also an astronomical clock that shows the sun's movement over time. Ongnu‘s power mechanism used is a water-hammering method applied to automatic time-signal device. The appearance of Ongnu is modeled by Gasan (pasted-paper imitation mountain and Binpungdo (landscape of farming work scene is drawn at the foot of the mountain. The structure of Ongnu is divided into the top of the mountain, the foot of the mountain and the flatland. There located are sunmovement device, Ongnyeo (jade female immortal; I and Four gods (shaped of animal-like immortals at the top of the mountain, Sasin (jack hour and Musa (warrior at the foot of the mountain, and Twelve gods, Ongnyeo (II and Gwanin on the flatland. In this study, we clearly and systematically understood the time-announcing mechanism of each puppet. Also, we showed the working mechanism of the sun-movement device. Finally, we completely established the 3D model of Ongnu based on this study.

  14. A Study on the Operation Mechanism of Ongnu, the Astronomical Clock in Sejong Era

    Science.gov (United States)

    Kim, Sang Hyuk; Lee, Yong Sam; Lee, Min Soo

    2011-03-01

    Ongnu (Jade Clepsydra; also called Heumgyeonggaknu) is a water clock was made by Jang Yeong-sil in 1438. It is not only an automatic water clock that makes the sound at every hour on the hour by striking bell, drum and gong, but also an astronomical clock that shows the sun's movement over time. Ongnu's power mechanism used is a water-hammering method applied to automatic time-signal device. The appearance of Ongnu is modeled by Gasan (pasted-paper imitation mountain) and Binpungdo (landscape of farming work scene) is drawn at the foot of the mountain. The structure of Ongnu is divided into the top of the mountain, the foot of the mountain and the flatland. There located are sunmovement device, Ongnyeo (jade female immortal; I) and Four gods (shaped of animal-like immortals) at the top of the mountain, Sasin (jack hour) and Musa (warrior) at the foot of the mountain, and Twelve gods, Ongnyeo (II) and Gwanin on the flatland. In this study, we clearly and systematically understood the time-announcing mechanism of each puppet.Also, we showed the working mechanism of the sun-movement device. Finally, we completely established the 3D model of Ongnu based on this study.

  15. 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

  16. 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.

  17. Catalytic cracking with deasphalted oil

    Energy Technology Data Exchange (ETDEWEB)

    Beaton, W.I.; Taylor, J.L.; Peck, L.B.; Mosby, J.F.

    1990-07-10

    This patent describes a catalytic cracking process. It comprises: hydrotreating resid; thereafter deasphalting the hydrotreated resid to produce substantially deasphalted oil; catalytically cracking the hydrotreated oil in a catalytic cracking unit in the presence of a cracking catalyst to produce upgraded oil leaving coked catalyst; and regenerating the coked catalyst in the presence of a combustion-supporting gas comprising excess molecular oxygen in an amount greater than the stoichiometric amount required for substantially completely combusting the coke on the catalyst to carbon dioxide.

  18. 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.

  19. 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...

  20. Monitoring of Basic Parameters for Selective Catalytic Reduction System Used in an Agricultural Tractor

    Directory of Open Access Journals (Sweden)

    Antonín Skřivánek

    2014-01-01

    Full Text Available Presented paper describes monitoring of basic parameters for selective catalytic reduction (SCR system used in an agricultural tractor. SCR systems are used to reduce emissions of nitrogen oxides (NOx produced by combustion of fuel. The usage of SCR catalytic converters entails certain disadvantages in the use of reducing agent and the necessity of suitable operating conditions to achieve optimum efficiency of the catalytic converter. This paper aims to predict consumption of AdBlue depending on the temperature of SCR catalytic converter, which reflects the engine load and monitoring the effectiveness of SCR catalytic converter when operating a tractor engine with a maximum dose of fuel. To fulfill those aims, the measurements have been performed on the Case Puma 185 CVX agricultural tractor. As the measurement results indicate, the lowest NOx emissions correspond to high consumption of AdBlue. Other studies imply that the catalytic converter operates at optimal operating temperature and with the highest efficiency of NOx emission reduction. The effectiveness of NOx emission reduction is thus affected not only by quantity of injected reagent but also by catalytic converter thermal load. Further measurement results indicate that the lowest amount of emissions of NOx (and the highest efficiency rate is achieved by catalytic converter in a range in which the engine operates with the highest engine efficiency.

  1. Catalytic Membrane Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.

    1998-12-01

    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  2. 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.)

  3. Vibration upshot of operating mechanical sewing machine: an insight into common peroneal nerve conduction study.

    Science.gov (United States)

    Yadav, Prakash Kumar; Yadav, Ram Lochan; Sharma, Deepak; Shah, Dev Kumar; Sapkota, Niraj Khatri; Thakur, Dilip; Limbu, Nirmala; Islam, Md Nazrul

    2017-01-01

    Most of the people associated with tailoring occupation in Nepal are still using mechanical sewing machine as an alternative of new technology for tailoring. Common peroneal nerves of both right and left legs are exposed to strenuous and chronic stress exerted by vibration and paddling of mechanical sewing machine. The study included 30 healthy male tailors and 30 healthy male individuals. Anthropometric variables as well as cardio respiratory variables were determined for each subject. Standard Nerve Conduction Techniques using constant measured distances were applied to evaluate common peroneal nerve (motor) in both legs of each individual. Data were analyzed and compared between study and control groups using Man Whitney U test setting the significance level p  ≤ 0.05. Anthropometric and cardio respiratory variables were not significantly altered between the study and control groups. The Compound muscle action potential (CMAP) latency of common peroneal nerves of both right [(11.29 ± 1.25 vs. 10.03 ± 1.37), P  sewing machine by paddling chronically and arduously could have attributed to abnormal nerve conduction study parameters due to vibration effect of the machine on right and left common peroneal nerves. The results of present study follow the trend towards presymptomatic or asymptomatic neuropathy similar to subclinical neuropathy.

  4. 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.

  5. Release of hydrogen sulfide during microwave pyrolysis of sewage sludge: Effect of operating parameters and mechanism.

    Science.gov (United States)

    Zhang, Jun; Zuo, Wei; Tian, Yu; Yin, Linlin; Gong, Zhenlong; Zhang, Jie

    2017-06-05

    The effects of sludge characteristics, pyrolysis temperature, heating rate and catalysts on the release of H 2 S and mechanism of H 2 S formation during sludge pyrolysis were investigated in a microwave heating reactor (MHR). The evolution of sulfur-containing compounds in the pyrolysis chars obtained at temperature range of 400-800°C was characterized by XPS. For a given temperature, the maximum concentration of H 2 S appeared at moisture content of 80%. Compared to the influence of heating rate on the H 2 S yields, pyrolysis temperature and catalyst played a more significant role on the release of H 2 S during microwave pyrolysis process. The H 2 S concentration increased with increasing temperature from 400°C to 800°C while decreased with increasing heating rate. Both the Nickel-based catalyst and Dolomite displayed significant desulfurization effect and Ni-based catalyst exhibited the larger desulfurization capability than that of Dolomite. The organic sulfur compounds accounted for about 60% of the total sulfur in the sludge which was the main reason for the formation of H 2 S. The mechanism analysis indicated that the cleavage reactions of mercaptan and aromatic-S compounds at temperatures below 600°C and the cracking reaction of sulfate above 700°C respectively were responsible for the H 2 S release during sludge pyrolysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. 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

  7. 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

  8. Catalytic pyrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Seshan, Kulathuiyer; Sa, Jacinto

    2014-01-01

    This chapter reports on the latest developments of biomass catalytic pyrolysis for the production of fuels. The primary focus is on the role of catalysts in the process, namely, their influence in the liquefaction of lignocellulosic biomass.

  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. 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.

  11. 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)

  12. Current concepts of molecular defence mechanisms operative during urinary tract infection.

    Science.gov (United States)

    Weichhart, T; Haidinger, M; Hörl, W H; Säemann, M D

    2008-10-01

    Mucosal tissues such as the gastrointestinal tract are typically exposed to a tremendous number of microorganisms and many of them are potentially dangerous to the host. In contrast, the urogenital tract is rather infrequently colonized with bacterial organisms and also devoid of physical barriers as a multi-layered mucus or ciliated epithelia, thereby necessitating separate host defence mechanisms. Recurrent urinary tract infection (UTI) represents the successful case of microbial host evasion and poses a major medical and economic health problem. During recent years considerable advances have been made in our understanding of the mechanisms underlying the immune homeostasis of the urogenital tract. Hence, the system of pathogen-recognition receptors including the Toll-like receptors (TLRs) is able to sense danger signalling and thus activate the host immune system of the genitourinary tract. Additionally, various soluble antimicrobial molecules including iron-sequestering proteins, defensins, cathelicidin and Tamm-Horsfall protein (THP), as well as their role for the prevention of UTI by modulating innate and adaptive immunity, have been more clearly defined. Furthermore, signalling mediators like cyclic adenosine monophosphate (cAMP) or the circulatory hormone vasopressin were shown to be involved in the defence of uropathogenic microbes and maintenance of mucosal integrity. Beyond this, specific receptors e.g. CD46 or beta1/beta 3-integrins, have been elucidated that are hijacked by uropathogenic E. coli to enable invasion and survival within the urogenital system paving the way for chronic forms of urinary tract infection. Collectively, the majority of these findings offer novel avenues for basic and translational research implying effective therapies against the diverse forms of acute and chronic UTI.

  13. Effect of operating parameters on mechanical expression of solvent-soaked soybean-grits.

    Science.gov (United States)

    Sinha, Lalan Kumar; Haldar, Swarrna; Majumdar, Gautam Chandra

    2015-05-01

    Oil from soybean is obtained mostly by solvent extraction of soybean flakes. Legislation banning the use of hexane as solvent for extracting edible vegetable oil has forced a search for an alternative solvent and for developing a suitable oil recovery process. Expellers are being used for obtaining vegetable oil by mechanical means (expression) from oil seeds having oil content higher than 20 %. It was felt, in view of the stiffness of the soybean matrix, a combination of solvent treatment and expression could be a cheaper alternative; thus an attempt has been made here to develop a two stage process constituting soaking of soybean grits in solvent followed by mechanical compression (hydraulic press) of solvent-soaked grits to recover oil. The present work aimed at studying the effect of various process parameters on oil yield from solvent soaked soybean-grits during soaking as well as pressing stages using the solvents: hexane, ethanol (alternative solvent). The process parameters were identified through holistic approach. The dependant variable was oil recovery (expressed as fraction of initial oil content of soybean) whereas the independent parameters were particle size, solvent-bean mass ratio, soaking time, soaking temperature, applied pressure and pressing time. The effect of each of the above parameters on fractional oil recovery (FOR) was studied. The results of the present study indicate that the above parameters have a significant effect on the fractional oil recovery with particle size, soaking temperature, soaking time and pressing time being the most significant factors. The present study also indicates that ethanol can be used as an alternate solvent to hexane by optimizing the factors as discussed in this paper.

  14. Effects of continuous positive airway pressure on lung mechanics of babies after operation for congenital heart disease.

    Science.gov (United States)

    Cogswell, J J; Hatch, D J; Kerr, A A; Taylor, B

    1975-01-01

    The effect of continuous positive airway pressure (CPAP) on lung mechanics was investigated in 12 babies after operation for severe congenital heart disease. At the time of study all babies were receiving or being weaned from ventilatory support and had abnormally low lung volume or compliance. During CPAP there was a fall in the pulmonary resistance which, with a slight decrease in minute ventilation, resulted in a significant decrease in the work of breathing. It is suggested that lowering the oxygen cost of breathing may contribute to the improvement in arterial oxygenation seen when CPAP is used. PMID:801862

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. A novel multi-objective electromagnetism-like mechanism algorithm with applications in reservoir flood control operation.

    Science.gov (United States)

    Ouyang, Shuo; Zhou, Jianzhong; Qin, Hui; Liao, Xiang; Wang, Hao

    2014-01-01

    Reservoir flood control operation (RFCO) is a complex problem that involves various constraints and purposes, which include the safety of the dam, watershed flood control and navigation. These objectives often conflict with each other. Thus, traditional methods have difficulty in solving the multi-objective problem efficiently. In this paper, a multi-objective self-adaptive electromagnetism-like mechanism (MOSEM) algorithm is introduced in the local searching operation of the proposed method. To enhance the optimization ability of EM, a self-adaptive parameter is applied in the local search operation of MOSEM for adjusting the values of parameters dynamically. Moreover, MOSEM is tested by several benchmark test problems and compared with some well-known multi-objective evolutionary algorithms. A case study is also used for solving RFCO problems of the Three Georges Reservoir by using the multi-objective cultured differential evolution (MOCDE), non-dominated sorting genetic algorithm-II (NSGA-II) and proposed MOSEM methods. The study results reveal that MOSEM can provide alternative Pareto-optimal solutions (POS) with better convergence properties and diversification.

  1. Mechanism

    Directory of Open Access Journals (Sweden)

    Yao Yu

    2010-01-01

    Full Text Available The kinematics analysis method of a novel 3-DOF wind tunnel mechanism based on cable-driven parallel mechanism is provided. Rodrigues' parameters are applied to express the transformation matrix of the wire-driven mechanism in the paper. The analytical forward kinematics model is described as three quadratic equations using three Rodridgues' parameters based on the fundamental theory of parallel mechanism. Elimination method is used to remove two of the variables, so that an eighth-order polynomial with one variable is derived. From the equation, the eight sets of Rodridgues' parameters and corresponding Euler angles for the forward kinematical problem can be obtained. In the end, numerical example of both forward and inverse kinematics is included to demonstrate the presented forward-kinematics solution method. The numerical results show that the method for the position analysis of this mechanism is effective.

  2. 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.

  3. Newton Leibniz integration for ket bra operators in quantum mechanics (IV)—Integrations within Weyl ordered product of operators and their applications

    Science.gov (United States)

    Fan, Hong-yi

    2008-02-01

    We show that the technique of integration within normal ordering of operators [Hong-yi Fan, Hai-liang Lu, Yue Fan, Ann. Phys. 321 (2006) 480-494] applied to tackling Newton-Leibniz integration over ket-bra projection operators, can be generalized to the technique of integration within Weyl ordered product (IWWOP) of operators. The Weyl ordering symbol

  4. Catalytic oxidation for treatment of ECLSS and PMMS waste streams

    Science.gov (United States)

    Akse, James R.; Jolly, Clifford D.

    1991-01-01

    It is shown that catalytic oxidation is an effective technique for the removal of trace organic contaminants in a multifiltration potable processor's effluent. Essential elements of this technology are devices that deliver oxygen to the influent, and remove gaseous reaction byproducts from the effluent, via hollow-tube, gas-permeable membranes. Iodine, which poisons existing catalysis, is removed by a small deiodination bed prior to catalytic reactor entrance. The catalyst used is a mixture of Pt and Ru deposited on carbon, operating at 125-160 C and 39-90 psi pressures.

  5. Highly efficient catalytic reductive degradation of various organic ...

    Indian Academy of Sciences (India)

    Highly improved catalytic reductive degradation of different organic dyes, in the presence of excess NaBH₄ over Au/CeO₂-TiO₂ nano-hybrid as the catalyst is reported ... Different parameters that affect the rate of the reaction are discussed. A plausible mechanism for methylene blue degradation has also been proposed.

  6. RUTHENIUM(III) DETERMINATION BY KINETIC-CATALYTIC ...

    African Journals Online (AJOL)

    +, H+, ClO2- and catalyst. The pertinent mechanism, consistent with the experimental results is proposed. Based on the high sensitivity and selectivity of the reaction to the presence of Ru(III), using its catalytic efficiency on the oxidation of Nile ...

  7. 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.

  8. 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...... of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations...

  9. 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...

  10. 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

  11. Advanced low emissions catalytic combustor program at General Electric

    Science.gov (United States)

    Dodds, W. J.

    1979-01-01

    The Advanced Low Emissions Catalytic Combustors Program (ALECC) is being undertaken to evaluate the feasibility of employing catalytic combustion technology in aircraft gas turbine engines as a means to control emission of oxides of nitrogen during subsonic stratospheric cruise operation. The ALECC Program is being conducted in three phases. The first phase, which was completed in November, 1978, consisted of a design study to identify catalytic combustor designs having the greatest potential to meet the emissions and performance goals specified. The primary emissions goal of this program was to obtain cruise NO emissions of less than 1g/kg (compared with levels of 15 to 20 g/x obtained with current designs)/ However, good overall performance and feasibility for engine development were heavily weighted in the evaluation of combustor designs.

  12. 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)

  13. Comparative study between dexmedetomidine and fentanyl for sedation during mechanical ventilation in post-operative paediatric cardiac surgical patients

    Directory of Open Access Journals (Sweden)

    S R Prasad

    2012-01-01

    Full Text Available Aims and Objectives: To compare the efficacy of sedation and time taken for extubation using dexmedetomidine and fentanyl sedation in post-operative paediatric cardiac surgical patients. Methods: A prospective randomized double-blind study involving 60 children undergoing open heart surgery was conducted. The patients were divided into two groups, each involving 30 patients. One group received fentanyl at 1 μg/kg/h (Group A and the other received dexmedetomidine at 0.5 μg/kg/h (Group B for post-operative sedation with intermittent rescue fentanyl 0.5 μg/kg bolus in either group as per requirement during suctioning. The efficacy of sedation was assessed using the Ramsay sedation score, paediatric intensive care unit sedation score and the tracheal suction score. The time taken for extubation from the stoppage of infusion was noted. Results: Haemodynamic parameters between the two groups were comparable. All sedation scores were comparable in the fentanyl and dexmedetomidine groups. Average time (in minutes required for extubation was 131.0 (±51.06 SD in the dexmedetomidine group compared with 373.0 (±121.4 SD in the fentanyl group. The difference in mean time for extubation was statistically significant. Conclusions: Dexmedetomidine facilitates adequate sedation for mechanical ventilation and also early extubation as compared with fentanyl.

  14. Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

    Science.gov (United States)

    Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

    2015-11-01

    Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

  15. Non-Catalytic Thruster for High Performance Advanced Monopropellant, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Systima Technologies, Inc. has demonstrated a low power non-catalytic ignition technology for advanced green monopropellant thrusters operating with HAN-based...

  16. Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed.

    Science.gov (United States)

    Paul, Indrajit; Goswami, Abir; Mittal, Nikita; Schmittel, Michael

    2018-01-02

    Three supramolecular slider-on-deck systems DS1-DS3 were obtained as two-component aggregates from the sliders S1-S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two-footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two N pyr →ZnPor interactions. Accordingly, the sliders move over the three zinc porphyrins in the deck at different speeds, namely with 32.2, 220, and 440 kHz at room temperature. The addition of N-methylpyrrolidine as an organocatalyst to DS1-DS3 generates catalytic three-component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider-on-deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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...

  18. 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.

  19. 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

  20. Catalytic Promiscuity of Ancestral Esterases and Hydroxynitrile Lyases.

    Science.gov (United States)

    Devamani, Titu; Rauwerdink, Alissa M; Lunzer, Mark; Jones, Bryan J; Mooney, Joanna L; Tan, Maxilmilien Alaric O; Zhang, Zhi-Jun; Xu, Jian-He; Dean, Antony M; Kazlauskas, Romas J

    2016-01-27

    Catalytic promiscuity is a useful, but accidental, enzyme property, so finding catalytically promiscuous enzymes in nature is inefficient. Some ancestral enzymes were branch points in the evolution of new enzymes and are hypothesized to have been promiscuous. To test the hypothesis that ancestral enzymes were more promiscuous than their modern descendants, we reconstructed ancestral enzymes at four branch points in the divergence hydroxynitrile lyases (HNL's) from esterases ∼ 100 million years ago. Both enzyme types are α/β-hydrolase-fold enzymes and have the same catalytic triad, but differ in reaction type and mechanism. Esterases catalyze hydrolysis via an acyl enzyme intermediate, while lyases catalyze an elimination without an intermediate. Screening ancestral enzymes and their modern descendants with six esterase substrates and six lyase substrates found higher catalytic promiscuity among the ancestral enzymes (P promiscuous and catalyzed both hydrolysis and lyase reactions with many substrates. A broader screen tested mechanistically related reactions that were not selected for by evolution: decarboxylation, Michael addition, γ-lactam hydrolysis and 1,5-diketone hydrolysis. The ancestral enzymes were more promiscuous than their modern descendants (P = 0.04). Thus, these reconstructed ancestral enzymes are catalytically promiscuous, but HNL1 is especially so.

  1. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    ... improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies ...

  2. 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

  3. Catalytic carboxyester hydrolysis by diaminodiphenols

    Indian Academy of Sciences (India)

    Administrator

    Two diaminodiphenols, 1 and 2, have been examined as catalysts for the hydrolysis of 4- nitrophenyl acetate (NA) and 4-nitrophenylphosphate (NP) in aqueous-acetonitrile (25% acetonitrile v/v) media at 35ºC, I = 1·0 mol dm–3. The compound 1 enhances the hydrolysis rate of NA more than 105 times. Its catalytic efficiency ...

  4. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so ...

  5. 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.

  6. 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

  7. How do patients’ clinical phenotype and the physiological mechanisms of the operations impact the choice of bariatric procedure?

    Directory of Open Access Journals (Sweden)

    Bächler T

    2016-07-01

    Full Text Available Thomas Bächler,1 Carel W le Roux,2,3 Marco Bueter4 1Department of General and Visceral Surgery, Fribourg Cantonal Hospital (HFR, Fribourg, Switzerland; 2Diabetes Complications Research Centre, Conway Institute, University College Dublin, Dublin, Ireland; 3Gastrosurgical Laboratory, University of Gothenburg, Gothenburg, Sweden; 4Division of Visceral and Transplantation Surgery, University Hospital Zurich (USZ, Zürich, Switzerland Abstract: Bariatric surgery is currently the most effective option for the treatment of morbid obesity and its associated comorbidities. Recent clinical and experimental findings have challenged the role of mechanical restriction and caloric malabsorption as the main mechanisms for weight loss and health benefits. Instead, other mechanisms including increased levels of satiety gut hormones, altered gut microbiota, changes in bile acid metabolism, and/or energy expenditure have been proposed as explanations for benefits of bariatric surgery. Beside the standard proximal Roux-en-Y gastric bypass and the biliopancreatic diversion with or without duodenal switch, where parts of the small intestine are excluded from contact with nutrients, resectional techniques like the sleeve gastrectomy (SG have recently been added to the armory of bariatric surgeons. The variation of weight loss and glycemic control is vast between but also within different bariatric operations. We surveyed members of the Swiss Society for the Study of Morbid Obesity and Metabolic Disorders to assess the extent to which the phenotype of patients influences the choice of bariatric procedure. Swiss bariatric surgeons preferred Roux-en-Y gastric bypass and SG for patients with type 2 diabetes mellitus and patients with a body mass index >50 kg/m2, which is consistent with the literature. An SG was preferred in patients with a high anesthetic risk or previous laparotomy. The surgeons’ own experience was a major determinant as there is little evidence in

  8. 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)

  9. Catalytic steam reforming of bio-oil

    DEFF Research Database (Denmark)

    Trane, R.; Dahl, S.; Skjøth-Rasmussen, M.S.

    2012-01-01

    Hydrogen and synthesis gas can be produced in an environmentally friendly and sustainable way through steam reforming (SR) of bio-oil and this review presents the state-of-the-art of SR of bio-oil and model compounds hereof. The possible reactions, which can occur in the SR process and the influe......Hydrogen and synthesis gas can be produced in an environmentally friendly and sustainable way through steam reforming (SR) of bio-oil and this review presents the state-of-the-art of SR of bio-oil and model compounds hereof. The possible reactions, which can occur in the SR process...... and the influence of operating conditions will be presented along with the catalysts and processes investigated in the literature.Several catalytic systems with Ni, Ru, or Rh can achieve good performance with respect to initial conversion and yield of hydrogen, but the main problem is that the catalysts...

  10. Techno-economic assessment of catalytic gasification of biomass powders for methanol production.

    Science.gov (United States)

    Carvalho, Lara; Furusjö, Erik; Kirtania, Kawnish; Wetterlund, Elisabeth; Lundgren, Joakim; Anheden, Marie; Wolf, Jens

    2017-08-01

    This study evaluated the techno-economic performance and potential benefits of methanol production through catalytic gasification of forest residues and lignin. The results showed that while catalytic gasification enables increased cold gas efficiencies and methanol yields compared to non-catalytic gasification, the additional pre-treatment energy and loss of electricity production result in small or no system efficiency improvements. The resulting required methanol selling prices (90-130€/MWh) are comparable with production costs for other biofuels. It is concluded that catalytic gasification of forest residues can be an attractive option as it provides operational advantages at production costs comparable to non-catalytic gasification. The addition of lignin would require lignin costs below 25€/MWh to be economically beneficial. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. 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

  12. An investigation into the characteristics and formation mechanisms of particles originating from the operation of laser printers.

    Science.gov (United States)

    Morawska, Lidia; He, Congrong; Johnson, Graham; Jayaratne, Rohan; Salthammer, Tunga; Wang, Hao; Uhde, Erik; Bostrom, Thor; Modini, Robin; Ayoko, Godwin; McGarry, Peter; Wensing, Michael

    2009-02-15

    While current research has demonstrated that the operation of some laser printers results in emission of high concentrations of ultrafine particles, fundamental gaps in knowledge in relation to the emissions still remain. In particular, there have been no answers provided to questions such as the following: (1) What is the composition of the particles? (2) What are their formation mechanisms? (3) Why are some printers high emitters, while others are low? Considering the widespread use of printers and human exposure to these particles, understanding the process of particle formation is of critical importance. This study, using state-of-the-art instrumental methods, has addressed these three points. We present experimental evidence that indicates that intense bursts of particles are associated with temperature fluctuations and suggest that the difference between high and low emitters lies in the speed and sophistication of the temperature control. We have also shown, for the first time, that the particles are volatile and are of secondary nature, being formed in the air from VOC originating from both the paper and hot toner. Some of the toner is initially deposited on the fuser roller, after which the organic compounds evaporate and then form particles, through one of two main reaction pathways: homogeneous nucleation or secondary particle formation involving ozone.

  13. 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....

  14. Vapor Phase Catalytic Ammonia Reduction

    Science.gov (United States)

    Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

  15. Inorganic membranes and catalytic reactors

    OpenAIRE

    Rangel, Maria do Carmo

    1997-01-01

    Membrane reactors are reviewed with emphasis in their applications in catalysis field. The basic principles of these systems are presented as well as a historical development. The several kinds of catalytic membranes and their preparations are discussed including the problems, needs and challenges to be solved in order to use these reactors in commercial processes. Some applications of inorganic membrane reactors are also shown. It was concluded that these systems have a great potential for i...

  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. 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...

  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. 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...... with the experimental values for both substrates, but only when migratory extrusion of 00 was selected as the rate-determining step....

  20. Synthesis and electrochemistry of β-pyrrole nitro-substituted cobalt(II) porphyrins. The effect of the NO₂ group on redox potentials, the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media.

    Science.gov (United States)

    Sun, Bin; Ou, Zhongping; Yang, Shuibo; Meng, Deying; Lu, Guifen; Fang, Yuanyuan; Kadish, Karl M

    2014-07-28

    Four cobalt(II) porphyrins, two of which contain a β-pyrrole nitro substituent, were synthesized and characterized by electrochemistry and spectroelectrochemistry. The investigated compounds are represented as (TRPP)Co and (NO2TRPP)Co, where TRPP is the dianion of a substituted tetraphenylporphyrin and R is a CH3 or OCH3 substituent on the four phenyl rings of the macrocycle. Two reductions and three oxidations are observed for each compound in CH2Cl2 containing 0.10 M tetra-n-butylammonium perchlorate. The first reduction of the compounds without a nitro substituent is metal-centered and leads to formation of a Co(I) porphyrin which then reacts with the CH2Cl2 solvent to generate a carbon σ-bonded Co(III)-R complex. A further reduction then occurs at more negative potentials to generate an unstable Co(II) σ-bonded compound. In contrast to these reactions, the first reduction of the nitro-substituted porphyrins is macrocycle-centered under the same solution conditions and gives a Co(II) porphyrin π-anion radical product. This reversible electron transfer is then followed at more negative potentials by a second reversible one-electron addition to give a Co(II) dianion. Three reversible one-electron oxidations are also seen for each compound. The first is metal-centered and the next two involve the conjugated π-system of the macrocycle. Each neutral Co(II) porphyrin was also examined as to its catalytic activity for electroreduction of molecular oxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO4. The β-pyrrole nitro-substituted derivatives were shown to be better catalysts than the non-nitro substituted compounds under the utilized experimental conditions.

  1. 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

  2. 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...

  3. Mechanized farming in the humid tropics with special reference to soil tillage, workability and timeliness of farm operations : a case study for the Zanderij area of Suriname

    NARCIS (Netherlands)

    Goense, D.

    1987-01-01

    The reported investigations concern aspects of mechanized farming for the production of rainfed crops on the loamy soils of the Zanderij formation in Suriname and in particular, the effect of tillage on crop yield and soil properties, workability of field operations and timeliness of field

  4. 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

  5. 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.

  6. 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

  7. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X...... as the nanoparticles are reduced. The Cu/ZnO nanoparticles are tested on a  µ-reactor platform and prove to be active towards methanol synthesis, making it an excellent model system for further investigations into activity depended morphology changes....

  8. Catalytic Combustion of Ethyl Acetate

    OpenAIRE

    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden

    2014-01-01

    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  9. 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

  10. Catalytic Promiscuity of the Radical S-adenosyl-L-methionine Enzyme NosL.

    Science.gov (United States)

    Ding, Wei; Ji, Xinjian; Li, Yongzhen; Zhang, Qi

    2016-01-01

    Catalytic promiscuity plays a key role in enzyme evolution and the acquisition of novel biological functions. Because of the high reactivity of radical species, in our view enzymes involving radical-mediated mechanisms could intrinsically be more prone to catalytic promiscuity. This mini-review summarizes the recent advances in the study of NosL, a radical S-adenosyl-L-methionine (SAM)-dependent L-tryptophan (L-Trp) lyase. We demonstrate here the interesting chemistry and remarkable catalytic promiscuity of NosL, and attempt to highlight the high evolvability of radical SAM enzymes and the potential to engineer these enzymes for novel and improved activities.

  11. Critical analysis of mechanisms of incentive regulation operators of electricity and natural gas networks and infrastructures. Final report. Public version, 23 November 2015

    International Nuclear Information System (INIS)

    2015-01-01

    As the first mechanisms of incentive regulation of electricity and gas network operators have been introduced by the French Commission for Energy Regulation (CRE) since 2008 (the report recalls the main objectives of these mechanisms and their consequences), this report proposes a critical analysis of such mechanisms related to investments and to exploitation expenses of operators and which have been implemented in Germany, Spain, Ireland and in the United Kingdom. For each country, the report proposes a detailed description of these mechanisms for the electric power sector and the gas sector (general overview of the regulation framework, objectives, determination of the authorised income, shift processing, specific incentive mechanisms, modalities of management by the regulator), and a feedback of the different concerned actors (operators and regulators). The last part proposes a description of the status of the French regulation, and an analysis of transposition of the four foreign regulations, and states some propositions for evolutions (objectives, overview of recommended evolutions, focus on three types of regulation evolution: processing of arbitral charges, processing of other incited capital charges, processing of arbitral charges)

  12. 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.

  13. 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

  14. 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).

  15. Catalytic cracking of bio-oil to organic liquid product (OLP).

    Science.gov (United States)

    Hew, K L; Tamidi, A M; Yusup, S; Lee, K T; Ahmad, M M

    2010-11-01

    The main objective of this paper is to find the optimum operating condition to upgrade the EFB-derived pyrolysis oil (bio-oil) to liquid fuel, mainly gasoline using Taguchi Method. From the analysis that has been done, it is found that the optimum operating condition for heterogeneous catalytic cracking process is at 400 degrees C, 15min of reaction time using 30g of catalyst weight where operating at this condition produced the highest yield of gasoline fraction which is 91.67 wt.%. This observation proves that EFB-derived pyrolysis oil could be upgraded via heterogeneous catalytic cracking to produce gasoline.

  16. Catalytic conversion of CO2 into valuable products

    International Nuclear Information System (INIS)

    Pham-Huu, C.; Ledoux, M.J.

    2008-01-01

    Complete text of publication follows: Synthesis gas, a mixture of H 2 and CO, is an important feed-stock for several chemical processes operated in the production of methanol and synthetic fuels through a Fischer- Tropsch synthesis. Synthesis gas is produced via an endothermic steam reforming of methane (CH 4 + H 2 O → CO + 3H 2 , ΔH = +225.4 kJ.mol -1 ), catalytic or direct partial oxidation of methane (CH 4 + (1/2)O 2 → CO + 2H 2 , ΔH -38 kJ.mol -1 ) and CO 2 reforming of methane (CH 4 + CO 2 → 2CO + 2H 2 , ΔH= +247 kJ.mol -1 ). The main disadvantage of these processes is the high coke formation, essentially in the nano-filament form, which may cause severe deactivation of the catalyst by pore or active site blocking and sometimes, physical disintegration of the catalyst body causing a high pressure drop along the catalyst bed and even, in some cases, inducing damage to the reactor itself. Previous results obtained in the catalytic partial oxidation of methane have shown that due to the hot spot and carbon nano-filaments formation, especially in the case of the CO 2 reforming, the alumina-based catalyst in an extrudate form was broken into powder which induces a significant pressure drop across the catalytic bed. In the case of endothermic reactions, steam and CO 2 reforming, the temperature drop within the catalyst bed could also modified the activity of the catalyst. Silicon carbide (SiC) exhibits a high thermal conductivity, a high resistance towards oxidation, a high mechanical strength, and chemical inertness, all of which make it a good candidate for use as catalyst support in several endothermic and exothermic reactions such as dehydrogenation, selective partial oxidation, and Fischer-Tropsch synthesis. The gas-solid reaction allows the preparation of SiC with medium surface area, i.e. 10 to 40 m 2 .g -1 , and controlled macroscopic shape, i.e. grains, extrudates or foam, for it subsequence use as catalyst support. In addition, due to its chemical

  17. Evaluation of catalytic combustion of actual coal-derived gas

    Science.gov (United States)

    Blanton, J. C.; Shisler, R. A.

    1982-01-01

    The combustion characteristics of a Pt-Pl catalytic reactor burning coal-derived, low-Btu gas were investigated. A large matrix of test conditions was explored involving variations in fuel/air inlet temperature and velocity, reactor pressure, and combustor exit temperature. Other data recorded included fuel gas composition, reactor temperatures, and exhaust emissions. Operating experience with the reactor was satisfactory. Combustion efficiencies were quite high (over 95 percent) over most of the operating range. Emissions of NOx were quite high (up to 500 ppm V and greater), owing to the high ammonia content of the fuel gas.

  18. Heterogeneous Catalytic Oligomerization of Ethylene

    Science.gov (United States)

    Jan, Oliver Dennis

    increased with temperature, with 17 wt.% observed at 190ºC. Higher reaction temperatures led to the formation of odd-numbered oligomers primarily due to acid-catalyzed cracking reactions. In the range of space velocities tested, a moderate WHSV of 2.0 hr-1 resulted in a local maximum of 10.6 wt.% of liquid hydrocarbon yield. A moderate nickel loading of 3.4 wt.% also resulted in the highest liquid yield out of the three loadings tested (10.6 wt.%). The variation in nickel loading revealed the importance of having a synergistic balance of nickel and acid sites on the catalyst to maximize ethylene conversion and maintain high liquid hydrocarbon yield. Lastly, we used supercritical ethylene as both a solvent and as a reactant for ethylene oligomerization over two silica-alumina type catalysts: Ni-Hbeta and Ni-Al-SBA-15. Specifically, the effect of pressure and temperature on the overall conversion and product selectivity were evaluated in the range from 0 to 65 bar and 30 to 120ºC. At subcritical conditions, the ethylene conversion reached a plateau of around 50%. By increasing the pressure past the critical point of ethylene, the conversion drastically increased to 71%. The increased conversion can be attributed to the solubility of certain oligomers, namely butene, in supercritical ethylene that promotes desorption from catalytic active site before further oligomerization. We also tested a mesoporous catalyst, Ni-Al-SBA-15 and observed conversion trends analogous to that of Ni-Hbeta. At supercritical conditions, ethylene oligomerization over Ni-Al-SBA-15 was more selective towards the butene product, with nearly 74 wt.% butenes observed. The catalyst activity increased with temperature from 30ºC to 120ºC. The experiment conducted at 30ºC showed very little activity and ethylene conversion, however it effectively heavy molecular weight species from the catalyst. This condition, albeit being not effective for ethylene oligomerization, could be implemented as an in

  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 great sustainability challenge. However, the waste sector can provide significant opportunities for improving livelihoods, generating jobs and developing enterprises, through the recovery of valuable recyclables. Co-operatives are recognised as a means...

  20. Mechanical behaviour of umbrella-shaped, Ni-Ti memory alloy femoral head support device during implant operation: a finite element analysis study.

    Directory of Open Access Journals (Sweden)

    Wei Yi

    Full Text Available A new instrument used for treating femoral head osteonecrosis was recently proposed: the umbrella-shaped, Ni-Ti memory femoral head support device. The device has an efficacy rate of 82.35%. Traditional radiographic study provides limited information about the mechanical behaviour of the support device during an implant operation. Thus, this study proposes a finite element analysis method, which includes a 3-step formal head model construction scheme and a unique material assignment strategy for evaluating mechanical behaviour during an implant operation. Four different scenarios with different constraints, initial positions and bone qualities are analyzed using the simulation method. The max radium of the implanted device was consistent with observation data, which confirms the accuracy of the proposed method. To ensure that the device does not unexpectedly open and puncture the femoral head, the constraint on the impact device should be strong. The initial position of sleeve should be in the middle to reduce the damage to the decompression channel. The operation may fail because of poor bone quality caused by severe osteoporosis. The proposed finite element analysis method has proven to be an accurate tool for studying the mechanical behaviour of umbrella-shaped, Ni-Ti memory alloy femoral head support device during an implant operation. The 3-step construct scheme can be implemented with any kind of bone structure meshed with multiple element types.

  1. The catalytic oxidation of organic contaminants in a packed bed reactor

    NARCIS (Netherlands)

    van de Beld, L.; Bijl, M.P.G.; Reinders, A.; van der Wert, B.; Westerterp, K.R.

    1994-01-01

    The catalytic oxidation of several hydrocarbons was studied over noble metal and metal oxide catalysts. A fast empirical method was developed to determine the minimum operating temperature required to guarantee complete conversion of the hydrocarbon. The influence of the operating parameters such as

  2. Adaptive Model Predictive Control of Diesel Engine Selective Catalytic Reduction (SCR) Systems

    Science.gov (United States)

    McKinley, Thomas L.

    2009-01-01

    Selective catalytic reduction or SCR is coming into worldwide use for diesel engine emissions reduction for on- and off-highway vehicles. These applications are characterized by broad operating range as well as rapid and unpredictable changes in operating conditions. Significant nonlinearity, input and output constraints, and stringent performance…

  3. Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

    African Journals Online (AJOL)

    Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

  4. Catalytic gasification of dry and wet biomass

    NARCIS (Netherlands)

    van Rossum, G.; Potic, B.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

    2009-01-01

    Catalytic gasification of dry biomass and of wet biomass streams in hot compressed water are reviewed and discussed as potential technologies for the production of synthesis gas, hydrogen- and methane-rich gas. Next to literature data also new experimental results from our laboratory on catalytic

  5. Operation and maintenance of the RA Reactor in 1985, Part 1, Annex D - Report of the Mechanics Service

    International Nuclear Information System (INIS)

    Sulem, B.

    1985-01-01

    Service for mechanical components at the RA reactor includes: control and maintenance of utility components, mechanical workshop, hot cells and storage. Control and maintenance of main components covers: reactor core, heavy water system, technical water system, gas system. This service is responsible for the following auxiliary systems: transportation units; spent fuel storage pool; special ventilation system; personal protection appliances; hot cells. Maintenance of the reactor building, ventilation, heating, water supply, sewage, fire protection devices, gas and compressed air systems are included [sr

  6. Non-catalytic recuperative reformer

    Science.gov (United States)

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  7. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  8. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  9. Thermally assisted mechanical dewatering (TAMD) of suspensions of fine particles: analysis of the influence of the operating conditions using the response surface methodology.

    Science.gov (United States)

    Mahmoud, Akrama; Fernandez, Aurora; Chituchi, Toma-Mihai; Arlabosse, Patricia

    2008-08-01

    Thermally assisted mechanical dewatering (TAMD) is a new process for energy-efficient liquid/solids separation which enhances conventional-device efficiency. The main idea of this process is to supply a flow of heat in mechanical dewatering processes to favour the reduction of the liquid content. This is not a new idea but the proposed combination, especially the chosen operating conditions (temperature bentonite sludge provided by Soletanche Bachy Company. Experiment showed that the extent of TAMD for a given material is particularly dependent on their physical and chemical properties but also on processing parameters.

  10. Finely tunable fabrication and catalytic activity of gold multipod nanoparticles.

    Science.gov (United States)

    Choi, Soon; Moon, Youngseo; Yoo, Hyojong

    2016-05-01

    Gold multipod nanoparticles (Au Multipod NPs) containing multi-branches with sharp edges and tips were synthesized in high yield through a facile seed-mediated method using cetyltrimethylammonium bromide (CTAB), Brij35, Au seed nanoparticles, Ag(+) ions, ascorbic acid, and sodium salicylate. The branch lengths of Au Multipod NPs were finely controlled by adjusting the molar ratio of mixed surfactants, and in particular by changing the amount of sodium salicylate. A formation mechanism for the star-shaped topologies was proposed and experimentally proved. The catalytic activity of the synthesized Au Multipod NPs was evaluated in ethanol electrooxidation reaction. The dependence of the catalytic performances on the nanostructural morphology was investigated. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Formulation and catalytic performance of MOF-derived Fe@C/Al composites for high temperature Fischer–Tropsch synthesis

    KAUST Repository

    Oar-Arteta, Lide

    2017-11-15

    High productivity towards C-2-C-4 olefins together with high catalyst stability are key for optimum operation in high temperature Fischer-Tropsch synthesis (HT-FTS). Here, we report the fabrication of Fe@C/Al composites that combine both the outstanding catalytic properties of the Fe-BTC MOF-derived Fe catalyst and the excellent mechanical resistance and textural properties provided by the inorganic AlOOH binder. The addition of AlOOH to Fe-BTC followed by pyrolysis in N-2 atmosphere at 500 degrees C results in composites with a large mesoporosity, a high Fe/Fe3O4 ratio, 10-35 nm average Fe crystallite size and coordinatively unsaturated Al3+ sites. In catalytic terms, the addition of AlOOH binder gives rise to enhanced C-2-C-4 selectivity and catalyst mechanical stability in HT-FTS, but at high Al contents the activity decreases. Altogether, the productivity of these Fe@C/Al composites is well above most known Fe catalysts for this process.

  12. Catalytic strategy used by the myosin motor to hydrolyze ATP.

    Science.gov (United States)

    Kiani, Farooq Ahmad; Fischer, Stefan

    2014-07-22

    Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

  13. Homogeneous and single-side-operational connector mechanism for self-reconfigurable, self-assembly and self-healing systems

    Science.gov (United States)

    Shen, Wei-Min (Inventor); Kovac, Robert M. (Inventor)

    2012-01-01

    Designs of single-end-operative reconfigurable genderless connectors that include a base, a plurality of movable jaws that are formed on the base and can engage to the jaws of another connector, and an actuator that is mounted on the base and can engage and move the jaws of the reconfigurable connector to connect the reconfigurable connector with another connector.

  14. Microstructural analysis and the mechanism if the coke formation in a refractory castable used in a fluidized catalytic cracking unit; Analise microestructural e mecanismo de formacao do coque em um concreto refratario utilizado em unidades de craqueamento catalitico fludizado

    Energy Technology Data Exchange (ETDEWEB)

    Cabrelon, M.D.; Rodrigues, J.A. [Universidade Federal de Sao Carlos (GEMM/UFSCAR), Sao Carlos, SP (Brazil). Grupo de Engenharia de Microestrutura de Materiais], Email: marcelodezena@gmail.com; Medeiros, J. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas; Toledo Filho, R.D. [Coordenacao dos Programas de Pos-Graduacao de Engenharia (COPPE/UFRJ), Rio de Janeiro, RJ (Brazil). Lab. de Estruturas e Materiais

    2010-07-01

    The cokes formation in the refractory castables for FCC's unit is cited as one the most relevant problem in the internal face of the petrochemical Riser, but its mechanism is still unknown. In this sense, was made a microstructural study with a anti-erosive refractory castable class C, exposed to a cokemaker atmosphere, aiming to identify a mechanism to explain the coke's formation. For this reason, test samples were molded and subjected to a cokemaker process in the reactor pilot from CENPES-PETROBRAS-RJ, under an atmosphere of propene, as one temperature of 540 deg C and soaking time ranging between 10 and 480h. These samples had their internal and surface microstructures analyzed by Optical and Scanning Electron Microscopy. The results showed that the aggregates had deterioration and your internal pores were filled with coke. In this point, starts the growth of microspheres of coke on the external face, coalescing and forming 'columns' in which become denser when increasing the exposure time to a saturated atmosphere with hydrocarbon. (author)

  15. Investigation of polypyrrole/polyvinyl alcohol-titanium dioxide composite films for photo-catalytic applications

    Science.gov (United States)

    Cao, Shaoqiang; Zhang, Hongyang; Song, Yuanqing; Zhang, Jianling; Yang, Haigang; Jiang, Long; Dan, Yi

    2015-07-01

    Polypyrrole/polyvinyl alcohol-titanium dioxide (PPy/PVA-TiO2) composite films used as photo-catalysts were fabricated by combining TiO2 sol with PPy/PVA solution in which PPy was synthesized by in situ polymerization of pyrrole (Py) in polyvinyl alcohol (PVA) matrix and loaded on glass. The prepared photo-catalysts were investigated by X-ray diffraction (XRD), ultraviolet-visible diffuse reflection spectroscopy (UV-vis DRS), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectra and photoluminescence (PL). The results indicate that the composites have same crystal structure as the TiO2 and extend the optic absorption from UV region to visible light region. By detecting the variation ratio, detected by ultraviolet-vis spectroscopy, of model pollutant rhodamine B (RhB) solution in the presence of the composite films under both UV and visible light irradiation, the photo-catalytic performance of the composite films was investigated. The results show that the PPy/PVA-TiO2 composite films show better photo-catalytic properties than TiO2 film both under UV and visible light irradiation, and the photo-catalytic degradation of RhB follows the first-order kinetics. The effects of the composition of composite films and the concentration of RhB on the photo-catalytic performance, as well as the possible photo-catalytic mechanism, were also discussed. By photo-catalytic recycle experiments, the structure stability of the PPy/PVA-TiO2 composite film was investigated and the results show that the photo-catalytic activity under both UV and visible light irradiation have no significant decrease after four times of recycle experiments, suggesting that the photo-catalyst film is stable during the photo-catalytic process, which was also confirmed by the XRD pattern and FT-IR spectra of the composite film before and after photo-catalytic.

  16. Study on fundamental mechanism of nuclear advanced robot. Some consideration of driving mechanism on remotely operated and submerged vehicle using the maintenance for nuclear power plant

    International Nuclear Information System (INIS)

    Ohki, Arahiko; Hirano, Sigeo; Oogihara, Hirotugu

    1998-01-01

    A propulsion system of fish was studied as a research of the driving mechanism of robot for nuclear maintenance in water. Fish sailing with higher speed than a constant value can sail by an Ostraciform type swimming method. Fish can advance by a winding actuation. The movement of fishes trunk and caudal at the stationary movement was studied in this paper. The hypothetical formulae of movement were constructed on the basis of the movements of trunk and caudal. The elements related to the driving force were analysed and evaluated. Then, a model for reproducing the movement was designed. The movement of model was tested. The theoretical formula proved that the driving forces were consisted of the force vectors in the forward direction to be generated by the phase differences of each points of trunk and caudal in their cyclic movements. (S.Y.)

  17. Process for catalytic flue gas denoxing

    International Nuclear Information System (INIS)

    Woldhuis, A.; Goudriaan, F.; Groeneveld, M.; Samson, R.

    1991-01-01

    With the increasing concern for the environment, stringency of legislation and industry's awareness of its own environmental responsibility, the demand for the reduction of emission levels of nitrogen oxides is becoming increasingly urgent. This paper reports that Shell has developed a low temperature catalytic deNOx system for deep removal of nitrogen oxides, which includes a low-pressure-drop reactor. This process is able to achieve over 90% removal of nitrogen oxides and therefore can be expected to meet legislation requirements for the coming years. The development of a low-temperature catalyst makes it possible to operate at temperatures as low as 120 degrees C, compared to 300-400 degrees C for the conventional honeycomb and plate-type catalysts. This allows an add-on construction, which is most often a more economical solution than the retrofits in the hot section required with conventional deNOx catalysts. The Lateral Flow Reactor (LFR), which is used for dust-free flue gas applications, and the Parallel Passage Reactor (PPR) for dust-containing flue gas applications, have been developed to work with pressure drops below 10 mbar

  18. Dimerization interface of 3-hydroxyacyl-CoA dehydrogenase tunes the formation of its catalytic intermediate.

    Directory of Open Access Journals (Sweden)

    Yingzhi Xu

    Full Text Available 3-Hydroxyacyl-CoA dehydrogenase (HAD, EC 1.1.1.35 is a homodimeric enzyme localized in the mitochondrial matrix, which catalyzes the third step in fatty acid β-oxidation. The crystal structures of human HAD and subsequent complexes with cofactor/substrate enabled better understanding of HAD catalytic mechanism. However, numerous human diseases were found related to mutations at HAD dimerization interface that is away from the catalytic pocket. The role of HAD dimerization in its catalytic activity needs to be elucidated. Here, we solved the crystal structure of Caenorhabditis elegans HAD (cHAD that is highly conserved to human HAD. Even though the cHAD mutants (R204A, Y209A and R204A/Y209A with attenuated interactions on the dimerization interface still maintain a dimerization form, their enzymatic activities significantly decrease compared to that of the wild type. Such reduced activities are in consistency with the reduced ratios of the catalytic intermediate formation. Further molecular dynamics simulations results reveal that the alteration of the dimerization interface will increase the fluctuation of a distal region (a.a. 60-80 that plays an important role in the substrate binding. The increased fluctuation decreases the stability of the catalytic intermediate formation, and therefore the enzymatic activity is attenuated. Our study reveals the molecular mechanism about the essential role of the HAD dimerization interface in its catalytic activity via allosteric effects.

  19. Catalytic Ozonation of Phenolic Wastewater: Identification and Toxicity of Intermediates

    Directory of Open Access Journals (Sweden)

    Mahdi Farzadkia

    2014-01-01

    Full Text Available A new strategy in catalytic ozonation removal method for degradation and detoxification of phenol from industrial wastewater was investigated. Magnetic carbon nanocomposite, as a novel catalyst, was synthesized and then used in the catalytic ozonation process (COP and the effects of operational conditions such as initial pH, reaction time, and initial concentration of phenol on the degradation efficiency and the toxicity assay have been investigated. The results showed that the highest catalytic potential was achieved at optimal neutral pH and the removal efficiency of phenol and COD is 98.5% and 69.8%, respectively. First-order modeling demonstrated that the reactions were dependent on the initial concentration of phenol, with kinetic constants varying from 0.038 min−1  ([phenol]o = 1500 mg/L to 1.273 min−1 ([phenol]o = 50 mg/L. Bioassay analysis showed that phenol was highly toxic to Daphnia magna (LC50 96 h=5.6 mg/L. Comparison of toxicity units (TU of row wastewater (36.01 and the treated effluent showed that TU value, after slightly increasing in the first steps of ozonation for construction of more toxic intermediates, severely reduced at the end of reaction (2.23. Thus, COP was able to effectively remove the toxicity of intermediates which were formed during the chemical oxidation of phenolic wastewaters.

  20. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.